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Chinese Chemical Letters
Chinese Chemical Letters
主管 : 中国科学技术协会
刊期 : 月刊主编 : 钱旭红
语种 : 英文主办 : 中国化学会、中国医学科学院药物研究所
ISSN : 1001-8417 CN : 11-2710/O6本刊创办于1990年7月，是由中国化学会主办，中国医学科学院药物研究所承办的核心期刊。本刊由著名化学家梁晓天院士任主编，其内容涵盖化学研究的各个领域，及时报道我国化学界各个研究领域的最新进展及世界上一些化学研究的热点问题。本刊自1993年起为SCI、CA、日本科技文献速报等收录，2000年美国化学文摘引用中国期刊频次中位列第四。展开 > - 影响因子: 8.9
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期刊内热点文章
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Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation
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Recent progress in the synthesis of sulfonyl fluorides for SuFEx click chemistry
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Development of electron and hole selective contact materials for perovskite solar cells
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Superiority of poly(L-lactic acid) microspheres as dermal fillers
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期刊内下载排行
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Synthesis of a new ratiometric emission Ca2+ indicator for in vivo bioimaging
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Synthesis of a water-soluble macromolecular light stabilizer containing hindered amine structures
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Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation
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Superiority of poly(L-lactic acid) microspheres as dermal fillers
2026, 37(11): 111505
doi: 10.1016/j.cclet.2025.111505
摘要:
Strong metal-support interaction (SMSI) offers innovative strategies for designing efficient oxygen reduction reaction (ORR) synergetic catalysts. Herein, an ultrafine platinum (Pt) cluster (∼2.2 nm) catalyst encapsulated with Pyri-N-rich graphene (Pt UC@NG-800) is developed within the angstrom-level (Å) interlayer cavities to improve the exposure and stabilization of Pt active sites as well as promote the O2 adsorption and transfer. Consequently, Pt UC@NG-800 shows superior 4e- ORR activity with half-wave potentials (E1/2) of 0.99 V and 0.93 V (vs. RHE), which are enhanced by 110 mV and 80 mV compared to commercial Pt/C (20%) (0.88 V and 0.85 V) in alkaline and acidic media, respectively. Furthermore, the mass activity (MA) of Pt UC@NG-800 are 49.6 and 51.1 times higher than that of Pt/C in both media, respectively. After 50,000 accelerated durability tests and 120 h of long-term operation, Pt UC@NG-800 displays negligible degradation with ∆E1/2 of 5 mV (alkaline) or 10 mV (acid) and little current fading in both alkaline and acid media, respectively, implying superior durability with enhanced resistance to Pt dissolution and carbon corrosion. This work presents a novel framework and practical approach for developing ultrafine cluster catalysts with highly stable and exposed active sites for superior ORR performance.
Strong metal-support interaction (SMSI) offers innovative strategies for designing efficient oxygen reduction reaction (ORR) synergetic catalysts. Herein, an ultrafine platinum (Pt) cluster (∼2.2 nm) catalyst encapsulated with Pyri-N-rich graphene (Pt UC@NG-800) is developed within the angstrom-level (Å) interlayer cavities to improve the exposure and stabilization of Pt active sites as well as promote the O2 adsorption and transfer. Consequently, Pt UC@NG-800 shows superior 4e- ORR activity with half-wave potentials (E1/2) of 0.99 V and 0.93 V (vs. RHE), which are enhanced by 110 mV and 80 mV compared to commercial Pt/C (20%) (0.88 V and 0.85 V) in alkaline and acidic media, respectively. Furthermore, the mass activity (MA) of Pt UC@NG-800 are 49.6 and 51.1 times higher than that of Pt/C in both media, respectively. After 50,000 accelerated durability tests and 120 h of long-term operation, Pt UC@NG-800 displays negligible degradation with ∆E1/2 of 5 mV (alkaline) or 10 mV (acid) and little current fading in both alkaline and acid media, respectively, implying superior durability with enhanced resistance to Pt dissolution and carbon corrosion. This work presents a novel framework and practical approach for developing ultrafine cluster catalysts with highly stable and exposed active sites for superior ORR performance.
2026, 37(11): 111643
doi: 10.1016/j.cclet.2025.111643
摘要:
High sensitivity, accuracy, stability, and convenience are desirable features for the development of glucose sensors. Here we present a simple, wafer-scale strategy for engineering optical glucose sensors by self-assembling pH-responsive block-copolymer films and glucose oxidase (GOx) inside Fabry–Pérot (F–P) TiO2 nanotube interferometers. The resulting hybrid membranes combine the nanoconfinement of TiO2 tubes with the reversible swelling of poly(4-vinylpyridine) domains, transducing enzymatically generated pH shifts into large, reproducible shifts of the effective optical thickness (EOT) that are directly read in situ by reflective interferometric Fourier-transform spectroscopy (RIFTS). A cascade reaction—Prussian blue-catalysed oxidation of 4–chloro-1-naphthol by H2O2—precipitates 4–chloro-1,2-naphthoquinone within the tubes, amplifying the refractive index change and boosting sensitivity. The as-formed chips quantify glucose from 1 µmol/L to 10 mmol/L with two linear regimes (1–100 µmol/L, 0.1–10 mmol/L) and achieve a 0.9 µmol/L limit of detection, outperforming previously reported F–P and colorimetric platforms while retaining full functionality after multiple sensing/rinsing cycles. Owing to the excellent pH-responsive ability of BCP and the high sensitivity of RIFTS to EOT changes, the proposed F–P interferometer represents a promising device for the simulation and in situ investigation of enzymatic reactions in biochannels.
High sensitivity, accuracy, stability, and convenience are desirable features for the development of glucose sensors. Here we present a simple, wafer-scale strategy for engineering optical glucose sensors by self-assembling pH-responsive block-copolymer films and glucose oxidase (GOx) inside Fabry–Pérot (F–P) TiO2 nanotube interferometers. The resulting hybrid membranes combine the nanoconfinement of TiO2 tubes with the reversible swelling of poly(4-vinylpyridine) domains, transducing enzymatically generated pH shifts into large, reproducible shifts of the effective optical thickness (EOT) that are directly read in situ by reflective interferometric Fourier-transform spectroscopy (RIFTS). A cascade reaction—Prussian blue-catalysed oxidation of 4–chloro-1-naphthol by H2O2—precipitates 4–chloro-1,2-naphthoquinone within the tubes, amplifying the refractive index change and boosting sensitivity. The as-formed chips quantify glucose from 1 µmol/L to 10 mmol/L with two linear regimes (1–100 µmol/L, 0.1–10 mmol/L) and achieve a 0.9 µmol/L limit of detection, outperforming previously reported F–P and colorimetric platforms while retaining full functionality after multiple sensing/rinsing cycles. Owing to the excellent pH-responsive ability of BCP and the high sensitivity of RIFTS to EOT changes, the proposed F–P interferometer represents a promising device for the simulation and in situ investigation of enzymatic reactions in biochannels.
2026, 37(11): 111665
doi: 10.1016/j.cclet.2025.111665
摘要:
Flame-assisted spray pyrolysis (FASP) is a promising manufacturing technology for preparing LiNi1-x-yCoxMnyO2 (NCM) cathode materials for lithium-ion batteries, which involves four metal elements: Li, Ni, Co, and Mn. The transformation routes of inorganic salts associated with these elements during FASP, leading to the synthesis of NCM cathode materials, are complex and remains unclear. In the present study, theoretical thermodynamic calculations and experimental thermogravimetric analysis were employed. Results show that LiNO3 begins to decompose at 660 ℃, significantly higher than the decomposition temperatures of Ni, Co, and Mn nitrates (below 300 ℃). Therefore, the thermal decomposition routes of the four nitrates can be categorized into two groups: Ni, Co, and Mn nitrates decompose into non-reactive stable oxides, while LiNO3 is converted to the reactive Li2O, ultimately forming LiOH and Li2CO3 in the presence of CO2 and H2O. The above finding greatly simplifies and enhances the understanding of fundamental mechanism governing the complex FASP preparation process for NCM cathode materials. Furthermore, to reveal the effect of the Li element on NCM cathode materials properties, a two-step FASP approach was proposed for preparing LiNi1/3Co1/3Mn1/3O2 (NCM111) using three lithium salts: LiNO3, Li2CO3, and LiOH·H2O. Results indicate that the lithium salts significantly influence NCM cathode material structure and electrochemical performance, with NCM111 prepared using LiOH·H2O exhibiting the optimal structure and electrochemical performance.
Flame-assisted spray pyrolysis (FASP) is a promising manufacturing technology for preparing LiNi1-x-yCoxMnyO2 (NCM) cathode materials for lithium-ion batteries, which involves four metal elements: Li, Ni, Co, and Mn. The transformation routes of inorganic salts associated with these elements during FASP, leading to the synthesis of NCM cathode materials, are complex and remains unclear. In the present study, theoretical thermodynamic calculations and experimental thermogravimetric analysis were employed. Results show that LiNO3 begins to decompose at 660 ℃, significantly higher than the decomposition temperatures of Ni, Co, and Mn nitrates (below 300 ℃). Therefore, the thermal decomposition routes of the four nitrates can be categorized into two groups: Ni, Co, and Mn nitrates decompose into non-reactive stable oxides, while LiNO3 is converted to the reactive Li2O, ultimately forming LiOH and Li2CO3 in the presence of CO2 and H2O. The above finding greatly simplifies and enhances the understanding of fundamental mechanism governing the complex FASP preparation process for NCM cathode materials. Furthermore, to reveal the effect of the Li element on NCM cathode materials properties, a two-step FASP approach was proposed for preparing LiNi1/3Co1/3Mn1/3O2 (NCM111) using three lithium salts: LiNO3, Li2CO3, and LiOH·H2O. Results indicate that the lithium salts significantly influence NCM cathode material structure and electrochemical performance, with NCM111 prepared using LiOH·H2O exhibiting the optimal structure and electrochemical performance.
2026, 37(11): 111697
doi: 10.1016/j.cclet.2025.111697
摘要:
Atomically precise metal nanoclusters stabilised by organic ligands represent a distinct class of catalyst materials. However, the synthesis of efficient ligated cluster catalysts and understanding how they work, especially under the full exposure of surface ligands, remains challenging. In this study, we describe a stable ligand-protected [Au5Cu2(dppm)2(C7H7S)6]+ (dppm is bis(diphenylphosphino)methane, and RSH is 4-methylbenzenethiol) cluster that exhibits exceptional activity in the electrocatalytic hydrogen evolution (HER) reaction. The cluster demonstrates HER activity comparable to commercial Pt/C in acidic media and retains its performance over extended operation. Mechanism studies using theoretical computations reveal that the thiolate ligands in the cluster undergo protonation-induced removal and reconstruction. These atomically dynamic surfaces transiently expose active metal sites, leading to a substantial enhancement in HER activity. The dynamic catalysis mechanism of the cluster has also been validated by X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) experiments. This study not only rationalises the controversial issue of how ligated metal clusters drive chemical transformations with high activity but also highlights the importance of surface dynamics in governing the catalysis of metal nanoclusters.
Atomically precise metal nanoclusters stabilised by organic ligands represent a distinct class of catalyst materials. However, the synthesis of efficient ligated cluster catalysts and understanding how they work, especially under the full exposure of surface ligands, remains challenging. In this study, we describe a stable ligand-protected [Au5Cu2(dppm)2(C7H7S)6]+ (dppm is bis(diphenylphosphino)methane, and RSH is 4-methylbenzenethiol) cluster that exhibits exceptional activity in the electrocatalytic hydrogen evolution (HER) reaction. The cluster demonstrates HER activity comparable to commercial Pt/C in acidic media and retains its performance over extended operation. Mechanism studies using theoretical computations reveal that the thiolate ligands in the cluster undergo protonation-induced removal and reconstruction. These atomically dynamic surfaces transiently expose active metal sites, leading to a substantial enhancement in HER activity. The dynamic catalysis mechanism of the cluster has also been validated by X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) experiments. This study not only rationalises the controversial issue of how ligated metal clusters drive chemical transformations with high activity but also highlights the importance of surface dynamics in governing the catalysis of metal nanoclusters.
2026, 37(11): 111698
doi: 10.1016/j.cclet.2025.111698
摘要:
As an important branch of polyoxometalates (POMs), polyoxothiometalates (POTMs) exhibit significant proton enrichment capabilities due to their high negative charge density and strong hydrophilicity. Their oxygen-rich surfaces provide an ideal platform for constructing long-range ordered hydrogen-bond networks, demonstrating unique advantages in proton conductor design. In this work, two novel POTM clusters based on [Mo2O2S2]2+ building blocks were synthesized via an in situ strategy. Ligand and anionic template coordination modes critically direct structural assembly. Utilizing the AsO43- template, with glyphosine (Gly) and 4,4′-sulfonyldibenzoic acid (H2SDB) serving as bridging ligands to form dimeric structures: H11K4[(Co3(AsO4)2(Mo2O2S2)6(OH)6O3(Gly)3(H2O)5]·35H2O (compound 1) and H16K4[(AsO4)4(Mo2O2S2)12(OH)12O4(H2SDB)6(H2O)2]·36H2O (compound 2), with the latter exhibiting an edge-interlocking polyhedral architecture. Crystallography studies have shown that the rigid ligand H2SDB in compound 2 significantly expands the framework porosity by geometrically fitting the {AsMo6} unit, which has an inherent bending angle. To release the structural stress, two dimer construction units are vertically cross-linked after being rotated 180°, forming a unique edge-interlocking structure. Proton conduction measurements demonstrated that under conditions of 85 °C and 80% relative humidity, Compounds 1 and 2 exhibit proton conductivities of 9.64 × 10-3 and 2.18 × 10-2 S/cm, respectively, highlighting their significant potential as proton-conductive materials. This work provides a new strategy for the structure-oriented design of POM-based proton conductors.
As an important branch of polyoxometalates (POMs), polyoxothiometalates (POTMs) exhibit significant proton enrichment capabilities due to their high negative charge density and strong hydrophilicity. Their oxygen-rich surfaces provide an ideal platform for constructing long-range ordered hydrogen-bond networks, demonstrating unique advantages in proton conductor design. In this work, two novel POTM clusters based on [Mo2O2S2]2+ building blocks were synthesized via an in situ strategy. Ligand and anionic template coordination modes critically direct structural assembly. Utilizing the AsO43- template, with glyphosine (Gly) and 4,4′-sulfonyldibenzoic acid (H2SDB) serving as bridging ligands to form dimeric structures: H11K4[(Co3(AsO4)2(Mo2O2S2)6(OH)6O3(Gly)3(H2O)5]·35H2O (compound 1) and H16K4[(AsO4)4(Mo2O2S2)12(OH)12O4(H2SDB)6(H2O)2]·36H2O (compound 2), with the latter exhibiting an edge-interlocking polyhedral architecture. Crystallography studies have shown that the rigid ligand H2SDB in compound 2 significantly expands the framework porosity by geometrically fitting the {AsMo6} unit, which has an inherent bending angle. To release the structural stress, two dimer construction units are vertically cross-linked after being rotated 180°, forming a unique edge-interlocking structure. Proton conduction measurements demonstrated that under conditions of 85 °C and 80% relative humidity, Compounds 1 and 2 exhibit proton conductivities of 9.64 × 10-3 and 2.18 × 10-2 S/cm, respectively, highlighting their significant potential as proton-conductive materials. This work provides a new strategy for the structure-oriented design of POM-based proton conductors.
2026, 37(11): 111699
doi: 10.1016/j.cclet.2025.111699
摘要:
Owing to the structural and compositional flexibility feature, antiperovskites have garnered widespread attention, and been regarded as promising catalysts. However, their intrinsic sluggish kinetics impede their practical applications. Herein, a CoN0.73Co3@CoFeN(OH)x is constructed by a developed oxidation technology, endowing exceptional performance toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) at ampere-level current densities. The advanced nature of our as-prepared antiperovskite could be further evidenced by an assembled alkaline electrolyzer (CoN0.73Co3@CoFeN(OH)xCoN0.73Co3@CoFeN(OH)x), yielding a current density of 1000 mA/cm2 with 1.89 V, and stable working for over 100 h. Operando characterizations clarify that iron atoms in the antiperovskite skin promote the generation of CoOOH active species. Theoretical calculations are referred to understand the decent catalytic activity, which reveals that Fe atoms are responsible for the favorable adsorption of the OOH oxygen intermediate and modulate the hydrogen adsorption strength. This work paves a solid way for engineering the antiperovskites for green hydrogen generation applications.
Owing to the structural and compositional flexibility feature, antiperovskites have garnered widespread attention, and been regarded as promising catalysts. However, their intrinsic sluggish kinetics impede their practical applications. Herein, a CoN0.73Co3@CoFeN(OH)x is constructed by a developed oxidation technology, endowing exceptional performance toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) at ampere-level current densities. The advanced nature of our as-prepared antiperovskite could be further evidenced by an assembled alkaline electrolyzer (CoN0.73Co3@CoFeN(OH)xCoN0.73Co3@CoFeN(OH)x), yielding a current density of 1000 mA/cm2 with 1.89 V, and stable working for over 100 h. Operando characterizations clarify that iron atoms in the antiperovskite skin promote the generation of CoOOH active species. Theoretical calculations are referred to understand the decent catalytic activity, which reveals that Fe atoms are responsible for the favorable adsorption of the OOH oxygen intermediate and modulate the hydrogen adsorption strength. This work paves a solid way for engineering the antiperovskites for green hydrogen generation applications.
2026, 37(11): 111701
doi: 10.1016/j.cclet.2025.111701
摘要:
Solar-driven hydrogen peroxide (H2O2) production offers a sustainable alternative to the energy-intensive anthraquinone process, yet conventional photocatalysts suffer from poor selectivity and uncontrollable reaction pathways. Inspired by catechol oxidase enzymes, we design dopamine-grafted lipoic acid-protected gold nanoclusters (DA-LA-Au NCs) that shift photocatalytic active sites from the metal core to redox-active ligands. This ligand-centric architecture leverages dopamine’s reversible catechol/quinone interconversion to gate a biomimetic proton-coupled electron transfer (PCET) pathway, enabling exclusive 2e- oxygen reduction with near-100% H2O2 selectivity while completely suppressing superoxide radical (·O2-) generation. Transient absorption spectroscopy and molecular dynamics confirm enhanced electron transfer kinetics and O2 enrichment at ligand sites. Encapsulation in ZIF-8 stabilizes the system, achieving a record H2O2 yield of 1198 µmol/L under visible light without sacrificial agents and a 0.39% solar-to-chemical conversion efficiency, surpassing most reported photocatalysts. This "ligand-as-catalyst" strategy merges enzymatic precision with nanocluster functionality for sustainable oxidant synthesis.
Solar-driven hydrogen peroxide (H2O2) production offers a sustainable alternative to the energy-intensive anthraquinone process, yet conventional photocatalysts suffer from poor selectivity and uncontrollable reaction pathways. Inspired by catechol oxidase enzymes, we design dopamine-grafted lipoic acid-protected gold nanoclusters (DA-LA-Au NCs) that shift photocatalytic active sites from the metal core to redox-active ligands. This ligand-centric architecture leverages dopamine’s reversible catechol/quinone interconversion to gate a biomimetic proton-coupled electron transfer (PCET) pathway, enabling exclusive 2e- oxygen reduction with near-100% H2O2 selectivity while completely suppressing superoxide radical (·O2-) generation. Transient absorption spectroscopy and molecular dynamics confirm enhanced electron transfer kinetics and O2 enrichment at ligand sites. Encapsulation in ZIF-8 stabilizes the system, achieving a record H2O2 yield of 1198 µmol/L under visible light without sacrificial agents and a 0.39% solar-to-chemical conversion efficiency, surpassing most reported photocatalysts. This "ligand-as-catalyst" strategy merges enzymatic precision with nanocluster functionality for sustainable oxidant synthesis.
2026, 37(11): 111702
doi: 10.1016/j.cclet.2025.111702
摘要:
Stable radicals have applications in numerous fields, yet their generation and stabilization remain methodologically challenging, with current achievements primarily limited to metal-organic frameworks (MOFs). In this work, we report the stabilization of radicals within metal-oxo clusters (MOCs) through an acidity modulation method, resulting in two thorium-oxo nanoclusters with identical structures but distinct photophysical properties. Under high-acidity conditions, yellow single crystals of Th-aca-Y, containing highly stable radical species, are obtained in situ, whereas lower acidity leads to the formation of Th-aca-C, a colorless and radical-free counterpart. Remarkably, the radical formed through acid modulation in Th-aca-Y exhibits unique UV-vis absorbance properties and considerably enhanced stability compared to the Xe light-induced radicals in Th-aca-C-Xe. Fourier-transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and photoluminescence characterization further confirmed the fundamentally different nature of the in situ generated radicals in Th-aca-Y compared to the light-induced radicals in Th-aca-C-Xe. In addition, these clusters display multi-stimuli-responsive properties, including photochromism, photothermal conversion, and notably, mechanochromic luminescence, which represents the first such instance in actinide-based materials.
Stable radicals have applications in numerous fields, yet their generation and stabilization remain methodologically challenging, with current achievements primarily limited to metal-organic frameworks (MOFs). In this work, we report the stabilization of radicals within metal-oxo clusters (MOCs) through an acidity modulation method, resulting in two thorium-oxo nanoclusters with identical structures but distinct photophysical properties. Under high-acidity conditions, yellow single crystals of Th-aca-Y, containing highly stable radical species, are obtained in situ, whereas lower acidity leads to the formation of Th-aca-C, a colorless and radical-free counterpart. Remarkably, the radical formed through acid modulation in Th-aca-Y exhibits unique UV-vis absorbance properties and considerably enhanced stability compared to the Xe light-induced radicals in Th-aca-C-Xe. Fourier-transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and photoluminescence characterization further confirmed the fundamentally different nature of the in situ generated radicals in Th-aca-Y compared to the light-induced radicals in Th-aca-C-Xe. In addition, these clusters display multi-stimuli-responsive properties, including photochromism, photothermal conversion, and notably, mechanochromic luminescence, which represents the first such instance in actinide-based materials.
2026, 37(11): 111726
doi: 10.1016/j.cclet.2025.111726
摘要:
Strong interfacial coupling between a semiconductor photocatalyst and a cocatalyst is crucial for enhancing photocatalytic hydrogen production. This study employs an anion exchange strategy to construct atomically thin two-dimensional MoSe2 nanosheets on one-dimensional CdS nanorods, achieving strong interfacial coupling for effective hydrogen production. Consequently, the CdS@MoSe2 heterojunctions exhibits a high H2 evolution rate of 15 mmol h−1 g−1 and an apparent quantum yield of 65% at 420 nm. This remarkable performance is attributed to the well-defined interface structure, in which chemical bonds are formed via strain-driven atomic substitution. The detailed interface structure between CdS and MoSe2 is clearly revealed through experimental characterizations, while the substitution process is thoroughly explained using theoretical methods. This work introduces a novel approach for optimizing the structure and quality of nanohybrid interfaces via strain-driven atomic substitution.
Strong interfacial coupling between a semiconductor photocatalyst and a cocatalyst is crucial for enhancing photocatalytic hydrogen production. This study employs an anion exchange strategy to construct atomically thin two-dimensional MoSe2 nanosheets on one-dimensional CdS nanorods, achieving strong interfacial coupling for effective hydrogen production. Consequently, the CdS@MoSe2 heterojunctions exhibits a high H2 evolution rate of 15 mmol h−1 g−1 and an apparent quantum yield of 65% at 420 nm. This remarkable performance is attributed to the well-defined interface structure, in which chemical bonds are formed via strain-driven atomic substitution. The detailed interface structure between CdS and MoSe2 is clearly revealed through experimental characterizations, while the substitution process is thoroughly explained using theoretical methods. This work introduces a novel approach for optimizing the structure and quality of nanohybrid interfaces via strain-driven atomic substitution.
2026, 37(11): 111730
doi: 10.1016/j.cclet.2025.111730
摘要:
Endless semiconductor sensitive materials have emerged and exhibited unprecedented application prospects in chemiresistive gas sensors, including clinical diagnosis, environmental monitoring, industrial production, aerospace and other fields. To satisfy the demands of integrated and miniaturized devices, efficient gas sensors with low power consumption have become a new research hotspot and highly potential direction. Herein, a facile and general in-situ domain-confined growth strategy was proposed to elaborately tailoring the versatile Co3O4 nanocrystals (NCs)-decorated reduced graphene oxide nanosheets (Co3O4-rGO), and the microstructure (e.g., size, dispersibility) of anchored Co3O4 NCs could be precisely controlled via adjusting the content of solution (i.e., water and ethanol). The rationally designed Co3O4-rGO composites showed the superior selectivity and high sensitivity towards formaldehyde molecules at low working temperature (ca. 78 °C). Among them, the ultra-small Co3O4 NCs (ca. 3 nm) decorated 5% rGO nanosheets exhibited the optimal formaldehyde sensing performance, such as low detection limit (100 ppb), high stability and excellent anti-humidity. Such an excellent performance was attributed to the high catalytic activity of crystalline Co3O4 NCs and abundant oxygen-containing groups of rGO. This work provides a new concept of “nanocrystals catalysis-sensing” to guide the low-temperature formaldehyde monitoring.
Endless semiconductor sensitive materials have emerged and exhibited unprecedented application prospects in chemiresistive gas sensors, including clinical diagnosis, environmental monitoring, industrial production, aerospace and other fields. To satisfy the demands of integrated and miniaturized devices, efficient gas sensors with low power consumption have become a new research hotspot and highly potential direction. Herein, a facile and general in-situ domain-confined growth strategy was proposed to elaborately tailoring the versatile Co3O4 nanocrystals (NCs)-decorated reduced graphene oxide nanosheets (Co3O4-rGO), and the microstructure (e.g., size, dispersibility) of anchored Co3O4 NCs could be precisely controlled via adjusting the content of solution (i.e., water and ethanol). The rationally designed Co3O4-rGO composites showed the superior selectivity and high sensitivity towards formaldehyde molecules at low working temperature (ca. 78 °C). Among them, the ultra-small Co3O4 NCs (ca. 3 nm) decorated 5% rGO nanosheets exhibited the optimal formaldehyde sensing performance, such as low detection limit (100 ppb), high stability and excellent anti-humidity. Such an excellent performance was attributed to the high catalytic activity of crystalline Co3O4 NCs and abundant oxygen-containing groups of rGO. This work provides a new concept of “nanocrystals catalysis-sensing” to guide the low-temperature formaldehyde monitoring.
2026, 37(11): 111752
doi: 10.1016/j.cclet.2025.111752
摘要:
This work presents the design and synthesis of a novel class of ether-free poly(dibenzothiophene methylimidazole oxindole) membranes via a one-step, superacid-catalyzed polycondensation using highly reactive monomers, denoted as P(DBT-Melmx-OxI1 - x), to meet the rising demand for high temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). The incorporation of π-conjugated dibenzothiophene units imparts structural rigidity by limiting rotational freedom, thereby disrupting dense chain packing and generating a twisted architecture with ample free volume. These structural features, along with additional hydrogen-bonding sites, create efficient pathways for proton transport. Simultaneously, oxindole units contribute to enhanced mechanical and dimensional stability. Among the series, the P(DBT-Melm0.5-OxI0.5)/190%PA membrane exhibits the highest performance, achieving a peak power density of 893 mW/cm2 at 180 °C under dry H2/O2 conditions without backpressure. These results highlight the potential of P(DBT-Melmx-OxI1 - x) membranes as high-performance, structurally robust alternatives for next-generation HT-PEMFCs.
This work presents the design and synthesis of a novel class of ether-free poly(dibenzothiophene methylimidazole oxindole) membranes via a one-step, superacid-catalyzed polycondensation using highly reactive monomers, denoted as P(DBT-Melmx-OxI1 - x), to meet the rising demand for high temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). The incorporation of π-conjugated dibenzothiophene units imparts structural rigidity by limiting rotational freedom, thereby disrupting dense chain packing and generating a twisted architecture with ample free volume. These structural features, along with additional hydrogen-bonding sites, create efficient pathways for proton transport. Simultaneously, oxindole units contribute to enhanced mechanical and dimensional stability. Among the series, the P(DBT-Melm0.5-OxI0.5)/190%PA membrane exhibits the highest performance, achieving a peak power density of 893 mW/cm2 at 180 °C under dry H2/O2 conditions without backpressure. These results highlight the potential of P(DBT-Melmx-OxI1 - x) membranes as high-performance, structurally robust alternatives for next-generation HT-PEMFCs.
2026, 37(11): 111753
doi: 10.1016/j.cclet.2025.111753
摘要:
During the sintering process of Ni-rich cathode materials, the ultimate morphology of grains significantly impact capacity and cycling performance. However, revealing the quantified morphology variation of grains during the sintering process is challenging. Therefore, this paper proposes a modeling method for dynamic grain morphology evolution of Ni-rich cathode materials and analyzes the morphology-performance relationships. First, based on the morphological evolution laws, an indicator reflecting the degree to which the grain tends to become circle is designed to quantitatively describe the grain morphology, named roundness. Evolution models of grain roundness are established separately according to the characteristics of thermodynamics and microstructural evolution in each stage of sintering. During the heating stage, the mixture density network estimates grain size and roundness distributions, which are then used to generate initial grain distribution images for constant temperature stage modeling. For the constant temperature stage, a cellular automata based on grain growth mechanisms is proposed to simulate dynamic morphological changes in grains. Building upon the above framework, this study constructs a predictive relationship between grain roundness and specific surface area, then investigates the correlation mechanism between grain roundness distribution and electrochemical performance. Simulation results indicate that this method can accurately predict morphological changes during grain growth and provide theoretical guidance for cathode material preparation.
During the sintering process of Ni-rich cathode materials, the ultimate morphology of grains significantly impact capacity and cycling performance. However, revealing the quantified morphology variation of grains during the sintering process is challenging. Therefore, this paper proposes a modeling method for dynamic grain morphology evolution of Ni-rich cathode materials and analyzes the morphology-performance relationships. First, based on the morphological evolution laws, an indicator reflecting the degree to which the grain tends to become circle is designed to quantitatively describe the grain morphology, named roundness. Evolution models of grain roundness are established separately according to the characteristics of thermodynamics and microstructural evolution in each stage of sintering. During the heating stage, the mixture density network estimates grain size and roundness distributions, which are then used to generate initial grain distribution images for constant temperature stage modeling. For the constant temperature stage, a cellular automata based on grain growth mechanisms is proposed to simulate dynamic morphological changes in grains. Building upon the above framework, this study constructs a predictive relationship between grain roundness and specific surface area, then investigates the correlation mechanism between grain roundness distribution and electrochemical performance. Simulation results indicate that this method can accurately predict morphological changes during grain growth and provide theoretical guidance for cathode material preparation.
2026, 37(11): 111755
doi: 10.1016/j.cclet.2025.111755
摘要:
The rational synthesis of structurally novel metal oxo clusters remains pivotal for advancing materials chemistry and catalysis. Herein, we report four unprecedented iron oxo clusters, featuring groundbreaking structural motifs and exceptional catalytic activity. The heptanuclear clusters [Fe7O2(SO4)2(CH3O)10Cl6]·3(C5H6N)·5(H2O) (abbreviated as Fe7(SO4)2) and [Fe7O2(SeO4)2(CH3O)10Cl6]·3(C5H6N)·6(H2O) (abbreviated as Fe7(SeO4)2) represent not only the first iron clusters but also rare homometallic clusters that exhibit β-Anderson-type structures. Strikingly, substituting pyridine with 3-methylpyridine in solvothermal synthesis reactions results in the formation of two tetranuclear iron clusters, [Fe4O(SO4)2(CH3O)5Cl4]·3(C6H8N) (abbreviated as Fe4(SO4)2) and [Fe4O(SeO4)2(CH3O)5Cl4]·3(C6H8N)·(CH3OH)·9(H2O) (abbreviated as Fe4(SeO4)2), which exhibit unusual structures with half β-Anderson configuration. These results demonstrate the critical role of organic amines in directing the formation and nuclearity of iron oxo clusters. All clusters exhibit similar antiferromagnetic behaviors and ultraviolet-visible (UV-vis) adsorption spectra arising from the ligand-to-metal charge transfer. Most importantly, they show excellent Lewis acid catalytic activities and stabilities in the cyanosilylation reaction of aldehydes, highlighting the promising applications of iron oxo clusters as a sustainable, high-performance catalysis. This work establishes an organic amine-guided strategy for designing polynuclear iron architectures with combined structural novelty and catalytic prowess.
The rational synthesis of structurally novel metal oxo clusters remains pivotal for advancing materials chemistry and catalysis. Herein, we report four unprecedented iron oxo clusters, featuring groundbreaking structural motifs and exceptional catalytic activity. The heptanuclear clusters [Fe7O2(SO4)2(CH3O)10Cl6]·3(C5H6N)·5(H2O) (abbreviated as Fe7(SO4)2) and [Fe7O2(SeO4)2(CH3O)10Cl6]·3(C5H6N)·6(H2O) (abbreviated as Fe7(SeO4)2) represent not only the first iron clusters but also rare homometallic clusters that exhibit β-Anderson-type structures. Strikingly, substituting pyridine with 3-methylpyridine in solvothermal synthesis reactions results in the formation of two tetranuclear iron clusters, [Fe4O(SO4)2(CH3O)5Cl4]·3(C6H8N) (abbreviated as Fe4(SO4)2) and [Fe4O(SeO4)2(CH3O)5Cl4]·3(C6H8N)·(CH3OH)·9(H2O) (abbreviated as Fe4(SeO4)2), which exhibit unusual structures with half β-Anderson configuration. These results demonstrate the critical role of organic amines in directing the formation and nuclearity of iron oxo clusters. All clusters exhibit similar antiferromagnetic behaviors and ultraviolet-visible (UV-vis) adsorption spectra arising from the ligand-to-metal charge transfer. Most importantly, they show excellent Lewis acid catalytic activities and stabilities in the cyanosilylation reaction of aldehydes, highlighting the promising applications of iron oxo clusters as a sustainable, high-performance catalysis. This work establishes an organic amine-guided strategy for designing polynuclear iron architectures with combined structural novelty and catalytic prowess.
2026, 37(11): 111774
doi: 10.1016/j.cclet.2025.111774
摘要:
Due to the high cost and environmental concerns related to the use of cobalt in conventional layered cathode materials based on transition metals, such as NCM, high-nickel and cobalt-free layered oxides have emerged as promising candidates for lithium-ion batteries, offering potentially higher capacities and lower costs. However, the transition to these materials is not without its hurdles, as they typically exhibit poor cycling stability. In light of this, LiNiO2 (LNO), which serves as a prototype for high-nickel and cobalt-free materials, has been the subject of this investigation. Hereby, we have developed a one-step synthesis method for an Al-doped and La4NiLiO8-coated synergistically modified LNO (LA-LNO), involving in situ wet coating followed by high-temperature lithiation, demonstrating that this modification reduces the Ni2+ content in LA-LNO. These alterations effectively alleviate stress variations within the particles during cycling and prevent electrolyte attack on the bulk material in the event of particle fracturing. The La4NiLiO8 epitaxial coating acts as a protective interfacial barrier while also diminishing interface impedance due to its superior electronic and ionic conductivity. This highlights the substantial improvement in the electrochemical performance of LNO achieved through La/Al synergistic modification, providing a valuable benchmark for the synthesis of high-nickel and cobalt-free cathode materials.
Due to the high cost and environmental concerns related to the use of cobalt in conventional layered cathode materials based on transition metals, such as NCM, high-nickel and cobalt-free layered oxides have emerged as promising candidates for lithium-ion batteries, offering potentially higher capacities and lower costs. However, the transition to these materials is not without its hurdles, as they typically exhibit poor cycling stability. In light of this, LiNiO2 (LNO), which serves as a prototype for high-nickel and cobalt-free materials, has been the subject of this investigation. Hereby, we have developed a one-step synthesis method for an Al-doped and La4NiLiO8-coated synergistically modified LNO (LA-LNO), involving in situ wet coating followed by high-temperature lithiation, demonstrating that this modification reduces the Ni2+ content in LA-LNO. These alterations effectively alleviate stress variations within the particles during cycling and prevent electrolyte attack on the bulk material in the event of particle fracturing. The La4NiLiO8 epitaxial coating acts as a protective interfacial barrier while also diminishing interface impedance due to its superior electronic and ionic conductivity. This highlights the substantial improvement in the electrochemical performance of LNO achieved through La/Al synergistic modification, providing a valuable benchmark for the synthesis of high-nickel and cobalt-free cathode materials.
2026, 37(11): 111783
doi: 10.1016/j.cclet.2025.111783
摘要:
As an anode material for sodium/potassium-ion batteries, Fe3O4 possesses advantages such as high theoretical capacity and abundant natural resources. However, its practical application is hindered by poor intrinsic conductivity and significant volume expansion. Herein, the P-doped and N-adsorbed hollow core-shell Fe3O4@carbon composite (PNHCS-Fe3O4@C) is successfully synthesized for the first time. Benefiting from the synergism of hollow core-shell structure design and N adsorption/P doping co-modification strategy, the PNHCS-Fe3O4@C anode achieves significantly enhanced sodium/potassium storage properties. Specifically, the PNHCS-Fe3O4@C electrode in sodium-ion batteries exhibits a high specific capacity of 256.7 mAh/g at 10,000 mA/g and splendid cycling stability with nearly 100% capacity retention after 500 cycles at 5000 mA/g. More impressively, the PNHCS-Fe3O4@C electrode in potassium-ion batteries delivers a high specific capacity of 116.7 mAh/g at 10,000 mA/g and outstanding cycling stability with approximately 100% capacity retention after 500 cycles at 1000 mA/g. Density functional theory (DFT) calculations confirm that N adsorption/P doping reduces the adsorption energy of Na+/K+ and accelerates the charge transfer kinetics, thereby significantly improving the electrochemical performance. This innovative synergistic modification strategy provides good guidance for developing high-performance anode materials for sodium/potassium-ion batteries.
As an anode material for sodium/potassium-ion batteries, Fe3O4 possesses advantages such as high theoretical capacity and abundant natural resources. However, its practical application is hindered by poor intrinsic conductivity and significant volume expansion. Herein, the P-doped and N-adsorbed hollow core-shell Fe3O4@carbon composite (PNHCS-Fe3O4@C) is successfully synthesized for the first time. Benefiting from the synergism of hollow core-shell structure design and N adsorption/P doping co-modification strategy, the PNHCS-Fe3O4@C anode achieves significantly enhanced sodium/potassium storage properties. Specifically, the PNHCS-Fe3O4@C electrode in sodium-ion batteries exhibits a high specific capacity of 256.7 mAh/g at 10,000 mA/g and splendid cycling stability with nearly 100% capacity retention after 500 cycles at 5000 mA/g. More impressively, the PNHCS-Fe3O4@C electrode in potassium-ion batteries delivers a high specific capacity of 116.7 mAh/g at 10,000 mA/g and outstanding cycling stability with approximately 100% capacity retention after 500 cycles at 1000 mA/g. Density functional theory (DFT) calculations confirm that N adsorption/P doping reduces the adsorption energy of Na+/K+ and accelerates the charge transfer kinetics, thereby significantly improving the electrochemical performance. This innovative synergistic modification strategy provides good guidance for developing high-performance anode materials for sodium/potassium-ion batteries.
2026, 37(11): 111802
doi: 10.1016/j.cclet.2025.111802
摘要:
The capture of CO2 from flue gas is of utmost significance as it can significantly reduce the heavy emissions of CO2 from power plants. However, the efficient capture of CO2 from flue gas using porous materials remains a challenge under practical conditions. The adsorption sites may become inactive due to weaker interactions at high temperatures and/or coordination by water molecules in humid conditions. To address the issue, a stable hydrogen-bonded metal-complex framework (FJI-W35) stabilized by rarely seen charge-assisted C–H···O hydrogen bonds has been deliberately synthesized. In FJI-W35, positive charge sites are arranged in an orderly manner on the pore surfaces of the one-dimensional triangular channels. Single component gas isotherms exhibit that this porous framework can effectively capture CO2 from room temperature to 373 K but barely adsorb N2. Dynamic breakthrough experiments validate this material can selectively capture CO2 from flue gas over a wide range of temperature and humidity, which is of great significance in the practical CO2 capture process. Furthermore, CO2-loaded single-crystal structure verifies that the inherent charged sites contribute much to the excellent separation performance.
The capture of CO2 from flue gas is of utmost significance as it can significantly reduce the heavy emissions of CO2 from power plants. However, the efficient capture of CO2 from flue gas using porous materials remains a challenge under practical conditions. The adsorption sites may become inactive due to weaker interactions at high temperatures and/or coordination by water molecules in humid conditions. To address the issue, a stable hydrogen-bonded metal-complex framework (FJI-W35) stabilized by rarely seen charge-assisted C–H···O hydrogen bonds has been deliberately synthesized. In FJI-W35, positive charge sites are arranged in an orderly manner on the pore surfaces of the one-dimensional triangular channels. Single component gas isotherms exhibit that this porous framework can effectively capture CO2 from room temperature to 373 K but barely adsorb N2. Dynamic breakthrough experiments validate this material can selectively capture CO2 from flue gas over a wide range of temperature and humidity, which is of great significance in the practical CO2 capture process. Furthermore, CO2-loaded single-crystal structure verifies that the inherent charged sites contribute much to the excellent separation performance.
2026, 37(11): 111803
doi: 10.1016/j.cclet.2025.111803
摘要:
Developing effective electrocatalytic materials to enhance the hydrogen evolution reaction (HER) is essential for advancing hydrogen economy. In this study, molybdenum boride (MoBx) electrocatalyst was successfully fabricated via the molten salt method, followed by Pt loading onto MoBx using the impregnation-adsorption method. The introduction of Pt significantly boosted the electrocatalytic performance. The optimal Pt-MoBx exhibited superior HER performance in 0.5 mol/L H2SO4, acquiring an overpotential of 49 mV at 10 mA/cm2. Additionally, the Pt-MoBx catalyst demonstrated exceptional stability in acidic medium, showing a negligible drop after 20 h of constant potential operation. The study presents a novel approach to design stable, high-efficiency HER electrocatalysts based on metal borides.
Developing effective electrocatalytic materials to enhance the hydrogen evolution reaction (HER) is essential for advancing hydrogen economy. In this study, molybdenum boride (MoBx) electrocatalyst was successfully fabricated via the molten salt method, followed by Pt loading onto MoBx using the impregnation-adsorption method. The introduction of Pt significantly boosted the electrocatalytic performance. The optimal Pt-MoBx exhibited superior HER performance in 0.5 mol/L H2SO4, acquiring an overpotential of 49 mV at 10 mA/cm2. Additionally, the Pt-MoBx catalyst demonstrated exceptional stability in acidic medium, showing a negligible drop after 20 h of constant potential operation. The study presents a novel approach to design stable, high-efficiency HER electrocatalysts based on metal borides.
2026, 37(11): 111807
doi: 10.1016/j.cclet.2025.111807
摘要:
Achieving high negative Poisson’s ratios (NPR) in atomically thin materials remains a fundamental challenge, yet critical for next-generation impact-resistant metamaterials and flexible electronics. However, achieving high NPR values in two-dimensional (2D) systems remains fundamentally challenging. Herein, we report a systematic computational exploration of NPR phenomena in monolayer M2C MXenes (M = Sc, Ti, Zr, V, Nb, Ta, Mo), revealing an electronic hybridization-driven auxetic mechanism in Mo2C (υ = -0.11) distinct from geometric re-entrant paradigms. Through transition metal doping, we achieve unprecedented NPR enhancement, Re-doped Mo2C attains an ultrahigh υ = -0.59, representing a 5-fold improvement and setting a new benchmark for 2D auxetics. Crucially, these engineered systems concurrently exhibit exceptional hydrogen evolution reaction (HER) catalytic activity, with Ni-doped Mo2C (3.13%) achieving a near-ideal ΔG*H of -0.06 eV, surpassing platinum’s performance. Orbital reconstruction and electronic redistribution synergistically enable dual-functionality: NPR amplification and catalytic optimization within a single material platform. We propose doped MXenes as a universal design paradigm for multifunctional metamaterials, simultaneously addressing mechanical resilience and sustainable energy conversion.
Achieving high negative Poisson’s ratios (NPR) in atomically thin materials remains a fundamental challenge, yet critical for next-generation impact-resistant metamaterials and flexible electronics. However, achieving high NPR values in two-dimensional (2D) systems remains fundamentally challenging. Herein, we report a systematic computational exploration of NPR phenomena in monolayer M2C MXenes (M = Sc, Ti, Zr, V, Nb, Ta, Mo), revealing an electronic hybridization-driven auxetic mechanism in Mo2C (υ = -0.11) distinct from geometric re-entrant paradigms. Through transition metal doping, we achieve unprecedented NPR enhancement, Re-doped Mo2C attains an ultrahigh υ = -0.59, representing a 5-fold improvement and setting a new benchmark for 2D auxetics. Crucially, these engineered systems concurrently exhibit exceptional hydrogen evolution reaction (HER) catalytic activity, with Ni-doped Mo2C (3.13%) achieving a near-ideal ΔG*H of -0.06 eV, surpassing platinum’s performance. Orbital reconstruction and electronic redistribution synergistically enable dual-functionality: NPR amplification and catalytic optimization within a single material platform. We propose doped MXenes as a universal design paradigm for multifunctional metamaterials, simultaneously addressing mechanical resilience and sustainable energy conversion.
2026, 37(11): 111813
doi: 10.1016/j.cclet.2025.111813
摘要:
The development of heterostructure catalysts has been deemed as an appropriate strategy for water splitting. Yet, their further advancement is hindered by limited intrinsic activity. Recently, single-atom catalysts have garnered significant attention due to its ultrahigh atomic utilization efficiency near 100%. Herein, we propose a cross-scale manipulation strategy to couple Ru single atoms with NiFe-LDH/MoNiS core-shell heterostructure. The surface of MoNiS nanorods is uniformly covered by NiFe-LDH ultrathin nanosheets, resulting in electron redistribution across the interface. Isolated Ru atoms are stabilized on NiFe-LDH to form Ru−O−Ni motifs, which activates the metal center and enables catalyst structure to a certain robustness. The optimum RuSA/NiFe-LDH/MoNiS delivers large current densities of 500 and 1000 mA/cm2 with ultralow overpotentials of 234 and 320 mV for hydrogen evolution reaction (HER) in 1 mol/L KOH. Moreover, the electrode shows remarkable durability over 1000 cycles and long-term stability over 200 h. The assembled water electrolyzer exhibits a low cell voltage of 1.85 V to attain 500 mA/cm2. In-situ spectroscopy and theoretical calculations demonstrate that the active Ru−O−Ni motifs accelerate the adsorption/dissociation of water molecules and balance the adsorption of *H, thus greatly improving the hydrogen generation.
The development of heterostructure catalysts has been deemed as an appropriate strategy for water splitting. Yet, their further advancement is hindered by limited intrinsic activity. Recently, single-atom catalysts have garnered significant attention due to its ultrahigh atomic utilization efficiency near 100%. Herein, we propose a cross-scale manipulation strategy to couple Ru single atoms with NiFe-LDH/MoNiS core-shell heterostructure. The surface of MoNiS nanorods is uniformly covered by NiFe-LDH ultrathin nanosheets, resulting in electron redistribution across the interface. Isolated Ru atoms are stabilized on NiFe-LDH to form Ru−O−Ni motifs, which activates the metal center and enables catalyst structure to a certain robustness. The optimum RuSA/NiFe-LDH/MoNiS delivers large current densities of 500 and 1000 mA/cm2 with ultralow overpotentials of 234 and 320 mV for hydrogen evolution reaction (HER) in 1 mol/L KOH. Moreover, the electrode shows remarkable durability over 1000 cycles and long-term stability over 200 h. The assembled water electrolyzer exhibits a low cell voltage of 1.85 V to attain 500 mA/cm2. In-situ spectroscopy and theoretical calculations demonstrate that the active Ru−O−Ni motifs accelerate the adsorption/dissociation of water molecules and balance the adsorption of *H, thus greatly improving the hydrogen generation.
2026, 37(11): 111814
doi: 10.1016/j.cclet.2025.111814
摘要:
The design of an efficient catalyst is crucial for sulfur reduction reaction (SRR) in lean electrolyte lithium-sulfur (Li–S) batteries. However, most existing catalysts primarily focus on polysulfide-catalyst interactions and generally demonstrate high activity only with an excessive electrolyte. In this study, we propose high-entropy alloy (HEA) composite to enhance the SRR under lean-electrolyte conditions by optimizing the solvent-catalyst interaction. As evidenced by in situ spectroscopy, nuclear magnetic resonance (NMR), density functional theory (DFT) calculations, and experimental investigations, the strong interaction between the solvent and HEA catalysts enables the Li–S battery to achieve a high capacity of 1007.9 mAh/g with a low E/S ratio of 10 µL/mg, and capacity retention of 77% after 200 cycles at lower E/S ratio of 4.5 µL/mg. The enhanced SRR performance in lean electrolyte conditions is primarily attributed to d–d electron interactions among the constituent metals and the presence of multiple active sites with optimized energy barriers in the HEA catalysts. This work underscores the significance of solvent-catalyst interactions in regulating the SRR of lean electrolyte Li–S battery and offers insights into the rational design of HEA catalysts to advance Li−S batteries.
The design of an efficient catalyst is crucial for sulfur reduction reaction (SRR) in lean electrolyte lithium-sulfur (Li–S) batteries. However, most existing catalysts primarily focus on polysulfide-catalyst interactions and generally demonstrate high activity only with an excessive electrolyte. In this study, we propose high-entropy alloy (HEA) composite to enhance the SRR under lean-electrolyte conditions by optimizing the solvent-catalyst interaction. As evidenced by in situ spectroscopy, nuclear magnetic resonance (NMR), density functional theory (DFT) calculations, and experimental investigations, the strong interaction between the solvent and HEA catalysts enables the Li–S battery to achieve a high capacity of 1007.9 mAh/g with a low E/S ratio of 10 µL/mg, and capacity retention of 77% after 200 cycles at lower E/S ratio of 4.5 µL/mg. The enhanced SRR performance in lean electrolyte conditions is primarily attributed to d–d electron interactions among the constituent metals and the presence of multiple active sites with optimized energy barriers in the HEA catalysts. This work underscores the significance of solvent-catalyst interactions in regulating the SRR of lean electrolyte Li–S battery and offers insights into the rational design of HEA catalysts to advance Li−S batteries.
2026, 37(11): 111827
doi: 10.1016/j.cclet.2025.111827
摘要:
Co-amorphous systems (CAMS) effectively enhance the solubility and dissolution of poorly soluble drugs and enable combined formulations with enhanced compatibility. Here, we report a novel ionic liquid intermediate (ILI) strategy for green CAMS preparation, which uses trace water to form an ionic liquid intermediate under mild heating, followed by dehydration to yield co-amorphous products. ILI was applied to produce co-amorphous of vildagliptin and valsartan (VV-ILI), compared to rotary evaporation (VV-RE) and ball milling (VV-BM) products. Characterization revealed three distinct polyamorphs with varied intermolecular interactions. Molecular electrostatic potential and the Artificial Bee Colony algorithm were employed to simulate possible hydrogen bonding modes. All co-amorphous systems decreased the solubility and dissolution rate of vildagliptin while greatly enhancing those of valsartan, with VV-ILI demonstrating the greatest modification. Besides, all systems exhibit well stability under accelerated conditions. Overall, the ILI strategy provides a green, mild, and energy-efficient approach for engineering co-amorphous systems with tailored physicochemical properties.
Co-amorphous systems (CAMS) effectively enhance the solubility and dissolution of poorly soluble drugs and enable combined formulations with enhanced compatibility. Here, we report a novel ionic liquid intermediate (ILI) strategy for green CAMS preparation, which uses trace water to form an ionic liquid intermediate under mild heating, followed by dehydration to yield co-amorphous products. ILI was applied to produce co-amorphous of vildagliptin and valsartan (VV-ILI), compared to rotary evaporation (VV-RE) and ball milling (VV-BM) products. Characterization revealed three distinct polyamorphs with varied intermolecular interactions. Molecular electrostatic potential and the Artificial Bee Colony algorithm were employed to simulate possible hydrogen bonding modes. All co-amorphous systems decreased the solubility and dissolution rate of vildagliptin while greatly enhancing those of valsartan, with VV-ILI demonstrating the greatest modification. Besides, all systems exhibit well stability under accelerated conditions. Overall, the ILI strategy provides a green, mild, and energy-efficient approach for engineering co-amorphous systems with tailored physicochemical properties.
2026, 37(11): 111832
doi: 10.1016/j.cclet.2025.111832
摘要:
The electrocatalytic oxygen reduction reaction (ORR) holds significant importance in new energy conversion and storage technologies. Improving the activity of the ORR is vital for the practical applications of these technologies. Herein, we report on the construction of a dinuclear Co corrole complex 1 featuring a bimetallic active center and its electrocatalytic ORR features in acidic, neutral, and alkaline aqueous solutions. Experimental studies demonstrate that Co corrole 1 exhibits excellent electrocatalytic ORR activity for the four-electron reduction of O2 to water. In a 0.1 mol/L KOH solution, 1 achieves a half-wave potential (E1/2) of 0.88 V versus RHE, significantly outperforming its mononuclear analogue Co corrole 2 (0.75 V versus RHE). Importantly, complex 1 also exhibits large anodic shifts of 290 mV (in pH 7.0 phosphate buffer) and 150 mV (in 0.5 mol/L H2SO4) for the half-wave potential as compared to its mononuclear analogue 2. Moreover, the number of electrons transferred during the electrocatalytic ORR with dinuclear complex 1 is up to 3.86. These findings demonstrated that dinuclear Co corrole sites significantly facilitate the four-electron ORR. Therefore, this work is significant to present dinuclear Co corrole 1 as a highly active and selective electrocatalyst for the four-electron ORR and to demonstrate the crucial synergistic effect of well-designed bimetallic active sites for efficient electrocatalytic ORR.
The electrocatalytic oxygen reduction reaction (ORR) holds significant importance in new energy conversion and storage technologies. Improving the activity of the ORR is vital for the practical applications of these technologies. Herein, we report on the construction of a dinuclear Co corrole complex 1 featuring a bimetallic active center and its electrocatalytic ORR features in acidic, neutral, and alkaline aqueous solutions. Experimental studies demonstrate that Co corrole 1 exhibits excellent electrocatalytic ORR activity for the four-electron reduction of O2 to water. In a 0.1 mol/L KOH solution, 1 achieves a half-wave potential (E1/2) of 0.88 V versus RHE, significantly outperforming its mononuclear analogue Co corrole 2 (0.75 V versus RHE). Importantly, complex 1 also exhibits large anodic shifts of 290 mV (in pH 7.0 phosphate buffer) and 150 mV (in 0.5 mol/L H2SO4) for the half-wave potential as compared to its mononuclear analogue 2. Moreover, the number of electrons transferred during the electrocatalytic ORR with dinuclear complex 1 is up to 3.86. These findings demonstrated that dinuclear Co corrole sites significantly facilitate the four-electron ORR. Therefore, this work is significant to present dinuclear Co corrole 1 as a highly active and selective electrocatalyst for the four-electron ORR and to demonstrate the crucial synergistic effect of well-designed bimetallic active sites for efficient electrocatalytic ORR.
2026, 37(11): 111847
doi: 10.1016/j.cclet.2025.111847
摘要:
Unravelling the mechanism of electronic state evolution is ultimately important when attempting to functionalize two dimensional (2D) materials through electronic state regulation. However, there is still a lack of understanding in how the individual local functionalized regions could influence the entire 2D-layered property. Herein, we report the observation of surface electronic behavior during these functionalization process when utilizing the electron-deficient aluminium ion (Al3+) to passivate 2D black phosphorus (BP). Interestingly, the local electron density change in response to a certain functionalization can induce the periodic electron density gradient via inductive integration effect and spread over the entire 2D surface layer. Such 2D coupling effect is evidently supported by the combined investigation of in-situ/ex-situ experimental analysis and theoretical calculation, upon the model Al3+-BP modulating process. This work discloses the electron-level relationship between the individual and the whole during the functionalization process and therefore provides a direction for precise manipulation of electronic behavior in functionalized 2D materials.
Unravelling the mechanism of electronic state evolution is ultimately important when attempting to functionalize two dimensional (2D) materials through electronic state regulation. However, there is still a lack of understanding in how the individual local functionalized regions could influence the entire 2D-layered property. Herein, we report the observation of surface electronic behavior during these functionalization process when utilizing the electron-deficient aluminium ion (Al3+) to passivate 2D black phosphorus (BP). Interestingly, the local electron density change in response to a certain functionalization can induce the periodic electron density gradient via inductive integration effect and spread over the entire 2D surface layer. Such 2D coupling effect is evidently supported by the combined investigation of in-situ/ex-situ experimental analysis and theoretical calculation, upon the model Al3+-BP modulating process. This work discloses the electron-level relationship between the individual and the whole during the functionalization process and therefore provides a direction for precise manipulation of electronic behavior in functionalized 2D materials.
Electroactive nitrogen–engineered MoN nanospheres for electrochemical uranium recovery from seawater
2026, 37(11): 111848
doi: 10.1016/j.cclet.2025.111848
摘要:
The vast reserves of uranium in seawater offer a sustainable feedstock for nuclear energy, yet their exploitation is hindered by ultralow concentrations and a complex ionic milieu. We report a structurally engineered molybdenum nitride–carbon cloth (E-MoN/CC) electrode that combines high surface area (95.8 m2/g) with tailored electronic structure for highly efficient electrochemical uranium recovery. Nitrogen incorporation into MoN creates catalytically active sites that accelerate the reduction of uranyl species, while etching-induced hierarchical porosity enhances electron transport and facilitates ion diffusion. In uranium-spiked artificial seawater (10 ppm), E-MoN/CC delivers a capacity of 586 mg/g at −0.9 V vs. RHE, exceeding MoO3/CC by 1.2-fold, and achieves 99% removal within 1 h. The electrode sustains a record the maximum extraction capacity of 11,990 mg/g in uranium-spiked seawater, while maintaining negligible performance loss over seven cycles. This work establishes metal nitride architectures as robust, scalable platforms for green electrochemical uranium extraction from complex marine environments.
The vast reserves of uranium in seawater offer a sustainable feedstock for nuclear energy, yet their exploitation is hindered by ultralow concentrations and a complex ionic milieu. We report a structurally engineered molybdenum nitride–carbon cloth (E-MoN/CC) electrode that combines high surface area (95.8 m2/g) with tailored electronic structure for highly efficient electrochemical uranium recovery. Nitrogen incorporation into MoN creates catalytically active sites that accelerate the reduction of uranyl species, while etching-induced hierarchical porosity enhances electron transport and facilitates ion diffusion. In uranium-spiked artificial seawater (10 ppm), E-MoN/CC delivers a capacity of 586 mg/g at −0.9 V vs. RHE, exceeding MoO3/CC by 1.2-fold, and achieves 99% removal within 1 h. The electrode sustains a record the maximum extraction capacity of 11,990 mg/g in uranium-spiked seawater, while maintaining negligible performance loss over seven cycles. This work establishes metal nitride architectures as robust, scalable platforms for green electrochemical uranium extraction from complex marine environments.
2026, 37(11): 111854
doi: 10.1016/j.cclet.2025.111854
摘要:
Bioinspired surfaces exhibiting superspreading properties have garnered notable attention for their potential in various applications, including heat management and water purification. However, achieving three-dimensional (3D) superspreading remains a challenge. Here, a helical leaves-stem array (HLSA) mimicking the moss Racomitrium canescens is fabricated, which enables 3D superspreading, a process that facilitates rapid multidirectional spreading, enhances water retention, and ensures efficient liquid distribution across the surface, ultimately supporting sustained evaporation. The wedge-shaped interfaces between the leaves and stem, along with the continuous 3D microchannels formed by the helical arrangement of the leaves, drive this phenomenon through enhanced capillary forces. Inspired by this 3D superspreading mechanism, HLSA-based evaporators demonstrate promising applications in both thermal management and solar desalination, achieving a temperature reduction of 8.3 °C in cooling systems and a seawater evaporation rate of 1.08 kg m⁻2 h⁻1. Notably, the seawater evaporation process features an autonomous salt crystal removal and exhibits multi-angle light absorption. These findings offer insights into bioinspired thermal dissipation and pave the way for advanced evaporative systems.
Bioinspired surfaces exhibiting superspreading properties have garnered notable attention for their potential in various applications, including heat management and water purification. However, achieving three-dimensional (3D) superspreading remains a challenge. Here, a helical leaves-stem array (HLSA) mimicking the moss Racomitrium canescens is fabricated, which enables 3D superspreading, a process that facilitates rapid multidirectional spreading, enhances water retention, and ensures efficient liquid distribution across the surface, ultimately supporting sustained evaporation. The wedge-shaped interfaces between the leaves and stem, along with the continuous 3D microchannels formed by the helical arrangement of the leaves, drive this phenomenon through enhanced capillary forces. Inspired by this 3D superspreading mechanism, HLSA-based evaporators demonstrate promising applications in both thermal management and solar desalination, achieving a temperature reduction of 8.3 °C in cooling systems and a seawater evaporation rate of 1.08 kg m⁻2 h⁻1. Notably, the seawater evaporation process features an autonomous salt crystal removal and exhibits multi-angle light absorption. These findings offer insights into bioinspired thermal dissipation and pave the way for advanced evaporative systems.
2026, 37(11): 111855
doi: 10.1016/j.cclet.2025.111855
摘要:
Limited by the cobalt scarcity, price fluctuations, and toxicity, the next-generation lithium-ion batteries cathode materials tend to be nickel-rich and cobalt-free. However, the poor cycle stability of cobalt-free nickel-rich cathode material prevents its wide application. Element doping helps to improve the cycle stability of cathode materials, but the introduction of inactive elements usually leads to capacity decay. To address the above difficulties, the present study proposed a Mg/Mo co-doping strategy to simultaneously improve cycle stability and capacity, by developing the method of flame-assisted spray pyrolysis (FASP) for preparation of nanostructured materials in a one-step scheme. The effects of flame temperature on the structure, morphology and electrochemical performance of the material were investigated. Results showed that the doping of Mg-Mo dual-element effectively improved the electrochemical performance of the FASP prepared materials. On the one hand, the dual-element doping reduced the size of primary particles, which inhibited the generation and propagation of microcracks in the bulk and on the surface of the particles, thus helped to achieve long cycle. On the other hand, the dual-element doping expanded the thickness of the Li slab in the cathode material, which combined with smaller primary particles, was conducive to the rapid diffusion of Li+ and improved the specific capacity and rate performance. At the same time, the flame temperature was shown to impact the lithium volatilization and particle nucleation. Overall, the findings in the present study provided new ideas for the preparation of the next-generation high performance cobalt-free nickel-rich lithium-ion batteries cathode materials.
Limited by the cobalt scarcity, price fluctuations, and toxicity, the next-generation lithium-ion batteries cathode materials tend to be nickel-rich and cobalt-free. However, the poor cycle stability of cobalt-free nickel-rich cathode material prevents its wide application. Element doping helps to improve the cycle stability of cathode materials, but the introduction of inactive elements usually leads to capacity decay. To address the above difficulties, the present study proposed a Mg/Mo co-doping strategy to simultaneously improve cycle stability and capacity, by developing the method of flame-assisted spray pyrolysis (FASP) for preparation of nanostructured materials in a one-step scheme. The effects of flame temperature on the structure, morphology and electrochemical performance of the material were investigated. Results showed that the doping of Mg-Mo dual-element effectively improved the electrochemical performance of the FASP prepared materials. On the one hand, the dual-element doping reduced the size of primary particles, which inhibited the generation and propagation of microcracks in the bulk and on the surface of the particles, thus helped to achieve long cycle. On the other hand, the dual-element doping expanded the thickness of the Li slab in the cathode material, which combined with smaller primary particles, was conducive to the rapid diffusion of Li+ and improved the specific capacity and rate performance. At the same time, the flame temperature was shown to impact the lithium volatilization and particle nucleation. Overall, the findings in the present study provided new ideas for the preparation of the next-generation high performance cobalt-free nickel-rich lithium-ion batteries cathode materials.
2026, 37(11): 111856
doi: 10.1016/j.cclet.2025.111856
摘要:
We present the first example of reversible polymorphism in 2D Ag cluster-based layered structures constructed from Cl@Ag16(tBuS)8(CF3COO)7 nodes (Ag16) connected by μ4-TPPE linkers. The two polymorphs (Ag16-TPPE-a & Ag16-TPPE-b) further individually adopt orthorhombic and monoclinic crystalline forms, which can also be reversibly transformed to each other by virtue of tuning inter-layer C−H···F interaction through altering solvent system. Correspondingly, inter-layer C−H···F forces and dense stacking arrangement in Ag16-TPPE-a substantially restricts the molecular rotations or vibrations of TPPE and thus considerably facilitates the radiative transitions in the crystalline state, leading to enhancement in photoluminescence intensity, PLQY, and lifetime. Notwithstanding, benefiting from the suppression of photoluminescence, Ag16-TPPE-b exhibits higher photothermal conversion efficiency. This work provides a valuable approach for layer-sliding-driven tailoring photoluminescence and photothermal conversion effect in 2D supramolecular polymorphic silver cluster assembled materials.
We present the first example of reversible polymorphism in 2D Ag cluster-based layered structures constructed from Cl@Ag16(tBuS)8(CF3COO)7 nodes (Ag16) connected by μ4-TPPE linkers. The two polymorphs (Ag16-TPPE-a & Ag16-TPPE-b) further individually adopt orthorhombic and monoclinic crystalline forms, which can also be reversibly transformed to each other by virtue of tuning inter-layer C−H···F interaction through altering solvent system. Correspondingly, inter-layer C−H···F forces and dense stacking arrangement in Ag16-TPPE-a substantially restricts the molecular rotations or vibrations of TPPE and thus considerably facilitates the radiative transitions in the crystalline state, leading to enhancement in photoluminescence intensity, PLQY, and lifetime. Notwithstanding, benefiting from the suppression of photoluminescence, Ag16-TPPE-b exhibits higher photothermal conversion efficiency. This work provides a valuable approach for layer-sliding-driven tailoring photoluminescence and photothermal conversion effect in 2D supramolecular polymorphic silver cluster assembled materials.
2026, 37(11): 111867
doi: 10.1016/j.cclet.2025.111867
摘要:
The unsatisfied energy density and power density of zinc-ion capacitors necessitate the development of carbonaceous cathodes with both functional groups and abundant porosities. In this work, a carbonyl-enriched porous carbon nanomaterial is synthesized via Scholl coupling and dual molten salt treatment using p-benzoquinone as the precursor. Theoretical analysis indicates that appropriate pore size can enhance the transport capability of [Zn(H2O)6]2+, while a high carbonyl content strengthens the chemical interaction between [Zn(H2O)6]2+ and the electrode. Experimental results reveal that the pore structure and carbonyl content are influenced by zinc chloride and iron chloride molten salts, respectively, and the use of dual molten salts synergistically optimizes the formation of abundant pore structures with appropriate sizes and high carbonyl content. Consequently, the derived CPC-FeZn exhibits the highest effective specific surface area (SSAd ＞ 0.86 nm, 1292 m2/g) and carbonyl content (3.01 at%), endowing CPC-FeZn with a specific capacitance of 256.1 F/g at 0.1 A/g, an excellent rate capability (66.7% capacitance retention at 20 A/g), and a high energy density of 91.1 Wh/kg at 80 W/kg. This work establishes CPC-FeZn as a high-performance cathode for zinc-ion capacitors, providing a design paradigm for sustainable energy storage technologies.
The unsatisfied energy density and power density of zinc-ion capacitors necessitate the development of carbonaceous cathodes with both functional groups and abundant porosities. In this work, a carbonyl-enriched porous carbon nanomaterial is synthesized via Scholl coupling and dual molten salt treatment using p-benzoquinone as the precursor. Theoretical analysis indicates that appropriate pore size can enhance the transport capability of [Zn(H2O)6]2+, while a high carbonyl content strengthens the chemical interaction between [Zn(H2O)6]2+ and the electrode. Experimental results reveal that the pore structure and carbonyl content are influenced by zinc chloride and iron chloride molten salts, respectively, and the use of dual molten salts synergistically optimizes the formation of abundant pore structures with appropriate sizes and high carbonyl content. Consequently, the derived CPC-FeZn exhibits the highest effective specific surface area (SSAd ＞ 0.86 nm, 1292 m2/g) and carbonyl content (3.01 at%), endowing CPC-FeZn with a specific capacitance of 256.1 F/g at 0.1 A/g, an excellent rate capability (66.7% capacitance retention at 20 A/g), and a high energy density of 91.1 Wh/kg at 80 W/kg. This work establishes CPC-FeZn as a high-performance cathode for zinc-ion capacitors, providing a design paradigm for sustainable energy storage technologies.
2026, 37(11): 112173
doi: 10.1016/j.cclet.2025.112173
摘要:
Existing therapies for diabetic wounds often deliver insufficient outcomes. Bacterial infection, oxidative stress, and deficient vascularization during tissue regeneration critically impede recovery. To address this substantial unmet clinical need, we developed an injectable hydrogel biomaterial, named QDP1, specifically engineered to accelerate tissue regeneration in diabetic wounds. This formulation integrates a polysaccharide matrix combining quaternized chitosan with dialdehyde pullulan, augmented by procyanidin/Fe3O4 nanoparticles. Following localized administration, QDP1 promptly forms a protective hydrogel barrier. The dressing exhibits powerful antibacterial properties alongside efficient scavenging of harmful oxidative molecules. Together, these effects shift the wound milieu from chronic inflammation towards a constructive proliferative phase. A key benefit involves the hydrogel's intrinsic biodegradability post-treatment, ensuring complete clearance once fulfilling its regenerative role. Results from both in vitro experiments and preclinical models demonstrate that QDP1 significantly accelerates wound repair. As a novel therapeutic platform, QDP1 presents a notably hopeful strategy for diabetic wound management, ultimately improving patient outcomes for this challenging condition.
Existing therapies for diabetic wounds often deliver insufficient outcomes. Bacterial infection, oxidative stress, and deficient vascularization during tissue regeneration critically impede recovery. To address this substantial unmet clinical need, we developed an injectable hydrogel biomaterial, named QDP1, specifically engineered to accelerate tissue regeneration in diabetic wounds. This formulation integrates a polysaccharide matrix combining quaternized chitosan with dialdehyde pullulan, augmented by procyanidin/Fe3O4 nanoparticles. Following localized administration, QDP1 promptly forms a protective hydrogel barrier. The dressing exhibits powerful antibacterial properties alongside efficient scavenging of harmful oxidative molecules. Together, these effects shift the wound milieu from chronic inflammation towards a constructive proliferative phase. A key benefit involves the hydrogel's intrinsic biodegradability post-treatment, ensuring complete clearance once fulfilling its regenerative role. Results from both in vitro experiments and preclinical models demonstrate that QDP1 significantly accelerates wound repair. As a novel therapeutic platform, QDP1 presents a notably hopeful strategy for diabetic wound management, ultimately improving patient outcomes for this challenging condition.
2026, 37(11): 112185
doi: 10.1016/j.cclet.2025.112185
摘要:
Supramolecular nanoproteins based on host-guest interaction can integrate different therapeutic functions into a single nano delivery system to overcome chemoresistance in tumor therapy. In this work, the biohybrid supramolecular glycosyl-nanoproteins (Bio-WP5G-Avi) were constructed via self-assembly of biotinylated glycosyl-supramolecule complex (Bio-WP5G) with streptavidin (Avi), where Bio-WP5G has formed through host-guest interaction between biotinylated pillar[5]arene (Bio-WP5) and galactosamine derivative (G), which displays excellent GSH responsiveness, enhanced hepatoma-targetability, and efficient drug co-delivery. The host molecule Bio-WP5 contains disulfide bonds that respond to high concentrations of GSH in the tumor microenvironment, while the guest molecule G contains ammonium cations for loading of polyanionic siRNA by electrostatic interaction and galactose residues for targeting hepatoma cells by carbohydrate-lectin interactions. in vitro experiments, Bio-WP5G-Avi@DOX/siRNA not only significantly improved the transfection efficiency of siRNA and exhibited effective gene silencing ability but also enhanced the toxicity of drugs to HepG2/ADR cells. Furthermore, in vivo experiments with Bio-WP5G-Avi@DOX/siRNA using HepG2/ADR tumor-bearing nude mice model confirmed good biosafety, enrichment at tumors, and enhanced therapeutic efficacy. This work provides a unique strategy to construct a supramolecular glycosyl-nanoproteins delivery system for targeted co-delivery of drug/siRNA, which could pave a novel way for targeted and combination cancer therapy.
Supramolecular nanoproteins based on host-guest interaction can integrate different therapeutic functions into a single nano delivery system to overcome chemoresistance in tumor therapy. In this work, the biohybrid supramolecular glycosyl-nanoproteins (Bio-WP5G-Avi) were constructed via self-assembly of biotinylated glycosyl-supramolecule complex (Bio-WP5G) with streptavidin (Avi), where Bio-WP5G has formed through host-guest interaction between biotinylated pillar[5]arene (Bio-WP5) and galactosamine derivative (G), which displays excellent GSH responsiveness, enhanced hepatoma-targetability, and efficient drug co-delivery. The host molecule Bio-WP5 contains disulfide bonds that respond to high concentrations of GSH in the tumor microenvironment, while the guest molecule G contains ammonium cations for loading of polyanionic siRNA by electrostatic interaction and galactose residues for targeting hepatoma cells by carbohydrate-lectin interactions. in vitro experiments, Bio-WP5G-Avi@DOX/siRNA not only significantly improved the transfection efficiency of siRNA and exhibited effective gene silencing ability but also enhanced the toxicity of drugs to HepG2/ADR cells. Furthermore, in vivo experiments with Bio-WP5G-Avi@DOX/siRNA using HepG2/ADR tumor-bearing nude mice model confirmed good biosafety, enrichment at tumors, and enhanced therapeutic efficacy. This work provides a unique strategy to construct a supramolecular glycosyl-nanoproteins delivery system for targeted co-delivery of drug/siRNA, which could pave a novel way for targeted and combination cancer therapy.
2026, 37(11): 112186
doi: 10.1016/j.cclet.2025.112186
摘要:
Four pairs of cadinane sesquiterpenoid dimers, distahlianoids A–D (1–4), featuring three distinct structural scaffolds, were isolated from the Dai medicinal plant Stahlianthus involucratus using a mass spectrometry (MS)-molecular networking (MN)-based activity-structure approach. Structurally, compound 1 exhibits a unique fused heptacyclic architecture comprising 5/6/6/6/6/6/5 ring system, characterized by a novel 9-methyl-2-oxabicyclo[3.3.1]nona-3,7‑dien-9-ol core structure. Compounds 2 and 3 feature unusual 5/6/6/5/6/6/5 and 5/6/6/5/6/6 polycyclic frameworks, respectively. Compound 4 is a skeleton-rearranged dimer containing a unique 2-methyl-[2,2′-bifuran]-3,5′(2H,2′H)‑dione motif. Given the enantiomeric nature of these compounds, their biosynthetic pathways were proposed, along with the stereoselective formation regularities. Compounds 1–4 significantly inhibited lipid accumulation in 3T3-L1 adipocytes, with (–)-4 showing the strongest effect (half maximal effective concentration (EC50) = 1.04 ± 0.34 μmol/L) and high selectivity (selectivity index (SI) > 96).
Four pairs of cadinane sesquiterpenoid dimers, distahlianoids A–D (1–4), featuring three distinct structural scaffolds, were isolated from the Dai medicinal plant Stahlianthus involucratus using a mass spectrometry (MS)-molecular networking (MN)-based activity-structure approach. Structurally, compound 1 exhibits a unique fused heptacyclic architecture comprising 5/6/6/6/6/6/5 ring system, characterized by a novel 9-methyl-2-oxabicyclo[3.3.1]nona-3,7‑dien-9-ol core structure. Compounds 2 and 3 feature unusual 5/6/6/5/6/6/5 and 5/6/6/5/6/6 polycyclic frameworks, respectively. Compound 4 is a skeleton-rearranged dimer containing a unique 2-methyl-[2,2′-bifuran]-3,5′(2H,2′H)‑dione motif. Given the enantiomeric nature of these compounds, their biosynthetic pathways were proposed, along with the stereoselective formation regularities. Compounds 1–4 significantly inhibited lipid accumulation in 3T3-L1 adipocytes, with (–)-4 showing the strongest effect (half maximal effective concentration (EC50) = 1.04 ± 0.34 μmol/L) and high selectivity (selectivity index (SI) > 96).
2026, 37(11): 112187
doi: 10.1016/j.cclet.2025.112187
摘要:
Disulfiram/copper (DSF/Cu) co-delivery systems exhibit significant potential for tumor-specific chemotherapy. However, their efficacy is severely limited by premature interaction between DSF and Cu, which triggers off-target generation of cytotoxic copper−diethyldithiocarbamate complexes (CuET) and degradation. Herein, we develop a spatial-isolated oil-water biphasic Pickering emulsion (DBCP) stabilized by bovine serum albumin-copper nanoclusters (BSA-CuNCs), designed to inhibit such premature interaction through phase-separated co-delivery. Specifically, lipophilic DSF is encapsulated in the oil phase, while hydrophilic Cu2+ is chelated in the BSA-based emulsifier layer at the oil-water interface, achieving strict spatial segregation to block their untimely reaction. Endowed with enhanced permeability and retention (EPR) effect and BSA-mediated active targeting, DBCP accumulates specifically in tumor tissues. Upon cellular uptake, pH/glutathione dual stimulation triggers synchronous release of DSF and Cu, which then generate cytotoxic CuET in situ, catalyze Fenton-like reaction for chemotherapy, and induce cuproptosis via mitochondrial copper accumulation and dihydrolipoamide S-acetyltransferase (DLAT) binding, finally realizing enhanced chemo-cuproptosis synergy. In vitro, DBCP exhibits an median inhibition concentration (IC50) as low as 0.60 µmol/L against 4T1 cells, markedly enhancing DSF's antitumor activity. In vivo, it achieves a 74.41% tumor inhibition rate in 4T1-bearing mice (vs. 52.67% for 5-Fu) with negligible toxicity. This spatial-isolated oil-water biphasic Pickering emulsion offers a novel strategy to harness the therapeutic potential of DSF/Cu for clinical translation.
Disulfiram/copper (DSF/Cu) co-delivery systems exhibit significant potential for tumor-specific chemotherapy. However, their efficacy is severely limited by premature interaction between DSF and Cu, which triggers off-target generation of cytotoxic copper−diethyldithiocarbamate complexes (CuET) and degradation. Herein, we develop a spatial-isolated oil-water biphasic Pickering emulsion (DBCP) stabilized by bovine serum albumin-copper nanoclusters (BSA-CuNCs), designed to inhibit such premature interaction through phase-separated co-delivery. Specifically, lipophilic DSF is encapsulated in the oil phase, while hydrophilic Cu2+ is chelated in the BSA-based emulsifier layer at the oil-water interface, achieving strict spatial segregation to block their untimely reaction. Endowed with enhanced permeability and retention (EPR) effect and BSA-mediated active targeting, DBCP accumulates specifically in tumor tissues. Upon cellular uptake, pH/glutathione dual stimulation triggers synchronous release of DSF and Cu, which then generate cytotoxic CuET in situ, catalyze Fenton-like reaction for chemotherapy, and induce cuproptosis via mitochondrial copper accumulation and dihydrolipoamide S-acetyltransferase (DLAT) binding, finally realizing enhanced chemo-cuproptosis synergy. In vitro, DBCP exhibits an median inhibition concentration (IC50) as low as 0.60 µmol/L against 4T1 cells, markedly enhancing DSF's antitumor activity. In vivo, it achieves a 74.41% tumor inhibition rate in 4T1-bearing mice (vs. 52.67% for 5-Fu) with negligible toxicity. This spatial-isolated oil-water biphasic Pickering emulsion offers a novel strategy to harness the therapeutic potential of DSF/Cu for clinical translation.
2026, 37(11): 112195
doi: 10.1016/j.cclet.2025.112195
摘要:
Due to improvements in living standards and shifts in dietary patterns, the prevalence of hyperuricemia and gout has been steadily increasing, making it the second most common metabolic disorder after diabetes. Exogenous uricase has emerged as a promising therapeutic option for patients with severe and refractory gout, owing to its potent urate-lowering efficacy and ability to alleviate pain, thereby significantly improving patient quality of life. Pegloticase remains the only uricase-based drug approved by the U.S. Food and Drug Administration (FDA) for the treatment of chronic gout unresponsive to standard therapies. However, the current pipeline of exogenous uricase candidates is limited, and high immunogenicity continues to pose a major challenge, highlighting the urgent need for further innovation in this field. Here, we investigate the non-conserved amino acid residues located at the entrance of the uric acid channel and proposes a mutation-based strategy to enhance the catalytic activity of Arthrobacter globiformis uricase, achieving a maximum activity increase of 27%. Furthermore, the introduction of a K129C mutation enables the formation of a disulfide bond at the dimer–dimer interface within the tetramer, thereby significantly enhancing the thermal stability of the enzyme, with the tetrameric Tm increased by 5.88 ℃. The combination of activity-enhancing and thermostability-improving mutations resulted in uricase variants with both high catalytic efficiency and improved structural resilience. This study offers mechanistic insights into the structure–function relationship of the urate channel and proposes an innovative approach for engineering next-generation uricase therapeutics.
Due to improvements in living standards and shifts in dietary patterns, the prevalence of hyperuricemia and gout has been steadily increasing, making it the second most common metabolic disorder after diabetes. Exogenous uricase has emerged as a promising therapeutic option for patients with severe and refractory gout, owing to its potent urate-lowering efficacy and ability to alleviate pain, thereby significantly improving patient quality of life. Pegloticase remains the only uricase-based drug approved by the U.S. Food and Drug Administration (FDA) for the treatment of chronic gout unresponsive to standard therapies. However, the current pipeline of exogenous uricase candidates is limited, and high immunogenicity continues to pose a major challenge, highlighting the urgent need for further innovation in this field. Here, we investigate the non-conserved amino acid residues located at the entrance of the uric acid channel and proposes a mutation-based strategy to enhance the catalytic activity of Arthrobacter globiformis uricase, achieving a maximum activity increase of 27%. Furthermore, the introduction of a K129C mutation enables the formation of a disulfide bond at the dimer–dimer interface within the tetramer, thereby significantly enhancing the thermal stability of the enzyme, with the tetrameric Tm increased by 5.88 ℃. The combination of activity-enhancing and thermostability-improving mutations resulted in uricase variants with both high catalytic efficiency and improved structural resilience. This study offers mechanistic insights into the structure–function relationship of the urate channel and proposes an innovative approach for engineering next-generation uricase therapeutics.
2026, 37(11): 112204
doi: 10.1016/j.cclet.2025.112204
摘要:
Regarding the biological and clinical significance of in situ real-time detection of p53 dual mutations, this study ingeniously utilized the relationship between the genomic guardian p53 and the tumor promoter cyclooxygenase-2 (COX-2), attempting to develop a COX-2-activated fluorescence probe with cascade response for dual-mutant p53. We developed a novel class of fluorescent probes based on protected dihydroresorufin conjugated with a photo-crosslinking group. This design enables the sequential release of the fluorophore, effectively preventing over-oxidation and allowing for rapid detection of COX-2 activity with enhanced signal-to-background contrast in living cells. Furthermore, these probes can specific recognize dual-mutant p53 based on markedly elevated activity of COX-2 in SW480 cells compared to other colorectal cancer (CRC) cell lines with wild-type or mono-mutant p53 for the first time. This specifically recognition of the dual mutant p53 also enables its implementation in tissues and xenografts. Additionally, metabolomic profiling showed increased acylcarnitine levels in dual-mutant p53 SW480 cells, which could activate COX-2 and enhance prostaglandin E2 (PGE2) production. In situ real-time detection of dual-mutant p53 is of great significance for precise tumor diagnosis and grading, individualized treatment, prognosis judgment and recurrence monitoring, and new drug development.
Regarding the biological and clinical significance of in situ real-time detection of p53 dual mutations, this study ingeniously utilized the relationship between the genomic guardian p53 and the tumor promoter cyclooxygenase-2 (COX-2), attempting to develop a COX-2-activated fluorescence probe with cascade response for dual-mutant p53. We developed a novel class of fluorescent probes based on protected dihydroresorufin conjugated with a photo-crosslinking group. This design enables the sequential release of the fluorophore, effectively preventing over-oxidation and allowing for rapid detection of COX-2 activity with enhanced signal-to-background contrast in living cells. Furthermore, these probes can specific recognize dual-mutant p53 based on markedly elevated activity of COX-2 in SW480 cells compared to other colorectal cancer (CRC) cell lines with wild-type or mono-mutant p53 for the first time. This specifically recognition of the dual mutant p53 also enables its implementation in tissues and xenografts. Additionally, metabolomic profiling showed increased acylcarnitine levels in dual-mutant p53 SW480 cells, which could activate COX-2 and enhance prostaglandin E2 (PGE2) production. In situ real-time detection of dual-mutant p53 is of great significance for precise tumor diagnosis and grading, individualized treatment, prognosis judgment and recurrence monitoring, and new drug development.
2026, 37(11): 112206
doi: 10.1016/j.cclet.2025.112206
摘要:
Oncolytic virus therapy represents a promising avenue in the battle against cancer, however, its efficacy is frequently constrained by the hostile tumor microenvironment and insufficient therapeutic responses. Herein, we engineered a pH/glutathione dual-responsive supramolecular prodrug nanomedicine (termed PGPP), derived from gossypol, designed to synergize with oncolytic herpes simplex virus (oHSV) therapy for the treatment of triple-negative breast cancer (TNBC). Our findings revealed that PGPP exhibited remarkable tumor-targeting accumulation and retention, significantly enhancing the cytotoxic potency of gossypol within malignant tissues. Crucially, PGPP effectively disrupted vascular endothelial growth factor (VEGF)-driven angiogenesis, fostering a more permissive milieu for oncolytic viral infiltration. The incorporation of oHSV in turn amplified the antitumor activity of PGPP, promoting cancer cell apoptosis and augmenting immunogenic cell death, ultimately resulting in robust tumor growth inhibition. This coordinated combination strategy-based supramolecular prodrug delivers a powerful blow against TNBC, offering a promising paradigm for future cancer treatments.
Oncolytic virus therapy represents a promising avenue in the battle against cancer, however, its efficacy is frequently constrained by the hostile tumor microenvironment and insufficient therapeutic responses. Herein, we engineered a pH/glutathione dual-responsive supramolecular prodrug nanomedicine (termed PGPP), derived from gossypol, designed to synergize with oncolytic herpes simplex virus (oHSV) therapy for the treatment of triple-negative breast cancer (TNBC). Our findings revealed that PGPP exhibited remarkable tumor-targeting accumulation and retention, significantly enhancing the cytotoxic potency of gossypol within malignant tissues. Crucially, PGPP effectively disrupted vascular endothelial growth factor (VEGF)-driven angiogenesis, fostering a more permissive milieu for oncolytic viral infiltration. The incorporation of oHSV in turn amplified the antitumor activity of PGPP, promoting cancer cell apoptosis and augmenting immunogenic cell death, ultimately resulting in robust tumor growth inhibition. This coordinated combination strategy-based supramolecular prodrug delivers a powerful blow against TNBC, offering a promising paradigm for future cancer treatments.
2026, 37(11): 112211
doi: 10.1016/j.cclet.2025.112211
摘要:
Disialoganglioside (GD2) is a key target for the diagnosis and treatment of multiple malignant tumors. However, the shortage of effective targeting probes for GD2 remains a major challenge in this field. This study developed a pH-activated targeted optical nanoprobe based on functional DNA-modified persistent luminescent nanoparticles (PLNPs), utilizing the targeting specificity of GD2 aptamers (Apt) and the pH-activated of Ⅰ-motif (IMO) structure, achieving sensitive and specific molecular imaging of neuroblastoma. First, Cr3+-doped amino-modified PLNPs (PLNPs-NH2) with dual-mode imaging were synthesized using a hydrothermal method. Subsequently, an Apt@IMO nanostructure was designed and synthesized, and covalently modified on the surface of the PLNPs-NH2 to enhance the dispersibility and imaging targeting of the nanoprobe PLNPs-Apt@IMO. Furthermore, in vitro experiments confirmed the specific binding of the GD2 aptamer to the neuroblastoma cell surface marker GD2 and the pH-responsive performance of the IMO structure. Finally, in vivo imaging experiments showed that the nanoprobe PLNPs-Apt@IMO effectively distinguishes tumors from normal tissues in animal models, indicating strong tumor specificity and significant imaging depth. It provides a new method for sensitive molecular imaging of neuroblastoma. In conclusion, this technology holds great promise for enhancing tumor resolution and assisting tumor resection surgery.
Disialoganglioside (GD2) is a key target for the diagnosis and treatment of multiple malignant tumors. However, the shortage of effective targeting probes for GD2 remains a major challenge in this field. This study developed a pH-activated targeted optical nanoprobe based on functional DNA-modified persistent luminescent nanoparticles (PLNPs), utilizing the targeting specificity of GD2 aptamers (Apt) and the pH-activated of Ⅰ-motif (IMO) structure, achieving sensitive and specific molecular imaging of neuroblastoma. First, Cr3+-doped amino-modified PLNPs (PLNPs-NH2) with dual-mode imaging were synthesized using a hydrothermal method. Subsequently, an Apt@IMO nanostructure was designed and synthesized, and covalently modified on the surface of the PLNPs-NH2 to enhance the dispersibility and imaging targeting of the nanoprobe PLNPs-Apt@IMO. Furthermore, in vitro experiments confirmed the specific binding of the GD2 aptamer to the neuroblastoma cell surface marker GD2 and the pH-responsive performance of the IMO structure. Finally, in vivo imaging experiments showed that the nanoprobe PLNPs-Apt@IMO effectively distinguishes tumors from normal tissues in animal models, indicating strong tumor specificity and significant imaging depth. It provides a new method for sensitive molecular imaging of neuroblastoma. In conclusion, this technology holds great promise for enhancing tumor resolution and assisting tumor resection surgery.
2026, 37(11): 112226
doi: 10.1016/j.cclet.2025.112226
摘要:
Aggregation-induced emission (AIE)-based photosensitizers have emerged as promising candidates for image-guided antibacterial therapy. However, achieving efficient reactive oxygen species (ROS) generation under hypoxic infection conditions while maintaining broad-spectrum antimicrobial activity remains a significant challenge. Herein, we report two cationic triphenylamine-armed D–A–D’ type AIE photosensitizers, BTBH and BTBF, rationally designed to optimize their electronic structures and photophysical properties. Both photosensitizers exhibit strong selectivity toward bacteria and efficiently produce ROS through synergistic type Ⅰ and type Ⅱ photodynamic pathways. Notably, compared with the fluorine-free BTBH, the fluorinated analogue BTBF shows greater ROS-generating capacity. Moreover, BTBF demonstrates intrinsic dark toxicity by disrupting bacterial membranes, which, together with its photodynamic activity, enables a synergistic dual-mode antibacterial effect, resulting in superior antibacterial efficiency and broad-spectrum antimicrobial performance. This work highlights a fluorination strategy for sensitive bacterial detection and highly effective antibacterial therapy, providing a promising platform for theranostic applications against bacterial infections.
Aggregation-induced emission (AIE)-based photosensitizers have emerged as promising candidates for image-guided antibacterial therapy. However, achieving efficient reactive oxygen species (ROS) generation under hypoxic infection conditions while maintaining broad-spectrum antimicrobial activity remains a significant challenge. Herein, we report two cationic triphenylamine-armed D–A–D’ type AIE photosensitizers, BTBH and BTBF, rationally designed to optimize their electronic structures and photophysical properties. Both photosensitizers exhibit strong selectivity toward bacteria and efficiently produce ROS through synergistic type Ⅰ and type Ⅱ photodynamic pathways. Notably, compared with the fluorine-free BTBH, the fluorinated analogue BTBF shows greater ROS-generating capacity. Moreover, BTBF demonstrates intrinsic dark toxicity by disrupting bacterial membranes, which, together with its photodynamic activity, enables a synergistic dual-mode antibacterial effect, resulting in superior antibacterial efficiency and broad-spectrum antimicrobial performance. This work highlights a fluorination strategy for sensitive bacterial detection and highly effective antibacterial therapy, providing a promising platform for theranostic applications against bacterial infections.
2026, 37(11): 112232
doi: 10.1016/j.cclet.2025.112232
摘要:
Because of the high aggressiveness and particularity of glioblastoma (GBM), the post-surgical minimal residual lesion is usually unavoidable and represents a crucial factor to the postoperative recurrence. Upon their combination with chemotherapy, the targeted delivery of therapeutic agents to the residual lesion is greatly challenged, ultimately causing the unfavorable prognosis. Inspired by the histopathological features of GBM tumors, a bioinspired fibrin hydrogel (FHL) system loading natural albumin nanoparticles was optimized from 4 different formulations by characterizing the targeting and penetrating ability in the postoperative residual lesion of GL261-induced GBM model. After surgical resection of GBM tumors, the intracranial injection of FHL loading albumin-paclitaxel nanoparticles exhibited specific targeting and notable intratumor penetration in the residual lesion, thereby significantly retarding the tumor relapse and producing a 2.16-fold prolongation of survival time. Therefore, the bioinspired FHL loading albumin nanoparticles provides an encouraging targeted delivery platform for postoperative GBM therapy.
Because of the high aggressiveness and particularity of glioblastoma (GBM), the post-surgical minimal residual lesion is usually unavoidable and represents a crucial factor to the postoperative recurrence. Upon their combination with chemotherapy, the targeted delivery of therapeutic agents to the residual lesion is greatly challenged, ultimately causing the unfavorable prognosis. Inspired by the histopathological features of GBM tumors, a bioinspired fibrin hydrogel (FHL) system loading natural albumin nanoparticles was optimized from 4 different formulations by characterizing the targeting and penetrating ability in the postoperative residual lesion of GL261-induced GBM model. After surgical resection of GBM tumors, the intracranial injection of FHL loading albumin-paclitaxel nanoparticles exhibited specific targeting and notable intratumor penetration in the residual lesion, thereby significantly retarding the tumor relapse and producing a 2.16-fold prolongation of survival time. Therefore, the bioinspired FHL loading albumin nanoparticles provides an encouraging targeted delivery platform for postoperative GBM therapy.
2026, 37(11): 112245
doi: 10.1016/j.cclet.2025.112245
摘要:
Alcohol-associated liver disease (ALD) is responsible for a growing number of deaths and economic losses every year. However, there is no approved specific pharmacotherapy for alcoholic liver injury. Starting from the non-selective phosphodiesterase (PDE) inhibitor caffeine skeleton, we successfully identified a novel pyrrolo[2,3-d]pyrimidin-4-one derivative, ZHB12 (50% inhibitory concentration (IC50) against PDE7A = 0.2 µmol/L), as a PDE7 inhibitor through the artificial intelligence (AI) driven "molecular factory" module. ZHB12 exhibits favorable physicochemical properties, good selectivity, and satisfactory bioavailability (F = 24.8%), as well as a non-toxic dose of 500 mg/kg. Additionally, ZHB12 demonstrated a significant therapeutic effect against alcoholic liver injury by increasing cyclic adenosine monophosphate (cAMP) levels and decreasing levels of inflammatory cytokines and transaminases. Notably, ZHB12 also reduced the abnormal levels of aminotransferases, inflammatory factors, and fibrosis-related genes in the alcoholic liver fibrosis (ALF) model mice, thereby improving ALF symptoms. These findings suggest that ZHB12 may be a promising candidate for the treatment of ALD.
Alcohol-associated liver disease (ALD) is responsible for a growing number of deaths and economic losses every year. However, there is no approved specific pharmacotherapy for alcoholic liver injury. Starting from the non-selective phosphodiesterase (PDE) inhibitor caffeine skeleton, we successfully identified a novel pyrrolo[2,3-d]pyrimidin-4-one derivative, ZHB12 (50% inhibitory concentration (IC50) against PDE7A = 0.2 µmol/L), as a PDE7 inhibitor through the artificial intelligence (AI) driven "molecular factory" module. ZHB12 exhibits favorable physicochemical properties, good selectivity, and satisfactory bioavailability (F = 24.8%), as well as a non-toxic dose of 500 mg/kg. Additionally, ZHB12 demonstrated a significant therapeutic effect against alcoholic liver injury by increasing cyclic adenosine monophosphate (cAMP) levels and decreasing levels of inflammatory cytokines and transaminases. Notably, ZHB12 also reduced the abnormal levels of aminotransferases, inflammatory factors, and fibrosis-related genes in the alcoholic liver fibrosis (ALF) model mice, thereby improving ALF symptoms. These findings suggest that ZHB12 may be a promising candidate for the treatment of ALD.
2026, 37(11): 112247
doi: 10.1016/j.cclet.2025.112247
摘要:
Responsive peptide-based hydrogels have attracted considerable attention for applications in drug delivery, diagnostics, and catalysis; however, most stimuli reported to date operate in the liquid or solid phase. Here, we report a tyrosine-based self-assembling peptide (Npx-YYY) that undergoes selective hydrogel formation in response to CO2 gas. The resulting dissipative hydrogel is formed through reversible peptide–CO2 interactions and holds promise for applications in catalysis as well as CO2 capture and release.
Responsive peptide-based hydrogels have attracted considerable attention for applications in drug delivery, diagnostics, and catalysis; however, most stimuli reported to date operate in the liquid or solid phase. Here, we report a tyrosine-based self-assembling peptide (Npx-YYY) that undergoes selective hydrogel formation in response to CO2 gas. The resulting dissipative hydrogel is formed through reversible peptide–CO2 interactions and holds promise for applications in catalysis as well as CO2 capture and release.
2026, 37(11): 112248
doi: 10.1016/j.cclet.2025.112248
摘要:
Lipid droplets are specialized organelles within cells that serve as the primary storage sites for neutral lipids and participate in the physiological activities of cells. Changes in the polarity and aggregation of lipid droplets can serve as indicators for diagnosing certain diseases. Therefore, a specific fluorescence probe LD-1 with donor-acceptor (D-A) structure, which exhibited low cytotoxicity, accurate targeting ability, excellent photostability, sensitivity to polarity, and deep tissue penetration, was designed for tracking lipid droplets in vivo. LD-1 exhibited remarkable two-photon characteristics, with a two-photon absorption (TPA) cross-section over 200 GM, and enabled deep tissue imaging (~16 µm) in a non-alcoholic fatty liver disease (NAFLD) model. Additionally, LD-1 could selectively stain lipid droplets in the liver tissues of fatty liver model mice, providing deeper insights into the pathological and physiological aspects of fatty liver disease.
Lipid droplets are specialized organelles within cells that serve as the primary storage sites for neutral lipids and participate in the physiological activities of cells. Changes in the polarity and aggregation of lipid droplets can serve as indicators for diagnosing certain diseases. Therefore, a specific fluorescence probe LD-1 with donor-acceptor (D-A) structure, which exhibited low cytotoxicity, accurate targeting ability, excellent photostability, sensitivity to polarity, and deep tissue penetration, was designed for tracking lipid droplets in vivo. LD-1 exhibited remarkable two-photon characteristics, with a two-photon absorption (TPA) cross-section over 200 GM, and enabled deep tissue imaging (~16 µm) in a non-alcoholic fatty liver disease (NAFLD) model. Additionally, LD-1 could selectively stain lipid droplets in the liver tissues of fatty liver model mice, providing deeper insights into the pathological and physiological aspects of fatty liver disease.
2026, 37(11): 112265
doi: 10.1016/j.cclet.2025.112265
摘要:
Periodontitis, a prevalent chronic inflammatory disease, poses significant therapeutic challenges due to its complex pathological microenvironment. Current treatment strategies often fail to simultaneously address bacterial infection, microenvironment dysregulation and tissue regeneration. To overcome these limitations, we developed a novel ZnS/KAFAK@PLEL composite hydrogel platform for targeted periodontitis treatment. The engineered hydrogel exhibits a unique temperature-triggered sol-gel transition at body temperature, significantly prolonging its retention in periodontal pockets. In vitro studies demonstrate that the KAFAK (LAARLYRKALARQLGVAA) anti-inflammatory peptide effectively modulates cellular inflammatory responses, while ZnS nanoparticles scavenge reactive oxygen species (ROS), collectively promoting osteogenic differentiation of human periodontal ligament stem cells. Comprehensive antibacterial evaluations, including colony formation assays, live/dead staining, and bacterial morphological analysis, confirm the composite hydrogel with antibacterial performance against Porphyromonas gingivalis and Staphylococcus aureus. In a rat periodontitis model, the ZnS/KAFAK@PLEL hydrogel significantly attenuated alveolar bone resorption while enhancing bone mineral density and bone volume fraction. This multifunctional composite hydrogel combines anti-bacterial, anti-inflammatory and osteoinducible properties, demonstrating remarkable potential for clinical translation in periodontitis management.
Periodontitis, a prevalent chronic inflammatory disease, poses significant therapeutic challenges due to its complex pathological microenvironment. Current treatment strategies often fail to simultaneously address bacterial infection, microenvironment dysregulation and tissue regeneration. To overcome these limitations, we developed a novel ZnS/KAFAK@PLEL composite hydrogel platform for targeted periodontitis treatment. The engineered hydrogel exhibits a unique temperature-triggered sol-gel transition at body temperature, significantly prolonging its retention in periodontal pockets. In vitro studies demonstrate that the KAFAK (LAARLYRKALARQLGVAA) anti-inflammatory peptide effectively modulates cellular inflammatory responses, while ZnS nanoparticles scavenge reactive oxygen species (ROS), collectively promoting osteogenic differentiation of human periodontal ligament stem cells. Comprehensive antibacterial evaluations, including colony formation assays, live/dead staining, and bacterial morphological analysis, confirm the composite hydrogel with antibacterial performance against Porphyromonas gingivalis and Staphylococcus aureus. In a rat periodontitis model, the ZnS/KAFAK@PLEL hydrogel significantly attenuated alveolar bone resorption while enhancing bone mineral density and bone volume fraction. This multifunctional composite hydrogel combines anti-bacterial, anti-inflammatory and osteoinducible properties, demonstrating remarkable potential for clinical translation in periodontitis management.
2026, 37(11): 112276
doi: 10.1016/j.cclet.2025.112276
摘要:
The second near-infrared (NIR-Ⅱ) phototherapy agent has the advantages of optical imaging, non-invasive treatment mode and high photothermal conversion efficiency. Herein, a novel 3,5-trithienyl-substituted aza-boron-dipyrromethene (aza-BODIPY) (TerS-BDP) was synthesized via site-specific terthienyl functionalization at the 3,5-positions. According to X-ray single crystal analysis, TerS-BDP is an extremely twisted configuration, which is beneficial for intersystem crossing (ISC) to produce reactive oxygen species (ROS). In addition, the self-assembled TerS-BDP nanoparticles (TerS-BDP NPs) displayed excellent photothermal conversion efficiency (η = 62%), and can induce apoptosis of tumor cells through the combination of photothermal therapy and photodynamic therapy. This design strategy of terthienyl segment for NIR-Ⅱ aza-BODIPY provides a new idea and method for the study of phototherapy.
The second near-infrared (NIR-Ⅱ) phototherapy agent has the advantages of optical imaging, non-invasive treatment mode and high photothermal conversion efficiency. Herein, a novel 3,5-trithienyl-substituted aza-boron-dipyrromethene (aza-BODIPY) (TerS-BDP) was synthesized via site-specific terthienyl functionalization at the 3,5-positions. According to X-ray single crystal analysis, TerS-BDP is an extremely twisted configuration, which is beneficial for intersystem crossing (ISC) to produce reactive oxygen species (ROS). In addition, the self-assembled TerS-BDP nanoparticles (TerS-BDP NPs) displayed excellent photothermal conversion efficiency (η = 62%), and can induce apoptosis of tumor cells through the combination of photothermal therapy and photodynamic therapy. This design strategy of terthienyl segment for NIR-Ⅱ aza-BODIPY provides a new idea and method for the study of phototherapy.
2026, 37(11): 112277
doi: 10.1016/j.cclet.2025.112277
摘要:
While chemotherapy combined with radiotherapy constitutes the standard postoperative tumor treatment, its therapeutic efficacy is frequently compromised by cancer cell resistance to chemoradiation. To enhance combretastatin A4 (CA4)-based chemotherapy and X-ray radiotherapy, we developed a glutathione (GSH)-responsive nanoplatform (CA4-DNBS@ICG) capable of generating sulfur dioxide (SO2) for breast cancer therapy. The engineered CA4-DNBS@ICG nanoparticles are engulfed by tumor cells and subsequently release both SO2 and CA4 upon encountering GSH-overexpressed tumor microenvironment. X-ray radiotherapy can induce DNA damages and elevate intracellular oxidative stress, while CA4 inhibits tubulin polymerization in cancer cells. SO2 potentiates this effect by depleting GSH and amplifying oxidative stress, thereby dramatically increasing reactive oxygen species generation. This cascade significantly sensitizes 4T1 cancer cells to both chemotherapy and radiotherapy. In vitro/in vivo experiments demonstrated that CA4-DNBS@ICG selectively eliminates 4T1 cancer cells and potently suppresses tumor growth with minimal systemic toxicity. Compared with conventional CA4 administration combined with radiotherapy, CA4-DNBS@ICG exhibited superior anticancer efficacy in 4T1 tumor-bearing mice via integrated gas/chemo-/radiotherapy, establishing a promising therapeutic strategy against breast cancer.
While chemotherapy combined with radiotherapy constitutes the standard postoperative tumor treatment, its therapeutic efficacy is frequently compromised by cancer cell resistance to chemoradiation. To enhance combretastatin A4 (CA4)-based chemotherapy and X-ray radiotherapy, we developed a glutathione (GSH)-responsive nanoplatform (CA4-DNBS@ICG) capable of generating sulfur dioxide (SO2) for breast cancer therapy. The engineered CA4-DNBS@ICG nanoparticles are engulfed by tumor cells and subsequently release both SO2 and CA4 upon encountering GSH-overexpressed tumor microenvironment. X-ray radiotherapy can induce DNA damages and elevate intracellular oxidative stress, while CA4 inhibits tubulin polymerization in cancer cells. SO2 potentiates this effect by depleting GSH and amplifying oxidative stress, thereby dramatically increasing reactive oxygen species generation. This cascade significantly sensitizes 4T1 cancer cells to both chemotherapy and radiotherapy. In vitro/in vivo experiments demonstrated that CA4-DNBS@ICG selectively eliminates 4T1 cancer cells and potently suppresses tumor growth with minimal systemic toxicity. Compared with conventional CA4 administration combined with radiotherapy, CA4-DNBS@ICG exhibited superior anticancer efficacy in 4T1 tumor-bearing mice via integrated gas/chemo-/radiotherapy, establishing a promising therapeutic strategy against breast cancer.
2026, 37(11): 112287
doi: 10.1016/j.cclet.2025.112287
摘要:
Heart failure (HF) constitutes a global health burden with elevated mortality and rehospitalization, underscoring the urgent need for novel therapeutics to improve outcomes. Herein, we reported the discovery of a psoralen analog, xanthotoxin (XAT), which is a natural product isolated from Synotis nagensium with cardioprotective effects. To overcome XAT's phototoxicity and poor aqueous solubility, the rational structural optimization was performed to yield 26 psoralen derivatives. Among them, A22 emerged as the optimal derivative, showing abolished phototoxicity, improved aqueous solubility, and potent efficacy at 5 mg/kg in both isoproterenol (ISO)-induced and myocardial infarction (MI)-induced HF models. Mechanistic studies demonstrated that A22 attenuated oxidative stress and cardiomyocyte apoptosis via activation of the Kelch-like ECH-associated protein 1 (Keap1)–nuclear factor erythroid 2-related factor 2 (Nrf2)–antioxidant response element (ARE) pathway. Favorable safety and pharmacokinetic profiles further supported its translational potential. Together, these data supported A22 as a promising candidate for HF therapy and justified continued preclinical investigation toward clinical development.
Heart failure (HF) constitutes a global health burden with elevated mortality and rehospitalization, underscoring the urgent need for novel therapeutics to improve outcomes. Herein, we reported the discovery of a psoralen analog, xanthotoxin (XAT), which is a natural product isolated from Synotis nagensium with cardioprotective effects. To overcome XAT's phototoxicity and poor aqueous solubility, the rational structural optimization was performed to yield 26 psoralen derivatives. Among them, A22 emerged as the optimal derivative, showing abolished phototoxicity, improved aqueous solubility, and potent efficacy at 5 mg/kg in both isoproterenol (ISO)-induced and myocardial infarction (MI)-induced HF models. Mechanistic studies demonstrated that A22 attenuated oxidative stress and cardiomyocyte apoptosis via activation of the Kelch-like ECH-associated protein 1 (Keap1)–nuclear factor erythroid 2-related factor 2 (Nrf2)–antioxidant response element (ARE) pathway. Favorable safety and pharmacokinetic profiles further supported its translational potential. Together, these data supported A22 as a promising candidate for HF therapy and justified continued preclinical investigation toward clinical development.
2026, 37(11): 112288
doi: 10.1016/j.cclet.2025.112288
摘要:
A highly enantioselective Brønsted acid-catalyzed [3 + 3] cyclization between p-quinamines and azomethine imines has been developed, providing efficient access to 6/6/6/6-fused tetracyclic 1,2,4-triazinanes bearing three nitrogen-containing stereocenters. This transformation proceeds under mild conditions mediated by a chiral phosphoric acid catalyst, affording products in up to 94% yield and 99% ee. The reaction exhibits broad substrate scope, tolerating diverse functional groups including alkyl, aryl, heteroaryl, and alkynyl substituents. The utility of this method is demonstrated through gram-scale synthesis and diverse downstream transformations, leading to structurally complex polycyclic and cage-like heterocyclic frameworks. This metal-free strategy not only complements existing metal-catalyzed enantioselective routes to 1,2,4-triazine derivatives but also established a new paradigm for asymmetric [3 + 3] cyclization of p-quinamines. Notably, evaluation of the antifibrotic activity of selected 1,2,4-triazinanes identified the derivative 10 as a promising candidate against liver fibrosis.
A highly enantioselective Brønsted acid-catalyzed [3 + 3] cyclization between p-quinamines and azomethine imines has been developed, providing efficient access to 6/6/6/6-fused tetracyclic 1,2,4-triazinanes bearing three nitrogen-containing stereocenters. This transformation proceeds under mild conditions mediated by a chiral phosphoric acid catalyst, affording products in up to 94% yield and 99% ee. The reaction exhibits broad substrate scope, tolerating diverse functional groups including alkyl, aryl, heteroaryl, and alkynyl substituents. The utility of this method is demonstrated through gram-scale synthesis and diverse downstream transformations, leading to structurally complex polycyclic and cage-like heterocyclic frameworks. This metal-free strategy not only complements existing metal-catalyzed enantioselective routes to 1,2,4-triazine derivatives but also established a new paradigm for asymmetric [3 + 3] cyclization of p-quinamines. Notably, evaluation of the antifibrotic activity of selected 1,2,4-triazinanes identified the derivative 10 as a promising candidate against liver fibrosis.
2026, 37(11): 112289
doi: 10.1016/j.cclet.2025.112289
摘要:
The escalating global prevalence of antibiotic-resistant Helicobacter pylori infections necessitates the development of novel therapeutics targeting specific bacterial pathways. From Icacina oliviformis leaves, we isolated twelve novel diterpenoids (1–12), including two unprecedented dimeric scaffolds, alongside four known analogs (13–16). Structural elucidation via nuclear magnetic resonance (NMR), high-resolution mass spectrometry (HRMS), electronic circular dichroism (ECD), DP4+ analysis, and X-ray crystallography revealed three groundbreaking architectures: 1–3 (oliviformisones A–C) as the first ent-kaurane-(8,14-seco-ent-kaurane) spiro-heterodimers featuring a unique 6/6/6/5/6/7/6/6-fused octocyclic core with a 2-oxatricyclo[6.2.1.03,8]hendecane spiro linker; 4–6 (oliviformisones D–F) as pioneering ent-kaurane-(ent-abietane) dimers via an unprecedented C-17–C-17′ linkage; 7 and 8 as the first ent-kaurane-(8,14-seco-ent-kaurane) dimers bridged by a 1,3-dioxane moiety. Proposed biosynthetic pathways for 1, 2, 4, and 5 involve key retro-aldol and nucleophilic reactions. Notably, 1 and 3 exhibited potent anti-H. pylori activity (minimum inhibitory concentration (MIC) = 2–16 μg/mL), with 3 showing additive effects with amoxicillin (fractional inhibitory concentration index (FICI) = 0.625). Mechanistic studies confirmed 1 as a high-affinity fatty acid biosynthesis enoyl-acyl carrier protein reductase Ⅰ (FabI) inhibitor (Kd = 6.34 nmol/L), competitively blocking enoyl-acyl carrier protein (ACP) reductase (Ki = 8.9 μmol/L) to down-regulate bacterial fatty acid biosynthesis. Comparative enzymatic and docking analyses further revealed that 1 selectively inhibits H. pylori FabI over human and commensal homologs, while showing low cytotoxicity toward normal gastric epithelial cells. This work identifies 1 as the first natural product-derived selective FabI inhibitor with anti-H. pylori activity, validates FabI as a target for species-selective therapy, and unveils ent-kaurane diterpenoids as a structurally diverse pharmacophore for antibacterial development.
The escalating global prevalence of antibiotic-resistant Helicobacter pylori infections necessitates the development of novel therapeutics targeting specific bacterial pathways. From Icacina oliviformis leaves, we isolated twelve novel diterpenoids (1–12), including two unprecedented dimeric scaffolds, alongside four known analogs (13–16). Structural elucidation via nuclear magnetic resonance (NMR), high-resolution mass spectrometry (HRMS), electronic circular dichroism (ECD), DP4+ analysis, and X-ray crystallography revealed three groundbreaking architectures: 1–3 (oliviformisones A–C) as the first ent-kaurane-(8,14-seco-ent-kaurane) spiro-heterodimers featuring a unique 6/6/6/5/6/7/6/6-fused octocyclic core with a 2-oxatricyclo[6.2.1.03,8]hendecane spiro linker; 4–6 (oliviformisones D–F) as pioneering ent-kaurane-(ent-abietane) dimers via an unprecedented C-17–C-17′ linkage; 7 and 8 as the first ent-kaurane-(8,14-seco-ent-kaurane) dimers bridged by a 1,3-dioxane moiety. Proposed biosynthetic pathways for 1, 2, 4, and 5 involve key retro-aldol and nucleophilic reactions. Notably, 1 and 3 exhibited potent anti-H. pylori activity (minimum inhibitory concentration (MIC) = 2–16 μg/mL), with 3 showing additive effects with amoxicillin (fractional inhibitory concentration index (FICI) = 0.625). Mechanistic studies confirmed 1 as a high-affinity fatty acid biosynthesis enoyl-acyl carrier protein reductase Ⅰ (FabI) inhibitor (Kd = 6.34 nmol/L), competitively blocking enoyl-acyl carrier protein (ACP) reductase (Ki = 8.9 μmol/L) to down-regulate bacterial fatty acid biosynthesis. Comparative enzymatic and docking analyses further revealed that 1 selectively inhibits H. pylori FabI over human and commensal homologs, while showing low cytotoxicity toward normal gastric epithelial cells. This work identifies 1 as the first natural product-derived selective FabI inhibitor with anti-H. pylori activity, validates FabI as a target for species-selective therapy, and unveils ent-kaurane diterpenoids as a structurally diverse pharmacophore for antibacterial development.
2026, 37(11): 112290
doi: 10.1016/j.cclet.2025.112290
摘要:
Phototherapy has great potential in combating drug-resistant bacterial infections due to its minimal tendency to induce resistance. However, a single mode of light-based treatment may require high doses of agent or laser power, which may damage healthy tissues. To address these challenges, this study designed and constructed AuNR@CuS core−shell hybrid nanoparticles (ACSNPs) with precise interface engineering. This structural design effectively enhances absorption in the near-infrared (NIR) region and promotes efficient separation of photogenerated carriers through the built-in electric field. Consequently, the ACSNPs exhibit a synergistically enhanced photothermal therapy (PTT) and photodynamic therapy (PDT) effect. Under 808 nm laser irradiation, ACSNPs demonstrated a photothermal conversion efficiency as high as 46.6% and generated substantial hydroxyl radicals. The synergistic PTT/PDT achieve the effective elimination of methicillin-resistant Staphylococcus aureus. Complete eradication of bacteria was achieved at a low concentration (20 µg/mL) within 10 min of NIR irradiation. Furthermore, in vivo experiments confirmed the excellent antibacterial efficacy of ACSNPs in healing infected skin wounds. Notably, no significant cytotoxicity was observed at their effective antibacterial concentration. This study demonstrates that interface-engineered hybrid nanoparticles serve as an efficient synergistic platform, offering a novel therapeutic strategy for treating drug-resistant bacterial infections.
Phototherapy has great potential in combating drug-resistant bacterial infections due to its minimal tendency to induce resistance. However, a single mode of light-based treatment may require high doses of agent or laser power, which may damage healthy tissues. To address these challenges, this study designed and constructed AuNR@CuS core−shell hybrid nanoparticles (ACSNPs) with precise interface engineering. This structural design effectively enhances absorption in the near-infrared (NIR) region and promotes efficient separation of photogenerated carriers through the built-in electric field. Consequently, the ACSNPs exhibit a synergistically enhanced photothermal therapy (PTT) and photodynamic therapy (PDT) effect. Under 808 nm laser irradiation, ACSNPs demonstrated a photothermal conversion efficiency as high as 46.6% and generated substantial hydroxyl radicals. The synergistic PTT/PDT achieve the effective elimination of methicillin-resistant Staphylococcus aureus. Complete eradication of bacteria was achieved at a low concentration (20 µg/mL) within 10 min of NIR irradiation. Furthermore, in vivo experiments confirmed the excellent antibacterial efficacy of ACSNPs in healing infected skin wounds. Notably, no significant cytotoxicity was observed at their effective antibacterial concentration. This study demonstrates that interface-engineered hybrid nanoparticles serve as an efficient synergistic platform, offering a novel therapeutic strategy for treating drug-resistant bacterial infections.
2026, 37(11): 112330
doi: 10.1016/j.cclet.2025.112330
摘要:
High-mobility and thermally stable organic semiconductors are crucial for advancing practical organic electronics. Here, we designed and synthesized three p-type asymmetric anthracene derivatives, namely C6-ADN, ADN-C6, and C6-ADN-C6, by varying the alkyl chain substitution positions. Ultrathin single crystals with monolayer and bi-layer thickness were obtained by the drop-casting method. Single-crystal field-effect transistors (SCFETs) based on C6-ADN, ADN-C6, and C6-ADN-C6 exhibited maximum hole mobilities of 1.91, 4.05, and 1.30 cm2 V-1 s-1, respectively. Furthermore, the thermal stabilities of these SCFETs were investigated. At 140 ℃, the ADN-C6 SCFET retains > 80% of its initial performance, whereas the C6-ADN and C6-ADN-C6 devices exhibit a performance below this threshold. These results demonstrate that the strategic positioning of the alkyl chain in asymmetric anthracene derivatives significantly enhances thermal stability, thereby facilitating the development of high-performance and thermally robust ultrathin SCFETs.
High-mobility and thermally stable organic semiconductors are crucial for advancing practical organic electronics. Here, we designed and synthesized three p-type asymmetric anthracene derivatives, namely C6-ADN, ADN-C6, and C6-ADN-C6, by varying the alkyl chain substitution positions. Ultrathin single crystals with monolayer and bi-layer thickness were obtained by the drop-casting method. Single-crystal field-effect transistors (SCFETs) based on C6-ADN, ADN-C6, and C6-ADN-C6 exhibited maximum hole mobilities of 1.91, 4.05, and 1.30 cm2 V-1 s-1, respectively. Furthermore, the thermal stabilities of these SCFETs were investigated. At 140 ℃, the ADN-C6 SCFET retains > 80% of its initial performance, whereas the C6-ADN and C6-ADN-C6 devices exhibit a performance below this threshold. These results demonstrate that the strategic positioning of the alkyl chain in asymmetric anthracene derivatives significantly enhances thermal stability, thereby facilitating the development of high-performance and thermally robust ultrathin SCFETs.
2026, 37(11): 112331
doi: 10.1016/j.cclet.2025.112331
摘要:
Unsymmetrical disulfides are ubiquitous in the field of chemical biology, pharmaceutical science, food chemistry and polymer science. Given the significance of disulfides and the urgent demand for their expeditious synthetic methods, we herein develop a [1 + 1 + 2] three-component strategy to access various disulfide molecules, enabled by commercially available boronic acids, K2S2O5 and thiols. In this study, C-S and S-S bonds are simultaneously formed during the one-pot reaction, in which pyrosulfite acts as both a promoter for the unprecedented 1,3-metallate migration process and a dual-deoxygenation activator for the in-situ generation of the novel divalent sulfur electrophiles. Notably, this method obviates the use of pre-functionalized disulfurating reagents and hazardous SO2 gas, featuring transition-metal-free conditions, a broad substrate scope, and the late-stage disulfide modification of bioactive molecules including captopril and estrone. It therefore offers a concise alternative to the modular assembly of versatile disulfides from more abundant and commercially available feedstocks.
Unsymmetrical disulfides are ubiquitous in the field of chemical biology, pharmaceutical science, food chemistry and polymer science. Given the significance of disulfides and the urgent demand for their expeditious synthetic methods, we herein develop a [1 + 1 + 2] three-component strategy to access various disulfide molecules, enabled by commercially available boronic acids, K2S2O5 and thiols. In this study, C-S and S-S bonds are simultaneously formed during the one-pot reaction, in which pyrosulfite acts as both a promoter for the unprecedented 1,3-metallate migration process and a dual-deoxygenation activator for the in-situ generation of the novel divalent sulfur electrophiles. Notably, this method obviates the use of pre-functionalized disulfurating reagents and hazardous SO2 gas, featuring transition-metal-free conditions, a broad substrate scope, and the late-stage disulfide modification of bioactive molecules including captopril and estrone. It therefore offers a concise alternative to the modular assembly of versatile disulfides from more abundant and commercially available feedstocks.
2026, 37(11): 112340
doi: 10.1016/j.cclet.2025.112340
摘要:
Triphenylamine (TPA)-based fluorescent probes offer strong aggregation-induced emission (AIE) and versatile donor–acceptor (D–A) motifs, yet their practical applicability is limited by poor selectivity and background emission from non-specific acceptor reactions. Herein, we present TPA-PROXYL, a photoinduced electron transfer (PET)–mediated "OFF–ON" probe that merges AIE-active TPA scaffold with a stable 2,2,5,5-tetramethyl-3-pyrrolin-1-oxyl (PROXYL) radical for highly specific benzoyl peroxide (BPO) detection. Upon selective oxidation of the PROXYL moiety by BPO in DMF at 100 ℃ for 1 h, PET is suppressed, and yielding a strong fluorescence turn-on at 465 nm (λex = 365 nm). Notably, the probe is activated at 0.5 mmol/L BPO and achieves a low detection limit of 211 nmol/L with good linearity, while maintaining high selectivity against redox interferents such as glutathione (GSH), ascorbic acid (VC), and cysteine (CYS). Furthermore, the recovery rate exceeding 84% in real sample applications demonstrates the robustness and practicality of TPA-PROXYL. By integrating the PET modulation with AIE activity, this strategy establishes a high-fidelity sensing platform with exceptional specificity and sensitivity, offering strong potential for on-site BPO surveillance and broader small-molecule detection in complex matrices.
Triphenylamine (TPA)-based fluorescent probes offer strong aggregation-induced emission (AIE) and versatile donor–acceptor (D–A) motifs, yet their practical applicability is limited by poor selectivity and background emission from non-specific acceptor reactions. Herein, we present TPA-PROXYL, a photoinduced electron transfer (PET)–mediated "OFF–ON" probe that merges AIE-active TPA scaffold with a stable 2,2,5,5-tetramethyl-3-pyrrolin-1-oxyl (PROXYL) radical for highly specific benzoyl peroxide (BPO) detection. Upon selective oxidation of the PROXYL moiety by BPO in DMF at 100 ℃ for 1 h, PET is suppressed, and yielding a strong fluorescence turn-on at 465 nm (λex = 365 nm). Notably, the probe is activated at 0.5 mmol/L BPO and achieves a low detection limit of 211 nmol/L with good linearity, while maintaining high selectivity against redox interferents such as glutathione (GSH), ascorbic acid (VC), and cysteine (CYS). Furthermore, the recovery rate exceeding 84% in real sample applications demonstrates the robustness and practicality of TPA-PROXYL. By integrating the PET modulation with AIE activity, this strategy establishes a high-fidelity sensing platform with exceptional specificity and sensitivity, offering strong potential for on-site BPO surveillance and broader small-molecule detection in complex matrices.
2026, 37(11): 112341
doi: 10.1016/j.cclet.2025.112341
摘要:
Precisely controlling the regioselectivity on remote C–H bonds of polycyclic aromatic hydrocarbons could rapidly access to unique molecules among natural products, materials and pharmaceuticals. Compared to conventional homoannular C–H functionalizations, heteroannular remote C–H bonds are difficult to reach due to the lack of spatial or electronic biases. Herein, simple, commercially available nitrile-based directing templates have been well-designed to achieve the high-efficient transannular C7-H alkenylation, allylation, and acetoxylation in diverse polycyclic aromatic substrates. Excellent C7-regioselectivity was observed in the presence of the less-sterically but electronically similar C3-H bond. Detailed mechanistic studies revealed that Ag salt acts as co-catalyst in the C–H activation step by facilitating the formation of an active Pd−Ag bimetallic complex. Our findings not only necessitate a practical synthetic approach to useful polycyclic aromatic hydrocarbons and related natural products but also provide mechanistic insights for building hybridized catalysis in the remote C–H activation on (hetero)aromatic systems.
Precisely controlling the regioselectivity on remote C–H bonds of polycyclic aromatic hydrocarbons could rapidly access to unique molecules among natural products, materials and pharmaceuticals. Compared to conventional homoannular C–H functionalizations, heteroannular remote C–H bonds are difficult to reach due to the lack of spatial or electronic biases. Herein, simple, commercially available nitrile-based directing templates have been well-designed to achieve the high-efficient transannular C7-H alkenylation, allylation, and acetoxylation in diverse polycyclic aromatic substrates. Excellent C7-regioselectivity was observed in the presence of the less-sterically but electronically similar C3-H bond. Detailed mechanistic studies revealed that Ag salt acts as co-catalyst in the C–H activation step by facilitating the formation of an active Pd−Ag bimetallic complex. Our findings not only necessitate a practical synthetic approach to useful polycyclic aromatic hydrocarbons and related natural products but also provide mechanistic insights for building hybridized catalysis in the remote C–H activation on (hetero)aromatic systems.
2026, 37(11): 112342
doi: 10.1016/j.cclet.2025.112342
摘要:
Conductive eutectogels based on deep eutectic solvents (DESs) represent a promising platform for flexible electronics, addressing key limitations of conventional hydrogels such as freezing and unstable water content. Here, we develop a multi-network eutectogel (CML) through molecular integration of host–guest DESs and type Ⅳ DESs, composed of β-cyclodextrin, L-(-)-malic acid, and LiCl. The synergistic dynamic hydrogen-bond network and host–guest interactions endow the gel with tunable mechanical strength (Young's modulus: 39.35 MPa to 0.04 MPa), strong adhesion, and autonomous self-healing at low temperatures, while the ion-conducting network ensures high electrical conductivity. The CML eutectogel performs as a high-sensitivity strain and pressure sensor capable of detecting subtle human motions, and exhibits remarkable temperature sensitivity (2.37% per degree in the 34–42 ℃ range). Moreover, its intrinsic fluorescence under 365 nm light enables applications in information encryption and anti-counterfeiting. This multifunctional eutectogel demonstrates great potential for advanced wearable electronics and intelligent systems.
Conductive eutectogels based on deep eutectic solvents (DESs) represent a promising platform for flexible electronics, addressing key limitations of conventional hydrogels such as freezing and unstable water content. Here, we develop a multi-network eutectogel (CML) through molecular integration of host–guest DESs and type Ⅳ DESs, composed of β-cyclodextrin, L-(-)-malic acid, and LiCl. The synergistic dynamic hydrogen-bond network and host–guest interactions endow the gel with tunable mechanical strength (Young's modulus: 39.35 MPa to 0.04 MPa), strong adhesion, and autonomous self-healing at low temperatures, while the ion-conducting network ensures high electrical conductivity. The CML eutectogel performs as a high-sensitivity strain and pressure sensor capable of detecting subtle human motions, and exhibits remarkable temperature sensitivity (2.37% per degree in the 34–42 ℃ range). Moreover, its intrinsic fluorescence under 365 nm light enables applications in information encryption and anti-counterfeiting. This multifunctional eutectogel demonstrates great potential for advanced wearable electronics and intelligent systems.
2026, 37(11): 112354
doi: 10.1016/j.cclet.2025.112354
摘要:
An efficient catalytic thiolation/dethiolation strategy for the ring-opening transformation of cyclopropenes is reported. The reaction occurs via the formation of a vinylogous Pummerer intermediate followed by a dethiolation Pummerer fragmentation step. A wide range of valuable products including α,β-unsaturated nitriles and carbonyl compounds can be efficiently synthesized in these reactions. The resultant products are readily transformed into other valuable molecules. The hydrogenation experiment supports the generation of the vinylogous thionium ion as a crucial intermediate in this transformation.
An efficient catalytic thiolation/dethiolation strategy for the ring-opening transformation of cyclopropenes is reported. The reaction occurs via the formation of a vinylogous Pummerer intermediate followed by a dethiolation Pummerer fragmentation step. A wide range of valuable products including α,β-unsaturated nitriles and carbonyl compounds can be efficiently synthesized in these reactions. The resultant products are readily transformed into other valuable molecules. The hydrogenation experiment supports the generation of the vinylogous thionium ion as a crucial intermediate in this transformation.
2026, 37(11): 112356
doi: 10.1016/j.cclet.2025.112356
摘要:
This study elucidates the mechanism of copper-catalyzed C(sp3)–H borylation through density functional theory (DFT) calculations. We reveal the triple catalytic role of CuCl2, which acts as a catalyst for hydrolytic cleavage of B2cat2, a photosensitize generating reactive chlorine radicals (Cl•), and a dehydrating agent that facilitates the condensation of HOBcat intermediates to regenerate the active borylation species O(Bcat)2. Key mechanistic insights include the dominance of Cl• in hydrogen atom transfer (HAT), where direct hydrogen abstraction by Cl• exhibits significantly lower activation barriers compared to alternative pathways involving preformed chlororadical-borate complexes. Computational analysis also identifies steric effects, rather than bond dissociation energy (BDE) trends, as the origin of primary C–H selectivity, with bulky intermediates preferentially accessing sterically accessible sites. These findings challenge conventional mechanistic assumptions and establish a unified framework for radical-mediated C–H functionalization, offering strategic principles for designing regioselective, atom-economical catalytic systems.
This study elucidates the mechanism of copper-catalyzed C(sp3)–H borylation through density functional theory (DFT) calculations. We reveal the triple catalytic role of CuCl2, which acts as a catalyst for hydrolytic cleavage of B2cat2, a photosensitize generating reactive chlorine radicals (Cl•), and a dehydrating agent that facilitates the condensation of HOBcat intermediates to regenerate the active borylation species O(Bcat)2. Key mechanistic insights include the dominance of Cl• in hydrogen atom transfer (HAT), where direct hydrogen abstraction by Cl• exhibits significantly lower activation barriers compared to alternative pathways involving preformed chlororadical-borate complexes. Computational analysis also identifies steric effects, rather than bond dissociation energy (BDE) trends, as the origin of primary C–H selectivity, with bulky intermediates preferentially accessing sterically accessible sites. These findings challenge conventional mechanistic assumptions and establish a unified framework for radical-mediated C–H functionalization, offering strategic principles for designing regioselective, atom-economical catalytic systems.
2026, 37(11): 112366
doi: 10.1016/j.cclet.2026.112366
摘要:
Overcoming the challenge of efficient lignin depolymerization is central to the economic viability of lignocellulosic biorefining. While Ni-Al catalysts offer a promising alternative to noble metals for C–O bond hydrogenation, their practical application is limited by suboptimal activity and elusive depolymerization mechanisms. Herein, a hierarchical-porous Ni-Al silicate catalyst (PMS-96-r) is engineered, which delivers a 49 wt% lignin monomer yield from poplar sawdust through reductive catalytic fractionation (RCF) under mild conditions (220 ℃, 1 MPa H2), while maintaining catalytic stability over five cycles. Characterizations and DFT calculations reveal that Al modulates the electronic properties of Ni via the Ni–O–Al structure, enhancing methoxy coordination and lowering the activation energy for β–O–4 cleavage. Moreover, molecular dynamics simulations reveal that the hierarchical porosity of PMS-96-r enhances lignin fragment diffusion through mesopores and enhances monomer transport via micropores, collectively shifting reaction equilibrium. This electronic-structural dual-engineering strategy establishes a mechanistic foundation for designing high-performance catalysts for sustainable lignin valorization.
Overcoming the challenge of efficient lignin depolymerization is central to the economic viability of lignocellulosic biorefining. While Ni-Al catalysts offer a promising alternative to noble metals for C–O bond hydrogenation, their practical application is limited by suboptimal activity and elusive depolymerization mechanisms. Herein, a hierarchical-porous Ni-Al silicate catalyst (PMS-96-r) is engineered, which delivers a 49 wt% lignin monomer yield from poplar sawdust through reductive catalytic fractionation (RCF) under mild conditions (220 ℃, 1 MPa H2), while maintaining catalytic stability over five cycles. Characterizations and DFT calculations reveal that Al modulates the electronic properties of Ni via the Ni–O–Al structure, enhancing methoxy coordination and lowering the activation energy for β–O–4 cleavage. Moreover, molecular dynamics simulations reveal that the hierarchical porosity of PMS-96-r enhances lignin fragment diffusion through mesopores and enhances monomer transport via micropores, collectively shifting reaction equilibrium. This electronic-structural dual-engineering strategy establishes a mechanistic foundation for designing high-performance catalysts for sustainable lignin valorization.
2026, 37(11): 112367
doi: 10.1016/j.cclet.2026.112367
摘要:
An I2-DMSO mediated cascade annulation has been established, with precise steric control serving as the core design principle. This protocol enables the chemo- and regioselective construction of the dibenzo[b,f][1,7]naphthyridine scaffold using commercially available aryl methyl ketones, arylamines, and o-alkynylanilines. The metal-free process involves N-H/α,β-C(sp)−H trifunctionalization of o-alkynylanilines, facilitating the formation of two C-N bonds, two C-C bonds, and two rings in a one-pot manner. Moreover, this domino strategy not only broadens the reaction versatility of o-alkynylanilines but also underscores the utility of steric regulation in the selective synthesis of fused heterocycle.
An I2-DMSO mediated cascade annulation has been established, with precise steric control serving as the core design principle. This protocol enables the chemo- and regioselective construction of the dibenzo[b,f][1,7]naphthyridine scaffold using commercially available aryl methyl ketones, arylamines, and o-alkynylanilines. The metal-free process involves N-H/α,β-C(sp)−H trifunctionalization of o-alkynylanilines, facilitating the formation of two C-N bonds, two C-C bonds, and two rings in a one-pot manner. Moreover, this domino strategy not only broadens the reaction versatility of o-alkynylanilines but also underscores the utility of steric regulation in the selective synthesis of fused heterocycle.
2026, 37(11): 112369
doi: 10.1016/j.cclet.2026.112369
摘要:
A palladium-catalyzed and ligand-controlled regiodivergent intramolecular cyclization of ketone–vinylbicyclo[1.1.0]butanes (Ketone-VC-BCBs) has been developed. Using Trost-Ph-Phos as the ligand, intramolecular nucleophilic attack of the carbonyl group onto the zwitterionic palladium species followed by a proton transfer affords oxaspiro[3.4]oct-1-en-5-one derivatives in moderate yields with excellent diastereoselectivities. In contrast, employment of 1,4-bis(diphenylphosphino)butane (DPPB, L3) promotes intramolecular a proton migration and a rearrangement to generate a novel zwitterionic palladium species, which subsequently undergoes cyclization to deliver unexpected rearranged products as bicyclo[3.1.1]heptanes in good yields. Ligand-controlled modulation of proton transfer pathways governs the divergent reaction outcomes, enabling the selective formation of two structurally distinct products. The proposed mechanisms were further supported by deuterium-labeling experiments and DFT calculations. The further transformation of the obtained products has also been presented.
A palladium-catalyzed and ligand-controlled regiodivergent intramolecular cyclization of ketone–vinylbicyclo[1.1.0]butanes (Ketone-VC-BCBs) has been developed. Using Trost-Ph-Phos as the ligand, intramolecular nucleophilic attack of the carbonyl group onto the zwitterionic palladium species followed by a proton transfer affords oxaspiro[3.4]oct-1-en-5-one derivatives in moderate yields with excellent diastereoselectivities. In contrast, employment of 1,4-bis(diphenylphosphino)butane (DPPB, L3) promotes intramolecular a proton migration and a rearrangement to generate a novel zwitterionic palladium species, which subsequently undergoes cyclization to deliver unexpected rearranged products as bicyclo[3.1.1]heptanes in good yields. Ligand-controlled modulation of proton transfer pathways governs the divergent reaction outcomes, enabling the selective formation of two structurally distinct products. The proposed mechanisms were further supported by deuterium-labeling experiments and DFT calculations. The further transformation of the obtained products has also been presented.
2026, 37(11): 112370
doi: 10.1016/j.cclet.2026.112370
摘要:
Owing to the strong rigidity and difficult diastereoselectivity control, the construction of angularly fused tricyclic scaffolds containing multiple contiguous stereocenters has become one of the most challenging research topics. Herein, we report an efficient method to prepare various angularly fused 6-5-5 tricyclic isoxazolines containing five contiguous stereocenters in good yields with high diastereoselectivity from N-cyclopentenyl nitrones and nitroalkenes under mild reaction conditions. Mechanistic studies revealed that the reaction underwent a quinine-catalyzed (3+2) cycloaddition, [3,3]-rearrangement, and intramolecular cyclization in a one-pot reaction and quinine catalyst played an important role on the intramolecular cyclization through hydrogen-bonding effect. The reaction was easily performed in gram scales and converted into various useful tricyclic building blocks. More importantly, the use of chiral quinine-derived squaramide as the catalyst, the angularly fused tricyclic isoxazolines containing five contiguous stereocenters can be obtained in excellent enantioselectivity (83%-93% ee) and diastereoselectivity (dr > 20:1).
Owing to the strong rigidity and difficult diastereoselectivity control, the construction of angularly fused tricyclic scaffolds containing multiple contiguous stereocenters has become one of the most challenging research topics. Herein, we report an efficient method to prepare various angularly fused 6-5-5 tricyclic isoxazolines containing five contiguous stereocenters in good yields with high diastereoselectivity from N-cyclopentenyl nitrones and nitroalkenes under mild reaction conditions. Mechanistic studies revealed that the reaction underwent a quinine-catalyzed (3+2) cycloaddition, [3,3]-rearrangement, and intramolecular cyclization in a one-pot reaction and quinine catalyst played an important role on the intramolecular cyclization through hydrogen-bonding effect. The reaction was easily performed in gram scales and converted into various useful tricyclic building blocks. More importantly, the use of chiral quinine-derived squaramide as the catalyst, the angularly fused tricyclic isoxazolines containing five contiguous stereocenters can be obtained in excellent enantioselectivity (83%-93% ee) and diastereoselectivity (dr > 20:1).
2026, 37(11): 112371
doi: 10.1016/j.cclet.2026.112371
摘要:
The asymmetric hydroalkylation of conjugated dienes is a key strategy for the direct synthesis of chiral molecules. While notable progress has been made in the study of linear and branched dienes, research on the asymmetric hydroalkylation of conjugated dienes embedded in heterocyclic systems remains limited. Here we report for the first time the asymmetric hydroalkylation of heterocycle-embedded dienes. Using palladium and a chiral urea-phosphine ligand, a series of chiral coumarin derivatives with adjacent chiral centers were synthesized with excellent enantioselectivity, diastereoselectivity, and regioselectivity. Furthermore, the reaction is scalable and adaptable, and the resulting coumarin derivatives exhibit selective antitumor activity. The enantiocontrol model is proposed based on density functional theory (DFT) results, where the bifunctional ligand plays a crucial role in this enantioselective control.
The asymmetric hydroalkylation of conjugated dienes is a key strategy for the direct synthesis of chiral molecules. While notable progress has been made in the study of linear and branched dienes, research on the asymmetric hydroalkylation of conjugated dienes embedded in heterocyclic systems remains limited. Here we report for the first time the asymmetric hydroalkylation of heterocycle-embedded dienes. Using palladium and a chiral urea-phosphine ligand, a series of chiral coumarin derivatives with adjacent chiral centers were synthesized with excellent enantioselectivity, diastereoselectivity, and regioselectivity. Furthermore, the reaction is scalable and adaptable, and the resulting coumarin derivatives exhibit selective antitumor activity. The enantiocontrol model is proposed based on density functional theory (DFT) results, where the bifunctional ligand plays a crucial role in this enantioselective control.
2026, 37(11): 112372
doi: 10.1016/j.cclet.2026.112372
摘要:
The specific recognition and stable pairing of nucleobases in aqueous solution are challenging due to strong competitive solvation effects. Although synthetic hosts based on cationic scaffolds have successfully stabilized base pairs through synergistic electrostatic and hydrophobic effects, whether hydrogen bonding alone, given its high adaptability and programmability, can drive nucleobase pairing remains an open question. Herein, we present a neutral and expanded oligourea macrocycle, H[14]U, which features a preorganized cavity tailored for nucleotides binding. This host first strongly binds the phosphate groups of mononucleotides through up to fourteen hydrogen bonds. Within its confined microenvironment, the macrocycle facilitates the formation of both homodimers (U·U) and, more importantly, biologically relevant heterodimer (A·U). The 1:2 host-guest complexes were comprehensively characterized by a combination of NMR, ITC, MS, and CD spectroscopy. ITC studies revealed high-affinity binding with remarkable positive cooperativity. This work demonstrates that hydrogen-bonding interactions, without electrostatic assistance, are sufficient to drive nucleotide base pairing, offering a new design strategy for artificial systems targeting nucleobase recognition and assembly.
The specific recognition and stable pairing of nucleobases in aqueous solution are challenging due to strong competitive solvation effects. Although synthetic hosts based on cationic scaffolds have successfully stabilized base pairs through synergistic electrostatic and hydrophobic effects, whether hydrogen bonding alone, given its high adaptability and programmability, can drive nucleobase pairing remains an open question. Herein, we present a neutral and expanded oligourea macrocycle, H[14]U, which features a preorganized cavity tailored for nucleotides binding. This host first strongly binds the phosphate groups of mononucleotides through up to fourteen hydrogen bonds. Within its confined microenvironment, the macrocycle facilitates the formation of both homodimers (U·U) and, more importantly, biologically relevant heterodimer (A·U). The 1:2 host-guest complexes were comprehensively characterized by a combination of NMR, ITC, MS, and CD spectroscopy. ITC studies revealed high-affinity binding with remarkable positive cooperativity. This work demonstrates that hydrogen-bonding interactions, without electrostatic assistance, are sufficient to drive nucleotide base pairing, offering a new design strategy for artificial systems targeting nucleobase recognition and assembly.
2026, 37(11): 112404
doi: 10.1016/j.cclet.2026.112404
摘要:
The electronic structure and stability of active sites are crucial for catalytic activity in hydrogenation. Herein, we report a structural–electronic dual-engineering strategy for constructing highly dispersed, electron-rich Ni0 active sites within Ce-MOFs (Ce-TCPP-XMAA), achieving high efficiency and durability. Structurally, in situ introduction of mercaptoacetic acid (MAA) in Ce-TCPP enhanced metal–support electronic interactions and, together with pore confinement, synergistically stabilized highly dispersed Ni sites. Electronically, in situ alloying of Ni and Cu fosters intimate Ni–Cu coupling, while the high reduction potential of Cu, together with the pronounced redox activity and 4f orbital features of Ce nodes, synergistically modulates the electronic structure of Ni to form electron-rich Ni0 centers. The optimized NiCu0.1@Ce-TCPP-20MAA catalyst achieves nearly 100% conversion and selectivity in dicyclopentadiene hydrogenation under mild conditions, maintaining activity over eight cycles. Comparative experimental and computational results demonstrated that thiol anchoring, pore confinement, Cu-induced lattice distortion, and electron transfer from Ce collectively preserved the dispersion and stability of Ni0 under reaction conditions. This work offers new insights into designing non-noble metal hydrogenation catalysts.
The electronic structure and stability of active sites are crucial for catalytic activity in hydrogenation. Herein, we report a structural–electronic dual-engineering strategy for constructing highly dispersed, electron-rich Ni0 active sites within Ce-MOFs (Ce-TCPP-XMAA), achieving high efficiency and durability. Structurally, in situ introduction of mercaptoacetic acid (MAA) in Ce-TCPP enhanced metal–support electronic interactions and, together with pore confinement, synergistically stabilized highly dispersed Ni sites. Electronically, in situ alloying of Ni and Cu fosters intimate Ni–Cu coupling, while the high reduction potential of Cu, together with the pronounced redox activity and 4f orbital features of Ce nodes, synergistically modulates the electronic structure of Ni to form electron-rich Ni0 centers. The optimized NiCu0.1@Ce-TCPP-20MAA catalyst achieves nearly 100% conversion and selectivity in dicyclopentadiene hydrogenation under mild conditions, maintaining activity over eight cycles. Comparative experimental and computational results demonstrated that thiol anchoring, pore confinement, Cu-induced lattice distortion, and electron transfer from Ce collectively preserved the dispersion and stability of Ni0 under reaction conditions. This work offers new insights into designing non-noble metal hydrogenation catalysts.
2026, 37(11): 112421
doi: 10.1016/j.cclet.2026.112421
摘要:
Photocatalytic water splitting is a promising strategy for sustainable hydrogen production, offering a clean and renewable alternative to fossil fuels. In this work, an S-scheme heterojunction, COF/Cd0.95Ni0.05S, was developed which features a large interfacial contact area and efficient charge transfer pathways. Used as photocatalysts for hydrogen evolution, the COF/Cd0.95Ni0.05S composite achieves a hydrogen production rate of 750.7 μmol h-1 g-1, which is 2.5 times that of Cd0.95Ni0.05S and 3753.5 times that of COF alone. Ex-situ/in-situ experiments reveal that the enhanced performance arises from the optimized band structure, which induces a built-in electric field at the heterojunction interface, accelerating charge separation. Ni doping also suppresses CdS photocorrosion by h+, while COF provides abundant active sites. These synergistic effects highlight a promising strategy for designing cost-effective and efficient photocatalysts for hydrogen production.
Photocatalytic water splitting is a promising strategy for sustainable hydrogen production, offering a clean and renewable alternative to fossil fuels. In this work, an S-scheme heterojunction, COF/Cd0.95Ni0.05S, was developed which features a large interfacial contact area and efficient charge transfer pathways. Used as photocatalysts for hydrogen evolution, the COF/Cd0.95Ni0.05S composite achieves a hydrogen production rate of 750.7 μmol h-1 g-1, which is 2.5 times that of Cd0.95Ni0.05S and 3753.5 times that of COF alone. Ex-situ/in-situ experiments reveal that the enhanced performance arises from the optimized band structure, which induces a built-in electric field at the heterojunction interface, accelerating charge separation. Ni doping also suppresses CdS photocorrosion by h+, while COF provides abundant active sites. These synergistic effects highlight a promising strategy for designing cost-effective and efficient photocatalysts for hydrogen production.
2026, 37(11): 112438
doi: 10.1016/j.cclet.2026.112438
摘要:
Molecular structure design is pivotal for enhancing the performance of non-fused-ring electron acceptors (NFREAs), yet systematic exploration of optimal side-group substitution sites remains underexplored. Via targeted modification of molecular structures, we designed and synthesized two asymmetric NFREAs, 3TT-m-2F and 3TT-o-2F, as structural isomers differing in fluorine substitution positions on their side chains. The integration of asymmetric molecular architectures and side-group fluorination significantly modulated their electronic properties and aggregation behaviors. Notably, 3TT-o-2F exhibited a redshifted absorption spectrum, enhanced molecular packing density, and extended exciton diffusion length compared to its meta-substituted counterpart. The D18:3TT-o-2F blend film formed a well-defined nanofiber network, promoting efficient charge migration and achieving a high charge mobility. Consequently, the corresponding organic solar cell (OSC) demonstrated a remarkable power conversion efficiency (PCE) of 17.16%, outperforming the 3TT-m-2F-based device (PCE = 15.36%). These findings provide valuable guidelines for rational molecular engineering of high-performance NFREAs in OSCs.
Molecular structure design is pivotal for enhancing the performance of non-fused-ring electron acceptors (NFREAs), yet systematic exploration of optimal side-group substitution sites remains underexplored. Via targeted modification of molecular structures, we designed and synthesized two asymmetric NFREAs, 3TT-m-2F and 3TT-o-2F, as structural isomers differing in fluorine substitution positions on their side chains. The integration of asymmetric molecular architectures and side-group fluorination significantly modulated their electronic properties and aggregation behaviors. Notably, 3TT-o-2F exhibited a redshifted absorption spectrum, enhanced molecular packing density, and extended exciton diffusion length compared to its meta-substituted counterpart. The D18:3TT-o-2F blend film formed a well-defined nanofiber network, promoting efficient charge migration and achieving a high charge mobility. Consequently, the corresponding organic solar cell (OSC) demonstrated a remarkable power conversion efficiency (PCE) of 17.16%, outperforming the 3TT-m-2F-based device (PCE = 15.36%). These findings provide valuable guidelines for rational molecular engineering of high-performance NFREAs in OSCs.
2026, 37(11): 112506
doi: 10.1016/j.cclet.2026.112506
摘要:
This work herein demonstrates the first palladium-catalyzed chirality transfer from enantioenriched allylic substrates to efficiently and selectively construct both indenes and acyclic alkene atropisomers through tunable intra- and intermolecular Heck reactions. Experimental and computational studies reveal a mechanistic divergence between intramolecular and intermolecular Heck reactions, as evidenced by their distinct β-hydride elimination orientations. The intramolecular pathway is favored by the thermodynamic stability provided by conjugation and the alleviation of steric strain through ring formation, enabling direct atroposelective cyclization. In contrast, the intermolecular pathway lacks the substantial energetic benefit of ring closure, while introducing significant steric encumbrance, thereby leading to divergent pathways in the β-hydride elimination step. Despite this, subsequent olefin positional and Z/E geometric isomerization following the Heck reaction can also effectively construct acyclic axially chiral alkene frameworks. The reaction demonstrates broad substrate scope with consistently high enantioselectivity for both product classes.
This work herein demonstrates the first palladium-catalyzed chirality transfer from enantioenriched allylic substrates to efficiently and selectively construct both indenes and acyclic alkene atropisomers through tunable intra- and intermolecular Heck reactions. Experimental and computational studies reveal a mechanistic divergence between intramolecular and intermolecular Heck reactions, as evidenced by their distinct β-hydride elimination orientations. The intramolecular pathway is favored by the thermodynamic stability provided by conjugation and the alleviation of steric strain through ring formation, enabling direct atroposelective cyclization. In contrast, the intermolecular pathway lacks the substantial energetic benefit of ring closure, while introducing significant steric encumbrance, thereby leading to divergent pathways in the β-hydride elimination step. Despite this, subsequent olefin positional and Z/E geometric isomerization following the Heck reaction can also effectively construct acyclic axially chiral alkene frameworks. The reaction demonstrates broad substrate scope with consistently high enantioselectivity for both product classes.
2026, 37(11): 112559
doi: 10.1016/j.cclet.2026.112559
摘要:
Per- and polyfluoroalkyl substances (PFAS) are organic pollutants that contaminate the environment and pose significant risks to human health. Adsorption is widely practiced for removing PFAS from the aqueous environment. This study presents a rapid and visual method for evaluating the performance of various PFAS adsorbents, including four metal-organic frameworks (MOFs), granular activated carbon (GAC), and zeolite, utilizing an aqueous/liquid crystal (LC) interface. The LC produces a dark image in the presence of PFAS. After PFAS adsorption on the adsorbent, the LC generates a bright image. The effectiveness of various adsorbents is assessed from the dark-to-bright image change of the LC based on adsorption time, adsorbent concentration, and adsorption capacity. Among the tested MOFs, a zirconium-based MOF (NU-1000) displays the shortest adsorption equilibrium time of 1 min, requires a low adsorbent concentration of 200 mg/L, and demonstrates the highest adsorption capacity of 736 mg/g. The results from the LC-based platform are comparable to those from HPLC analysis and are supported by Brunauer-Emmett-Teller (BET) data. Thus, LC at the aqueous interface can be employed to efficiently screen adsorbents for PFAS adsorption, emphasizing its considerable potential for practical applications.
Per- and polyfluoroalkyl substances (PFAS) are organic pollutants that contaminate the environment and pose significant risks to human health. Adsorption is widely practiced for removing PFAS from the aqueous environment. This study presents a rapid and visual method for evaluating the performance of various PFAS adsorbents, including four metal-organic frameworks (MOFs), granular activated carbon (GAC), and zeolite, utilizing an aqueous/liquid crystal (LC) interface. The LC produces a dark image in the presence of PFAS. After PFAS adsorption on the adsorbent, the LC generates a bright image. The effectiveness of various adsorbents is assessed from the dark-to-bright image change of the LC based on adsorption time, adsorbent concentration, and adsorption capacity. Among the tested MOFs, a zirconium-based MOF (NU-1000) displays the shortest adsorption equilibrium time of 1 min, requires a low adsorbent concentration of 200 mg/L, and demonstrates the highest adsorption capacity of 736 mg/g. The results from the LC-based platform are comparable to those from HPLC analysis and are supported by Brunauer-Emmett-Teller (BET) data. Thus, LC at the aqueous interface can be employed to efficiently screen adsorbents for PFAS adsorption, emphasizing its considerable potential for practical applications.
2026, 37(11): 112564
doi: 10.1016/j.cclet.2026.112564
摘要:
Ovarian cancer is a lethal gynecological malignancy in adult women. Metabolic reprogramming not only facilitates the survival and proliferation of ovarian cancer cells but also contributes to metastasis and chemoresistance acquisition. Spatially resolved profiling of aberrant metabolic patterns in ovarian cancer tissues can reveal tumor-specific metabolic alterations underlying cancer development and progression. Here, we employed ambient airflow-assisted desorption electrospray ionization mass spectrometry imaging (AFADESI-MSI) to characterize the metabolic profiles of high-grade serous ovarian carcinoma and normal ovarian tissues. AFADESI-MSI enabled clear visualization of a broad range of small molecules, spanning from polar metabolites to lipids. Spatial mapping revealed tumor-specific metabolite accumulation or depletion, with distinct patterns aligned to histological boundaries. Tumor and non-tumor regions were distinctly demarcated based exclusively on region-specific metabolite distributions. Spatially resolved metabolomics analysis identified 127 differential metabolites, predominantly lipids (69.29%), including fatty acyls, glycerophospholipids, steroids, and glycerolipids. The dysregulated metabolic pathways encompassed unsaturated fatty acid biosynthesis, steroid hormone metabolism, glycerophospholipid metabolism, and amino acid metabolism. Overall, this technique uncovered tumor-associated metabolic alterations, demonstrating potential to augment histological diagnosis and identify therapeutic metabolic vulnerabilities in ovarian cancer.
Ovarian cancer is a lethal gynecological malignancy in adult women. Metabolic reprogramming not only facilitates the survival and proliferation of ovarian cancer cells but also contributes to metastasis and chemoresistance acquisition. Spatially resolved profiling of aberrant metabolic patterns in ovarian cancer tissues can reveal tumor-specific metabolic alterations underlying cancer development and progression. Here, we employed ambient airflow-assisted desorption electrospray ionization mass spectrometry imaging (AFADESI-MSI) to characterize the metabolic profiles of high-grade serous ovarian carcinoma and normal ovarian tissues. AFADESI-MSI enabled clear visualization of a broad range of small molecules, spanning from polar metabolites to lipids. Spatial mapping revealed tumor-specific metabolite accumulation or depletion, with distinct patterns aligned to histological boundaries. Tumor and non-tumor regions were distinctly demarcated based exclusively on region-specific metabolite distributions. Spatially resolved metabolomics analysis identified 127 differential metabolites, predominantly lipids (69.29%), including fatty acyls, glycerophospholipids, steroids, and glycerolipids. The dysregulated metabolic pathways encompassed unsaturated fatty acid biosynthesis, steroid hormone metabolism, glycerophospholipid metabolism, and amino acid metabolism. Overall, this technique uncovered tumor-associated metabolic alterations, demonstrating potential to augment histological diagnosis and identify therapeutic metabolic vulnerabilities in ovarian cancer.
2026, 37(11): 112565
doi: 10.1016/j.cclet.2026.112565
摘要:
Pharmaceutical solid form engineering through co-crystallization represents a transformative strategy for enhancing drug bioavailability and physicochemical properties, yet remains hindered by labor-intensive experimental screening and the notable absence of computational models capable of simultaneously classifying co-crystals, salts, and physical mixtures. Here, we present an intelligent multi-modal graph neural network (GNN) framework that synergistically integrates molecular graph representations, molecular fingerprints, and quantum chemical descriptors to enable automated three-class classification of pharmaceutical solid forms, addressing a critical gap in current computational pharmaceutical research. Our innovative feature fusion strategy combines topological molecular graphs with traditional molecular fingerprints and computationally-derived quantum chemical properties, creating a comprehensive multi-dimensional representation of pharmaceutical compounds. The developed integrated model achieves exceptional classification accuracy exceeding 98% across all evaluation phases, demonstrating the superior performance of combined structural, topological, and electronic feature representations in complex multi-component pharmaceutical systems. Rigorous validation using three independent active pharmaceutical ingredient datasets, theophylline, ligustrazine, and piperazine, yields outstanding success rates, confirming the model's remarkable generalizability and practical applicability across diverse chemical spaces. Most significantly, our artificial intelligence (AI)-driven multi-modal predictions successfully guided the experimental synthesis of two novel co-crystalline phases: Emodin-ligustrazine and emodin-metformin, validating the predictive power of integrated molecular feature representations in real-world pharmaceutical development.
Pharmaceutical solid form engineering through co-crystallization represents a transformative strategy for enhancing drug bioavailability and physicochemical properties, yet remains hindered by labor-intensive experimental screening and the notable absence of computational models capable of simultaneously classifying co-crystals, salts, and physical mixtures. Here, we present an intelligent multi-modal graph neural network (GNN) framework that synergistically integrates molecular graph representations, molecular fingerprints, and quantum chemical descriptors to enable automated three-class classification of pharmaceutical solid forms, addressing a critical gap in current computational pharmaceutical research. Our innovative feature fusion strategy combines topological molecular graphs with traditional molecular fingerprints and computationally-derived quantum chemical properties, creating a comprehensive multi-dimensional representation of pharmaceutical compounds. The developed integrated model achieves exceptional classification accuracy exceeding 98% across all evaluation phases, demonstrating the superior performance of combined structural, topological, and electronic feature representations in complex multi-component pharmaceutical systems. Rigorous validation using three independent active pharmaceutical ingredient datasets, theophylline, ligustrazine, and piperazine, yields outstanding success rates, confirming the model's remarkable generalizability and practical applicability across diverse chemical spaces. Most significantly, our artificial intelligence (AI)-driven multi-modal predictions successfully guided the experimental synthesis of two novel co-crystalline phases: Emodin-ligustrazine and emodin-metformin, validating the predictive power of integrated molecular feature representations in real-world pharmaceutical development.
2026, 37(11): 112570
doi: 10.1016/j.cclet.2026.112570
摘要:
The efficiency of in-situ production of H2O2 from O2 and subsequent conversion of H2O2 into reactive oxygen species (ROS) in the electro-Fenton (EF) system is a key limiting factor for its widespread application in practical water treatment. To address this key issue, we propose a design strategy based on the synergistic interaction between iron single-atom catalysts (SACs) and iron nanoparticles (PCs). The introduction of Fe0/Fe7C3 PCs not only significantly accelerates the redox cycle of iron species and enhances electron transfer efficiency, but also precisely induces an asymmetric redistribution of electrons around the Fe SACs, increasing the electron cloud density. This electron enrichment subsequently enhances the adsorption capacity of H2O2 at the active sites and thereby improving its activation efficiency. Experimental results show that the incorporation of Fe PCs increases the first-order kinetic constant of FeSAC-PC@NC to 3.8 times that of FeSAC@NC, and the degradation efficiency for various pollutants exceeds 93%. Moreover, the catalyst maintains excellent stability and performance under continuous degradation tests and scaled-up experiment, with an energy efficiency of oxidation (EEO) as low as 3.7 kWh/m3, highlighting its promising potential for industrial application. This study demonstrates that the synergistic strategy of Fe SACs and Fe0/Fe7C3 PCs provides a research direction and technical pathway for enhancing H2O2 activation efficiency in the EF system.
The efficiency of in-situ production of H2O2 from O2 and subsequent conversion of H2O2 into reactive oxygen species (ROS) in the electro-Fenton (EF) system is a key limiting factor for its widespread application in practical water treatment. To address this key issue, we propose a design strategy based on the synergistic interaction between iron single-atom catalysts (SACs) and iron nanoparticles (PCs). The introduction of Fe0/Fe7C3 PCs not only significantly accelerates the redox cycle of iron species and enhances electron transfer efficiency, but also precisely induces an asymmetric redistribution of electrons around the Fe SACs, increasing the electron cloud density. This electron enrichment subsequently enhances the adsorption capacity of H2O2 at the active sites and thereby improving its activation efficiency. Experimental results show that the incorporation of Fe PCs increases the first-order kinetic constant of FeSAC-PC@NC to 3.8 times that of FeSAC@NC, and the degradation efficiency for various pollutants exceeds 93%. Moreover, the catalyst maintains excellent stability and performance under continuous degradation tests and scaled-up experiment, with an energy efficiency of oxidation (EEO) as low as 3.7 kWh/m3, highlighting its promising potential for industrial application. This study demonstrates that the synergistic strategy of Fe SACs and Fe0/Fe7C3 PCs provides a research direction and technical pathway for enhancing H2O2 activation efficiency in the EF system.
2026, 37(11): 112579
doi: 10.1016/j.cclet.2026.112579
摘要:
Transition metal hexacyanoferrates (MHCFs) have emerged as attractive materials for salinity gradient (SG) energy recovery. However, inconsistent evaluation methods have hindered systematic material selection. First–principles calculations were carried out to identify electronic structure determinants of voltage profiles and reaction stability in four MHCF variants (M = Mn, Ni, Cu, Zn), with emphasis on partial Na+ deintercalation under SG. It was found that d orbital interactions controlled redox performance: t2g orbitals governed voltages in Mn, Ni, and Zn systems, whereas Cu exhibited coupled t2g and eg behavior. CuHCF and NiHCF were predicted to deliver voltages above 1.26 V due to combined Fe3+/Fe2+ and Mn+/M(n-1)+ redox processes. In contrast, MnHCF and ZnHCF were limited to voltages below 0.87 V owing to single–pair redox activity. Experimental validation using coprecipitation synthesized MHCFs confirmed these predictions; cyclic voltammetry measurements matched the theoretical redox assignments. A design principle was thus established: Participation of eg orbitals in transition metal centers enhances theoretical voltage. This study bridges fundamental d orbital physics and practical electrode design for SG energy conversion.
Transition metal hexacyanoferrates (MHCFs) have emerged as attractive materials for salinity gradient (SG) energy recovery. However, inconsistent evaluation methods have hindered systematic material selection. First–principles calculations were carried out to identify electronic structure determinants of voltage profiles and reaction stability in four MHCF variants (M = Mn, Ni, Cu, Zn), with emphasis on partial Na+ deintercalation under SG. It was found that d orbital interactions controlled redox performance: t2g orbitals governed voltages in Mn, Ni, and Zn systems, whereas Cu exhibited coupled t2g and eg behavior. CuHCF and NiHCF were predicted to deliver voltages above 1.26 V due to combined Fe3+/Fe2+ and Mn+/M(n-1)+ redox processes. In contrast, MnHCF and ZnHCF were limited to voltages below 0.87 V owing to single–pair redox activity. Experimental validation using coprecipitation synthesized MHCFs confirmed these predictions; cyclic voltammetry measurements matched the theoretical redox assignments. A design principle was thus established: Participation of eg orbitals in transition metal centers enhances theoretical voltage. This study bridges fundamental d orbital physics and practical electrode design for SG energy conversion.
2026, 37(11): 112580
doi: 10.1016/j.cclet.2026.112580
摘要:
The optimization of active sites to enables enhanced sluggish N2 adsorption and activation while suppressing the thermodynamically favored hydrogen evolution reaction (HER) is extremely important for N2-to-NH3 conversion by electrocatalytic nitrogen reduction reaction (NRR), but it remains a great challenge. Herein, a highly efficient oxygen vacancy-rich Fe2O3 nanospindles electrocatalyst is successfully constructed via Co incorporation, which induces the attenuation of electron cloud around the Fe site and enhances the adsorption and activation ability of the catalyst to N2 molecules. It is noteworthy that oxygen vacancies in Fe2O3 can be easily controlled by adjusting the amount of Co dopants and the competitive HER process can be effectively inhibited. The optimal Vo:Co-Fe2O3–5 demonstrates remarkably enhanced electrocatalytic activity towards NRR with a high NH3 yield rate of 30.4 μg h-1 mg-1cat. and a large FE of 16.4% under a potential of -0.5 V vs. RHE. Experimental results certificate that Co doping and oxygen vacancy modification modulate the local electronic structure and prolong the Fe-O bond in Fe2O3 that lead to the facilitated electron transfer and enhanced N2 adsorption and activation. This work provides a simple catalyst-design way for the development of advanced metal oxide materials for future energy applications.
The optimization of active sites to enables enhanced sluggish N2 adsorption and activation while suppressing the thermodynamically favored hydrogen evolution reaction (HER) is extremely important for N2-to-NH3 conversion by electrocatalytic nitrogen reduction reaction (NRR), but it remains a great challenge. Herein, a highly efficient oxygen vacancy-rich Fe2O3 nanospindles electrocatalyst is successfully constructed via Co incorporation, which induces the attenuation of electron cloud around the Fe site and enhances the adsorption and activation ability of the catalyst to N2 molecules. It is noteworthy that oxygen vacancies in Fe2O3 can be easily controlled by adjusting the amount of Co dopants and the competitive HER process can be effectively inhibited. The optimal Vo:Co-Fe2O3–5 demonstrates remarkably enhanced electrocatalytic activity towards NRR with a high NH3 yield rate of 30.4 μg h-1 mg-1cat. and a large FE of 16.4% under a potential of -0.5 V vs. RHE. Experimental results certificate that Co doping and oxygen vacancy modification modulate the local electronic structure and prolong the Fe-O bond in Fe2O3 that lead to the facilitated electron transfer and enhanced N2 adsorption and activation. This work provides a simple catalyst-design way for the development of advanced metal oxide materials for future energy applications.
2026, 37(11): 112629
doi: 10.1016/j.cclet.2026.112629
摘要:
Monatomic oxygen ions (O–), superoxide (O2–), peroxide (O22–), singlet oxygen (1O2) and active lattice oxygen species are traditional reactive oxygen species (ROS) that boosting oxidation reactions in cell growing, life activities and industrial production. However, other ROS is rarely reported due to lack of evidence. Here, a new reactive chemisorbed oxygen species named lattice-superoxide species (LSO) was found, which exclusively generated on the surface oxygen vacancy over CuO (010) nanosheets. In situ near-ambient pressure X-ray photoelectron spectroscopy (in situ NAP-XPS) shows that the LSO possesses binding energy in between ordinary superoxide and the lattice oxygen. Theoretical calculations show that LSO adsorbs in a side-on configuration, with comparable electron (bader charge) on OI and OII (0.22 vs. 0.20 e-), and a lower O-O bond crystal orbital Hamilton population (COHP) than ordinary superoxides (12.45 vs. 15.37). The LSO works as a new adsorption site for C3H6 with lower C-H bond broken barrier, follow the ethylene pathway with lower activation energy for propene combustion. A considerably improved oxidation activity (T90% = 229 ℃ vs. 312 ℃) compare to CuO catalyst without LSO can be achieved. This study establishes new pathway for constructing new reactive oxygen species and provides high-performance alternative for oxidation reactions.
Monatomic oxygen ions (O–), superoxide (O2–), peroxide (O22–), singlet oxygen (1O2) and active lattice oxygen species are traditional reactive oxygen species (ROS) that boosting oxidation reactions in cell growing, life activities and industrial production. However, other ROS is rarely reported due to lack of evidence. Here, a new reactive chemisorbed oxygen species named lattice-superoxide species (LSO) was found, which exclusively generated on the surface oxygen vacancy over CuO (010) nanosheets. In situ near-ambient pressure X-ray photoelectron spectroscopy (in situ NAP-XPS) shows that the LSO possesses binding energy in between ordinary superoxide and the lattice oxygen. Theoretical calculations show that LSO adsorbs in a side-on configuration, with comparable electron (bader charge) on OI and OII (0.22 vs. 0.20 e-), and a lower O-O bond crystal orbital Hamilton population (COHP) than ordinary superoxides (12.45 vs. 15.37). The LSO works as a new adsorption site for C3H6 with lower C-H bond broken barrier, follow the ethylene pathway with lower activation energy for propene combustion. A considerably improved oxidation activity (T90% = 229 ℃ vs. 312 ℃) compare to CuO catalyst without LSO can be achieved. This study establishes new pathway for constructing new reactive oxygen species and provides high-performance alternative for oxidation reactions.
2026, 37(11): 112648
doi: 10.1016/j.cclet.2026.112648
摘要:
Antibiotic resistance genes (ARGs) have emerged as a critical global threat to public health and environmental sustainability. Carbonate radical anion (CO3•−), a potent reactive species, plays a significant role in both aquatic environments and biological systems, contributing to various oxidative biochemical processes. However, the effects of CO3•− on the transfer of ARGs in aquatic ecosystems and the human intestinal microbiome remain poorly understood. In this study, we investigated the conjugative transfer of the RP4 plasmid, harboring ARGs, in both water environments and the human intestinal microbiome under CO3•− exposure. Our findings revealed that low concentrations of CO3•− in water significantly enhanced the transfer of ARGs, while higher concentrations suppressed this process. The inhibitory effects at elevated CO3•− concentrations were linked to a reduction in the SOS response, decreased ATP synthesis through the electron transport chain and tricarboxylic acid cycle, and diminished intercellular contact. Machine learning analysis further confirmed that SOS response, cellular contact, and energy supply are pivotal factors in regulating ARGs transfer under CO3•− exposure. Additionally, low CO3•− levels markedly altered the human intestinal microbiome, influencing pathogenic bacteria, ARGs, and transport proteins, resulting in a 47.5% increase in the conjugative transfer of ARGs. This study elucidates the mechanisms by which CO3•− facilitates ARGs spread in aquatic and intestinal environments, offering novel insights into the potential health risks associated with ARG dissemination.
Antibiotic resistance genes (ARGs) have emerged as a critical global threat to public health and environmental sustainability. Carbonate radical anion (CO3•−), a potent reactive species, plays a significant role in both aquatic environments and biological systems, contributing to various oxidative biochemical processes. However, the effects of CO3•− on the transfer of ARGs in aquatic ecosystems and the human intestinal microbiome remain poorly understood. In this study, we investigated the conjugative transfer of the RP4 plasmid, harboring ARGs, in both water environments and the human intestinal microbiome under CO3•− exposure. Our findings revealed that low concentrations of CO3•− in water significantly enhanced the transfer of ARGs, while higher concentrations suppressed this process. The inhibitory effects at elevated CO3•− concentrations were linked to a reduction in the SOS response, decreased ATP synthesis through the electron transport chain and tricarboxylic acid cycle, and diminished intercellular contact. Machine learning analysis further confirmed that SOS response, cellular contact, and energy supply are pivotal factors in regulating ARGs transfer under CO3•− exposure. Additionally, low CO3•− levels markedly altered the human intestinal microbiome, influencing pathogenic bacteria, ARGs, and transport proteins, resulting in a 47.5% increase in the conjugative transfer of ARGs. This study elucidates the mechanisms by which CO3•− facilitates ARGs spread in aquatic and intestinal environments, offering novel insights into the potential health risks associated with ARG dissemination.
2026, 37(11): 112649
doi: 10.1016/j.cclet.2026.112649
摘要:
Urological cancers with high mortality are often diagnosed incidentally or through biopsies. Developing a universal, non-invasive molecular diagnostic tool for these cancers is both urgent and challenging. Herein, we engineer a two-dimensional incremental architecture involving multiple optimizations in both composition and structure, based on cobalt-iron oxides and noble metals. In brief, the first-dimensional increment was achieved by precisely tuning the density of sharp-tipped iron-nanorods on the cobalt-based architecture, resulting in a two-fold amplification of the MS signal. The second incremental step was achieved by incorporating the surface plasmon resonance effects of noble metals, which offer enhanced light absorption and photocurrent response, yielding about three-fold signal increase. Consequently, the engineered product enables the direct efficient extraction of serum metabolic profiles from healthy control and various urological cancers, including prostate cancer (PCa), bladder cancer (BCa), and renal cancer (RCa). In the end, the artificial intelligence (AI)-driven direct four-category diagnostic strategy, based on three key features, achieves an impressive average the area under the curve (AUC) value of 0.979 and an average accuracy of 90.9%. This work underscores the need for incremental engineering and the feasibility of non-invasive, high-performance diagnostic tools.
Urological cancers with high mortality are often diagnosed incidentally or through biopsies. Developing a universal, non-invasive molecular diagnostic tool for these cancers is both urgent and challenging. Herein, we engineer a two-dimensional incremental architecture involving multiple optimizations in both composition and structure, based on cobalt-iron oxides and noble metals. In brief, the first-dimensional increment was achieved by precisely tuning the density of sharp-tipped iron-nanorods on the cobalt-based architecture, resulting in a two-fold amplification of the MS signal. The second incremental step was achieved by incorporating the surface plasmon resonance effects of noble metals, which offer enhanced light absorption and photocurrent response, yielding about three-fold signal increase. Consequently, the engineered product enables the direct efficient extraction of serum metabolic profiles from healthy control and various urological cancers, including prostate cancer (PCa), bladder cancer (BCa), and renal cancer (RCa). In the end, the artificial intelligence (AI)-driven direct four-category diagnostic strategy, based on three key features, achieves an impressive average the area under the curve (AUC) value of 0.979 and an average accuracy of 90.9%. This work underscores the need for incremental engineering and the feasibility of non-invasive, high-performance diagnostic tools.
2026, 37(11): 112650
doi: 10.1016/j.cclet.2026.112650
摘要:
Patterns to generating complex and intensified oxidation pathways by activating heterojunctions remains unclear, and the deactivation mechanisms of antibiotic-resistant bacteria (ARB) under high oxidative stress also require further elucidation. Herein, a typical ternary heterojunction BiOCl/Bi5O7I/Bi2O3 completely eliminated ARB within 45 min with antimicrobial resistance inhibition above 80% and over 20% reduction in resistant gene dissemination. The synergistic action of multiple reactive oxygen species (ROS) generated from the ternary heterojunction demonstrated superiority efficacy over standalone oxidation pathway from binary heterojunctions. Particularly, the dual Z-scheme configuration illustrated the mechanism of complex ROS generation by energy band measurements and calculations. Extracellular ROS facilitated cell inactivation by cell membrane damage, intracellular ROS accumulation, and cellular repairing ceasing, ultimately establishing a lethal cycle of "ROS burst-repair failure" and metabolic malfunction. This work established a connection between the various oxidation pathways via photocatalysts configuration and the mechanisms responsible for ARB deactivation.
Patterns to generating complex and intensified oxidation pathways by activating heterojunctions remains unclear, and the deactivation mechanisms of antibiotic-resistant bacteria (ARB) under high oxidative stress also require further elucidation. Herein, a typical ternary heterojunction BiOCl/Bi5O7I/Bi2O3 completely eliminated ARB within 45 min with antimicrobial resistance inhibition above 80% and over 20% reduction in resistant gene dissemination. The synergistic action of multiple reactive oxygen species (ROS) generated from the ternary heterojunction demonstrated superiority efficacy over standalone oxidation pathway from binary heterojunctions. Particularly, the dual Z-scheme configuration illustrated the mechanism of complex ROS generation by energy band measurements and calculations. Extracellular ROS facilitated cell inactivation by cell membrane damage, intracellular ROS accumulation, and cellular repairing ceasing, ultimately establishing a lethal cycle of "ROS burst-repair failure" and metabolic malfunction. This work established a connection between the various oxidation pathways via photocatalysts configuration and the mechanisms responsible for ARB deactivation.
2026, 37(11): 112651
doi: 10.1016/j.cclet.2026.112651
摘要:
Nitridated zero-valent iron (N-ZVI) exhibits distinct advantages in the reductive pollutant removal, while its driven Fenton-like oxidation process for water purification remains largely unexplored. This study shows that mechanically N-ZVI enhanced the degradation kinetics of five typical pollutants by 3.5–9.4 times relative to pristine ZVI via H2O2 activation. Moreover, the N-ZVI/H2O2 system demonstrated considerable potential for practical water treatment applications owing to its substantially improved total organic carbon removal efficiency, enhanced cyclic stability, extended continuous operational lifespan and reduced acute toxicity of degradation products. While •OH, O2•-, and 1O2 were detected in the N-ZVI/H2O2 system, •OH was identified as the dominant reactive oxygen species (ROS) responsible for pollutant degradation. Mechanistic investigations reveal that the Fe-Nx coordination structures on N-ZVI facilitated electron transfer from the Fe(0) core to the surface, thereby accelerating both Fe(0) corrosion and surface Fe(Ⅲ)/Fe(Ⅱ) cycle for H2O2 activation, which enhances the generation of surface •OH via Fenton-like reaction. This study advances the fundamental understanding of ZVI-based advanced oxidation processes for water purification.
Nitridated zero-valent iron (N-ZVI) exhibits distinct advantages in the reductive pollutant removal, while its driven Fenton-like oxidation process for water purification remains largely unexplored. This study shows that mechanically N-ZVI enhanced the degradation kinetics of five typical pollutants by 3.5–9.4 times relative to pristine ZVI via H2O2 activation. Moreover, the N-ZVI/H2O2 system demonstrated considerable potential for practical water treatment applications owing to its substantially improved total organic carbon removal efficiency, enhanced cyclic stability, extended continuous operational lifespan and reduced acute toxicity of degradation products. While •OH, O2•-, and 1O2 were detected in the N-ZVI/H2O2 system, •OH was identified as the dominant reactive oxygen species (ROS) responsible for pollutant degradation. Mechanistic investigations reveal that the Fe-Nx coordination structures on N-ZVI facilitated electron transfer from the Fe(0) core to the surface, thereby accelerating both Fe(0) corrosion and surface Fe(Ⅲ)/Fe(Ⅱ) cycle for H2O2 activation, which enhances the generation of surface •OH via Fenton-like reaction. This study advances the fundamental understanding of ZVI-based advanced oxidation processes for water purification.
2026, 37(11): 112654
doi: 10.1016/j.cclet.2026.112654
摘要:
The high freezing point (Tf) of aqueous electrolytes, stemming from strong H-bonds of water, severely restricts the application of rechargeable zinc-metal batteries (RZMBs) in cold regions. Organic co-solvents can disrupt the H-bond network of water, reducing the Tf of aqueous electrolytes. However, limited by the polarity matching principle, most low-Tf organic molecules are excluded from the range of co-solvents due to their inability to dissociate zinc salts and immiscibility with water. Herein, we propose an anion-driven strategy for reconstructing the polarity of the electrolyte microenvironment. Relying on the “bridging” effect of the amphiphilic trifluoromethanesulfonate (OTf−), the weakly polar 2-methyltetrahydrofuran (2-MeTHF) is successfully induced into the strongly polar electrolytes, endowing the optimized electrolyte with a dramatically reduced Tf of −112.1 °C. Moreover, this strategy enables long-term stability in ZnZn cells and full cells operated at −30 °C, broadening the selection of antifreeze co-solvents and offering insights into cold-region energy storage devices.
The high freezing point (Tf) of aqueous electrolytes, stemming from strong H-bonds of water, severely restricts the application of rechargeable zinc-metal batteries (RZMBs) in cold regions. Organic co-solvents can disrupt the H-bond network of water, reducing the Tf of aqueous electrolytes. However, limited by the polarity matching principle, most low-Tf organic molecules are excluded from the range of co-solvents due to their inability to dissociate zinc salts and immiscibility with water. Herein, we propose an anion-driven strategy for reconstructing the polarity of the electrolyte microenvironment. Relying on the “bridging” effect of the amphiphilic trifluoromethanesulfonate (OTf−), the weakly polar 2-methyltetrahydrofuran (2-MeTHF) is successfully induced into the strongly polar electrolytes, endowing the optimized electrolyte with a dramatically reduced Tf of −112.1 °C. Moreover, this strategy enables long-term stability in ZnZn cells and full cells operated at −30 °C, broadening the selection of antifreeze co-solvents and offering insights into cold-region energy storage devices.
2026, 37(11): 112674
doi: 10.1016/j.cclet.2026.112674
摘要:
The passivation of nanoscale zero-valent iron (nZVI) limits its long-term effectiveness in groundwater remediation. While low-molecular-weight organic acids (LMWOAs) can mitigate this issue, how their molecular structures reactivate passivated nZVI (P-ZVI) and regulate its reactivity is not yet fully understood. This study systematically investigated the activation behaviors of eight different LMWOAs on various nZVI systems through material characterization, solution chemistry modeling, and density functional theory (DFT) calculations. Results demonstrate that multi-carboxyl LMWOAs effectively achieve high-efficiency reactivation by synergistically dissolving the passivation layer via proton-ligand interactions, combined with the Fe(Ⅱ)/Fe(Ⅲ) cycle driven by strong complexation stabilization and interfacial electron transfer. This effect remains significant in the presence of pollutants. In contrast, mono-carboxylic acids primarily rely on proton etching, resulting in limited efficiency. Ascorbic acid, with its strong electron transfer capability, shifts the reaction pathway from •OH radical-dominated degradation to ligand-to-metal charge transfer, highlighting the multiple activation effects of LMWOAs on P-ZVI. Finally, this study deciphered the three-level “molecular structure–fundamental property–macroscopic performance” structure-activity relationship through multiple linear regression, deciphering the intrinsic mechanisms of how LMWOAs regulate nZVI reactivity. This provides a theoretical basis for the targeted application of LMWOAs in groundwater remediation and the sustainable performance enhancement of nZVI.
The passivation of nanoscale zero-valent iron (nZVI) limits its long-term effectiveness in groundwater remediation. While low-molecular-weight organic acids (LMWOAs) can mitigate this issue, how their molecular structures reactivate passivated nZVI (P-ZVI) and regulate its reactivity is not yet fully understood. This study systematically investigated the activation behaviors of eight different LMWOAs on various nZVI systems through material characterization, solution chemistry modeling, and density functional theory (DFT) calculations. Results demonstrate that multi-carboxyl LMWOAs effectively achieve high-efficiency reactivation by synergistically dissolving the passivation layer via proton-ligand interactions, combined with the Fe(Ⅱ)/Fe(Ⅲ) cycle driven by strong complexation stabilization and interfacial electron transfer. This effect remains significant in the presence of pollutants. In contrast, mono-carboxylic acids primarily rely on proton etching, resulting in limited efficiency. Ascorbic acid, with its strong electron transfer capability, shifts the reaction pathway from •OH radical-dominated degradation to ligand-to-metal charge transfer, highlighting the multiple activation effects of LMWOAs on P-ZVI. Finally, this study deciphered the three-level “molecular structure–fundamental property–macroscopic performance” structure-activity relationship through multiple linear regression, deciphering the intrinsic mechanisms of how LMWOAs regulate nZVI reactivity. This provides a theoretical basis for the targeted application of LMWOAs in groundwater remediation and the sustainable performance enhancement of nZVI.
2026, 37(11): 112698
doi: 10.1016/j.cclet.2026.112698
摘要:
With limited organic components conversion and deteriorated product quality, melanoidins (MLD) by-products represent an immense obstacle for the recycling of waste activated sludge resources during thermal hydrolysis and pyrolysis. This study taps MLD with underappreciated catalytic activity, eliciting the pyrolysis reactivity of low temperature-thermal hydrolyzed sludge. Notably, the optimum catalytic activity of 2.5 mg/g dry sludge (DS) MLD at 500 °C was confirmed, while 5–10 mg/g DS MLD exhibited activity-limited levels. 2.5 mg/g DS MLD mediated the methane catalytic cracking and methane dry reforming pathways, promoting hydrogen yield increased by 108.47%, C2–C3 hydrocarbon (C2H4, C2H6, and C3H8) yields augmented by 15.87%–325.77%. The positive effect of MLD on gas production is weakened at a high temperature of 700 °C. The catalytic activity of MLD was demonstrated by the formation of aliphatic alkane and nitrogen-containing structures, in which active pyridinic-N specifically induced the transformation of protein-N and pyrrolic-N in biochar into unsaturated aromatic N in bio-oil, thereby evolving into small-molecule reducing gas. Critically, MLD triggered the synergistic activity of Si-, Al-, and Fe-containing minerals by modulating biochar's tighter aromatic porous structure and electron-accepting capacity, which accelerates the degradation of macromolecular proteins and polysaccharides by cleaving hydroxyl, carbonyl, ether bonds, and methylene, further improving the degradability of derived soluble organics. Finally, MLD facilitated the transformation of heavy components into light components, evolved into organic (aliphatic hydrocarbon, pyridine-N/pyrrole-N/nitrile-N) and aqueous compounds (aldehydes, acids, alcohols, and phenols), generating hydrogen cracked from protein and carbohydrate, and lipid and lignin contributed C2–C3 hydrocarbons via fragmentation and cyclization. This study opens a new avenue for finding the catalytic mechanism of MLD by-products and promoting the recovery of high-value energy during pyrolysis.
With limited organic components conversion and deteriorated product quality, melanoidins (MLD) by-products represent an immense obstacle for the recycling of waste activated sludge resources during thermal hydrolysis and pyrolysis. This study taps MLD with underappreciated catalytic activity, eliciting the pyrolysis reactivity of low temperature-thermal hydrolyzed sludge. Notably, the optimum catalytic activity of 2.5 mg/g dry sludge (DS) MLD at 500 °C was confirmed, while 5–10 mg/g DS MLD exhibited activity-limited levels. 2.5 mg/g DS MLD mediated the methane catalytic cracking and methane dry reforming pathways, promoting hydrogen yield increased by 108.47%, C2–C3 hydrocarbon (C2H4, C2H6, and C3H8) yields augmented by 15.87%–325.77%. The positive effect of MLD on gas production is weakened at a high temperature of 700 °C. The catalytic activity of MLD was demonstrated by the formation of aliphatic alkane and nitrogen-containing structures, in which active pyridinic-N specifically induced the transformation of protein-N and pyrrolic-N in biochar into unsaturated aromatic N in bio-oil, thereby evolving into small-molecule reducing gas. Critically, MLD triggered the synergistic activity of Si-, Al-, and Fe-containing minerals by modulating biochar's tighter aromatic porous structure and electron-accepting capacity, which accelerates the degradation of macromolecular proteins and polysaccharides by cleaving hydroxyl, carbonyl, ether bonds, and methylene, further improving the degradability of derived soluble organics. Finally, MLD facilitated the transformation of heavy components into light components, evolved into organic (aliphatic hydrocarbon, pyridine-N/pyrrole-N/nitrile-N) and aqueous compounds (aldehydes, acids, alcohols, and phenols), generating hydrogen cracked from protein and carbohydrate, and lipid and lignin contributed C2–C3 hydrocarbons via fragmentation and cyclization. This study opens a new avenue for finding the catalytic mechanism of MLD by-products and promoting the recovery of high-value energy during pyrolysis.
2026, 37(11): 112700
doi: 10.1016/j.cclet.2026.112700
摘要:
Electroreduction of CO2 to value-added products remained hindered by the lack of active sites within the catalytic materials and the hydrogen evolution side reaction. Inspired by the copper (Cu)-based bimetallic tandem catalytic mechanism, we designed an ultrafast electrodeposition technique and successfully obtained a series of CuAg and CuPd electrodes. The optimal CuAg-10 electrode demonstrated remarkable CO2 electrocatalytic performance in a H-cell, achieving the Faradaic efficiency of methane (FECH4) of 86.93% at −1.5 V (vs. RHE) in 0.1 mol/L KHCO3. Meanwhile, the optimal CuPd-10 electrode exhibited excellent Faradaic efficiency for ethylene (FEC2H4) of 67.10% at −1.4 V (vs. RHE) in 0.1 mol/L KI. Density functional theory (DFT) calculations revealed that Ag atoms facilitated the stabilization of the *CH2O intermediate in the CO2-to-CH4 pathway, whereas Pd atoms promoted the asymmetric coupling of *CO and *CHO intermediates in CO2-to-C2H4 process. This study furnished theoretical insights guiding the design of Cu-based bimetallic electrodes for the efficient electrochemical reduction of CO2 to C1 or C2 products.
Electroreduction of CO2 to value-added products remained hindered by the lack of active sites within the catalytic materials and the hydrogen evolution side reaction. Inspired by the copper (Cu)-based bimetallic tandem catalytic mechanism, we designed an ultrafast electrodeposition technique and successfully obtained a series of CuAg and CuPd electrodes. The optimal CuAg-10 electrode demonstrated remarkable CO2 electrocatalytic performance in a H-cell, achieving the Faradaic efficiency of methane (FECH4) of 86.93% at −1.5 V (vs. RHE) in 0.1 mol/L KHCO3. Meanwhile, the optimal CuPd-10 electrode exhibited excellent Faradaic efficiency for ethylene (FEC2H4) of 67.10% at −1.4 V (vs. RHE) in 0.1 mol/L KI. Density functional theory (DFT) calculations revealed that Ag atoms facilitated the stabilization of the *CH2O intermediate in the CO2-to-CH4 pathway, whereas Pd atoms promoted the asymmetric coupling of *CO and *CHO intermediates in CO2-to-C2H4 process. This study furnished theoretical insights guiding the design of Cu-based bimetallic electrodes for the efficient electrochemical reduction of CO2 to C1 or C2 products.
2026, 37(11): 112702
doi: 10.1016/j.cclet.2026.112702
摘要:
Organic photoelectrochemical transistor is now reshaping neuromorphic optoelectronics as it innovates in chemically synaptic transmission in aqueous media. Herein we report on the first OPECT biosensor capable of mimicking visual nociceptive system (VNS) based on synergizing neurotransmitter (glutamate, Glu) biosensing with chemically synaptic transmission, demonstrating hardware implementation of VNS with Glu-dependent neuromorphic functions and feedback actuation of artificial pupil. In contrast to previous studies, this work reveals that artificial nociceptive systems can be incorporated with endogenous biochemical mechanisms to bridge the gap between classic solid-state nociceptive electronics and biological systems, forging smoother interfaces between them.
Organic photoelectrochemical transistor is now reshaping neuromorphic optoelectronics as it innovates in chemically synaptic transmission in aqueous media. Herein we report on the first OPECT biosensor capable of mimicking visual nociceptive system (VNS) based on synergizing neurotransmitter (glutamate, Glu) biosensing with chemically synaptic transmission, demonstrating hardware implementation of VNS with Glu-dependent neuromorphic functions and feedback actuation of artificial pupil. In contrast to previous studies, this work reveals that artificial nociceptive systems can be incorporated with endogenous biochemical mechanisms to bridge the gap between classic solid-state nociceptive electronics and biological systems, forging smoother interfaces between them.
2026, 37(11): 112867
doi: 10.1016/j.cclet.2026.112867
摘要:
The sluggish redox kinetics and limited conversion efficiency of lithium polysulfides (LiPSs) constitute major bottlenecks in achieving optimized sulfur utilization and long-term cycling stability in lithium-sulfur (Li-S) batteries. This study addresses above challenge by constructing a highly efficient synergistic catalyst (Cu20−Mo154) via the hydrogen-bonding assembly of atomically precise copper nanoclusters (Cu20) and high-nuclear polyoxomolybdate clusters (Mo154) into a supramolecular composite. When deployed as a functional separator coating in Li-S batteries, the Cu20−Mo154 composite effectively captures LiPSs and catalytically promotes their conversion to insoluble lithium sulfides (Li2S/Li2S2) through synergistic effects. The supramolecular architecture crucially inhibits the dissolution of individual clusters in the electrolyte, preserving the catalyst's integrity and activity. Mechanism investigations reveal that Mo154 provides the primary catalytic sites, while the Cu20 clusters facilitate efficient electro-transport, collectively stabilizing the structure and enhancing the overall catalytic performance. As a result, the batteries equipped with the Cu20−Mo154 modified separator exhibit exceptional cycling stability, sustaining over 1000 cycles with remarkable capacity retention at a high rate of 10 C, which represents a performance metric rarely achieved in Li-S batteries. This work demonstrates a novel cluster-assembly strategy to attain exceptional synergistic catalytic performance for LiPSs conversion, offering a promising technical route for the development of high-energy-density and fast-charging Li-S batteries.
The sluggish redox kinetics and limited conversion efficiency of lithium polysulfides (LiPSs) constitute major bottlenecks in achieving optimized sulfur utilization and long-term cycling stability in lithium-sulfur (Li-S) batteries. This study addresses above challenge by constructing a highly efficient synergistic catalyst (Cu20−Mo154) via the hydrogen-bonding assembly of atomically precise copper nanoclusters (Cu20) and high-nuclear polyoxomolybdate clusters (Mo154) into a supramolecular composite. When deployed as a functional separator coating in Li-S batteries, the Cu20−Mo154 composite effectively captures LiPSs and catalytically promotes their conversion to insoluble lithium sulfides (Li2S/Li2S2) through synergistic effects. The supramolecular architecture crucially inhibits the dissolution of individual clusters in the electrolyte, preserving the catalyst's integrity and activity. Mechanism investigations reveal that Mo154 provides the primary catalytic sites, while the Cu20 clusters facilitate efficient electro-transport, collectively stabilizing the structure and enhancing the overall catalytic performance. As a result, the batteries equipped with the Cu20−Mo154 modified separator exhibit exceptional cycling stability, sustaining over 1000 cycles with remarkable capacity retention at a high rate of 10 C, which represents a performance metric rarely achieved in Li-S batteries. This work demonstrates a novel cluster-assembly strategy to attain exceptional synergistic catalytic performance for LiPSs conversion, offering a promising technical route for the development of high-energy-density and fast-charging Li-S batteries.
2026, 37(11): 112911
doi: 10.1016/j.cclet.2026.112911
摘要:
Despite the tremendous progress that immunotherapy has made from a marginal concept to a first-line treatment for cancer, the effective activation of innate immunity remains a challenge. The foremost strategy for effective immune activation focuses on harnessing the adaptive immune response. Currently, stimulator of interferon genes (STING) and Toll-like receptor 9 (TLR9) have emerged as particularly promising targets for bridging innate and adaptive immunity. However, single-agonist therapies targeting TLR9 and STING are inadequate for immune activation due to their limited function and susceptibility to the compensatory mechanisms of the tumor microenvironment (TME), and are accompanied by off-target effects, which limit their wide clinical application. Here, we demonstrate a dual-stimuli-responsive nanoagonist named ZIF@AC by integration of acid-degradable zeolitic imidazolate framework-8 (ZIF-8) and adenosine 5′-triphosphate (ATP)-activatable CpG oligonucleotides (ODNs) for TLR9 and STING co-activation. We found that ZIF@AC not only exhibited a favorable safety profile but also effectively reversed immunosuppression within the TME. This reversal was achieved by increasing the M1-type macrophage ratio, promoting dendritic cell (DC) maturation, and enhancing the secretion of pro-inflammatory factors. Consequently, these changes led to an increase in the infiltration of effector T cells and potentiated the antitumor immune response in vivo, and ultimately resulted in effective tumor suppression. This nanoagonist represents a pivotal advance toward optimally safe and potent cancer immunotherapies.
Despite the tremendous progress that immunotherapy has made from a marginal concept to a first-line treatment for cancer, the effective activation of innate immunity remains a challenge. The foremost strategy for effective immune activation focuses on harnessing the adaptive immune response. Currently, stimulator of interferon genes (STING) and Toll-like receptor 9 (TLR9) have emerged as particularly promising targets for bridging innate and adaptive immunity. However, single-agonist therapies targeting TLR9 and STING are inadequate for immune activation due to their limited function and susceptibility to the compensatory mechanisms of the tumor microenvironment (TME), and are accompanied by off-target effects, which limit their wide clinical application. Here, we demonstrate a dual-stimuli-responsive nanoagonist named ZIF@AC by integration of acid-degradable zeolitic imidazolate framework-8 (ZIF-8) and adenosine 5′-triphosphate (ATP)-activatable CpG oligonucleotides (ODNs) for TLR9 and STING co-activation. We found that ZIF@AC not only exhibited a favorable safety profile but also effectively reversed immunosuppression within the TME. This reversal was achieved by increasing the M1-type macrophage ratio, promoting dendritic cell (DC) maturation, and enhancing the secretion of pro-inflammatory factors. Consequently, these changes led to an increase in the infiltration of effector T cells and potentiated the antitumor immune response in vivo, and ultimately resulted in effective tumor suppression. This nanoagonist represents a pivotal advance toward optimally safe and potent cancer immunotherapies.
2026, 37(11): 113210
doi: 10.1016/j.cclet.2026.113210
摘要:
The coke-resistance property of industrial catalysts for dry reforming of methane (DRM) reaction is still a challenge. Herein, the multifunctional nanocatalysts of binary Ni-Ce active sites embedded on 3D ordered macro-mesoporous ZrO2 (NiCeOx/3DOMM-ZrO2) were successfully fabricated by the carboxy-modified colloidal crystal templating (CMCCT)-impregnation method. 3DOMM structure can improve the mass transfer and diffusion of reactants (CH4 and CO2) in the pore channel, which can increase the contact efficiency between reactants and binary Ni-Ce active sites. The Ni-sites in binary Ni-Ce active components can activate the C—H bond dissociation of CH4, while the oxygen vacancy of CeOx-component can trap the oxygen atom in CO2 reactant. NiCeOx/3DOMM-ZrO2 catalyst exhibits the highest catalytic activity and stability during DRM reaction in comparison with single Ni- or Ce-based catalysts, and its coke-resistance property is dependent on 3DOMM nanostructure of ZrO2, i.e., its conversion rates of CH4 and CO2 remain above 91% at 750 °C for 50 h, and its apparent activation energy (Ea) decreases to 70.2 kJ/mol. Based on the results of the in situ DRIFTS and DFT, the catalytic mechanism of NiCeOx/3DOMM-ZrO2 catalyst for DRM was proposed: the synergy effect of binary Ni-Ce active sites can promote the rate key steps of C—H and C—O bond dissociation, and the formed coke in the macropores during DRM can accessibly react with the surface oxygen on the binary Ni-Ce active sites to CO, which effectively inhibits the formation of carbon deposits. It provides an effective strategy to develop high-efficient coke-resistance catalysts during DRM reaction.
The coke-resistance property of industrial catalysts for dry reforming of methane (DRM) reaction is still a challenge. Herein, the multifunctional nanocatalysts of binary Ni-Ce active sites embedded on 3D ordered macro-mesoporous ZrO2 (NiCeOx/3DOMM-ZrO2) were successfully fabricated by the carboxy-modified colloidal crystal templating (CMCCT)-impregnation method. 3DOMM structure can improve the mass transfer and diffusion of reactants (CH4 and CO2) in the pore channel, which can increase the contact efficiency between reactants and binary Ni-Ce active sites. The Ni-sites in binary Ni-Ce active components can activate the C—H bond dissociation of CH4, while the oxygen vacancy of CeOx-component can trap the oxygen atom in CO2 reactant. NiCeOx/3DOMM-ZrO2 catalyst exhibits the highest catalytic activity and stability during DRM reaction in comparison with single Ni- or Ce-based catalysts, and its coke-resistance property is dependent on 3DOMM nanostructure of ZrO2, i.e., its conversion rates of CH4 and CO2 remain above 91% at 750 °C for 50 h, and its apparent activation energy (Ea) decreases to 70.2 kJ/mol. Based on the results of the in situ DRIFTS and DFT, the catalytic mechanism of NiCeOx/3DOMM-ZrO2 catalyst for DRM was proposed: the synergy effect of binary Ni-Ce active sites can promote the rate key steps of C—H and C—O bond dissociation, and the formed coke in the macropores during DRM can accessibly react with the surface oxygen on the binary Ni-Ce active sites to CO, which effectively inhibits the formation of carbon deposits. It provides an effective strategy to develop high-efficient coke-resistance catalysts during DRM reaction.
2026, 37(11): 111696
doi: 10.1016/j.cclet.2025.111696
摘要:
Rechargeable lithium (Li) batteries have garnered significant academic research interest and achieved remarkable commercial success. Inactive lithium is one of the important reasons for the capacity degradation. To extend the battery lifespan, reactivation of inactive lithium is highly expected, and becomes one of the current research hotspots. With ongoing advancements, new insights and reactivation strategies have been developed for addressing this issue. This review presents a comprehensive summary of current methods for recovering inactive lithium, mainly including pulse-induced techniques, electric-field relaxation, and redox-mediated strategies. Beyond evaluating their potential for industrial applications, this review also provides a foundation for future research on the recovery of other inactive materials in next-generation alkali metal-based batteries.
Rechargeable lithium (Li) batteries have garnered significant academic research interest and achieved remarkable commercial success. Inactive lithium is one of the important reasons for the capacity degradation. To extend the battery lifespan, reactivation of inactive lithium is highly expected, and becomes one of the current research hotspots. With ongoing advancements, new insights and reactivation strategies have been developed for addressing this issue. This review presents a comprehensive summary of current methods for recovering inactive lithium, mainly including pulse-induced techniques, electric-field relaxation, and redox-mediated strategies. Beyond evaluating their potential for industrial applications, this review also provides a foundation for future research on the recovery of other inactive materials in next-generation alkali metal-based batteries.
2026, 37(11): 111725
doi: 10.1016/j.cclet.2025.111725
摘要:
The hydrogen evolution reaction (HER) is pivotal in the realm of sustainable energy generation, driving widespread efforts to develop highly efficient electrocatalysts. Among the numerous materials under investigation, ruthenium (Ru)-based metal chalcogenides have emerged as highly promising candidates, owing to their distinctive electronic configurations and robust catalytic properties. This review explores the key factors that enhance the HER performance of Ru-based metal chalcogenides, including the influence of defects, heterostructure engineering, doping strategies, and phase transitions. We also highlight recent progress, identify critical challenges, and discuss future opportunities for leveraging these materials in HER catalysis, which are crucial for advancing sustainable hydrogen production. By integrating the latest research findings and outlining key challenges and prospective research pathways, this review endeavors to furnish valuable insights into the design and optimization of Ru-based metal chalcogenide electrocatalysts to augment HER performance.
The hydrogen evolution reaction (HER) is pivotal in the realm of sustainable energy generation, driving widespread efforts to develop highly efficient electrocatalysts. Among the numerous materials under investigation, ruthenium (Ru)-based metal chalcogenides have emerged as highly promising candidates, owing to their distinctive electronic configurations and robust catalytic properties. This review explores the key factors that enhance the HER performance of Ru-based metal chalcogenides, including the influence of defects, heterostructure engineering, doping strategies, and phase transitions. We also highlight recent progress, identify critical challenges, and discuss future opportunities for leveraging these materials in HER catalysis, which are crucial for advancing sustainable hydrogen production. By integrating the latest research findings and outlining key challenges and prospective research pathways, this review endeavors to furnish valuable insights into the design and optimization of Ru-based metal chalcogenide electrocatalysts to augment HER performance.
2026, 37(11): 111808
doi: 10.1016/j.cclet.2025.111808
摘要:
Molecular assembly plays a significant role in the fields of nanoscience, bionanomaterials, and electronic devices, among others. The weak interaction is the primary driving force behind molecular assembly, and its dynamic, reversible, and synergistic properties provide the possibility for constructing functionalized and complex materials. It is generally considered a central goal of molecular assembly to elucidate the synergistic effects therein and to enhance control over weak interactions. In view of this, scanning probe microscopy stands out as a powerful tool for the study of weak interactions. Its atomic spatial resolution and applicability to a wide range of materials and scenarios facilitate the in-situ characterization and precise manipulation. However, despite great progress having been made in material preparation, it remains a challenge in the study of structure-property relationships, stability enhancement, and scale-up applications for weak-bonded materials. There has been some literature summarizing the design strategies for conventional catalysts and lubricants, but the collation on the application of weak-bonded materials in the two fields is limited. Given the considerable progress in the novel design of weak-bonded catalysts and lubrication strategies, this review here summarises the strategies for designing and modulating weak interactions through scanning probe microscopy, as well as advanced progress in weak-bonded materials applied to catalysis and friction scenarios. Finally, this review presents current challenges and future opportunities for weak-bonded materials through the multiphysics modulation and scale-up preparation, as well as technological innovations in scanning probe microscopy.
Molecular assembly plays a significant role in the fields of nanoscience, bionanomaterials, and electronic devices, among others. The weak interaction is the primary driving force behind molecular assembly, and its dynamic, reversible, and synergistic properties provide the possibility for constructing functionalized and complex materials. It is generally considered a central goal of molecular assembly to elucidate the synergistic effects therein and to enhance control over weak interactions. In view of this, scanning probe microscopy stands out as a powerful tool for the study of weak interactions. Its atomic spatial resolution and applicability to a wide range of materials and scenarios facilitate the in-situ characterization and precise manipulation. However, despite great progress having been made in material preparation, it remains a challenge in the study of structure-property relationships, stability enhancement, and scale-up applications for weak-bonded materials. There has been some literature summarizing the design strategies for conventional catalysts and lubricants, but the collation on the application of weak-bonded materials in the two fields is limited. Given the considerable progress in the novel design of weak-bonded catalysts and lubrication strategies, this review here summarises the strategies for designing and modulating weak interactions through scanning probe microscopy, as well as advanced progress in weak-bonded materials applied to catalysis and friction scenarios. Finally, this review presents current challenges and future opportunities for weak-bonded materials through the multiphysics modulation and scale-up preparation, as well as technological innovations in scanning probe microscopy.
2026, 37(11): 111828
doi: 10.1016/j.cclet.2025.111828
摘要:
Pharmaceutical cocrystals, multi-component crystalline systems, enhance the solubility, stability, and bioavailability of active pharmaceutical ingredients (APIs) through tailored intermolecular interactions. Traditional screening methods, such as solvent evaporation and mechanochemical approaches, have long been used to identify and prepare cocrystals but are often time-consuming and resource-intensive. Machine learning (ML) has emerged as a transformative tool, leveraging molecular descriptors and large datasets to streamline cocrystal development. This review traces the evolution from conventional screening techniques to ML-facilitated approaches, systematically exploring ML applications in cocrystal discovery, preparation, and physicochemical property evaluation. It examines key methodologies, challenges like data limitations, and opportunities for integrating ML with experimental methods to advance cocrystal design.
Pharmaceutical cocrystals, multi-component crystalline systems, enhance the solubility, stability, and bioavailability of active pharmaceutical ingredients (APIs) through tailored intermolecular interactions. Traditional screening methods, such as solvent evaporation and mechanochemical approaches, have long been used to identify and prepare cocrystals but are often time-consuming and resource-intensive. Machine learning (ML) has emerged as a transformative tool, leveraging molecular descriptors and large datasets to streamline cocrystal development. This review traces the evolution from conventional screening techniques to ML-facilitated approaches, systematically exploring ML applications in cocrystal discovery, preparation, and physicochemical property evaluation. It examines key methodologies, challenges like data limitations, and opportunities for integrating ML with experimental methods to advance cocrystal design.
2026, 37(11): 111830
doi: 10.1016/j.cclet.2025.111830
摘要:
Solar light-driven photocatalytic energy conversion over robust semiconductor materials represents a promising route. Among which, photocatalytic water splitting with the aid of methanol has drawn significant attention. However, depth exploration of methanol conversion for C2+ chemicals in this process remains limited. Basic knowledge about the potential transformation products of methanol, the selective activation mechanisms for each chemical bond within methanol, and the application of methanol activation for the creation of high-value C2+ compounds, etc., is still inadequate, and worthy of thorough investigation. So, in this review, we highlighted recent advances and trials on the photocatalytic conversion of methanol for C2+ compounds, including ethylene glycol, ethanol, 1,1-dimethoxymethane and N-methylation compounds. Particular emphasis is placed on an in-depth exploration of the reaction intermediates, mechanisms of each unique catalytic system and the intricate relationship between structure and activity. Finally, current challenges and future opportunities in photocatalytic methanol reforming research are also presented.
Solar light-driven photocatalytic energy conversion over robust semiconductor materials represents a promising route. Among which, photocatalytic water splitting with the aid of methanol has drawn significant attention. However, depth exploration of methanol conversion for C2+ chemicals in this process remains limited. Basic knowledge about the potential transformation products of methanol, the selective activation mechanisms for each chemical bond within methanol, and the application of methanol activation for the creation of high-value C2+ compounds, etc., is still inadequate, and worthy of thorough investigation. So, in this review, we highlighted recent advances and trials on the photocatalytic conversion of methanol for C2+ compounds, including ethylene glycol, ethanol, 1,1-dimethoxymethane and N-methylation compounds. Particular emphasis is placed on an in-depth exploration of the reaction intermediates, mechanisms of each unique catalytic system and the intricate relationship between structure and activity. Finally, current challenges and future opportunities in photocatalytic methanol reforming research are also presented.
2026, 37(11): 111890
doi: 10.1016/j.cclet.2025.111890
摘要:
Oxygen evolution reaction (OER) is a pivotal key-reaction in energy technologies, facing kinetic challenges due to multi-step electron transfer. Spinel oxides (AB2O4) emerge as promising OER catalysts owing to their dual-cation coordination, enabling electronic structure tailoring. However, their intrinsic configuration favors the adsorbate evolution mechanism (AEM) with a theoretical limitation due to scaling relationships between *OOH and *O intermediates. To overcome the limitation, implementation of the lattice oxygen-mediated mechanism (LOM) becomes imperative. Compared with the AEM, the LOM enables direct O—O coupling to circumvent the inherent scaling relationship limitations, thus arousing widespread attention from researchers. Herein, we firstly systematically investigate the activation prerequisites for transformation from the AEM to the LOM in spinel oxides. Subsequently, rational design strategies to tailor LOM-dominant spinel oxide catalysts are comprehensively summarized. Finally, critical challenges in commercialization are subsequently addressed, outlining a roadmap for advancing these high-performance materials toward industrial energy conversion applications.
Oxygen evolution reaction (OER) is a pivotal key-reaction in energy technologies, facing kinetic challenges due to multi-step electron transfer. Spinel oxides (AB2O4) emerge as promising OER catalysts owing to their dual-cation coordination, enabling electronic structure tailoring. However, their intrinsic configuration favors the adsorbate evolution mechanism (AEM) with a theoretical limitation due to scaling relationships between *OOH and *O intermediates. To overcome the limitation, implementation of the lattice oxygen-mediated mechanism (LOM) becomes imperative. Compared with the AEM, the LOM enables direct O—O coupling to circumvent the inherent scaling relationship limitations, thus arousing widespread attention from researchers. Herein, we firstly systematically investigate the activation prerequisites for transformation from the AEM to the LOM in spinel oxides. Subsequently, rational design strategies to tailor LOM-dominant spinel oxide catalysts are comprehensively summarized. Finally, critical challenges in commercialization are subsequently addressed, outlining a roadmap for advancing these high-performance materials toward industrial energy conversion applications.
2026, 37(11): 112205
doi: 10.1016/j.cclet.2025.112205
摘要:
Neural damage remains a serious clinical challenge. While electrical stimulation (ES) is a potent strategy to promote repair, traditional implantable electrodes face issues of invasiveness, rigidity, and finite longevity. In recent years, electroactive biomaterials have emerged as a revolutionary platform to overcome these hurdles by seamlessly integrating bio-mimetic conductivity with tunable biological and mechanical properties. This review outlines the types, advantages and disadvantages, preparation methods, and progress of conductive biomaterials commonly employed in nerve repair, and focus on pioneering non-invasive self-generating systems based on piezoelectric, magnetoelectric, and biofuel cell technologies. In addition, based on the relevant electrophysiological properties of electroactive materials, we synthesize a unified framework for their mechanisms of action, elucidating how electroactive interfaces orchestrate regeneration through tripartite regulation: Cellular behavior, signaling pathways, and microenvironment regulation. Finally, we discuss ongoing challenges and future perspectives, particularly regarding biodegradation, clinical translation, and the integration of smart feedback systems. This review aims to serve as a foundational reference for guiding the rational design of next-generation electroactive therapies for neural repair.
Neural damage remains a serious clinical challenge. While electrical stimulation (ES) is a potent strategy to promote repair, traditional implantable electrodes face issues of invasiveness, rigidity, and finite longevity. In recent years, electroactive biomaterials have emerged as a revolutionary platform to overcome these hurdles by seamlessly integrating bio-mimetic conductivity with tunable biological and mechanical properties. This review outlines the types, advantages and disadvantages, preparation methods, and progress of conductive biomaterials commonly employed in nerve repair, and focus on pioneering non-invasive self-generating systems based on piezoelectric, magnetoelectric, and biofuel cell technologies. In addition, based on the relevant electrophysiological properties of electroactive materials, we synthesize a unified framework for their mechanisms of action, elucidating how electroactive interfaces orchestrate regeneration through tripartite regulation: Cellular behavior, signaling pathways, and microenvironment regulation. Finally, we discuss ongoing challenges and future perspectives, particularly regarding biodegradation, clinical translation, and the integration of smart feedback systems. This review aims to serve as a foundational reference for guiding the rational design of next-generation electroactive therapies for neural repair.
2026, 37(11): 112212
doi: 10.1016/j.cclet.2025.112212
摘要:
Molybdenum (Mo) was initially discovered in 1778, which was recognized as an essential element. Over the past few decades, Mo-based materials emerged as popular member in the field of industrial manufacture such as electrodes and catalysts due to their appealing strength and corrosion resistance. In recent years, with the vigorous development of nanotechnology, Mo-based nanomaterials have gradually drawn extensive attention in biomedical field due to their physicochemical versatility including excellent biocompatibility, high catalytic activity, redox chemistry and strong photothermal conversion efficiency (PCE), which greatly promoted diversified applications of Mo-based nanomaterials in biomedical area. Up to date, scientific workers have exhibited thousands of bio-applications of Mo-based nanomaterials, but a systematical overview in this filed is still rare. In this review, the specific applications outline of Mo-contained nanomaterials in biomedical field are summarized via six aspects including reactive oxygen species (ROS) scavenging, photodynamic therapy (PDT) and photothermal therapy (PTT), antibacterial performance, drug delivery, bioimaging, and biosensors. And the unique properties of Mo-based nanomaterial momentous to its biomedical applications are accordingly expounded. Finally, the relevant existing challenges and future objectives of Mo-contained nanomaterials applied in biomedicine are thoroughly discussed.
Molybdenum (Mo) was initially discovered in 1778, which was recognized as an essential element. Over the past few decades, Mo-based materials emerged as popular member in the field of industrial manufacture such as electrodes and catalysts due to their appealing strength and corrosion resistance. In recent years, with the vigorous development of nanotechnology, Mo-based nanomaterials have gradually drawn extensive attention in biomedical field due to their physicochemical versatility including excellent biocompatibility, high catalytic activity, redox chemistry and strong photothermal conversion efficiency (PCE), which greatly promoted diversified applications of Mo-based nanomaterials in biomedical area. Up to date, scientific workers have exhibited thousands of bio-applications of Mo-based nanomaterials, but a systematical overview in this filed is still rare. In this review, the specific applications outline of Mo-contained nanomaterials in biomedical field are summarized via six aspects including reactive oxygen species (ROS) scavenging, photodynamic therapy (PDT) and photothermal therapy (PTT), antibacterial performance, drug delivery, bioimaging, and biosensors. And the unique properties of Mo-based nanomaterial momentous to its biomedical applications are accordingly expounded. Finally, the relevant existing challenges and future objectives of Mo-contained nanomaterials applied in biomedicine are thoroughly discussed.
2026, 37(11): 112219
doi: 10.1016/j.cclet.2025.112219
摘要:
The pathogenesis of inflammatory bowel disease (IBD) is complex and multifactorial, involving intestinal microbiota imbalance, immune system abnormalities, genetic predispositions, and other factors. Therefore, the attainment of a complete cure for IBD through a single therapeutic modality remains a formidable challenge. In recent years, probiotics have received considerable attention in the treatment of IBD due to their properties of regulating intestinal microecology, immune activation, anti-infection and metabolic regulation. In order to further improve the safety, efficacy and clinical translation prospects of probiotics in the treatment of IBD, the engineering modification of probiotics has become the current research focus. In this review, we systematically summarize the probiotic species with promising clinical applications. Subsequently, the primary methods of engineering modifications (physical, chemical, genetic, etc.) are described and the role of these methods and their mechanisms in the treatment of IBD using engineered probiotics are discussed. Finally, we explore in depth the current challenges in the field and proposes potential future solutions. This review aims to present a comprehensive perspective on the development of a new generation of engineered probiotics and their application in IBD therapy.
The pathogenesis of inflammatory bowel disease (IBD) is complex and multifactorial, involving intestinal microbiota imbalance, immune system abnormalities, genetic predispositions, and other factors. Therefore, the attainment of a complete cure for IBD through a single therapeutic modality remains a formidable challenge. In recent years, probiotics have received considerable attention in the treatment of IBD due to their properties of regulating intestinal microecology, immune activation, anti-infection and metabolic regulation. In order to further improve the safety, efficacy and clinical translation prospects of probiotics in the treatment of IBD, the engineering modification of probiotics has become the current research focus. In this review, we systematically summarize the probiotic species with promising clinical applications. Subsequently, the primary methods of engineering modifications (physical, chemical, genetic, etc.) are described and the role of these methods and their mechanisms in the treatment of IBD using engineered probiotics are discussed. Finally, we explore in depth the current challenges in the field and proposes potential future solutions. This review aims to present a comprehensive perspective on the development of a new generation of engineered probiotics and their application in IBD therapy.
2026, 37(11): 112225
doi: 10.1016/j.cclet.2025.112225
摘要:
Nitric oxide (NO) is a crucial signaling molecule with vital roles in both physiological and pathological processes. However, NO with gas characteristics, such as rapid diffusion, short half-life, low targeting efficiency, and dose-dependent efficacy, has greatly limited its clinical application. To address these challenges, nanotechnology-enabled NO delivery systems have emerged as a pivotal strategy for achieving spatiotemporally precise and on-demand release of NO This review summarizes recent advances in NO delivery systems, analyzes the properties of various NO nanocarriers, and further systematically dissects intelligent NO nanoplatforms that respond to endogenous triggers (e.g., glutathione, pH, reactive oxygen species, glucose) or exogenous stimuli (e.g., near-infrared light, ultrasound, X-rays, microwave) for precision therapeutics. Furthermore, we discuss the remaining challenges in NO delivery systems, including delivery efficiency, long-term stability, real-time NO quantification, and efficacy assessment, and propose forward-looking solutions. Finally, we provide an outlook on future directions, with the expectation of developing the next generation of NO delivery systems to achieve new breakthroughs.
Nitric oxide (NO) is a crucial signaling molecule with vital roles in both physiological and pathological processes. However, NO with gas characteristics, such as rapid diffusion, short half-life, low targeting efficiency, and dose-dependent efficacy, has greatly limited its clinical application. To address these challenges, nanotechnology-enabled NO delivery systems have emerged as a pivotal strategy for achieving spatiotemporally precise and on-demand release of NO This review summarizes recent advances in NO delivery systems, analyzes the properties of various NO nanocarriers, and further systematically dissects intelligent NO nanoplatforms that respond to endogenous triggers (e.g., glutathione, pH, reactive oxygen species, glucose) or exogenous stimuli (e.g., near-infrared light, ultrasound, X-rays, microwave) for precision therapeutics. Furthermore, we discuss the remaining challenges in NO delivery systems, including delivery efficiency, long-term stability, real-time NO quantification, and efficacy assessment, and propose forward-looking solutions. Finally, we provide an outlook on future directions, with the expectation of developing the next generation of NO delivery systems to achieve new breakthroughs.
2026, 37(11): 112244
doi: 10.1016/j.cclet.2025.112244
摘要:
Tumor vaccines have emerged as a potentially effective strategy for inducing a strong antitumor immune response and lasting immune memory. In lymph nodes (LNs), tumor-associated antigens (TAAs) or tumor-specific antigens (TSAs, neoantigens) are presented to antigen-presenting cells (APCs), particularly dendritic cells (DCs), to stimulate T-cell responses against tumor cells. By leveraging patient-specific mutations, personalized neoantigen-based vaccines offer a more targeted approach, enhancing efficacy while minimizing off-target effects. Vaccines based on peptides are a better source of neoantigens due to their affordability, safety, and ease of modification. However, problems such as low accumulation in LNs, inefficient antigen presentation, and low immunogenicity have hampered their clinical progression. To solve these problems, vaccine development is increasingly utilizing nanotechnologies. By preventing antigen degradation, ensuring controlled release, and facilitating targeted delivery to LNs and APCs, nanoparticles (NPs) significantly enhance vaccine immunogenicity. Their adaptable and versatile physicochemical characteristics enable improved APCs uptake and co-delivery of adjuvants, boosting the immune response. The role of NP-based platforms in the development of peptide neoantigen vaccines is examined in this review. Important tactics for maximizing their efficacy, such as the design of peptide neoantigens with multiple epitopes, the choice of optimal nanomaterials, combinatorial approaches, and multiadjuvant approaches, are highlighted. Furthermore, a review of the present obstacles to the development of nanovaccines, including biocompatibility, stability, and scalability, is provided, along with a roadmap for potential future clinical use.
Tumor vaccines have emerged as a potentially effective strategy for inducing a strong antitumor immune response and lasting immune memory. In lymph nodes (LNs), tumor-associated antigens (TAAs) or tumor-specific antigens (TSAs, neoantigens) are presented to antigen-presenting cells (APCs), particularly dendritic cells (DCs), to stimulate T-cell responses against tumor cells. By leveraging patient-specific mutations, personalized neoantigen-based vaccines offer a more targeted approach, enhancing efficacy while minimizing off-target effects. Vaccines based on peptides are a better source of neoantigens due to their affordability, safety, and ease of modification. However, problems such as low accumulation in LNs, inefficient antigen presentation, and low immunogenicity have hampered their clinical progression. To solve these problems, vaccine development is increasingly utilizing nanotechnologies. By preventing antigen degradation, ensuring controlled release, and facilitating targeted delivery to LNs and APCs, nanoparticles (NPs) significantly enhance vaccine immunogenicity. Their adaptable and versatile physicochemical characteristics enable improved APCs uptake and co-delivery of adjuvants, boosting the immune response. The role of NP-based platforms in the development of peptide neoantigen vaccines is examined in this review. Important tactics for maximizing their efficacy, such as the design of peptide neoantigens with multiple epitopes, the choice of optimal nanomaterials, combinatorial approaches, and multiadjuvant approaches, are highlighted. Furthermore, a review of the present obstacles to the development of nanovaccines, including biocompatibility, stability, and scalability, is provided, along with a roadmap for potential future clinical use.
2026, 37(11): 112263
doi: 10.1016/j.cclet.2025.112263
摘要:
Histone deacetylases (HDACs), recognized as promising anticancer targets, maintain cellular homeostasis by catalyzing histone deacetylation and play crucial roles in regulating gene expression. Although seven HDAC inhibitors (HDACis) have been approved by the U.S. Food and Drug Administration (FDA) and/or National Medical Products Administration (NMPA), they still face clinical challenges such as insufficient selectivity, poor metabolic stability, and dose-limiting toxicities in epigenetic therapy. Hydrazide-based HDACis exhibit high potency, metabolic stability and resistance to glucuronidation, attributed to their bidentate chelation of the catalytic Zn2+ through the carbonyl oxygen and hydrazide nitrogen, demonstrating therapeutic potential in diseases such as cancer, inflammation, and neurodegenerative diseases. In addition, the alkyl chain length at the hydrazide terminus could be tailored to adapt to the substrate pockets of different HDAC isoforms, modulating inhibitory selectivity. The Cap group further serves as a versatile attachment point for diverse pharmacophores, enabling the rational design of dual-target inhibitors or proteolysis-targeting chimera (PROTAC) degraders. Currently, numerous hydrazide-based HDACis, including single-target HDACis, dual-target HDACis, and PROTAC degraders, have been reported and demonstrate promising therapeutic potential in cancer, immune or inflammation, though candidates remain that have not yet progressed to clinical trials. Therefore, we here summarized the rational design, molecular docking studies, inhibitory activities, and therapeutic potential of hydrazide-based HDACis, encompassing single-target, dual-target, and PROTAC-based agents, for various diseases, providing insights for developing novel HDACi-based therapeutics.
Histone deacetylases (HDACs), recognized as promising anticancer targets, maintain cellular homeostasis by catalyzing histone deacetylation and play crucial roles in regulating gene expression. Although seven HDAC inhibitors (HDACis) have been approved by the U.S. Food and Drug Administration (FDA) and/or National Medical Products Administration (NMPA), they still face clinical challenges such as insufficient selectivity, poor metabolic stability, and dose-limiting toxicities in epigenetic therapy. Hydrazide-based HDACis exhibit high potency, metabolic stability and resistance to glucuronidation, attributed to their bidentate chelation of the catalytic Zn2+ through the carbonyl oxygen and hydrazide nitrogen, demonstrating therapeutic potential in diseases such as cancer, inflammation, and neurodegenerative diseases. In addition, the alkyl chain length at the hydrazide terminus could be tailored to adapt to the substrate pockets of different HDAC isoforms, modulating inhibitory selectivity. The Cap group further serves as a versatile attachment point for diverse pharmacophores, enabling the rational design of dual-target inhibitors or proteolysis-targeting chimera (PROTAC) degraders. Currently, numerous hydrazide-based HDACis, including single-target HDACis, dual-target HDACis, and PROTAC degraders, have been reported and demonstrate promising therapeutic potential in cancer, immune or inflammation, though candidates remain that have not yet progressed to clinical trials. Therefore, we here summarized the rational design, molecular docking studies, inhibitory activities, and therapeutic potential of hydrazide-based HDACis, encompassing single-target, dual-target, and PROTAC-based agents, for various diseases, providing insights for developing novel HDACi-based therapeutics.
2026, 37(11): 112266
doi: 10.1016/j.cclet.2025.112266
摘要:
Small-molecule self-assembled nanodrugs (SMSNDs), as an emerging therapeutic strategy in nanomedicine, have shown great potential for biomedical applications. SMSNDs are created through the spontaneous assembly of small molecules via non-covalent interactions, which provides structural flexibility, responsiveness to stimuli, and a high capacity for drug loading. These features improve drug solubility, facilitate targeted delivery, reduce systemic toxicity, and enhance therapeutic accuracy. They hold significant promise across various biomedical fields, including cancer, cardiovascular and cerebrovascular diseases, neurodegenerative and metabolic diseases management, and antimicrobial therapy. This review first explores the assembly mechanisms, drug release strategies, and structural patterns of SMSNDs. Additionally, it thoroughly presents the research progress of SMSNDs in various biological applications, including diagnostics and therapeutics. Finally, the review addresses the challenges faced by SMSNDs. It discusses future directions for their development, aiming to provide a solid theoretical foundation and practical guidance for the clinical translation of these nanodrugs.
Small-molecule self-assembled nanodrugs (SMSNDs), as an emerging therapeutic strategy in nanomedicine, have shown great potential for biomedical applications. SMSNDs are created through the spontaneous assembly of small molecules via non-covalent interactions, which provides structural flexibility, responsiveness to stimuli, and a high capacity for drug loading. These features improve drug solubility, facilitate targeted delivery, reduce systemic toxicity, and enhance therapeutic accuracy. They hold significant promise across various biomedical fields, including cancer, cardiovascular and cerebrovascular diseases, neurodegenerative and metabolic diseases management, and antimicrobial therapy. This review first explores the assembly mechanisms, drug release strategies, and structural patterns of SMSNDs. Additionally, it thoroughly presents the research progress of SMSNDs in various biological applications, including diagnostics and therapeutics. Finally, the review addresses the challenges faced by SMSNDs. It discusses future directions for their development, aiming to provide a solid theoretical foundation and practical guidance for the clinical translation of these nanodrugs.
2026, 37(11): 112563
doi: 10.1016/j.cclet.2026.112563
摘要:
Polylactic acid (PLA), a bio-based biodegradable plastic, is often misperceived as environmentally harmless, obscuring critical environmental risk gaps. Previous PLA reviews focus primarily on performance optimization or isolated degradation pathways, while discussions on environmental risks and targeted modification strategies are scattered, creating a gap between risk identification and mitigation design. To address this gap, this review systematically integrates PLA’s lifecycle environmental risks and sustainable modification strategies via a bibliometric framework. Drawing on 1810 Web of Science Core Collection publications (2004–2025), we employed CiteSpace and VOSviewer for knowledge mapping, integrated with degradation and modification mechanism analysis. Three core findings emerged. First, incomplete PLA degradation (driven by photoaging, hydrolysis and thermal oxidation) produces persistent microplastics (MPs) and nanoplastics (NPs), which accumulate in diverse ecosystems, act as pollutant vectors and induce ecological toxicity. Second, sustainable modification has evolved into three targeted pathways: chemical, physical and biological modification. Third, machine learning (ML) is a key integrated tool, linking PLA’s lifecycle environmental risk assessment with sustainable modification optimization to enhance research systematicity and efficiency. This review bridges PLA degradation mechanism understanding with ecological risks, links sustainable modification strategies to targeted risk mitigation, and provides a theoretical foundation for low-risk PLA material development.
Polylactic acid (PLA), a bio-based biodegradable plastic, is often misperceived as environmentally harmless, obscuring critical environmental risk gaps. Previous PLA reviews focus primarily on performance optimization or isolated degradation pathways, while discussions on environmental risks and targeted modification strategies are scattered, creating a gap between risk identification and mitigation design. To address this gap, this review systematically integrates PLA’s lifecycle environmental risks and sustainable modification strategies via a bibliometric framework. Drawing on 1810 Web of Science Core Collection publications (2004–2025), we employed CiteSpace and VOSviewer for knowledge mapping, integrated with degradation and modification mechanism analysis. Three core findings emerged. First, incomplete PLA degradation (driven by photoaging, hydrolysis and thermal oxidation) produces persistent microplastics (MPs) and nanoplastics (NPs), which accumulate in diverse ecosystems, act as pollutant vectors and induce ecological toxicity. Second, sustainable modification has evolved into three targeted pathways: chemical, physical and biological modification. Third, machine learning (ML) is a key integrated tool, linking PLA’s lifecycle environmental risk assessment with sustainable modification optimization to enhance research systematicity and efficiency. This review bridges PLA degradation mechanism understanding with ecological risks, links sustainable modification strategies to targeted risk mitigation, and provides a theoretical foundation for low-risk PLA material development.
Recent advance of heavy metal complexes treatment: Conventional, oxidative, and reductive strategies
2026, 37(11): 112569
doi: 10.1016/j.cclet.2026.112569
摘要:
The widespread use of complexing agents (e.g., ethylenediaminetetraacetic acid, citrate) in industrial processes has resulted in the predominance of highly stable heavy metal complexes (HMCs) in wastewater. Conventional treatment technologies are rendered ineffective due to steric hindrance and strong coordination stability inherent to these complexes. To address this emerging challenge, diverse strategies for treating HMCs-contaminated wastewater have been developed. While advanced oxidation processes (AOPs) dominate current research, the adaptive optimization of conventional methods and the untapped potential of efficient reduction technologies remain significantly understudied. This review systematically integrates three technological frameworks, enhanced conventional processes, AOPs-based decomplexation, and high-efficiency reductive recovery, thereby bridging a critical knowledge gap. We comprehensively evaluate recent advances in HMCs treatment technologies, discussing their mechanisms, performance-enhancing strategies, and key limitations. Furthermore, we identify fundamental barriers to industrial translation and propose potential solutions, aiming to provide actionable guidance for managing complex heavy metal pollution.
The widespread use of complexing agents (e.g., ethylenediaminetetraacetic acid, citrate) in industrial processes has resulted in the predominance of highly stable heavy metal complexes (HMCs) in wastewater. Conventional treatment technologies are rendered ineffective due to steric hindrance and strong coordination stability inherent to these complexes. To address this emerging challenge, diverse strategies for treating HMCs-contaminated wastewater have been developed. While advanced oxidation processes (AOPs) dominate current research, the adaptive optimization of conventional methods and the untapped potential of efficient reduction technologies remain significantly understudied. This review systematically integrates three technological frameworks, enhanced conventional processes, AOPs-based decomplexation, and high-efficiency reductive recovery, thereby bridging a critical knowledge gap. We comprehensively evaluate recent advances in HMCs treatment technologies, discussing their mechanisms, performance-enhancing strategies, and key limitations. Furthermore, we identify fundamental barriers to industrial translation and propose potential solutions, aiming to provide actionable guidance for managing complex heavy metal pollution.
2026, 37(11): 112630
doi: 10.1016/j.cclet.2026.112630
摘要:
Rare earth elements (REEs) play an irreplaceable role in advanced fields such as electronics, optics and nuclear energy, giving rise to unprecedented global demand. but their similar atomic structures, ionic radii and intimate paragenesis in minerals make their purification and separation extremely challenging. Traditional REE separation materials, including organic extractants and inorganic adsorbents, are limited by poor selectivity, insufficient stability and difficulty in recycling, failing to meet the demand for efficient and green separation. Covalent organic frameworks (COFs), as a class of crystalline porous materials connected by covalent bonds, have attracted extensive attention due to their precisely designable pore structures, high-density tunable active sites, excellent chemical stability and good structural modifiability. In recent years, great progress has been made in the research of COFs for REE separation, and their unique structural advantages enable them to realize selective capture and separation of REEs through multiple synergistic mechanisms. This review outlines the design principles and synthetic strategies for chemically stable COFs and highlights recent advances in their application for efficient REE recovery. Key performance indicators such as adsorption capacity, recovery efficiency, and selectivity as well as critical influencing factors are systematically summarized. The mechanisms underlying COFs mediated REE separation are also critically examined. Finally, current challenges and future research directions are discussed, offering insights to guide the rational design, development, and industrial deployment of COFs for sustainable REE separation and recovery.
Rare earth elements (REEs) play an irreplaceable role in advanced fields such as electronics, optics and nuclear energy, giving rise to unprecedented global demand. but their similar atomic structures, ionic radii and intimate paragenesis in minerals make their purification and separation extremely challenging. Traditional REE separation materials, including organic extractants and inorganic adsorbents, are limited by poor selectivity, insufficient stability and difficulty in recycling, failing to meet the demand for efficient and green separation. Covalent organic frameworks (COFs), as a class of crystalline porous materials connected by covalent bonds, have attracted extensive attention due to their precisely designable pore structures, high-density tunable active sites, excellent chemical stability and good structural modifiability. In recent years, great progress has been made in the research of COFs for REE separation, and their unique structural advantages enable them to realize selective capture and separation of REEs through multiple synergistic mechanisms. This review outlines the design principles and synthetic strategies for chemically stable COFs and highlights recent advances in their application for efficient REE recovery. Key performance indicators such as adsorption capacity, recovery efficiency, and selectivity as well as critical influencing factors are systematically summarized. The mechanisms underlying COFs mediated REE separation are also critically examined. Finally, current challenges and future research directions are discussed, offering insights to guide the rational design, development, and industrial deployment of COFs for sustainable REE separation and recovery.
2026, 37(11): 112724
doi: 10.1016/j.cclet.2026.112724
摘要:
C–S bonds are ubiquitous in a wide range of natural products and pharmaceutical molecules, and exert indispensable regulatory functions in biological systems; accordingly, the efficient construction of C–S bonds is of profound research significance. In recent years, with the rapid advancement of photocatalytic technology, photocatalytic reactions have emerged as a promising strategy featuring milder reaction conditions, greener synthetic processes, and superior catalytic activity. As a result, the photocatalytic construction of C–S bonds mediated by organic or inorganic mediators has garnered growing attention from the chemistry research community. In light of the above research background, this review categorizes carbon atoms according to their hybridization states, systematically summarizes the recent research advances in the photocatalytic synthesis of C–S(Ⅵ) bonds, and further presents an outlook on the future development trends of this field.
C–S bonds are ubiquitous in a wide range of natural products and pharmaceutical molecules, and exert indispensable regulatory functions in biological systems; accordingly, the efficient construction of C–S bonds is of profound research significance. In recent years, with the rapid advancement of photocatalytic technology, photocatalytic reactions have emerged as a promising strategy featuring milder reaction conditions, greener synthetic processes, and superior catalytic activity. As a result, the photocatalytic construction of C–S bonds mediated by organic or inorganic mediators has garnered growing attention from the chemistry research community. In light of the above research background, this review categorizes carbon atoms according to their hybridization states, systematically summarizes the recent research advances in the photocatalytic synthesis of C–S(Ⅵ) bonds, and further presents an outlook on the future development trends of this field.
2026, 37(11): 112727
doi: 10.1016/j.cclet.2026.112727
摘要:
Electron donor-acceptor (EDA) complex photochemistry has emerged as a powerful strategy for expanding the potential of visible light-driven radical synthetic chemistry. This photochemical strategy intrinsically differs from photoredox catalysis since it does not rely on the use of exogenous photocatalysts. The majority of reported EDA complex-driven photosynthesis rely on the use of stoichiometric electron-donor and acceptor substrates, leading to a limited efficiency and scope of the photochemical processes. An important advance is to implement the EDA complex photochemistry within a catalytic regime, where either the donor or acceptor is employed catalytically. This approach provided opportunities to expand the efficiency and versatility of the EDA complex photochemistry, while implementing asymmetric radical processes by using a chiral catalyst. The aim of this review is to highlight the recent advances in catalytic EDA complex photochemistry. The review is organized into two primary categories: reactions mediated by catalytic electron donors and those by catalytic electron acceptors. We focus on the discussion of different EDA catalysis models and reaction mechanisms. Finally, the review concludes with an analysis of prevailing challenges and perspectives on future research directions.
Electron donor-acceptor (EDA) complex photochemistry has emerged as a powerful strategy for expanding the potential of visible light-driven radical synthetic chemistry. This photochemical strategy intrinsically differs from photoredox catalysis since it does not rely on the use of exogenous photocatalysts. The majority of reported EDA complex-driven photosynthesis rely on the use of stoichiometric electron-donor and acceptor substrates, leading to a limited efficiency and scope of the photochemical processes. An important advance is to implement the EDA complex photochemistry within a catalytic regime, where either the donor or acceptor is employed catalytically. This approach provided opportunities to expand the efficiency and versatility of the EDA complex photochemistry, while implementing asymmetric radical processes by using a chiral catalyst. The aim of this review is to highlight the recent advances in catalytic EDA complex photochemistry. The review is organized into two primary categories: reactions mediated by catalytic electron donors and those by catalytic electron acceptors. We focus on the discussion of different EDA catalysis models and reaction mechanisms. Finally, the review concludes with an analysis of prevailing challenges and perspectives on future research directions.
2026, 37(11): 112854
doi: 10.1016/j.cclet.2026.112854
摘要:
Persulfate-based advanced oxidation processes (PS-AOPs) have gained extensive attention for removing refractory organic contaminants. In PS-AOPs, mineralization and polymerization pathways exhibit significant contrasts in removal mechanisms and product characteristics. This review established a comparative framework from three dimensions: catalyst performance, reactor design, and economic-environmental benefits. First, based on total organic carbon (TOC) removal efficiency and activity decay, catalyst activity and stability in both pathways were systematically compared and analyzed, with deactivation mechanisms and control strategies identified. Second, the adaptability and operational modes of existing reactors were evaluated, and design concepts including electrochemical regeneration and backwashing were proposed for polymerization applications. Finally, the economic cost and environmental benefits of two pathways were compared based on continuous-flow data. Results indicate that polymerization pathways achieve a TOC removal rate three times higher than mineralization, with single-atom and metal catalysts performing outstandingly, but the stability requires urgent improvement. In continuous operation, the dosage of oxidant was a key factor affecting the treatment cost and environmental benefit. Mineralization pathways are more economical for treating low-concentration wastewater, whereas polymerization pathways work better overall cost-effectiveness for high-concentration wastewater. This review examines the differences between mineralization and polymerization from a global perspective, providing a theoretical basis and practical guidance for adaptive regulation of PS-AOPs pathways.
Persulfate-based advanced oxidation processes (PS-AOPs) have gained extensive attention for removing refractory organic contaminants. In PS-AOPs, mineralization and polymerization pathways exhibit significant contrasts in removal mechanisms and product characteristics. This review established a comparative framework from three dimensions: catalyst performance, reactor design, and economic-environmental benefits. First, based on total organic carbon (TOC) removal efficiency and activity decay, catalyst activity and stability in both pathways were systematically compared and analyzed, with deactivation mechanisms and control strategies identified. Second, the adaptability and operational modes of existing reactors were evaluated, and design concepts including electrochemical regeneration and backwashing were proposed for polymerization applications. Finally, the economic cost and environmental benefits of two pathways were compared based on continuous-flow data. Results indicate that polymerization pathways achieve a TOC removal rate three times higher than mineralization, with single-atom and metal catalysts performing outstandingly, but the stability requires urgent improvement. In continuous operation, the dosage of oxidant was a key factor affecting the treatment cost and environmental benefit. Mineralization pathways are more economical for treating low-concentration wastewater, whereas polymerization pathways work better overall cost-effectiveness for high-concentration wastewater. This review examines the differences between mineralization and polymerization from a global perspective, providing a theoretical basis and practical guidance for adaptive regulation of PS-AOPs pathways.
2026, 37(11): 113086
doi: 10.1016/j.cclet.2026.113086
摘要:
Covalent organic frameworks (COFs) have emerged as highly promising candidates for solar-to-chemical energy conversion. However, the macroscopic catalytic performance of COF-based photocatalysts remains severely constrained by rapid charge-carrier recombination, highlighting the need for high-performance S-scheme heterojunctions. Despite the rapid growth in this field, a fundamental challenge persists: The lack of a systematic understanding of diverse interfacial interactions ranging from weak van der Waals forces and π-π stacking to robust chemical bonds, which precisely modulate electronic coupling, band bending, and charge migration dynamics. To address this knowledge gap, this review provides a comprehensive perspective by classifying COF-based S-scheme heterojunctions according to the nature of their interfacial interactions and systematically elucidating their decisive roles in charge separation and internal electric field formation. We further summarize the latest advances in synthetic strategies, advanced characterization techniques for probing interface engineering, and diverse photocatalytic applications, including H2 evolution, H2O2 photosynthesis, CO2 reduction, and organic pollutant degradation. Ultimately, this work offers a critical analysis of current limitations and future prospects, establishing a robust theoretical framework and design principles to guide the rational synthesis and interface engineering of highly efficient, stable COF-based photocatalytic systems.
Covalent organic frameworks (COFs) have emerged as highly promising candidates for solar-to-chemical energy conversion. However, the macroscopic catalytic performance of COF-based photocatalysts remains severely constrained by rapid charge-carrier recombination, highlighting the need for high-performance S-scheme heterojunctions. Despite the rapid growth in this field, a fundamental challenge persists: The lack of a systematic understanding of diverse interfacial interactions ranging from weak van der Waals forces and π-π stacking to robust chemical bonds, which precisely modulate electronic coupling, band bending, and charge migration dynamics. To address this knowledge gap, this review provides a comprehensive perspective by classifying COF-based S-scheme heterojunctions according to the nature of their interfacial interactions and systematically elucidating their decisive roles in charge separation and internal electric field formation. We further summarize the latest advances in synthetic strategies, advanced characterization techniques for probing interface engineering, and diverse photocatalytic applications, including H2 evolution, H2O2 photosynthesis, CO2 reduction, and organic pollutant degradation. Ultimately, this work offers a critical analysis of current limitations and future prospects, establishing a robust theoretical framework and design principles to guide the rational synthesis and interface engineering of highly efficient, stable COF-based photocatalytic systems.
2026, 37(11): 112622
doi: 10.1016/j.cclet.2026.112622
摘要:
Fluorescence imaging technologies have revolutionized biomedical research and clinical practice, with fluorescence-guided surgery (FGS) and fluorescence super-resolution microscopy (FL-SRM) representing two landmark applications that have transformed cancer treatment and cellular biology, respectively. Despite these pivotal advances, both modalities share a fundamental limitation: Their dependence on external excitation light, which inevitably leads to insufficient tissue penetration depth, endogenous autofluorescence background interference, and excitation-induced phototoxicity, critical barriers to in vivo deep-tissue imaging in FGS and long-term dynamic observation in FL-SRM. Bioluminescence (BL), which generates photons through luciferase-catalyzed substrate oxidation without any external excitation, offers a compelling alternative that fundamentally circumvents these limitations. In this perspective, we systematically review the state-of-the-art advances and inherent bottlenecks of the two fluorescence imaging frontiers, highlight the disruptive potential of BL imaging to redefine next-generation image-guided surgery and super-resolution microscopy, and critically analyze the key remaining challenges for its clinical translation.
Fluorescence imaging technologies have revolutionized biomedical research and clinical practice, with fluorescence-guided surgery (FGS) and fluorescence super-resolution microscopy (FL-SRM) representing two landmark applications that have transformed cancer treatment and cellular biology, respectively. Despite these pivotal advances, both modalities share a fundamental limitation: Their dependence on external excitation light, which inevitably leads to insufficient tissue penetration depth, endogenous autofluorescence background interference, and excitation-induced phototoxicity, critical barriers to in vivo deep-tissue imaging in FGS and long-term dynamic observation in FL-SRM. Bioluminescence (BL), which generates photons through luciferase-catalyzed substrate oxidation without any external excitation, offers a compelling alternative that fundamentally circumvents these limitations. In this perspective, we systematically review the state-of-the-art advances and inherent bottlenecks of the two fluorescence imaging frontiers, highlight the disruptive potential of BL imaging to redefine next-generation image-guided surgery and super-resolution microscopy, and critically analyze the key remaining challenges for its clinical translation.
2026, 37(11): 112808
doi: 10.1016/j.cclet.2026.112808
摘要:
2026, 37(11): 112994
doi: 10.1016/j.cclet.2026.112994
摘要:
2026, 37(11): 113041
doi: 10.1016/j.cclet.2026.113041
摘要:
2026, 37(5): 110827
doi: 10.1016/j.cclet.2025.110827
摘要:
Oxidation-coupled clusters of [E9]4– are rarely synthesised, and the investigation of their reactivity is profoundly hindered by their high charge and limited yield. In this study, we successfully synthesized two Nb-containing clusters [(Ge9–Ge9)(NbCp2)2]4– (1a) and [(Ge9=Ge9=Ge9)NbCp2]5– (2a), by reacting [Ge9–Ge9]6– and [Ge9=Ge9=Ge9]6– with NbCp4. Theoretical calculations indicate that the formation of 1a and 2a from dimer and trimer is thermodynamically favorable. Furthermore, a Au-containing cluster incorporating the dimeric [Sn9–Sn9]6– cluster, [Au(Sn9–Sn9)]5– (3a), was successfully synthesized, despite the inability to independently synthesize [Sn9–Sn9]6–. A systematic bonding analysis was conducted on these newly synthesized clusters and their parent structures to investigate their bonding patterns.
Oxidation-coupled clusters of [E9]4– are rarely synthesised, and the investigation of their reactivity is profoundly hindered by their high charge and limited yield. In this study, we successfully synthesized two Nb-containing clusters [(Ge9–Ge9)(NbCp2)2]4– (1a) and [(Ge9=Ge9=Ge9)NbCp2]5– (2a), by reacting [Ge9–Ge9]6– and [Ge9=Ge9=Ge9]6– with NbCp4. Theoretical calculations indicate that the formation of 1a and 2a from dimer and trimer is thermodynamically favorable. Furthermore, a Au-containing cluster incorporating the dimeric [Sn9–Sn9]6– cluster, [Au(Sn9–Sn9)]5– (3a), was successfully synthesized, despite the inability to independently synthesize [Sn9–Sn9]6–. A systematic bonding analysis was conducted on these newly synthesized clusters and their parent structures to investigate their bonding patterns.
2026, 37(5): 110829
doi: 10.1016/j.cclet.2025.110829
摘要:
The rise of antibiotic-resistant bacteria and the formation of biofilms are significant challenges in surgical practice, posing a serious threat to public health due to postoperative wound infections. A promising approach to tackle this issue is the combination of photothermal therapy (PTT) and chemodynamic therapy (CDT), which has shown remarkable effectiveness in treating both cancer and wound infections. In our study, we developed an innovative artificial nanoplatform called Ni-2@F127 by encapsulating Ni-2 in a biocompatible Pluronic. When exposed to 880 nm laser irradiation, Ni-2@F127 exhibited exceptional photothermal performance, achieving a photothermal conversion efficiency of 60.4%, along with significant photocatalytic capabilities. This platform activates a Fenton-like reaction that catalyzes hydrogen peroxide (H₂O₂), producing toxic hydroxyl radicals (•OH) effectively. The synergistic effects of hyperthermia and •OH not only destroy tumor cells but also demonstrate powerful antimicrobial activity, significantly inhibiting the growth of Escherichia coli and Staphylococcus aureus (S. aureus) in vitro under near-infrared (NIR) irradiation. Importantly, in animal models, Ni-2@F127 effectively eliminates S. aureus from deep tissues in cases of subcutaneous abscesses and knife injuries, significantly accelerating abscess resolution and promoting wound healing. The compelling evidence suggests that Ni-based metal complexes could serve as transformative antibacterial agents in phototherapy, unlocking vast potential for their application in wound healing and the treatment of bacterial infections.
The rise of antibiotic-resistant bacteria and the formation of biofilms are significant challenges in surgical practice, posing a serious threat to public health due to postoperative wound infections. A promising approach to tackle this issue is the combination of photothermal therapy (PTT) and chemodynamic therapy (CDT), which has shown remarkable effectiveness in treating both cancer and wound infections. In our study, we developed an innovative artificial nanoplatform called Ni-2@F127 by encapsulating Ni-2 in a biocompatible Pluronic. When exposed to 880 nm laser irradiation, Ni-2@F127 exhibited exceptional photothermal performance, achieving a photothermal conversion efficiency of 60.4%, along with significant photocatalytic capabilities. This platform activates a Fenton-like reaction that catalyzes hydrogen peroxide (H₂O₂), producing toxic hydroxyl radicals (•OH) effectively. The synergistic effects of hyperthermia and •OH not only destroy tumor cells but also demonstrate powerful antimicrobial activity, significantly inhibiting the growth of Escherichia coli and Staphylococcus aureus (S. aureus) in vitro under near-infrared (NIR) irradiation. Importantly, in animal models, Ni-2@F127 effectively eliminates S. aureus from deep tissues in cases of subcutaneous abscesses and knife injuries, significantly accelerating abscess resolution and promoting wound healing. The compelling evidence suggests that Ni-based metal complexes could serve as transformative antibacterial agents in phototherapy, unlocking vast potential for their application in wound healing and the treatment of bacterial infections.
2026, 37(5): 110851
doi: 10.1016/j.cclet.2025.110851
摘要:
Solid-state lithium (Li) metal batteries have attracted significant attention due to their high energy density and improved safety performance. However, sluggish Li-ion transport and rapid anion migration in solid-state electrolytes often result in heterogeneous Li-ion flux distribution and thus Li dendrite growth. Herein, we developed a highly conductive composite solid electrolyte with an elevated Li-ion transference number through incorporating Gd-doped CeO2 (GDC) nanofillers with abundant surface oxygen defects into poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrices. The defect concentrations were effectively controlled by regulating the Gd doping ratio in CeO2. As a result, the highest oxygen concentration of 12.2% is achieved for the GDC with 10% Gd doping (GDC-10). The GDC-10 electrolyte demonstrated a high Li-ion transference number of 0.59 and an improved ionic conductivity of 0.40 mS/cm at room temperature, attributed to anion immobilization and enhanced Li-salt dissociation. This was due to the strong interactions between positively charged oxygen vacancies and anions, which effectively reduces surface concentration polarization and homogenizes Li-ion flux. Therefore, LiLi symmetric cells exhibited exceptional cycling stability of 1500 h without noticeable Li dendrite growth at 1 mA/cm2 and 1 mAh/cm2. Furthermore, LiLiFePO4 full cell also stably cycles for 500 cycles with a capacity retention of 90.44% at 1 C. This work provides new insights into the design of composite solid electrolytes through the defect regulation of fillers.
Solid-state lithium (Li) metal batteries have attracted significant attention due to their high energy density and improved safety performance. However, sluggish Li-ion transport and rapid anion migration in solid-state electrolytes often result in heterogeneous Li-ion flux distribution and thus Li dendrite growth. Herein, we developed a highly conductive composite solid electrolyte with an elevated Li-ion transference number through incorporating Gd-doped CeO2 (GDC) nanofillers with abundant surface oxygen defects into poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrices. The defect concentrations were effectively controlled by regulating the Gd doping ratio in CeO2. As a result, the highest oxygen concentration of 12.2% is achieved for the GDC with 10% Gd doping (GDC-10). The GDC-10 electrolyte demonstrated a high Li-ion transference number of 0.59 and an improved ionic conductivity of 0.40 mS/cm at room temperature, attributed to anion immobilization and enhanced Li-salt dissociation. This was due to the strong interactions between positively charged oxygen vacancies and anions, which effectively reduces surface concentration polarization and homogenizes Li-ion flux. Therefore, LiLi symmetric cells exhibited exceptional cycling stability of 1500 h without noticeable Li dendrite growth at 1 mA/cm2 and 1 mAh/cm2. Furthermore, LiLiFePO4 full cell also stably cycles for 500 cycles with a capacity retention of 90.44% at 1 C. This work provides new insights into the design of composite solid electrolytes through the defect regulation of fillers.
2026, 37(5): 110852
doi: 10.1016/j.cclet.2025.110852
摘要:
High-entropy alloys (HEAs) have emerged as promising electrocatalysts due to their unique compositional complexity and tunable electronic structures. However, achieving rapid and efficient synthesis of HEA nanoparticles (NPs) with high electrocatalytic activity and understanding their structural and electronic characteristics remains challenging. Here, we report the synthesis of FeCoNiCuCr HEA NPs via an ultrafast carbon thermal shock (CTS) method. Local structural investigations combining synchrotron pair distribution function (PDF) and X-ray absorption fine structure (XAFS) reveal that incorporating Cr introduces local tetragonal distortions, resulting in residual strain that enhances catalytic performance. This local distortion could be attributed to atomic-scale elemental segregation between Cr and Cu, further stabilizing the structure and improving activity. These synergistic effects, combined with uniform carbon-loaded NPs morphology achieved by the CTS process, enable superior OER performance. This study highlights the role of structural and electronic modulation in HEA catalysts, offering valuable insights for the design of next-generation electrocatalysts.
High-entropy alloys (HEAs) have emerged as promising electrocatalysts due to their unique compositional complexity and tunable electronic structures. However, achieving rapid and efficient synthesis of HEA nanoparticles (NPs) with high electrocatalytic activity and understanding their structural and electronic characteristics remains challenging. Here, we report the synthesis of FeCoNiCuCr HEA NPs via an ultrafast carbon thermal shock (CTS) method. Local structural investigations combining synchrotron pair distribution function (PDF) and X-ray absorption fine structure (XAFS) reveal that incorporating Cr introduces local tetragonal distortions, resulting in residual strain that enhances catalytic performance. This local distortion could be attributed to atomic-scale elemental segregation between Cr and Cu, further stabilizing the structure and improving activity. These synergistic effects, combined with uniform carbon-loaded NPs morphology achieved by the CTS process, enable superior OER performance. This study highlights the role of structural and electronic modulation in HEA catalysts, offering valuable insights for the design of next-generation electrocatalysts.
2026, 37(5): 110858
doi: 10.1016/j.cclet.2025.110858
摘要:
Zero-dimensional (0D) hybrid copper halides have attracted significant attention owing to their unique photophysical properties and remarkable structural diversity. In this work, two 0D self-assemblies compounds of copper iodide dimers were synthesized, namely, (4-MBTP)2(Cu2I4)0.5I (1) and (4-MBTP)(Cu2I4)0.5 (2) (4-MBTP = (4-methylbenzyl)triphenylphosphonium chloride). Compound 1 exhibits blue emission centered at 474 nm, while compound 2 shows yellow emission centered at 559 nm at room temperature. The results combined with crystal structure, spectroscopy analysis, characterization, and theoretical studies reveal that the blue light of compound 1 stems from multiple defect states caused by the presence of I vacancies, while the yellow emission of compound 2 is attributed to through-space charge-transfer (TSCT) and cluster-centered (CC) excited state. Strikingly, the crystal structure can transform from compound 1 into compound 2 with luminescence color change from blue to yellow through treating with methanol. This work provides a structural transformation strategy of hybrid copper halides, as well as realizes the regulation of light emission from defect states to non-defect states, making them feasible candidates for information encryption and optical data storage.
Zero-dimensional (0D) hybrid copper halides have attracted significant attention owing to their unique photophysical properties and remarkable structural diversity. In this work, two 0D self-assemblies compounds of copper iodide dimers were synthesized, namely, (4-MBTP)2(Cu2I4)0.5I (1) and (4-MBTP)(Cu2I4)0.5 (2) (4-MBTP = (4-methylbenzyl)triphenylphosphonium chloride). Compound 1 exhibits blue emission centered at 474 nm, while compound 2 shows yellow emission centered at 559 nm at room temperature. The results combined with crystal structure, spectroscopy analysis, characterization, and theoretical studies reveal that the blue light of compound 1 stems from multiple defect states caused by the presence of I vacancies, while the yellow emission of compound 2 is attributed to through-space charge-transfer (TSCT) and cluster-centered (CC) excited state. Strikingly, the crystal structure can transform from compound 1 into compound 2 with luminescence color change from blue to yellow through treating with methanol. This work provides a structural transformation strategy of hybrid copper halides, as well as realizes the regulation of light emission from defect states to non-defect states, making them feasible candidates for information encryption and optical data storage.
2026, 37(5): 110859
doi: 10.1016/j.cclet.2025.110859
摘要:
Rechargeable aqueous zinc-ion batteries (RAZIBs) have been considered as viable alternatives to lithium-ion batteries in electrochemical energy storage due to their intrinsic safety, low cost, and environmental friendliness. However, the further practical application of RAZIBs is restricted by the growth of zinc dendrites and severe side reactions during cycling. To address these issues, we proposed a new lysine (Lys) additive to the ZnSO4 electrolyte, the hydrolyzed Lys+ cations can be adsorbed on the Zn anode's surface to modify the interface between the zinc electrode and the ZnSO4 electrolyte. This modification helps weaken the "tip effect" and guides the uniform zinc deposition, effectively alleviating the formation of zinc dendrites. Additionally, introducing alkaline Lys can regulate the pH value of the ZnSO4 electrolyte and suppress side reactions, thereby decreasing the production of by-products. Consequently, the Zn||Zn symmetric cell with Lys additive stably cycled for 4500 h at 1 mA/cm2, and the Zn||NH4V4O10 full cell with Lys additive exhibited improved performance (with a capacity retention of 72% after 1000 cycles) at 5 A/g. This strategy provides valuable insights for developing stable Zn anode toward high-performance RAZIBs.
Rechargeable aqueous zinc-ion batteries (RAZIBs) have been considered as viable alternatives to lithium-ion batteries in electrochemical energy storage due to their intrinsic safety, low cost, and environmental friendliness. However, the further practical application of RAZIBs is restricted by the growth of zinc dendrites and severe side reactions during cycling. To address these issues, we proposed a new lysine (Lys) additive to the ZnSO4 electrolyte, the hydrolyzed Lys+ cations can be adsorbed on the Zn anode's surface to modify the interface between the zinc electrode and the ZnSO4 electrolyte. This modification helps weaken the "tip effect" and guides the uniform zinc deposition, effectively alleviating the formation of zinc dendrites. Additionally, introducing alkaline Lys can regulate the pH value of the ZnSO4 electrolyte and suppress side reactions, thereby decreasing the production of by-products. Consequently, the Zn||Zn symmetric cell with Lys additive stably cycled for 4500 h at 1 mA/cm2, and the Zn||NH4V4O10 full cell with Lys additive exhibited improved performance (with a capacity retention of 72% after 1000 cycles) at 5 A/g. This strategy provides valuable insights for developing stable Zn anode toward high-performance RAZIBs.
2026, 37(5): 110862
doi: 10.1016/j.cclet.2025.110862
摘要:
The dissolution of lithium polysulfides (Li2Sx, 4 ≤ x ≤ 8, LiPSs) intermediates and slow redox kinetics are the main factors leading to the rapid capacity degradation of lithium-sulfur batteries (LSBs), significantly limits the practical development of LSBs. To overcome challenges, NbN embedded in nitrogen-doped carbon nanotubes (NbN@NCNT) composites were synthesized here as sulfur hosts by taking advantage of the superior electrical conductivity and excellent catalytic activity of the metal nitride NbN. The incorporation of NbN enhanced the polysulfides conversion efficiency and suppressed the shuttling effect, thereby enhancing cycling stability in LSBs. XPS results revealed the formation of Li2S, indicating that Li2S8 was sufficiently effectively reduced and catalytically converted to the Li2S. Consequently, after 100 cycles, the capacity retention rate of LSBs using the S/NbN@NCNT electrode reached 71.5% at a current density of 2 mA/cm2 with a high sulfur loading of 3 mg/cm2. More importantly, even at high current density of 8 mA/cm2, the battery assembled with NbN@NCNT was still able to reach the high capacity of 878.14 mAh/g, demonstrating outstanding rate capability. This study offered novel insights into the potential for enhancing the sulfur reaction kinetics in LSBs.
The dissolution of lithium polysulfides (Li2Sx, 4 ≤ x ≤ 8, LiPSs) intermediates and slow redox kinetics are the main factors leading to the rapid capacity degradation of lithium-sulfur batteries (LSBs), significantly limits the practical development of LSBs. To overcome challenges, NbN embedded in nitrogen-doped carbon nanotubes (NbN@NCNT) composites were synthesized here as sulfur hosts by taking advantage of the superior electrical conductivity and excellent catalytic activity of the metal nitride NbN. The incorporation of NbN enhanced the polysulfides conversion efficiency and suppressed the shuttling effect, thereby enhancing cycling stability in LSBs. XPS results revealed the formation of Li2S, indicating that Li2S8 was sufficiently effectively reduced and catalytically converted to the Li2S. Consequently, after 100 cycles, the capacity retention rate of LSBs using the S/NbN@NCNT electrode reached 71.5% at a current density of 2 mA/cm2 with a high sulfur loading of 3 mg/cm2. More importantly, even at high current density of 8 mA/cm2, the battery assembled with NbN@NCNT was still able to reach the high capacity of 878.14 mAh/g, demonstrating outstanding rate capability. This study offered novel insights into the potential for enhancing the sulfur reaction kinetics in LSBs.
2026, 37(5): 110863
doi: 10.1016/j.cclet.2025.110863
摘要:
Semiconducting metal oxide based gas sensors exhibit great promise for convenient detection of acetone, a biomarker gas in the exhaled breath of type-Ⅰ diabetes patients. However, the detection usually suffers the interference from exhaled moisture. To overcome this challenge, in this work, a novel hierarchical heterojunction structure consisting of SnO2 nanofiber core and Co3O4 nanosheet shell (denoted as SnO2@Co3O4 core-shell composite) was proposed for fabricating acetone sensor with excellent humidity resistance. Compared with SnO2 nanofibers and Co3O4 nanosheets, the SnO2@Co3O4 showed the highest sensing response, with a response value (Rg/Ra) of 11.27-50 ppm acetone at 110 ℃. In addition, the hierarchical SnO2@Co3O4 core-shell structure shows fast response/recovery speed (19/43 s), lower detection limit (125 ppb), excellent selectivity and stability in a humidity environment (relative humidity 30%-90%) with a relative change of only 3%. The enhanced gas sensing performance toward acetone is attributed to the synergistic effect between the two components, the unique core-shell hierarchical structure and the rich oxygen vacancy density. Density functional theory calculations reveal that the SnO2@Co3O4 has higher acetone adsorption energy than the two components. In addition, a novel SnO2@Co3O4 gas sensing module and smart portable sensor device enable efficient real-time monitoring of acetone concentrations on a smartphone via Bluetooth communication.
Semiconducting metal oxide based gas sensors exhibit great promise for convenient detection of acetone, a biomarker gas in the exhaled breath of type-Ⅰ diabetes patients. However, the detection usually suffers the interference from exhaled moisture. To overcome this challenge, in this work, a novel hierarchical heterojunction structure consisting of SnO2 nanofiber core and Co3O4 nanosheet shell (denoted as SnO2@Co3O4 core-shell composite) was proposed for fabricating acetone sensor with excellent humidity resistance. Compared with SnO2 nanofibers and Co3O4 nanosheets, the SnO2@Co3O4 showed the highest sensing response, with a response value (Rg/Ra) of 11.27-50 ppm acetone at 110 ℃. In addition, the hierarchical SnO2@Co3O4 core-shell structure shows fast response/recovery speed (19/43 s), lower detection limit (125 ppb), excellent selectivity and stability in a humidity environment (relative humidity 30%-90%) with a relative change of only 3%. The enhanced gas sensing performance toward acetone is attributed to the synergistic effect between the two components, the unique core-shell hierarchical structure and the rich oxygen vacancy density. Density functional theory calculations reveal that the SnO2@Co3O4 has higher acetone adsorption energy than the two components. In addition, a novel SnO2@Co3O4 gas sensing module and smart portable sensor device enable efficient real-time monitoring of acetone concentrations on a smartphone via Bluetooth communication.
2026, 37(5): 110864
doi: 10.1016/j.cclet.2025.110864
摘要:
Metal-organic framework [Zn2(tz)2(ox)] (CALF-20) has attracted great attention due to its excellent ability to capture carbon dioxide. There are great interests to develop similar adsorbents for gas adsorption and separation. To develop more efficient porous adsorbent, it is essential to study the relationship between these structures and properties. Neutron diffraction has been proved to be an excellent tool for determining both the structural details of MOF host and the precise locations of adsorbed gas within the pore, offering unique opportunities for understanding the structure-properties relationship. Herein, we report the synthesis and structure characterization of MOF [Zn2(mtz)2(ox)], which exhibits high CO2 adsorption capacity. Neutron powder diffraction experiment on the solvated, the activated and CO2 loaded samples unveils the preferred binding sites of CO2 within the MOFs, where CO2 locates toward the center of the pore and interacts with methyl group or triazole via CH···O hydrogen bonding. The adsorption process of CO2 in [Zn2(mtz)2(ox)] is accompanied by the cell volume expansion, so [Zn2(mtz)2(ox)] with more compact structure can show a better adsorption performance. The structure-properties relationship in [Zn2(mtz)2(ox)] elucidated by present study offer a path to develop more advanced porous physisorbent materials.
Metal-organic framework [Zn2(tz)2(ox)] (CALF-20) has attracted great attention due to its excellent ability to capture carbon dioxide. There are great interests to develop similar adsorbents for gas adsorption and separation. To develop more efficient porous adsorbent, it is essential to study the relationship between these structures and properties. Neutron diffraction has been proved to be an excellent tool for determining both the structural details of MOF host and the precise locations of adsorbed gas within the pore, offering unique opportunities for understanding the structure-properties relationship. Herein, we report the synthesis and structure characterization of MOF [Zn2(mtz)2(ox)], which exhibits high CO2 adsorption capacity. Neutron powder diffraction experiment on the solvated, the activated and CO2 loaded samples unveils the preferred binding sites of CO2 within the MOFs, where CO2 locates toward the center of the pore and interacts with methyl group or triazole via CH···O hydrogen bonding. The adsorption process of CO2 in [Zn2(mtz)2(ox)] is accompanied by the cell volume expansion, so [Zn2(mtz)2(ox)] with more compact structure can show a better adsorption performance. The structure-properties relationship in [Zn2(mtz)2(ox)] elucidated by present study offer a path to develop more advanced porous physisorbent materials.
2026, 37(5): 110889
doi: 10.1016/j.cclet.2025.110889
摘要:
The replacement of Pt/C catalysts with Pt-based alloy catalysts was considered a promising strategy to reduce platinum-group-metal (PGM) content in proton exchange membrane fuel cell. However, inexpensive transition metal atoms in Pt-based alloy catalysts are subject to metal dissolution issues, leading to stability issues of oxygen reduction reaction (ORR) catalysts. In this work, a PtCuNi/C-WO3-x catalyst is designed employing non-stoichiometric WO3-x with abundant oxygen vacancies (Ovac). The WO3-x can dramatically improve the stability of PtCuNi without sacrificing the activity. Theoretical calculation suggests a decreased vacancy formation energy of W in WO3-x at the presence of Ovac, as well as increased vacancy formation energies of Pt/Cu/Ni in PtCuNi alloy particles with the existence of surface W dopant. Combined with the experimental discovery of slower dissolution rates of metals in PtCuNi/C-WO3-x catalyst, a dissolution-induced stability enhancement mechanism is proposed, whereby facilitated dissolution of W atoms from WO3-x bulk could re-deposit on Pt-alloy surface and inhibit the dissolution of catalytically active metal atoms, revealing a dynamic process that enhances the stability. The PtCuNi/C-WO3-x also shows great potential to be used as cathode catalyst in membrane electrode assembly for high-temperature proton exchange membrane fuel cells.
The replacement of Pt/C catalysts with Pt-based alloy catalysts was considered a promising strategy to reduce platinum-group-metal (PGM) content in proton exchange membrane fuel cell. However, inexpensive transition metal atoms in Pt-based alloy catalysts are subject to metal dissolution issues, leading to stability issues of oxygen reduction reaction (ORR) catalysts. In this work, a PtCuNi/C-WO3-x catalyst is designed employing non-stoichiometric WO3-x with abundant oxygen vacancies (Ovac). The WO3-x can dramatically improve the stability of PtCuNi without sacrificing the activity. Theoretical calculation suggests a decreased vacancy formation energy of W in WO3-x at the presence of Ovac, as well as increased vacancy formation energies of Pt/Cu/Ni in PtCuNi alloy particles with the existence of surface W dopant. Combined with the experimental discovery of slower dissolution rates of metals in PtCuNi/C-WO3-x catalyst, a dissolution-induced stability enhancement mechanism is proposed, whereby facilitated dissolution of W atoms from WO3-x bulk could re-deposit on Pt-alloy surface and inhibit the dissolution of catalytically active metal atoms, revealing a dynamic process that enhances the stability. The PtCuNi/C-WO3-x also shows great potential to be used as cathode catalyst in membrane electrode assembly for high-temperature proton exchange membrane fuel cells.
2026, 37(5): 110891
doi: 10.1016/j.cclet.2025.110891
摘要:
Structural design is an effective way to realize the functional construction of hole transporting materials (HTMs). In order to have an insight into the relationship between molecular structure and function of HTMs, three isomeric HTMs (RQ1, RQ2 and RQ3) are constructed with functional group of dibenzothiophene which is connected to different positions on the side chains of carbazole-aromatic derivatives. In combination with computational simulation and experimental study, although the isomeric RQ1–RQ3 with the same molecular formula exhibit similar frontier molecular orbital energy levels and optical absorption, their hole transporting ability and interaction at perovskite/HTMs interface in perovskite solar cells (PSCs) are completely different. In comparison with the RQ2 (18.69%) and RQ3 (22.56%), the results indicate that the molecule RQ1 in PSCs application can yield higher power conversion efficiency (23.50%) because of its higher hole mobility and effective charge transfer at perovskite/HTMs interface. Moreover, the mutually corroborating between the computational simulation and the experimental results demonstrate the reliability of the theoretical model for molecular design of isomeric HTMs. This strategy of obtaining high-performance HTMs through simple structural design is expected to inspire researchers to further optimize the efficiency of PSCs.
Structural design is an effective way to realize the functional construction of hole transporting materials (HTMs). In order to have an insight into the relationship between molecular structure and function of HTMs, three isomeric HTMs (RQ1, RQ2 and RQ3) are constructed with functional group of dibenzothiophene which is connected to different positions on the side chains of carbazole-aromatic derivatives. In combination with computational simulation and experimental study, although the isomeric RQ1–RQ3 with the same molecular formula exhibit similar frontier molecular orbital energy levels and optical absorption, their hole transporting ability and interaction at perovskite/HTMs interface in perovskite solar cells (PSCs) are completely different. In comparison with the RQ2 (18.69%) and RQ3 (22.56%), the results indicate that the molecule RQ1 in PSCs application can yield higher power conversion efficiency (23.50%) because of its higher hole mobility and effective charge transfer at perovskite/HTMs interface. Moreover, the mutually corroborating between the computational simulation and the experimental results demonstrate the reliability of the theoretical model for molecular design of isomeric HTMs. This strategy of obtaining high-performance HTMs through simple structural design is expected to inspire researchers to further optimize the efficiency of PSCs.
2026, 37(5): 110892
doi: 10.1016/j.cclet.2025.110892
摘要:
Traditional polycrystalline P2 layered oxides face challenges such as irreversible phase transitions, poor air stability, and structural distortion, which negatively impact their electrochemical performance. In this study, a single-crystal material, P2-Na2/3Ni1/4Mn2/3Mg1/12O2 (SC-NMM), was synthesized using co-precipitation coupled with the molten salt method. Owing to the strong integrity and high thermal stability of the main {001} planes of the large-sized single crystal, SC-NMM exhibits a high reversible specific capacity (173.5 mAh/g at 20 mA/g) and stable cycle performance (93.38% capacity retention after 100 cycles at 100 mA/g) at high voltage. Additionally, the Na-ion full cell constructed with the SC-NMM cathode and hard carbon anode demonstrates a cathode energy density of 397.4 Wh/kg. The excellent electrochemical performance of SC-NMM originates from the reversible anion redox and single-phase solid solution reaction mechanism. This work provides a reference for synthesizing single-crystal layered transition metal oxides with high electrochemical performance by eliminating irreversible phase transitions through crystal orientation modulation.
Traditional polycrystalline P2 layered oxides face challenges such as irreversible phase transitions, poor air stability, and structural distortion, which negatively impact their electrochemical performance. In this study, a single-crystal material, P2-Na2/3Ni1/4Mn2/3Mg1/12O2 (SC-NMM), was synthesized using co-precipitation coupled with the molten salt method. Owing to the strong integrity and high thermal stability of the main {001} planes of the large-sized single crystal, SC-NMM exhibits a high reversible specific capacity (173.5 mAh/g at 20 mA/g) and stable cycle performance (93.38% capacity retention after 100 cycles at 100 mA/g) at high voltage. Additionally, the Na-ion full cell constructed with the SC-NMM cathode and hard carbon anode demonstrates a cathode energy density of 397.4 Wh/kg. The excellent electrochemical performance of SC-NMM originates from the reversible anion redox and single-phase solid solution reaction mechanism. This work provides a reference for synthesizing single-crystal layered transition metal oxides with high electrochemical performance by eliminating irreversible phase transitions through crystal orientation modulation.
2026, 37(5): 110893
doi: 10.1016/j.cclet.2025.110893
摘要:
Aqueous zinc-ion batteries (AZIBs) have emerged as strong contenders for large-scale energy storage solutions, attributed to their cost-effectiveness and enhanced safety profiles. Nevertheless, their widespread adoption is currently hindered by their poor performance in low-temperature conditions. Herein, an electrolyte is developed by utilizing weakly solvated and film-forming molecule dimethyl sulfite (DMS) to achieve smooth de-solvation and high ionic conductivity at low temperature. The DMS disrupts the hydrogen bonding network of water and lowers the freezing point of the electrolyte to -40.9 ℃. The designed electrolyte achieves ionic conductivity up to 10.75 mS/cm at -30 ℃. Due to the chemical reactivity of DMS and trifluoromethanesulfonate anions in the Zn2+-solvation shell, a ZnF2-ZnS hybrid solid electrolyte interphase (SEI) is successively generated on Zn metal surface. Mechanistic studies reveal that such robust hybrid interphase can promote Zn2+ desolvation and rapid Zn2+ transport. In addition, the addition of DMS effectively suppresses the dendritic growth, hydrogen evolution reaction (HER), and corrosion-induced passivation on the anode surface, facilitating long-term cycling at subzero temperatures. At -40 ℃, the Zn//Zn symmetrical cell cycles for 1200 h at 0.5 mA/cm2 and 0.5 mAh/cm2, and the Zn//NVO cell achieves an ultra-long cycle life of 1000 cycles with a high capacity retention of 82.89% at 1 A/g.
Aqueous zinc-ion batteries (AZIBs) have emerged as strong contenders for large-scale energy storage solutions, attributed to their cost-effectiveness and enhanced safety profiles. Nevertheless, their widespread adoption is currently hindered by their poor performance in low-temperature conditions. Herein, an electrolyte is developed by utilizing weakly solvated and film-forming molecule dimethyl sulfite (DMS) to achieve smooth de-solvation and high ionic conductivity at low temperature. The DMS disrupts the hydrogen bonding network of water and lowers the freezing point of the electrolyte to -40.9 ℃. The designed electrolyte achieves ionic conductivity up to 10.75 mS/cm at -30 ℃. Due to the chemical reactivity of DMS and trifluoromethanesulfonate anions in the Zn2+-solvation shell, a ZnF2-ZnS hybrid solid electrolyte interphase (SEI) is successively generated on Zn metal surface. Mechanistic studies reveal that such robust hybrid interphase can promote Zn2+ desolvation and rapid Zn2+ transport. In addition, the addition of DMS effectively suppresses the dendritic growth, hydrogen evolution reaction (HER), and corrosion-induced passivation on the anode surface, facilitating long-term cycling at subzero temperatures. At -40 ℃, the Zn//Zn symmetrical cell cycles for 1200 h at 0.5 mA/cm2 and 0.5 mAh/cm2, and the Zn//NVO cell achieves an ultra-long cycle life of 1000 cycles with a high capacity retention of 82.89% at 1 A/g.
2026, 37(5): 110952
doi: 10.1016/j.cclet.2025.110952
摘要:
Aqueous zinc-ion batteries (AZIBs) are the low-cost and safe secondary battery technology with great application prospects, but remain hindered by the severe Zn-electrolyte interface compatibility, especially in extreme environmental temperature. Innovative electrolyte design is the key to solving the above problems. Here, we introduce an electrolyte additive of Poloxamer 407 (P407) as a solvation restructuring agent and H2O cluster modulator, effectively stabilizing H2O molecules and suppressing parasitic reactions. Meanwhile, P407 facilitates the formation of a stable solid electrolyte interphase (SEI) composed of organic-inorganic composite, thereby improving the interfacial chemistry. More importantly, the thermoreversible gelation property of P407 enhances the system’s high-temperature stability by forming micelle network structures that effectively retains H2O molecules, while at low temperature, it maintains the fluidity of the electrolyte, ensuring efficient ion transport. By using P407-containing electrolyte, the Zn anode achieves long cycling life of 4000, 850, and 1000 h at 30, 60 and −30 ℃, respectively. Moreover, the modified electrolyte enables the Zn-V2O5 full cells to achieve excellent rate performance and cycling stability in a wide temperature range from −30 ℃ to 60 ℃. This study highlights a simple yet effective strategy for electrolyte modification using P407, providing a pathway toward the development of high-performance AZIBs with broad temperature adaptability.
Aqueous zinc-ion batteries (AZIBs) are the low-cost and safe secondary battery technology with great application prospects, but remain hindered by the severe Zn-electrolyte interface compatibility, especially in extreme environmental temperature. Innovative electrolyte design is the key to solving the above problems. Here, we introduce an electrolyte additive of Poloxamer 407 (P407) as a solvation restructuring agent and H2O cluster modulator, effectively stabilizing H2O molecules and suppressing parasitic reactions. Meanwhile, P407 facilitates the formation of a stable solid electrolyte interphase (SEI) composed of organic-inorganic composite, thereby improving the interfacial chemistry. More importantly, the thermoreversible gelation property of P407 enhances the system’s high-temperature stability by forming micelle network structures that effectively retains H2O molecules, while at low temperature, it maintains the fluidity of the electrolyte, ensuring efficient ion transport. By using P407-containing electrolyte, the Zn anode achieves long cycling life of 4000, 850, and 1000 h at 30, 60 and −30 ℃, respectively. Moreover, the modified electrolyte enables the Zn-V2O5 full cells to achieve excellent rate performance and cycling stability in a wide temperature range from −30 ℃ to 60 ℃. This study highlights a simple yet effective strategy for electrolyte modification using P407, providing a pathway toward the development of high-performance AZIBs with broad temperature adaptability.
2026, 37(5): 110953
doi: 10.1016/j.cclet.2025.110953
摘要:
Solvated-ion co-intercalation mechanism with high-rate capability properties makes graphite anode reconsider as optional anode for sodium-ion batteries and capacitors. The size effect has been widely investigated for various transition metal oxide materials, but such influences on the co-intercalation mechanism remain largely unexplored. In this study, natural graphite anodes with different particle sizes ranging from 25 µm to 1.7 µm for [Na(diglyme)x]+ co-interaction are systematically investigated through detailed kinetics analysis and in-situ X-ray diffraction characterization. Importantly, we find that the reaction pathways of the co-intercalation and co-extraction are quite different. The reduced graphite size results in the loss of phase transitions during the co-extraction process and then the disappearance of the sharp anodic redox peak. The small-sized graphite anodes display boosted capacitor-like responses and provide additional surface adsorption with a slightly increased capacity. Finally, a hybrid sodium-ion capacitor (SIC), using graphite anode and activated carbon cathode, is assembled without complex presodiation treatments. Such optimized hybrid SICs deliver high energy densities of 60 Wh/kg at 240 W/kg and high power density of ~16,000 W/kg with 32 Wh/kg, and ultralong 30,000 stable cycles. This work provides fundamental insights into the Na+-solvent co-intercalation mechanism with tunable capacitor-like kinetics, representing a promising direction for high-power sodium-ion storage.
Solvated-ion co-intercalation mechanism with high-rate capability properties makes graphite anode reconsider as optional anode for sodium-ion batteries and capacitors. The size effect has been widely investigated for various transition metal oxide materials, but such influences on the co-intercalation mechanism remain largely unexplored. In this study, natural graphite anodes with different particle sizes ranging from 25 µm to 1.7 µm for [Na(diglyme)x]+ co-interaction are systematically investigated through detailed kinetics analysis and in-situ X-ray diffraction characterization. Importantly, we find that the reaction pathways of the co-intercalation and co-extraction are quite different. The reduced graphite size results in the loss of phase transitions during the co-extraction process and then the disappearance of the sharp anodic redox peak. The small-sized graphite anodes display boosted capacitor-like responses and provide additional surface adsorption with a slightly increased capacity. Finally, a hybrid sodium-ion capacitor (SIC), using graphite anode and activated carbon cathode, is assembled without complex presodiation treatments. Such optimized hybrid SICs deliver high energy densities of 60 Wh/kg at 240 W/kg and high power density of ~16,000 W/kg with 32 Wh/kg, and ultralong 30,000 stable cycles. This work provides fundamental insights into the Na+-solvent co-intercalation mechanism with tunable capacitor-like kinetics, representing a promising direction for high-power sodium-ion storage.
2026, 37(5): 110954
doi: 10.1016/j.cclet.2025.110954
摘要:
High-performance electrode materials are of paramount significance for practical applications in energy storage devices, and the design of hollow-structured active electrode materials is a simple effective strategy. Herin, a three-dimensional nickel cobalt cadmium ternary sulfide hollow nanoprism material (NiCoCd-S) was successfully synthesized by combination of refluxing, hydrothermal and calcination methods. The co-existence and synergism of Ni, Co and Cd endow the material surface with abundant catalytic active sites, facilitating the progress of the reaction, enabling it to exhibit better performance than single-metal or bimetallic compounds. The unique hollow structure facilitates increased contact between the electrolyte and more electroactive sites, while the shorter diffusion pathways enable rapid ion/electron transfer rates within the material, synergistically generating enhanced supercapacitive activity. The synthesized NiCoCd-S shows a high specific capacitance (Cg) of 1643.7 F/g@1 A/g, along with a prolonged cycling life (81.6% capacitance retention after 10,000 cycles). When assembling the NiCoCd-S//AC asymmetric supercapacitor, it demonstrates an impressive energy/power density of 105.9 Wh/kg and 919.2 W/kg, respectively. After 10,000 charging-discharging cycles, the initial capacitance can still be maintained at 88.5%. The present work offers a strategy for the rational design of hollow nanostructured polymetallic sulfides with high electrochemical performance and stability.
High-performance electrode materials are of paramount significance for practical applications in energy storage devices, and the design of hollow-structured active electrode materials is a simple effective strategy. Herin, a three-dimensional nickel cobalt cadmium ternary sulfide hollow nanoprism material (NiCoCd-S) was successfully synthesized by combination of refluxing, hydrothermal and calcination methods. The co-existence and synergism of Ni, Co and Cd endow the material surface with abundant catalytic active sites, facilitating the progress of the reaction, enabling it to exhibit better performance than single-metal or bimetallic compounds. The unique hollow structure facilitates increased contact between the electrolyte and more electroactive sites, while the shorter diffusion pathways enable rapid ion/electron transfer rates within the material, synergistically generating enhanced supercapacitive activity. The synthesized NiCoCd-S shows a high specific capacitance (Cg) of 1643.7 F/g@1 A/g, along with a prolonged cycling life (81.6% capacitance retention after 10,000 cycles). When assembling the NiCoCd-S//AC asymmetric supercapacitor, it demonstrates an impressive energy/power density of 105.9 Wh/kg and 919.2 W/kg, respectively. After 10,000 charging-discharging cycles, the initial capacitance can still be maintained at 88.5%. The present work offers a strategy for the rational design of hollow nanostructured polymetallic sulfides with high electrochemical performance and stability.
2026, 37(5): 110974
doi: 10.1016/j.cclet.2025.110974
摘要:
Electrochemical NO reduction reaction (NORR) has gained extensive attention as a promising approach to achieve both harmful NO removal and ambient NH3 production. Main-group metal-based single-atom catalysts (SACs) hold great promise for electrocatalysis but still lack adequate investigation. Herein, by means of the first-principles calculations, we systematically explore the potential of main-group metal-embedded BC3 monolayer (denoted as M@VB and M@VC, M = Mg, Ca, Al, Ga, In, Ge, Sn, Sb, and Bi) as highly efficient SACs for the NORR toward NH3 synthesis. After examining the structural stability, NO adsorbability, NORR catalytic performance, and NH3 selectivity, we screen Al@VB, Ga@VB, and Ge@VC out of 18 candidate systems. Remarkably, NO can be adsorbed and activated on them with moderate ΔG*NO of -1.27~-1.90 eV, and spontaneously reduced into NH3 without any limiting potential. Moreover, the three screened candidates can effectively inhibit the production of N2O/N2 byproducts under high NO converge, as well as the competing hydrogen evolution reaction (HER). Our work not only offers several high-efficiency NORR electrocatalysts, but also guides the rational design of potential main-group metal-based SACs.
Electrochemical NO reduction reaction (NORR) has gained extensive attention as a promising approach to achieve both harmful NO removal and ambient NH3 production. Main-group metal-based single-atom catalysts (SACs) hold great promise for electrocatalysis but still lack adequate investigation. Herein, by means of the first-principles calculations, we systematically explore the potential of main-group metal-embedded BC3 monolayer (denoted as M@VB and M@VC, M = Mg, Ca, Al, Ga, In, Ge, Sn, Sb, and Bi) as highly efficient SACs for the NORR toward NH3 synthesis. After examining the structural stability, NO adsorbability, NORR catalytic performance, and NH3 selectivity, we screen Al@VB, Ga@VB, and Ge@VC out of 18 candidate systems. Remarkably, NO can be adsorbed and activated on them with moderate ΔG*NO of -1.27~-1.90 eV, and spontaneously reduced into NH3 without any limiting potential. Moreover, the three screened candidates can effectively inhibit the production of N2O/N2 byproducts under high NO converge, as well as the competing hydrogen evolution reaction (HER). Our work not only offers several high-efficiency NORR electrocatalysts, but also guides the rational design of potential main-group metal-based SACs.
2026, 37(5): 111158
doi: 10.1016/j.cclet.2025.111158
摘要:
Phenylphosphonate functionalized fully-reduced hourglass-shaped organophosphomolybdate(V) hybrid (H2bib){Ni[Mo6(PO3C6H5)4O15H6]2}·9H2O (bib = 4,4′-bis(imidazolyl)bibpheny) was synthesized as a photoelectrochemical (PEC) sensor. Benefiting from the electron transfer interaction between organic phenyl groups and inorganic {P4Mo6} skeleton, compound achieved a low detection limit of 4.61 nmol/L and high sensitivity of 264.02 µA L/µmol toward the PEC detection of levofloxacin in aqueous solution, together with excellent practicality in milk sample.
Phenylphosphonate functionalized fully-reduced hourglass-shaped organophosphomolybdate(V) hybrid (H2bib){Ni[Mo6(PO3C6H5)4O15H6]2}·9H2O (bib = 4,4′-bis(imidazolyl)bibpheny) was synthesized as a photoelectrochemical (PEC) sensor. Benefiting from the electron transfer interaction between organic phenyl groups and inorganic {P4Mo6} skeleton, compound achieved a low detection limit of 4.61 nmol/L and high sensitivity of 264.02 µA L/µmol toward the PEC detection of levofloxacin in aqueous solution, together with excellent practicality in milk sample.
2026, 37(5): 111236
doi: 10.1016/j.cclet.2025.111236
摘要:
In drug discovery, it is extremely important to identify highly potent leads with desirable drug-like profiles. Almost all the marketed phosphodiesterase 5 (PDE5) inhibitors such as sildenafil, vardenafil, and tadalafil have poor selectivity over PDE6 or PDE11 and leading to several side effects. Herein, a metabolites-based scaffold hopping strategy was performed to discover selective PDE5 inhibitors with remarkable metabolic stability. The Eu(OTf)3-catalyzed Mannich-type reaction followed by l-selectride catalyzed reduction was used to prepare chiral 2,3,3a,4,5,6-hexahydro-1H-benzo[b]pyrido[2,3,4-de][1,6] naphthyridines as novel PDE5 inhibitors with high enantioselectivity (> 99% ee and > 30:1 dr). Lead L9 exhibited a half maximal inhibitory concentration (IC50) of 1.03 nmol/L with higher selectivity (> 898-fold) over PDE6 or PDE11 than sildenafil and tadalafil, implying the potential relief from side effects. Especially, the co-crystal binding pattern of L9 with PDE5 is revealed to be different from that of sildenafil, which possibly explain the former's high selectivity. And oral administration of L9·HCl (5.0 mg/kg) exhibited better therapeutic effects than pirfenidone (150 mg/kg) in a bleomycin-induced idiopathic pulmonary fibrosis (IPF) rat model, highlighting the potential of L9·HCl for the treatment of IPF.
In drug discovery, it is extremely important to identify highly potent leads with desirable drug-like profiles. Almost all the marketed phosphodiesterase 5 (PDE5) inhibitors such as sildenafil, vardenafil, and tadalafil have poor selectivity over PDE6 or PDE11 and leading to several side effects. Herein, a metabolites-based scaffold hopping strategy was performed to discover selective PDE5 inhibitors with remarkable metabolic stability. The Eu(OTf)3-catalyzed Mannich-type reaction followed by l-selectride catalyzed reduction was used to prepare chiral 2,3,3a,4,5,6-hexahydro-1H-benzo[b]pyrido[2,3,4-de][1,6] naphthyridines as novel PDE5 inhibitors with high enantioselectivity (> 99% ee and > 30:1 dr). Lead L9 exhibited a half maximal inhibitory concentration (IC50) of 1.03 nmol/L with higher selectivity (> 898-fold) over PDE6 or PDE11 than sildenafil and tadalafil, implying the potential relief from side effects. Especially, the co-crystal binding pattern of L9 with PDE5 is revealed to be different from that of sildenafil, which possibly explain the former's high selectivity. And oral administration of L9·HCl (5.0 mg/kg) exhibited better therapeutic effects than pirfenidone (150 mg/kg) in a bleomycin-induced idiopathic pulmonary fibrosis (IPF) rat model, highlighting the potential of L9·HCl for the treatment of IPF.
2026, 37(5): 111248
doi: 10.1016/j.cclet.2025.111248
摘要:
Intracerebral hemorrhage (ICH) is a devastating subtype of stroke with high mortality and poor prognosis among survivors. Neuroinflammation after ICH plays a critical role in both secondary brain injury and repair. In the early stages of ICH, excessive activation of microglia triggers pro-inflammation, leading to the release of various pro-inflammatory cytokines that exacerbate neuronal damage and worsen neurological deficits. Pterostilbene (PTE), a natural polyphenol with potent anti-inflammatory and antioxidant properties, is an ideal neuroprotective agent. However, its clinical application is limited by poor bioavailability and low blood-brain barrier (BBB) penetrability following oral administration. Here, we developed PTE-loaded methoxy poly(ethylene glycol)-poly(ε-caprolactone) (mPEG-PCL) nanoparticles (PTE-NPs) to enhance the bioavailability of PTE and performed an intranasal delivery strategy for non-invasive and efficient transport to the ICH lesion. PTE-NPs significantly suppressed pro-inflammatory microglia activation and cytokine release, thereby reducing inflammation-mediated neuronal damage in the peri–hematomal region. In the two ICH mouse models, PTE-NPs demonstrated significant therapeutic efficacy in improving neurological function with good biosafety. This study provides a potential therapeutic strategy for the treatment of ICH and its future clinical translation.
Intracerebral hemorrhage (ICH) is a devastating subtype of stroke with high mortality and poor prognosis among survivors. Neuroinflammation after ICH plays a critical role in both secondary brain injury and repair. In the early stages of ICH, excessive activation of microglia triggers pro-inflammation, leading to the release of various pro-inflammatory cytokines that exacerbate neuronal damage and worsen neurological deficits. Pterostilbene (PTE), a natural polyphenol with potent anti-inflammatory and antioxidant properties, is an ideal neuroprotective agent. However, its clinical application is limited by poor bioavailability and low blood-brain barrier (BBB) penetrability following oral administration. Here, we developed PTE-loaded methoxy poly(ethylene glycol)-poly(ε-caprolactone) (mPEG-PCL) nanoparticles (PTE-NPs) to enhance the bioavailability of PTE and performed an intranasal delivery strategy for non-invasive and efficient transport to the ICH lesion. PTE-NPs significantly suppressed pro-inflammatory microglia activation and cytokine release, thereby reducing inflammation-mediated neuronal damage in the peri–hematomal region. In the two ICH mouse models, PTE-NPs demonstrated significant therapeutic efficacy in improving neurological function with good biosafety. This study provides a potential therapeutic strategy for the treatment of ICH and its future clinical translation.
2026, 37(5): 111257
doi: 10.1016/j.cclet.2025.111257
摘要:
Target therapy represents a paradigm shift to a precise and personalized approach. Unlike the great success of antibody-drug conjugate (ADC) in clinical practice, peptide-drug conjugate (PDC) with good tissue penetration and drug loading capacity exhibits poor stability, quick blood clearance and cellular internalization that limit their translation. In this study, a feasible approach for constructing an in vivo self-assembling peptide-drug conjugate (sPDC) was proposed by rationally designing the combination of tumor-specific targeting peptide module, responsive self-assembling peptide module, and therapeutic drug. Two optimized sPDCs (sPDC1 and sPDC2) capable of specifically targeting human epidermal growth factor receptor 2 (HER2) on the surface of tumors were reported. sPDCs could selectively target HER2-positive tumors and effectively kill HER2 overexpressing tumor cells. In addition, weak but significant efficacy of sPDCs was also observed in HER2-negative tumors, which was likely by-stander effect due to the release of monomethyl auristatin E (MMAE) in the tumor microenvironment. Finally, in HER2-positive xenograft mouse models, sPDC1 showed superior therapeutic efficacy over the clinical HER2-targeted therapeutic agents trastuzumab and lapatinib, and roughly equivalent therapeutic efficacy compared with RC48 even in large tumor-bearing mouse models. Therefore, sPDC1 was promising to serve as a lead compound for further clinical development for oncology therapy.
Target therapy represents a paradigm shift to a precise and personalized approach. Unlike the great success of antibody-drug conjugate (ADC) in clinical practice, peptide-drug conjugate (PDC) with good tissue penetration and drug loading capacity exhibits poor stability, quick blood clearance and cellular internalization that limit their translation. In this study, a feasible approach for constructing an in vivo self-assembling peptide-drug conjugate (sPDC) was proposed by rationally designing the combination of tumor-specific targeting peptide module, responsive self-assembling peptide module, and therapeutic drug. Two optimized sPDCs (sPDC1 and sPDC2) capable of specifically targeting human epidermal growth factor receptor 2 (HER2) on the surface of tumors were reported. sPDCs could selectively target HER2-positive tumors and effectively kill HER2 overexpressing tumor cells. In addition, weak but significant efficacy of sPDCs was also observed in HER2-negative tumors, which was likely by-stander effect due to the release of monomethyl auristatin E (MMAE) in the tumor microenvironment. Finally, in HER2-positive xenograft mouse models, sPDC1 showed superior therapeutic efficacy over the clinical HER2-targeted therapeutic agents trastuzumab and lapatinib, and roughly equivalent therapeutic efficacy compared with RC48 even in large tumor-bearing mouse models. Therefore, sPDC1 was promising to serve as a lead compound for further clinical development for oncology therapy.
2026, 37(5): 111274
doi: 10.1016/j.cclet.2025.111274
摘要:
The poor biofilm colonization, charge transfer, and storage at the anode have long been major obstacles to achieving high power generation in bioelectrochemical systems (BES). To overcome this challenge, we developed electrospun carbon nanofiber-interpenetrated reduced graphene oxide aerogels (CNF/rGO-x, where x denotes the mass ratio of CNF to rGO, with x = 2, 4, 6) to modify the surface of carbon cloth (CC), significantly enhancing its electrochemical performance. The CNF/rGO-6 aerogel featured a porous, interconnected conductive scaffold, endowing the CC electrode with a larger electrochemically active area, higher specific capacitance, and a rougher surface. These properties significantly improved biofilm adhesion, extracellular electron transfer, and charge storage capabilities. As a result, the BES equipped with a CNF/rGO-6 electrode achieved an impressive power density of 3080.3 mW/m2, significantly higher than those of BES with CNF/rGO-4 (2426.3 mW/m2), CNF/rGO-2 (2717 mW/m2), rGO (1978.3 mW/m2), and pure CC (1050.4 mW/m2) electrodes. Furthermore, the CNF/rGO-6 electrode supported a high abundance of electroactive bacteria and enhanced their viability. With its simple fabrication, low weight, and exceptional electrochemical performance, the CNF/rGO-6 aerogel demonstrates significant potential as an electrode material for high-performance and cost-effective BES.
The poor biofilm colonization, charge transfer, and storage at the anode have long been major obstacles to achieving high power generation in bioelectrochemical systems (BES). To overcome this challenge, we developed electrospun carbon nanofiber-interpenetrated reduced graphene oxide aerogels (CNF/rGO-x, where x denotes the mass ratio of CNF to rGO, with x = 2, 4, 6) to modify the surface of carbon cloth (CC), significantly enhancing its electrochemical performance. The CNF/rGO-6 aerogel featured a porous, interconnected conductive scaffold, endowing the CC electrode with a larger electrochemically active area, higher specific capacitance, and a rougher surface. These properties significantly improved biofilm adhesion, extracellular electron transfer, and charge storage capabilities. As a result, the BES equipped with a CNF/rGO-6 electrode achieved an impressive power density of 3080.3 mW/m2, significantly higher than those of BES with CNF/rGO-4 (2426.3 mW/m2), CNF/rGO-2 (2717 mW/m2), rGO (1978.3 mW/m2), and pure CC (1050.4 mW/m2) electrodes. Furthermore, the CNF/rGO-6 electrode supported a high abundance of electroactive bacteria and enhanced their viability. With its simple fabrication, low weight, and exceptional electrochemical performance, the CNF/rGO-6 aerogel demonstrates significant potential as an electrode material for high-performance and cost-effective BES.
2026, 37(5): 111282
doi: 10.1016/j.cclet.2025.111282
摘要:
Oral leukoplakia (OLK) is a common and representative malignant disease of oral mucosa, and possess a higher risk of cancer. Compared with traditional surgical treatment, photodynamic therapy (PDT) has great potential in OLK treatment, due to its advantages of minimally invasiveness and low toxic side effects. However, traditional photosensitizer administration suffers from short retention time due to the fluid environment of saliva and extensive tongue movement, leading to poor drug (photosensitizer) utilization and limited therapeutic outcome. To address such issue, here a photosensitive guanosine (G)-based hydrogel system (G@GQD) was constructed, in which graphene quantum dots (GQDs) featuring high photosensitization activity was loaded through three dimensional (3D) fiber network physical encapsulation. The favorable adhesion of the G@GQD hydrogel on the tongue, together with sustained GQDs release, significantly enhanced the retention of GQDs within the oral cavity. As a result, G@GQD hydrogel could continuously generate high levels of reactive oxygen species (ROS) under irradiation, demonstrating a sustained therapeutic efficiency in vitro. Compared with free GQDs, G@GQD exhibited significantly improved PDT efficiency in treating 4-nitroquinoline 1-oxide (4-NQO)-induced OLK animals. This study presented a promising strategy in overcoming the drug retention barrier that caused by saliva and tongue movement, which has far-reaching significance for the future PDT therapies.
Oral leukoplakia (OLK) is a common and representative malignant disease of oral mucosa, and possess a higher risk of cancer. Compared with traditional surgical treatment, photodynamic therapy (PDT) has great potential in OLK treatment, due to its advantages of minimally invasiveness and low toxic side effects. However, traditional photosensitizer administration suffers from short retention time due to the fluid environment of saliva and extensive tongue movement, leading to poor drug (photosensitizer) utilization and limited therapeutic outcome. To address such issue, here a photosensitive guanosine (G)-based hydrogel system (G@GQD) was constructed, in which graphene quantum dots (GQDs) featuring high photosensitization activity was loaded through three dimensional (3D) fiber network physical encapsulation. The favorable adhesion of the G@GQD hydrogel on the tongue, together with sustained GQDs release, significantly enhanced the retention of GQDs within the oral cavity. As a result, G@GQD hydrogel could continuously generate high levels of reactive oxygen species (ROS) under irradiation, demonstrating a sustained therapeutic efficiency in vitro. Compared with free GQDs, G@GQD exhibited significantly improved PDT efficiency in treating 4-nitroquinoline 1-oxide (4-NQO)-induced OLK animals. This study presented a promising strategy in overcoming the drug retention barrier that caused by saliva and tongue movement, which has far-reaching significance for the future PDT therapies.
2026, 37(5): 111284
doi: 10.1016/j.cclet.2025.111284
摘要:
Light is a powerful tool for controlling hydrogel formation and drug release, which are essential in tissue engineering and drug delivery. Achieving orthogonal control over hydrogelation and drug release using different wavelengths of light offers precise spatiotemporal regulation but is challenged by limited penetration depth and spectral crosstalk of commonly used visible light. Herein, this work develops an orthogonal light-responsive hydrogel based on dual-wavelength upconversion nanoparticles (UCNPs) for controlled hydrogelation and drug release. Upon 808 nm excitation, these UCNPs emit green light, triggering the photopolymerization of hyaluronic acid-2-aminoethyl methacrylate hydrogels. While 980 nm induces ultraviolet emission, enabling controlled and sustained drug release. Through structural design, the emissions under dual-wavelength excitation exhibit no spectral crosstalk, enabling orthogonal light control of both processes. In vitro and in vivo experiments show that both hydrogel formation and drug release processes can be finely tuned by controlling the power density and excitation durations, significantly enhancing the spatiotemporal precision of drug delivery. This orthogonal light-responsive hydrogel holds significant potential for precise, spatiotemporally controlled drug delivery.
Light is a powerful tool for controlling hydrogel formation and drug release, which are essential in tissue engineering and drug delivery. Achieving orthogonal control over hydrogelation and drug release using different wavelengths of light offers precise spatiotemporal regulation but is challenged by limited penetration depth and spectral crosstalk of commonly used visible light. Herein, this work develops an orthogonal light-responsive hydrogel based on dual-wavelength upconversion nanoparticles (UCNPs) for controlled hydrogelation and drug release. Upon 808 nm excitation, these UCNPs emit green light, triggering the photopolymerization of hyaluronic acid-2-aminoethyl methacrylate hydrogels. While 980 nm induces ultraviolet emission, enabling controlled and sustained drug release. Through structural design, the emissions under dual-wavelength excitation exhibit no spectral crosstalk, enabling orthogonal light control of both processes. In vitro and in vivo experiments show that both hydrogel formation and drug release processes can be finely tuned by controlling the power density and excitation durations, significantly enhancing the spatiotemporal precision of drug delivery. This orthogonal light-responsive hydrogel holds significant potential for precise, spatiotemporally controlled drug delivery.
PROTAC degraders of FSP1 act as potent GPX4 sensitizers to induce ferroptosis for hepatoma treatment
2026, 37(5): 111285
doi: 10.1016/j.cclet.2025.111285
摘要:
Induction of ferroptosis is a promising strategy for tumor treatment. In light of the fact that the inhibition of ferroptosis suppressor protein 1 (FSP1) can enhance the susceptibility of hepatoma cells to glutathione peroxidase 4 (GPX4) inhibitors, we hypothesized that FSP1 degraders may conspicuously improve the therapeutic efficacy of GPX4 inhibitors against hepatoma. Here, we developed a strategy using an iFSP1 analog (FSP1 inhibitor) and the pomalidomide (E3 ligase ligand) to construct proteolysis targeting chimeras (PROTACs) for degrading FSP1. Among these, C7, the first-in-class PROTAC degrader of FSP1, induced FSP1 degradation with a half-maximal degradation concentration (DC50) value of 0.66 µmol/L. The synergistic application of C7 (1 µmol/L) and the GPX4 inhibitor ML162 (100 nmol/L) markedly induced ferroptosis and effectively inhibited hepatoma cells viability. Further mechanism studies revealed that C7 targets FSP1 and down-regulates it through the ubiquitin-proteasome pathway. In vivo experiments demonstrated that the therapeutic alliance of C7 and ML162 markedly surpassed the efficacy of iFSP1 (FSP1 inhibitor) and ML162 in suppressing tumor proliferation. Collectively, these findings indicated that PROTAC degraders of FSP1 function as potent sensitizers of GPX4 inhibitors to induce ferroptosis, thus representing a promising strategy for hepatoma treatment.
Induction of ferroptosis is a promising strategy for tumor treatment. In light of the fact that the inhibition of ferroptosis suppressor protein 1 (FSP1) can enhance the susceptibility of hepatoma cells to glutathione peroxidase 4 (GPX4) inhibitors, we hypothesized that FSP1 degraders may conspicuously improve the therapeutic efficacy of GPX4 inhibitors against hepatoma. Here, we developed a strategy using an iFSP1 analog (FSP1 inhibitor) and the pomalidomide (E3 ligase ligand) to construct proteolysis targeting chimeras (PROTACs) for degrading FSP1. Among these, C7, the first-in-class PROTAC degrader of FSP1, induced FSP1 degradation with a half-maximal degradation concentration (DC50) value of 0.66 µmol/L. The synergistic application of C7 (1 µmol/L) and the GPX4 inhibitor ML162 (100 nmol/L) markedly induced ferroptosis and effectively inhibited hepatoma cells viability. Further mechanism studies revealed that C7 targets FSP1 and down-regulates it through the ubiquitin-proteasome pathway. In vivo experiments demonstrated that the therapeutic alliance of C7 and ML162 markedly surpassed the efficacy of iFSP1 (FSP1 inhibitor) and ML162 in suppressing tumor proliferation. Collectively, these findings indicated that PROTAC degraders of FSP1 function as potent sensitizers of GPX4 inhibitors to induce ferroptosis, thus representing a promising strategy for hepatoma treatment.
2026, 37(5): 111291
doi: 10.1016/j.cclet.2025.111291
摘要:
Decellularized amniotic membrane (dAM) holds significant potential in tissue engineering; however, its inherent mechanical limitations and rapid degradation hinder its clinical translation. This study integrates dAM with high molecular weight polymer polycaprolactone (PCL) and natural gelatin (Gel) nanofibers using electrospinning technology and a 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) covalent crosslinking system to produce two composite biomaterials. Both PCL-dAM and Gel-dAM composites demonstrate enhanced strain, tensile strength, and elasticity compared to pure dAM, showcasing improved mechanical properties and significantly reduced degradation rates, with Gel-dAM exhibiting superior overall performance. Gel-dAM also shows considerably better compatibility with fibroblasts, macrophages, and tendon stem cells than PCL-dAM, suggesting that it more effectively supports cell adhesion, proliferation, and differentiation, thus providing a more favorable microenvironment for tissue repair. In macrophage immune modulation, Gel-dAM significantly promotes the polarization of macrophages toward the M2 phenotype, exhibiting potential anti-inflammatory and repair-enhancing effects, thereby offering new insights into the use of dAM in tissue regeneration. These advancements open new possibilities for the clinical application of dAM, particularly in tissue repair and wound dressing.
Decellularized amniotic membrane (dAM) holds significant potential in tissue engineering; however, its inherent mechanical limitations and rapid degradation hinder its clinical translation. This study integrates dAM with high molecular weight polymer polycaprolactone (PCL) and natural gelatin (Gel) nanofibers using electrospinning technology and a 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) covalent crosslinking system to produce two composite biomaterials. Both PCL-dAM and Gel-dAM composites demonstrate enhanced strain, tensile strength, and elasticity compared to pure dAM, showcasing improved mechanical properties and significantly reduced degradation rates, with Gel-dAM exhibiting superior overall performance. Gel-dAM also shows considerably better compatibility with fibroblasts, macrophages, and tendon stem cells than PCL-dAM, suggesting that it more effectively supports cell adhesion, proliferation, and differentiation, thus providing a more favorable microenvironment for tissue repair. In macrophage immune modulation, Gel-dAM significantly promotes the polarization of macrophages toward the M2 phenotype, exhibiting potential anti-inflammatory and repair-enhancing effects, thereby offering new insights into the use of dAM in tissue regeneration. These advancements open new possibilities for the clinical application of dAM, particularly in tissue repair and wound dressing.
2026, 37(5): 111292
doi: 10.1016/j.cclet.2025.111292
摘要:
Patchouli oil (PAO), a traditional herbal remedy with notable anti-inflammatory properties, has demonstrated significant therapeutic potential in gastrointestinal diseases. However, its instability in acidic environments and low bioavailability hinder PAO's clinical application. In this study, we developed a pharmaceutical solid-state form of PAO using a β-cyclodextrin (βCD)-based inclusion cocrystal technology, thus obtaining PAO-βCD cocrystals. PAO-βCD cocrystals exhibited enhanced dissolution and stability. We further encapsulated them in pH-sensitive Eudragit-coated pellets (PAO-βCD@pellet) to achieve site-specific delivery of PAO to the inflamed colon. In vivo results from the dextran sulfate sodium salt (DSS)-induced colitis mouse model showed that PAO-βCD@pellet significantly improved the colonic release of PAO, as evidenced by fluorescence tracking and quantitative analysis of patchouli alcohol, the main active compound of PAO. Furthermore, PAO-βCD@pellet demonstrated superior therapeutic efficacy, reducing disease activity index, preventing intestinal barrier damage, and modulating the gut microbiome. Histological examination confirmed alleviating intestinal epithelial cell damage caused by oxidative stress and inflammation. These findings suggest that PAO-βCD@pellet offers a promising targeted treatment strategy for inflammatory bowel disease (IBD) with enhanced stability, bioavailability, and therapeutic outcomes.
Patchouli oil (PAO), a traditional herbal remedy with notable anti-inflammatory properties, has demonstrated significant therapeutic potential in gastrointestinal diseases. However, its instability in acidic environments and low bioavailability hinder PAO's clinical application. In this study, we developed a pharmaceutical solid-state form of PAO using a β-cyclodextrin (βCD)-based inclusion cocrystal technology, thus obtaining PAO-βCD cocrystals. PAO-βCD cocrystals exhibited enhanced dissolution and stability. We further encapsulated them in pH-sensitive Eudragit-coated pellets (PAO-βCD@pellet) to achieve site-specific delivery of PAO to the inflamed colon. In vivo results from the dextran sulfate sodium salt (DSS)-induced colitis mouse model showed that PAO-βCD@pellet significantly improved the colonic release of PAO, as evidenced by fluorescence tracking and quantitative analysis of patchouli alcohol, the main active compound of PAO. Furthermore, PAO-βCD@pellet demonstrated superior therapeutic efficacy, reducing disease activity index, preventing intestinal barrier damage, and modulating the gut microbiome. Histological examination confirmed alleviating intestinal epithelial cell damage caused by oxidative stress and inflammation. These findings suggest that PAO-βCD@pellet offers a promising targeted treatment strategy for inflammatory bowel disease (IBD) with enhanced stability, bioavailability, and therapeutic outcomes.
2026, 37(5): 111318
doi: 10.1016/j.cclet.2025.111318
摘要:
Alzheimer's disease (AD) is a chronic, progressive neurodegenerative disorder with no effective therapeutic agents currently available. Inhibiting phosphodiesterase 4 (PDE4) has emerged as a promising strategy for AD treatment. In this study, we employed a synergistic approach combining generative recurrent neural network (RNN)-driven combinatorial compound design, virtual screening, and structure-activity relationship (SAR) analysis to discover novel PDE4 inhibitors. Utilizing α-mangostin as a hit compound (half maximal inhibitory concentration (IC50) = 1.31 µmol/L), we identified a novel PDE4 inhibitor, 13d (IC50 = 72.8 nmol/L) with moderate liver microsomal stability (rat liver microsomes (RLM), t1/2 = 32.4 min). In vitro activity results indicated that 13d exhibited favorable anti-inflammatory effects and promising neuroprotective activity. In vivo experiments demonstrated that 13d significantly improved AlCl3-induced zebrafish AD model by inhibiting PDE4 and reducing inflammatory cytokine. Further, 13d significantly alleviated AlCl3/d-galactose-induced AD mouse model. These findings highlight the potent PDE4 inhibitor 13d with promising anti-AD activity, underscoring the potential of artificial intelligence-driven drug discovery for novel therapeutic agents for AD.
Alzheimer's disease (AD) is a chronic, progressive neurodegenerative disorder with no effective therapeutic agents currently available. Inhibiting phosphodiesterase 4 (PDE4) has emerged as a promising strategy for AD treatment. In this study, we employed a synergistic approach combining generative recurrent neural network (RNN)-driven combinatorial compound design, virtual screening, and structure-activity relationship (SAR) analysis to discover novel PDE4 inhibitors. Utilizing α-mangostin as a hit compound (half maximal inhibitory concentration (IC50) = 1.31 µmol/L), we identified a novel PDE4 inhibitor, 13d (IC50 = 72.8 nmol/L) with moderate liver microsomal stability (rat liver microsomes (RLM), t1/2 = 32.4 min). In vitro activity results indicated that 13d exhibited favorable anti-inflammatory effects and promising neuroprotective activity. In vivo experiments demonstrated that 13d significantly improved AlCl3-induced zebrafish AD model by inhibiting PDE4 and reducing inflammatory cytokine. Further, 13d significantly alleviated AlCl3/d-galactose-induced AD mouse model. These findings highlight the potent PDE4 inhibitor 13d with promising anti-AD activity, underscoring the potential of artificial intelligence-driven drug discovery for novel therapeutic agents for AD.
2026, 37(5): 111324
doi: 10.1016/j.cclet.2025.111324
摘要:
Tumor-associated carbohydrate antigen (TACA)-based cancer vaccines face clinical challenges due to heterogeneous TACA expression, which compromises antibody-mediated tumor recognition and leads to suboptimal therapeutic outcomes. To address this limitation, we report a combined strategy that integrates vaccination with TACA-based antibody-recruiting molecules. This approach simultaneously redirects anti-TACA antibodies to tumor cells expressing a secondary target, thereby enhancing the efficacy of TACA-based vaccines. Using sialyl-Tn (sTn) as a model TACA and epidermal growth factor receptor (EGFR) and human epidermal growth factor receptor 2 (HER2) as model protein targets, we designed two nanobody (Nb)-sTn conjugates as TACA-based antibody-recruiting molecules: EGFR-targeting 7D12-sTn and HER2-targeting C7b-sTn. These conjugates were synthesized via sortase A-mediated ligation and demonstrated strong binding profiles. Importantly, they effectively redirected anti-sTn antibodies, generated by the Theratope vaccine, to target cells in situ, significantly improving the recognition of tumor cells by anti-sTn antibodies. The synergistic potential of these conjugates in amplifying the therapeutic effect of the sTn-KLH vaccine was further validated through complement-dependent cytotoxicity assays. This innovative strategy represents a highly promising approach to overcome the clinical challenges posed by TACA heterogeneity in cancer vaccine development.
Tumor-associated carbohydrate antigen (TACA)-based cancer vaccines face clinical challenges due to heterogeneous TACA expression, which compromises antibody-mediated tumor recognition and leads to suboptimal therapeutic outcomes. To address this limitation, we report a combined strategy that integrates vaccination with TACA-based antibody-recruiting molecules. This approach simultaneously redirects anti-TACA antibodies to tumor cells expressing a secondary target, thereby enhancing the efficacy of TACA-based vaccines. Using sialyl-Tn (sTn) as a model TACA and epidermal growth factor receptor (EGFR) and human epidermal growth factor receptor 2 (HER2) as model protein targets, we designed two nanobody (Nb)-sTn conjugates as TACA-based antibody-recruiting molecules: EGFR-targeting 7D12-sTn and HER2-targeting C7b-sTn. These conjugates were synthesized via sortase A-mediated ligation and demonstrated strong binding profiles. Importantly, they effectively redirected anti-sTn antibodies, generated by the Theratope vaccine, to target cells in situ, significantly improving the recognition of tumor cells by anti-sTn antibodies. The synergistic potential of these conjugates in amplifying the therapeutic effect of the sTn-KLH vaccine was further validated through complement-dependent cytotoxicity assays. This innovative strategy represents a highly promising approach to overcome the clinical challenges posed by TACA heterogeneity in cancer vaccine development.
2026, 37(5): 111334
doi: 10.1016/j.cclet.2025.111334
摘要:
The rapid proliferation of tumor cells is driven by metabolic reprogramming and redox regulation. Real-time monitoring of glutathione (GSH)/adenosine-5′-triphosphate (ATP) provides a dynamic perspective for tumor metabolism and is crucial for guiding precision treatment. We report a dual-site activatable fluorescent probe M901 for simultaneously detecting GSH and ATP without spectral overlap, and the detection range (GSH: 0–7 mmol/L, ATP: 0–6.5 mmol/L) matching the physiological concentration range. Based on this, M901 visualizes a bidirectional regulatory relationship between ATP synthesis↓ (energy imbalance) ↔ electron transport chain dysfunction ↔ reactive oxygen species (ROS)↑ ↔ GSH↓ (oxidative stress). Additionally, M901 reveals for the first time the dynamic compensatory mechanism between GSH and ATP in cellular oxidative stress induced by the inhibition of solute carrier family 7 member 11 (SLC7A11) or glutathione peroxidase 4 (GPX4). In vivo imaging further confirms oxidative stress and mitochondrial dysfunction are core pathological mechanisms leading to liver injury, with treatment efficacy positively correlated with GSH/ATP levels. Importantly, the dynamic visualization of GSH/ATP by M901 enables real-time evaluation of the anti-tumor effects of ferroptosis inducers and cisplatin, guiding successful precision resection of invasive malignant tumors (negative margins <0.2 mm). This study confirms the potential of M901 as a clinical visualization tool for diagnosing, treating and monitoring a variety of diseases.
The rapid proliferation of tumor cells is driven by metabolic reprogramming and redox regulation. Real-time monitoring of glutathione (GSH)/adenosine-5′-triphosphate (ATP) provides a dynamic perspective for tumor metabolism and is crucial for guiding precision treatment. We report a dual-site activatable fluorescent probe M901 for simultaneously detecting GSH and ATP without spectral overlap, and the detection range (GSH: 0–7 mmol/L, ATP: 0–6.5 mmol/L) matching the physiological concentration range. Based on this, M901 visualizes a bidirectional regulatory relationship between ATP synthesis↓ (energy imbalance) ↔ electron transport chain dysfunction ↔ reactive oxygen species (ROS)↑ ↔ GSH↓ (oxidative stress). Additionally, M901 reveals for the first time the dynamic compensatory mechanism between GSH and ATP in cellular oxidative stress induced by the inhibition of solute carrier family 7 member 11 (SLC7A11) or glutathione peroxidase 4 (GPX4). In vivo imaging further confirms oxidative stress and mitochondrial dysfunction are core pathological mechanisms leading to liver injury, with treatment efficacy positively correlated with GSH/ATP levels. Importantly, the dynamic visualization of GSH/ATP by M901 enables real-time evaluation of the anti-tumor effects of ferroptosis inducers and cisplatin, guiding successful precision resection of invasive malignant tumors (negative margins <0.2 mm). This study confirms the potential of M901 as a clinical visualization tool for diagnosing, treating and monitoring a variety of diseases.
2026, 37(5): 111336
doi: 10.1016/j.cclet.2025.111336
摘要:
Molecular networking-guided chemical investigation of the Euphorbia endophyte Malbranchea umbrina D16 led to the isolation of 14 novel unusually cyclized triterpenoids (UCT) involving three different skeletal types. Compounds 1–10 are tricyclic triterpenoids featuring a 1-cyclohexyloctahydro-1H-indene core, in which 1 incoporates an unusual 7,7-dimethyl-6,8-dioxabicyclo[3.1.2]octane motif. Compounds 11–13 represent a rare class of bicyclic triterpenes (6/5 ring system) containing various O-heterocycles at the side chain. Compound 14 is an acyclic triterpenoid with O-heterocycles at both ends. Their structures were assigned by spectroscopic, chemical, computational, and crystallographic means, which also allowed the stereochemical revisions of three previously reported analogues. Compound 1 significantly inhibited the adipogenesis in 3T3-L1 adipocytes via activating the AMP-activated protein kinase (AMPK) signalling.
Molecular networking-guided chemical investigation of the Euphorbia endophyte Malbranchea umbrina D16 led to the isolation of 14 novel unusually cyclized triterpenoids (UCT) involving three different skeletal types. Compounds 1–10 are tricyclic triterpenoids featuring a 1-cyclohexyloctahydro-1H-indene core, in which 1 incoporates an unusual 7,7-dimethyl-6,8-dioxabicyclo[3.1.2]octane motif. Compounds 11–13 represent a rare class of bicyclic triterpenes (6/5 ring system) containing various O-heterocycles at the side chain. Compound 14 is an acyclic triterpenoid with O-heterocycles at both ends. Their structures were assigned by spectroscopic, chemical, computational, and crystallographic means, which also allowed the stereochemical revisions of three previously reported analogues. Compound 1 significantly inhibited the adipogenesis in 3T3-L1 adipocytes via activating the AMP-activated protein kinase (AMPK) signalling.
2026, 37(5): 111337
doi: 10.1016/j.cclet.2025.111337
摘要:
Ferroptosis is a cell death pathway that plays a crucial role in numerous biological processes. Although closely related to ferrous ion, the execution of ferroptosis was found to be impacted by zinc ion (Zn2+) in recent years. However, most of the related researches focused on the effects of exogenously added Zn2+, while the fundamental understanding of endogenous Zn2+ during ferroptosis still needs further exploration. Herein, a ratiometric fluorescent probe based on pyridine-substituted boron dipyrromethene (BODIPY) fluorophore (BDP-p) was designed to track the endogenous Zn2+ in cells during ferroptosis process. Zn2+ coordination induced an enhancement on the intramolecular charge transfer (ICT), leading to an obvious red shift from 563 nm to 594 nm. In A549 cells, we found fluorescence ratio of the probe elevated in some discrete regions during erastin induced ferroptosis, and this change followed the same trend as the reactive oxygen species (ROS) level. The results suggested that the Zn2+ would be localized in some discrete areas in A549 cells during ferroptosis. This work not only provided a reliable design strategy for developing ratiometric probes of Zn2+, but also supplemented the current understanding of the non-negligible role of Zn2+ in ferroptosis.
Ferroptosis is a cell death pathway that plays a crucial role in numerous biological processes. Although closely related to ferrous ion, the execution of ferroptosis was found to be impacted by zinc ion (Zn2+) in recent years. However, most of the related researches focused on the effects of exogenously added Zn2+, while the fundamental understanding of endogenous Zn2+ during ferroptosis still needs further exploration. Herein, a ratiometric fluorescent probe based on pyridine-substituted boron dipyrromethene (BODIPY) fluorophore (BDP-p) was designed to track the endogenous Zn2+ in cells during ferroptosis process. Zn2+ coordination induced an enhancement on the intramolecular charge transfer (ICT), leading to an obvious red shift from 563 nm to 594 nm. In A549 cells, we found fluorescence ratio of the probe elevated in some discrete regions during erastin induced ferroptosis, and this change followed the same trend as the reactive oxygen species (ROS) level. The results suggested that the Zn2+ would be localized in some discrete areas in A549 cells during ferroptosis. This work not only provided a reliable design strategy for developing ratiometric probes of Zn2+, but also supplemented the current understanding of the non-negligible role of Zn2+ in ferroptosis.
2026, 37(5): 111338
doi: 10.1016/j.cclet.2025.111338
摘要:
Bacteria and stains on tooth and various dental materials severely harm dental health and beauty and require feasible solutions. In this study, a simple strategy was developed to produce nano-coating on different substrates for persistent antibacterial and whitening. The coating is formed by the lysozyme (Lys), hemoglobin (Hb), and glucose oxidase (GOD) via co-assembly, in which the phase transition of Lys initiated the co-assembly to anchor other two proteins. During therapy, the GOD continuously oxidizes glucose in the oral environment to cut off the nutrition of bacteria meanwhile generating H2O2, which would be further catalyzed by the ferrous ions in Hb to produce reactive oxygen species (ROS) for effective decomposition of surrounding bacteria and stains. Moreover, the Hb can perform persistent release of oxygen, which not only enhances the efficiency of glucose oxidation to produce more ROS but directly suppresses anaerobic bacteria via reversing the local hypoxia environment in the mouth. The experimental results indicated that our strategy is able to form nano-film of proteins both on the surface of dental orthosis and human tooth, which further causes obvious reduction of the bacteria not only on the coated substrate but in the surrounding tissue with up to 100% of the bacteriostatic rate. In addition, both the dental orthosis and human tooth were also rapidly cleaned due to the local ROS generation, leading to a sustained anti-staining property in the long term.
Bacteria and stains on tooth and various dental materials severely harm dental health and beauty and require feasible solutions. In this study, a simple strategy was developed to produce nano-coating on different substrates for persistent antibacterial and whitening. The coating is formed by the lysozyme (Lys), hemoglobin (Hb), and glucose oxidase (GOD) via co-assembly, in which the phase transition of Lys initiated the co-assembly to anchor other two proteins. During therapy, the GOD continuously oxidizes glucose in the oral environment to cut off the nutrition of bacteria meanwhile generating H2O2, which would be further catalyzed by the ferrous ions in Hb to produce reactive oxygen species (ROS) for effective decomposition of surrounding bacteria and stains. Moreover, the Hb can perform persistent release of oxygen, which not only enhances the efficiency of glucose oxidation to produce more ROS but directly suppresses anaerobic bacteria via reversing the local hypoxia environment in the mouth. The experimental results indicated that our strategy is able to form nano-film of proteins both on the surface of dental orthosis and human tooth, which further causes obvious reduction of the bacteria not only on the coated substrate but in the surrounding tissue with up to 100% of the bacteriostatic rate. In addition, both the dental orthosis and human tooth were also rapidly cleaned due to the local ROS generation, leading to a sustained anti-staining property in the long term.
2026, 37(5): 111343
doi: 10.1016/j.cclet.2025.111343
摘要:
Molecular glass refers to amorphous rigid small molecules with certain polymer-like properties. Herein, spirobixanthene is first adopted as the backbone to develop negative photoresist X4Ep with four epoxy moieties. F4Ep based on classical spirobifluorene is also synthesized as a benchmark against X4Ep. Both exhibit good thermostability and similar sensitivity. However, in e-beam lithography, performances of X4Ep completely surpass F4Ep. F4Ep lithography shows inevitably minor bridges no matter how we optimize process conditions. The relatively poor performances of F4Ep may be probably ascribed to its partial crystallization tendency inducing uneven photoacid generator (PAG) distribution and uneven acid diffusion, which thus promotes nonuniform epoxy crosslink to form rough patterns. X4Ep readily achieves dense lines without any defects. The superiority of X4Ep to F4Ep can be ascribed to the exceptional yet apparent structural distortion and asymmetry of spirobixanthene, which guarantees a perfect amorphous state and uniform crosslink. Finally, the optimal line/space (L/S) pattern with half pitch (HP) of 25 nm and line edge roughness (LER) of 2.7 nm is achieved. Therefore, spirobixanthene is a valuable molecular glass backbone for high-performance photoresists in the future.
Molecular glass refers to amorphous rigid small molecules with certain polymer-like properties. Herein, spirobixanthene is first adopted as the backbone to develop negative photoresist X4Ep with four epoxy moieties. F4Ep based on classical spirobifluorene is also synthesized as a benchmark against X4Ep. Both exhibit good thermostability and similar sensitivity. However, in e-beam lithography, performances of X4Ep completely surpass F4Ep. F4Ep lithography shows inevitably minor bridges no matter how we optimize process conditions. The relatively poor performances of F4Ep may be probably ascribed to its partial crystallization tendency inducing uneven photoacid generator (PAG) distribution and uneven acid diffusion, which thus promotes nonuniform epoxy crosslink to form rough patterns. X4Ep readily achieves dense lines without any defects. The superiority of X4Ep to F4Ep can be ascribed to the exceptional yet apparent structural distortion and asymmetry of spirobixanthene, which guarantees a perfect amorphous state and uniform crosslink. Finally, the optimal line/space (L/S) pattern with half pitch (HP) of 25 nm and line edge roughness (LER) of 2.7 nm is achieved. Therefore, spirobixanthene is a valuable molecular glass backbone for high-performance photoresists in the future.
2026, 37(5): 111347
doi: 10.1016/j.cclet.2025.111347
摘要:
Layered double hydroxides (LDHs) hold great promise for flexible solid-state supercapacitors owing to their high theoretical capacitance and distinctive architecture. However, their proneness to agglomeration and poor electrical conductivity have long hindered the manifestation of outstanding electrochemical performance. In a groundbreaking approach, we have engineered a hierarchical carbon nanofiber-based NiCo2S4/NiCo-LDH/C nanostructure array. The meticulously crafted hierarchical structure not only imparts remarkable stability to the electrode but also ingeniously harnesses the synergistic interplay among materials. Through density functional theory calculations, we have precisely identified and verified the active sites for charge transfer, unveiling a new understanding of the underlying mechanisms. This unique structure significantly facilitates ion transfer in the vicinity of NiCo-LDH, substantially elevates electrical conductivity, and notably increases the adsorption capacity of OH-. Moreover, it gives a substantial boost to the quantum capacitance. As a result, the electrode showcases a high specific capacitance of 1838.3 F/g. This research pioneers an effective and versatile strategy that can be readily applied to the majority of LDHs, opening up new avenues for enhancing their efficiency of supercapacitor materials.
Layered double hydroxides (LDHs) hold great promise for flexible solid-state supercapacitors owing to their high theoretical capacitance and distinctive architecture. However, their proneness to agglomeration and poor electrical conductivity have long hindered the manifestation of outstanding electrochemical performance. In a groundbreaking approach, we have engineered a hierarchical carbon nanofiber-based NiCo2S4/NiCo-LDH/C nanostructure array. The meticulously crafted hierarchical structure not only imparts remarkable stability to the electrode but also ingeniously harnesses the synergistic interplay among materials. Through density functional theory calculations, we have precisely identified and verified the active sites for charge transfer, unveiling a new understanding of the underlying mechanisms. This unique structure significantly facilitates ion transfer in the vicinity of NiCo-LDH, substantially elevates electrical conductivity, and notably increases the adsorption capacity of OH-. Moreover, it gives a substantial boost to the quantum capacitance. As a result, the electrode showcases a high specific capacitance of 1838.3 F/g. This research pioneers an effective and versatile strategy that can be readily applied to the majority of LDHs, opening up new avenues for enhancing their efficiency of supercapacitor materials.
2026, 37(5): 111350
doi: 10.1016/j.cclet.2025.111350
摘要:
The advent of the most representative commercially available formulations of paclitaxel, Taxol and Abraxane®, resolved the intravenous challenge of paclitaxel by increasing the water solubility. However, the severe excipient-related toxicity and poor stability of Taxol, along with the low drug loading (10%), complex preparation processes, and poor tumor selectivity of Abraxane®, present significant clinical dilemma. To overcome the challenges, 16-methylheptadecanoic acid (16-MH), with excellent biocompatibility was selected as the assembly module. The paclitaxel-16-MH prodrug nanoassemblies (PSSMH NPs) were constructed by conjugating 16-MH with redox-sensitive disulfide bonds and paclitaxel through an ethylene glycol. PSSMH NPs featured the advantages of easy preparation, high drug loading (> 50%) and superior stability (stable storage for 60 days at 25 ℃). Notably, the area under the concentration−time curve (AUC0–24 h) of PSSMH NPs was 14.95-fold compared with Taxol, indicating a significant improvement in the in vivo fate of paclitaxel. Moreover, the existence of redox-sensitive disulfide bonds endowed PSSMH NPs with increased tumor selectivity, resulting in exceptional tolerance and antitumor efficacy. Overall, the redox-triggered prodrug nano-system with high tumor selectivity and biocompatibility exhibits substantial potential for clinical translation.
The advent of the most representative commercially available formulations of paclitaxel, Taxol and Abraxane®, resolved the intravenous challenge of paclitaxel by increasing the water solubility. However, the severe excipient-related toxicity and poor stability of Taxol, along with the low drug loading (10%), complex preparation processes, and poor tumor selectivity of Abraxane®, present significant clinical dilemma. To overcome the challenges, 16-methylheptadecanoic acid (16-MH), with excellent biocompatibility was selected as the assembly module. The paclitaxel-16-MH prodrug nanoassemblies (PSSMH NPs) were constructed by conjugating 16-MH with redox-sensitive disulfide bonds and paclitaxel through an ethylene glycol. PSSMH NPs featured the advantages of easy preparation, high drug loading (> 50%) and superior stability (stable storage for 60 days at 25 ℃). Notably, the area under the concentration−time curve (AUC0–24 h) of PSSMH NPs was 14.95-fold compared with Taxol, indicating a significant improvement in the in vivo fate of paclitaxel. Moreover, the existence of redox-sensitive disulfide bonds endowed PSSMH NPs with increased tumor selectivity, resulting in exceptional tolerance and antitumor efficacy. Overall, the redox-triggered prodrug nano-system with high tumor selectivity and biocompatibility exhibits substantial potential for clinical translation.
2026, 37(5): 111356
doi: 10.1016/j.cclet.2025.111356
摘要:
The escalating threat of antimicrobial resistance necessitates advanced tools for rapid and selective antibiotic detection in environmental systems. Herein, we report polyphenol-derived carbon dots (P-CDs) synthesized via a one-step solvothermal method using polyphenols and citric acid, enabling dual-mode detection of tetracyclines and quinolones through pH-tunable fluorescence. The P-CDs exhibit distinct fluorescence quenching for tetracyclines (e.g., oxytetracycline (OTC)) and enhancement for quinolones (e.g., norfloxacin (NOR)), driven by synergistic multiple molecular interactions facilitated by surface phenolic groups. With detection limits of 8.19 µmol/L (OTC) and 5.27 µmol/L (NOR), P-CDs achieve 6-fold higher sensitivity compared to conventional carbon dots. Their pH adaptability (pH 2–12), specificity (> 90% selectivity against seven antibiotic classes), and robust performance in real water matrices (e.g., river water and wastewater) underscore their potential as eco-friendly sensors for on-site environmental monitoring. This work highlights a versatile platform to address antibiotic contamination and advance public health safety.
The escalating threat of antimicrobial resistance necessitates advanced tools for rapid and selective antibiotic detection in environmental systems. Herein, we report polyphenol-derived carbon dots (P-CDs) synthesized via a one-step solvothermal method using polyphenols and citric acid, enabling dual-mode detection of tetracyclines and quinolones through pH-tunable fluorescence. The P-CDs exhibit distinct fluorescence quenching for tetracyclines (e.g., oxytetracycline (OTC)) and enhancement for quinolones (e.g., norfloxacin (NOR)), driven by synergistic multiple molecular interactions facilitated by surface phenolic groups. With detection limits of 8.19 µmol/L (OTC) and 5.27 µmol/L (NOR), P-CDs achieve 6-fold higher sensitivity compared to conventional carbon dots. Their pH adaptability (pH 2–12), specificity (> 90% selectivity against seven antibiotic classes), and robust performance in real water matrices (e.g., river water and wastewater) underscore their potential as eco-friendly sensors for on-site environmental monitoring. This work highlights a versatile platform to address antibiotic contamination and advance public health safety.
2026, 37(5): 111381
doi: 10.1016/j.cclet.2025.111381
摘要:
Natural products bearing a bicyclo[3.2.2]nonane motif pose a considerable challenge to chemical synthesis. We developed a europium-promoted inverse-electron-demand Diels–Alder reaction of benzo[2,3]tropone derivatives with electron-rich olefins, which offers an expeditious approach to densely substituted bicyclo[3.2.2]nonanes. This method enabled the concise synthesis of a tetracyclic amine, subsequently identified as a downstream suppressor of autophagy.
Natural products bearing a bicyclo[3.2.2]nonane motif pose a considerable challenge to chemical synthesis. We developed a europium-promoted inverse-electron-demand Diels–Alder reaction of benzo[2,3]tropone derivatives with electron-rich olefins, which offers an expeditious approach to densely substituted bicyclo[3.2.2]nonanes. This method enabled the concise synthesis of a tetracyclic amine, subsequently identified as a downstream suppressor of autophagy.
2026, 37(5): 111399
doi: 10.1016/j.cclet.2025.111399
摘要:
Immunotherapy has emerged as a promising strategy for combating tumor metastasis and recurrence, however, its efficacy is often hampered by the immunosuppressive tumor microenvironment (TME). The integration of nanomedicine-based photothermal therapy (PTT) with immunotherapy offers great potential to reshape the immune landscape, thereby enhancing immune responses and therapeutic outcomes. Nevertheless, conventional hyperthermia may induce heat-related damage and excessive inflammation in normal tissues. To address this challenge, we developed a novel therapeutic platform that combines tumor-specific delivery of melittin (MLT) with mild PTT using two-dimensional palladium nanosheets (Pd NSs). This approach allows for selective accumulation of MLT at tumor sites via the enhanced permeability and retention (EPR) effect and TME-responsive release, thereby maximizing antitumor efficacy while minimizing off-target toxicity. The resulting nanocomposite, MLT@Pd@PEG, exhibits excellent biocompatibility and efficient photothermal conversion under 808 nm laser irradiation. The acidic pH and localized heat in the TME synergistically trigger the controlled release of MLT, which disrupts cancer cell membranes and promotes tumor cell apoptosis. Moreover, this treatment facilitates the release of tumor-associated antigens and danger-associated molecular patterns (DAMPs), thereby activating cytotoxic T lymphocytes and natural killer (NK) cells. In vivo studies demonstrate that the combination of immune checkpoint blockade and MLT@Pd@PEG not only eradicates primary and distant tumors in bilateral tumor-bearing mouse models but also prevents tumor recurrence and metastasis by inducing durable immune memory. This comprehensive strategy integrating precise MLT delivery with mild PTT holds significant promise for advancing next-generation cancer immunotherapy.
Immunotherapy has emerged as a promising strategy for combating tumor metastasis and recurrence, however, its efficacy is often hampered by the immunosuppressive tumor microenvironment (TME). The integration of nanomedicine-based photothermal therapy (PTT) with immunotherapy offers great potential to reshape the immune landscape, thereby enhancing immune responses and therapeutic outcomes. Nevertheless, conventional hyperthermia may induce heat-related damage and excessive inflammation in normal tissues. To address this challenge, we developed a novel therapeutic platform that combines tumor-specific delivery of melittin (MLT) with mild PTT using two-dimensional palladium nanosheets (Pd NSs). This approach allows for selective accumulation of MLT at tumor sites via the enhanced permeability and retention (EPR) effect and TME-responsive release, thereby maximizing antitumor efficacy while minimizing off-target toxicity. The resulting nanocomposite, MLT@Pd@PEG, exhibits excellent biocompatibility and efficient photothermal conversion under 808 nm laser irradiation. The acidic pH and localized heat in the TME synergistically trigger the controlled release of MLT, which disrupts cancer cell membranes and promotes tumor cell apoptosis. Moreover, this treatment facilitates the release of tumor-associated antigens and danger-associated molecular patterns (DAMPs), thereby activating cytotoxic T lymphocytes and natural killer (NK) cells. In vivo studies demonstrate that the combination of immune checkpoint blockade and MLT@Pd@PEG not only eradicates primary and distant tumors in bilateral tumor-bearing mouse models but also prevents tumor recurrence and metastasis by inducing durable immune memory. This comprehensive strategy integrating precise MLT delivery with mild PTT holds significant promise for advancing next-generation cancer immunotherapy.
2026, 37(5): 111401
doi: 10.1016/j.cclet.2025.111401
摘要:
In the treatment of B-cell lymphoma, chemotherapy as a monotherapy encounters significant challenges like drug resistance, side effects, and limited cytotoxicity. A novel strategy combining chemotherapy and photothermal therapy uses nanomaterials to convert light into heat, locally heating tumor tissues to induce thermal ablation while enhancing the effectiveness of chemotherapeutic agents and reducing toxic side effects on normal cells. Here, we developed a multifunctional black phosphorus nanosheets (BP NSs) for chemo-photothermal synergistic therapy of lymphoma. BP NSs were synthesized from bulk black phosphorus crystal powders utilizing a modified liquid exfoliation technique and functionalized with polyethylene glycol (PEG) to improve stability. The PEGylated BP NSs were loaded with two chemotherapeutic agents, gemcitabine (Gem) and doxorubicin (DOX), forming GD-BP@PEG NSs. The nanosheets exhibit excellent physical stability, efficient photothermal conversion, and pH/near-infrared (NIR) dual-responsive drug release. In vitro cell experiments demonstrated that GD-BP@PEG NSs significantly increased cytotoxicity and apoptosis, especially with NIR laser irradiation. Furthermore, in vivo studies in A20 lymphoma-bearing BALB/c nude mice revealed GD-BP@PEG NSs passively accumulated with high concentrations at the tumor site, efficiently inhibiting lymphoma growth with minimal systemic toxicity, demonstrating significant advantages over single treatments of chemotherapy or photothermal therapy alone. In summary, this pH/NIR dual-triggered BP NSs system could serve as a promising nanoplatform for chemo-photothermal synergistic treatment of B-cell lymphoma.
In the treatment of B-cell lymphoma, chemotherapy as a monotherapy encounters significant challenges like drug resistance, side effects, and limited cytotoxicity. A novel strategy combining chemotherapy and photothermal therapy uses nanomaterials to convert light into heat, locally heating tumor tissues to induce thermal ablation while enhancing the effectiveness of chemotherapeutic agents and reducing toxic side effects on normal cells. Here, we developed a multifunctional black phosphorus nanosheets (BP NSs) for chemo-photothermal synergistic therapy of lymphoma. BP NSs were synthesized from bulk black phosphorus crystal powders utilizing a modified liquid exfoliation technique and functionalized with polyethylene glycol (PEG) to improve stability. The PEGylated BP NSs were loaded with two chemotherapeutic agents, gemcitabine (Gem) and doxorubicin (DOX), forming GD-BP@PEG NSs. The nanosheets exhibit excellent physical stability, efficient photothermal conversion, and pH/near-infrared (NIR) dual-responsive drug release. In vitro cell experiments demonstrated that GD-BP@PEG NSs significantly increased cytotoxicity and apoptosis, especially with NIR laser irradiation. Furthermore, in vivo studies in A20 lymphoma-bearing BALB/c nude mice revealed GD-BP@PEG NSs passively accumulated with high concentrations at the tumor site, efficiently inhibiting lymphoma growth with minimal systemic toxicity, demonstrating significant advantages over single treatments of chemotherapy or photothermal therapy alone. In summary, this pH/NIR dual-triggered BP NSs system could serve as a promising nanoplatform for chemo-photothermal synergistic treatment of B-cell lymphoma.
2026, 37(5): 111403
doi: 10.1016/j.cclet.2025.111403
摘要:
The low tumor immunogenicity, high immunosuppressive microenvironment, and off-target toxicity severely limit the efficiency of the cyclic guanosine monophosphate-adenosine monophosphate synthase-stimulator of interferon genes (cGAS-STING) pathway that plays an important role in tumor immunotherapy. We herein develop a multifunctional nano-assembly with tumor targeting, double-stranded DNA (dsDNA) releasing, Mn2+ sensitizing and immune microenvironment reprogramming capabilities for improving cGAS-STING to bridge innate and adaptive immunity. The drug-free nano-assembly composed of organic AIE-type photosensitizer and MnO2 can improve the tumor immune microenvironment by consuming glutathione and producing oxygen in the presence of H2O2, concurrently enhancing the release of damaged dsDNA and sensitizing the cGAS by controlled release of Mn2+ to magnify cGAS-STING immunity. In vivo experiments reveal that the multi-mode synergistic activation of STING pathway at the headstream can not only damage the primary tumors to amplify innate immunity, but also facilitate the maturation of dendritic cells, infiltration of cytotoxic T lymphocytes and expansion of adaptive immunity to inhibit primary tumor metastasis and recurrence in the long term.
The low tumor immunogenicity, high immunosuppressive microenvironment, and off-target toxicity severely limit the efficiency of the cyclic guanosine monophosphate-adenosine monophosphate synthase-stimulator of interferon genes (cGAS-STING) pathway that plays an important role in tumor immunotherapy. We herein develop a multifunctional nano-assembly with tumor targeting, double-stranded DNA (dsDNA) releasing, Mn2+ sensitizing and immune microenvironment reprogramming capabilities for improving cGAS-STING to bridge innate and adaptive immunity. The drug-free nano-assembly composed of organic AIE-type photosensitizer and MnO2 can improve the tumor immune microenvironment by consuming glutathione and producing oxygen in the presence of H2O2, concurrently enhancing the release of damaged dsDNA and sensitizing the cGAS by controlled release of Mn2+ to magnify cGAS-STING immunity. In vivo experiments reveal that the multi-mode synergistic activation of STING pathway at the headstream can not only damage the primary tumors to amplify innate immunity, but also facilitate the maturation of dendritic cells, infiltration of cytotoxic T lymphocytes and expansion of adaptive immunity to inhibit primary tumor metastasis and recurrence in the long term.
2026, 37(5): 111405
doi: 10.1016/j.cclet.2025.111405
摘要:
Chiral phthalides are present in numerous natural products and bioactive molecules. Synthesizing phthalides from alkenes is an effective strategy. However, the challenges of facial-selectivity in the addition to Z/E mixed alkenes and diastereoselectivity at vicinal stereogenic centers have prevented the achievement of a highly selective stereoconvergent synthesis of chiral sulfonyl phthalides from Z/E alkene mixtures. Therefore, we have developed an efficient methodology for the stereoconvergent synthesis of chiral sulfonyl phthalides, using the Cu/PyBim catalytic system. This method enables the asymmetric construction of sulfonyl phthalides with multiple stereocenters for the first time. It exhibits broad applicability across various terminal and internal alkene substrates, and accommodates a diverse array of aryl, alkyl, and nitrogen radical precursors, all under exceptionally mild reaction conditions. The experimental results indicate that the reaction utilizes a Curtin-Hammett kinetic control strategy, leading to the stereoconvergent synthesis of Z/E internal alkene substrates with significant enantioselectivity and diastereoselectivity in the asymmetric construction of chiral sulfonyl phthalides.
Chiral phthalides are present in numerous natural products and bioactive molecules. Synthesizing phthalides from alkenes is an effective strategy. However, the challenges of facial-selectivity in the addition to Z/E mixed alkenes and diastereoselectivity at vicinal stereogenic centers have prevented the achievement of a highly selective stereoconvergent synthesis of chiral sulfonyl phthalides from Z/E alkene mixtures. Therefore, we have developed an efficient methodology for the stereoconvergent synthesis of chiral sulfonyl phthalides, using the Cu/PyBim catalytic system. This method enables the asymmetric construction of sulfonyl phthalides with multiple stereocenters for the first time. It exhibits broad applicability across various terminal and internal alkene substrates, and accommodates a diverse array of aryl, alkyl, and nitrogen radical precursors, all under exceptionally mild reaction conditions. The experimental results indicate that the reaction utilizes a Curtin-Hammett kinetic control strategy, leading to the stereoconvergent synthesis of Z/E internal alkene substrates with significant enantioselectivity and diastereoselectivity in the asymmetric construction of chiral sulfonyl phthalides.
2026, 37(5): 111407
doi: 10.1016/j.cclet.2025.111407
摘要:
Fluoroorganic chemistry is one of the most hectic areas of current chemical research, exerting a profound effect on the most vital industries such as medicine, pesticide, and material science. Synthesis of fluorine-containing organic molecules, particularly those that bear C(sp3)−F bonds, remains a great challenge in modern chemical synthesis. Herein, we disclose a new strategy for the construction of a carbon−fluorine quaternary center, which was accomplished with the silver(Ⅰ)-catalyzed intramolecular Wagner−Meerwein rearrangement fluorination of allylic gem-disubstituted alkene derivatives by using a hypervalent monofluoroiodine(Ⅲ) reagent 1 (AFBI). Interestingly, the tunable five/six-membered heterocycle selectivity is achieved by the intramolecular Wagner−Meerwein rearrangement fluorination via a judicious choice of the group R1 attached to the C−C double bond. This versatile strategy features simple starting materials, mild reaction conditions, good functional-group compatibility, high bond-forming efficiency (e.g., one C−F and one C−O bond), and excellent chemoselectivity. The proposed reaction mechanisms and the roles of the catalyst AgBF4 were understood by control experiments and density functional theory calculations.
Fluoroorganic chemistry is one of the most hectic areas of current chemical research, exerting a profound effect on the most vital industries such as medicine, pesticide, and material science. Synthesis of fluorine-containing organic molecules, particularly those that bear C(sp3)−F bonds, remains a great challenge in modern chemical synthesis. Herein, we disclose a new strategy for the construction of a carbon−fluorine quaternary center, which was accomplished with the silver(Ⅰ)-catalyzed intramolecular Wagner−Meerwein rearrangement fluorination of allylic gem-disubstituted alkene derivatives by using a hypervalent monofluoroiodine(Ⅲ) reagent 1 (AFBI). Interestingly, the tunable five/six-membered heterocycle selectivity is achieved by the intramolecular Wagner−Meerwein rearrangement fluorination via a judicious choice of the group R1 attached to the C−C double bond. This versatile strategy features simple starting materials, mild reaction conditions, good functional-group compatibility, high bond-forming efficiency (e.g., one C−F and one C−O bond), and excellent chemoselectivity. The proposed reaction mechanisms and the roles of the catalyst AgBF4 were understood by control experiments and density functional theory calculations.
2026, 37(5): 111419
doi: 10.1016/j.cclet.2025.111419
摘要:
Macrocyclic cascade supramolecular assembly could significantly enhance the fluorescence/phosphorescence resonance energy transfer (F/PRET) efficiency through macrocyclic and spatial dual confinement effect. Herein, we reported a cascade supramolecular assembly containing 6-bromoisoquinolinium-modified permethylated cyclodextrin (BQ-PCD), cucurbit[7]uril (CB[7]), and tetra(4-sulfonatophenyl)porphyrin (TPPS), in which the enhanced PRET from 6-bromoisoquinolinium (BQ) to TPPS could be achieved through the dual macrocyclic confinement for multicolor delayed luminescence and information encryption. In TPPS$\subset$BQ-PCD$\subset$CB[7], pure organic room temperature phosphorescence of BQ-PCD at 530 nm is induced by CB[7] macrocyclic confinement, which further transferred to TPPS via spatial confinement, achieving delayed fluorescence at 645 and 715 nm with high PRET efficiency and quantum yield (17.9%). Meanwhile, reversible TPPS concentration-dependent multicolor luminescence was achieved in presence of competitive guest (methionine peptide), followed by porphyrin-photosensitization process, being applied in information encryption. This research presents a facile strategy for efficient PRET through macrocyclic cascade confinement assembly.
Macrocyclic cascade supramolecular assembly could significantly enhance the fluorescence/phosphorescence resonance energy transfer (F/PRET) efficiency through macrocyclic and spatial dual confinement effect. Herein, we reported a cascade supramolecular assembly containing 6-bromoisoquinolinium-modified permethylated cyclodextrin (BQ-PCD), cucurbit[7]uril (CB[7]), and tetra(4-sulfonatophenyl)porphyrin (TPPS), in which the enhanced PRET from 6-bromoisoquinolinium (BQ) to TPPS could be achieved through the dual macrocyclic confinement for multicolor delayed luminescence and information encryption. In TPPS$\subset$BQ-PCD$\subset$CB[7], pure organic room temperature phosphorescence of BQ-PCD at 530 nm is induced by CB[7] macrocyclic confinement, which further transferred to TPPS via spatial confinement, achieving delayed fluorescence at 645 and 715 nm with high PRET efficiency and quantum yield (17.9%). Meanwhile, reversible TPPS concentration-dependent multicolor luminescence was achieved in presence of competitive guest (methionine peptide), followed by porphyrin-photosensitization process, being applied in information encryption. This research presents a facile strategy for efficient PRET through macrocyclic cascade confinement assembly.
2026, 37(5): 111426
doi: 10.1016/j.cclet.2025.111426
摘要:
The fabrication of three-component supramolecular organic frameworks (SOFs) is a considerable difficulty owing to the intricate noncovalent interactions and the constraints of current synthesis techniques. In this study, we designed and synthesized two photosensitive modules: a naphthalene-modified triphenylamine derivative (NA-TPA) as the donor unit, and a trimethylated viologen-modified triphenylamine (MV-TPA) as the acceptor unit. These modules can self-assemble into a novel two-dimensional SOF via encapsulation-enhanced donor-acceptor interactions with cucurbit[8]uril (CB[8]) in the aqueous solution. The resulting donor-acceptor SOF forms stable two-dimensional nanosheet structures in water. Compared to the individual monomers NA-TPA and MV-TPA, the SOF enhances electron transfer and significantly improves the generation of superoxide anion radicals (O2•−), which in turn effectively promotes the photocatalytic cyclization reaction between o-phenylenediamine and benzaldehyde in water, achieving a yield of up to 94%. This work offers valuable insights into the design and construction of three-component SOFs based on encapsulation-enhanced donor-acceptor interactions for photocatalytic applications.
The fabrication of three-component supramolecular organic frameworks (SOFs) is a considerable difficulty owing to the intricate noncovalent interactions and the constraints of current synthesis techniques. In this study, we designed and synthesized two photosensitive modules: a naphthalene-modified triphenylamine derivative (NA-TPA) as the donor unit, and a trimethylated viologen-modified triphenylamine (MV-TPA) as the acceptor unit. These modules can self-assemble into a novel two-dimensional SOF via encapsulation-enhanced donor-acceptor interactions with cucurbit[8]uril (CB[8]) in the aqueous solution. The resulting donor-acceptor SOF forms stable two-dimensional nanosheet structures in water. Compared to the individual monomers NA-TPA and MV-TPA, the SOF enhances electron transfer and significantly improves the generation of superoxide anion radicals (O2•−), which in turn effectively promotes the photocatalytic cyclization reaction between o-phenylenediamine and benzaldehyde in water, achieving a yield of up to 94%. This work offers valuable insights into the design and construction of three-component SOFs based on encapsulation-enhanced donor-acceptor interactions for photocatalytic applications.
2026, 37(5): 111429
doi: 10.1016/j.cclet.2025.111429
摘要:
The generation of transient radical species via carbon–metal bond homolysis is extremely useful, which can be harnessed to promote useful and selective radical-type transformations by the combination of transition metal catalysis. We herein establish a carbon–metal bond homolysis/recombination model for the formation of enantiomerically enriched carbon-metal species, which accounts for the Ni-catalyzed enantioconvergent carboxylation of racemic benzyl ammonium salts with CO2. Theoretical studies suggest a distinct pathway involving a stereoinvertive nucleophilic substitution-type oxidative addition of racemic benzyl ammonium salts to Ni(0), forming a racemic benzyl Ni(Ⅱ) intermediate. Subsequent C–Ni bond homolysis of one enantiomer enables the formation of a transient radical, followed by a dynamic rotation along C–C· bond and radical recombination forming another more thermodynamically favored enantiomer. Geometry analysis suggests less H–H repulsion between the benzyl group and chiral ligand in the more stable isomer. After the reduction and stereoretentive inner-sphere nucleophilic attack on CO2 process, the desired enantiomerically enriched carboxylic acid product is generated. ETS-NOCV analysis reveals a significant back-donation interaction between the dx2-y2 orbital of Ni atom and the unoccupied π* orbital of CO2 in inner-sphere transition state, thus effectively stabilizing the Ni–CO2 complex and facilitating subsequent C–C bond formation. The theoretical calculations provide critical insights into the systematic development of transition metal-catalyzed asymmetric carboxylation, highlighting significant potential for broad applications in synthetic organic chemistry.
The generation of transient radical species via carbon–metal bond homolysis is extremely useful, which can be harnessed to promote useful and selective radical-type transformations by the combination of transition metal catalysis. We herein establish a carbon–metal bond homolysis/recombination model for the formation of enantiomerically enriched carbon-metal species, which accounts for the Ni-catalyzed enantioconvergent carboxylation of racemic benzyl ammonium salts with CO2. Theoretical studies suggest a distinct pathway involving a stereoinvertive nucleophilic substitution-type oxidative addition of racemic benzyl ammonium salts to Ni(0), forming a racemic benzyl Ni(Ⅱ) intermediate. Subsequent C–Ni bond homolysis of one enantiomer enables the formation of a transient radical, followed by a dynamic rotation along C–C· bond and radical recombination forming another more thermodynamically favored enantiomer. Geometry analysis suggests less H–H repulsion between the benzyl group and chiral ligand in the more stable isomer. After the reduction and stereoretentive inner-sphere nucleophilic attack on CO2 process, the desired enantiomerically enriched carboxylic acid product is generated. ETS-NOCV analysis reveals a significant back-donation interaction between the dx2-y2 orbital of Ni atom and the unoccupied π* orbital of CO2 in inner-sphere transition state, thus effectively stabilizing the Ni–CO2 complex and facilitating subsequent C–C bond formation. The theoretical calculations provide critical insights into the systematic development of transition metal-catalyzed asymmetric carboxylation, highlighting significant potential for broad applications in synthetic organic chemistry.
2026, 37(5): 111430
doi: 10.1016/j.cclet.2025.111430
摘要:
Although C2-symmetric C–C atropisomeric diphosphines such as BINAP and SEGPHOS, have achieved tremendous success in enantioselective catalysis in recent centuries, developing diphosphines based on new structural scaffolds is still highly desirable. Here, C2-symmetric N–N atropisomeric diphosphines have been synthesized and comprehensively analyzed. These diphosphines exhibit excellent substituent-dependent tunable dihedral angles comparable to other useful electron-enriched diphosphines. With the aid of these newly developed diphosphines, the transition-metal catalyzed enantioselective dearomatization of heteroaryls is carried out to yield final products with excellent enantioselectivities, indicating their exceptional stereoinduction abilities.
Although C2-symmetric C–C atropisomeric diphosphines such as BINAP and SEGPHOS, have achieved tremendous success in enantioselective catalysis in recent centuries, developing diphosphines based on new structural scaffolds is still highly desirable. Here, C2-symmetric N–N atropisomeric diphosphines have been synthesized and comprehensively analyzed. These diphosphines exhibit excellent substituent-dependent tunable dihedral angles comparable to other useful electron-enriched diphosphines. With the aid of these newly developed diphosphines, the transition-metal catalyzed enantioselective dearomatization of heteroaryls is carried out to yield final products with excellent enantioselectivities, indicating their exceptional stereoinduction abilities.
2026, 37(5): 111442
doi: 10.1016/j.cclet.2025.111442
摘要:
Chiral 1,2,3,4-tetrahydro-1,5-naphthyridines are frequently encountered in many bioactive compounds. However, the methods for their asymmetric synthesis are quite limited. Herein, we developed a straightforward and efficient route to enantioenriched tetrahydro-1,5-naphthyridines from pyridine derivatives tethered with alkene moieties (34 examples, up to 99% yield, 93% ee). The reaction proceeded via Csp2–H activation pathway initiated by site-selective deprotonation with the assistance of La[N(SiMe3)2]3/PyBox, followed by alkene insertion into the resulting La-aryl bond. The potential utility of the current method in organic synthesis was highlighted by scale-up synthesis of chiral product and its further transformations. Moreover, some of the products show a pronounced inhibitory effect on A549 cell activity. In addition, experimental studies and DFT calculations were carried out to elucidate the origin of enantiocontrol.
Chiral 1,2,3,4-tetrahydro-1,5-naphthyridines are frequently encountered in many bioactive compounds. However, the methods for their asymmetric synthesis are quite limited. Herein, we developed a straightforward and efficient route to enantioenriched tetrahydro-1,5-naphthyridines from pyridine derivatives tethered with alkene moieties (34 examples, up to 99% yield, 93% ee). The reaction proceeded via Csp2–H activation pathway initiated by site-selective deprotonation with the assistance of La[N(SiMe3)2]3/PyBox, followed by alkene insertion into the resulting La-aryl bond. The potential utility of the current method in organic synthesis was highlighted by scale-up synthesis of chiral product and its further transformations. Moreover, some of the products show a pronounced inhibitory effect on A549 cell activity. In addition, experimental studies and DFT calculations were carried out to elucidate the origin of enantiocontrol.
2026, 37(5): 111443
doi: 10.1016/j.cclet.2025.111443
摘要:
A kind of inherently chiral molecular barrels were efficiently constructed by a directional cascade hooping strategy. This strategy involves the anchoring of three nonsymmetric connecting arms onto a cap-dissymmetric bis(tetraoxacalix[2]arene[2]triazine) cage core, followed by hooping via imine condensation and reduction to afford the target molecular barrels with well-defined connectivity. The precise and high-yielding synthesis stems from both the bidirectional Ctriazine-N bond flipping dynamics and the reversible nature of imine formation. The molecular barrels comprise a bis(tetraoxacalix[2]arene[2]triazine) core encircled by a 72-membered loop, forming three fan-shaped cavities with inherent chirality and multiple endo-functionalized sites. The existence of multiple diastereoisomeric conformers due to the restricted Ctriazine-N bond flipping by the constrained loop structure was revealed by variable-temperature NMR studies and DFT calculations.
A kind of inherently chiral molecular barrels were efficiently constructed by a directional cascade hooping strategy. This strategy involves the anchoring of three nonsymmetric connecting arms onto a cap-dissymmetric bis(tetraoxacalix[2]arene[2]triazine) cage core, followed by hooping via imine condensation and reduction to afford the target molecular barrels with well-defined connectivity. The precise and high-yielding synthesis stems from both the bidirectional Ctriazine-N bond flipping dynamics and the reversible nature of imine formation. The molecular barrels comprise a bis(tetraoxacalix[2]arene[2]triazine) core encircled by a 72-membered loop, forming three fan-shaped cavities with inherent chirality and multiple endo-functionalized sites. The existence of multiple diastereoisomeric conformers due to the restricted Ctriazine-N bond flipping by the constrained loop structure was revealed by variable-temperature NMR studies and DFT calculations.
2026, 37(5): 111454
doi: 10.1016/j.cclet.2025.111454
摘要:
The typical organic perylenetetracarboxylate (PTC) luminophore suffers from limited bio-application due to its aggregation-caused quenching (ACQ) induced undesirable electrochemiluminescence (ECL) efficiency in aqueous solution. Herein, the ECL emission of PTC was highly improved through the ingenious coordination of PTC (ligand) with Tb3+ (metal ion) to prepare the Tb-PTC metal-organic framework (Tb-PTC MOF), which prevented the π-π stacking and the aggregation of PTC molecules in a homogeneous phase. Moreover, we found that the ECL emission of Tb-PTC MOF was further enhanced by regulating its morphology, pore size and electron transfer ability using different solvents during its synthesis procedure. Notably, under the mixture of DMF, EtOH, and H2O (v/v/v, 1:1:1), a mesoporous Tb-PTC MOF exhibited an outstanding ECL intensity, which may be attributed to two reasons. Firstly, the mesopore and rough surface of Tb-PTC MOF (luminophore) provided abundant active sites and enlarged contact surfaces for S2O82– (coreactant). Secondly, Tb-PTC MOF with higher electron transfer ability could accelerate electron/hole recombination to enhance its ECL emission. Additionally, Tb-PTC MOF with excellent ECL performance was applied as a luminophore to fabricate an ultrasensitive ECL immunosensor for cardiac troponin Ⅰ (cTnI) detection, related to acute myocardial infarction. The constructed ECL immunosensor exhibited a satisfactory linear range (1 fg/mL − 20 ng/mL) and a low detection limit of 0.48 fg/mL. This study provides a new trend for the preparation of PTC-based nanomaterials with highly efficient ECL performance, broadening the scope for sensitive immunoassay in disease diagnosis.
The typical organic perylenetetracarboxylate (PTC) luminophore suffers from limited bio-application due to its aggregation-caused quenching (ACQ) induced undesirable electrochemiluminescence (ECL) efficiency in aqueous solution. Herein, the ECL emission of PTC was highly improved through the ingenious coordination of PTC (ligand) with Tb3+ (metal ion) to prepare the Tb-PTC metal-organic framework (Tb-PTC MOF), which prevented the π-π stacking and the aggregation of PTC molecules in a homogeneous phase. Moreover, we found that the ECL emission of Tb-PTC MOF was further enhanced by regulating its morphology, pore size and electron transfer ability using different solvents during its synthesis procedure. Notably, under the mixture of DMF, EtOH, and H2O (v/v/v, 1:1:1), a mesoporous Tb-PTC MOF exhibited an outstanding ECL intensity, which may be attributed to two reasons. Firstly, the mesopore and rough surface of Tb-PTC MOF (luminophore) provided abundant active sites and enlarged contact surfaces for S2O82– (coreactant). Secondly, Tb-PTC MOF with higher electron transfer ability could accelerate electron/hole recombination to enhance its ECL emission. Additionally, Tb-PTC MOF with excellent ECL performance was applied as a luminophore to fabricate an ultrasensitive ECL immunosensor for cardiac troponin Ⅰ (cTnI) detection, related to acute myocardial infarction. The constructed ECL immunosensor exhibited a satisfactory linear range (1 fg/mL − 20 ng/mL) and a low detection limit of 0.48 fg/mL. This study provides a new trend for the preparation of PTC-based nanomaterials with highly efficient ECL performance, broadening the scope for sensitive immunoassay in disease diagnosis.
2026, 37(5): 111461
doi: 10.1016/j.cclet.2025.111461
摘要:
Tertiary N–CF3 compounds have attracted intensive attention due to their great significance in discovery of new lead compounds, however, the synthesis of tertiary diaryl N–CF3 derivatives is still challenging. Herein, we successfully edit diaryl N–H into thiocarbamoyl fluorides with trifluoromethanesulfonyl chloride by use of a PⅢ/PⅤ redox catalyst, leading to the formation of series of diaryl N–CF3 with silver fluoride. In addition, this process is also highly efficient to dialkyl and alkylaryl secondary amines. The mechanism investigation illustrated that the use of hydrosilane is crucial to the success of this transformation. It acts as both terminal reductants to cycle the PⅢ/PⅤ couple and fluoride acceptor to promote the reaction between less reactive amine and thiocarbonyl difluoride intermediate.
Tertiary N–CF3 compounds have attracted intensive attention due to their great significance in discovery of new lead compounds, however, the synthesis of tertiary diaryl N–CF3 derivatives is still challenging. Herein, we successfully edit diaryl N–H into thiocarbamoyl fluorides with trifluoromethanesulfonyl chloride by use of a PⅢ/PⅤ redox catalyst, leading to the formation of series of diaryl N–CF3 with silver fluoride. In addition, this process is also highly efficient to dialkyl and alkylaryl secondary amines. The mechanism investigation illustrated that the use of hydrosilane is crucial to the success of this transformation. It acts as both terminal reductants to cycle the PⅢ/PⅤ couple and fluoride acceptor to promote the reaction between less reactive amine and thiocarbonyl difluoride intermediate.
2026, 37(5): 111484
doi: 10.1016/j.cclet.2025.111484
摘要:
The site-selective C(sp3)-H functionalization is of great importance in synthetic chemistry. However, γ-amino C(sp3)-H functionalization of aliphatic amines remains challenging. Herein, we develop an efficient γ-C(sp3)-H acylation of aliphatic amines by cooperative photoredox NHC/Pd catalysis. The process entails the following key steps: (ⅰ) photoinduced palladium-promoted formation of aryl radical, (ⅰ) generation of transient γ-amino alkyl radical through aryl radical-mediated 1,7-HAT, (ⅲ) single-electron oxidation of Breslow enolate intermediate to persistent ketyl radical, and (ⅳ) radical/radical coupling of γ-amino alkyl radical with ketyl radical. The synthetic utility of this γ-amino C(sp3)-H acylation is illustrated by the conversion of readily available aliphatic amines to a diverse collection of γ-aminoketones, which serve as versatile building blocks to enable the synthesis of pyrrolines of interest in medicinal chemistry. The radical mechanism is supported by the results of various control experiments, in situ EPR analysis, radical trapping experiment, and isotopic labeling studies.
The site-selective C(sp3)-H functionalization is of great importance in synthetic chemistry. However, γ-amino C(sp3)-H functionalization of aliphatic amines remains challenging. Herein, we develop an efficient γ-C(sp3)-H acylation of aliphatic amines by cooperative photoredox NHC/Pd catalysis. The process entails the following key steps: (ⅰ) photoinduced palladium-promoted formation of aryl radical, (ⅰ) generation of transient γ-amino alkyl radical through aryl radical-mediated 1,7-HAT, (ⅲ) single-electron oxidation of Breslow enolate intermediate to persistent ketyl radical, and (ⅳ) radical/radical coupling of γ-amino alkyl radical with ketyl radical. The synthetic utility of this γ-amino C(sp3)-H acylation is illustrated by the conversion of readily available aliphatic amines to a diverse collection of γ-aminoketones, which serve as versatile building blocks to enable the synthesis of pyrrolines of interest in medicinal chemistry. The radical mechanism is supported by the results of various control experiments, in situ EPR analysis, radical trapping experiment, and isotopic labeling studies.
2026, 37(5): 111499
doi: 10.1016/j.cclet.2025.111499
摘要:
Nanobelts have attracted significant attention in both synthetic and supramolecular chemistry due to their distinctive structures and promising applications. However, their synthesis remains challenging due to the high strain inherent in their ribbon-like configurations. A promising approach to mitigate this strain involves incorporating heteroatoms, such as sulfur and oxygen, which not only alleviate strain but also introduce new functionalities. In this study, we report the synthesis of a novel C2-symmetric nanobelt, [7]cyclophenoxathiin ([7]CP), through a multi-step process. The structure of [7]CP was confirmed using NMR, mass spectrometry, and single-crystal X-ray diffraction, revealing a heptagonal frustum-shaped geometry. Host-guest interactions between [7]CP and selected fullerenes were investigated using UV–vis absorption, 1H NMR, and X-ray crystallography. Our findings demonstrate that [7]CP forms 1:1 complexes with fullerenes, exhibiting moderate binding through π−π interactions, with binding constants of 1638, 2534, and 3682 L/mol for C60, C70, and PC61BM, respectively. The reduced cavity size of [7]CP prevents the formation of dimeric complexes observed with [7]cyclophenoxathiin, while still allowing it to function effectively as a molecular container.
Nanobelts have attracted significant attention in both synthetic and supramolecular chemistry due to their distinctive structures and promising applications. However, their synthesis remains challenging due to the high strain inherent in their ribbon-like configurations. A promising approach to mitigate this strain involves incorporating heteroatoms, such as sulfur and oxygen, which not only alleviate strain but also introduce new functionalities. In this study, we report the synthesis of a novel C2-symmetric nanobelt, [7]cyclophenoxathiin ([7]CP), through a multi-step process. The structure of [7]CP was confirmed using NMR, mass spectrometry, and single-crystal X-ray diffraction, revealing a heptagonal frustum-shaped geometry. Host-guest interactions between [7]CP and selected fullerenes were investigated using UV–vis absorption, 1H NMR, and X-ray crystallography. Our findings demonstrate that [7]CP forms 1:1 complexes with fullerenes, exhibiting moderate binding through π−π interactions, with binding constants of 1638, 2534, and 3682 L/mol for C60, C70, and PC61BM, respectively. The reduced cavity size of [7]CP prevents the formation of dimeric complexes observed with [7]cyclophenoxathiin, while still allowing it to function effectively as a molecular container.
2026, 37(5): 111501
doi: 10.1016/j.cclet.2025.111501
摘要:
Metal-free nanoparticles capable of executing synergistic photothermal therapy (PTT) and photodynamic therapy (PDT) under the action of a single-wavelength laser have garnered considerable attention. Here, a novel type of nitrogen-sulfur co-doped carbon nanoparticles (TG-CNPs) was synthesized from taurine and genipin using a solvothermal method in dimethylformamide. The TG-CNPs, with an average size of approximately 25 nm, demonstrated red and near-infrared absorption/emission in aqueous solution. TG-CNPs exhibited negligible dark cytotoxicity, excellent biocompatibility, and remarkable lysosomal localization ability. Upon 655-nm laser irradiation, TG-CNPs exhibited strong photothermal performance with a photothermal conversion efficiency of 30% along with the efficient generation of superoxide radicals (•O2−). Leveraging the enhanced permeability and retention (EPR) effect, TG-CNPs facilitated passive targeting and accumulation at the tumor site. Notably, following a single round of 655-nm laser treatment, the tumors in the mice were completely eradicated, with no evidence of recurrence observed over the subsequent five months. This study introduces a promising metal-free, heteroatom-doped carbon nanoparticle platform for effective synergistic PTT/PDT in tumor treatment.
Metal-free nanoparticles capable of executing synergistic photothermal therapy (PTT) and photodynamic therapy (PDT) under the action of a single-wavelength laser have garnered considerable attention. Here, a novel type of nitrogen-sulfur co-doped carbon nanoparticles (TG-CNPs) was synthesized from taurine and genipin using a solvothermal method in dimethylformamide. The TG-CNPs, with an average size of approximately 25 nm, demonstrated red and near-infrared absorption/emission in aqueous solution. TG-CNPs exhibited negligible dark cytotoxicity, excellent biocompatibility, and remarkable lysosomal localization ability. Upon 655-nm laser irradiation, TG-CNPs exhibited strong photothermal performance with a photothermal conversion efficiency of 30% along with the efficient generation of superoxide radicals (•O2−). Leveraging the enhanced permeability and retention (EPR) effect, TG-CNPs facilitated passive targeting and accumulation at the tumor site. Notably, following a single round of 655-nm laser treatment, the tumors in the mice were completely eradicated, with no evidence of recurrence observed over the subsequent five months. This study introduces a promising metal-free, heteroatom-doped carbon nanoparticle platform for effective synergistic PTT/PDT in tumor treatment.
2026, 37(5): 111544
doi: 10.1016/j.cclet.2025.111544
摘要:
Although the incorporation of deuterium has been widely researched, controlled deuterium labelling at precise sites is still very challenging. Herein, efficient catalytic synthesis of deuterated pyrroles is focused, the radical cyclizations of N-propargyl enamines were achieved from photoredox-mediated deuterated water splitting, giving deuterated pyrroles with deuterations at the C(sp2) and C(sp3) precisely. One or two-sites-deuterium incorporation as well as the controllable deuteration label at multi-H/D-exchange-sites, such as a methyl group, have been realized in high selectivity and efficiency via the solvent-controlled divergent deuterations. A halogen effect between solvents and substrates was proposed to initiate different catalytic cycles for the deuterations. The broad tolerance to substrates, the gram scale synthesis under natural sunlight irradiation and its applications in the synthesis of drug analogues further verified their practicality.
Although the incorporation of deuterium has been widely researched, controlled deuterium labelling at precise sites is still very challenging. Herein, efficient catalytic synthesis of deuterated pyrroles is focused, the radical cyclizations of N-propargyl enamines were achieved from photoredox-mediated deuterated water splitting, giving deuterated pyrroles with deuterations at the C(sp2) and C(sp3) precisely. One or two-sites-deuterium incorporation as well as the controllable deuteration label at multi-H/D-exchange-sites, such as a methyl group, have been realized in high selectivity and efficiency via the solvent-controlled divergent deuterations. A halogen effect between solvents and substrates was proposed to initiate different catalytic cycles for the deuterations. The broad tolerance to substrates, the gram scale synthesis under natural sunlight irradiation and its applications in the synthesis of drug analogues further verified their practicality.
2026, 37(5): 111555
doi: 10.1016/j.cclet.2025.111555
摘要:
A concise asymmetric synthesis of the anti-influenza drug (–)-oseltamivir phosphate (1) has been accomplished in 9 steps with an overall yield of 24%, starting from ethyl propiolate. The key features in this synthesis include an efficient biphasic Pd-catalyzed regioselectively intramolecular Heck-type cyclization to provide access to the highly valued chiral six-membered carbocyclic architecture, a regioselective and diastereoselective nitroso hetero-Diels-Alder reaction to construct the bicyclic oxazine 4 as well as a Cu(OTf)2-mediated regioselective and diastereoselective nucleophilic substitution reaction of bicyclic oxazine 4 with 3-pentanol to yield the trans-1,2-substituted diamino cyclohexyl amyl ether 16 with the correct three contiguous stereocenters. This rapid functionalization of the advanced molecular framework would offer an effective strategy for the asymmetric synthesis of other oseltamivir phosphate analogues.
A concise asymmetric synthesis of the anti-influenza drug (–)-oseltamivir phosphate (1) has been accomplished in 9 steps with an overall yield of 24%, starting from ethyl propiolate. The key features in this synthesis include an efficient biphasic Pd-catalyzed regioselectively intramolecular Heck-type cyclization to provide access to the highly valued chiral six-membered carbocyclic architecture, a regioselective and diastereoselective nitroso hetero-Diels-Alder reaction to construct the bicyclic oxazine 4 as well as a Cu(OTf)2-mediated regioselective and diastereoselective nucleophilic substitution reaction of bicyclic oxazine 4 with 3-pentanol to yield the trans-1,2-substituted diamino cyclohexyl amyl ether 16 with the correct three contiguous stereocenters. This rapid functionalization of the advanced molecular framework would offer an effective strategy for the asymmetric synthesis of other oseltamivir phosphate analogues.
2026, 37(5): 111614
doi: 10.1016/j.cclet.2025.111614
摘要:
The intrinsic scintillation property of uranium has recently endowed this heaviest naturally occurring element with new opportunities for X-ray radiation detection and visualization. However, the low radiation stability of most uranium compounds hinders their practical application, particularly in X-ray imaging. Here, we presented a flexible two-dimensional uranium-organic framework (UOF, SCU-334) as an air-stable scintillating material for X-ray detection and, for the first time, a systematic investigation of X-ray imaging in UOFs. Following continuous high dose rate X-ray irradiation exceeding 50 Gy, which equals thousands of chest X-ray diagnoses, SCU-334 retains over 90% of its initial performance, representing a significant improvement over previously reported scintillating UOFs. The upgraded radiation resistance of SCU-334 is attributed to its flexible structure that dissipates energy more efficiently under high-energy particle bombardment through conformation fluctuation and relaxation. This work offers a promising approach to improve the radiation resistance of uranium-based scintillators.
The intrinsic scintillation property of uranium has recently endowed this heaviest naturally occurring element with new opportunities for X-ray radiation detection and visualization. However, the low radiation stability of most uranium compounds hinders their practical application, particularly in X-ray imaging. Here, we presented a flexible two-dimensional uranium-organic framework (UOF, SCU-334) as an air-stable scintillating material for X-ray detection and, for the first time, a systematic investigation of X-ray imaging in UOFs. Following continuous high dose rate X-ray irradiation exceeding 50 Gy, which equals thousands of chest X-ray diagnoses, SCU-334 retains over 90% of its initial performance, representing a significant improvement over previously reported scintillating UOFs. The upgraded radiation resistance of SCU-334 is attributed to its flexible structure that dissipates energy more efficiently under high-energy particle bombardment through conformation fluctuation and relaxation. This work offers a promising approach to improve the radiation resistance of uranium-based scintillators.
2026, 37(5): 111615
doi: 10.1016/j.cclet.2025.111615
摘要:
Synthesizing 2-deoxyglycosides, prevalent motifs in bioactive molecules, presents significant challenges in stereocontrol and functional group tolerance. We report a metal-free, photo-induced O-glycosylation of glycals using acridinium salts under visible light. This method effectively couples diverse glycals with both carboxylic acids and alcohols, providing facile access to α-2-deoxyglycosides under mild conditions with broad substrate scope and functional group compatibility. The protocol exhibits high α-stereoselectivity with carboxylic acids and moderate α-selectivity with alcohols, enabling late-stage functionalization of complex molecules, including amino acids, peptides, and drugs. Mechanistic experiments implicate the possible involvement of radical intermediates, potentially operating via a chain reaction. Notably, 2-deoxyglycosylation of NSAIDs using this method enhanced their neuroprotective properties in vitro. This photo-induced strategy offers a practical and versatile platform for accessing complex 2-deoxyglycans relevant to medicinal chemistry and chemical biology.
Synthesizing 2-deoxyglycosides, prevalent motifs in bioactive molecules, presents significant challenges in stereocontrol and functional group tolerance. We report a metal-free, photo-induced O-glycosylation of glycals using acridinium salts under visible light. This method effectively couples diverse glycals with both carboxylic acids and alcohols, providing facile access to α-2-deoxyglycosides under mild conditions with broad substrate scope and functional group compatibility. The protocol exhibits high α-stereoselectivity with carboxylic acids and moderate α-selectivity with alcohols, enabling late-stage functionalization of complex molecules, including amino acids, peptides, and drugs. Mechanistic experiments implicate the possible involvement of radical intermediates, potentially operating via a chain reaction. Notably, 2-deoxyglycosylation of NSAIDs using this method enhanced their neuroprotective properties in vitro. This photo-induced strategy offers a practical and versatile platform for accessing complex 2-deoxyglycans relevant to medicinal chemistry and chemical biology.
2026, 37(5): 111616
doi: 10.1016/j.cclet.2025.111616
摘要:
Glial fibrillary acidic protein (GFAP) can serve as a promising early blood biomarker for Alzheimer's disease (AD). Existing assays mostly rely on antibody-based detection technologies, the preparation of antibodies is relatively complex, costly, and requires high storage conditions. In this study, we screened an aptamer specifically targeting GFAP (KD = 0.621 µmol/L) through systematic evolution of ligands by exponential enrichment (SELEX) technique for the first time and then applied which to develop a simple but sensitive fluorescent sensor by combining isothermal exponential amplification reaction (EXPAR) with hybridization chain reaction (HCR). The platform achieved a broad linear detection range (10 pg/mL to 10 µg/mL) and a low detection limit (0.24 pg/mL). The results detected by the proposed sensor were highly correlated with that detected by ELISA method (R = 0.9989, P < 0.0001). The work overcomes the limitations of antibody-based technologies and provides a promising solution for early diagnosis of AD.
Glial fibrillary acidic protein (GFAP) can serve as a promising early blood biomarker for Alzheimer's disease (AD). Existing assays mostly rely on antibody-based detection technologies, the preparation of antibodies is relatively complex, costly, and requires high storage conditions. In this study, we screened an aptamer specifically targeting GFAP (KD = 0.621 µmol/L) through systematic evolution of ligands by exponential enrichment (SELEX) technique for the first time and then applied which to develop a simple but sensitive fluorescent sensor by combining isothermal exponential amplification reaction (EXPAR) with hybridization chain reaction (HCR). The platform achieved a broad linear detection range (10 pg/mL to 10 µg/mL) and a low detection limit (0.24 pg/mL). The results detected by the proposed sensor were highly correlated with that detected by ELISA method (R = 0.9989, P < 0.0001). The work overcomes the limitations of antibody-based technologies and provides a promising solution for early diagnosis of AD.
2026, 37(5): 111617
doi: 10.1016/j.cclet.2025.111617
摘要:
The development of innovative strategies for inert B–H bond functionalization of carboranes and exploration of their potential applications represents a central task in organic chemistry. Here, we demonstrate the facile B–H bond functionalization in carboranes through a cage···Ⅰ(Ⅲ) interaction between a nido-carborane cluster and a hypervalent iodine(Ⅲ) unit. Both experimental and theoretical investigations reveal that the cage···Ⅰ(Ⅲ) interaction induces a charge transfer from the boron cage to the iodine moiety, which leads to a significant decrease of the negative charge at the B(9)–H site of nido-carborane. This facilitates the activation of the B–H bond and subsequent chemical transformations. The unprecedented cage···Ⅰ(Ⅲ) interaction offers a similar B–H bond activation mode as metal mediation. Furthermore, the treatment of nido-carboranes with the iodide(Ⅲ) reagent of PhI(OAc)2 affords nido-carborane-phenyl iodonium zwitterions as versatile synthons, which enable the modular construction of exopolyhedral B–O, B–N, B–P, and B–S bonds of carborane derivatives. This approach provides an efficient and scalable synthetic platform for metal-free and site-selective B–H bond functionalization of nido-carboranes under mild conditions. Notably, the developed 2D-3D fused structures can be used as ligands for the facile construction of novel boron cluster-fused hetero-polycyclic metal complexes in one step. These compounds demonstrate intriguing photophysical properties including aggregation-induced emission, tunable emission wavelength, and oxygen sensing.
The development of innovative strategies for inert B–H bond functionalization of carboranes and exploration of their potential applications represents a central task in organic chemistry. Here, we demonstrate the facile B–H bond functionalization in carboranes through a cage···Ⅰ(Ⅲ) interaction between a nido-carborane cluster and a hypervalent iodine(Ⅲ) unit. Both experimental and theoretical investigations reveal that the cage···Ⅰ(Ⅲ) interaction induces a charge transfer from the boron cage to the iodine moiety, which leads to a significant decrease of the negative charge at the B(9)–H site of nido-carborane. This facilitates the activation of the B–H bond and subsequent chemical transformations. The unprecedented cage···Ⅰ(Ⅲ) interaction offers a similar B–H bond activation mode as metal mediation. Furthermore, the treatment of nido-carboranes with the iodide(Ⅲ) reagent of PhI(OAc)2 affords nido-carborane-phenyl iodonium zwitterions as versatile synthons, which enable the modular construction of exopolyhedral B–O, B–N, B–P, and B–S bonds of carborane derivatives. This approach provides an efficient and scalable synthetic platform for metal-free and site-selective B–H bond functionalization of nido-carboranes under mild conditions. Notably, the developed 2D-3D fused structures can be used as ligands for the facile construction of novel boron cluster-fused hetero-polycyclic metal complexes in one step. These compounds demonstrate intriguing photophysical properties including aggregation-induced emission, tunable emission wavelength, and oxygen sensing.
2026, 37(5): 111649
doi: 10.1016/j.cclet.2025.111649
摘要:
Metal-organic frameworks (MOFs) with tunable structures provide a versatile platform for exploring active sites and show great potential in enzyme-like catalysis. In this study, arginine was employed as a modulator to synthesize an arginine-copper metal-organic framework (Arg-Cu-MOF), which demonstrated superior peroxidase-like activity and stability in comparison to unmodified Cu-MOF. The improved activity resulted from an increased density of Cu+ active sites, facilitating efficient •OH generation through H2O2 decomposition. Glyphosate interacts with the copper sites in a way that affects •OH generation and chromogenic substrate oxidation, leading to detectable colorimetric changes. By integrating Arg-Cu-MOF into a needle sensor, we allowed sample handling, reagent mixing, and signal readout, enabling both precise instrumental measurements and semi-quantitative visual detection of glyphosate. This sensor offers a detection range of 0.05–200 µg/mL with a detection limit of 0.049 µg/mL. This work highlights the potential of MOF modulation strategies and integrated detection platforms to enhance analytical performance, improve user-friendliness, and expand the application scope of biomimetic nanomaterials.
Metal-organic frameworks (MOFs) with tunable structures provide a versatile platform for exploring active sites and show great potential in enzyme-like catalysis. In this study, arginine was employed as a modulator to synthesize an arginine-copper metal-organic framework (Arg-Cu-MOF), which demonstrated superior peroxidase-like activity and stability in comparison to unmodified Cu-MOF. The improved activity resulted from an increased density of Cu+ active sites, facilitating efficient •OH generation through H2O2 decomposition. Glyphosate interacts with the copper sites in a way that affects •OH generation and chromogenic substrate oxidation, leading to detectable colorimetric changes. By integrating Arg-Cu-MOF into a needle sensor, we allowed sample handling, reagent mixing, and signal readout, enabling both precise instrumental measurements and semi-quantitative visual detection of glyphosate. This sensor offers a detection range of 0.05–200 µg/mL with a detection limit of 0.049 µg/mL. This work highlights the potential of MOF modulation strategies and integrated detection platforms to enhance analytical performance, improve user-friendliness, and expand the application scope of biomimetic nanomaterials.
2026, 37(5): 111706
doi: 10.1016/j.cclet.2025.111706
摘要:
The host-guest doped strategy has become the main method for constructing organic phosphorescence materials. In the doped system, guest molecules emit phosphorescence, therefore, improving the luminescence performance of guests is the key to optimizing the phosphorescence property of the doped materials. Herein, we designed to introduce the carbonyl group on the guest molecules. Carbonyl group can effectively promote n-π* transitions, thereby increasing the spin-orbit coupling (SOC) constant of the guests, ultimately improving the phosphorescence performance of the doped materials. Using the indazole derivative (IZ) as the initial guest, two other guests containing carboxyl group (IZ-CG) or ethoxycarbonyl group (IZ-EG) were successfully obtained. Further selected two small molecules and two polymers as the hosts to construct four doped systems. Among these doped systems, the phosphorescence performance of doped materials with IZ-CG or IZ-EG as the guest is significantly better than that of doped materials with IZ as the guest. The phosphorescence lifetime has increased by 2.3-5.0 times, and the phosphorescence quantum yield has increased by 3.0-5.7 times. Theoretical calculations and single crystal structures indicated that carbonyl groups can not only increase the SOC constant, but also enhance the intermolecular interactions of the guests. In addition, doped material can be effectively used for imaging subcutaneous and lymph nodes in mice, achieving a high signal-to-noise ratio.
The host-guest doped strategy has become the main method for constructing organic phosphorescence materials. In the doped system, guest molecules emit phosphorescence, therefore, improving the luminescence performance of guests is the key to optimizing the phosphorescence property of the doped materials. Herein, we designed to introduce the carbonyl group on the guest molecules. Carbonyl group can effectively promote n-π* transitions, thereby increasing the spin-orbit coupling (SOC) constant of the guests, ultimately improving the phosphorescence performance of the doped materials. Using the indazole derivative (IZ) as the initial guest, two other guests containing carboxyl group (IZ-CG) or ethoxycarbonyl group (IZ-EG) were successfully obtained. Further selected two small molecules and two polymers as the hosts to construct four doped systems. Among these doped systems, the phosphorescence performance of doped materials with IZ-CG or IZ-EG as the guest is significantly better than that of doped materials with IZ as the guest. The phosphorescence lifetime has increased by 2.3-5.0 times, and the phosphorescence quantum yield has increased by 3.0-5.7 times. Theoretical calculations and single crystal structures indicated that carbonyl groups can not only increase the SOC constant, but also enhance the intermolecular interactions of the guests. In addition, doped material can be effectively used for imaging subcutaneous and lymph nodes in mice, achieving a high signal-to-noise ratio.
2026, 37(5): 111717
doi: 10.1016/j.cclet.2025.111717
摘要:
Coupling photocatalytic H2 generation with antibiotic degradation offers a promising strategy for addressing energy and environmental challenges, leveraging the synergistic benefits of these processes. Herein, a novel heterojunction photocatalyst consisting of ultrafine CeO2 nanoparticles anchored onto CdS nanosheets was prepared using a simple one-pot in-situ hydrothermal method, enabling the simultaneous photocatalytic H2 generation and tetracycline (TC) degradation. The H2 generation efficiency of the optimal CeO2/CdS (CC-0.10) is 3544 µmol g-1 h-1, which surpasses pure CdS by 29.3 times. Additionally, TC is degraded by CC-0.10 at a rate constant (k value) of 0.0352 min-1, 2.73 times faster than CdS (0.0129 min-1). The free radical quenching and electron spin resonance experiments revealed the active involvement of •OH and •O2- radicals in the TC degradation process. Moreover, the unique CeO2/CdS heterojunction photocatalyst was also effective in degrading TC wastewater with an H2 yield of 1374 µmol g-1 h-1, displaying its dual performance in simultaneously degrading antibiotic wastewater and producing H2. The CeO2/CdS type Ⅱ charge transfer mechanism is confirmed by XPS, EPR, KPFM, fs-TAS, and DFT calculations. This work introduces a promising approach to constructing rare-earth oxide/metal sulfide nanocomposites for addressing the interconnected challenges of energy production and environmental pollution.
Coupling photocatalytic H2 generation with antibiotic degradation offers a promising strategy for addressing energy and environmental challenges, leveraging the synergistic benefits of these processes. Herein, a novel heterojunction photocatalyst consisting of ultrafine CeO2 nanoparticles anchored onto CdS nanosheets was prepared using a simple one-pot in-situ hydrothermal method, enabling the simultaneous photocatalytic H2 generation and tetracycline (TC) degradation. The H2 generation efficiency of the optimal CeO2/CdS (CC-0.10) is 3544 µmol g-1 h-1, which surpasses pure CdS by 29.3 times. Additionally, TC is degraded by CC-0.10 at a rate constant (k value) of 0.0352 min-1, 2.73 times faster than CdS (0.0129 min-1). The free radical quenching and electron spin resonance experiments revealed the active involvement of •OH and •O2- radicals in the TC degradation process. Moreover, the unique CeO2/CdS heterojunction photocatalyst was also effective in degrading TC wastewater with an H2 yield of 1374 µmol g-1 h-1, displaying its dual performance in simultaneously degrading antibiotic wastewater and producing H2. The CeO2/CdS type Ⅱ charge transfer mechanism is confirmed by XPS, EPR, KPFM, fs-TAS, and DFT calculations. This work introduces a promising approach to constructing rare-earth oxide/metal sulfide nanocomposites for addressing the interconnected challenges of energy production and environmental pollution.
2026, 37(5): 111720
doi: 10.1016/j.cclet.2025.111720
摘要:
Regulating gas diffusion is essential for a range of natural and industrial processes, including underwater breathing, aeration reactor and energy device. Natural organisms, e.g., water boatman, utilize their superaerophilic (SAL) abdomen to create a plastron underwater, enabling efficient gas exchange with dissolved oxygen. Herein, inspired by nature, we have developed a superaerophilic stripe that can form an air film underwater to enhance gas diffusion. Increasing the width (w) of the superaerophilic stripe and height (h) of water, along with decreasing the distance between the bubble and the stripe (d), can improve gas diffusion. Due to the improved dissolved gas diffusion, an efficient hydrogen evolution reaction driven by enhanced H2 diffusion was successfully achieved, resulting in an electrode potential decrease ~13 mV at the same current density of 1 mA/cm2 compared to that without the SAL stripe. This research offers important theoretical insights into the dynamics of gas diffusion and presents practical methods for enhancing gas mass transfer.
Regulating gas diffusion is essential for a range of natural and industrial processes, including underwater breathing, aeration reactor and energy device. Natural organisms, e.g., water boatman, utilize their superaerophilic (SAL) abdomen to create a plastron underwater, enabling efficient gas exchange with dissolved oxygen. Herein, inspired by nature, we have developed a superaerophilic stripe that can form an air film underwater to enhance gas diffusion. Increasing the width (w) of the superaerophilic stripe and height (h) of water, along with decreasing the distance between the bubble and the stripe (d), can improve gas diffusion. Due to the improved dissolved gas diffusion, an efficient hydrogen evolution reaction driven by enhanced H2 diffusion was successfully achieved, resulting in an electrode potential decrease ~13 mV at the same current density of 1 mA/cm2 compared to that without the SAL stripe. This research offers important theoretical insights into the dynamics of gas diffusion and presents practical methods for enhancing gas mass transfer.
2026, 37(5): 111789
doi: 10.1016/j.cclet.2025.111789
摘要:
Exposure to different neonicotinoid insecticides (NNIs) can cause varying degrees of harm to mammals and may even be carcinogenic. Due to their similar molecular structures, it is not only difficult to distinguish NNIs in analysis, but also cross-reactions can also occur. These cross-reactions cause the calibration curves to exhibit strong nonlinearities that cannot be fitted by usual mathematical models. Here, we present an electrochemical sensor array comprising three sensing units for the simultaneous determination of imidacloprid, thiamethoxam, and nitenpyram. The method eliminates cross-reaction with the aid of machine learning. The machine learning model comprises three components: the Douglas-Peucker algorithm for data compression, principal component analysis for classification, and an artificial neural network for quantification. The randomly assigned validation set showed a classification accuracy of 96.3% for the model. The prediction accuracy was 98.77%. The limit of detection was < 0.037 µmol/L, with a detection range from 0.1 µmol/L to 200 µmol/L. Finally, the spiked tea samples were tested, and a satisfactory agreement was obtained between the expected and predicted values.
Exposure to different neonicotinoid insecticides (NNIs) can cause varying degrees of harm to mammals and may even be carcinogenic. Due to their similar molecular structures, it is not only difficult to distinguish NNIs in analysis, but also cross-reactions can also occur. These cross-reactions cause the calibration curves to exhibit strong nonlinearities that cannot be fitted by usual mathematical models. Here, we present an electrochemical sensor array comprising three sensing units for the simultaneous determination of imidacloprid, thiamethoxam, and nitenpyram. The method eliminates cross-reaction with the aid of machine learning. The machine learning model comprises three components: the Douglas-Peucker algorithm for data compression, principal component analysis for classification, and an artificial neural network for quantification. The randomly assigned validation set showed a classification accuracy of 96.3% for the model. The prediction accuracy was 98.77%. The limit of detection was < 0.037 µmol/L, with a detection range from 0.1 µmol/L to 200 µmol/L. Finally, the spiked tea samples were tested, and a satisfactory agreement was obtained between the expected and predicted values.
2026, 37(5): 111790
doi: 10.1016/j.cclet.2025.111790
摘要:
In this work, bis-trimethylammonium pillar[5]arene (TP5) was synthesized for ionic pair assembly with 4,4′-biphenyldisulfonic acid (BA) to prepare a new kind of ionic single crystals (TP5-BA). The single crystal structure revealed that TP5-BA adopted an ordered cross-stacked arrangement under the combined influence of electrostatic interactions and π-π stacking forces. It is worth noting that TP5-BA exhibited exceptional performance in the adsorption of iodine vapor, with an adsorption capacity as high as 3.27 g/g. After 6 days, its retention rate remained at a high level of 99.71%. This finding may open up a new direction in supramolecular chemistry with ionic pair self-assembly, not only for the development of novel iodine adsorbent materials but also for many other potential applications such as catalysis and energy.
In this work, bis-trimethylammonium pillar[5]arene (TP5) was synthesized for ionic pair assembly with 4,4′-biphenyldisulfonic acid (BA) to prepare a new kind of ionic single crystals (TP5-BA). The single crystal structure revealed that TP5-BA adopted an ordered cross-stacked arrangement under the combined influence of electrostatic interactions and π-π stacking forces. It is worth noting that TP5-BA exhibited exceptional performance in the adsorption of iodine vapor, with an adsorption capacity as high as 3.27 g/g. After 6 days, its retention rate remained at a high level of 99.71%. This finding may open up a new direction in supramolecular chemistry with ionic pair self-assembly, not only for the development of novel iodine adsorbent materials but also for many other potential applications such as catalysis and energy.
2026, 37(5): 111791
doi: 10.1016/j.cclet.2025.111791
摘要:
Benzohydroxamic acid (BHA) occurs as recalcitrant organic pollutant discharged from mining industry. While Fenton-like oxidation based on peroxymonosulfate (PMS) has been extensively applied for organic contamination mitigation, its conventional reaction pathway dependent on free radicals needs high energy input with elevated carbon emission. Here, we meticulously developed a novel single-atom catalyst featuring Co-N4 coordination (Cox@NC) to initiate a non-radical Fenton-like oxidation for BHA treatment. Results showed single-atom Co-N4 with the considerable Co content (>2 wt%) and quantitative N coordination displayed exceptional reactivity to activate PMS for BHA degradation with a turnover frequency > 16 min−1. Such single-atom Co-N4 formed a surface-reactive complexes with mild oxidation potential by coordinating with PMS to mediate electron transfer for oxidation of BHA. The mediated ETP further triggered polymerization transformation pathway of BHA through formation and coupling of phenoxy-like radicals, resulting in a considerable recovery yield of BHA polymers (~43%) and superior utilization efficiency of PMS (~434%). Combined with ultrahigh-resolution mass analysis, the identified polymerized products illustrated the related polymerization mechanisms of BHA including hydroxylation, monomer radical generation, dimerization, and chain extension. Such Fenton-like catalysis of single-atom Co-N4 exhibited more remarkable application potentials in mineral processing wastewater treatment compared to traditional Fenton reaction, reducing oxidant consumption and increasing organic carbon recovery. This study enhances development of resource-efficient Fenton-like oxidation technologies for mineral processing wastewater treatment.
Benzohydroxamic acid (BHA) occurs as recalcitrant organic pollutant discharged from mining industry. While Fenton-like oxidation based on peroxymonosulfate (PMS) has been extensively applied for organic contamination mitigation, its conventional reaction pathway dependent on free radicals needs high energy input with elevated carbon emission. Here, we meticulously developed a novel single-atom catalyst featuring Co-N4 coordination (Cox@NC) to initiate a non-radical Fenton-like oxidation for BHA treatment. Results showed single-atom Co-N4 with the considerable Co content (>2 wt%) and quantitative N coordination displayed exceptional reactivity to activate PMS for BHA degradation with a turnover frequency > 16 min−1. Such single-atom Co-N4 formed a surface-reactive complexes with mild oxidation potential by coordinating with PMS to mediate electron transfer for oxidation of BHA. The mediated ETP further triggered polymerization transformation pathway of BHA through formation and coupling of phenoxy-like radicals, resulting in a considerable recovery yield of BHA polymers (~43%) and superior utilization efficiency of PMS (~434%). Combined with ultrahigh-resolution mass analysis, the identified polymerized products illustrated the related polymerization mechanisms of BHA including hydroxylation, monomer radical generation, dimerization, and chain extension. Such Fenton-like catalysis of single-atom Co-N4 exhibited more remarkable application potentials in mineral processing wastewater treatment compared to traditional Fenton reaction, reducing oxidant consumption and increasing organic carbon recovery. This study enhances development of resource-efficient Fenton-like oxidation technologies for mineral processing wastewater treatment.
2026, 37(5): 111811
doi: 10.1016/j.cclet.2025.111811
摘要:
Metallocenes are a wide family of organometallic compounds, in which two cyclopentadienyl ligands "sandwich" a metal ion, M(η5-C5R5)2, and have considerable potential for use as components in molecular electronics applications. Here we have studied the electronic transport properties of the matallocenes MCp2 (M = V, Cr, Mn, Fe, Co, Ni, Ru; Cp = η5-C5H5) and MCp*2 (M = Mn, Fe, Co; Cp* = η5-C5Me5). Molecular junctions have been fabricated using either two gold, or one gold and one graphene electrode(s), giving rise to single-molecule conductance values of the order of -4 to -3 log(G/G0)) depending on both the nature of the metallocene and the electrode materials. Calculations on model junctions at the density functional theory level of theory reveal significant charge transfer from the metallocene to the junction electrodes and changes in the nature of the primary charge transport pathways in response to the nature of the metal, supporting ligands, molecular oxidation state and electrode composition.
Metallocenes are a wide family of organometallic compounds, in which two cyclopentadienyl ligands "sandwich" a metal ion, M(η5-C5R5)2, and have considerable potential for use as components in molecular electronics applications. Here we have studied the electronic transport properties of the matallocenes MCp2 (M = V, Cr, Mn, Fe, Co, Ni, Ru; Cp = η5-C5H5) and MCp*2 (M = Mn, Fe, Co; Cp* = η5-C5Me5). Molecular junctions have been fabricated using either two gold, or one gold and one graphene electrode(s), giving rise to single-molecule conductance values of the order of -4 to -3 log(G/G0)) depending on both the nature of the metallocene and the electrode materials. Calculations on model junctions at the density functional theory level of theory reveal significant charge transfer from the metallocene to the junction electrodes and changes in the nature of the primary charge transport pathways in response to the nature of the metal, supporting ligands, molecular oxidation state and electrode composition.
2026, 37(5): 111825
doi: 10.1016/j.cclet.2025.111825
摘要:
Nickel-iron double hydroxides are corroded by Cl− during seawater electrolysis, which reduces their catalytic activity and stability. Here, a high-performance bifunctional electrocatalyst (NiFe-LDH/MoNi4) with enhanced chloride corrosion resistance was synthesized. In the OER process, Mo element in the catalyst was reconstructed to form MoO42−, which repelled Cl− to prevent the catalyst from being corroded. Besides, the heterostructure of NiFe-LDH/MoNi4 decreased the reduction of HER active site during HER process (Mo element dissolves easily in alkaline media due to thermodynamic instability). Therefore, based on in-situ self-reconstruction of Mo element and heterostructure in alkaline seawater, NiFe-LDH/MoNi4 delivered a current density of 10 mA/cm2 for the HER (OER) at industrial temperatures (80 ℃) with an overpotential of merely 32 mV (139 mV). Additionally, when NiFe-LDH/MoNi4 is employed as both the anode and cathode, a battery voltage of just 1.39 V (3.13 V) is sufficient to attain a current density of 10 mA/cm2 (1 A/cm2). The system is also capable of sustained operation at a high current density of 500 mA/cm2 for a period of 50 h.
Nickel-iron double hydroxides are corroded by Cl− during seawater electrolysis, which reduces their catalytic activity and stability. Here, a high-performance bifunctional electrocatalyst (NiFe-LDH/MoNi4) with enhanced chloride corrosion resistance was synthesized. In the OER process, Mo element in the catalyst was reconstructed to form MoO42−, which repelled Cl− to prevent the catalyst from being corroded. Besides, the heterostructure of NiFe-LDH/MoNi4 decreased the reduction of HER active site during HER process (Mo element dissolves easily in alkaline media due to thermodynamic instability). Therefore, based on in-situ self-reconstruction of Mo element and heterostructure in alkaline seawater, NiFe-LDH/MoNi4 delivered a current density of 10 mA/cm2 for the HER (OER) at industrial temperatures (80 ℃) with an overpotential of merely 32 mV (139 mV). Additionally, when NiFe-LDH/MoNi4 is employed as both the anode and cathode, a battery voltage of just 1.39 V (3.13 V) is sufficient to attain a current density of 10 mA/cm2 (1 A/cm2). The system is also capable of sustained operation at a high current density of 500 mA/cm2 for a period of 50 h.
2026, 37(5): 111838
doi: 10.1016/j.cclet.2025.111838
摘要:
Although periodate (PI) activation via iron-based Fenton-like reactions effectively generates reactive oxygen species (ROS) for pollutant degradation, Fe(Ⅲ) accumulation poses a major challenge to sustained ROS generation. Here, amorphous-boron (AB) was employed as a co-catalyst for boosting Fenton-like activation of PI (primarily Fe(Ⅲ)/PI) towards water decontamination, and the AB/Fe(Ⅲ)/PI process can promptly and steadily oxidize sulfamethoxazole (SMX) during 5 cycling tests. Through integrated qualitative and semi-quantitative analyses of ROS, including EPR, quenching, and chemical probes, AB can directly activate PI to produce hydroxyl radical and indirectly accelerate Fenton-like activation of PI to produce Fe(Ⅳ) by reducing Fe(Ⅲ). The synergetic routes of radical (hydroxyl radical) and non-radical (Fe(Ⅳ)) ensure the high capability of AB/Fe(Ⅲ)/PI for degrading a wide variety of contaminants with diversiform molecular structures. Moreover, characterizations (XPS, EPR, HAADF-STEM, HRTEM, Raman, and XRD) reveals the stepwise boron oxidation via B-B bond cleavage can sustainably donate electron for direct and indirect activation of PI. The self-cleaning surface caused by the synergetic stepwise oxidation of boron and dissolution of boron oxide maintains the high stability of AB for co-catalyzing Fenton-like activation of PI during long-term operation. Therefore, this study proposes a novel Fenton-like technique for eliminating organic contaminants with low iron sludge output and long-term stability.
Although periodate (PI) activation via iron-based Fenton-like reactions effectively generates reactive oxygen species (ROS) for pollutant degradation, Fe(Ⅲ) accumulation poses a major challenge to sustained ROS generation. Here, amorphous-boron (AB) was employed as a co-catalyst for boosting Fenton-like activation of PI (primarily Fe(Ⅲ)/PI) towards water decontamination, and the AB/Fe(Ⅲ)/PI process can promptly and steadily oxidize sulfamethoxazole (SMX) during 5 cycling tests. Through integrated qualitative and semi-quantitative analyses of ROS, including EPR, quenching, and chemical probes, AB can directly activate PI to produce hydroxyl radical and indirectly accelerate Fenton-like activation of PI to produce Fe(Ⅳ) by reducing Fe(Ⅲ). The synergetic routes of radical (hydroxyl radical) and non-radical (Fe(Ⅳ)) ensure the high capability of AB/Fe(Ⅲ)/PI for degrading a wide variety of contaminants with diversiform molecular structures. Moreover, characterizations (XPS, EPR, HAADF-STEM, HRTEM, Raman, and XRD) reveals the stepwise boron oxidation via B-B bond cleavage can sustainably donate electron for direct and indirect activation of PI. The self-cleaning surface caused by the synergetic stepwise oxidation of boron and dissolution of boron oxide maintains the high stability of AB for co-catalyzing Fenton-like activation of PI during long-term operation. Therefore, this study proposes a novel Fenton-like technique for eliminating organic contaminants with low iron sludge output and long-term stability.
2026, 37(5): 111839
doi: 10.1016/j.cclet.2025.111839
摘要:
The utilization of photoelectrocatalytic (PEC) technology for water pollution treatment and value-added chemical production is important in sustainable development strategies. A system combining Ag3PO4/g-C3N4 S-scheme heterojunction photoanodic oxidation with natural air diffusion electrode (NADE) reduction was designed. The PEC system could remove 94.5% of tetracycline (TC) with the first-order kinetic rate constant of 0.148 min-1, while the H2O2 yield in the cathodic chamber reached 4.3 µmol-1 h-1 cm-2 under 2.0 V cell voltage. The rate constant of TC degradation by the Ag3PO4/g-C3N4 coupled NADE PEC system was 4.4 times that of Ag3PO4/g-C3N4 coupled Pt PEC system (0.034 min-1). This was attributed to the synergistic effect between accelerated photoanode carrier transfer and increased H2O2 yield. The production of H2O2 in the cathode chamber of the PEC system with the presence of TC was 2.3 times that of absence of TC (1.9 µmol-1 h-1 cm-2). The active substances playing a major role in this PEC system were mainly h+ followed by •OH. Significantly, the efficient operation of the PEC system under actual sunlight will be conducive to the exploration of practical applications in the future. This study provides new insights for constructing efficient cathode-anode coupled PEC systems for water purification and simultaneous H2O2 production.
The utilization of photoelectrocatalytic (PEC) technology for water pollution treatment and value-added chemical production is important in sustainable development strategies. A system combining Ag3PO4/g-C3N4 S-scheme heterojunction photoanodic oxidation with natural air diffusion electrode (NADE) reduction was designed. The PEC system could remove 94.5% of tetracycline (TC) with the first-order kinetic rate constant of 0.148 min-1, while the H2O2 yield in the cathodic chamber reached 4.3 µmol-1 h-1 cm-2 under 2.0 V cell voltage. The rate constant of TC degradation by the Ag3PO4/g-C3N4 coupled NADE PEC system was 4.4 times that of Ag3PO4/g-C3N4 coupled Pt PEC system (0.034 min-1). This was attributed to the synergistic effect between accelerated photoanode carrier transfer and increased H2O2 yield. The production of H2O2 in the cathode chamber of the PEC system with the presence of TC was 2.3 times that of absence of TC (1.9 µmol-1 h-1 cm-2). The active substances playing a major role in this PEC system were mainly h+ followed by •OH. Significantly, the efficient operation of the PEC system under actual sunlight will be conducive to the exploration of practical applications in the future. This study provides new insights for constructing efficient cathode-anode coupled PEC systems for water purification and simultaneous H2O2 production.
2026, 37(5): 111840
doi: 10.1016/j.cclet.2025.111840
摘要:
Improving the reactivity of Fe(Ⅲ) is the bottleneck in the catalytic activity of persulfate-based Fenton-like chemistry. In this study, the Fe(Ⅲ)-PA catalyst was prepared for the activation of persulfate (PMS) by co-precipitation of phytate with iron ions. In particular, the Fe(Ⅲ)-PA/PMS system achieved efficient degradation of the target pollutant TCH under a wide range of pH conditions from 3.0 to 9.0. In the Fe(Ⅲ) PA/PMS/TCH system, the oxidative degradation of TCH was mainly via the direct electron transfer pathway. Density functional theory (DFT) calculations revealed the mechanism of PMS activation potentiation, that is, phytate reduced the adsorption energy of the catalyst for PMS from -0.43 eV to -2.72 eV by coordination with the ferrihydrite. Moreover, Fe(Ⅲ)-PA functions as an electron shuttle and accelerates the electron transfer process between TCH and PMS. The removal of TCH under the electron transfer process (ETP) mediated by Fe(Ⅲ)-PA was selective, thereby demonstrating less sensitivity to the presence of co-existing ions and natural organic matter (NOMs). This work provides a viable case for ligand-enhanced Fe(Ⅲ) activation of PMS and reveals the critical role of direct electron transfer in pollutant elimination.
Improving the reactivity of Fe(Ⅲ) is the bottleneck in the catalytic activity of persulfate-based Fenton-like chemistry. In this study, the Fe(Ⅲ)-PA catalyst was prepared for the activation of persulfate (PMS) by co-precipitation of phytate with iron ions. In particular, the Fe(Ⅲ)-PA/PMS system achieved efficient degradation of the target pollutant TCH under a wide range of pH conditions from 3.0 to 9.0. In the Fe(Ⅲ) PA/PMS/TCH system, the oxidative degradation of TCH was mainly via the direct electron transfer pathway. Density functional theory (DFT) calculations revealed the mechanism of PMS activation potentiation, that is, phytate reduced the adsorption energy of the catalyst for PMS from -0.43 eV to -2.72 eV by coordination with the ferrihydrite. Moreover, Fe(Ⅲ)-PA functions as an electron shuttle and accelerates the electron transfer process between TCH and PMS. The removal of TCH under the electron transfer process (ETP) mediated by Fe(Ⅲ)-PA was selective, thereby demonstrating less sensitivity to the presence of co-existing ions and natural organic matter (NOMs). This work provides a viable case for ligand-enhanced Fe(Ⅲ) activation of PMS and reveals the critical role of direct electron transfer in pollutant elimination.
2026, 37(5): 111844
doi: 10.1016/j.cclet.2025.111844
摘要:
Aqueously dispersed nanomaterials exhibiting circularly polarized luminescence (CPL) hold great potentials in biological fields due to the inherent chirality of biological systems and its excellent biocompatibility. However, the limited availability of biodegradable CPL nanoparticles in aqueous media has severely constrained the development of biomedical CPL. Here, we present a facile strategy for achieving tunable CPL of aqueously dispersed nanotoroids through the co-assembly of a homopolypeptide with three achiral triphenylamine derivatives, showing a CPL performance depending on the architecture and doping content of small molecules. Remarkably, a deep-red CPL can be achieved with a record luminescence dissymmetry factor (glum = 1.1 × 10−2) among aqueously polypeptide-based nanoparticles. Furthermore, the densely packed nanostructure completely suppressed the intrinsic reactive oxygen species generation of the chromophores by restricting oxygen diffusion and quenching exciton-energy transfer, thereby eliminating phototoxic risks while preserving imaging fidelity. Overall, this work not only provides a facile method for achieving aqueous CPL from achiral molecules but also establishes a structure-property relationship between chromophore geometry and supramolecular CPL performance, advancing their potential in biological fields.
Aqueously dispersed nanomaterials exhibiting circularly polarized luminescence (CPL) hold great potentials in biological fields due to the inherent chirality of biological systems and its excellent biocompatibility. However, the limited availability of biodegradable CPL nanoparticles in aqueous media has severely constrained the development of biomedical CPL. Here, we present a facile strategy for achieving tunable CPL of aqueously dispersed nanotoroids through the co-assembly of a homopolypeptide with three achiral triphenylamine derivatives, showing a CPL performance depending on the architecture and doping content of small molecules. Remarkably, a deep-red CPL can be achieved with a record luminescence dissymmetry factor (glum = 1.1 × 10−2) among aqueously polypeptide-based nanoparticles. Furthermore, the densely packed nanostructure completely suppressed the intrinsic reactive oxygen species generation of the chromophores by restricting oxygen diffusion and quenching exciton-energy transfer, thereby eliminating phototoxic risks while preserving imaging fidelity. Overall, this work not only provides a facile method for achieving aqueous CPL from achiral molecules but also establishes a structure-property relationship between chromophore geometry and supramolecular CPL performance, advancing their potential in biological fields.
2026, 37(5): 111851
doi: 10.1016/j.cclet.2025.111851
摘要:
Lactate (LA) is now recognized as a critical carbon source for tumor metabolism, making its transport blockade a promising anticancer therapeutic strategy. In this study, we incorporated α-cyano-4-hydroxycinnamate (CHC) into hollow-structured CuS@PCN nanoparticles to inhibit LA influx by suppressing the expression of the monocarboxylate transporter 1 (MCT1) in tumor cells. This intervention shifted tumor cell metabolism from LA-fueled oxidative phosphorylation towards anaerobic glycolysis, consequently elevating intratumoral oxygen (O2) levels. The photosensitizer-based metal-organic framework (PCN) component was then able to efficiently convert this elevated O2 into abundant reactive oxygen species (ROS), thereby enhancing photodynamic therapy (PDT) efficacy. Notably, the hollow mesoporous CuS nanoparticle core functioned dually as a high-capacity CHC carrier and a photothermal agent that enables CHC release under near-infrared (NIR) irradiation. Further surface conjugation with folic acid-polyethylene glycol (FA-PEG) imparted tumor-targeting specificity via folate receptor recognition and prolonged systemic circulation. Both in vitro and in vivo evaluations demonstrated the excellent biocompatibility and significantly improved PDT performance of the synthesized CHC-CuS@PCN-FA (CHC-CP-FA) nanoplatform. These findings underscore the considerable potential of CHC-CP-FA for future cancer treatment applications.
Lactate (LA) is now recognized as a critical carbon source for tumor metabolism, making its transport blockade a promising anticancer therapeutic strategy. In this study, we incorporated α-cyano-4-hydroxycinnamate (CHC) into hollow-structured CuS@PCN nanoparticles to inhibit LA influx by suppressing the expression of the monocarboxylate transporter 1 (MCT1) in tumor cells. This intervention shifted tumor cell metabolism from LA-fueled oxidative phosphorylation towards anaerobic glycolysis, consequently elevating intratumoral oxygen (O2) levels. The photosensitizer-based metal-organic framework (PCN) component was then able to efficiently convert this elevated O2 into abundant reactive oxygen species (ROS), thereby enhancing photodynamic therapy (PDT) efficacy. Notably, the hollow mesoporous CuS nanoparticle core functioned dually as a high-capacity CHC carrier and a photothermal agent that enables CHC release under near-infrared (NIR) irradiation. Further surface conjugation with folic acid-polyethylene glycol (FA-PEG) imparted tumor-targeting specificity via folate receptor recognition and prolonged systemic circulation. Both in vitro and in vivo evaluations demonstrated the excellent biocompatibility and significantly improved PDT performance of the synthesized CHC-CuS@PCN-FA (CHC-CP-FA) nanoplatform. These findings underscore the considerable potential of CHC-CP-FA for future cancer treatment applications.
2026, 37(5): 111853
doi: 10.1016/j.cclet.2025.111853
摘要:
Chemical scavengers are frequently used to quantify the contribution of target radicals to contaminant removal in natural and engineered waters. While favored for their ease of use and versatility across systems, improper selection can lead to significant kinetic and mechanistic misinterpretations. This study presents a critical evaluation of chemical scavengers in radical-induced reactions across various environmental scenarios. Specifically, we demonstrate that in systems containing both target and coexisting radicals, commonly used scavengers can react with both species, complicating the measurement of reaction kinetics and leading to misinterpretation of target radical contributions. In addition, we discuss the challenges associated with applying scavengers in heterogeneous systems, where the distribution of scavengers and target compounds across interfaces significantly impacts the evaluation of radical contributions. Further, our insights from non-steady-state systems into radicals' dynamic behavior and transient phenomena are often overlooked in other steady-state conditions. We address interactions between scavengers and triplet excited-state compounds in photochemical systems, emphasizing the importance of selecting appropriate scavengers to ensure accurate kinetic profiling and radical quantification. These findings hold significant implications for advancing scavenger research across a broad range of chemical research and practical applications.
Chemical scavengers are frequently used to quantify the contribution of target radicals to contaminant removal in natural and engineered waters. While favored for their ease of use and versatility across systems, improper selection can lead to significant kinetic and mechanistic misinterpretations. This study presents a critical evaluation of chemical scavengers in radical-induced reactions across various environmental scenarios. Specifically, we demonstrate that in systems containing both target and coexisting radicals, commonly used scavengers can react with both species, complicating the measurement of reaction kinetics and leading to misinterpretation of target radical contributions. In addition, we discuss the challenges associated with applying scavengers in heterogeneous systems, where the distribution of scavengers and target compounds across interfaces significantly impacts the evaluation of radical contributions. Further, our insights from non-steady-state systems into radicals' dynamic behavior and transient phenomena are often overlooked in other steady-state conditions. We address interactions between scavengers and triplet excited-state compounds in photochemical systems, emphasizing the importance of selecting appropriate scavengers to ensure accurate kinetic profiling and radical quantification. These findings hold significant implications for advancing scavenger research across a broad range of chemical research and practical applications.
2026, 37(5): 111857
doi: 10.1016/j.cclet.2025.111857
摘要:
Chlorine is not only widely used as an important basic chemical, but also shows promising in-situ electrochemical remediation. Unfortunately, its electrochemical production usually relies on expensive noble-metal dimensionally stable anode (DSA). Herein, a high-performance non-noble metal Co3O4/Ti anode was developed by a simple electrodeposition-calcination method, demonstrating a high efficiency in producing active chlorine in a wide pH range (3–11) and at relatively low Cl- concentration close to different real environmental requirements due to its abundant surface area and active sites provided by the interlaced nanosheet structure anode. Compared with commercial DSA, the Co3O4/Ti anode offered significant advantages in terms of Faraday efficiency, electric energy consumption and economic cost, achieving the rate of active chlorine production of 14.97 mg L-1 min-1 in 0.5 mol/L NaCl electrolyte solution (pH 6) with a Faraday efficiency of 96.8% and low energy consumption of 2.49 kWh/kg. Moreover, the robust backbone structure of the anode enabled the Faraday efficiency to be maintained at about 92.2% without deactivation after ten cycles of reaction. In addition, this Co3O4/Ti electrode demonstrated effectiveness in treating organic pollutants and mariculture wastewater and seawater rapid sterilization. This study provides new inspirations for the construction of highly efficient, low-cost, and low energy consumption non-noble metal cobalt-based anode for the in-situ environmental remediation application.
Chlorine is not only widely used as an important basic chemical, but also shows promising in-situ electrochemical remediation. Unfortunately, its electrochemical production usually relies on expensive noble-metal dimensionally stable anode (DSA). Herein, a high-performance non-noble metal Co3O4/Ti anode was developed by a simple electrodeposition-calcination method, demonstrating a high efficiency in producing active chlorine in a wide pH range (3–11) and at relatively low Cl- concentration close to different real environmental requirements due to its abundant surface area and active sites provided by the interlaced nanosheet structure anode. Compared with commercial DSA, the Co3O4/Ti anode offered significant advantages in terms of Faraday efficiency, electric energy consumption and economic cost, achieving the rate of active chlorine production of 14.97 mg L-1 min-1 in 0.5 mol/L NaCl electrolyte solution (pH 6) with a Faraday efficiency of 96.8% and low energy consumption of 2.49 kWh/kg. Moreover, the robust backbone structure of the anode enabled the Faraday efficiency to be maintained at about 92.2% without deactivation after ten cycles of reaction. In addition, this Co3O4/Ti electrode demonstrated effectiveness in treating organic pollutants and mariculture wastewater and seawater rapid sterilization. This study provides new inspirations for the construction of highly efficient, low-cost, and low energy consumption non-noble metal cobalt-based anode for the in-situ environmental remediation application.
2026, 37(5): 111858
doi: 10.1016/j.cclet.2025.111858
摘要:
Per- and polyfluoroalkyl substances (PFASs), especially perfluorooctanoic acid (PFOA), pose a significant threat to ecosystems and human health due to their extreme persistence and bioaccumulative properties. Although metal-organic frameworks (MOFs) show potential for adsorption, their efficiency is limited by insufficient active sites and the inability to control the design of adsorption centers, which is a key bottleneck for practical application. In this study, defect engineering was employed to synthesize NH2-UiO-66 derivatives with gradient defect densities (NH2-UiO-66, -LD, -HD), exposing unsaturated Zr sites to enhance PFOA capture. The optimized NH2-UiO-66-HD exhibited ultrafast kinetics, achieving 95% removal within 30 min and a theoretical adsorption capacity of up to 739.31 mg/g, surpassing most MOFs and traditional adsorbents. Mechanistic studies revealed that defect-induced unsaturated Zr sites act as high-affinity anchors, strongly coordinating with the -COO- group of PFOA, while forming a triple interaction mechanism with N–H···F hydrogen bonds and electrostatic interactions (-NH3+), a synergy not previously reported. The material maintained over 90% efficiency through seven cycles, addressing long-standing regenerability challenges in PFAS remediation. This research pioneers a programmable defect-control approach to create hierarchical active sites in MOFs and first demonstrates the synergy of Zr coordination, hydrogen bonding, and electrostatic attraction for ultra-efficient PFAS removal.
Per- and polyfluoroalkyl substances (PFASs), especially perfluorooctanoic acid (PFOA), pose a significant threat to ecosystems and human health due to their extreme persistence and bioaccumulative properties. Although metal-organic frameworks (MOFs) show potential for adsorption, their efficiency is limited by insufficient active sites and the inability to control the design of adsorption centers, which is a key bottleneck for practical application. In this study, defect engineering was employed to synthesize NH2-UiO-66 derivatives with gradient defect densities (NH2-UiO-66, -LD, -HD), exposing unsaturated Zr sites to enhance PFOA capture. The optimized NH2-UiO-66-HD exhibited ultrafast kinetics, achieving 95% removal within 30 min and a theoretical adsorption capacity of up to 739.31 mg/g, surpassing most MOFs and traditional adsorbents. Mechanistic studies revealed that defect-induced unsaturated Zr sites act as high-affinity anchors, strongly coordinating with the -COO- group of PFOA, while forming a triple interaction mechanism with N–H···F hydrogen bonds and electrostatic interactions (-NH3+), a synergy not previously reported. The material maintained over 90% efficiency through seven cycles, addressing long-standing regenerability challenges in PFAS remediation. This research pioneers a programmable defect-control approach to create hierarchical active sites in MOFs and first demonstrates the synergy of Zr coordination, hydrogen bonding, and electrostatic attraction for ultra-efficient PFAS removal.
2026, 37(5): 111860
doi: 10.1016/j.cclet.2025.111860
摘要:
The high sensitivity of platinum (Pt)-based catalysts to CO during the hydrogen oxidation reaction (HOR) at the anode is one of the key issues for the long-term stable development of proton exchange membrane fuel cells (PEMFCs). Modulating the electronic structure of Pt is considered an effective approach to enhancing HOR activity and improving CO tolerance. Herein, we utilized the synergistic effect between the transition metal interstitial compounds (TMICs) of VN and Pt to develop a Pt-VN heterojunction-loaded carbon nanofiber catalyst (Pt-VN/NCNF) for CO tolerance in HOR. The introduction of VN causes electronic orbitals rearrangement of Pt, thereby optimizing the adsorption of H on the Pt surface. Meanwhile, the overlap of the d-band of the electron-deficient Pt with the 1π and 5σ bonding orbitals of CO was significantly reduced, which suppresses the strong CO adsorption on Pt surfaces and leave more active sites for H2 adsorption and oxidation. As a result, Pt-VN/NCNF exhibits a mass activity of 1.26 mA/µgPt, 41 times higher than that of commercial Pt/C. Encouragingly, Pt-VN/NCNF maintains 96.7% of its original activity even in the presence of 1000 ppm CO. As anticipated, Pt-VN/NCNF-based PEMFCs demonstrate superior CO tolerance to Pt/C in H2/CO mixtures with CO concentrations ranging from 10 ppm to 1000 ppm.
The high sensitivity of platinum (Pt)-based catalysts to CO during the hydrogen oxidation reaction (HOR) at the anode is one of the key issues for the long-term stable development of proton exchange membrane fuel cells (PEMFCs). Modulating the electronic structure of Pt is considered an effective approach to enhancing HOR activity and improving CO tolerance. Herein, we utilized the synergistic effect between the transition metal interstitial compounds (TMICs) of VN and Pt to develop a Pt-VN heterojunction-loaded carbon nanofiber catalyst (Pt-VN/NCNF) for CO tolerance in HOR. The introduction of VN causes electronic orbitals rearrangement of Pt, thereby optimizing the adsorption of H on the Pt surface. Meanwhile, the overlap of the d-band of the electron-deficient Pt with the 1π and 5σ bonding orbitals of CO was significantly reduced, which suppresses the strong CO adsorption on Pt surfaces and leave more active sites for H2 adsorption and oxidation. As a result, Pt-VN/NCNF exhibits a mass activity of 1.26 mA/µgPt, 41 times higher than that of commercial Pt/C. Encouragingly, Pt-VN/NCNF maintains 96.7% of its original activity even in the presence of 1000 ppm CO. As anticipated, Pt-VN/NCNF-based PEMFCs demonstrate superior CO tolerance to Pt/C in H2/CO mixtures with CO concentrations ranging from 10 ppm to 1000 ppm.
2026, 37(5): 111862
doi: 10.1016/j.cclet.2025.111862
摘要:
To elucidate the regulatory mechanisms of interlayers on interfacial polymerization (IP) dynamics and thin-film composite (TFC) membrane performance, UiO-66 and its derivatives with tailored properties were synthesized and employed as interlayers to fabricate TFC membranes. The influence of interlayer's charge and porosity on IP reaction was systematically investigated based on the forward osmosis (FO) system. Results showed that the introduction of the UiO-66 interlayer promoted the diffusion of the reactive monomer during the initial stage of the IP reaction, resulting in a wrinkled and thin polyamide (PA) layer. Compared to the pristine TFC membrane, the UiO-66–0% interlayered TFC membrane exhibited 2.7-fold enhanced water permeability (21.67 L m−2 h−1 (LMH)) but reduced salt rejection (3.69 g m−2 h−1 (gMH)). Incorporation of amino-functionalized UiO-66–30% with enhanced positive charge induced a double-layer PA structure, reducing water flux to 15.13 LMH. Engineering hierarchically porous UiO-66 (HP-UiO-66–30%) achieved balanced performance, maintaining high flux (21.04 LMH) while significantly improving rejection (1.39 gMH). This study demonstrates that strategic modulation of nanomaterial functionality and porosity enables precise PA layer engineering for high-performance TFC membranes with simultaneously enhanced permeability and selectivity.
To elucidate the regulatory mechanisms of interlayers on interfacial polymerization (IP) dynamics and thin-film composite (TFC) membrane performance, UiO-66 and its derivatives with tailored properties were synthesized and employed as interlayers to fabricate TFC membranes. The influence of interlayer's charge and porosity on IP reaction was systematically investigated based on the forward osmosis (FO) system. Results showed that the introduction of the UiO-66 interlayer promoted the diffusion of the reactive monomer during the initial stage of the IP reaction, resulting in a wrinkled and thin polyamide (PA) layer. Compared to the pristine TFC membrane, the UiO-66–0% interlayered TFC membrane exhibited 2.7-fold enhanced water permeability (21.67 L m−2 h−1 (LMH)) but reduced salt rejection (3.69 g m−2 h−1 (gMH)). Incorporation of amino-functionalized UiO-66–30% with enhanced positive charge induced a double-layer PA structure, reducing water flux to 15.13 LMH. Engineering hierarchically porous UiO-66 (HP-UiO-66–30%) achieved balanced performance, maintaining high flux (21.04 LMH) while significantly improving rejection (1.39 gMH). This study demonstrates that strategic modulation of nanomaterial functionality and porosity enables precise PA layer engineering for high-performance TFC membranes with simultaneously enhanced permeability and selectivity.
2026, 37(5): 111864
doi: 10.1016/j.cclet.2025.111864
摘要:
Porous liquids (PLs), as a new class of porous materials with permanent porosity and liquid fluidity, have attracted extensive research interest due to their excellent physical and chemical properties. Herein, we synthesized a chiral porous liquid D-his-ZIF-8-[Bpy][NTf2] based on a metal-organic framework (MOF) and used it as a new stationary phase to investigate its separation performance by high-resolution gas chromatography. The porosity of this porous liquid system was verified through Brunauer-Emmett-Teller (BET) and positron (e+) annihilation lifetime spectroscopy (PALS). The results showed that the D-his-ZIF-8-[Bpy][NTf2] coated capillary column (column A) exhibited excellent separation performance for n-alkanes, n-alcohols, alkylbenzens, isomers, and racemic compounds. Among them, fifteen pairs of enantiomers including alcohols, esters, epoxides, ketones, haloalkanes, and amino acid derivatives were well separated on column A with good reproducibility and stability. The relative standard deviations (RSDs) of the retention time and peak area of two analytes (3-butyne-2-ol and dichlorobenzene) were <1.80% and 0.80%, respectively. By comparing the chiral recognition ability of D-his-ZIF-8-[Bpy][NTf2] coated column A with D-his-ZIF-8 coated column B, the column A has better separation efficiency for chiral compounds than column B. In addition, the chiral recognition ability of column A is complementary to that of commercially available β-DEX 120 column (column C). Compared with the commercial HP-35 column and the previously reported P5A-C10–2NH2 column for the separation of organic mixtures and/or isomers, column A exhibits similar separation performance and has a good separation complementarity to these two columns. Hence, this work opens up a new way for the practical application of porous framework solid materials in gas chromatography.
Porous liquids (PLs), as a new class of porous materials with permanent porosity and liquid fluidity, have attracted extensive research interest due to their excellent physical and chemical properties. Herein, we synthesized a chiral porous liquid D-his-ZIF-8-[Bpy][NTf2] based on a metal-organic framework (MOF) and used it as a new stationary phase to investigate its separation performance by high-resolution gas chromatography. The porosity of this porous liquid system was verified through Brunauer-Emmett-Teller (BET) and positron (e+) annihilation lifetime spectroscopy (PALS). The results showed that the D-his-ZIF-8-[Bpy][NTf2] coated capillary column (column A) exhibited excellent separation performance for n-alkanes, n-alcohols, alkylbenzens, isomers, and racemic compounds. Among them, fifteen pairs of enantiomers including alcohols, esters, epoxides, ketones, haloalkanes, and amino acid derivatives were well separated on column A with good reproducibility and stability. The relative standard deviations (RSDs) of the retention time and peak area of two analytes (3-butyne-2-ol and dichlorobenzene) were <1.80% and 0.80%, respectively. By comparing the chiral recognition ability of D-his-ZIF-8-[Bpy][NTf2] coated column A with D-his-ZIF-8 coated column B, the column A has better separation efficiency for chiral compounds than column B. In addition, the chiral recognition ability of column A is complementary to that of commercially available β-DEX 120 column (column C). Compared with the commercial HP-35 column and the previously reported P5A-C10–2NH2 column for the separation of organic mixtures and/or isomers, column A exhibits similar separation performance and has a good separation complementarity to these two columns. Hence, this work opens up a new way for the practical application of porous framework solid materials in gas chromatography.
2026, 37(5): 111874
doi: 10.1016/j.cclet.2025.111874
摘要:
Geometrical configurations at the nanometer scale are inherently linked to electronic properties, offering exciting opportunity to engineer the latter through precise structural control. The honeycomb structure, a prominent geometry in two-dimensional materials like graphene, has become a versatile platform for advancing energy technologies, quantum computing, and nanoscale sensing. Achieving a perfect honeycomb network at large scale remains challenging but desired, especially when atomic defects and disorder can severely impact materials' properties and performances. Intrinsic topological defects often persist due to the conformational flexibility of the precursor skeletons, which allows precursor monomers to deform despite variations in preparation parameters. To address this challenge, we employ a tripod molecular precursor, pTBPT, combined with ultrahigh vacuum on-surface synthesis. Networks comprising rings of different edges are initially formed after deposition of pTBPT on Cu (111) at room temperature to 420 K. At low coverage (~0.015 monolayer) selenium doping, we achieve the fabrication of ordered honeycomb networks with much improved structural homogeneity. Selenium doping facilitated the formation of ordered two-dimensional metal-organic nanostructure from 360 K to 480 K. The disorder−order transition of molecular networks through selenium doping on Cu (111) is explored through high-resolution scanning tunneling microscopy (STM). A persistent homology method is resorted to quantify the degree of order of our patterns. The regulation of energy diagrams in the absence or presence of the selenium atom is revealed by density functional theory (DFT) calculations. These findings can enrich the on-surface synthesis toolbox of conformationally flexible precursors, for the design of ordered nanoarchitectures, and for future development of engineered honeycomb nanomaterials.
Geometrical configurations at the nanometer scale are inherently linked to electronic properties, offering exciting opportunity to engineer the latter through precise structural control. The honeycomb structure, a prominent geometry in two-dimensional materials like graphene, has become a versatile platform for advancing energy technologies, quantum computing, and nanoscale sensing. Achieving a perfect honeycomb network at large scale remains challenging but desired, especially when atomic defects and disorder can severely impact materials' properties and performances. Intrinsic topological defects often persist due to the conformational flexibility of the precursor skeletons, which allows precursor monomers to deform despite variations in preparation parameters. To address this challenge, we employ a tripod molecular precursor, pTBPT, combined with ultrahigh vacuum on-surface synthesis. Networks comprising rings of different edges are initially formed after deposition of pTBPT on Cu (111) at room temperature to 420 K. At low coverage (~0.015 monolayer) selenium doping, we achieve the fabrication of ordered honeycomb networks with much improved structural homogeneity. Selenium doping facilitated the formation of ordered two-dimensional metal-organic nanostructure from 360 K to 480 K. The disorder−order transition of molecular networks through selenium doping on Cu (111) is explored through high-resolution scanning tunneling microscopy (STM). A persistent homology method is resorted to quantify the degree of order of our patterns. The regulation of energy diagrams in the absence or presence of the selenium atom is revealed by density functional theory (DFT) calculations. These findings can enrich the on-surface synthesis toolbox of conformationally flexible precursors, for the design of ordered nanoarchitectures, and for future development of engineered honeycomb nanomaterials.
2026, 37(5): 111903
doi: 10.1016/j.cclet.2025.111903
摘要:
In light of the prevalent issues associated with metal ion dissolution, secondary pollution, and poor stability in traditional metal-based Fenton catalysts, this study innovatively developed a metal-free carbon-based catalyst co-doped with Si-O bonds and graphitic nitrogen using natural diatomite as the precursor. By leveraging the synergistic effects of Si-O bonds and graphitic nitrogen, the electronic structure of the carbon matrix was effectively modulated, establishing an efficient electron transport channel for peroxymonosulfate (PMS) activation. Results showed that the Fenton-like performance of the resulting catalysts was far superior to those of traditional metal catalysts and can be comparable to various single-atom catalysts. Both the radical and 1O2 pathways exhibited a negligible role in the metal-free Si-O/N@DM/PMS systems. In contrast, electron transfer process (ETP) was the predominate oxidation pathway for acetaminophen (PCM) degradation in the Si-O/N@DM/PMS systems. To facilitate engineering applications, we further designed a proton membrane reactor integrated with a four-channel PMS system, which could introduce an enlarged ETP pathway for pollutant degradation; this addresses the key issues of both sulfate pollution and metal leaching in water caused by traditional metal-based Fenton systems.
In light of the prevalent issues associated with metal ion dissolution, secondary pollution, and poor stability in traditional metal-based Fenton catalysts, this study innovatively developed a metal-free carbon-based catalyst co-doped with Si-O bonds and graphitic nitrogen using natural diatomite as the precursor. By leveraging the synergistic effects of Si-O bonds and graphitic nitrogen, the electronic structure of the carbon matrix was effectively modulated, establishing an efficient electron transport channel for peroxymonosulfate (PMS) activation. Results showed that the Fenton-like performance of the resulting catalysts was far superior to those of traditional metal catalysts and can be comparable to various single-atom catalysts. Both the radical and 1O2 pathways exhibited a negligible role in the metal-free Si-O/N@DM/PMS systems. In contrast, electron transfer process (ETP) was the predominate oxidation pathway for acetaminophen (PCM) degradation in the Si-O/N@DM/PMS systems. To facilitate engineering applications, we further designed a proton membrane reactor integrated with a four-channel PMS system, which could introduce an enlarged ETP pathway for pollutant degradation; this addresses the key issues of both sulfate pollution and metal leaching in water caused by traditional metal-based Fenton systems.
2026, 37(5): 111914
doi: 10.1016/j.cclet.2025.111914
摘要:
Eliminating heavy metals from industrial high-salinity wastewater is imperative for sustainable industrial development and environmental protection. Herein, a citrate-modified biochar that demonstrated robust anti-salt interference was developed. The sorbent achieved an adsorption capacity of 252.14 mg/g in 4.1 mol/L NaCl solution and 232.55 mg/g in 1.4 mol/L Na2SO4 solution, maintaining efficient Cu(Ⅱ) adsorption over four cycles. It retained an adsorption capacity of 236.89 mg/g in real waste salt-derived brine. Adsorption followed pseudo-first-order kinetics (k = 0.0901 min-1) and conformed to the Langmuir isotherm (qmax = 251.21 mg/g) model, indicating that physical adsorption on a homogeneous surface primarily governs the adsorption mechanisms. Thermodynamic analysis revealed that the adsorption is spontaneous and endothermic, with enhanced affinity for Cu(Ⅱ) at higher temperatures. Oxygen-containing groups, especially the hydroxyl group, drove adsorption via surface precipitation/complexation, ultimately generating posnjakite (Cu4(SO4)(OH)6·2H2O). Cost analysis showed that the total expenditure for treating 1000 L of wastewater (300 mgCu/L) was ＄28.89 (＄0.0963/gCu(Ⅱ)) and the treatment capacity using fixed-bed columns was 120 L/kg. These findings offer a viable and cost-effective strategy for Cu(Ⅱ) elimination from high-salinity wastewater.
Eliminating heavy metals from industrial high-salinity wastewater is imperative for sustainable industrial development and environmental protection. Herein, a citrate-modified biochar that demonstrated robust anti-salt interference was developed. The sorbent achieved an adsorption capacity of 252.14 mg/g in 4.1 mol/L NaCl solution and 232.55 mg/g in 1.4 mol/L Na2SO4 solution, maintaining efficient Cu(Ⅱ) adsorption over four cycles. It retained an adsorption capacity of 236.89 mg/g in real waste salt-derived brine. Adsorption followed pseudo-first-order kinetics (k = 0.0901 min-1) and conformed to the Langmuir isotherm (qmax = 251.21 mg/g) model, indicating that physical adsorption on a homogeneous surface primarily governs the adsorption mechanisms. Thermodynamic analysis revealed that the adsorption is spontaneous and endothermic, with enhanced affinity for Cu(Ⅱ) at higher temperatures. Oxygen-containing groups, especially the hydroxyl group, drove adsorption via surface precipitation/complexation, ultimately generating posnjakite (Cu4(SO4)(OH)6·2H2O). Cost analysis showed that the total expenditure for treating 1000 L of wastewater (300 mgCu/L) was ＄28.89 (＄0.0963/gCu(Ⅱ)) and the treatment capacity using fixed-bed columns was 120 L/kg. These findings offer a viable and cost-effective strategy for Cu(Ⅱ) elimination from high-salinity wastewater.
2026, 37(5): 111923
doi: 10.1016/j.cclet.2025.111923
摘要:
Non-noble metal catalysts have garnered significant attention as sustainable alternatives to precious metal catalysts for the abatement of hydrocarbon emissions and mitigating environmental pollution. In this study, we employed an in-situ exsolution strategy coupled with oxidation stabilization to engineer the surface of cobalt-doped LaFeO3-δ catalysts, successfully extending their application in an oxygen-rich scenario. The formed unique socket-like structure facilitates the exposure of highly reactive CoOx particles with superior homogeneity in both size and distribution. The optimized catalyst, CoOx@LFCO-3, achieved 90% toluene conversion at a notably lower temperature of 237 ℃ with a space velocity of 20,000 mL g−1 h−1. Mechanistic studies revealed that the enhanced interaction between exsolved cobalt oxides and the perovskite support, along with abundant active sites, significantly improved the catalyst's performance in low-temperature toluene oxidation. This work presents a scalable approach for developing cost-effective, high-performance perovskite oxide catalysts for environmental applications.
Non-noble metal catalysts have garnered significant attention as sustainable alternatives to precious metal catalysts for the abatement of hydrocarbon emissions and mitigating environmental pollution. In this study, we employed an in-situ exsolution strategy coupled with oxidation stabilization to engineer the surface of cobalt-doped LaFeO3-δ catalysts, successfully extending their application in an oxygen-rich scenario. The formed unique socket-like structure facilitates the exposure of highly reactive CoOx particles with superior homogeneity in both size and distribution. The optimized catalyst, CoOx@LFCO-3, achieved 90% toluene conversion at a notably lower temperature of 237 ℃ with a space velocity of 20,000 mL g−1 h−1. Mechanistic studies revealed that the enhanced interaction between exsolved cobalt oxides and the perovskite support, along with abundant active sites, significantly improved the catalyst's performance in low-temperature toluene oxidation. This work presents a scalable approach for developing cost-effective, high-performance perovskite oxide catalysts for environmental applications.
2026, 37(5): 111927
doi: 10.1016/j.cclet.2025.111927
摘要:
The preparation of porous molecularly imprinted polymers (MIPs) from starch, a natural product, presents significant challenges. In this study, we developed a straightforward method for preparing porous MIPs (DFP-MIPs) by crosslinking short amylose as a functional monomer with decafluorobiphenyl (DFP) as a cross-linker. Experimental results indicated that DFP-MIPs exhibited a larger specific surface area (14.06 m2/g) and adsorption capacity (26.3 mg/g), and a high imprinting factor of 3.14 for estradiol (E2), compared to MIPs prepared using tetrafluorobenzenediamine with a single benzene ring as the cross-linker. A method for detecting E2 in milk and meat samples was also established using DFP-MIPs as the adsorbent in conjunction with high-performance liquid chromatography. Under optimal conditions, this method demonstrated a linear range of 0.0200–0.400 µg/g, a detection limit of 0.00300 µg/g, and a recovery rate of 85.2% to 101.4%. The proposed method for preparing DFP-MIPs is expected to provide a new pathway for the development of porous and highly selective MIPs using amylose.
The preparation of porous molecularly imprinted polymers (MIPs) from starch, a natural product, presents significant challenges. In this study, we developed a straightforward method for preparing porous MIPs (DFP-MIPs) by crosslinking short amylose as a functional monomer with decafluorobiphenyl (DFP) as a cross-linker. Experimental results indicated that DFP-MIPs exhibited a larger specific surface area (14.06 m2/g) and adsorption capacity (26.3 mg/g), and a high imprinting factor of 3.14 for estradiol (E2), compared to MIPs prepared using tetrafluorobenzenediamine with a single benzene ring as the cross-linker. A method for detecting E2 in milk and meat samples was also established using DFP-MIPs as the adsorbent in conjunction with high-performance liquid chromatography. Under optimal conditions, this method demonstrated a linear range of 0.0200–0.400 µg/g, a detection limit of 0.00300 µg/g, and a recovery rate of 85.2% to 101.4%. The proposed method for preparing DFP-MIPs is expected to provide a new pathway for the development of porous and highly selective MIPs using amylose.
2026, 37(5): 111931
doi: 10.1016/j.cclet.2025.111931
摘要:
Developing a supramolecular polymer gel based on carbonized polymer dots with highly efficient lubrication properties is very challenging. Here, we obtained a kind of carbonized polymer dots (CPDs) by thermal reflux of long-chain aliphatic amines in halogenated benzene solvents. The CPDs nano-gel achieved high lubrication performance due to entangling effect of long chain and reversible thixotropic behavior after gel formation. Two-dimensional correlation synchronous (2D-COS) showed the CPDs connect small carbon dots into large hydrophobic structures through their own dense chain entanglement, thus trapping oil to form gel. Chain entanglement, as a non-permanent crosslinking, can slide under stress, and this flexible and dynamic characteristic allows it to maintain efficient and long-lasting lubrication without hysteresis during friction. The tribological test results showed a significant reduction of 38.14% in the coefficient of friction and 93.71% in wear scar diameter after lubrication with CPDs nano-gel. Moreover, the serial analysis for the friction interface and computational methodologies revealed that the formation of tribochemical film between friction pairs is the key to reduce wear. This study underscored the possibility of utilizing carbonized polymer dots for self-assembly applications, and we anticipate that supramolecular carbonized polymer dots gels have great potential in lubrication and emission reduction, ultimately contributing to the development of a sustainable society.
Developing a supramolecular polymer gel based on carbonized polymer dots with highly efficient lubrication properties is very challenging. Here, we obtained a kind of carbonized polymer dots (CPDs) by thermal reflux of long-chain aliphatic amines in halogenated benzene solvents. The CPDs nano-gel achieved high lubrication performance due to entangling effect of long chain and reversible thixotropic behavior after gel formation. Two-dimensional correlation synchronous (2D-COS) showed the CPDs connect small carbon dots into large hydrophobic structures through their own dense chain entanglement, thus trapping oil to form gel. Chain entanglement, as a non-permanent crosslinking, can slide under stress, and this flexible and dynamic characteristic allows it to maintain efficient and long-lasting lubrication without hysteresis during friction. The tribological test results showed a significant reduction of 38.14% in the coefficient of friction and 93.71% in wear scar diameter after lubrication with CPDs nano-gel. Moreover, the serial analysis for the friction interface and computational methodologies revealed that the formation of tribochemical film between friction pairs is the key to reduce wear. This study underscored the possibility of utilizing carbonized polymer dots for self-assembly applications, and we anticipate that supramolecular carbonized polymer dots gels have great potential in lubrication and emission reduction, ultimately contributing to the development of a sustainable society.
2026, 37(5): 111935
doi: 10.1016/j.cclet.2025.111935
摘要:
Rational design of nonmetallic heteroatom-doped biochar catalysts for peroxymonosulfate (PMS) activation faces dual challenges in regulating electronic structures and clarifying non-radical pathways. This study addressed this through a nitrogen-oxygen co-doped biochar (NOBCBM) synthesized via mechanochemical ball milling and chemical doping. Co-doping of C=O, pyridinic N, and graphitic N synergistically enhanced electron transfer and PMS activation efficiency compared to single N-doped biochar systems. The optimized NOBCBM removed 94% oxytetracycline (OTC) (20 mg/L) in 30 min, with a kinetic constant (kobs = 0.1523 min−1) over twice that of NSBCBM (0.0664 min−1). Radical quenching and electron paramagnetic resonance identified singlet oxygen (1O2) and electron transfer as dominant non-radical pathways. Density functional theory (DFT) calculations revealed oxygen doping elevates local electrostatic potential and redistributes electron density at N-active sites, amplifying catalytic activity. The system demonstrated robust catalytic performance across pH 3–11, high salinity, and complex water matrices, maintaining > 80% OTC removal over 72 h. Plant growth assays and life cycle assessment (LCA) confirmed minimal ecological impacts, with purified water supporting normal seedling development. This work elucidates the critical role of N/O co-doping in steering PMS activation toward non-radical mechanisms while establishing a sustainable paradigm for metal-free biochar catalysis in water remediation.
Rational design of nonmetallic heteroatom-doped biochar catalysts for peroxymonosulfate (PMS) activation faces dual challenges in regulating electronic structures and clarifying non-radical pathways. This study addressed this through a nitrogen-oxygen co-doped biochar (NOBCBM) synthesized via mechanochemical ball milling and chemical doping. Co-doping of C=O, pyridinic N, and graphitic N synergistically enhanced electron transfer and PMS activation efficiency compared to single N-doped biochar systems. The optimized NOBCBM removed 94% oxytetracycline (OTC) (20 mg/L) in 30 min, with a kinetic constant (kobs = 0.1523 min−1) over twice that of NSBCBM (0.0664 min−1). Radical quenching and electron paramagnetic resonance identified singlet oxygen (1O2) and electron transfer as dominant non-radical pathways. Density functional theory (DFT) calculations revealed oxygen doping elevates local electrostatic potential and redistributes electron density at N-active sites, amplifying catalytic activity. The system demonstrated robust catalytic performance across pH 3–11, high salinity, and complex water matrices, maintaining > 80% OTC removal over 72 h. Plant growth assays and life cycle assessment (LCA) confirmed minimal ecological impacts, with purified water supporting normal seedling development. This work elucidates the critical role of N/O co-doping in steering PMS activation toward non-radical mechanisms while establishing a sustainable paradigm for metal-free biochar catalysis in water remediation.
2026, 37(5): 111975
doi: 10.1016/j.cclet.2025.111975
摘要:
Spontaneous resolution is a way for constructing chiral compounds from achiral modules, but the products are usually stochastic, which is unsuitable for enantioselective applications. Herein, a pair of chiral hydrogen-bonded frameworks assembled from achiral modules was reported. By introducing reusable chiral inducers, enantiomerically enriched NKU-777-xD/xL were obtained and exhibited superior enantioselective sensing performance. Notably, the amount of chiral inducer shows a positive correlation with the enantioselective sensing function, reflecting the degree of enantiomeric excess of NKU-777-xD/xL. Molecular-level mechanism studies reveal that competitive absorption governs the sensing functions of NKU-777-xD/xL, and the enantioselectivity is due to the enantioselective interactions of the hydrogen-bonded frameworks with targeting chiral molecules. This work not only provides a facile way to synthesize enantiomerically enriched chiral hydrogen-bonded frameworks from achiral modules using reusable chiral inducer but also gains insights into the inducer-controlled enantiomerically enriched chiral compounds for enantioselective applications.
Spontaneous resolution is a way for constructing chiral compounds from achiral modules, but the products are usually stochastic, which is unsuitable for enantioselective applications. Herein, a pair of chiral hydrogen-bonded frameworks assembled from achiral modules was reported. By introducing reusable chiral inducers, enantiomerically enriched NKU-777-xD/xL were obtained and exhibited superior enantioselective sensing performance. Notably, the amount of chiral inducer shows a positive correlation with the enantioselective sensing function, reflecting the degree of enantiomeric excess of NKU-777-xD/xL. Molecular-level mechanism studies reveal that competitive absorption governs the sensing functions of NKU-777-xD/xL, and the enantioselectivity is due to the enantioselective interactions of the hydrogen-bonded frameworks with targeting chiral molecules. This work not only provides a facile way to synthesize enantiomerically enriched chiral hydrogen-bonded frameworks from achiral modules using reusable chiral inducer but also gains insights into the inducer-controlled enantiomerically enriched chiral compounds for enantioselective applications.
2026, 37(5): 112064
doi: 10.1016/j.cclet.2025.112064
摘要:
Molecular glues (MGs) represent a promising approach in protein regulation, especially for "undruggable" targets. Despite the advantages over traditional protein inhibitors and proteolysis-targeting chimeras (PROTACs), MGs show various off-target effects, inducing general toxicities in patients. Herein, we describe a structure-guided design of visible-light photocaged MGs (vc-MGs), which precisely and spatiotemporally control the G1 to S phase transition 1 (GSPT1) protein level and Burkitt's lymphoma through visible-light irradiation in vitro and in vivo. Notably, activated VL-MG-9 showed a potent antitumor effect in the RAMOS xenograft mouse model, while VL-MG-9 alone has no GSPT1 degradation activity or general toxicity in various organs even at high dose. Furthermore, proteomics assay and apoptosis analysis confirmed the selectivity and safety of VL-MG-9. Significantly, pharmacokinetic results demonstrated the enhanced permeability and bioavailability (F%) of VL-MG-9. These data clearly reveal the practicality and importance of vc-MGs as preliminary tool for the targeted therapy of malignancies with reduced systemic toxicity and improved druggability.
Molecular glues (MGs) represent a promising approach in protein regulation, especially for "undruggable" targets. Despite the advantages over traditional protein inhibitors and proteolysis-targeting chimeras (PROTACs), MGs show various off-target effects, inducing general toxicities in patients. Herein, we describe a structure-guided design of visible-light photocaged MGs (vc-MGs), which precisely and spatiotemporally control the G1 to S phase transition 1 (GSPT1) protein level and Burkitt's lymphoma through visible-light irradiation in vitro and in vivo. Notably, activated VL-MG-9 showed a potent antitumor effect in the RAMOS xenograft mouse model, while VL-MG-9 alone has no GSPT1 degradation activity or general toxicity in various organs even at high dose. Furthermore, proteomics assay and apoptosis analysis confirmed the selectivity and safety of VL-MG-9. Significantly, pharmacokinetic results demonstrated the enhanced permeability and bioavailability (F%) of VL-MG-9. These data clearly reveal the practicality and importance of vc-MGs as preliminary tool for the targeted therapy of malignancies with reduced systemic toxicity and improved druggability.
2026, 37(5): 112202
doi: 10.1016/j.cclet.2025.112202
摘要:
The visible light photocatalytic gem‑carboamination reactions of α-diazo esters by using o-hydroxyaryl enaminones and amines as reaction partners have been realized, leading to the straightforward synthesis of chromone derived α-amino esters which could be easily hydrolyzed to functionalized α-amino acids. The reactions mediated by molecular iodine proceed via free radical pathway under metal-free conditions. Unlike the conventional carbene-based functionalization of diazo compounds involving nucleophilic/electrophilic or two electron neutral groups, the current protocol allows the installation of two nucleophilic functional structures to the carbon center, providing practical new tool for the synthesis of amino acids.
The visible light photocatalytic gem‑carboamination reactions of α-diazo esters by using o-hydroxyaryl enaminones and amines as reaction partners have been realized, leading to the straightforward synthesis of chromone derived α-amino esters which could be easily hydrolyzed to functionalized α-amino acids. The reactions mediated by molecular iodine proceed via free radical pathway under metal-free conditions. Unlike the conventional carbene-based functionalization of diazo compounds involving nucleophilic/electrophilic or two electron neutral groups, the current protocol allows the installation of two nucleophilic functional structures to the carbon center, providing practical new tool for the synthesis of amino acids.
2026, 37(5): 112348
doi: 10.1016/j.cclet.2025.112348
摘要:
The unstable solid electrolyte interphase (SEI) characterized by sluggish ion transport kinetics and consecutive side reactions poses a major challenge to the commercialization of sodium-ion batteries (SIBs). Here, ethoxy (pentafluoro) cyclotriphosphazene (PFPN) as a multifunctional electrolyte additive is reported to construct stable and highly ion-conductive SEI. PFPN decomposes preferentially to form the NaF, Na3N-rich SEI with fast Na+ migration kinetics due to its low lowest unoccupied molecular orbital energy and strong adsorption on hard carbon (HC) anode. Meanwhile, the incorporation of PFPN effectively suppresses exothermic reactions at the electrode/electrolyte interface, thereby reducing the risk of thermal runaway. As expected, the HCNa cell with PFPN additive demonstrates homogeneous sodium deposition on HC anode and delivers a high reversible capacity of 248.5 mAh/g with negligible capacity decay after 1000 cycles at 0.1 A/g. The NaNi0.33Fe0.33Mn0.33O2 (NFM)HC full cell also yields enhanced cycling stability under -20 ℃. This study proposes a simple and effective SEI regulation strategy for high-performance and safe SIBs.
The unstable solid electrolyte interphase (SEI) characterized by sluggish ion transport kinetics and consecutive side reactions poses a major challenge to the commercialization of sodium-ion batteries (SIBs). Here, ethoxy (pentafluoro) cyclotriphosphazene (PFPN) as a multifunctional electrolyte additive is reported to construct stable and highly ion-conductive SEI. PFPN decomposes preferentially to form the NaF, Na3N-rich SEI with fast Na+ migration kinetics due to its low lowest unoccupied molecular orbital energy and strong adsorption on hard carbon (HC) anode. Meanwhile, the incorporation of PFPN effectively suppresses exothermic reactions at the electrode/electrolyte interface, thereby reducing the risk of thermal runaway. As expected, the HCNa cell with PFPN additive demonstrates homogeneous sodium deposition on HC anode and delivers a high reversible capacity of 248.5 mAh/g with negligible capacity decay after 1000 cycles at 0.1 A/g. The NaNi0.33Fe0.33Mn0.33O2 (NFM)HC full cell also yields enhanced cycling stability under -20 ℃. This study proposes a simple and effective SEI regulation strategy for high-performance and safe SIBs.
2026, 37(5): 112373
doi: 10.1016/j.cclet.2026.112373
摘要:
A homogeneous dual catalytic system that synergistically merges photochemical and halogen-bond catalysis has been developed for the radical sulfonylation-annulation of (hetero)arene-tethered alkynes and alkenes with RSO2Cl. This protocol efficiently constructs a variety of sulfonylated fused-(hetero)arenes with good functional group compatibility under mild and eco-friendly conditions. The process is initiated by halogen-bond activation of RSO2Cl, which facilitates subsequent photocatalyzed heterolytic S-Cl cleavage via a SET pathway to generate RSO2 radicals; an alternative EnT pathway for radical generation was also identified.
A homogeneous dual catalytic system that synergistically merges photochemical and halogen-bond catalysis has been developed for the radical sulfonylation-annulation of (hetero)arene-tethered alkynes and alkenes with RSO2Cl. This protocol efficiently constructs a variety of sulfonylated fused-(hetero)arenes with good functional group compatibility under mild and eco-friendly conditions. The process is initiated by halogen-bond activation of RSO2Cl, which facilitates subsequent photocatalyzed heterolytic S-Cl cleavage via a SET pathway to generate RSO2 radicals; an alternative EnT pathway for radical generation was also identified.
2026, 37(5): 112417
doi: 10.1016/j.cclet.2026.112417
摘要:
Despite the enormous potential of heteroatom-doped carbon materials for sodium storage applications, direct doping strategies still face two critical unresolved challenges: Elucidating the modulation mechanism of heteroatom doping on the hybrid energy storage behavior of sodium-ion hybrid capacitors (SIHCs), and maintaining structural integrity while achieving high sulfur-nitrogen (S, N) co-doping levels. Herein, we report a facile and controllable synthetic approach for preparing highly S, N co-doped porous carbon (denoted as SNGN-1), using sodium gallate, pre-synthesized via the neutralization reaction of gallic acid with sodium hydroxide, as the precursor. The as-fabricated SNGN-1 possesses a high nitrogen content of 4.02 at% and a sulfur content of 1.31 at%, coupled with abundant structural defects, a large specific surface area, superior electronic conductivity, exceptional sodium storage capability and robust cycling stability. Computational results demonstrate that the Na+ adsorption energy (Ead) of SNGN-1 is -1.936 eV, corresponding to a substantial increase in the absolute value relative to its undoped counterpart; additionally, the incorporation of heteroatoms leads to a marked intensification of the valence and conduction band peaks near the Fermi level. When employed as the anode for sodium-ion half-cells, SNGN-1 delivers a high reversible capacity of 585 mAh/g at a current density of 0.1 A/g, and retains stable cycling performance even after 1000 cycles at 2 A/g. More impressively, the SIHC device assembled with SNGN-1 as the anode achieves remarkable energy/power density metrics, delivering a high energy density of 165.2 Wh/kg at a power density of 218.6 W/kg. These findings highlight the great potential of SNGN-1 as a high-performance anode material for advanced sodium-ion batteries and SIHCs, thereby paving the way for the development of next-generation low-cost energy storage systems.
Despite the enormous potential of heteroatom-doped carbon materials for sodium storage applications, direct doping strategies still face two critical unresolved challenges: Elucidating the modulation mechanism of heteroatom doping on the hybrid energy storage behavior of sodium-ion hybrid capacitors (SIHCs), and maintaining structural integrity while achieving high sulfur-nitrogen (S, N) co-doping levels. Herein, we report a facile and controllable synthetic approach for preparing highly S, N co-doped porous carbon (denoted as SNGN-1), using sodium gallate, pre-synthesized via the neutralization reaction of gallic acid with sodium hydroxide, as the precursor. The as-fabricated SNGN-1 possesses a high nitrogen content of 4.02 at% and a sulfur content of 1.31 at%, coupled with abundant structural defects, a large specific surface area, superior electronic conductivity, exceptional sodium storage capability and robust cycling stability. Computational results demonstrate that the Na+ adsorption energy (Ead) of SNGN-1 is -1.936 eV, corresponding to a substantial increase in the absolute value relative to its undoped counterpart; additionally, the incorporation of heteroatoms leads to a marked intensification of the valence and conduction band peaks near the Fermi level. When employed as the anode for sodium-ion half-cells, SNGN-1 delivers a high reversible capacity of 585 mAh/g at a current density of 0.1 A/g, and retains stable cycling performance even after 1000 cycles at 2 A/g. More impressively, the SIHC device assembled with SNGN-1 as the anode achieves remarkable energy/power density metrics, delivering a high energy density of 165.2 Wh/kg at a power density of 218.6 W/kg. These findings highlight the great potential of SNGN-1 as a high-performance anode material for advanced sodium-ion batteries and SIHCs, thereby paving the way for the development of next-generation low-cost energy storage systems.
2026, 37(5): 110860
doi: 10.1016/j.cclet.2025.110860
摘要:
In the context of the continuously increasing energy demand, the ongoing advancement of innovative energy storage technologies is regarded as an important strategy to alleviate the energy crisis. Among various energy storage technologies, supercapacitors (SCs) demonstrate significant potential in the future energy storage sector due to their exceptional high-power density and long cycle life. As the core component of SCs, the choice of electrode materials is crucial to their performance, with carbon materials being favored for their excellent electrical conductivity and large specific surface area. In particular, porous carbon materials derived from biomass-based polymers have become a research hotspot due to their unique advantages. Through chemical modification and high-temperature carbonization, these materials can form more stable and optimized porous structures, significantly enhancing their electrochemical performance while meeting environmental protection requirements, thereby highlighting their superiority as electrode materials. This article aims to review the sources, production, and applications of carbon materials derived from biomass-based polymers. We have deeply summarized the preparation and activation methods of carbon from different biomass-based polymer sources. In addition, a comprehensive analysis and systematic comparison of novel modification techniques, such as heteroatom doping, copolymerization, and the incorporation of nanomaterials, were performed to enhance the performance of SCs. Finally, according to the technical challenges to be solved, the goal of large-scale development of biomass-based polymer-derived porous carbon in the field of energy storage is proposed, which is crucial for coping with the global energy crisis and reducing environmental impact.
In the context of the continuously increasing energy demand, the ongoing advancement of innovative energy storage technologies is regarded as an important strategy to alleviate the energy crisis. Among various energy storage technologies, supercapacitors (SCs) demonstrate significant potential in the future energy storage sector due to their exceptional high-power density and long cycle life. As the core component of SCs, the choice of electrode materials is crucial to their performance, with carbon materials being favored for their excellent electrical conductivity and large specific surface area. In particular, porous carbon materials derived from biomass-based polymers have become a research hotspot due to their unique advantages. Through chemical modification and high-temperature carbonization, these materials can form more stable and optimized porous structures, significantly enhancing their electrochemical performance while meeting environmental protection requirements, thereby highlighting their superiority as electrode materials. This article aims to review the sources, production, and applications of carbon materials derived from biomass-based polymers. We have deeply summarized the preparation and activation methods of carbon from different biomass-based polymer sources. In addition, a comprehensive analysis and systematic comparison of novel modification techniques, such as heteroatom doping, copolymerization, and the incorporation of nanomaterials, were performed to enhance the performance of SCs. Finally, according to the technical challenges to be solved, the goal of large-scale development of biomass-based polymer-derived porous carbon in the field of energy storage is proposed, which is crucial for coping with the global energy crisis and reducing environmental impact.
2026, 37(5): 110973
doi: 10.1016/j.cclet.2025.110973
摘要:
Solid-state batteries that present lower risk factors and higher energy density are promising for advanced energy storage and applications. In particular, solid-state electrolytes (SSEs) are the critical components that responsible for ionic transport between negative electrodes and positive electrodes. It is crucial to fundamentally understand the ionic transport models and behaviors in the SSEs, with purpose of enhancing ion transport rate and stability of SSEs. To rationally improve the solid-state ion transport behavior of electrolytes, this review summarizes recent progresses on the transport principles and multiscale characterization methods of ion transport in SSEs, including traditional electrochemical methods, frequency-dependent spectroscopy, two-dimensional morphological imaging and three-dimensional morphological imaging. It is emphasized that combination of multiscale and multiple methods would be a developing trend for fundamentally understanding the mechanism of ion transport in SSEs. According to comprehensive transport principle and behaviors, hierarchical fillers are designed for composite electrolytes with fast ionic transport abilities. The remaining challenges for establishing advanced multiscale characterization methods are also discussed.
Solid-state batteries that present lower risk factors and higher energy density are promising for advanced energy storage and applications. In particular, solid-state electrolytes (SSEs) are the critical components that responsible for ionic transport between negative electrodes and positive electrodes. It is crucial to fundamentally understand the ionic transport models and behaviors in the SSEs, with purpose of enhancing ion transport rate and stability of SSEs. To rationally improve the solid-state ion transport behavior of electrolytes, this review summarizes recent progresses on the transport principles and multiscale characterization methods of ion transport in SSEs, including traditional electrochemical methods, frequency-dependent spectroscopy, two-dimensional morphological imaging and three-dimensional morphological imaging. It is emphasized that combination of multiscale and multiple methods would be a developing trend for fundamentally understanding the mechanism of ion transport in SSEs. According to comprehensive transport principle and behaviors, hierarchical fillers are designed for composite electrolytes with fast ionic transport abilities. The remaining challenges for establishing advanced multiscale characterization methods are also discussed.
2026, 37(5): 111262
doi: 10.1016/j.cclet.2025.111262
摘要:
Inflammatory bowel disease (IBD), which includes Crohn’s disease and ulcerative colitis, represents a significant health challenge due to its intricate interplay of genetic, environmental, and immunological factors. While current treatments are effective at managing symptoms, they are not without drawbacks, such as potential side effects, the financial strain on patients, and the risk of complications. Nanotechnology presents an innovative solution to these challenges, offering the potential to improve the bioavailability, stability, and precise delivery of natural compounds with potent anti-inflammatory properties. This review examines the array of nanoparticle (NP) delivery systems that are revolutionizing IBD treatment, including lipid-based NPs, polymeric NPs, metallic NPs, plant-derived exosomes, and mesoporous silica NPs. Furthermore, the review explores the various responsive mechanisms of NPs, including pH-responsive, reactive oxygen species (ROS)-responsive, enzyme-responsive, charge-mediated, ligand-receptor targeted, and multi-responsive systems. The therapeutic potential of nanomedicines derived from natural products is highlighted, with a focus on their roles in immunomodulation, reducing inflammation, repairing the intestinal barrier, and modulating the gut microbiota. Nanotechnology boosts IBD treatment with novel natural NPs. NPs delivery systems offer notable benefits, such as improving drug solubility, increasing the efficiency of absorption, alongside providing a controlled and sustained release of therapeutic agents directly at the inflammation site. Despite the promising capabilities of nanotechnology in IBD treatment, obstacles remain. These include the necessity for comprehensive toxicological assessments, formulating strategies to guarantee the safety and effectiveness of these innovative treatments. Therefore, this review provides a systematic analysis that provides guidance for the research and development of NPs based natural products.
Inflammatory bowel disease (IBD), which includes Crohn’s disease and ulcerative colitis, represents a significant health challenge due to its intricate interplay of genetic, environmental, and immunological factors. While current treatments are effective at managing symptoms, they are not without drawbacks, such as potential side effects, the financial strain on patients, and the risk of complications. Nanotechnology presents an innovative solution to these challenges, offering the potential to improve the bioavailability, stability, and precise delivery of natural compounds with potent anti-inflammatory properties. This review examines the array of nanoparticle (NP) delivery systems that are revolutionizing IBD treatment, including lipid-based NPs, polymeric NPs, metallic NPs, plant-derived exosomes, and mesoporous silica NPs. Furthermore, the review explores the various responsive mechanisms of NPs, including pH-responsive, reactive oxygen species (ROS)-responsive, enzyme-responsive, charge-mediated, ligand-receptor targeted, and multi-responsive systems. The therapeutic potential of nanomedicines derived from natural products is highlighted, with a focus on their roles in immunomodulation, reducing inflammation, repairing the intestinal barrier, and modulating the gut microbiota. Nanotechnology boosts IBD treatment with novel natural NPs. NPs delivery systems offer notable benefits, such as improving drug solubility, increasing the efficiency of absorption, alongside providing a controlled and sustained release of therapeutic agents directly at the inflammation site. Despite the promising capabilities of nanotechnology in IBD treatment, obstacles remain. These include the necessity for comprehensive toxicological assessments, formulating strategies to guarantee the safety and effectiveness of these innovative treatments. Therefore, this review provides a systematic analysis that provides guidance for the research and development of NPs based natural products.
2026, 37(5): 111319
doi: 10.1016/j.cclet.2025.111319
摘要:
Infected bone defects (IBD) are intricate and formidable conditions characterized by elevated rates of infection recurrence and delayed healing, resulting from dysregulation of the bone immune microenvironment (IME) mediated by microbes. The conventional approaches including surgical intervention and antibiotic therapy encounter challenges such as antibiotic resistance and susceptibility to postoperative infections. Considering the diverse impacts of various immune cells (ICs) and cytokines, the investigations into the IME have been conducted to offer potential strategies for treating IBD by addressing the requirements of infection eradication and bone regeneration (BREG). However, there is still a lack of review discussing the impacts of IME on IBD in light of its diverse components. Hydrogels, as promising materials in the treatment of IBD, can mimic the extracellular matrix of natural tissues, providing an optimal environment for cell growth and tissue regeneration. Recent studies have focused on investigating immune modulation through hydrogel delivery for treating IBD. This review aims to discuss the effects of different types of ICs and cytokines on the IME in IBD while summarizing current progress and strategies targeting this microenvironment using hydrogels. The insights gained from this review will aid the development of future immunomodulatory approaches for IBD treatment.
Infected bone defects (IBD) are intricate and formidable conditions characterized by elevated rates of infection recurrence and delayed healing, resulting from dysregulation of the bone immune microenvironment (IME) mediated by microbes. The conventional approaches including surgical intervention and antibiotic therapy encounter challenges such as antibiotic resistance and susceptibility to postoperative infections. Considering the diverse impacts of various immune cells (ICs) and cytokines, the investigations into the IME have been conducted to offer potential strategies for treating IBD by addressing the requirements of infection eradication and bone regeneration (BREG). However, there is still a lack of review discussing the impacts of IME on IBD in light of its diverse components. Hydrogels, as promising materials in the treatment of IBD, can mimic the extracellular matrix of natural tissues, providing an optimal environment for cell growth and tissue regeneration. Recent studies have focused on investigating immune modulation through hydrogel delivery for treating IBD. This review aims to discuss the effects of different types of ICs and cytokines on the IME in IBD while summarizing current progress and strategies targeting this microenvironment using hydrogels. The insights gained from this review will aid the development of future immunomodulatory approaches for IBD treatment.
2026, 37(5): 111390
doi: 10.1016/j.cclet.2025.111390
摘要:
Hepatocellular carcinoma (HCC) is the most common type of primary liver cancer and is among the leading causes of cancer-related mortality. Immunotherapy strategies targeting HCC are widely used in clinical practice. However, the pronounced immunosuppressive characteristics of the tumor microenvironment in HCC significantly hinder the efficacy of immunotherapy, often leading to suboptimal therapeutic outcomes. Innovative immunomodulatory delivery systems offer a promising path for HCC therapy by enabling precise targeting of tumor sites and significantly reducing the chances of systemic toxicity and side effects. This study describes the immune microenvironment of HCC and the mechanisms leading to immune evasion. This study then explores the issues and restrictions of current mainstream immunotherapies, highlighting the breakthroughs achieved through drug delivery systems crafted with innovative micro-nanomaterials for HCC immunotherapy. Besides, the application scenarios and challenges encountered by micro-nanomaterials in clinical translational applications were also discussed, and future development trends in this field were prospected, offering a theoretical foundation for the design of efficient HCC treatment strategies.
Hepatocellular carcinoma (HCC) is the most common type of primary liver cancer and is among the leading causes of cancer-related mortality. Immunotherapy strategies targeting HCC are widely used in clinical practice. However, the pronounced immunosuppressive characteristics of the tumor microenvironment in HCC significantly hinder the efficacy of immunotherapy, often leading to suboptimal therapeutic outcomes. Innovative immunomodulatory delivery systems offer a promising path for HCC therapy by enabling precise targeting of tumor sites and significantly reducing the chances of systemic toxicity and side effects. This study describes the immune microenvironment of HCC and the mechanisms leading to immune evasion. This study then explores the issues and restrictions of current mainstream immunotherapies, highlighting the breakthroughs achieved through drug delivery systems crafted with innovative micro-nanomaterials for HCC immunotherapy. Besides, the application scenarios and challenges encountered by micro-nanomaterials in clinical translational applications were also discussed, and future development trends in this field were prospected, offering a theoretical foundation for the design of efficient HCC treatment strategies.
2026, 37(5): 111392
doi: 10.1016/j.cclet.2025.111392
摘要:
Ocular posterior segment diseases (OPSDs), including uveitis, glaucoma, retinitis pigmentosa (RP), fundus neovascular diseases (FNDs), and age-related macular degeneration (AMD), are major causes of global blindness. The eye's biological barriers often prevent conventional drugs from reaching the posterior segment effectively, while potentially causing adverse effects. Nanocarrier-based drug delivery systems (DDS) offer promising solutions, with their small size, tunable properties, and high biocompatibility enhancing drug permeability, stability, and targeted delivery. These systems may reduce administration frequency, prolong therapeutic effects, minimize side effects, and improve patient compliance. Unlike previous reviews, this article comprehensively examines novel nanocarriers for OPSD treatment. We first analyze small molecules, their nanocarriers, and administration methods based on recent two-decade research. Next, we compare nanocarrier stability, biocompatibility, ocular penetration, drug release kinetics, and formulation ease, emphasizing recent advances in design, preparation, and functional modification. Finally, by evaluating clinical applications and challenges, we discuss translational hurdles and future prospects for OPSD nanotherapeutics. Greater research efforts are needed to realize nanocarriers' full potential in OPSD treatment.
Ocular posterior segment diseases (OPSDs), including uveitis, glaucoma, retinitis pigmentosa (RP), fundus neovascular diseases (FNDs), and age-related macular degeneration (AMD), are major causes of global blindness. The eye's biological barriers often prevent conventional drugs from reaching the posterior segment effectively, while potentially causing adverse effects. Nanocarrier-based drug delivery systems (DDS) offer promising solutions, with their small size, tunable properties, and high biocompatibility enhancing drug permeability, stability, and targeted delivery. These systems may reduce administration frequency, prolong therapeutic effects, minimize side effects, and improve patient compliance. Unlike previous reviews, this article comprehensively examines novel nanocarriers for OPSD treatment. We first analyze small molecules, their nanocarriers, and administration methods based on recent two-decade research. Next, we compare nanocarrier stability, biocompatibility, ocular penetration, drug release kinetics, and formulation ease, emphasizing recent advances in design, preparation, and functional modification. Finally, by evaluating clinical applications and challenges, we discuss translational hurdles and future prospects for OPSD nanotherapeutics. Greater research efforts are needed to realize nanocarriers' full potential in OPSD treatment.
2026, 37(5): 111396
doi: 10.1016/j.cclet.2025.111396
摘要:
Tetrahedral framework nucleic acids (tFNAs), a novel class of nanodelivery carriers, demonstrate significant potential due to their well-defined topological structure, programmable molecular recognition capabilities, and exceptional biocompatibility. This article systematically reviews the dynamic behavior of tFNAs across multi-scale delivery processes. At the macroscale, it elucidates the organ accumulation and metabolism of tFNAs following various routes of administration. At the microscale, it delves into the transmembrane transport mechanisms and subcellular localization characteristics of tFNAs. Furthermore, this review discusses the current research status of strategies aimed at improving the delivery efficiency of tFNAs through active targeted modifications and proposes cutting-edge approaches to developing precision delivery systems leveraging engineering modifications and intelligent response designs.
Tetrahedral framework nucleic acids (tFNAs), a novel class of nanodelivery carriers, demonstrate significant potential due to their well-defined topological structure, programmable molecular recognition capabilities, and exceptional biocompatibility. This article systematically reviews the dynamic behavior of tFNAs across multi-scale delivery processes. At the macroscale, it elucidates the organ accumulation and metabolism of tFNAs following various routes of administration. At the microscale, it delves into the transmembrane transport mechanisms and subcellular localization characteristics of tFNAs. Furthermore, this review discusses the current research status of strategies aimed at improving the delivery efficiency of tFNAs through active targeted modifications and proposes cutting-edge approaches to developing precision delivery systems leveraging engineering modifications and intelligent response designs.
2026, 37(5): 111707
doi: 10.1016/j.cclet.2025.111707
摘要:
Hydrogels, soft materials made from polymer networks capable of absorbing water, demonstrate remarkable compatibility in diverse hybridizations. When the fillers that can undergo reversible crystallization are used for incorporation, the materials’ mechanical properties and functions would be significantly improved. Therefore, these hydrogels, named crystal hydrogels, are emerging as a class of new advanced functional materials. This review offers a comprehensive examination of these materials from five distinct angles. We first discuss their fundamental characteristics and then elaborate on the synthesis methods of crystal hydrogels, categorizing them into three types based on their crystal formation mechanisms. The third section is dedicated to describing the properties of crystal hydrogels. Furthermore, we explore the diverse and remarkable applications that have emerged with the advancement of crystal hydrogels. The review concludes by summarizing the core concepts and assessing the recent opportunities and challenges faced by crystal hydrogels.
Hydrogels, soft materials made from polymer networks capable of absorbing water, demonstrate remarkable compatibility in diverse hybridizations. When the fillers that can undergo reversible crystallization are used for incorporation, the materials’ mechanical properties and functions would be significantly improved. Therefore, these hydrogels, named crystal hydrogels, are emerging as a class of new advanced functional materials. This review offers a comprehensive examination of these materials from five distinct angles. We first discuss their fundamental characteristics and then elaborate on the synthesis methods of crystal hydrogels, categorizing them into three types based on their crystal formation mechanisms. The third section is dedicated to describing the properties of crystal hydrogels. Furthermore, we explore the diverse and remarkable applications that have emerged with the advancement of crystal hydrogels. The review concludes by summarizing the core concepts and assessing the recent opportunities and challenges faced by crystal hydrogels.
2026, 37(5): 111843
doi: 10.1016/j.cclet.2025.111843
摘要:
Myocardial infarction (MI) is a disease with a very high mortality rate among cardiovascular diseases. It causes extensive damage to myocardial cells due to prolonged and repeated ischemia and hypoxia. Early coronary revascularization is the best method for treating MI. However, the reperfusion process in MI can produce reactive oxygen species, further damaging myocardial tissue, and triggering MI-reperfusion injury (MI/RI). Although various traditional treatment strategies exist, the treatment of myocardial ischemia including MI and MI/RI remain a significant challenge. Mitochondrial dysfunction plays an important role in the emergence and development of myocardial ischemia. In recent years, with the advancement of nanobiomedicine, therapeutic strategies for targeting mitochondria have gained increasing attentions in diseases' therapy. Thus, nanobiomedicine targeting mitochondria has shown great promise in the treatment of myocardial ischemia. This review first comprehensively elaborates on the mechanisms of mitochondrial homeostasis in MI and MI/RI, and then focuses on the application progress of nanomaterials targeting mitochondrial homeostasis (oxidative stress, mitophagy, mitochondrial fusion and fission, etc.) in improving myocardial ischemia. Ultimately, this article looks forward to the prospects of nanomaterials in the targeting treatment of MI and MI/RI, aiming to provide more effective and innovative ideas for clinical treatments.
Myocardial infarction (MI) is a disease with a very high mortality rate among cardiovascular diseases. It causes extensive damage to myocardial cells due to prolonged and repeated ischemia and hypoxia. Early coronary revascularization is the best method for treating MI. However, the reperfusion process in MI can produce reactive oxygen species, further damaging myocardial tissue, and triggering MI-reperfusion injury (MI/RI). Although various traditional treatment strategies exist, the treatment of myocardial ischemia including MI and MI/RI remain a significant challenge. Mitochondrial dysfunction plays an important role in the emergence and development of myocardial ischemia. In recent years, with the advancement of nanobiomedicine, therapeutic strategies for targeting mitochondria have gained increasing attentions in diseases' therapy. Thus, nanobiomedicine targeting mitochondria has shown great promise in the treatment of myocardial ischemia. This review first comprehensively elaborates on the mechanisms of mitochondrial homeostasis in MI and MI/RI, and then focuses on the application progress of nanomaterials targeting mitochondrial homeostasis (oxidative stress, mitophagy, mitochondrial fusion and fission, etc.) in improving myocardial ischemia. Ultimately, this article looks forward to the prospects of nanomaterials in the targeting treatment of MI and MI/RI, aiming to provide more effective and innovative ideas for clinical treatments.
2026, 37(5): 111861
doi: 10.1016/j.cclet.2025.111861
摘要:
The electrochemical CO2 reduction (CO2R) holds the potential to manufacture carbon-based chemicals and fuels while advancing toward carbon neutrality. On the path to achieving practical CO2R, a significant challenge lies in the formation of carbonate salts due to the interplay between CO2, local alkalinity and metal cations. The carbonate issue leads to the wastage of CO2 reactant, thus resulting in low carbon utilization efficiency and high costs for carbonate regeneration. Additionally, such salt formation can threaten the operation stability of the CO2R in electrolyzers equipped with gas diffusion electrodes (GDE). These challenges motivate us to conduct the present review, aiming to provide a comprehensive understanding and propose solution strategies for the carbonate problem. We start from the mechanism insights into carbonate formation with specific analysis on the kinetics of carbonate formation, mass transfer process, and the influence of interfacial pH, followed by the exposition of advanced techniques to monitor the carbonate accumulation. Next, the design strategies to solve the carbonate problem including the optimization of electrolyte, electrode, membranes and operation conditions, are presented, with a highlight on acidic CO2 electrolysis system without introducing metal cations into electrolyte systems. We finally end up by offering future opportunities in this evolving field. These timely and inspiring perspectives can guide researchers in addressing carbonate-related issues and advance CO2R toward practical feasibility.
The electrochemical CO2 reduction (CO2R) holds the potential to manufacture carbon-based chemicals and fuels while advancing toward carbon neutrality. On the path to achieving practical CO2R, a significant challenge lies in the formation of carbonate salts due to the interplay between CO2, local alkalinity and metal cations. The carbonate issue leads to the wastage of CO2 reactant, thus resulting in low carbon utilization efficiency and high costs for carbonate regeneration. Additionally, such salt formation can threaten the operation stability of the CO2R in electrolyzers equipped with gas diffusion electrodes (GDE). These challenges motivate us to conduct the present review, aiming to provide a comprehensive understanding and propose solution strategies for the carbonate problem. We start from the mechanism insights into carbonate formation with specific analysis on the kinetics of carbonate formation, mass transfer process, and the influence of interfacial pH, followed by the exposition of advanced techniques to monitor the carbonate accumulation. Next, the design strategies to solve the carbonate problem including the optimization of electrolyte, electrode, membranes and operation conditions, are presented, with a highlight on acidic CO2 electrolysis system without introducing metal cations into electrolyte systems. We finally end up by offering future opportunities in this evolving field. These timely and inspiring perspectives can guide researchers in addressing carbonate-related issues and advance CO2R toward practical feasibility.
2026, 37(5): 111902
doi: 10.1016/j.cclet.2025.111902
摘要:
Organophosphorus (OPs) compounds are extensively utilized in pesticides, chemical warfare agents, pharmaceuticals, and industrial applications due to their distinctive chemical properties, including biological activity, persistence, and hydrophobicity. However, their excessive use has led to significant environmental toxicity and pollution concerns, underscoring the urgent need for sustainable methods to monitor OPs pollutants. Traditional detection relies on bulky instruments, whereas organic fluorescent probes present advantages such as high selectivity, sensitivity, and portability. This review summarizes recent advancements in these probes for OPs detection, outlines characterization strategies based on underlying mechanisms, discusses challenges and future directions, and introduces OPs’ features, probe mechanisms, and design guidelines, providing theoretical insights and technical references for the development of novel organic fluorescent probes.
Organophosphorus (OPs) compounds are extensively utilized in pesticides, chemical warfare agents, pharmaceuticals, and industrial applications due to their distinctive chemical properties, including biological activity, persistence, and hydrophobicity. However, their excessive use has led to significant environmental toxicity and pollution concerns, underscoring the urgent need for sustainable methods to monitor OPs pollutants. Traditional detection relies on bulky instruments, whereas organic fluorescent probes present advantages such as high selectivity, sensitivity, and portability. This review summarizes recent advancements in these probes for OPs detection, outlines characterization strategies based on underlying mechanisms, discusses challenges and future directions, and introduces OPs’ features, probe mechanisms, and design guidelines, providing theoretical insights and technical references for the development of novel organic fluorescent probes.
2026, 37(5): 111904
doi: 10.1016/j.cclet.2025.111904
摘要:
Electrocatalytic CO2 reduction to formate using renewable energy offers a promising route for sustainable chemical production and carbon utilization. Bismuth-based catalysts stand out for their exceptional selectivity towards formate, combining intrinsic advantages with practical viability. This review critically examines recent advances in strategically tailoring bismuth-based catalysts for selective CO2-to-formate conversion. Moving beyond conventional material classifications, we emphasize mechanistic understanding of the reaction pathways and active sites governing formate generation. Crucially, we dissect the synthesis strategies enabling precise control over catalyst properties—ranging from metallic bismuth nanostructures and single atoms to tailored compounds, heterostructures, and alloys—and link these design principles to performance optimization. In addition, we incorporate operando characterization and computational insights within catalyst-specific case studies to examine selected dynamic reaction mechanisms and key enhancement mechanisms under operational conditions. Finally, we outline forward-looking research trajectories, addressing critical challenges like achieving industrially relevant performance and stability, and proposing innovative pathways focused on advanced catalyst architectures, microenvironment engineering, and predictive frameworks for scalable implementation.
Electrocatalytic CO2 reduction to formate using renewable energy offers a promising route for sustainable chemical production and carbon utilization. Bismuth-based catalysts stand out for their exceptional selectivity towards formate, combining intrinsic advantages with practical viability. This review critically examines recent advances in strategically tailoring bismuth-based catalysts for selective CO2-to-formate conversion. Moving beyond conventional material classifications, we emphasize mechanistic understanding of the reaction pathways and active sites governing formate generation. Crucially, we dissect the synthesis strategies enabling precise control over catalyst properties—ranging from metallic bismuth nanostructures and single atoms to tailored compounds, heterostructures, and alloys—and link these design principles to performance optimization. In addition, we incorporate operando characterization and computational insights within catalyst-specific case studies to examine selected dynamic reaction mechanisms and key enhancement mechanisms under operational conditions. Finally, we outline forward-looking research trajectories, addressing critical challenges like achieving industrially relevant performance and stability, and proposing innovative pathways focused on advanced catalyst architectures, microenvironment engineering, and predictive frameworks for scalable implementation.
2026, 37(5): 111915
doi: 10.1016/j.cclet.2025.111915
摘要:
Electrocatalytic oxygen reduction reaction (ORR) is a key sustainable energy process, but its efficiency and durability are severely affected by reactive oxygen species (ROS) such as hydroxyl radicals and superoxide anions. Understanding the kinetics of these transient intermediates is crucial for revealing the ORR mechanism and designing novel electrocatalysts. Many new in situ and operando characterization techniques have emerged in ROS detection. This article reviews recent progress in the detection and quantification methods for ROS during the electrocatalytic ORR, including fluorescence spectroscopy, UV–vis absorption spectroscopy, electron paramagnetic spectroscopy, scanning electrochemical microscopy, and electrochemiluminescence related technologies. The aim is to provide latest references for researchers in this field and promote further development of electrocatalytic ORR related research.
Electrocatalytic oxygen reduction reaction (ORR) is a key sustainable energy process, but its efficiency and durability are severely affected by reactive oxygen species (ROS) such as hydroxyl radicals and superoxide anions. Understanding the kinetics of these transient intermediates is crucial for revealing the ORR mechanism and designing novel electrocatalysts. Many new in situ and operando characterization techniques have emerged in ROS detection. This article reviews recent progress in the detection and quantification methods for ROS during the electrocatalytic ORR, including fluorescence spectroscopy, UV–vis absorption spectroscopy, electron paramagnetic spectroscopy, scanning electrochemical microscopy, and electrochemiluminescence related technologies. The aim is to provide latest references for researchers in this field and promote further development of electrocatalytic ORR related research.
2026, 37(5): 111929
doi: 10.1016/j.cclet.2025.111929
摘要:
Asymmetric reduction of unsaturated compounds via dynamic kinetic resolution (DKR) has significantly enhanced the efficiency and selectivity of synthesizing enantiomerically pure compounds from racemic substrates. This approach combines the simultaneous racemization of substrates with enantioselective reduction, enabling quantitative yields and high enantiomeric excess. In the past several years, remarkable advances in this field have been achieved, ranging from the development of innovative catalytic systems, novel synthetic strategies, expansion of substrate scope, deeper mechanistic understanding, and their applications. These advancements offer alternative and efficient methods in the asymmetric synthesis of chiral molecules bearing multiple consecutive stereogenic centers, particularly beneficial for the synthesis of natural products or chiral intermediates in pharmaceuticals and fine chemicals. In this review, we summarize the recent advances during the last several years according to the substrate types in this powerful and productive field, with an emphasis on the development of new catalytic systems and the insight into the DKR process.
Asymmetric reduction of unsaturated compounds via dynamic kinetic resolution (DKR) has significantly enhanced the efficiency and selectivity of synthesizing enantiomerically pure compounds from racemic substrates. This approach combines the simultaneous racemization of substrates with enantioselective reduction, enabling quantitative yields and high enantiomeric excess. In the past several years, remarkable advances in this field have been achieved, ranging from the development of innovative catalytic systems, novel synthetic strategies, expansion of substrate scope, deeper mechanistic understanding, and their applications. These advancements offer alternative and efficient methods in the asymmetric synthesis of chiral molecules bearing multiple consecutive stereogenic centers, particularly beneficial for the synthesis of natural products or chiral intermediates in pharmaceuticals and fine chemicals. In this review, we summarize the recent advances during the last several years according to the substrate types in this powerful and productive field, with an emphasis on the development of new catalytic systems and the insight into the DKR process.
2026, 37(5): 111960
doi: 10.1016/j.cclet.2025.111960
摘要:
The growing global demand for sustainable energy makes biodiesel an important renewable alternative to alleviate the energy crisis and reduce greenhouse gas emissions. Therefore, there is an urgent need to develop efficient, environmentally friendly and economically viable biodiesel production methods. Hypercrosslinked polymers (HCPs), as aromatic porous organic polymers, are solid frameworks that can be used as heterogeneous catalyst, and they are a promising platform for biodiesel catalytic conversion due to their low cost, highly accessible active site, tunable catalytic site types. In addition, innovative green synthesis strategies make environmentally begin production of HCPs possible. In recent years, HCPs has developed rapidly in the field of biomass catalysis. Unfortunately, to the best of our knowledge, there are no publications focusing on the green synthesis and application of HCPs-based materials for biodiesel production. This review provides an update on the synthesis and utilisation of green and efficient HCPs for catalytic biodiesel production. Initially, the green routes for HCPs synthesis are described, followed by a comprehensive summary of the various approaches to biodiesel production. The primary focus is on the utilisation of HCPs as carriers of active sites in the catalytic conversion of biodiesel, with particular emphasis on catalyst design, morphology control, and intelligent management in terms of application extension. Ultimately, thought-provoking recommendations are proposed to utilize improved green HCPs in combination with advanced production processes to achieve more efficient and sustainable development.
The growing global demand for sustainable energy makes biodiesel an important renewable alternative to alleviate the energy crisis and reduce greenhouse gas emissions. Therefore, there is an urgent need to develop efficient, environmentally friendly and economically viable biodiesel production methods. Hypercrosslinked polymers (HCPs), as aromatic porous organic polymers, are solid frameworks that can be used as heterogeneous catalyst, and they are a promising platform for biodiesel catalytic conversion due to their low cost, highly accessible active site, tunable catalytic site types. In addition, innovative green synthesis strategies make environmentally begin production of HCPs possible. In recent years, HCPs has developed rapidly in the field of biomass catalysis. Unfortunately, to the best of our knowledge, there are no publications focusing on the green synthesis and application of HCPs-based materials for biodiesel production. This review provides an update on the synthesis and utilisation of green and efficient HCPs for catalytic biodiesel production. Initially, the green routes for HCPs synthesis are described, followed by a comprehensive summary of the various approaches to biodiesel production. The primary focus is on the utilisation of HCPs as carriers of active sites in the catalytic conversion of biodiesel, with particular emphasis on catalyst design, morphology control, and intelligent management in terms of application extension. Ultimately, thought-provoking recommendations are proposed to utilize improved green HCPs in combination with advanced production processes to achieve more efficient and sustainable development.
2026, 37(5): 112142
doi: 10.1016/j.cclet.2025.112142
摘要:
Hydrogen-bonded frameworks (HOFs) are attracting interest for industrial and environmental applications. This review emphasizes recent developments in HOFs, concentrating on their structural characteristics, types of hydrogen bonding, and the connections that affect their mechanical properties and environmental responsiveness. It highlights hinge-like flexibility, rigidity, and framework retention, which enhance adaptability and structural integrity while trapping gases. A proposed mechanism for the selective adsorption of noble gases and light hydrocarbons emphasizes their potential in gas storage and environmental remediation. Overall, HOFs are presented as versatile materials ready to tackle emerging industrial challenges.
Hydrogen-bonded frameworks (HOFs) are attracting interest for industrial and environmental applications. This review emphasizes recent developments in HOFs, concentrating on their structural characteristics, types of hydrogen bonding, and the connections that affect their mechanical properties and environmental responsiveness. It highlights hinge-like flexibility, rigidity, and framework retention, which enhance adaptability and structural integrity while trapping gases. A proposed mechanism for the selective adsorption of noble gases and light hydrocarbons emphasizes their potential in gas storage and environmental remediation. Overall, HOFs are presented as versatile materials ready to tackle emerging industrial challenges.
2026, 37(5): 112235
doi: 10.1016/j.cclet.2025.112235
摘要:
The stereoselective synthesis of 1,2-cis-galacturonic acid and 2-amino-2-deoxy-galacturonic acid glycosides remains a critical challenge in carbohydrate chemistry owing to the electronic and steric effects imposed by the C5-carboxyl group and C2 substituents. The available synthetic strategies can be divided into two divergent pathways: the construction of the glycan backbone before introducing the carboxyl group and the use of pre-formed uronic acid donors during glycosylation. Key advances include the use of remotely participating acyl groups, conformational control via 3,6-lactone intermediates, chelation-directed anomerisation and steric shielding by bulky protecting groups such as 4,6-O-di-tert-butylsilylene and 4,6-O-benzylidene. This review comprehensively overviews the current strategies that overcome stereo-chemical challenges in the synthesis of 1,2-cis-galacturonic and aminogalacturonic acid–containing glycans. In addition, the application of these methodologies to the synthesis of biologically relevant carbohydrates is examined.
The stereoselective synthesis of 1,2-cis-galacturonic acid and 2-amino-2-deoxy-galacturonic acid glycosides remains a critical challenge in carbohydrate chemistry owing to the electronic and steric effects imposed by the C5-carboxyl group and C2 substituents. The available synthetic strategies can be divided into two divergent pathways: the construction of the glycan backbone before introducing the carboxyl group and the use of pre-formed uronic acid donors during glycosylation. Key advances include the use of remotely participating acyl groups, conformational control via 3,6-lactone intermediates, chelation-directed anomerisation and steric shielding by bulky protecting groups such as 4,6-O-di-tert-butylsilylene and 4,6-O-benzylidene. This review comprehensively overviews the current strategies that overcome stereo-chemical challenges in the synthesis of 1,2-cis-galacturonic and aminogalacturonic acid–containing glycans. In addition, the application of these methodologies to the synthesis of biologically relevant carbohydrates is examined.
2026, 37(5): 111876
doi: 10.1016/j.cclet.2025.111876
摘要:
2026, 37(5): 112260
doi: 10.1016/j.cclet.2025.112260
摘要:
