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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: 9.4
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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
2025, 36(7): 109775
doi: 10.1016/j.cclet.2024.109775
摘要:
Weak water stability and lithium reactivity are two major stability issues of sulfide solid-state electrolytes (SSEs) for all-solid-state lithium metal batteries. Here, we report on nano-sized boron nitride (BN)-coated Li5.7PS4.7Cl1.3 (BN@LPSC1.3) sulfide SSE, which exhibits reduced H2S emission and improved ionic conductivity retention after relative humidity 1.2%–1.5% ambient condition exposure. Furthermore, BN can partially react with lithium metal to create stable Li3N, resulting in BN@LPSC1.3 showing reduced reactivity against lithium metal and a higher critical current density of 2.2 mA/cm2. The Li/BN@LPSC/Li symmetrical battery also shows considerably greater stability for >2000 h at a current density of 0.1 mA/cm2. Despite the high cathode mass loading of 13.38 mg/cm2, the LiNi0.8Co0.1Mn0.1O2/BN@LPSC1.3/Li all-solid-state lithium metal battery achieves 84.34% capacity retention even after 500 cycles at 0.1 C and room temperature (25 ℃).
Weak water stability and lithium reactivity are two major stability issues of sulfide solid-state electrolytes (SSEs) for all-solid-state lithium metal batteries. Here, we report on nano-sized boron nitride (BN)-coated Li5.7PS4.7Cl1.3 (BN@LPSC1.3) sulfide SSE, which exhibits reduced H2S emission and improved ionic conductivity retention after relative humidity 1.2%–1.5% ambient condition exposure. Furthermore, BN can partially react with lithium metal to create stable Li3N, resulting in BN@LPSC1.3 showing reduced reactivity against lithium metal and a higher critical current density of 2.2 mA/cm2. The Li/BN@LPSC/Li symmetrical battery also shows considerably greater stability for >2000 h at a current density of 0.1 mA/cm2. Despite the high cathode mass loading of 13.38 mg/cm2, the LiNi0.8Co0.1Mn0.1O2/BN@LPSC1.3/Li all-solid-state lithium metal battery achieves 84.34% capacity retention even after 500 cycles at 0.1 C and room temperature (25 ℃).
2025, 36(7): 110090
doi: 10.1016/j.cclet.2024.110090
摘要:
Comparing to the conventional polyoxometalate (POM)-templated silver (Ag) clusters, asymmetrically covered POM-templated Ag clusters have been rarely reported. In this work, a new Ag cluster, H[Co(SiW11O39)Co4(OH)3(NO3)2(SiW9O34)@Ag37(tBuC≡C)23(NO3)2(DMF)3] (Ag37Co5), has been successfully prepared using a facile solvothermal approach. Such a unique asymmetrical architecture is ascribed to the uneven charge distribution of the in situ generated [Co(SiW11O39)]6− and [Co4(OH)3(NO3)2(SiW9O34)]7− moieties, leading to the asymmetrical coverage of alkynyl-protected Ag shell. Various physicochemical and catalytic studies revealed that the resulting solid-state Ag37Co5 crystals exhibited interesting temperature-dependent photoluminescence property, efficient and recyclable photothermal conversion ability, and good catalytic activity towards the detoxication of 4-nitrophenol.
Comparing to the conventional polyoxometalate (POM)-templated silver (Ag) clusters, asymmetrically covered POM-templated Ag clusters have been rarely reported. In this work, a new Ag cluster, H[Co(SiW11O39)Co4(OH)3(NO3)2(SiW9O34)@Ag37(tBuC≡C)23(NO3)2(DMF)3] (Ag37Co5), has been successfully prepared using a facile solvothermal approach. Such a unique asymmetrical architecture is ascribed to the uneven charge distribution of the in situ generated [Co(SiW11O39)]6− and [Co4(OH)3(NO3)2(SiW9O34)]7− moieties, leading to the asymmetrical coverage of alkynyl-protected Ag shell. Various physicochemical and catalytic studies revealed that the resulting solid-state Ag37Co5 crystals exhibited interesting temperature-dependent photoluminescence property, efficient and recyclable photothermal conversion ability, and good catalytic activity towards the detoxication of 4-nitrophenol.
2025, 36(7): 110091
doi: 10.1016/j.cclet.2024.110091
摘要:
A larger counter-ion could change the environment of trigonal bipyramidal cobalt(Ⅱ) to some extent, diluting the cobalt-containing complex and slowing their magnetic relaxation. Considering this observation, we used a sulfur organic ligand NS3tBu to obtain two trigonal bipyramidal Co(Ⅱ) complexes, namely, [Co(NS3tBu)Cl]Y, Y = PF6– (1), ClO4– (2). The resulting compound 1 (with a larger counter-ion PF6–) exhibits a longer relaxation time in comparison to compound 2 prepared with the smaller counter-ion ClO4–, even though the presence of weak rhombicity decreases the energy barrier and speeds up the relaxation of the magnetization for the two compounds. Concurrently, we demonstrate that compound 1 has smaller effective energy barrier and displays slower magnetic relaxation rather than compound 2. A smaller dc magnetic field could almost suppress all the quantum tunneling of magnetization (QTM), direct and Raman processes in compound 1, but not in compound 2, which presents all the Orbach, QTM, direct and Raman processes.
A larger counter-ion could change the environment of trigonal bipyramidal cobalt(Ⅱ) to some extent, diluting the cobalt-containing complex and slowing their magnetic relaxation. Considering this observation, we used a sulfur organic ligand NS3tBu to obtain two trigonal bipyramidal Co(Ⅱ) complexes, namely, [Co(NS3tBu)Cl]Y, Y = PF6– (1), ClO4– (2). The resulting compound 1 (with a larger counter-ion PF6–) exhibits a longer relaxation time in comparison to compound 2 prepared with the smaller counter-ion ClO4–, even though the presence of weak rhombicity decreases the energy barrier and speeds up the relaxation of the magnetization for the two compounds. Concurrently, we demonstrate that compound 1 has smaller effective energy barrier and displays slower magnetic relaxation rather than compound 2. A smaller dc magnetic field could almost suppress all the quantum tunneling of magnetization (QTM), direct and Raman processes in compound 1, but not in compound 2, which presents all the Orbach, QTM, direct and Raman processes.
2025, 36(7): 110092
doi: 10.1016/j.cclet.2024.110092
摘要:
2D Ruddlesden-Popper (RP) polar perovskite, displaying the intrinsic optical anisotropy and structural polarity, has a fantastic application perspective in self-powered polarized light detection. However, the weak van der Waals interaction between the organic spacing bilayers is insufficient to preserve the stability of RP-type materials. Hence, it is of great significance to explore new stable 2D RP-phase candidates. In this work, we have successfully constructed a highly-stable polar 2D perovskite, (t-ACH)2PbI4 (1, where t-ACH+ is HOOC8H12NH3+), by adopting a hydrophobic carboxylate trans-isomer of tranexamic acid as the spacing component. Strikingly, strong O-H···O hydrogen bonds between t-ACH+ organic bilayers compose the dimer, thus decreasing van der Waals gap and enhancing structural stability. Besides, such orientational hydrogen bonds contribute to the formation of structural polarity and generate an obvious bulk photovoltaic effect in 1, which facilitates its self-powered photodetection. As predicted, the combination of inherent anisotropy and polarity leads to self-powered polarized-light detection with a high ratio of around ~5.3, superior to those of inorganic 2D counterparts. This work paves a potential way to design highly-stable 2D perovskites for high-performance optoelectronic devices.
2D Ruddlesden-Popper (RP) polar perovskite, displaying the intrinsic optical anisotropy and structural polarity, has a fantastic application perspective in self-powered polarized light detection. However, the weak van der Waals interaction between the organic spacing bilayers is insufficient to preserve the stability of RP-type materials. Hence, it is of great significance to explore new stable 2D RP-phase candidates. In this work, we have successfully constructed a highly-stable polar 2D perovskite, (t-ACH)2PbI4 (1, where t-ACH+ is HOOC8H12NH3+), by adopting a hydrophobic carboxylate trans-isomer of tranexamic acid as the spacing component. Strikingly, strong O-H···O hydrogen bonds between t-ACH+ organic bilayers compose the dimer, thus decreasing van der Waals gap and enhancing structural stability. Besides, such orientational hydrogen bonds contribute to the formation of structural polarity and generate an obvious bulk photovoltaic effect in 1, which facilitates its self-powered photodetection. As predicted, the combination of inherent anisotropy and polarity leads to self-powered polarized-light detection with a high ratio of around ~5.3, superior to those of inorganic 2D counterparts. This work paves a potential way to design highly-stable 2D perovskites for high-performance optoelectronic devices.
2025, 36(7): 110110
doi: 10.1016/j.cclet.2024.110110
摘要:
The development of highly active and easily coupled non-noble metal electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is of great significance for the H2 production by water electrolysis. Here, we have shown an anion-modulated HER and OER activity of 1D Co-Mo based interstitial compound heterojunctions for effective overall water splitting. The Co-Mo based complex nanowires from a one-pot route with high yields can be converted into MoC–Co heterojunction nanowires under N2 atmosphere, while a pyrolysis under NH3 can give CoMoN–CoN heterostructures. The work function revealed Mott-Schottky effect between interfaces of two heterostructures, which can introduce electron redistribution and thus promote the HER/OER process. The MoC–Co heterojunction nanowires delivers good HER activity at a low overpotential of 39 mV to afford a current density of 10 mA/cm2. Density functional theory calculations show that the heterogeneous interface formed between the Co and MoC optimizes the hydrogen adsorption free energy. Concurrently, CoMoN–CoN heterojunction nanowires exhibits good OER performance with a low overpotential of 260 mV to reach 10 mA/cm2, being superior to RuO2. The two catalysts can be coupled to assemble a two-electrode cell with a solar-to-hydrogen efficiency of 12.3% at 1.54 V. This work provides an effective means to design easily coupled HER and OER catalysts for H2 production by water electrolysis.
The development of highly active and easily coupled non-noble metal electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is of great significance for the H2 production by water electrolysis. Here, we have shown an anion-modulated HER and OER activity of 1D Co-Mo based interstitial compound heterojunctions for effective overall water splitting. The Co-Mo based complex nanowires from a one-pot route with high yields can be converted into MoC–Co heterojunction nanowires under N2 atmosphere, while a pyrolysis under NH3 can give CoMoN–CoN heterostructures. The work function revealed Mott-Schottky effect between interfaces of two heterostructures, which can introduce electron redistribution and thus promote the HER/OER process. The MoC–Co heterojunction nanowires delivers good HER activity at a low overpotential of 39 mV to afford a current density of 10 mA/cm2. Density functional theory calculations show that the heterogeneous interface formed between the Co and MoC optimizes the hydrogen adsorption free energy. Concurrently, CoMoN–CoN heterojunction nanowires exhibits good OER performance with a low overpotential of 260 mV to reach 10 mA/cm2, being superior to RuO2. The two catalysts can be coupled to assemble a two-electrode cell with a solar-to-hydrogen efficiency of 12.3% at 1.54 V. This work provides an effective means to design easily coupled HER and OER catalysts for H2 production by water electrolysis.
2025, 36(7): 110120
doi: 10.1016/j.cclet.2024.110120
摘要:
Photocatalytic water splitting for hydrogen evolution reaction (HER) has emerged as one of the most promising approaches for solar energy utilization. Porous easily functionalized metal-organic framework (MOF) represents a rising crystalline material for photocatalytic application. Yet, most MOFs still face challenges like chemical instability in solution media, no photosensitization, and ambiguous active sites. Herein, thiol-dense Hf- or Zr-based porous frameworks (Hf-, Zr-TBAPy-8SH) were prepared as platforms for facile construction of HER active sites by anchoring transition metal (TM) ions as well as forming heterojunction with nanoscale semiconductor (CdS). The highest HER rate of 8.15 mmol g–1 h–1 by Co(Ⅱ)-loaded Hf-based composite highlight (1) [S––Co] motifs as competent HER site, (2) match heterojunction outweighing traditional photosensitizer-mediated HER, (3) regulating electron density of metal-oxo cluster as a way to harness HER activity. This study firstly demonstrates synergy of Hf-oxo clusters, thiol functionalities and heterojunction as an easy yet controllable strategy to form integrated photocatalyst.
Photocatalytic water splitting for hydrogen evolution reaction (HER) has emerged as one of the most promising approaches for solar energy utilization. Porous easily functionalized metal-organic framework (MOF) represents a rising crystalline material for photocatalytic application. Yet, most MOFs still face challenges like chemical instability in solution media, no photosensitization, and ambiguous active sites. Herein, thiol-dense Hf- or Zr-based porous frameworks (Hf-, Zr-TBAPy-8SH) were prepared as platforms for facile construction of HER active sites by anchoring transition metal (TM) ions as well as forming heterojunction with nanoscale semiconductor (CdS). The highest HER rate of 8.15 mmol g–1 h–1 by Co(Ⅱ)-loaded Hf-based composite highlight (1) [S––Co] motifs as competent HER site, (2) match heterojunction outweighing traditional photosensitizer-mediated HER, (3) regulating electron density of metal-oxo cluster as a way to harness HER activity. This study firstly demonstrates synergy of Hf-oxo clusters, thiol functionalities and heterojunction as an easy yet controllable strategy to form integrated photocatalyst.
2025, 36(7): 110122
doi: 10.1016/j.cclet.2024.110122
摘要:
The pore structure and pseudo-graphitic phase (domain size and content) of a hard carbon anode play key roles in improving the plateau capacity of sodium-ion batteries (SIBs), while it is hard to regulate them effectively and simultaneously. This study delves into the synthesis of hard carbons with tailored microstructures from esterified sodium carboxymethyl cellulose (CMCNa). The hard carbon (EHC-500) with maximized pseudo-graphitic content (73%) and abundant uniformly dispersed closed pores was fabricated, which provides sufficient active sites for sodium ion intercalation and pore filling. Furthermore, minimized lateral width (La) of pseudo-graphitic domains in EHC-500 is simultaneously realized to improve the accessibility of sodium ions to the intercalation sites and filling sites. Therefore, the optimized microstructure of EHC-500 contributes to a remarkable reversible capacity of 340 mAh/g with a high plateau capacity of 236.7 mAh/g (below 0.08 V). These findings underscore the pivotal role of microcrystalline structure and pore structure in the electrochemical performance of hard carbons and provide a novel route to guide the design of hard carbons with optimal microstructures towards enhanced sodium storage performance.
The pore structure and pseudo-graphitic phase (domain size and content) of a hard carbon anode play key roles in improving the plateau capacity of sodium-ion batteries (SIBs), while it is hard to regulate them effectively and simultaneously. This study delves into the synthesis of hard carbons with tailored microstructures from esterified sodium carboxymethyl cellulose (CMCNa). The hard carbon (EHC-500) with maximized pseudo-graphitic content (73%) and abundant uniformly dispersed closed pores was fabricated, which provides sufficient active sites for sodium ion intercalation and pore filling. Furthermore, minimized lateral width (La) of pseudo-graphitic domains in EHC-500 is simultaneously realized to improve the accessibility of sodium ions to the intercalation sites and filling sites. Therefore, the optimized microstructure of EHC-500 contributes to a remarkable reversible capacity of 340 mAh/g with a high plateau capacity of 236.7 mAh/g (below 0.08 V). These findings underscore the pivotal role of microcrystalline structure and pore structure in the electrochemical performance of hard carbons and provide a novel route to guide the design of hard carbons with optimal microstructures towards enhanced sodium storage performance.
2025, 36(7): 110144
doi: 10.1016/j.cclet.2024.110144
摘要:
Germanium (Ge)-air battery, a new type of semiconductor-air battery, has garnered increasing attention owing to its environmental friendliness, safety, and excellent dynamic performance. However, the flat Ge anode is prone to passivation, owing to GeO2 accumulation on its surface, resulting in premature discharge termination. In this study, various nano-Ge pyramid structures (GePS) were prepared using chemical etching (CE) and metal-assisted chemical etching (MACE) methods to enhance the specific surface area of the Ge anode, thereby facilitating the dissolution of the passivation layer. This study revealed that the MACE method significantly accelerated the etching rate of the Ge surface, producing exceptional GePS. Furthermore, Ge-air batteries employing Ge anodes prepared using MACE demonstrated an exceptional discharge life of up to 9240 h (385 days). The peak power density reached 3.03 mW/cm2, representing improvements of more than 2 times and 1.8 times, respectively, compared with batteries using flat Ge anodes. This study presents a straightforward approach to enhance Ge anode performance, thereby expanding the potential applications of Ge-air batteries
Germanium (Ge)-air battery, a new type of semiconductor-air battery, has garnered increasing attention owing to its environmental friendliness, safety, and excellent dynamic performance. However, the flat Ge anode is prone to passivation, owing to GeO2 accumulation on its surface, resulting in premature discharge termination. In this study, various nano-Ge pyramid structures (GePS) were prepared using chemical etching (CE) and metal-assisted chemical etching (MACE) methods to enhance the specific surface area of the Ge anode, thereby facilitating the dissolution of the passivation layer. This study revealed that the MACE method significantly accelerated the etching rate of the Ge surface, producing exceptional GePS. Furthermore, Ge-air batteries employing Ge anodes prepared using MACE demonstrated an exceptional discharge life of up to 9240 h (385 days). The peak power density reached 3.03 mW/cm2, representing improvements of more than 2 times and 1.8 times, respectively, compared with batteries using flat Ge anodes. This study presents a straightforward approach to enhance Ge anode performance, thereby expanding the potential applications of Ge-air batteries
2025, 36(7): 110145
doi: 10.1016/j.cclet.2024.110145
摘要:
NASICON type solid electrolyte Li1+xAlxGe2−x(PO4)3 (LAGP) is one of the most potential candidates in view of their high ionic conductivity, high oxidation resistance and excellent air stability. However, inevitable interface issues often cause severe performance degradation, seriously affecting its commercial application. Herein, a lithiophilic carbon buffer layer is constructed on the LAGP surface adjacent to the Li electrode side by a facile pyrolysis reaction, then the LiCx interlayer is generated in situ between the carbon buffer layer and lithium metal, which can guide uniform ion transport while improving interface contact. Thus, the LiCx-LAGP showed excellent ionic conductivity, high flexibility and lithiophilic interphase. Specially, the LiLiCx-LAGPLi battery has achieved a 1000 h stable cycles at 0.1 mA/cm2, remarkably, the LiLiCx-LAGPLFP battery retains 85% of their initial capacity after 200 cycles under 1 C, even for the NCM811 cathode, the battery still has a good cycle performance.
NASICON type solid electrolyte Li1+xAlxGe2−x(PO4)3 (LAGP) is one of the most potential candidates in view of their high ionic conductivity, high oxidation resistance and excellent air stability. However, inevitable interface issues often cause severe performance degradation, seriously affecting its commercial application. Herein, a lithiophilic carbon buffer layer is constructed on the LAGP surface adjacent to the Li electrode side by a facile pyrolysis reaction, then the LiCx interlayer is generated in situ between the carbon buffer layer and lithium metal, which can guide uniform ion transport while improving interface contact. Thus, the LiCx-LAGP showed excellent ionic conductivity, high flexibility and lithiophilic interphase. Specially, the LiLiCx-LAGPLi battery has achieved a 1000 h stable cycles at 0.1 mA/cm2, remarkably, the LiLiCx-LAGPLFP battery retains 85% of their initial capacity after 200 cycles under 1 C, even for the NCM811 cathode, the battery still has a good cycle performance.
2025, 36(7): 110150
doi: 10.1016/j.cclet.2024.110150
摘要:
The development of efficient and robust non-precious metal electrocatalyst to drive the sluggish hydrogen oxidation reaction (HOR) is the key to the practical application of anion exchange membrane fuel cells (AEMFC), which relies on the rational regulation of intermediates' binding strength. Herein, we reported a simple strategy to manipulate the adsorption energy of OH* on electrocatalyst surface via engineering Ni/NbOx heterostructures with manageable oxygen vacancy (Ov). Theoretical calculations confirm that the electronic effect between Ni and NbOx could weaken the hydrogen adsorption on Ni, and the interfacial oxygen vacancy tailor hydroxide binding energy (OHBE). The optimized HBE and OHBE contribute to reduce formation energy of water during the alkaline HOR process. Furthermore, in situ Raman spectroscopy monitor the dynamic process that OH* adsorbed on oxygen vacancy and react with adjacent H* adsorbed Ni, confirming the vital role of OH* for alkaline HOR process. As a result, the optimal Ni/NbOx exhibits a remarkable intrinsic activity with a specific activity of 0.036 mA/cm2, which is 4-fold than that of pristine Ni counterpart and surpasses most non-precious electrocatalysts ever reported.
The development of efficient and robust non-precious metal electrocatalyst to drive the sluggish hydrogen oxidation reaction (HOR) is the key to the practical application of anion exchange membrane fuel cells (AEMFC), which relies on the rational regulation of intermediates' binding strength. Herein, we reported a simple strategy to manipulate the adsorption energy of OH* on electrocatalyst surface via engineering Ni/NbOx heterostructures with manageable oxygen vacancy (Ov). Theoretical calculations confirm that the electronic effect between Ni and NbOx could weaken the hydrogen adsorption on Ni, and the interfacial oxygen vacancy tailor hydroxide binding energy (OHBE). The optimized HBE and OHBE contribute to reduce formation energy of water during the alkaline HOR process. Furthermore, in situ Raman spectroscopy monitor the dynamic process that OH* adsorbed on oxygen vacancy and react with adjacent H* adsorbed Ni, confirming the vital role of OH* for alkaline HOR process. As a result, the optimal Ni/NbOx exhibits a remarkable intrinsic activity with a specific activity of 0.036 mA/cm2, which is 4-fold than that of pristine Ni counterpart and surpasses most non-precious electrocatalysts ever reported.
2025, 36(7): 110152
doi: 10.1016/j.cclet.2024.110152
摘要:
Aqueous alkaline zinc batteries have received widespread attention owing to its higher electrode potential and faster reaction kinetics compared to in mild aqueous electrolyte. However, Zn metal anode in alkaline electrolyte usually suffers more severe corrosion, passivation, and hydrogen evolution reaction. Herein, an interface chemical regulation strategy employs to in-situ construct a Zn-Sn alloy layer during cycling. The K2[Sn(OH)6] has been introduced into the electrolyte as the deposition overpotential of Zn and Sn in alkaline electrolyte is approximate leading to their simultaneously plating. The Zn-Sn alloy layer not only prevents Zn anode corrosion and suppresses the dendrite growth but also promotes the reaction kinetics. Therefore, the ZnZn cell exhibits a long life of 400 h in alkaline electrolyte about 20 times of that in without K2[Sn(OH)6] electrolyte. Moreover, the NNCP@PQxZn full cell displays a superior cycle performance of 4000 cycles with 93% capacity retention at 2 A/g.
Aqueous alkaline zinc batteries have received widespread attention owing to its higher electrode potential and faster reaction kinetics compared to in mild aqueous electrolyte. However, Zn metal anode in alkaline electrolyte usually suffers more severe corrosion, passivation, and hydrogen evolution reaction. Herein, an interface chemical regulation strategy employs to in-situ construct a Zn-Sn alloy layer during cycling. The K2[Sn(OH)6] has been introduced into the electrolyte as the deposition overpotential of Zn and Sn in alkaline electrolyte is approximate leading to their simultaneously plating. The Zn-Sn alloy layer not only prevents Zn anode corrosion and suppresses the dendrite growth but also promotes the reaction kinetics. Therefore, the ZnZn cell exhibits a long life of 400 h in alkaline electrolyte about 20 times of that in without K2[Sn(OH)6] electrolyte. Moreover, the NNCP@PQxZn full cell displays a superior cycle performance of 4000 cycles with 93% capacity retention at 2 A/g.
2025, 36(7): 110171
doi: 10.1016/j.cclet.2024.110171
摘要:
Ethylene (C2H4) is a core raw material for the petrochemical industry. It is of economic and environmental significance to use C2H6 as the fuel and proton-conducting solid oxide fuel cells (P-SOFC) as the reactor to co-generate electricity and C2H4. However, the large-sized Ni particles in the conventional Ni-cermet anode directly crack C2H6; and oxide materials with a mild capability of breaking CC bonds are generally limited to electrolyte-supported structures with high ohmic impedance. This research for the first time constructs an anode-supported cell using BZCY as the porous scaffold and impregnated double perovskite (PrBa)0.95(Fe0.8Ni0.2)1.8Mo0.2O6-δ (PBFNM0.2) as the anode electrocatalysis. FeNi3 nanoparticles exsolve from PBFNM0.2 in H2 and uniformly distribute on the surface of perovskite substrate, acting as an active component for C2H6 dehydrogenation and electrochemical performance enhancement. The cell with 30 wt% PBFNM0.2 impregnated anode showing a high power density of 508 and 386 mW/cm2 with H2 and C2H6 fuels, respectively; high C2H6 conversion of 50.9%, C2H4 selectivity of 92.1%, and C2H4 yield of 46.9% are achieved at 750 ℃ and 700 mA/cm2, which outperforms all previously electrolyte-supported cells for co-generated electricity and ethylene. Moreover, the cell demonstrated excellent recoverability throughout three dehydrogenation-regeneration cycles. This work provides a practical way with broad application potential to create a novel anode-supported cell efficiently realizing the co-generation of electricity and C2H4 from C2H6.
Ethylene (C2H4) is a core raw material for the petrochemical industry. It is of economic and environmental significance to use C2H6 as the fuel and proton-conducting solid oxide fuel cells (P-SOFC) as the reactor to co-generate electricity and C2H4. However, the large-sized Ni particles in the conventional Ni-cermet anode directly crack C2H6; and oxide materials with a mild capability of breaking CC bonds are generally limited to electrolyte-supported structures with high ohmic impedance. This research for the first time constructs an anode-supported cell using BZCY as the porous scaffold and impregnated double perovskite (PrBa)0.95(Fe0.8Ni0.2)1.8Mo0.2O6-δ (PBFNM0.2) as the anode electrocatalysis. FeNi3 nanoparticles exsolve from PBFNM0.2 in H2 and uniformly distribute on the surface of perovskite substrate, acting as an active component for C2H6 dehydrogenation and electrochemical performance enhancement. The cell with 30 wt% PBFNM0.2 impregnated anode showing a high power density of 508 and 386 mW/cm2 with H2 and C2H6 fuels, respectively; high C2H6 conversion of 50.9%, C2H4 selectivity of 92.1%, and C2H4 yield of 46.9% are achieved at 750 ℃ and 700 mA/cm2, which outperforms all previously electrolyte-supported cells for co-generated electricity and ethylene. Moreover, the cell demonstrated excellent recoverability throughout three dehydrogenation-regeneration cycles. This work provides a practical way with broad application potential to create a novel anode-supported cell efficiently realizing the co-generation of electricity and C2H4 from C2H6.
2025, 36(7): 110172
doi: 10.1016/j.cclet.2024.110172
摘要:
The construction of frustrated Lewis acid-base pairs (FLPs) in porous systems is very important for the field of industrial hydrogenation catalysis, but there is still a great challenge. Based on the Ce3+/Ce4+ redox pairs and abundant defects in porous Ce-based metal-organic frameworks (Ce-MOFs), FLP sites consisting of ligand-defective Ce sites (Lewis acid, LA) and neighboring terminal O sites (Lewis base, LB) were constructed in situ by a simple vacuum thermal activation method in lamellar Ce-UiO-66-F. Defects/oxygen vacancies in the Ce-MOFs structure result in the difference in the electron cloud density between Ce and O, which is suitable for HH hetero-cleavage and H-transfer in the dicyclopentadiene (DCPD) hydrogenation process. Particularly, Ce-UiO-66-F-200 achieved 96.9% conversion of DCPD and 97.8% selectivity of 8, 9-dihydrodicyclopentadiene (8, 9-DHDCPD) at 100 ℃ under 2 MPa H2 for 10 h, which is 9.4 times higher than 10.2% conversion of DCPD over the unactivated Ce-UiO-66-F. This research promotes the understanding of solid MOFs-based porous FLPs for H2 activation, and encourages the in-depth investigation of surface solid FLPs to the whole material FLPs.
The construction of frustrated Lewis acid-base pairs (FLPs) in porous systems is very important for the field of industrial hydrogenation catalysis, but there is still a great challenge. Based on the Ce3+/Ce4+ redox pairs and abundant defects in porous Ce-based metal-organic frameworks (Ce-MOFs), FLP sites consisting of ligand-defective Ce sites (Lewis acid, LA) and neighboring terminal O sites (Lewis base, LB) were constructed in situ by a simple vacuum thermal activation method in lamellar Ce-UiO-66-F. Defects/oxygen vacancies in the Ce-MOFs structure result in the difference in the electron cloud density between Ce and O, which is suitable for HH hetero-cleavage and H-transfer in the dicyclopentadiene (DCPD) hydrogenation process. Particularly, Ce-UiO-66-F-200 achieved 96.9% conversion of DCPD and 97.8% selectivity of 8, 9-dihydrodicyclopentadiene (8, 9-DHDCPD) at 100 ℃ under 2 MPa H2 for 10 h, which is 9.4 times higher than 10.2% conversion of DCPD over the unactivated Ce-UiO-66-F. This research promotes the understanding of solid MOFs-based porous FLPs for H2 activation, and encourages the in-depth investigation of surface solid FLPs to the whole material FLPs.
2025, 36(7): 110173
doi: 10.1016/j.cclet.2024.110173
摘要:
Birefringent materials possess significant optical anisotropy, making them pivotal in modulating light polarization, particularly in laser technology and scientific applications. In this study, five variants of antimony potassium fluoronitrates named SbF3·KNO3 (1), SbF3·3KNO3 (2), SbF3·3KSbF4·KNO3 (3), KSb2F7·3KNO3 (4), and KSb2F7·2KNO3 (5) were obtained. Remarkably, each compound contains distinct Sb-polyhedra configurations. Compounds 1 and 2 consist of singular [SbF3] units, compound 3 harbors a mixture of [SbF3] and [SbF4] units, while compounds 4 and 5 feature single [SbF4] units. Interestingly, the birefringence escalates progressively from 1 to 5, and notably, compound 5 exhibits the most pronounced birefringence among all reported inorganic antimony oxysalts. Detailed structural and property analyses affirm that the structural variance among the five compounds underpins the observed differences in birefringence. Moreover, the synergistic interplay between planar π-conjugated NO3− groups and Sb3+ ions with lone-pair electrons facilitates the emergence of substantial polarization anisotropy.
Birefringent materials possess significant optical anisotropy, making them pivotal in modulating light polarization, particularly in laser technology and scientific applications. In this study, five variants of antimony potassium fluoronitrates named SbF3·KNO3 (1), SbF3·3KNO3 (2), SbF3·3KSbF4·KNO3 (3), KSb2F7·3KNO3 (4), and KSb2F7·2KNO3 (5) were obtained. Remarkably, each compound contains distinct Sb-polyhedra configurations. Compounds 1 and 2 consist of singular [SbF3] units, compound 3 harbors a mixture of [SbF3] and [SbF4] units, while compounds 4 and 5 feature single [SbF4] units. Interestingly, the birefringence escalates progressively from 1 to 5, and notably, compound 5 exhibits the most pronounced birefringence among all reported inorganic antimony oxysalts. Detailed structural and property analyses affirm that the structural variance among the five compounds underpins the observed differences in birefringence. Moreover, the synergistic interplay between planar π-conjugated NO3− groups and Sb3+ ions with lone-pair electrons facilitates the emergence of substantial polarization anisotropy.
2025, 36(7): 110184
doi: 10.1016/j.cclet.2024.110184
摘要:
Anion modification has been considered as a strategy to improve water splitting efficiency upon oxygen evolution reaction (OER). However, constructing a novel catalysis system with high catalytic activity and precise structures is still a huge challenge due to the tedious procedure of precursor synthesis and anion selection. Here, a bimetallic (FeNi) nanowire self-assembled superstructure was synthesized using the Hoffmann rearrangement method, and then functionalized with four anions (P, Se, S, and O). Notably, the Fe3Se4/Ni3Se4 catalyst shows a high conductivity, enhances the adsorption of intermediate products, accelerates the rate-determining step, and consequently results to improved electrocatalytic performance. Using the Fe3Se4/Ni3Se4 catalyst exhibits enhanced performance with overpotential of 316 mV at 10 mA/cm2, in stark contrast to Fe2P/Ni2P (357 mV), Fe7S8/NiS (379 mV), and Fe3O4/NiO (464 mV). Moreover, the formation mechanism of superstructure and the relationship between electronegativities and electrocatalytic properties, are elucidated. Accordingly, this work provides an efficient approach to Hoffmann-type coordination polymer catalyst for oxygen evolution towards a near future.
Anion modification has been considered as a strategy to improve water splitting efficiency upon oxygen evolution reaction (OER). However, constructing a novel catalysis system with high catalytic activity and precise structures is still a huge challenge due to the tedious procedure of precursor synthesis and anion selection. Here, a bimetallic (FeNi) nanowire self-assembled superstructure was synthesized using the Hoffmann rearrangement method, and then functionalized with four anions (P, Se, S, and O). Notably, the Fe3Se4/Ni3Se4 catalyst shows a high conductivity, enhances the adsorption of intermediate products, accelerates the rate-determining step, and consequently results to improved electrocatalytic performance. Using the Fe3Se4/Ni3Se4 catalyst exhibits enhanced performance with overpotential of 316 mV at 10 mA/cm2, in stark contrast to Fe2P/Ni2P (357 mV), Fe7S8/NiS (379 mV), and Fe3O4/NiO (464 mV). Moreover, the formation mechanism of superstructure and the relationship between electronegativities and electrocatalytic properties, are elucidated. Accordingly, this work provides an efficient approach to Hoffmann-type coordination polymer catalyst for oxygen evolution towards a near future.
2025, 36(7): 110186
doi: 10.1016/j.cclet.2024.110186
摘要:
Rechargeable lithium-carbon dioxide (Li-CO2) batteries have emerged as a highly promising approach to simultaneously address energy shortages and the greenhouse effect. However, certain limitations exist in Li-CO2 batteries like high charge overpotential and unstable Li metal interface, which adversely affect the energy efficiency and cycling life. The incorporation of soluble redox mediators (RMs) has proven effective in enhancing the charge transfer between lithium carbonate (Li2CO3) and cathode, thereby substantially reducing the charge overpotential. Nevertheless, the severe shuttle effect of RMs results in the reactions with Li anode, not only exacerbating the corrosion of Li anode but also leading to the depletion of RMs and electrical energy efficiency. In this work, an organic compound containing large cation group, 1-ethyl-3-methylimidazole bromide (EMIBr) is proposed as the defense donor RM for Li anode in Li-CO2 batteries to address the above problems simultaneously. During charging, Li2CO3 oxidation kinetics can be accelerated by bromide anion pair (Br3−/Br−). Meanwhile, the cations (EMI+) are preferentially adsorbed around the protruding tips of Li anode through electrostatic interaction driven by surface free energy, forming protective layers that effectively inhibit further Li deposition at these tips, which is verified by DFT calculations. Additionally, Li dendrites growth is inhibited by the electrostatic repulsion of polar groups in EMIBr, resulting in uniform Li deposition. Consequently, a lower overpotential (~1.17 V) and a longer cycle life (~200 cycles) have been obtained for Li-CO2 battery incorporating EMIBr.
Rechargeable lithium-carbon dioxide (Li-CO2) batteries have emerged as a highly promising approach to simultaneously address energy shortages and the greenhouse effect. However, certain limitations exist in Li-CO2 batteries like high charge overpotential and unstable Li metal interface, which adversely affect the energy efficiency and cycling life. The incorporation of soluble redox mediators (RMs) has proven effective in enhancing the charge transfer between lithium carbonate (Li2CO3) and cathode, thereby substantially reducing the charge overpotential. Nevertheless, the severe shuttle effect of RMs results in the reactions with Li anode, not only exacerbating the corrosion of Li anode but also leading to the depletion of RMs and electrical energy efficiency. In this work, an organic compound containing large cation group, 1-ethyl-3-methylimidazole bromide (EMIBr) is proposed as the defense donor RM for Li anode in Li-CO2 batteries to address the above problems simultaneously. During charging, Li2CO3 oxidation kinetics can be accelerated by bromide anion pair (Br3−/Br−). Meanwhile, the cations (EMI+) are preferentially adsorbed around the protruding tips of Li anode through electrostatic interaction driven by surface free energy, forming protective layers that effectively inhibit further Li deposition at these tips, which is verified by DFT calculations. Additionally, Li dendrites growth is inhibited by the electrostatic repulsion of polar groups in EMIBr, resulting in uniform Li deposition. Consequently, a lower overpotential (~1.17 V) and a longer cycle life (~200 cycles) have been obtained for Li-CO2 battery incorporating EMIBr.
2025, 36(7): 110187
doi: 10.1016/j.cclet.2024.110187
摘要:
Extensive first-principles calculations have been performed to examine the electrochemical properties of Na-ion-intercalatable heterostructures formed by transitional metal dichalcogenides (MS2, where M = Ti, V, Nb and Mo) and blue phosphorus (BlueP), which have been reported as potential anode materials for rechargeable sodium-ion batteries. Upon formation of heterostructures, much improved structural stabilities have observed compared with the pristine MS2 and BlueP. Metallic T-TiS2, T-MoS2, H(T)-VS2 and H(T)-NbS2 would retain the conductive character after formation of heterostructures with BlueP, however, H-TiS2/BlueP and H-MoS2/BlueP would undergo a semiconductor to metallic transition accompanied by Na intercalation. Moreover, the presence of relatively low diffusion barriers ranging from 0.04 eV to 0.08 eV, coupled with the suitable average open-circuit voltage spanning from 0.12 eV to 0.89 eV, guarantee exceptional charge-discharge rates and ensure the safety of battery performance. Among these heterostructures, H(T)-NbS2/BlueP and T-TiS2/BlueP exhibit best Na adsorption ability of up to 4 layers, corresponding to theoretical capacities of 570.2 and 746.7 mAh/g, respectively. These encouraging properties indicate that T-TiS2/BlueP and H(T)-NbS2/BlueP could serve as suitable anode materials for high-performance sodium-ion batteries.
Extensive first-principles calculations have been performed to examine the electrochemical properties of Na-ion-intercalatable heterostructures formed by transitional metal dichalcogenides (MS2, where M = Ti, V, Nb and Mo) and blue phosphorus (BlueP), which have been reported as potential anode materials for rechargeable sodium-ion batteries. Upon formation of heterostructures, much improved structural stabilities have observed compared with the pristine MS2 and BlueP. Metallic T-TiS2, T-MoS2, H(T)-VS2 and H(T)-NbS2 would retain the conductive character after formation of heterostructures with BlueP, however, H-TiS2/BlueP and H-MoS2/BlueP would undergo a semiconductor to metallic transition accompanied by Na intercalation. Moreover, the presence of relatively low diffusion barriers ranging from 0.04 eV to 0.08 eV, coupled with the suitable average open-circuit voltage spanning from 0.12 eV to 0.89 eV, guarantee exceptional charge-discharge rates and ensure the safety of battery performance. Among these heterostructures, H(T)-NbS2/BlueP and T-TiS2/BlueP exhibit best Na adsorption ability of up to 4 layers, corresponding to theoretical capacities of 570.2 and 746.7 mAh/g, respectively. These encouraging properties indicate that T-TiS2/BlueP and H(T)-NbS2/BlueP could serve as suitable anode materials for high-performance sodium-ion batteries.
2025, 36(7): 110188
doi: 10.1016/j.cclet.2024.110188
摘要:
Organic ferroelastics with metal free features and intrinsically light weight are highly desirable for future applications in flexible, smart and biocompatible devices. However, organoferroelastics with plastic phase transition have rarely been reported yet. Herein, we discovered ferroelasticity in a pair of organic enantiomers, (1S and/or 1R)-2,10-camphorsultam (S- and R-CPS), which undergoes a high-Tc plastic phase transition. Both large entropies change of ~45 J mol-1 K-1 and evidently ductile deformation process confirm the plastic phase feature. Strip-like ferroelastic domain patterns and bidirectional domain movements have been observed via polarized light microscopy and nanoindentation technique, respectively. This work highlights the discovery of organic ferroelastic combining the features of enantiomers and plastic phase transition, which contributes insights into exploration of organic multifunctional materials.
Organic ferroelastics with metal free features and intrinsically light weight are highly desirable for future applications in flexible, smart and biocompatible devices. However, organoferroelastics with plastic phase transition have rarely been reported yet. Herein, we discovered ferroelasticity in a pair of organic enantiomers, (1S and/or 1R)-2,10-camphorsultam (S- and R-CPS), which undergoes a high-Tc plastic phase transition. Both large entropies change of ~45 J mol-1 K-1 and evidently ductile deformation process confirm the plastic phase feature. Strip-like ferroelastic domain patterns and bidirectional domain movements have been observed via polarized light microscopy and nanoindentation technique, respectively. This work highlights the discovery of organic ferroelastic combining the features of enantiomers and plastic phase transition, which contributes insights into exploration of organic multifunctional materials.
2025, 36(7): 110331
doi: 10.1016/j.cclet.2024.110331
摘要:
The organic fluorescent probes were widely explored for specific detection of chemical nerve agent simulants. However, the fluorescence quenching, long-time response, and limitation of detection further impeded their practical applications. Herein, the fluorescent nanofiber chitosan-1 was prepared through the modification of chitosan with 1,8-naphthalimide as fluorophore and piperazine as the detection segment. The high specific surface of fluorescent nanofiber chitosan-1 showed ultrasensitive and selective detection of diethyl chlorophosphate (DCP) in solution and vapor. The satisfied linear relationship between the fluorescent intensity and the concentration of DCP ranging from 0 µmol/L to 100 µmol/L was obtained. The limitation of detection was measured as low as 2.2 nmol/L within 30 s. The sensing mechanism was explored through the photoinduced electron transfer (PET) mechanism which was confirmed by 1H, 31P NMR, and mass spectra (MS). The ultrasensitive detection of nanofibers may provide valuable insights for enhancing the sensing performance in visually detecting chemical nerve agents.
The organic fluorescent probes were widely explored for specific detection of chemical nerve agent simulants. However, the fluorescence quenching, long-time response, and limitation of detection further impeded their practical applications. Herein, the fluorescent nanofiber chitosan-1 was prepared through the modification of chitosan with 1,8-naphthalimide as fluorophore and piperazine as the detection segment. The high specific surface of fluorescent nanofiber chitosan-1 showed ultrasensitive and selective detection of diethyl chlorophosphate (DCP) in solution and vapor. The satisfied linear relationship between the fluorescent intensity and the concentration of DCP ranging from 0 µmol/L to 100 µmol/L was obtained. The limitation of detection was measured as low as 2.2 nmol/L within 30 s. The sensing mechanism was explored through the photoinduced electron transfer (PET) mechanism which was confirmed by 1H, 31P NMR, and mass spectra (MS). The ultrasensitive detection of nanofibers may provide valuable insights for enhancing the sensing performance in visually detecting chemical nerve agents.
2025, 36(7): 110332
doi: 10.1016/j.cclet.2024.110332
摘要:
Light exposure can accelerate phase transformation of Schwertmannite (Sch) coexisting with low-molecular-weight organic acids (LMWOAs), affecting the cycling of Fe in acid mine drainage (AMD). However, it is still unclear how this process relates to the fate of heavy metal contaminants. The study comprehensively reports the significant role and speciation redistribution of Cu(Ⅱ) during the photochemical transformation of a Sch/tartaric acid (TA) system. Based on X-ray diffractometer and Fourier transform infrared spectra results, the presence of TA in simulated AMD significantly promoted photoreductive dissolution and phase transformation of Sch to magnetite (Mt) and goethite (Gt) under anoxic and oxic conditions, respectively. With the addition of 10–30 mg/L Cu(Ⅱ), this transformation of Sch/TA system was significantly inhibited, i.e., only Gt occurred as product under anoxic conditions and even no phase transformation under oxic conditions. The results of EPR and adsorbed Fe(Ⅱ) indicated that the coexistence of Cu(Ⅱ) suppressed the amount of adsorbed Fe(Ⅱ) available for the transformation of Sch via competitive adsorption with Fe(Ⅱ) and inhibition of ligand-to-metal charge transfer (LMCT) of Sch-TA complexes. Chemical speciation and X-ray photoelectron spectroscopy analysis revealed the proportions of adsorbed and structural Cu(Ⅱ) of Sch/TA system were observably enhanced due to an increase in pH and recrystallization/nucleation growth of newly formed Gt. Under anoxic conditions, 62.7%-75.88% of Cu(Ⅱ) was adsorbed on the mineral surface, and during the nucleation and growth of secondary mineral phases, 15.49%-17.01% of Cu(Ⅱ) was incorporated into their crystal structure. The changes in distribution of Cu(Ⅱ) further suggested the photochemical transformation of Sch facilitated the sequestration of heavy metals and reduced their bioavailability. These findings enhance the understanding of role and redistribution of Cu(Ⅱ) during the transformation of Sch/LMWOA system in euphotic zone of AMD and provid insights of exploring engineered strategies of AMD remediation.
Light exposure can accelerate phase transformation of Schwertmannite (Sch) coexisting with low-molecular-weight organic acids (LMWOAs), affecting the cycling of Fe in acid mine drainage (AMD). However, it is still unclear how this process relates to the fate of heavy metal contaminants. The study comprehensively reports the significant role and speciation redistribution of Cu(Ⅱ) during the photochemical transformation of a Sch/tartaric acid (TA) system. Based on X-ray diffractometer and Fourier transform infrared spectra results, the presence of TA in simulated AMD significantly promoted photoreductive dissolution and phase transformation of Sch to magnetite (Mt) and goethite (Gt) under anoxic and oxic conditions, respectively. With the addition of 10–30 mg/L Cu(Ⅱ), this transformation of Sch/TA system was significantly inhibited, i.e., only Gt occurred as product under anoxic conditions and even no phase transformation under oxic conditions. The results of EPR and adsorbed Fe(Ⅱ) indicated that the coexistence of Cu(Ⅱ) suppressed the amount of adsorbed Fe(Ⅱ) available for the transformation of Sch via competitive adsorption with Fe(Ⅱ) and inhibition of ligand-to-metal charge transfer (LMCT) of Sch-TA complexes. Chemical speciation and X-ray photoelectron spectroscopy analysis revealed the proportions of adsorbed and structural Cu(Ⅱ) of Sch/TA system were observably enhanced due to an increase in pH and recrystallization/nucleation growth of newly formed Gt. Under anoxic conditions, 62.7%-75.88% of Cu(Ⅱ) was adsorbed on the mineral surface, and during the nucleation and growth of secondary mineral phases, 15.49%-17.01% of Cu(Ⅱ) was incorporated into their crystal structure. The changes in distribution of Cu(Ⅱ) further suggested the photochemical transformation of Sch facilitated the sequestration of heavy metals and reduced their bioavailability. These findings enhance the understanding of role and redistribution of Cu(Ⅱ) during the transformation of Sch/LMWOA system in euphotic zone of AMD and provid insights of exploring engineered strategies of AMD remediation.
2025, 36(7): 110340
doi: 10.1016/j.cclet.2024.110340
摘要:
The electrochemical reduction of carbon dioxide (CO2RR) is a promising strategy for achieving carbon neutralization. The Ni-N4 site is well known as the active site in metal single atoms on N-doped carbon catalysts, while its symmetric charge distribution nature is not favorable for electron transfer and then hindering the efficient CO2RR. Herein, we constructed a Ni SA/CNs single-atom catalyst. Notably, it features unique Ni-N4-O active sites, featuring one axial O atom and four planar N atoms, constituting a broken symmetrical electronic structure of Ni-N4 sites. Furthermore, hierarchical pore structures were obtained with the assistance of NaNO3 pore-forming agent during thermal treatment process, which promote electronic and mass transfer. And the resulting high specific surface area can host more Ni-N4-O active sites. These specialized active sites promote the key intermediate (*CO) adsorption/desorption and suppresses hydrogen evolution. Consequently, the Ni SA/CNs catalyst exhibits a high turnover frequency (TOF) value, reaching 34,081 h−1 at -0.98 V vs. RHE. Additionally, it achieves an excellent CO Faradaic efficiency, exceeding 90%, over a wide potential range from -0.4 V to -1.0 V vs. RHE. This work not only offers a new method for the rational synthesize single-atom catalysts with unique Ni-N4-O active sites, but also provides in-depth insight into the origin of catalytic activity of porous carbon-base catalysts.
The electrochemical reduction of carbon dioxide (CO2RR) is a promising strategy for achieving carbon neutralization. The Ni-N4 site is well known as the active site in metal single atoms on N-doped carbon catalysts, while its symmetric charge distribution nature is not favorable for electron transfer and then hindering the efficient CO2RR. Herein, we constructed a Ni SA/CNs single-atom catalyst. Notably, it features unique Ni-N4-O active sites, featuring one axial O atom and four planar N atoms, constituting a broken symmetrical electronic structure of Ni-N4 sites. Furthermore, hierarchical pore structures were obtained with the assistance of NaNO3 pore-forming agent during thermal treatment process, which promote electronic and mass transfer. And the resulting high specific surface area can host more Ni-N4-O active sites. These specialized active sites promote the key intermediate (*CO) adsorption/desorption and suppresses hydrogen evolution. Consequently, the Ni SA/CNs catalyst exhibits a high turnover frequency (TOF) value, reaching 34,081 h−1 at -0.98 V vs. RHE. Additionally, it achieves an excellent CO Faradaic efficiency, exceeding 90%, over a wide potential range from -0.4 V to -1.0 V vs. RHE. This work not only offers a new method for the rational synthesize single-atom catalysts with unique Ni-N4-O active sites, but also provides in-depth insight into the origin of catalytic activity of porous carbon-base catalysts.
2025, 36(7): 110342
doi: 10.1016/j.cclet.2024.110342
摘要:
Antifungal resistance is the leading cause of antifungal treatment failure in invasive candidiasis. Metabolic rewiring could become a new insight to account for antifungal resistance as to find innovative clinical therapies. Here, we show that dynamic surface-enhanced Raman spectroscopy is a promising tool to identify the metabolic differences between fluconazole (Diflucan)-resistant and fluconazole (Diflucan)-sensitive Candida albicans through the signatures of biochemical components and complemented with machine learning algorithms and two-dimensional correlation spectroscopy, an underlying resistance mechanism, that is, the change of purine metabolites induced the resistance of Candida albicans has been clarified yet never reported anywhere. We hope the integrated methodology introduced in this work could be beneficial for the interpretation of cellular regulation, propelling the development of targeted antifungal therapies and diagnostic tools for more efficient management of severe antifungal resistance.
Antifungal resistance is the leading cause of antifungal treatment failure in invasive candidiasis. Metabolic rewiring could become a new insight to account for antifungal resistance as to find innovative clinical therapies. Here, we show that dynamic surface-enhanced Raman spectroscopy is a promising tool to identify the metabolic differences between fluconazole (Diflucan)-resistant and fluconazole (Diflucan)-sensitive Candida albicans through the signatures of biochemical components and complemented with machine learning algorithms and two-dimensional correlation spectroscopy, an underlying resistance mechanism, that is, the change of purine metabolites induced the resistance of Candida albicans has been clarified yet never reported anywhere. We hope the integrated methodology introduced in this work could be beneficial for the interpretation of cellular regulation, propelling the development of targeted antifungal therapies and diagnostic tools for more efficient management of severe antifungal resistance.
2025, 36(7): 110400
doi: 10.1016/j.cclet.2024.110400
摘要:
The high band gap of zinc oxide (ZnO) has significantly limited its potential application for organic contaminant removal in photocatalysis. In this study, ZnO/halloysites (HNTs) composites (ZnO/HNTs) were prepared using a high-temperature calcination method to enhance the removal of tetracycline hydrochloride (TCH). The experimental results demonstrated that the band gap of ZnO/HNTs decreased to 3.12 eV, compared to 3.21 eV for pure ZnO. The observed removal rate (kobs) of TCH in the ZnO/HNTs/vis system was 1.90 × 10–2 min-1, significantly higher than the rates in the HNTs/vis (1.25 × 10–3 min-1) and ZnO/vis (1.13 × 10–2 min-1) systems. Additionally, ZnO/HNTs exhibited strong resistance to coexisting natural organic and inorganic matter, maintaining high pollutant removal efficiency in natural water samples. The ZnO/HNTs/vis system also effectively removed other common organic pollutants, such as ciprofloxacin and methylene blue. Cycle tests indicated that the ZnO/HNTs/vis system retained 65.57% of its original efficiency, demonstrating good reusability and versatility. Scavenging and electron paramagnetic resonance experiments identified that h+ was the primary species in the ZnO/HNTs/vis system, with other species playing auxiliary roles in TCH degradation. This study provides valuable insights into the design of novel ZnO-based photocatalysts for the degradation of organic pollutants in water.
The high band gap of zinc oxide (ZnO) has significantly limited its potential application for organic contaminant removal in photocatalysis. In this study, ZnO/halloysites (HNTs) composites (ZnO/HNTs) were prepared using a high-temperature calcination method to enhance the removal of tetracycline hydrochloride (TCH). The experimental results demonstrated that the band gap of ZnO/HNTs decreased to 3.12 eV, compared to 3.21 eV for pure ZnO. The observed removal rate (kobs) of TCH in the ZnO/HNTs/vis system was 1.90 × 10–2 min-1, significantly higher than the rates in the HNTs/vis (1.25 × 10–3 min-1) and ZnO/vis (1.13 × 10–2 min-1) systems. Additionally, ZnO/HNTs exhibited strong resistance to coexisting natural organic and inorganic matter, maintaining high pollutant removal efficiency in natural water samples. The ZnO/HNTs/vis system also effectively removed other common organic pollutants, such as ciprofloxacin and methylene blue. Cycle tests indicated that the ZnO/HNTs/vis system retained 65.57% of its original efficiency, demonstrating good reusability and versatility. Scavenging and electron paramagnetic resonance experiments identified that h+ was the primary species in the ZnO/HNTs/vis system, with other species playing auxiliary roles in TCH degradation. This study provides valuable insights into the design of novel ZnO-based photocatalysts for the degradation of organic pollutants in water.
2025, 36(7): 110401
doi: 10.1016/j.cclet.2024.110401
摘要:
Despite the expansive applications of gas-phase unfolding techniques, the molecular mechanism for the solvent-free forced unfolding pathway which substrate multidomain proteins usually adopt remains elusive at the secondary structure level. Herein, upon carefully selecting CRM197 as a therapeutically-relevant model system containing multiple secondary structure-separated domains, we systematically examine its solvent-free unfolding pathway. Further-more, utilizing the hybrid of noncovalent chemical probing with niacinamide and ion mobility-mass spectrometry-guided all-atom molecular dynamics simulations, we map a nearly complete unfolding atlas for the conjugate vaccine carrier protein CRM197 in a domain- and secondary structure-resolved manner. The totality of our data supports the preferential unfolding of the sheet-rich domain, indicating the dynamic transition from β-sheet to α-helix, and demonstrating that helix exhibit comparatively higher stability than β-sheets. We propose that this sheet-to-helix dynamic transition may be central to the gas-phase unfolding pathways of multidomain proteins, suggesting the need for systematic studies on additional multidomain protein systems.
Despite the expansive applications of gas-phase unfolding techniques, the molecular mechanism for the solvent-free forced unfolding pathway which substrate multidomain proteins usually adopt remains elusive at the secondary structure level. Herein, upon carefully selecting CRM197 as a therapeutically-relevant model system containing multiple secondary structure-separated domains, we systematically examine its solvent-free unfolding pathway. Further-more, utilizing the hybrid of noncovalent chemical probing with niacinamide and ion mobility-mass spectrometry-guided all-atom molecular dynamics simulations, we map a nearly complete unfolding atlas for the conjugate vaccine carrier protein CRM197 in a domain- and secondary structure-resolved manner. The totality of our data supports the preferential unfolding of the sheet-rich domain, indicating the dynamic transition from β-sheet to α-helix, and demonstrating that helix exhibit comparatively higher stability than β-sheets. We propose that this sheet-to-helix dynamic transition may be central to the gas-phase unfolding pathways of multidomain proteins, suggesting the need for systematic studies on additional multidomain protein systems.
2025, 36(7): 110409
doi: 10.1016/j.cclet.2024.110409
摘要:
Cancer is a serious global health issue, and exploring effective treatment methods is of great significance for cancer prevention and control. Carbon monoxide (CO), as an important gas signaling molecule in the life system, has been proven to have good anti-cancer effects. However, how to controllably, safely, and effectively deliver CO to the tumor site for clinical treatment remains a challenge. Herein, a new metal-free CO-releasing molecule COR-XAC was developed for controlling CO release and cancer therapy. COR-XAC is based on the hybrid of 3‑hydroxyl flavone and oxanthracene fluorophores, showing visible light-controlled CO-releasing properties and near-infrared (NIR) ratiometric fluorescence changes at 690 and 760 nm. COR-XAC shows low cytotoxicity and can be successfully applied to release CO in cells and tumors, and the CO-releasing and delivery process could be monitored by its own NIR ratiometric fluorescence changes. More importantly, the anti-cancer performance of COR-XAC was evaluated in 4T1 tumor mice, and it was found that COR-XAC plus light illumination showed excellent tumor inhibition effect, which provided a promising new effective method for cancer treatment.
Cancer is a serious global health issue, and exploring effective treatment methods is of great significance for cancer prevention and control. Carbon monoxide (CO), as an important gas signaling molecule in the life system, has been proven to have good anti-cancer effects. However, how to controllably, safely, and effectively deliver CO to the tumor site for clinical treatment remains a challenge. Herein, a new metal-free CO-releasing molecule COR-XAC was developed for controlling CO release and cancer therapy. COR-XAC is based on the hybrid of 3‑hydroxyl flavone and oxanthracene fluorophores, showing visible light-controlled CO-releasing properties and near-infrared (NIR) ratiometric fluorescence changes at 690 and 760 nm. COR-XAC shows low cytotoxicity and can be successfully applied to release CO in cells and tumors, and the CO-releasing and delivery process could be monitored by its own NIR ratiometric fluorescence changes. More importantly, the anti-cancer performance of COR-XAC was evaluated in 4T1 tumor mice, and it was found that COR-XAC plus light illumination showed excellent tumor inhibition effect, which provided a promising new effective method for cancer treatment.
2025, 36(7): 110410
doi: 10.1016/j.cclet.2024.110410
摘要:
Strict regulations on heavy metal (HM) limits impede the sludge land utilization for carbon emission reduction. This study aimed to evaluate the impact of bioavailable HMs (Cd, Cu, and Zn) on soil nitrification and determine toxicity thresholds via two cycles of sludge land application tests over 185 days. HMs inhibited gene abundance in their labile fractions, with the most affected being nitrite-oxidizing bacteria (NOB)-nxrB, followed by ammonia-oxidizing bacteria (AOB)-amoA, NOB-nxrA, and ammonia oxidizing archaea (AOA)-amoA. Toxicity thresholds for incremental labile fractions of HMs (in mg/kg) were determined as 0.35 for Cd, 21.73 for Cu, and 84.04 for Zn. Additionally, AOB, as the core nitrifiers, significantly correlated (P < 0.05) with ammonia nitrogen, soil organic matter, total phosphorus, and total potassium, playing a pivotal role in maintaining intricate interactions within HMs-spiked sludge-treated soil systems. The acute toxicity effects of HMs on potential ammonia oxidation (PAO), measured by inhibition rates, were 77.04%, 73.63%, and 67.06% for Cd, Cu, and Zn, with labile fractions contributing 33.79%, 40.19%, and 28.37%, respectively. Long-term sludge land application revealed chronic toxicity of HMs to PAO through the reshaping of ammonia-oxidizing microorganisms, particularly Cu and Zn. These findings provide insights into HM toxicity thresholds and their impact on nitrification, supporting sustainable sludge land management.
Strict regulations on heavy metal (HM) limits impede the sludge land utilization for carbon emission reduction. This study aimed to evaluate the impact of bioavailable HMs (Cd, Cu, and Zn) on soil nitrification and determine toxicity thresholds via two cycles of sludge land application tests over 185 days. HMs inhibited gene abundance in their labile fractions, with the most affected being nitrite-oxidizing bacteria (NOB)-nxrB, followed by ammonia-oxidizing bacteria (AOB)-amoA, NOB-nxrA, and ammonia oxidizing archaea (AOA)-amoA. Toxicity thresholds for incremental labile fractions of HMs (in mg/kg) were determined as 0.35 for Cd, 21.73 for Cu, and 84.04 for Zn. Additionally, AOB, as the core nitrifiers, significantly correlated (P < 0.05) with ammonia nitrogen, soil organic matter, total phosphorus, and total potassium, playing a pivotal role in maintaining intricate interactions within HMs-spiked sludge-treated soil systems. The acute toxicity effects of HMs on potential ammonia oxidation (PAO), measured by inhibition rates, were 77.04%, 73.63%, and 67.06% for Cd, Cu, and Zn, with labile fractions contributing 33.79%, 40.19%, and 28.37%, respectively. Long-term sludge land application revealed chronic toxicity of HMs to PAO through the reshaping of ammonia-oxidizing microorganisms, particularly Cu and Zn. These findings provide insights into HM toxicity thresholds and their impact on nitrification, supporting sustainable sludge land management.
2025, 36(7): 110418
doi: 10.1016/j.cclet.2024.110418
摘要:
Development of accurate analytical protocols for cancer biomarkers is used for the initial prescreening of malignant tumors, disease surveillance, and efficacy assessment with significant clinical benefits. In this work, we reported a liposome-mediated signal-off photoelectrochemical (PEC) immunoassay for the sensitive detection of carcinoembryonic antigen (CEA) using ternary transition metal sulfide CuS/ZnCdS as the photoactive material. Good photocurrents were acquired on the basis of specific oxidation reaction of dopamine on the CuS/ZnCdS. The energy band relationship of CuS/ZnCdS was determined, and the well-matched oxidation potential of dopamine was verified. To achieve accurate recovery of low-abundance CEA, systematic PEC evaluation from human serum samples was performed by combining with classical immunoreaction and liposome-induced dopamine amplification strategy with high stability and selectivity. Under optimum conditions, PEC immunoassay displayed good photocurrent responses toward target CEA with a dynamic linear range of 0.1–50 ng/mL with a detection limit of 31.6 pg/mL. Importantly, this system by combining with a discussion of energy level matching between semiconductor energy bands and small-molecules opens a new horizon for development of high-efficient PEC immunoassays.
Development of accurate analytical protocols for cancer biomarkers is used for the initial prescreening of malignant tumors, disease surveillance, and efficacy assessment with significant clinical benefits. In this work, we reported a liposome-mediated signal-off photoelectrochemical (PEC) immunoassay for the sensitive detection of carcinoembryonic antigen (CEA) using ternary transition metal sulfide CuS/ZnCdS as the photoactive material. Good photocurrents were acquired on the basis of specific oxidation reaction of dopamine on the CuS/ZnCdS. The energy band relationship of CuS/ZnCdS was determined, and the well-matched oxidation potential of dopamine was verified. To achieve accurate recovery of low-abundance CEA, systematic PEC evaluation from human serum samples was performed by combining with classical immunoreaction and liposome-induced dopamine amplification strategy with high stability and selectivity. Under optimum conditions, PEC immunoassay displayed good photocurrent responses toward target CEA with a dynamic linear range of 0.1–50 ng/mL with a detection limit of 31.6 pg/mL. Importantly, this system by combining with a discussion of energy level matching between semiconductor energy bands and small-molecules opens a new horizon for development of high-efficient PEC immunoassays.
2025, 36(7): 110419
doi: 10.1016/j.cclet.2024.110419
摘要:
NiMn-MOF was prepared via one-step hydrothermal method, and then Ni/MnO/C composites were synthesized by high-temperature pyrolysis. The findings indicate that the sample acquired at the pyrolysis temperature of 700 ℃ demonstrate superior microwave absorption capabilities. The minimum reflection value achieves -19.2 dB at a thickness of 1.4 mm, and the effective absorption bandwidth extends to 5.04 GHz at a mere 1.6 mm. The exceptional microwave absorption proficiency can be ascribed to the multiple reflections and scattering generated by the material's unique porous spherical structure, optimized impedance matching, suitable conduction loss, rich interfacial and dipole polarization, and magnetic loss. This study presents a straightforward procedural technique for the fabrication of effective composite absorbers.
NiMn-MOF was prepared via one-step hydrothermal method, and then Ni/MnO/C composites were synthesized by high-temperature pyrolysis. The findings indicate that the sample acquired at the pyrolysis temperature of 700 ℃ demonstrate superior microwave absorption capabilities. The minimum reflection value achieves -19.2 dB at a thickness of 1.4 mm, and the effective absorption bandwidth extends to 5.04 GHz at a mere 1.6 mm. The exceptional microwave absorption proficiency can be ascribed to the multiple reflections and scattering generated by the material's unique porous spherical structure, optimized impedance matching, suitable conduction loss, rich interfacial and dipole polarization, and magnetic loss. This study presents a straightforward procedural technique for the fabrication of effective composite absorbers.
2025, 36(7): 110420
doi: 10.1016/j.cclet.2024.110420
摘要:
In this study, novel CePO4 supported Cr catalyst was applied to eliminate slipping NH3 from stationary sources in the presence of SO2. Experimental results revealed that over 85% NH3 conversion and well N2 selectivity could be achieved on Cr/CePO4 catalyst within 300–450 ℃ after 20 h reaction running in the presence of SO2. Importantly, superior SCO activity (about 95%) could be maintained during the stability test. Characterization results indicated that active Cr sites could form strong interactions with acidic CePO4 support on Cr/CePO4 catalyst, which slightly suppressed reactivity of active Cr species but showed enhanced surface acidity. Importantly, the existed strong interactions and enhanced surface acidity significantly impeded the adsorption and oxidation process of SO2, which weakened the deposition and thermal stability of sulfate species and retained more active sites to participate in SCO reactions, thereby enhancing sulfur tolerance of Cr/CePO4 catalyst. Such findings could pave a new way for development of highly efficient SCO catalysts with well sulfur tolerance for real application.
In this study, novel CePO4 supported Cr catalyst was applied to eliminate slipping NH3 from stationary sources in the presence of SO2. Experimental results revealed that over 85% NH3 conversion and well N2 selectivity could be achieved on Cr/CePO4 catalyst within 300–450 ℃ after 20 h reaction running in the presence of SO2. Importantly, superior SCO activity (about 95%) could be maintained during the stability test. Characterization results indicated that active Cr sites could form strong interactions with acidic CePO4 support on Cr/CePO4 catalyst, which slightly suppressed reactivity of active Cr species but showed enhanced surface acidity. Importantly, the existed strong interactions and enhanced surface acidity significantly impeded the adsorption and oxidation process of SO2, which weakened the deposition and thermal stability of sulfate species and retained more active sites to participate in SCO reactions, thereby enhancing sulfur tolerance of Cr/CePO4 catalyst. Such findings could pave a new way for development of highly efficient SCO catalysts with well sulfur tolerance for real application.
2025, 36(7): 110433
doi: 10.1016/j.cclet.2024.110433
摘要:
Oxidative stress, characterized by the excessive accumulation of reactive oxygen species (ROS), is linked to various pathological conditions, including myocardial infarction, cancer, and neurodegenerative diseases. Addressing ROS-induced cell damage has become a critical focus of biomedical research. In this study, a thermo-sensitive poly(amino acid) hydrogel, composed of poly(ethylene glycol)-block-poly(l-methionine), was prepared for cytoprotection through ROS scavenging. The sol-to-gel transition mechanism of the hydrogel was elucidated, and its potent antioxidant properties and cell protective effects were validated using hydrogen peroxide (H2O2)-induced oxidative stress and oxygen-glucose deprivation (OGD) models. The hydrogel significantly mitigated H2O2-induced damage in L929 cells, doubling their survival rate. Additionally, it scavenged approximately 35.8% of the ROS during OGD, reducing mitochondrial oxidative damage and resulting in a 29.4% decrease in apoptotic cell number. These findings underscore the potential biomedical applications of thermo-sensitive poly(amino acid) hydrogels, particularly in treating oxidative stress-related cell damage.
Oxidative stress, characterized by the excessive accumulation of reactive oxygen species (ROS), is linked to various pathological conditions, including myocardial infarction, cancer, and neurodegenerative diseases. Addressing ROS-induced cell damage has become a critical focus of biomedical research. In this study, a thermo-sensitive poly(amino acid) hydrogel, composed of poly(ethylene glycol)-block-poly(l-methionine), was prepared for cytoprotection through ROS scavenging. The sol-to-gel transition mechanism of the hydrogel was elucidated, and its potent antioxidant properties and cell protective effects were validated using hydrogen peroxide (H2O2)-induced oxidative stress and oxygen-glucose deprivation (OGD) models. The hydrogel significantly mitigated H2O2-induced damage in L929 cells, doubling their survival rate. Additionally, it scavenged approximately 35.8% of the ROS during OGD, reducing mitochondrial oxidative damage and resulting in a 29.4% decrease in apoptotic cell number. These findings underscore the potential biomedical applications of thermo-sensitive poly(amino acid) hydrogels, particularly in treating oxidative stress-related cell damage.
2025, 36(7): 110434
doi: 10.1016/j.cclet.2024.110434
摘要:
The switchable cross-coupling of indoles and pyridotriazoles through carbene insertion at C2- or C3-positon has been developed in this paper. This highly site-selective C−H carbenoid functionalization is determined by both the Rh-catalyst species and auxiliary groups. [Cp*RhCl2]2 and coordinating pyrimidyl group direct the C−H carbenoid functionalization to occur at the C2-position, while Rh2OAc4 and non-coordinating benzyl group lead the reaction to occur at the C3-position of the indoles. This regioselective C−H functionalization strategy is of significant importance for the discovery of indole drugs.
The switchable cross-coupling of indoles and pyridotriazoles through carbene insertion at C2- or C3-positon has been developed in this paper. This highly site-selective C−H carbenoid functionalization is determined by both the Rh-catalyst species and auxiliary groups. [Cp*RhCl2]2 and coordinating pyrimidyl group direct the C−H carbenoid functionalization to occur at the C2-position, while Rh2OAc4 and non-coordinating benzyl group lead the reaction to occur at the C3-position of the indoles. This regioselective C−H functionalization strategy is of significant importance for the discovery of indole drugs.
2025, 36(7): 110435
doi: 10.1016/j.cclet.2024.110435
摘要:
Novel benzo-bridged hexaphyrin(2.1.2.1.2.1) and its copper complex were synthesized. Single-crystal structures showed typical figure-of-eight Hückel topologies. NMR, NICS, HOMA, ACID, and EDDB analysis supported their non-aromatic properties owning to the strong local aromatic benzo rings cutting the global aromatic ring of the benzo-bridged figure-of-eight hexaphyrin(2.1.2.1.2.1). The redox properties and degenerate HOMOs and LUMOs levels indicate multielectron donating and accepting abilities.
Novel benzo-bridged hexaphyrin(2.1.2.1.2.1) and its copper complex were synthesized. Single-crystal structures showed typical figure-of-eight Hückel topologies. NMR, NICS, HOMA, ACID, and EDDB analysis supported their non-aromatic properties owning to the strong local aromatic benzo rings cutting the global aromatic ring of the benzo-bridged figure-of-eight hexaphyrin(2.1.2.1.2.1). The redox properties and degenerate HOMOs and LUMOs levels indicate multielectron donating and accepting abilities.
2025, 36(7): 110436
doi: 10.1016/j.cclet.2024.110436
摘要:
Developing an accurate and visual sensing strategy for trace levels of fluoroquinolone residues that pose threat to food safety and human health is highly desired but remains challenging. Herein, a target self-calibration ratiometric fluorescent sensing platform has been designed for sensitive visual detection of levofloxacin (LEV) based on fluorescent europium metal-organic framework (Eu-MOF) probe. Specifically, the Eu-MOF was facilely synthesized via directly mixing Eu3+ with 1,10-phenanthroline-2,9-dicarboxylic acid (PDA) ligand at room temperature, which exhibited well-stable red fluorescence at 612 nm. Upon the addition of target LEV, the significant fluorescence quenching from Eu3+ was observed owing to the inner filter effect between the Eu-MOF and LEV. While the intrinsic fluorescence for LEV at 462 nm was gradually enhanced, thereby realizing the self-calibration ratiometric fluorescence responses to LEV. Through this strategy, LEV can be detected down to 27 nmol/L. Furthermore, a test paper-based Eu-MOF integrated with the smartphone assisted RGB color analysis was exploited for the quantitative monitoring of LEV through the multi-color changes from red to blue, thus achieved portable, convenient and visual detection of LEV in honey and milk samples. Therefore, the developed strategy could provide a useful tool for supporting the practical on-site test in food samples.
Developing an accurate and visual sensing strategy for trace levels of fluoroquinolone residues that pose threat to food safety and human health is highly desired but remains challenging. Herein, a target self-calibration ratiometric fluorescent sensing platform has been designed for sensitive visual detection of levofloxacin (LEV) based on fluorescent europium metal-organic framework (Eu-MOF) probe. Specifically, the Eu-MOF was facilely synthesized via directly mixing Eu3+ with 1,10-phenanthroline-2,9-dicarboxylic acid (PDA) ligand at room temperature, which exhibited well-stable red fluorescence at 612 nm. Upon the addition of target LEV, the significant fluorescence quenching from Eu3+ was observed owing to the inner filter effect between the Eu-MOF and LEV. While the intrinsic fluorescence for LEV at 462 nm was gradually enhanced, thereby realizing the self-calibration ratiometric fluorescence responses to LEV. Through this strategy, LEV can be detected down to 27 nmol/L. Furthermore, a test paper-based Eu-MOF integrated with the smartphone assisted RGB color analysis was exploited for the quantitative monitoring of LEV through the multi-color changes from red to blue, thus achieved portable, convenient and visual detection of LEV in honey and milk samples. Therefore, the developed strategy could provide a useful tool for supporting the practical on-site test in food samples.
2025, 36(7): 110440
doi: 10.1016/j.cclet.2024.110440
摘要:
Optogenetic has been widely applied in various pathogenesis investigations of neuropathic diseases since its accurate and targeted regulation of neuronal activity. However, due to the mismatch between the soft tissues and the optical waveguide, the long-term neural regulation within soft tissue (such as brain and spinal cord) by implantable optical fibers is a large challenge. Herein, we designed a modulus self-adaptive hydrogel optical fiber (MSHOF) with tunable mechanical properties (Young’ modulus was tunable in the range of 0.32–10.56 MPa) and low light attenuation (0.12–0.21 dB/cm, 472 nm laser light), which adapts to light transmission under soft tissues. These advantages of MSHOF can ensure the effectiveness of optogenetic stimulation meanwhile safeguarding the safety of the brain/materials interaction interface. In addition, this work provides more design possibilities of MSHOF for photogenetic stimuli and has significant application prospects in photomedical therapy.
Optogenetic has been widely applied in various pathogenesis investigations of neuropathic diseases since its accurate and targeted regulation of neuronal activity. However, due to the mismatch between the soft tissues and the optical waveguide, the long-term neural regulation within soft tissue (such as brain and spinal cord) by implantable optical fibers is a large challenge. Herein, we designed a modulus self-adaptive hydrogel optical fiber (MSHOF) with tunable mechanical properties (Young’ modulus was tunable in the range of 0.32–10.56 MPa) and low light attenuation (0.12–0.21 dB/cm, 472 nm laser light), which adapts to light transmission under soft tissues. These advantages of MSHOF can ensure the effectiveness of optogenetic stimulation meanwhile safeguarding the safety of the brain/materials interaction interface. In addition, this work provides more design possibilities of MSHOF for photogenetic stimuli and has significant application prospects in photomedical therapy.
2025, 36(7): 110441
doi: 10.1016/j.cclet.2024.110441
摘要:
Oral ulcers may greatly diminish patient life quality and potentially result in malignant transformations. Using gels or films as pseudomembrane barriers is an effective method for promoting ulcer healing. However, these pseudomembranes face challenges such as saliva flushing, dynamic changes, and the presence of abundant microorganisms in the complex oral environment. Herein, we developed an injectable, photoinduction, in situ-enhanceable oral ulcer repair hydrogel (named as GIL2) by incorporating dynamic phenylboronic acid ester bonds and imidazole ions into a methacrylated gelatin matrix. GIL2 exhibited rapid gelation (3 s), low swelling properties (1.07 g/g), robust tensile strength (56.83 kPa) and high adhesive strength (63.38 kPa), allowing it to adhere effectively to the ulcer surface. Moreover, the GIL2 demonstrated intrinsic antibacterial and antioxidant qualities. Within a diabetic rat model for oral ulcers, GIL2 effectively eased oxidative stress and decreased the inflammation present in ulcerated wounds, thereby greatly hastening the healing process of these ulcers. Together, GIL2 hydrogel demonstrates remarkable adaptability within the oral milieu, revitalizing clinical strategy advancements for treating bacterial-infected oral ulcers.
Oral ulcers may greatly diminish patient life quality and potentially result in malignant transformations. Using gels or films as pseudomembrane barriers is an effective method for promoting ulcer healing. However, these pseudomembranes face challenges such as saliva flushing, dynamic changes, and the presence of abundant microorganisms in the complex oral environment. Herein, we developed an injectable, photoinduction, in situ-enhanceable oral ulcer repair hydrogel (named as GIL2) by incorporating dynamic phenylboronic acid ester bonds and imidazole ions into a methacrylated gelatin matrix. GIL2 exhibited rapid gelation (3 s), low swelling properties (1.07 g/g), robust tensile strength (56.83 kPa) and high adhesive strength (63.38 kPa), allowing it to adhere effectively to the ulcer surface. Moreover, the GIL2 demonstrated intrinsic antibacterial and antioxidant qualities. Within a diabetic rat model for oral ulcers, GIL2 effectively eased oxidative stress and decreased the inflammation present in ulcerated wounds, thereby greatly hastening the healing process of these ulcers. Together, GIL2 hydrogel demonstrates remarkable adaptability within the oral milieu, revitalizing clinical strategy advancements for treating bacterial-infected oral ulcers.
2025, 36(7): 110450
doi: 10.1016/j.cclet.2024.110450
摘要:
Pulmonary artery remodeling is a critical pathological feature of pulmonary arterial hypertension (PAH), a fatal lung disease without cure, resulting in poor pulmonary hemodynamics and compliance. The remodeling could be aggravated by various factors, particularly by the hyperproliferation of pulmonary artery smooth muscle cells (PASMCs) and perivascular inflammation. Meanwhile, the hyperproliferation of PASMCs can be driven by the overexpression of miR138. In this study, we developed anti-inflammatory baicalein-assisted anti-miR138 gene therapy against PAH. The system was fabricated by anchoring the nucleic acid onto the nanocrystals through electrostatic interaction, followed by glucuronic acid (GA) coating for targeting the glucose transport-1 (GLUT-1) receptor. The results demonstrated that the system had a 201-nm in diameter with a rod shape and allowed a 12-fold increase in pulmonary artery (PA) targeting versus free drug administration. The preparation injection reduced the PA thickness by 20% via effectively promoting PASMC apoptosis, likely by strengthening the pathway of Bcl-2 associated X protein/B-cell lymphoma-2/caspase 3 (Bax/Bcl-2/Cas-3). The in vivo efficacy in the monocrotaline (MCT)-PAH model demonstrated significant improvement in the pulmonary hemodynamics, e.g., a 50% decrease in mean pulmonary artery pressure (mPAP), 61% increase in pulmonary artery acceleration time (PAAT), and 82% increase in cardiac output (CO). In conclusion, targeted codelivery of the inflammation inhibitor and anti-miR138 to PAs is promising to combat PAH. Rod-shaped nanomedicines represent an effective PA-targeting strategy.
Pulmonary artery remodeling is a critical pathological feature of pulmonary arterial hypertension (PAH), a fatal lung disease without cure, resulting in poor pulmonary hemodynamics and compliance. The remodeling could be aggravated by various factors, particularly by the hyperproliferation of pulmonary artery smooth muscle cells (PASMCs) and perivascular inflammation. Meanwhile, the hyperproliferation of PASMCs can be driven by the overexpression of miR138. In this study, we developed anti-inflammatory baicalein-assisted anti-miR138 gene therapy against PAH. The system was fabricated by anchoring the nucleic acid onto the nanocrystals through electrostatic interaction, followed by glucuronic acid (GA) coating for targeting the glucose transport-1 (GLUT-1) receptor. The results demonstrated that the system had a 201-nm in diameter with a rod shape and allowed a 12-fold increase in pulmonary artery (PA) targeting versus free drug administration. The preparation injection reduced the PA thickness by 20% via effectively promoting PASMC apoptosis, likely by strengthening the pathway of Bcl-2 associated X protein/B-cell lymphoma-2/caspase 3 (Bax/Bcl-2/Cas-3). The in vivo efficacy in the monocrotaline (MCT)-PAH model demonstrated significant improvement in the pulmonary hemodynamics, e.g., a 50% decrease in mean pulmonary artery pressure (mPAP), 61% increase in pulmonary artery acceleration time (PAAT), and 82% increase in cardiac output (CO). In conclusion, targeted codelivery of the inflammation inhibitor and anti-miR138 to PAs is promising to combat PAH. Rod-shaped nanomedicines represent an effective PA-targeting strategy.
2025, 36(7): 110458
doi: 10.1016/j.cclet.2024.110458
摘要:
Developing high-efficient, multi spectral applicable one-component macrophotoinitiators (Macro-PIs) with excellent performance that can simultaneously initiate cationic polymerization (CP), free radical polymerization (FRP), and hybrid polymerization (HP) has been a charming research direction. Herein, we synthesized a novel cationic macro-PI (P-CSS) by copolymerizing polymerizable coumarin sulfonium salt (CSS) and methyl methacrylate (MMA). Photochemical and photophysical investigations indicated that the extraordinary absorption ability and the 50 nm redshift of P-CSS may be due to chromophores aggregating on the side chain. Photopolymerization kinetics studies established that P-CSS has effective initiating ability for FRP and CP both under LED@365, 405 nm and under Laser@980 nm (with upconversion particles, UCPs). The migration stability experiments showed that the migration rate of P-CSS in trimethylolpropane triacrylate (TMTPA) polymer is 1.25% of CSS, and in 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate (EPOX) polymer is 1.96%. These results indicate the great potential of P-CSS in preparing biosafety and environmentally friendly polymers for packaging and biological materials.
Developing high-efficient, multi spectral applicable one-component macrophotoinitiators (Macro-PIs) with excellent performance that can simultaneously initiate cationic polymerization (CP), free radical polymerization (FRP), and hybrid polymerization (HP) has been a charming research direction. Herein, we synthesized a novel cationic macro-PI (P-CSS) by copolymerizing polymerizable coumarin sulfonium salt (CSS) and methyl methacrylate (MMA). Photochemical and photophysical investigations indicated that the extraordinary absorption ability and the 50 nm redshift of P-CSS may be due to chromophores aggregating on the side chain. Photopolymerization kinetics studies established that P-CSS has effective initiating ability for FRP and CP both under LED@365, 405 nm and under Laser@980 nm (with upconversion particles, UCPs). The migration stability experiments showed that the migration rate of P-CSS in trimethylolpropane triacrylate (TMTPA) polymer is 1.25% of CSS, and in 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate (EPOX) polymer is 1.96%. These results indicate the great potential of P-CSS in preparing biosafety and environmentally friendly polymers for packaging and biological materials.
2025, 36(7): 110459
doi: 10.1016/j.cclet.2024.110459
摘要:
The tumor microenvironment (TME)-activatable probes have proven effective in enhancing the signal-to-background ratio (SBR) for precise fluorescence imaging in tumor diagnosis. However, many fluorophores have suboptimal emission spectra and a short Stokes shift, which may lead to overlap with bio-autofluorescence, excitation, and emission spectra, limiting their use in intraoperative guidance. Herein, a γ-glutathione (GSH) responsive near-infrared (NIR) BODIPY probe, named "Pro-Dye" was synthesized with a large Stokes shift of 91 nm. The Pro-Dye can be rapidly and specifically activated by high concentrations of GSH both in solution and inside cancer cells, while remaining inactive in normal cells (Human umbilical vein endothelial cells, HUVECs). The Pro-Dye was further encapsulated by 1, 2-distearoyl-sn‑glycero-3-phosphoethanolamine-N-(polyethylene glycol)-5000 (DSPE-PEG5000) to form Pro-Dye nanoparticles (NPs), making it water-dispersible for in vivo application. In vivo fluorescence imaging demonstrated that Pro-Dye NPs can accumulate at the tumor and exhibit an improved SBR compared to the "always-on" probe (Dye NPs). Moreover, the tumor can be precisely resected under the real-time guidance of fluorescence imaging of Pro-Dye NPs, showing a well-defined tumor margin.
The tumor microenvironment (TME)-activatable probes have proven effective in enhancing the signal-to-background ratio (SBR) for precise fluorescence imaging in tumor diagnosis. However, many fluorophores have suboptimal emission spectra and a short Stokes shift, which may lead to overlap with bio-autofluorescence, excitation, and emission spectra, limiting their use in intraoperative guidance. Herein, a γ-glutathione (GSH) responsive near-infrared (NIR) BODIPY probe, named "Pro-Dye" was synthesized with a large Stokes shift of 91 nm. The Pro-Dye can be rapidly and specifically activated by high concentrations of GSH both in solution and inside cancer cells, while remaining inactive in normal cells (Human umbilical vein endothelial cells, HUVECs). The Pro-Dye was further encapsulated by 1, 2-distearoyl-sn‑glycero-3-phosphoethanolamine-N-(polyethylene glycol)-5000 (DSPE-PEG5000) to form Pro-Dye nanoparticles (NPs), making it water-dispersible for in vivo application. In vivo fluorescence imaging demonstrated that Pro-Dye NPs can accumulate at the tumor and exhibit an improved SBR compared to the "always-on" probe (Dye NPs). Moreover, the tumor can be precisely resected under the real-time guidance of fluorescence imaging of Pro-Dye NPs, showing a well-defined tumor margin.
2025, 36(7): 110460
doi: 10.1016/j.cclet.2024.110460
摘要:
Therapy-induced modulation of the tumor microenvironment (TME) to overcome the immunosuppressive TME is considered to be a chance for cancer treatment. Herein, we prepared near-infrared absorbing aza-BODIPY PhEt-azaBDP with 1-phenylethyl group at 1, 7-sites, a type I photodynamic-photothermal therapy (PDT-PTT) agent. Self-assembly PhEt-azaBDP nanoparticles (NPs) can provide combined phototherapeutic effects under light irradiation and simultaneously induce inflammatory TME, by monitoring tumor-associated macrophages (TAMs) repolarization. Utilizing cluster of differentiation 86 (CD86) and CD163 as the M1-type marker and M2-type marker respectively, PhEt-azaBDP NPs resulted in the increasement of the expression of CD86 and the decreasement of the expression of CD163 in TAMs under near-infrared (NIR) light irradiation, promoting TAMs to switch from M2-phenotype to M1-phenotype. Inflammatory cytokines, interleukin-1β (IL-1β) and tumor necrosis factor-α (TNF-α), could be the key cytokine involved in the phototherapy-induced TME reprogramming. PhEt-azaBDP NPs could be a potential theranostic scaffold for the simultaneous induction and detection of TME reprogramming triggered by phototherapy.
Therapy-induced modulation of the tumor microenvironment (TME) to overcome the immunosuppressive TME is considered to be a chance for cancer treatment. Herein, we prepared near-infrared absorbing aza-BODIPY PhEt-azaBDP with 1-phenylethyl group at 1, 7-sites, a type I photodynamic-photothermal therapy (PDT-PTT) agent. Self-assembly PhEt-azaBDP nanoparticles (NPs) can provide combined phototherapeutic effects under light irradiation and simultaneously induce inflammatory TME, by monitoring tumor-associated macrophages (TAMs) repolarization. Utilizing cluster of differentiation 86 (CD86) and CD163 as the M1-type marker and M2-type marker respectively, PhEt-azaBDP NPs resulted in the increasement of the expression of CD86 and the decreasement of the expression of CD163 in TAMs under near-infrared (NIR) light irradiation, promoting TAMs to switch from M2-phenotype to M1-phenotype. Inflammatory cytokines, interleukin-1β (IL-1β) and tumor necrosis factor-α (TNF-α), could be the key cytokine involved in the phototherapy-induced TME reprogramming. PhEt-azaBDP NPs could be a potential theranostic scaffold for the simultaneous induction and detection of TME reprogramming triggered by phototherapy.
2025, 36(7): 110461
doi: 10.1016/j.cclet.2024.110461
摘要:
Transition-metal-catalyzed tandem cross-coupling reactions can rapidly construct complex molecules, but they often suffer from site- and regio- selectivity issues. Here, we designed a novel nickel-catalyzed three-component cross-electrophile coupling (cXEC) platform that enables access to valuable gem-difluoroalkenes. This multicomponent reaction proceeds through a chemoselective alkenylation of aryl halides, followed by alkylation of α-(trifluoromethyl)styrenes, providing a streamlined pathway towards this kind of building blocks.
Transition-metal-catalyzed tandem cross-coupling reactions can rapidly construct complex molecules, but they often suffer from site- and regio- selectivity issues. Here, we designed a novel nickel-catalyzed three-component cross-electrophile coupling (cXEC) platform that enables access to valuable gem-difluoroalkenes. This multicomponent reaction proceeds through a chemoselective alkenylation of aryl halides, followed by alkylation of α-(trifluoromethyl)styrenes, providing a streamlined pathway towards this kind of building blocks.
2025, 36(7): 110463
doi: 10.1016/j.cclet.2024.110463
摘要:
Azulene-fused acenes demonstrate enhanced stability, unique aromaticity, and distinctive photophysical properties, rendering them significant in organic electronics. In the present study, we report a new type of nonalternant analogue of pentacene incorporating a non-terminal azulene unit. Aromaticity analyses reveal that the five-membered rings in this analogue exhibit antiaromatic. The extensive conjugated aryl substituents on the acene's side shift the HOMO distributions from the naphthyl ring and metallacycle to the aryl groups, thereby narrowing the HOMO–LUMO energy gap and enhancing absorptions in the low-energy regions. Furthermore, these fused acenes readily react with base rather than acid, resulting in reversible base/acid stimuli responsiveness.
Azulene-fused acenes demonstrate enhanced stability, unique aromaticity, and distinctive photophysical properties, rendering them significant in organic electronics. In the present study, we report a new type of nonalternant analogue of pentacene incorporating a non-terminal azulene unit. Aromaticity analyses reveal that the five-membered rings in this analogue exhibit antiaromatic. The extensive conjugated aryl substituents on the acene's side shift the HOMO distributions from the naphthyl ring and metallacycle to the aryl groups, thereby narrowing the HOMO–LUMO energy gap and enhancing absorptions in the low-energy regions. Furthermore, these fused acenes readily react with base rather than acid, resulting in reversible base/acid stimuli responsiveness.
2025, 36(7): 110474
doi: 10.1016/j.cclet.2024.110474
摘要:
Catalytic syntheses of silaoxycarbocyclics from an interrupted Catellani reaction of 3-iodochromones with bridged olefins and octamethyl-1, 4-dioxacyclohexasilane is described. This protocol involves the oxidative addition of chromonyl-norbornyl-palladacycle generated through successive oxidative addition of Pd(0) to 3-iodochromones, migratory insertion of NBE and intramolecular ortho-C(sp2)−H activation to the tetrasilane, thus motivating a (4 + 6) annulation and ring expansion. The synthetic practicality of current strategy is further proved by the late-stage modification of pharmaceuticals and natural products, gram-scale experiments, as well as the transformations of functional groups of silaoxycarbocyclics.
Catalytic syntheses of silaoxycarbocyclics from an interrupted Catellani reaction of 3-iodochromones with bridged olefins and octamethyl-1, 4-dioxacyclohexasilane is described. This protocol involves the oxidative addition of chromonyl-norbornyl-palladacycle generated through successive oxidative addition of Pd(0) to 3-iodochromones, migratory insertion of NBE and intramolecular ortho-C(sp2)−H activation to the tetrasilane, thus motivating a (4 + 6) annulation and ring expansion. The synthetic practicality of current strategy is further proved by the late-stage modification of pharmaceuticals and natural products, gram-scale experiments, as well as the transformations of functional groups of silaoxycarbocyclics.
2025, 36(7): 110479
doi: 10.1016/j.cclet.2024.110479
摘要:
Hydrogel-based flexible sensors are emerging as ideal candidates for wearable devices and soft robotics. However, most current hydrogels possess limited physicochemical properties, which hinder their practical application in long-term and complex scenarios. Herein, inspired by the unique structure of the barnacle, we design multifunctional poly(DMAPA-co-PHEA) hydrogels (CP hydrogels) by employing multiple physical crosslinks in the presence of Ag nanoparticles and NaCl additives. Owing to the synergistic effect of cation-π interactions, hydrophobic interactions, and ionic bonds, the CP hydrogels exhibit high stretchability (strain up to 1430%), strong adhesion (22.8 kPa), satisfactory antibacterial activity, stable anti-icing ability (< 20 kPa after 20 icing-deicing cycles), and high electrical conductivity (18.5 mS/cm). Additionally, the CP hydrogels show fast and sensitive responsiveness and cycling stability and can attach directly to human skin to accurately detect both human motions and tiny physiological signals as a flexible wearable sensor. Collectively, this work significantly contributes a straightforward and efficient design strategy for the development of multifunctional hydrogels, broadening their application scenarios.
Hydrogel-based flexible sensors are emerging as ideal candidates for wearable devices and soft robotics. However, most current hydrogels possess limited physicochemical properties, which hinder their practical application in long-term and complex scenarios. Herein, inspired by the unique structure of the barnacle, we design multifunctional poly(DMAPA-co-PHEA) hydrogels (CP hydrogels) by employing multiple physical crosslinks in the presence of Ag nanoparticles and NaCl additives. Owing to the synergistic effect of cation-π interactions, hydrophobic interactions, and ionic bonds, the CP hydrogels exhibit high stretchability (strain up to 1430%), strong adhesion (22.8 kPa), satisfactory antibacterial activity, stable anti-icing ability (< 20 kPa after 20 icing-deicing cycles), and high electrical conductivity (18.5 mS/cm). Additionally, the CP hydrogels show fast and sensitive responsiveness and cycling stability and can attach directly to human skin to accurately detect both human motions and tiny physiological signals as a flexible wearable sensor. Collectively, this work significantly contributes a straightforward and efficient design strategy for the development of multifunctional hydrogels, broadening their application scenarios.
2025, 36(7): 110493
doi: 10.1016/j.cclet.2024.110493
摘要:
Though oncolytic viruses (OVs) hold significant potential for comprehensive treatment of malignant tumors, their systemic administration faces substantial challenges such as insufficient circulation time, inadequate tumor targeting, and spontaneous antiviral immune response of the body, which seriously limits the clinical application of OVs. Herein, we proposed a tumor targeting strategy of tumor cell membrane biomimetic liposomes to encapsulate OVs for intravenous delivery, which enables OVs to target the homotypic tumor lesions and exert their oncolytic effect. On the one hand, this cell membrane biomimetic carrier enhanced the encapsulation of OVs by the hybrid lipid membranes, concealed the viral capsid proteins, and diminished the neutralization and clearance of the virions from the bloodstream. On the other hand, enhanced tumor targeted delivery can be achieved through the utilization of homologous adhesion molecules on the surface of tumor cell membrane. In addition, this strategy also promoted the tumor infiltration of CD4+, CD8+ T cells mediated by the oncolytic effect of OVs and increased the levels of inflammatory factors such as tumor necrosis factor-α (TNF-α) and interleukin-6 (IL-6) in the tumor, thereby effectively enhancing the anti-tumor effect of intravenous administration of OVs. The findings of our study demonstrate that T-L@Ad11 offers a handy and efficient approach for targeting tumors, thereby enhancing the antitumor efficacy of intravenous administration of OVs.
Though oncolytic viruses (OVs) hold significant potential for comprehensive treatment of malignant tumors, their systemic administration faces substantial challenges such as insufficient circulation time, inadequate tumor targeting, and spontaneous antiviral immune response of the body, which seriously limits the clinical application of OVs. Herein, we proposed a tumor targeting strategy of tumor cell membrane biomimetic liposomes to encapsulate OVs for intravenous delivery, which enables OVs to target the homotypic tumor lesions and exert their oncolytic effect. On the one hand, this cell membrane biomimetic carrier enhanced the encapsulation of OVs by the hybrid lipid membranes, concealed the viral capsid proteins, and diminished the neutralization and clearance of the virions from the bloodstream. On the other hand, enhanced tumor targeted delivery can be achieved through the utilization of homologous adhesion molecules on the surface of tumor cell membrane. In addition, this strategy also promoted the tumor infiltration of CD4+, CD8+ T cells mediated by the oncolytic effect of OVs and increased the levels of inflammatory factors such as tumor necrosis factor-α (TNF-α) and interleukin-6 (IL-6) in the tumor, thereby effectively enhancing the anti-tumor effect of intravenous administration of OVs. The findings of our study demonstrate that T-L@Ad11 offers a handy and efficient approach for targeting tumors, thereby enhancing the antitumor efficacy of intravenous administration of OVs.
2025, 36(7): 110494
doi: 10.1016/j.cclet.2024.110494
摘要:
Herein, we reported an integrated device that was utilized to directly separate plasma and analyze glucose (Glu), cholesterol (Chol) from whole blood samples. The separating module primarily consists of a porous asymmetric polysulfone membrane. The vertical placement of membrane and the gravity settlement of blood cells can reduce mechanical damage to blood cells and blockage of the membrane, resulting in improved separation efficiency of the membrane. The detection module consists of a smart phone and a ratio fluorescence sensing system based on NH2−MIL-53(Al) and o-phenylenediamine (OPD). The sensing system presents a dual emission response to H2O2 the main oxidation product of Glu and Chol. Due to the fluorescence resonance energy transfer (FRET), the response of the fluorescence intensity ratio (F574 nm/F434 nm or F554 nm/F434 nm) gradually increases with increasing H2O2 concentration, accompanied by a color change from weak to strong. The visual detection of Glu and Chol can be realized through the recognition of RGB values by smart phones. The integrated device has been successfully used to analysis Glu and Chol in real blood samples, which provided a universal platform for sensing biocatalytic processes with H2O2 production.
Herein, we reported an integrated device that was utilized to directly separate plasma and analyze glucose (Glu), cholesterol (Chol) from whole blood samples. The separating module primarily consists of a porous asymmetric polysulfone membrane. The vertical placement of membrane and the gravity settlement of blood cells can reduce mechanical damage to blood cells and blockage of the membrane, resulting in improved separation efficiency of the membrane. The detection module consists of a smart phone and a ratio fluorescence sensing system based on NH2−MIL-53(Al) and o-phenylenediamine (OPD). The sensing system presents a dual emission response to H2O2 the main oxidation product of Glu and Chol. Due to the fluorescence resonance energy transfer (FRET), the response of the fluorescence intensity ratio (F574 nm/F434 nm or F554 nm/F434 nm) gradually increases with increasing H2O2 concentration, accompanied by a color change from weak to strong. The visual detection of Glu and Chol can be realized through the recognition of RGB values by smart phones. The integrated device has been successfully used to analysis Glu and Chol in real blood samples, which provided a universal platform for sensing biocatalytic processes with H2O2 production.
2025, 36(7): 110499
doi: 10.1016/j.cclet.2024.110499
摘要:
Herein we report the facial detection of formaldehyde (FA) by using an interesting red acidichromic carbon dots (ACDs) which turns blue when pH gradually decreases. The color change was attributed to the conversion between the double bonds (C=N) and single bonds (C-N) on the surface of the ACDs. Inspired by the reaction between FA and ammonium chloride that produces H+ and methenamine and decrease the pH value of the solution, a fast and simple visual detection method for FA was found with a minimum discriminated concentration of 0.04 mol/L. A fluorescence detection method for FA was also found with LOD of 0.029 mol/L and FA in real sample, e.g., shredded squid was successfully analyzed. This work provides a new idea of developing fast visual detection method for daily monitor or in-site semiquantitative assessment on FA.
Herein we report the facial detection of formaldehyde (FA) by using an interesting red acidichromic carbon dots (ACDs) which turns blue when pH gradually decreases. The color change was attributed to the conversion between the double bonds (C=N) and single bonds (C-N) on the surface of the ACDs. Inspired by the reaction between FA and ammonium chloride that produces H+ and methenamine and decrease the pH value of the solution, a fast and simple visual detection method for FA was found with a minimum discriminated concentration of 0.04 mol/L. A fluorescence detection method for FA was also found with LOD of 0.029 mol/L and FA in real sample, e.g., shredded squid was successfully analyzed. This work provides a new idea of developing fast visual detection method for daily monitor or in-site semiquantitative assessment on FA.
2025, 36(7): 110502
doi: 10.1016/j.cclet.2024.110502
摘要:
Wearable sensors are pivotal for point-of-care diagnostics, yet their application in extreme conditions is rarely conducted. In this work, we present a wearable pH sensor using tungsten oxide aerogel (TOA) as the sensing material. With the advantages of large specific surface area, high porosity and interconnected network structures, TOA not only provides excellent pH sensing performance but also demonstrates remarkable structural and sensing stability. The potentiometric pH sensor exhibits a high sensitivity (−63.70 mV/pH), a low detectable limit (0.05) and a superior stability (maintained over 50, 000 s). Integrated with a Bluetooth module, the wearable sensor achieves non-invasive and real-time pH monitoring on the human skin with minimal deviation (1.91%) compared to the commercial pH meter. More importantly, the anti-impact behaviors of the TOA-based sensing materials and chip, along with the pH wearable sensor on a pig exhibit an outstanding shock-resistance ability, with variations no more than 7.17% under an impact of 118.38 kPa. Therefore, this study shows great promise for the aerogel-based personalized health management in the extreme environment.
Wearable sensors are pivotal for point-of-care diagnostics, yet their application in extreme conditions is rarely conducted. In this work, we present a wearable pH sensor using tungsten oxide aerogel (TOA) as the sensing material. With the advantages of large specific surface area, high porosity and interconnected network structures, TOA not only provides excellent pH sensing performance but also demonstrates remarkable structural and sensing stability. The potentiometric pH sensor exhibits a high sensitivity (−63.70 mV/pH), a low detectable limit (0.05) and a superior stability (maintained over 50, 000 s). Integrated with a Bluetooth module, the wearable sensor achieves non-invasive and real-time pH monitoring on the human skin with minimal deviation (1.91%) compared to the commercial pH meter. More importantly, the anti-impact behaviors of the TOA-based sensing materials and chip, along with the pH wearable sensor on a pig exhibit an outstanding shock-resistance ability, with variations no more than 7.17% under an impact of 118.38 kPa. Therefore, this study shows great promise for the aerogel-based personalized health management in the extreme environment.
2025, 36(7): 110504
doi: 10.1016/j.cclet.2024.110504
摘要:
A "water" accelerated metal-free catalytic system has been discovered for the Mukaiyama-aldol reaction. The system involves the use of B(C6F5)3 as a catalyst, which is water-tolerant and able to activate the carbonyl group through a hydrogen bonding network generated by the catalyst. This activation method allows the reactions to be performed with very low catalyst loading, as low as 0.5 mol%. The scope of substrates is broad and a wide variety of functional groups are well tolerated. Diverse aliphatic aldehydes, aromatic aldehydes, unsaturated aldehydes and aromatic ketones coupled with silyl enol ethers/silyl ketone acetals to generate their corresponding β–hydroxy carbonyl compounds in moderate to good yields. This discovery represents a significant advancement in the field of organic synthesis, as it provides a new, practical and sustainable solution for carbon-carbon bond formation in water.
A "water" accelerated metal-free catalytic system has been discovered for the Mukaiyama-aldol reaction. The system involves the use of B(C6F5)3 as a catalyst, which is water-tolerant and able to activate the carbonyl group through a hydrogen bonding network generated by the catalyst. This activation method allows the reactions to be performed with very low catalyst loading, as low as 0.5 mol%. The scope of substrates is broad and a wide variety of functional groups are well tolerated. Diverse aliphatic aldehydes, aromatic aldehydes, unsaturated aldehydes and aromatic ketones coupled with silyl enol ethers/silyl ketone acetals to generate their corresponding β–hydroxy carbonyl compounds in moderate to good yields. This discovery represents a significant advancement in the field of organic synthesis, as it provides a new, practical and sustainable solution for carbon-carbon bond formation in water.
2025, 36(7): 110505
doi: 10.1016/j.cclet.2024.110505
摘要:
Selective defluorinative functionalization of trifluoromethylarenes (ArCF3) to obtain the pharmaceutically common α,α-difluorobenzylic motif is an attractive and elegant synthetic route. Over the past decade, although C(sp3)-F bonds functionalization have been greatly developed, catalytic cross-coupling of trifluoromethylarenes with CH of terminal alkynes remains a challenge. Here, we report an approach to achieve Sonogashira-type cross-coupling of trifluoromethylarenes with terminal alkynes C(sp)-H bonds via photoredox and Cu/L dual catalysis. Tridentate anionic ligand is pivotal to realize this C–H sp-sp3 cross-coupling. Moreover, this unique catalytic system is also suitable for cross-coupling of C(sp3)-F bonds with azoles C(sp2)-H bonds. A series of trifluoromethylarenes, terminal alkynes and azoles with various functional groups are compatible with this protocol affording a variety of defluoroalkynylation or defluoroazolation products. Preliminary mechanistic studies indicated that deprotonated BINOL involved as a photocatalyst to activate ArCF3 rather than a ligand to the metal.
Selective defluorinative functionalization of trifluoromethylarenes (ArCF3) to obtain the pharmaceutically common α,α-difluorobenzylic motif is an attractive and elegant synthetic route. Over the past decade, although C(sp3)-F bonds functionalization have been greatly developed, catalytic cross-coupling of trifluoromethylarenes with CH of terminal alkynes remains a challenge. Here, we report an approach to achieve Sonogashira-type cross-coupling of trifluoromethylarenes with terminal alkynes C(sp)-H bonds via photoredox and Cu/L dual catalysis. Tridentate anionic ligand is pivotal to realize this C–H sp-sp3 cross-coupling. Moreover, this unique catalytic system is also suitable for cross-coupling of C(sp3)-F bonds with azoles C(sp2)-H bonds. A series of trifluoromethylarenes, terminal alkynes and azoles with various functional groups are compatible with this protocol affording a variety of defluoroalkynylation or defluoroazolation products. Preliminary mechanistic studies indicated that deprotonated BINOL involved as a photocatalyst to activate ArCF3 rather than a ligand to the metal.
2025, 36(7): 110509
doi: 10.1016/j.cclet.2024.110509
摘要:
Photoswitchable fluorescent polymeric nanoparticles were widely concerned because of their excellent features including the flexible design, easy preparation and functionalization, and thus exhibited great application potential in information encryption, anti-counterfeiting, but remained challenging in improving the security. Herein, we described a self-erased time-resolved information encryption via using photoswitchable dual-color fluorescent polymeric nanoparticles (PDFPNs) containing two fluorescence dyes (blue and red) and photochromic spiroxazine derivatives. In view of the different thermo-induced isomerization rates of photochromic spiroxazine derivatives in different flexible substrates, the decoloration rate of PDFPNs can be programmatically tuned by regulating ratio between rigid polymer and flexible polymer. Therefore, after ultraviolet light (UV) irradiation, correct information could only be recognized in preestablished time during the self-erased process. Our results indicated that PDFPNs exhibited fast photo-responsibility (2 min), high fluorescence contrast, well-pleasing photo-reversibility (> 20 times), and programmable thermo-responsiveness (24 s-6 h). We thus demonstrated their application in the self-erased time-resolved information encryption and anti-counterfeiting with high security.
Photoswitchable fluorescent polymeric nanoparticles were widely concerned because of their excellent features including the flexible design, easy preparation and functionalization, and thus exhibited great application potential in information encryption, anti-counterfeiting, but remained challenging in improving the security. Herein, we described a self-erased time-resolved information encryption via using photoswitchable dual-color fluorescent polymeric nanoparticles (PDFPNs) containing two fluorescence dyes (blue and red) and photochromic spiroxazine derivatives. In view of the different thermo-induced isomerization rates of photochromic spiroxazine derivatives in different flexible substrates, the decoloration rate of PDFPNs can be programmatically tuned by regulating ratio between rigid polymer and flexible polymer. Therefore, after ultraviolet light (UV) irradiation, correct information could only be recognized in preestablished time during the self-erased process. Our results indicated that PDFPNs exhibited fast photo-responsibility (2 min), high fluorescence contrast, well-pleasing photo-reversibility (> 20 times), and programmable thermo-responsiveness (24 s-6 h). We thus demonstrated their application in the self-erased time-resolved information encryption and anti-counterfeiting with high security.
2025, 36(7): 110515
doi: 10.1016/j.cclet.2024.110515
摘要:
As a recently emerging wastewater treatment technology, Algal-bacterial granular sludge (ABGS) process shows significant advantages. However, current research on the ABGS system is a lack of a clear and complete understanding of the potential mechanism of signal molecules on the growth of ABGS. This study comprehensively explores the variations in the ABGS under different N-acyl-homoserine lactone (AHL) conditions by constructing three sequencing batch reactor (SBR) systems. The results indicate that N-hexanoyl-l-homoserine lactone (C6-HSL) accelerates the granulation process in the early stages by promoting the loosely bound extracellular polymeric substances (LB-EPS) secretion and filamentous bacteria growth, thereby shortening required time for initial granule formation. On the other hand, N-(3-oxodecanoyl)-l-homoserine lactone (3-oxo-C12-HSL) expedites the granulation process by promoting the tightly bound extracellular polymeric substances (TB-EPS) and aromatic protein secretion, benefiting structural stability and nitrogen and phosphorus removal efficiency of mature ABGS.
As a recently emerging wastewater treatment technology, Algal-bacterial granular sludge (ABGS) process shows significant advantages. However, current research on the ABGS system is a lack of a clear and complete understanding of the potential mechanism of signal molecules on the growth of ABGS. This study comprehensively explores the variations in the ABGS under different N-acyl-homoserine lactone (AHL) conditions by constructing three sequencing batch reactor (SBR) systems. The results indicate that N-hexanoyl-l-homoserine lactone (C6-HSL) accelerates the granulation process in the early stages by promoting the loosely bound extracellular polymeric substances (LB-EPS) secretion and filamentous bacteria growth, thereby shortening required time for initial granule formation. On the other hand, N-(3-oxodecanoyl)-l-homoserine lactone (3-oxo-C12-HSL) expedites the granulation process by promoting the tightly bound extracellular polymeric substances (TB-EPS) and aromatic protein secretion, benefiting structural stability and nitrogen and phosphorus removal efficiency of mature ABGS.
2025, 36(7): 110516
doi: 10.1016/j.cclet.2024.110516
摘要:
This study introduces a novel core-shell structured composite, Cu/SSZ-13@CeO2, designed to boost the catalyst’s resistance to hydrothermal conditions. Characterization results reveal that encapsulating Cu/SSZ-13 with a ceria (CeO2) shell markedly enhances hydrothermal stability by maintaining the functionality of [Cu(OH)]+ active sites and averting their deactivation. Furthermore, the CeO2 shell substantially prevents the loss of crucial Lewis and Brønsted acid sites, essential for effective SCR performance. A significant finding is the formation of a "Ce−O−Al" bond between the CeO2 shell and the Cu/SSZ-13 core, which plays a crucial role in reinforcing the structural stability of the zeolite framework. These insights contribute significantly to the development of robust anti-hydrothermal aging catalysts for mobile SCR applications, heralding the advancement of more efficient SCR catalyst technologies.
This study introduces a novel core-shell structured composite, Cu/SSZ-13@CeO2, designed to boost the catalyst’s resistance to hydrothermal conditions. Characterization results reveal that encapsulating Cu/SSZ-13 with a ceria (CeO2) shell markedly enhances hydrothermal stability by maintaining the functionality of [Cu(OH)]+ active sites and averting their deactivation. Furthermore, the CeO2 shell substantially prevents the loss of crucial Lewis and Brønsted acid sites, essential for effective SCR performance. A significant finding is the formation of a "Ce−O−Al" bond between the CeO2 shell and the Cu/SSZ-13 core, which plays a crucial role in reinforcing the structural stability of the zeolite framework. These insights contribute significantly to the development of robust anti-hydrothermal aging catalysts for mobile SCR applications, heralding the advancement of more efficient SCR catalyst technologies.
2025, 36(7): 110519
doi: 10.1016/j.cclet.2024.110519
摘要:
Oxaliplatin (OXA) can be used as a palliative treatment for advanced hepatocellular carcinoma (HCC). While most patients still have rapid disease progression after OXA due to the drug resistance. The lactate dehydrogenase A (LDHA) inhibitors can reduce the inflammation-induced effects, metastasis, and proliferation potential of cancer cells. Here, we adopt the water-in-oil attractive Pickering emulsion gel (APEG) to deliver OXA and LDHA inhibitor, GSK2837808A (GSK). OXA is dissolved in water and GSK is dissolved in iodized oil. This drugs-loaded APEG has good biocompatibility and can release OXA and GSK slowly. OXA + GSK@gel has significant anti-tumor effect on HCC model, which can effectively inhibit tumor cell proliferation and promote tumor cell apoptosis. Meanwhile, flow analysis confirm that it could activate the tumor immune microenvironment in HCC. The infiltration of CD8+ T cells is increased, thereby providing better anti-tumor effect. The results suggest that the APEGs loaded with OXA and GSK can effectively improve the delivery efficiency and enhance the anti-tumor therapy.
Oxaliplatin (OXA) can be used as a palliative treatment for advanced hepatocellular carcinoma (HCC). While most patients still have rapid disease progression after OXA due to the drug resistance. The lactate dehydrogenase A (LDHA) inhibitors can reduce the inflammation-induced effects, metastasis, and proliferation potential of cancer cells. Here, we adopt the water-in-oil attractive Pickering emulsion gel (APEG) to deliver OXA and LDHA inhibitor, GSK2837808A (GSK). OXA is dissolved in water and GSK is dissolved in iodized oil. This drugs-loaded APEG has good biocompatibility and can release OXA and GSK slowly. OXA + GSK@gel has significant anti-tumor effect on HCC model, which can effectively inhibit tumor cell proliferation and promote tumor cell apoptosis. Meanwhile, flow analysis confirm that it could activate the tumor immune microenvironment in HCC. The infiltration of CD8+ T cells is increased, thereby providing better anti-tumor effect. The results suggest that the APEGs loaded with OXA and GSK can effectively improve the delivery efficiency and enhance the anti-tumor therapy.
2025, 36(7): 110522
doi: 10.1016/j.cclet.2024.110522
摘要:
Houpolignols A–C (1–3), unprecedented oligomers of dearomatized obovatol with tetracyclo[9.3.1.02, 7.09, 14]pentadecane (1 and 2) and 8, 18-dioxapentacyclo[13.3.1.15, 9.04, 16.013, 20]icosane (3) core structures, together with their biosynthetic congener houpolignol D (4), were isolated from the cortex of Magnolia officinalis var. biloba. Their structures were determined by spectroscopic analyses, X-ray crystallography data, and quantum chemical calculations. Radical cascade cyclizations were proposed as crucial biosynthetic steps of 1–4. (±)-1 showed anti-nonalcoholic steatohepatitis (NASH) effect by promoting fatty acid beta-oxidation.
Houpolignols A–C (1–3), unprecedented oligomers of dearomatized obovatol with tetracyclo[9.3.1.02, 7.09, 14]pentadecane (1 and 2) and 8, 18-dioxapentacyclo[13.3.1.15, 9.04, 16.013, 20]icosane (3) core structures, together with their biosynthetic congener houpolignol D (4), were isolated from the cortex of Magnolia officinalis var. biloba. Their structures were determined by spectroscopic analyses, X-ray crystallography data, and quantum chemical calculations. Radical cascade cyclizations were proposed as crucial biosynthetic steps of 1–4. (±)-1 showed anti-nonalcoholic steatohepatitis (NASH) effect by promoting fatty acid beta-oxidation.
2025, 36(7): 110525
doi: 10.1016/j.cclet.2024.110525
摘要:
The stimulator of interferon genes (STING) agonists have been widely applied to active cyclic guanosine monophophate (GMP)-adenosine monophosphate (AMP) synthase (cGAS)-STING signaling for tumor immunotherapy. However, the therapeutic effect will be limited by factors such as the rapid degradation of STING protein and the immunosuppressive tumor microenvironment (TME). In this study, we constructed a manganese-based nano drug delivery system (NDDS) loaded with hydroxychloroquine (HCQ) for synergistic autophagy inhibition and STING activation-based immunotherapy. Hyaluronic acid (HA)/MnOOH@HCQ system can be uptake by 4T1 tumor cells via the CD44 receptor-mediated endocytosis. Subsequently, it responded to the acidic and reducing lysosomal microenvironment degradation to release Mn2+ and HCQ simultaneously. As a kind of STING agonist, Mn2+ can bind to cGAS in tumor cells, activating the cGAS-STING pathway and generating type Ⅰ-interferons (IFN-Ⅰ), which helped alleviate the immunosuppressive TME. Meanwhile, HCQ downregulated the autophagy level caused by cGAS-STING pathway to block STING degradation, further sensitizing the cGAS-STING signal. Benefiting from this synergistic mechanism, HA/MnOOH@HCQ demonstrated the best anti-tumor effect with the smallest tumor weight and volume after treatment. Moreover, HA/MnOOH@HCQ also exhibited a good inhibitory effect on lung metastasis. This study provided a new strategy for enhancing cGAS-STING pathway-mediated anti-tumor immunotherapy.
The stimulator of interferon genes (STING) agonists have been widely applied to active cyclic guanosine monophophate (GMP)-adenosine monophosphate (AMP) synthase (cGAS)-STING signaling for tumor immunotherapy. However, the therapeutic effect will be limited by factors such as the rapid degradation of STING protein and the immunosuppressive tumor microenvironment (TME). In this study, we constructed a manganese-based nano drug delivery system (NDDS) loaded with hydroxychloroquine (HCQ) for synergistic autophagy inhibition and STING activation-based immunotherapy. Hyaluronic acid (HA)/MnOOH@HCQ system can be uptake by 4T1 tumor cells via the CD44 receptor-mediated endocytosis. Subsequently, it responded to the acidic and reducing lysosomal microenvironment degradation to release Mn2+ and HCQ simultaneously. As a kind of STING agonist, Mn2+ can bind to cGAS in tumor cells, activating the cGAS-STING pathway and generating type Ⅰ-interferons (IFN-Ⅰ), which helped alleviate the immunosuppressive TME. Meanwhile, HCQ downregulated the autophagy level caused by cGAS-STING pathway to block STING degradation, further sensitizing the cGAS-STING signal. Benefiting from this synergistic mechanism, HA/MnOOH@HCQ demonstrated the best anti-tumor effect with the smallest tumor weight and volume after treatment. Moreover, HA/MnOOH@HCQ also exhibited a good inhibitory effect on lung metastasis. This study provided a new strategy for enhancing cGAS-STING pathway-mediated anti-tumor immunotherapy.
2025, 36(7): 110531
doi: 10.1016/j.cclet.2024.110531
摘要:
Hypochlorous acid (HClO) is a critical biomolecule in living organisms, playing an essential role in numerous physiological or pathological processes. Abnormal levels of HClO in the body may lead to a series of diseases, for instance, inflammation and cancer. Thus, accurate measurement of HClO levels should be more beneficial for understanding its role in diseases and gaining a deeper insight into the pathogenesis of diseases. In this work, we designed a near-infrared two-photon fluorescent probe (HDM-Cl-HClO) for detecting fluctuations in HClO levels in inflammatory and tumor-bearing mice. Notably, the probe can respond to HClO within 5 s and trigger a brilliant red fluorescence at 660 nm. It exhibits high specificity and sensitivity for HClO. The superior spectral capability of the probe has enabled the detection of HClO levels in cells and zebrafish, as well as achieved the detection of HClO in inflammatory and tumor mice. This work not only provides a novel strategy and tool for HClO imaging in living systems, but also holds great potential for the diagnosis of inflammation and cancer.
Hypochlorous acid (HClO) is a critical biomolecule in living organisms, playing an essential role in numerous physiological or pathological processes. Abnormal levels of HClO in the body may lead to a series of diseases, for instance, inflammation and cancer. Thus, accurate measurement of HClO levels should be more beneficial for understanding its role in diseases and gaining a deeper insight into the pathogenesis of diseases. In this work, we designed a near-infrared two-photon fluorescent probe (HDM-Cl-HClO) for detecting fluctuations in HClO levels in inflammatory and tumor-bearing mice. Notably, the probe can respond to HClO within 5 s and trigger a brilliant red fluorescence at 660 nm. It exhibits high specificity and sensitivity for HClO. The superior spectral capability of the probe has enabled the detection of HClO levels in cells and zebrafish, as well as achieved the detection of HClO in inflammatory and tumor mice. This work not only provides a novel strategy and tool for HClO imaging in living systems, but also holds great potential for the diagnosis of inflammation and cancer.
2025, 36(7): 110539
doi: 10.1016/j.cclet.2024.110539
摘要:
A robust bulky bornylimidazo[1,5–a]pyridin-3-ylidene allylic Pd complex was synthesized and well characterized. DFT calculations indicated that the ligand acts as a strong σ-donor and π-acceptor endowing the active Pd(0) center with high electron density and good coordination towards olefin. The introduction of a bulky, rigid bornyl ring further improved the catalytic efficacy due to the matched steric effects. This catalyst showed high efficiency and versatility in the α-arylation and Heck cyclization/Suzuki cross-coupling reactions at mild reaction conditions. Desired 3,3′-disubstituted oxindoles, especially featuring an allylic-derived C3-quaternary stereocenter were obtained in high yields. Furthermore, the concise synthesis of bioactive heterocycle-fused indoline alkaloids was successfully proved.
A robust bulky bornylimidazo[1,5–a]pyridin-3-ylidene allylic Pd complex was synthesized and well characterized. DFT calculations indicated that the ligand acts as a strong σ-donor and π-acceptor endowing the active Pd(0) center with high electron density and good coordination towards olefin. The introduction of a bulky, rigid bornyl ring further improved the catalytic efficacy due to the matched steric effects. This catalyst showed high efficiency and versatility in the α-arylation and Heck cyclization/Suzuki cross-coupling reactions at mild reaction conditions. Desired 3,3′-disubstituted oxindoles, especially featuring an allylic-derived C3-quaternary stereocenter were obtained in high yields. Furthermore, the concise synthesis of bioactive heterocycle-fused indoline alkaloids was successfully proved.
2025, 36(7): 110542
doi: 10.1016/j.cclet.2024.110542
摘要:
By investigating 17 peptide arylthioesters that were previously challenging to produce, this study reveals a clear correlation between increased ligation activity and decreased pKa values of their corresponding arylthiols. The observed differences are attributed to variations in thioester bond strength and steric hindrance. These insights have led to the development of an improved one-pot chemical protein synthesis approach that leverages the reactivity differences between peptide arylthioesters with C-terminal Ala-S-Ph(4-NO2) and Ala-S-Ph(2,6-diCH3). This approach eliminates the need for thiol-thioester exchange and additive removal steps while enabling in situ desulfurization, thereby significantly simplifying the protein synthesis process.
By investigating 17 peptide arylthioesters that were previously challenging to produce, this study reveals a clear correlation between increased ligation activity and decreased pKa values of their corresponding arylthiols. The observed differences are attributed to variations in thioester bond strength and steric hindrance. These insights have led to the development of an improved one-pot chemical protein synthesis approach that leverages the reactivity differences between peptide arylthioesters with C-terminal Ala-S-Ph(4-NO2) and Ala-S-Ph(2,6-diCH3). This approach eliminates the need for thiol-thioester exchange and additive removal steps while enabling in situ desulfurization, thereby significantly simplifying the protein synthesis process.
2025, 36(7): 110560
doi: 10.1016/j.cclet.2024.110560
摘要:
C-glycosides have been demonstrated to have distinct biological functions and therefore display notable pharmacological values, whereas the access to the versatile structural analog of C-glycosides is a significant challenge to their advancement as therapeutic agents. We herein disclose a facial and efficient catalytic C-glycosylation using a glycosyl ortho-2,2-dimethoxycarbonylcyclopropylbenzoate (CCBz) as the donor. The trailblazing glycosyl donor can be simply activated by a non-toxic and easily accessible Sc(Ⅲ) catalyst. The ring-strain release of the incorporated donor-acceptor cyclopropane (DAC) serves as a powerful driving force of the glycosylation system. The adaptability of current methods to different types of donors and acceptors was exemplified. Examinations on the synthetic potential were done with the one-pot synthesis of free C-indolyl-glycosides and the subsequent biological studies, unlocking the antibacterial potentials of these compounds.
C-glycosides have been demonstrated to have distinct biological functions and therefore display notable pharmacological values, whereas the access to the versatile structural analog of C-glycosides is a significant challenge to their advancement as therapeutic agents. We herein disclose a facial and efficient catalytic C-glycosylation using a glycosyl ortho-2,2-dimethoxycarbonylcyclopropylbenzoate (CCBz) as the donor. The trailblazing glycosyl donor can be simply activated by a non-toxic and easily accessible Sc(Ⅲ) catalyst. The ring-strain release of the incorporated donor-acceptor cyclopropane (DAC) serves as a powerful driving force of the glycosylation system. The adaptability of current methods to different types of donors and acceptors was exemplified. Examinations on the synthetic potential were done with the one-pot synthesis of free C-indolyl-glycosides and the subsequent biological studies, unlocking the antibacterial potentials of these compounds.
2025, 36(7): 110569
doi: 10.1016/j.cclet.2024.110569
摘要:
Infectious wound healing is complicated with and limited by infection and oxidative stress at the wound site. In recent years, various evidences suggest that nanozymes with multiple enzymatic activities have enabled the development of novel strategies for infectious wound healing. In this study, epigallocatechin gallate loaded polydopamine (P@E) was developed to act as a potent reactive oxygen species (ROS) scavenger for scavenging ROS, alleviating inflammatory responses, and promoting infectious wound healing. Combining with near infrared (NIR) irradiation, P@E presented excellent antibacterial ability of Escherichia coli (E. coli, 93.6%) and methicillin-resistant Staphylococcus aureus (MRSA, 87.6%). Specifically, P@E+NIR exhibited the most potent antioxidant, anti-inflammatory and cell proliferation behaviors through down-regulating intracellular ROS levels (81.9% and 94.3% for NIH3T3 and RAW264.7 respectively) and inducible nitric oxide synthase (iNOS) expression level (55.7%), and up-regulating the expression levels of arginase-1 (Arg-1, 71.4%), heat shock protein 70 (HSP70, 48.6%) and platelet endothelial cell adhesion molecule (CD31, 35.3%) compared to control group. Meanwhile, it also efficiently induced M2 directional polarization of lipopolysaccharide induced murine macrophages to achieve anti-inflammation, indicated by the down-regulation of CD86 (86.2%), and up-regulation of CD206 (85.6%). Significantly, it was also observed that P@E+NIR presented the excellent behaviors of inhibiting wound infection, alleviating wound inflammation, as well as promoting skin tissue repairing. Altogether, it has developed the strategy of using P@E combining with NIR irradiation for the synergistic enhanced healing of infectious skin wound, which can serve as a promising therapeutic strategy for its clinical treatment.
Infectious wound healing is complicated with and limited by infection and oxidative stress at the wound site. In recent years, various evidences suggest that nanozymes with multiple enzymatic activities have enabled the development of novel strategies for infectious wound healing. In this study, epigallocatechin gallate loaded polydopamine (P@E) was developed to act as a potent reactive oxygen species (ROS) scavenger for scavenging ROS, alleviating inflammatory responses, and promoting infectious wound healing. Combining with near infrared (NIR) irradiation, P@E presented excellent antibacterial ability of Escherichia coli (E. coli, 93.6%) and methicillin-resistant Staphylococcus aureus (MRSA, 87.6%). Specifically, P@E+NIR exhibited the most potent antioxidant, anti-inflammatory and cell proliferation behaviors through down-regulating intracellular ROS levels (81.9% and 94.3% for NIH3T3 and RAW264.7 respectively) and inducible nitric oxide synthase (iNOS) expression level (55.7%), and up-regulating the expression levels of arginase-1 (Arg-1, 71.4%), heat shock protein 70 (HSP70, 48.6%) and platelet endothelial cell adhesion molecule (CD31, 35.3%) compared to control group. Meanwhile, it also efficiently induced M2 directional polarization of lipopolysaccharide induced murine macrophages to achieve anti-inflammation, indicated by the down-regulation of CD86 (86.2%), and up-regulation of CD206 (85.6%). Significantly, it was also observed that P@E+NIR presented the excellent behaviors of inhibiting wound infection, alleviating wound inflammation, as well as promoting skin tissue repairing. Altogether, it has developed the strategy of using P@E combining with NIR irradiation for the synergistic enhanced healing of infectious skin wound, which can serve as a promising therapeutic strategy for its clinical treatment.
Catalytic asymmetric inverse-electron-demand Diels–Alder reaction of 2-pyrones with aryl enol ethers
2025, 36(7): 110581
doi: 10.1016/j.cclet.2024.110581
摘要:
Chiral aryl cyclohex-3-en ether scaffold is widely present in bioactive natural products and drugs. The exploitation of efficient and enantioselective methods for the construction of aryl cyclohex-3-en ether scaffold is significant. Herein we disclose a chiral N,N’-dioxide/Lewis acid complex-catalyzed asymmetric inverse-electron-demand Diels–Alder (IEDDA) reaction using electron-deficient 3-carboalkoxyl-2-pyrones and less electron-enriched aryl enol ethers as reactants. A wide range of non- and 1,2-disubstituted acyclic aryl enol ethers are applicable to deliver diverse chiral bridged bicyclic lactones in high yields and stereoselectivities (up to 96% yield, > 20:1 dr, 97:3 er). The bridged bicyclic lactone core can be easily converted into chiral aryl cyclohex-3-en ether scaffold. Notably, DFT calculations revealed a stepwise and endo mechanism to explain the high enantioselectivity controlled by the cooperative effect of the steric factors and the dispersion interactions between ligands and enol ethers.
Chiral aryl cyclohex-3-en ether scaffold is widely present in bioactive natural products and drugs. The exploitation of efficient and enantioselective methods for the construction of aryl cyclohex-3-en ether scaffold is significant. Herein we disclose a chiral N,N’-dioxide/Lewis acid complex-catalyzed asymmetric inverse-electron-demand Diels–Alder (IEDDA) reaction using electron-deficient 3-carboalkoxyl-2-pyrones and less electron-enriched aryl enol ethers as reactants. A wide range of non- and 1,2-disubstituted acyclic aryl enol ethers are applicable to deliver diverse chiral bridged bicyclic lactones in high yields and stereoselectivities (up to 96% yield, > 20:1 dr, 97:3 er). The bridged bicyclic lactone core can be easily converted into chiral aryl cyclohex-3-en ether scaffold. Notably, DFT calculations revealed a stepwise and endo mechanism to explain the high enantioselectivity controlled by the cooperative effect of the steric factors and the dispersion interactions between ligands and enol ethers.
2025, 36(7): 110598
doi: 10.1016/j.cclet.2024.110598
摘要:
The Pfitzinger reaction has long served as a notable synthesis pathway for quinoline-4-carboxylic acids. Although recognized for its synthetic potential since its discovery > 138 years ago, a truly catalytic variant has remained elusive until now. Herein, we present a novel 2–tert–butyl–1,1,3,3-tetramethylguanidine (BTMG)-catalyzed Pfitzinger reaction that employs N-[(α-trifluoromethyl)vinyl]isatins with amines and alcohols, providing direct routes to 2-CF3-quinoline-4-carboxamides and carboxylic esters. This method is not only green and environmentally benign but also accommodates the introduction of other functional groups like CF2H and CO2Me at the C2 position of quinoline skeleton. The utility of this methodology was demonstrated by the broad substrate scope, the late-stage modification of commercial drugs, and the diverse derivatization of quinoline framework. More importantly, this work not only opens up a new avenue for the activation of amide CN bonds in catalytic reaction development, but also unlocks the huge potential of some 2-trifluoromethyl quinolines with strong inhibitory activity against PTP1B or optoelectronic application in organic light-emitting diodes.
The Pfitzinger reaction has long served as a notable synthesis pathway for quinoline-4-carboxylic acids. Although recognized for its synthetic potential since its discovery > 138 years ago, a truly catalytic variant has remained elusive until now. Herein, we present a novel 2–tert–butyl–1,1,3,3-tetramethylguanidine (BTMG)-catalyzed Pfitzinger reaction that employs N-[(α-trifluoromethyl)vinyl]isatins with amines and alcohols, providing direct routes to 2-CF3-quinoline-4-carboxamides and carboxylic esters. This method is not only green and environmentally benign but also accommodates the introduction of other functional groups like CF2H and CO2Me at the C2 position of quinoline skeleton. The utility of this methodology was demonstrated by the broad substrate scope, the late-stage modification of commercial drugs, and the diverse derivatization of quinoline framework. More importantly, this work not only opens up a new avenue for the activation of amide CN bonds in catalytic reaction development, but also unlocks the huge potential of some 2-trifluoromethyl quinolines with strong inhibitory activity against PTP1B or optoelectronic application in organic light-emitting diodes.
2025, 36(7): 110599
doi: 10.1016/j.cclet.2024.110599
摘要:
Double bonds of internal olefins can be efficiently migrated to the terminal carbons and regioselectively hydroesterified with formates in the presence of Pd(OAc)2 and 1,2-DTBPMB under mild reaction conditions, providing a wide variety of corresponding linear carboxylic esters bearing various functional groups in good yields and > 20:1 linear/branch ratios. The reaction is optionally simple and does not need to use CO gas and acid co-catalysts.
Double bonds of internal olefins can be efficiently migrated to the terminal carbons and regioselectively hydroesterified with formates in the presence of Pd(OAc)2 and 1,2-DTBPMB under mild reaction conditions, providing a wide variety of corresponding linear carboxylic esters bearing various functional groups in good yields and > 20:1 linear/branch ratios. The reaction is optionally simple and does not need to use CO gas and acid co-catalysts.
2025, 36(7): 110604
doi: 10.1016/j.cclet.2024.110604
摘要:
Lithium-sulfur batteries (LSBs) are considered as the most promising energy storage technologies owing to their large theoretical energy density (2500 Wh/kg) and specific capacity (1675 mAh/g). However, the heavy shuttle effect of polysulfides and the growth of lithium dendrites greatly hinder their further development and commercial application. In this paper, cobalt-molybdenum bimetallic carbides heterostructure (Co6Mo6C2@Co@NC) was successfully prepared through chemical etching procedure of ZIF-67 precursor with sodium molybdate and the subsequent high temperature annealing process. The obtained dodecahedral Co6Mo6C2@Co@NC with hollow and porous structure provides large specific surface area and plentiful active sites, which speeds up the chemisorption and catalytic conversion of polysulfides, thus mitigating the shuttle effect of polysulfides and the generation of lithium dendrites. When applied as the LSBs separator modifier layer, the cell with modified separator present excellent rate capability and durable cycling stability. In particular, the cell with Co6Mo6C2@Co@NC/PP separator can maintain the high capacity of 738 mAh/g at the current density of 2 C and the specific capacity of 782.6 mAh/g after 300 cycles at 0.5 C, with the coulombic efficiency (CE) near to 100%. Moreover, the Co6Mo6C2@Co@NC/PP battery exhibits the impressive capacity of 431 mAh/g in high sulfur loading (4.096 mg/cm2) at 0.5 C after 200 cycles. This work paves the way for the development of bimetallic carbides heterostructure multifunctional catalysts for durable Li-S battery applications and reveals the synergistic regulation of polysulfides and lithium dendrites through the optimization of the structure and composition.
Lithium-sulfur batteries (LSBs) are considered as the most promising energy storage technologies owing to their large theoretical energy density (2500 Wh/kg) and specific capacity (1675 mAh/g). However, the heavy shuttle effect of polysulfides and the growth of lithium dendrites greatly hinder their further development and commercial application. In this paper, cobalt-molybdenum bimetallic carbides heterostructure (Co6Mo6C2@Co@NC) was successfully prepared through chemical etching procedure of ZIF-67 precursor with sodium molybdate and the subsequent high temperature annealing process. The obtained dodecahedral Co6Mo6C2@Co@NC with hollow and porous structure provides large specific surface area and plentiful active sites, which speeds up the chemisorption and catalytic conversion of polysulfides, thus mitigating the shuttle effect of polysulfides and the generation of lithium dendrites. When applied as the LSBs separator modifier layer, the cell with modified separator present excellent rate capability and durable cycling stability. In particular, the cell with Co6Mo6C2@Co@NC/PP separator can maintain the high capacity of 738 mAh/g at the current density of 2 C and the specific capacity of 782.6 mAh/g after 300 cycles at 0.5 C, with the coulombic efficiency (CE) near to 100%. Moreover, the Co6Mo6C2@Co@NC/PP battery exhibits the impressive capacity of 431 mAh/g in high sulfur loading (4.096 mg/cm2) at 0.5 C after 200 cycles. This work paves the way for the development of bimetallic carbides heterostructure multifunctional catalysts for durable Li-S battery applications and reveals the synergistic regulation of polysulfides and lithium dendrites through the optimization of the structure and composition.
2025, 36(7): 110627
doi: 10.1016/j.cclet.2024.110627
摘要:
Radical anions of electron-deficient perylene diimides (PDI) are attractive near-infrared (NIR) absorbers for photothermal conversion; however, their stability is often compromised by strong aggregation and reoxidation in air. Herein, we present a class of bacterial composites hybridized with a newly synthesized doubly-strapped PDI cyclophane, termed "Gemini Box" (GBox-34+), which features air-stable PDI radicals for NIR photothermal conversion. The effective spatial isolation provided by the double-sided cationic molecular straps allows GBox-34+ to completely suppress chromophore aggregation, even in concentrated aqueous solutions up to 2 mmol/L, thereby preserving its characteristic fluorescence for live-cell imaging. After incubation of bacteria with GBox-34+, the radical species PDI•– have been found to stably exist in the bacterial composites under ambient conditions, both in aqueous suspension and solid forms. Further experiments demonstrate that the air stability of the radical species relies on the simultaneous presence of the doubly-strapped PDI dye and the bacteria. Moreover, the dye-bacterial composites exhibited an high-efficiency NIR photothermal effect with high durability, enabling their application as photothermal agents for seawater desalination. This work provides a new access to the in situ fabrication of photothermal materials from biomass, relying on the rational molecular design and the unique microenvironment of bacteria.
Radical anions of electron-deficient perylene diimides (PDI) are attractive near-infrared (NIR) absorbers for photothermal conversion; however, their stability is often compromised by strong aggregation and reoxidation in air. Herein, we present a class of bacterial composites hybridized with a newly synthesized doubly-strapped PDI cyclophane, termed "Gemini Box" (GBox-34+), which features air-stable PDI radicals for NIR photothermal conversion. The effective spatial isolation provided by the double-sided cationic molecular straps allows GBox-34+ to completely suppress chromophore aggregation, even in concentrated aqueous solutions up to 2 mmol/L, thereby preserving its characteristic fluorescence for live-cell imaging. After incubation of bacteria with GBox-34+, the radical species PDI•– have been found to stably exist in the bacterial composites under ambient conditions, both in aqueous suspension and solid forms. Further experiments demonstrate that the air stability of the radical species relies on the simultaneous presence of the doubly-strapped PDI dye and the bacteria. Moreover, the dye-bacterial composites exhibited an high-efficiency NIR photothermal effect with high durability, enabling their application as photothermal agents for seawater desalination. This work provides a new access to the in situ fabrication of photothermal materials from biomass, relying on the rational molecular design and the unique microenvironment of bacteria.
2025, 36(7): 110640
doi: 10.1016/j.cclet.2024.110640
摘要:
The hydroformylation of olefins, known as the "oxo reaction", involves the use of syngas (CO/H2) to produce aldehyde with an additional carbon atom. However, side reactions such as the isomerization or hydrogenation of olefins often result in unexpected products and other by-products. Recent efforts in developing efficient ligands represent the most effective approach to addressing these challenges. In this study, we described a Bis-OPNN phosphorus ligand facilitated Rh-catalyzed hydroformylation with a high degree of linear selectivity across various olefins. Under mild conditions, a broad range of olefins were efficiently converted into linear aldehydes with high yields and excellent regioselectivity. The protocol also showed impressive functional group tolerance and was successfully applied to modify drugs and natural products, including the total synthesis of (±)-crispine A. Preliminary mechanistic studies revealed that this Bis-OPNN phosphorus ligand anchoring the rhodium catalyst is crucial for controlling the linear selectivity.
The hydroformylation of olefins, known as the "oxo reaction", involves the use of syngas (CO/H2) to produce aldehyde with an additional carbon atom. However, side reactions such as the isomerization or hydrogenation of olefins often result in unexpected products and other by-products. Recent efforts in developing efficient ligands represent the most effective approach to addressing these challenges. In this study, we described a Bis-OPNN phosphorus ligand facilitated Rh-catalyzed hydroformylation with a high degree of linear selectivity across various olefins. Under mild conditions, a broad range of olefins were efficiently converted into linear aldehydes with high yields and excellent regioselectivity. The protocol also showed impressive functional group tolerance and was successfully applied to modify drugs and natural products, including the total synthesis of (±)-crispine A. Preliminary mechanistic studies revealed that this Bis-OPNN phosphorus ligand anchoring the rhodium catalyst is crucial for controlling the linear selectivity.
2025, 36(7): 110646
doi: 10.1016/j.cclet.2024.110646
摘要:
A [3 + 4] annulation of α-substituted allenes and Schiff bases is reported. This methodology serves as a conduit for the construction of a series of biologically important benzazepine derivatives in good to excellent yields under mild conditions by an unprecedented mode involving β′-carbon of α-substituted allenes and the proposed mechanism is supported by capturing the intermediate. Moreover, this class of benzazepine derivatives exhibited potential ability of cytotoxicity toward cancer cells.
A [3 + 4] annulation of α-substituted allenes and Schiff bases is reported. This methodology serves as a conduit for the construction of a series of biologically important benzazepine derivatives in good to excellent yields under mild conditions by an unprecedented mode involving β′-carbon of α-substituted allenes and the proposed mechanism is supported by capturing the intermediate. Moreover, this class of benzazepine derivatives exhibited potential ability of cytotoxicity toward cancer cells.
2025, 36(7): 110911
doi: 10.1016/j.cclet.2025.110911
摘要:
The phase transition among different solid forms of active pharmaceutical ingredients can significantly influence their physicochemical properties, potentially leading to clinical safety risks. However, phase transition mechanisms remain under explored, especially in multi-component drugs. Here we report a novel ciprofloxacin-diclofenac salt system and investigate phase transitions among its anhydrate, dihydrate, and methanol solvate forms. The study focused on the influence of water activity and solvent vapor conditions, elucidating the role of guest molecules in driving these transitions. These findings offer new insights into polymorphic phase transitions, advancing our understanding of stability and performance in pharmaceutical formulations.
The phase transition among different solid forms of active pharmaceutical ingredients can significantly influence their physicochemical properties, potentially leading to clinical safety risks. However, phase transition mechanisms remain under explored, especially in multi-component drugs. Here we report a novel ciprofloxacin-diclofenac salt system and investigate phase transitions among its anhydrate, dihydrate, and methanol solvate forms. The study focused on the influence of water activity and solvent vapor conditions, elucidating the role of guest molecules in driving these transitions. These findings offer new insights into polymorphic phase transitions, advancing our understanding of stability and performance in pharmaceutical formulations.
2025, 36(7): 110958
doi: 10.1016/j.cclet.2025.110958
摘要:
A comprehensive understanding of the molecular details at spatial levels within heterogeneous cardiac tissue in heart failure (HF) is paramount for enhancing our knowledge of the pathophysiology of HF and pinpointing potential therapeutic targets. Here, we present an analytical strategy for the deep discovery of heterogeneous metabolism and drug response in the heart tissue of rats with HF using airflow-assisted desorption electrospray ionization mass spectrometry imaging (AFADESI-MSI) coupled with bulk RNA sequencing. Spatial metabolomics illustrated pronounced metabolic heterogeneity between the infarct (Ⅰ), infarct margin (IM), and non-infarct (NI) areas of heart tissue in HF. Integrated transcriptomics showed that increased mRNA expression of ATP citrate lyase disrupted the tricarboxylic acid (TCA) cycle in the NI area. Impairment of the carnitine shuttle system led to a significant accumulation of carnitines, suggesting potential abnormalities in fatty acid (FA) oxidation. Coupling on-tissue chemical derivatization with AFADESI-MSI enabled us to confirm the occurrence of incomplete oxidation of FAs in the NI area. Additionally, we observed a heterogeneous drug response between the anti-HF medications valsartan and Qishen Yiqi Dripping Pills (QDP). Valsartan exhibited a more pronounced effect on metabolic regulation in the Ⅰ area, whereas QDP exerted stronger regulatory effects on metabolism in the NI area. Utilizing this method, four potential therapeutic targets were identified in HF: CPT1A, PDHB, ACLY, and BCAT2, which were preliminarily validated by western blotting. Overall, integrating spatial metabolomics with transcriptomics facilitates comprehensive analyses that link differential metabolites and genes, enabling a more precise characterization of metabolic changes in heart injury microareas and providing effective methods for elucidating molecular mechanisms and identifying potential therapeutic targets for HF.
A comprehensive understanding of the molecular details at spatial levels within heterogeneous cardiac tissue in heart failure (HF) is paramount for enhancing our knowledge of the pathophysiology of HF and pinpointing potential therapeutic targets. Here, we present an analytical strategy for the deep discovery of heterogeneous metabolism and drug response in the heart tissue of rats with HF using airflow-assisted desorption electrospray ionization mass spectrometry imaging (AFADESI-MSI) coupled with bulk RNA sequencing. Spatial metabolomics illustrated pronounced metabolic heterogeneity between the infarct (Ⅰ), infarct margin (IM), and non-infarct (NI) areas of heart tissue in HF. Integrated transcriptomics showed that increased mRNA expression of ATP citrate lyase disrupted the tricarboxylic acid (TCA) cycle in the NI area. Impairment of the carnitine shuttle system led to a significant accumulation of carnitines, suggesting potential abnormalities in fatty acid (FA) oxidation. Coupling on-tissue chemical derivatization with AFADESI-MSI enabled us to confirm the occurrence of incomplete oxidation of FAs in the NI area. Additionally, we observed a heterogeneous drug response between the anti-HF medications valsartan and Qishen Yiqi Dripping Pills (QDP). Valsartan exhibited a more pronounced effect on metabolic regulation in the Ⅰ area, whereas QDP exerted stronger regulatory effects on metabolism in the NI area. Utilizing this method, four potential therapeutic targets were identified in HF: CPT1A, PDHB, ACLY, and BCAT2, which were preliminarily validated by western blotting. Overall, integrating spatial metabolomics with transcriptomics facilitates comprehensive analyses that link differential metabolites and genes, enabling a more precise characterization of metabolic changes in heart injury microareas and providing effective methods for elucidating molecular mechanisms and identifying potential therapeutic targets for HF.
2025, 36(7): 110969
doi: 10.1016/j.cclet.2025.110969
摘要:
Lignans have been established as a privileged scaffold in drug discovery, particularly in anticancer and antioxidant properties. Concise and efficient construction of lignans and their derivatives in a single operation holds great medicinal significance for structure-activity relationship studies yet remains challenging. Drawing inspiration from the biosynthesis of lignans, we present a general, high-step-economy palladium-catalyzed reaction that converts simple chemical feedstocks into dehydrodibenzylbutyrolactone lignans through the in-situ construction and coupling of two phenylpropanoid molecules. The diversity of organoboronic acids and the editability of enyne provide a powerful platform for the rapid construction of lignan libraries, featuring 82 lignans analogs, collective syntheses of 10 distinct lignan skeletons, and 13 hybrid molecules combining pharmacophore fragments with drug and derivatives. The subtle combination of phosphine ligands with quinones for switching chemoselectivity is vital to the success of this protocol.
Lignans have been established as a privileged scaffold in drug discovery, particularly in anticancer and antioxidant properties. Concise and efficient construction of lignans and their derivatives in a single operation holds great medicinal significance for structure-activity relationship studies yet remains challenging. Drawing inspiration from the biosynthesis of lignans, we present a general, high-step-economy palladium-catalyzed reaction that converts simple chemical feedstocks into dehydrodibenzylbutyrolactone lignans through the in-situ construction and coupling of two phenylpropanoid molecules. The diversity of organoboronic acids and the editability of enyne provide a powerful platform for the rapid construction of lignan libraries, featuring 82 lignans analogs, collective syntheses of 10 distinct lignan skeletons, and 13 hybrid molecules combining pharmacophore fragments with drug and derivatives. The subtle combination of phosphine ligands with quinones for switching chemoselectivity is vital to the success of this protocol.
2025, 36(7): 111028
doi: 10.1016/j.cclet.2025.111028
摘要:
Vinylene-bridged covalent organic frameworks (V-COFs), as fully conjugated polymer structures, offer promising prospects in optoelectronics. However, challenges such as poor bond reversibility and limited monomer availability persist. In this study, we introduce Ph-DPP-COF, synthesized from a diketopyrrolopyrrole (DPP) core with methyl groups via a Knoevenagel condensation reaction. The resulting material features an AA stacking mode, large nanopores, and broad light absorption across the ultraviolet to near-infrared spectrum. Notably, Ph-DPP-COF achieves a photothermal conversion efficiency of 53% under 660 nm laser irradiation. Its exceptional mechanical processability also offers considerable plasticity for practical applications. These findings suggest that Ph-DPP-COF not only provides a novel approach for developing photothermal conversion materials but also holds promise for future energy conversion and storage technologies.
Vinylene-bridged covalent organic frameworks (V-COFs), as fully conjugated polymer structures, offer promising prospects in optoelectronics. However, challenges such as poor bond reversibility and limited monomer availability persist. In this study, we introduce Ph-DPP-COF, synthesized from a diketopyrrolopyrrole (DPP) core with methyl groups via a Knoevenagel condensation reaction. The resulting material features an AA stacking mode, large nanopores, and broad light absorption across the ultraviolet to near-infrared spectrum. Notably, Ph-DPP-COF achieves a photothermal conversion efficiency of 53% under 660 nm laser irradiation. Its exceptional mechanical processability also offers considerable plasticity for practical applications. These findings suggest that Ph-DPP-COF not only provides a novel approach for developing photothermal conversion materials but also holds promise for future energy conversion and storage technologies.
2025, 36(7): 111029
doi: 10.1016/j.cclet.2025.111029
摘要:
Photocatalysis holds great promise for the conversion of plastic waste into valuable chemicals. However, the conversion efficiency is constrained by the poor carriers' separation efficiency over the single component photocatalyst. Herein, we synthesized a novel type Ⅱ Nb2O5/GCN heterojunction to investigate its efficiency in the photocatalytic upcycling of polybutylene adipate/terephthalate (PBAT) microplastics (MPs) into acids and alcohols under visible light irradiation (100 mW/cm2). The findings indicate that the charge transfer within the type Ⅱ Nb2O5/GCN occurs from the conduction band of GCN to the conduction band of Nb2O5, thereby enhancing the separation efficiency of carriers Notably, the rates of ethanol and acetic acid generation from 1.5 mg/mL PBAT MPs treated with the 60%Nb2O5/GCN photocatalyst were 21.8-fold and 1.8-fold higher, respectively, compared to those by Nb2O5 alone. Density functional theory calculations demonstrate that the hydroxyl radicals (•OH) produced by the Nb2O5/GCN heterojunction cleaves the ester bond (OC=O) of PBAT MP into the monomer. These monomers are subsequently converted into acids and alcohols through various reactions, including CC bond cleavage, hydrodeoxygenation, and CC bond coupling. This study highlights the effectiveness of heterojunction photocatalyst in converting PBAT MPs into valuable chemicals, thus significantly promoting advancements in bioplastics recycling.
Photocatalysis holds great promise for the conversion of plastic waste into valuable chemicals. However, the conversion efficiency is constrained by the poor carriers' separation efficiency over the single component photocatalyst. Herein, we synthesized a novel type Ⅱ Nb2O5/GCN heterojunction to investigate its efficiency in the photocatalytic upcycling of polybutylene adipate/terephthalate (PBAT) microplastics (MPs) into acids and alcohols under visible light irradiation (100 mW/cm2). The findings indicate that the charge transfer within the type Ⅱ Nb2O5/GCN occurs from the conduction band of GCN to the conduction band of Nb2O5, thereby enhancing the separation efficiency of carriers Notably, the rates of ethanol and acetic acid generation from 1.5 mg/mL PBAT MPs treated with the 60%Nb2O5/GCN photocatalyst were 21.8-fold and 1.8-fold higher, respectively, compared to those by Nb2O5 alone. Density functional theory calculations demonstrate that the hydroxyl radicals (•OH) produced by the Nb2O5/GCN heterojunction cleaves the ester bond (OC=O) of PBAT MP into the monomer. These monomers are subsequently converted into acids and alcohols through various reactions, including CC bond cleavage, hydrodeoxygenation, and CC bond coupling. This study highlights the effectiveness of heterojunction photocatalyst in converting PBAT MPs into valuable chemicals, thus significantly promoting advancements in bioplastics recycling.
2025, 36(7): 111034
doi: 10.1016/j.cclet.2025.111034
摘要:
Constructing vacancy-decorated metal halide perovskites (MHPs) have emerged as promising pathway to enhance photocatalytic activity and selectivity for solar CO2 reduction. However, the controllable construction of vacancy defects is still challenging, and our understanding of the roles of these defects, particularly their effects on the adsorption activation of surface reaction molecules, is still insufficient. Herein, we elaborately designed and synthesized adjustable Br vacancies in CsPbBr3 catalysts by manipulating the dissolution and recrystallization speed of precursors during the ball milling process using solvents with gradient polarities. We found that the Br vacancies could promote the charge separation, while having slight influence on the band structure of CsPbBr3. More importantly, temperature-programmed desorption results combined with theoretical calculations revealed that Br vacancies can significantly enhance the adsorption of CO2 and CO on the surface, specifically increasing the adsorption strength between CO and the active sites. This finding provides a substantial opportunity for achieving high activity and selectivity in photocatalytic CO2 methanation. Accordingly, a high rate of CO2 photoreduction to CH4 up to 17.94 ± 0.81 µmol g-1 h-1 along with superior selectivity of 95.8% were acquired for CsPbBr3HX featuring with the richest Br vacancy defects, which is 18.9-fold compared that of CsPbBr3CAN with the lowest Br vacancy defects. This investigation deepens insights into action mechanism of defects on halide perovskites catalysts, offering a novel strategy for the high-effective conversion of CO2 into valuable products.
Constructing vacancy-decorated metal halide perovskites (MHPs) have emerged as promising pathway to enhance photocatalytic activity and selectivity for solar CO2 reduction. However, the controllable construction of vacancy defects is still challenging, and our understanding of the roles of these defects, particularly their effects on the adsorption activation of surface reaction molecules, is still insufficient. Herein, we elaborately designed and synthesized adjustable Br vacancies in CsPbBr3 catalysts by manipulating the dissolution and recrystallization speed of precursors during the ball milling process using solvents with gradient polarities. We found that the Br vacancies could promote the charge separation, while having slight influence on the band structure of CsPbBr3. More importantly, temperature-programmed desorption results combined with theoretical calculations revealed that Br vacancies can significantly enhance the adsorption of CO2 and CO on the surface, specifically increasing the adsorption strength between CO and the active sites. This finding provides a substantial opportunity for achieving high activity and selectivity in photocatalytic CO2 methanation. Accordingly, a high rate of CO2 photoreduction to CH4 up to 17.94 ± 0.81 µmol g-1 h-1 along with superior selectivity of 95.8% were acquired for CsPbBr3HX featuring with the richest Br vacancy defects, which is 18.9-fold compared that of CsPbBr3CAN with the lowest Br vacancy defects. This investigation deepens insights into action mechanism of defects on halide perovskites catalysts, offering a novel strategy for the high-effective conversion of CO2 into valuable products.
2025, 36(7): 111057
doi: 10.1016/j.cclet.2025.111057
摘要:
Crystal defects and morphological modifications are popular strategies to enhance the catalytic activity of heterogeneous semiconductor photocatalysts. Despite defect engineering and morphology control show their successful applications in ZnO, the effects of curved surface modifications on the photocatalytic performance of ZnO and their interplay with the defect formation remain unclear. To resolve this puzzle, we systemically investigate the joint effects of curvature and defect formation on the electronic structure, optoelectronic properties, and photocatalytic performance of ZnO slabs using first-principles calculations. We find that curvature deformation effectively narrows the electronic bandgap by up to 1.6 eV and shifts the p-/d-band centers, thereby enhancing light absorption in the visible and near-ultraviolet regions. Besides, curvature deformation stimulates self-polarization, facilitating the separation of photo-generated electrons and holes. Also, curvature deformation promotes the formation of defects by reducing defect formation energy (by up to 1.0 eV), thus creating abundant reaction sites for photocatalysis. Intriguingly, the synergistic interaction between curvature and defect deformation further strengthens the self-polarization, narrows the electronic bandgaps, adjusts the p-/d-band centers to improve the optoelectronic properties, and influences the dissociation and free energy barriers of intermediates. Consequently, our findings reveal that this synergy substantially enhances the photocatalytic performance of ZnO slabs, providing deeper insights into the role of defect engineering and morphology control on photocatalysis.
Crystal defects and morphological modifications are popular strategies to enhance the catalytic activity of heterogeneous semiconductor photocatalysts. Despite defect engineering and morphology control show their successful applications in ZnO, the effects of curved surface modifications on the photocatalytic performance of ZnO and their interplay with the defect formation remain unclear. To resolve this puzzle, we systemically investigate the joint effects of curvature and defect formation on the electronic structure, optoelectronic properties, and photocatalytic performance of ZnO slabs using first-principles calculations. We find that curvature deformation effectively narrows the electronic bandgap by up to 1.6 eV and shifts the p-/d-band centers, thereby enhancing light absorption in the visible and near-ultraviolet regions. Besides, curvature deformation stimulates self-polarization, facilitating the separation of photo-generated electrons and holes. Also, curvature deformation promotes the formation of defects by reducing defect formation energy (by up to 1.0 eV), thus creating abundant reaction sites for photocatalysis. Intriguingly, the synergistic interaction between curvature and defect deformation further strengthens the self-polarization, narrows the electronic bandgaps, adjusts the p-/d-band centers to improve the optoelectronic properties, and influences the dissociation and free energy barriers of intermediates. Consequently, our findings reveal that this synergy substantially enhances the photocatalytic performance of ZnO slabs, providing deeper insights into the role of defect engineering and morphology control on photocatalysis.
2025, 36(7): 111058
doi: 10.1016/j.cclet.2025.111058
摘要:
The growing environmental concerns regarding rare earth elements in fluorescent powders, along with high production costs, have increased the demand for sustainable alternatives. We propose a promising solution using luminescent metal-organic frameworks (LMOFs) with large surface areas and tunable pore structures, combined with organic carbon quantum dots (CQDs). This study develops a novel white light-emitting diode (WLED) fluorescent powder by incorporating yellow-fluorescent quantum dots (CQDs-Y) into blue-emitting LMOF (ZJU-28), forming the composite material CQDs-Y-n@ZJU-28. The composite exhibits excellent thermal and chemical stability, long-term storage performance, and emits warm white light (CIE: 0.3277, 0.3281) when subjected to excitation at 365 nm, along with an external quantum efficiency (EQE) of 8.85%. Furthermore, it exhibits tunable emission characteristics and promising LED performance, showcasing a color rendering index (CRI) of 78 and a correlated color temperature of 3384 K. The emitted light undergoes minimal deviation in color towards the white end of the spectrum in the temperature range of 277–437 K, making it an ideal candidate for advanced WLED applications.
The growing environmental concerns regarding rare earth elements in fluorescent powders, along with high production costs, have increased the demand for sustainable alternatives. We propose a promising solution using luminescent metal-organic frameworks (LMOFs) with large surface areas and tunable pore structures, combined with organic carbon quantum dots (CQDs). This study develops a novel white light-emitting diode (WLED) fluorescent powder by incorporating yellow-fluorescent quantum dots (CQDs-Y) into blue-emitting LMOF (ZJU-28), forming the composite material CQDs-Y-n@ZJU-28. The composite exhibits excellent thermal and chemical stability, long-term storage performance, and emits warm white light (CIE: 0.3277, 0.3281) when subjected to excitation at 365 nm, along with an external quantum efficiency (EQE) of 8.85%. Furthermore, it exhibits tunable emission characteristics and promising LED performance, showcasing a color rendering index (CRI) of 78 and a correlated color temperature of 3384 K. The emitted light undergoes minimal deviation in color towards the white end of the spectrum in the temperature range of 277–437 K, making it an ideal candidate for advanced WLED applications.
2025, 36(7): 111064
doi: 10.1016/j.cclet.2025.111064
摘要:
Fluorinated fused azobenzene boron (FBAz) is a novel electron-deficient building block for polymer electron acceptors in all-polymer solar cells (all-PSC). The B←N bridging units impart a fixed configuration and low-lying LUMO/HOMO energy. Three polymer acceptor materials (P2f, P3f and P5f) with different fluorine substitution positions by copolymerizing FBAz with indacenodithiophene (IDT), are synthesized and investigated to study the influence of fluorinated forms on the all-polymer solar cell performance. The FBAz units are synthesized in just three steps, facilitating the straightforward production of polymer acceptors P2f, P3f, and P5f. These acceptors exhibit strong light absorption in the visible to near-infrared range of 500–1000 nm and possess suitable LUMO/HOMO energy levels of -3.99/-5.66 eV which are very complementary to that (ELUMO/HOMO = -3.59/-5.20 eV) of the widely-used polymer donor poly[(ethylhexylthiophenyl)-benzodithiophene-(ethylhexyl)-thienothiophene] (PTB7-Th). All-polymer solar cells (all-PSCs) with PTB7-Th as electron donor and P3f as electron acceptor exhibits highest power conversion efficiencies (PCE) 2.70%. When PC61BM is added as the third component, the device efficiency can reach 5.36%. These preliminary results indicate that FBAz is a promising strong electron acceptor for the development of n-type polymer semiconductors, especially in organic photovoltaics (OPVs). To the best of our knowledge, this is the first example demonstrating the unique photovoltaic properties of the N=N double bond as an acceptor material.
Fluorinated fused azobenzene boron (FBAz) is a novel electron-deficient building block for polymer electron acceptors in all-polymer solar cells (all-PSC). The B←N bridging units impart a fixed configuration and low-lying LUMO/HOMO energy. Three polymer acceptor materials (P2f, P3f and P5f) with different fluorine substitution positions by copolymerizing FBAz with indacenodithiophene (IDT), are synthesized and investigated to study the influence of fluorinated forms on the all-polymer solar cell performance. The FBAz units are synthesized in just three steps, facilitating the straightforward production of polymer acceptors P2f, P3f, and P5f. These acceptors exhibit strong light absorption in the visible to near-infrared range of 500–1000 nm and possess suitable LUMO/HOMO energy levels of -3.99/-5.66 eV which are very complementary to that (ELUMO/HOMO = -3.59/-5.20 eV) of the widely-used polymer donor poly[(ethylhexylthiophenyl)-benzodithiophene-(ethylhexyl)-thienothiophene] (PTB7-Th). All-polymer solar cells (all-PSCs) with PTB7-Th as electron donor and P3f as electron acceptor exhibits highest power conversion efficiencies (PCE) 2.70%. When PC61BM is added as the third component, the device efficiency can reach 5.36%. These preliminary results indicate that FBAz is a promising strong electron acceptor for the development of n-type polymer semiconductors, especially in organic photovoltaics (OPVs). To the best of our knowledge, this is the first example demonstrating the unique photovoltaic properties of the N=N double bond as an acceptor material.
2025, 36(7): 111065
doi: 10.1016/j.cclet.2025.111065
摘要:
Considering the challenges posed by severe electromagnetic wave pollution and escalating international tensions, there is a critical need to develop advanced electromagnetic wave absorbing (EMWA) materials that integrate radar stealth and thermal insulation capabilities. In this study, we have synthesized three-dimensional (3D) porous composites comprising V2O3 nanoparticles embedded in Juncus effusus cellulose-derived carbon aerogels (VCA) using a self-templating method followed by high-temperature pyrolysis. The V2O3 nanoparticles possess a 3D V-V framework and a relatively narrow bandgap, facilitating the Mott transition for enhanced conductivity. Furthermore, their uniform dispersion on hollow carbon tubes of Juncus effusus promotes efficient electron transfer and creates numerous heterogeneous interfaces. Consequently, VCA-2 demonstrates outstanding EMWA performance, achieving a minimum reflection loss of −63.92 dB at a matching thickness of 2.0 mm and a maximum effective absorption bandwidth of 8.24 GHz at a thickness of 2.44 mm, covering nearly half of the tested frequency range. Additionally, the radar cross-section reduction reaches a peak value of 29.40 dB m2, underscoring the excellent radar stealth capabilities of the material. In summary, VCA exhibits exceptional EMWA, radar stealth, and thermal insulation properties, highlighting its potential for multifunctional applications in EMWA material development.
Considering the challenges posed by severe electromagnetic wave pollution and escalating international tensions, there is a critical need to develop advanced electromagnetic wave absorbing (EMWA) materials that integrate radar stealth and thermal insulation capabilities. In this study, we have synthesized three-dimensional (3D) porous composites comprising V2O3 nanoparticles embedded in Juncus effusus cellulose-derived carbon aerogels (VCA) using a self-templating method followed by high-temperature pyrolysis. The V2O3 nanoparticles possess a 3D V-V framework and a relatively narrow bandgap, facilitating the Mott transition for enhanced conductivity. Furthermore, their uniform dispersion on hollow carbon tubes of Juncus effusus promotes efficient electron transfer and creates numerous heterogeneous interfaces. Consequently, VCA-2 demonstrates outstanding EMWA performance, achieving a minimum reflection loss of −63.92 dB at a matching thickness of 2.0 mm and a maximum effective absorption bandwidth of 8.24 GHz at a thickness of 2.44 mm, covering nearly half of the tested frequency range. Additionally, the radar cross-section reduction reaches a peak value of 29.40 dB m2, underscoring the excellent radar stealth capabilities of the material. In summary, VCA exhibits exceptional EMWA, radar stealth, and thermal insulation properties, highlighting its potential for multifunctional applications in EMWA material development.
2025, 36(7): 111074
doi: 10.1016/j.cclet.2025.111074
摘要:
A stable and efficient oxygen evolution reaction (OER) electrocatalyst in acidic medium is strongly required for the industrialization of polymer electrolyte membrane water splitting (PEMWS) technology. Herein, we devise the formation of nanoneedle-like RuO2/V2O5 heterostructure with the template of MIL 88B. The incorporation of V2O5 to RuO2 significantly increases the deprotonation capability resulting in a better OER performance demanding 216 mV overpotential at 10 mA/cm2, lowered by 27 mV with relative to benchmarked RuO2. Moreover, the electronic interplay between RuO2 and V2O5 contributes to an increment in oxidation of Ru to high valance state; thereby, a robust stability is achieved for RuO2/V2O5. From the theoretical calculation, it is noticed that the d band center of Ru is downshifted after V2O5 decoration; moreover, the eg filling of Ru is simultaneously increased; in this regard, the adsorption of OH* specie is weakened, in accordance to methanol detection, resulting in a higher OER performance.
A stable and efficient oxygen evolution reaction (OER) electrocatalyst in acidic medium is strongly required for the industrialization of polymer electrolyte membrane water splitting (PEMWS) technology. Herein, we devise the formation of nanoneedle-like RuO2/V2O5 heterostructure with the template of MIL 88B. The incorporation of V2O5 to RuO2 significantly increases the deprotonation capability resulting in a better OER performance demanding 216 mV overpotential at 10 mA/cm2, lowered by 27 mV with relative to benchmarked RuO2. Moreover, the electronic interplay between RuO2 and V2O5 contributes to an increment in oxidation of Ru to high valance state; thereby, a robust stability is achieved for RuO2/V2O5. From the theoretical calculation, it is noticed that the d band center of Ru is downshifted after V2O5 decoration; moreover, the eg filling of Ru is simultaneously increased; in this regard, the adsorption of OH* specie is weakened, in accordance to methanol detection, resulting in a higher OER performance.
2025, 36(7): 111075
doi: 10.1016/j.cclet.2025.111075
摘要:
The performance of hydrogel radical polymerization under ambient conditions is a major challenge because oxygen is an effective radical quencher and the steps to remove or neutralize it are time consuming and laborious. A self-initiating system consisting of transition metals and acetylacetone has been successfully developed. The system is capable of initiating free radical polymerization of hydrogels at room temperature under aerobic conditions, which is attributed to carbon radicals generated by the oxidation of acetylacetone. Some of these carbon radicals reduce oxygen to generate hydroxyl radicals, which together induce self-coagulation of hydrogels. The polymerization system was effective for a variety of monomer and hydrogel swelling and shrinking schemes, and the reaction remained successful when exposed to saturated oxygen. In conclusion, the results demonstrate that the present strategy is an effective approach to addressing the challenge of deoxygenation in polymer synthesis, and provides a convenient method for synthesizing multifunctional hydrogels under ambient conditions.
The performance of hydrogel radical polymerization under ambient conditions is a major challenge because oxygen is an effective radical quencher and the steps to remove or neutralize it are time consuming and laborious. A self-initiating system consisting of transition metals and acetylacetone has been successfully developed. The system is capable of initiating free radical polymerization of hydrogels at room temperature under aerobic conditions, which is attributed to carbon radicals generated by the oxidation of acetylacetone. Some of these carbon radicals reduce oxygen to generate hydroxyl radicals, which together induce self-coagulation of hydrogels. The polymerization system was effective for a variety of monomer and hydrogel swelling and shrinking schemes, and the reaction remained successful when exposed to saturated oxygen. In conclusion, the results demonstrate that the present strategy is an effective approach to addressing the challenge of deoxygenation in polymer synthesis, and provides a convenient method for synthesizing multifunctional hydrogels under ambient conditions.
2025, 36(7): 111092
doi: 10.1016/j.cclet.2025.111092
摘要:
Immune adjuvants are extremely important in tumor vaccines, which can amplify antigen-specific immune responses and enhance anti-tumor efficacy. Nevertheless, well-designed adjuvants and rational combination of adjuvants and antigens still remain a challenge in tumor vaccines. In this study, we designed and formulated carrier-free double-adjuvant nanoparticles (FPC-NPs) by self-assembling of fluoroalkane-grafted polyethylenimide (PEI) (Toll-like receptor 4 (TLR4) agonist) and cytosine-phosphate-guanine (CpG) (TLR9 agonist), and then obtained personalized tumor vaccines (FPC-NPs@TAAs) by electrostatic adsorption of tumor-associated antigens (TAAs) on the surface of FPC-NPs. The results showed that FPC-NPs@TAAs could promote cellular internalization of adjuvants, deliver antigens and adjuvants to the same antigen-presenting cell, which can effectively activate dendritic cells, encourage cross-presentation of antigens, and reduce the proportion of M2-type macrophages. Our work presents a simple method to realize the dual adjuvant combination of TLR4 and TLR9 via well-designed carrier-free nanoparticles, showing great promise for developing personalized tumor vaccines to enhance the efficacy of immunotherapy.
Immune adjuvants are extremely important in tumor vaccines, which can amplify antigen-specific immune responses and enhance anti-tumor efficacy. Nevertheless, well-designed adjuvants and rational combination of adjuvants and antigens still remain a challenge in tumor vaccines. In this study, we designed and formulated carrier-free double-adjuvant nanoparticles (FPC-NPs) by self-assembling of fluoroalkane-grafted polyethylenimide (PEI) (Toll-like receptor 4 (TLR4) agonist) and cytosine-phosphate-guanine (CpG) (TLR9 agonist), and then obtained personalized tumor vaccines (FPC-NPs@TAAs) by electrostatic adsorption of tumor-associated antigens (TAAs) on the surface of FPC-NPs. The results showed that FPC-NPs@TAAs could promote cellular internalization of adjuvants, deliver antigens and adjuvants to the same antigen-presenting cell, which can effectively activate dendritic cells, encourage cross-presentation of antigens, and reduce the proportion of M2-type macrophages. Our work presents a simple method to realize the dual adjuvant combination of TLR4 and TLR9 via well-designed carrier-free nanoparticles, showing great promise for developing personalized tumor vaccines to enhance the efficacy of immunotherapy.
2025, 36(7): 110121
doi: 10.1016/j.cclet.2024.110121
摘要:
Zinc metal batteries (ZMBs) are considered to be promising energy storage devices in the field of large-scale energy storage due to the advantages of high energy density, good safety and environmental friendliness. However, the commercialization of ZMBs has been hampered because of the problems caused by aqueous electrolytes, such as hydrogen evolution reaction, electrolyte leakage, and water evaporation. Gel polymer electrolytes (GPEs) have attracted extensive attention due to the features of high security and low water content. However, the disadvantages of poor ion transport rate, easily freezing at low temperature and low mechanical strength are not conducive to the rapid development and practical application of ZMBs. The rational design and fabrication of multifunctional polymer-based frameworks are considered to be effective strategy to obtain high-performance GPEs. In this review, the recent advancements of GPEs with various polymers are generalized. The strategies for the improvement of ionic conductivity, low temperature resistance and mechanical strength of these GPEs, such as adding inorganic fillers, building double cross-linked networks and introducing functional groups, are summarized. The effects of the GPEs on the self-healable ability, inhibiting dendrite growth, and cycling stability of the ZMBs are also discussed. Finally, the key problems and development prospects of GPEs are proposed, which will provide possibility for the further development of GPEs.
Zinc metal batteries (ZMBs) are considered to be promising energy storage devices in the field of large-scale energy storage due to the advantages of high energy density, good safety and environmental friendliness. However, the commercialization of ZMBs has been hampered because of the problems caused by aqueous electrolytes, such as hydrogen evolution reaction, electrolyte leakage, and water evaporation. Gel polymer electrolytes (GPEs) have attracted extensive attention due to the features of high security and low water content. However, the disadvantages of poor ion transport rate, easily freezing at low temperature and low mechanical strength are not conducive to the rapid development and practical application of ZMBs. The rational design and fabrication of multifunctional polymer-based frameworks are considered to be effective strategy to obtain high-performance GPEs. In this review, the recent advancements of GPEs with various polymers are generalized. The strategies for the improvement of ionic conductivity, low temperature resistance and mechanical strength of these GPEs, such as adding inorganic fillers, building double cross-linked networks and introducing functional groups, are summarized. The effects of the GPEs on the self-healable ability, inhibiting dendrite growth, and cycling stability of the ZMBs are also discussed. Finally, the key problems and development prospects of GPEs are proposed, which will provide possibility for the further development of GPEs.
2025, 36(7): 110151
doi: 10.1016/j.cclet.2024.110151
摘要:
In recent years, reducing carbon emissions to achieve carbon neutrality has become an urgent issue for environmental protection and sustainable development. Converting CO2 into valuable chemical products through electrocatalysis powered by renewable electricity exhibits great potential. However, the electro-reduction of CO2 heavily relies on efficient catalysts to overcome the required energy barrier due to the high stability of CO2. p-block metal-based MOFs and MOF-derived catalysts have been proven to be efficient catalysts for electrochemical CO2 reduction reaction (CO2RR) due to their unique electronic structure and clear active sites. However, factors such as conductivity and stability limit the practical application of p-block metal-based MOFs and MOF-derived catalysts. In this review, we summarize the latest progress of MOFs and MOF-derived catalysts based on typical p-block metals in the field of CO2RR. Then the modification strategies for MOFs-based catalysts and the related catalytic mechanism are briefly introduced. Furthermore, we offer the challenges and prospects of p-block metal-based MOFs and MOF-derived catalysts in the hope of providing guidance for potential applications.
In recent years, reducing carbon emissions to achieve carbon neutrality has become an urgent issue for environmental protection and sustainable development. Converting CO2 into valuable chemical products through electrocatalysis powered by renewable electricity exhibits great potential. However, the electro-reduction of CO2 heavily relies on efficient catalysts to overcome the required energy barrier due to the high stability of CO2. p-block metal-based MOFs and MOF-derived catalysts have been proven to be efficient catalysts for electrochemical CO2 reduction reaction (CO2RR) due to their unique electronic structure and clear active sites. However, factors such as conductivity and stability limit the practical application of p-block metal-based MOFs and MOF-derived catalysts. In this review, we summarize the latest progress of MOFs and MOF-derived catalysts based on typical p-block metals in the field of CO2RR. Then the modification strategies for MOFs-based catalysts and the related catalytic mechanism are briefly introduced. Furthermore, we offer the challenges and prospects of p-block metal-based MOFs and MOF-derived catalysts in the hope of providing guidance for potential applications.
2025, 36(7): 110411
doi: 10.1016/j.cclet.2024.110411
摘要:
Microbial chain elongation (CE), utilizing anaerobic fermentation for the synthesis of high-value medium chain fatty acids (MCFAs), merges as a promising strategy in resource sustainability. Recently, it has pivoted that the use of different types of additives or accelerantstowards enhancing the products yield and fermentation quality has got much attention, with carbon-based materials emerging as vital facilitators. Based on bibliometrics insights, this paper firstly commences with a comprehensive review of the past two decades' progress in applying carbon-based materials within anaerobic fermentation contexts. Subsequently, the recent advancements made by different research groups in order to enhance the performance of CE systemperformance are reviewed, with particular focus on the application, impact, and underlying mechanisms of carbon-based materials in expediting MCFAs biosynthesis via CE. Finally, the future research direction is prospected, aiming to inform innovative material design and sophisticated technological applications, as well as provide a reference for improving the efficiency of anaerobic fermentation of MCFAs using carbon-based material, thereby contributing to the broader discourse on enhancing sustainability and efficiency in bio-based processes.
Microbial chain elongation (CE), utilizing anaerobic fermentation for the synthesis of high-value medium chain fatty acids (MCFAs), merges as a promising strategy in resource sustainability. Recently, it has pivoted that the use of different types of additives or accelerantstowards enhancing the products yield and fermentation quality has got much attention, with carbon-based materials emerging as vital facilitators. Based on bibliometrics insights, this paper firstly commences with a comprehensive review of the past two decades' progress in applying carbon-based materials within anaerobic fermentation contexts. Subsequently, the recent advancements made by different research groups in order to enhance the performance of CE systemperformance are reviewed, with particular focus on the application, impact, and underlying mechanisms of carbon-based materials in expediting MCFAs biosynthesis via CE. Finally, the future research direction is prospected, aiming to inform innovative material design and sophisticated technological applications, as well as provide a reference for improving the efficiency of anaerobic fermentation of MCFAs using carbon-based material, thereby contributing to the broader discourse on enhancing sustainability and efficiency in bio-based processes.
2025, 36(7): 110442
doi: 10.1016/j.cclet.2024.110442
摘要:
Promoting chronic wound healing has always been a hot topic in the field of biomaterials due to its heavy burden on both patients' quality of life and healthcare systems. MXene is a type of two-dimensional (2D) nanomaterial with a unique physical structure and surface chemical properties. The remarkable antibacterial capacity, fast photothermal response ability and electrical conductivity of MXene, indicate that MXene-based hydrogels possess considerable potential for promoting chronic wound healing. In this review, we summarize the preparation and properties of MXene, and mainly focus on the applications of MXene-based hydrogels in chronic wound healing. The purpose of this review is to provide a reference for further study and promote the application of MXene-based hydrogels in clinical practice in the future.
Promoting chronic wound healing has always been a hot topic in the field of biomaterials due to its heavy burden on both patients' quality of life and healthcare systems. MXene is a type of two-dimensional (2D) nanomaterial with a unique physical structure and surface chemical properties. The remarkable antibacterial capacity, fast photothermal response ability and electrical conductivity of MXene, indicate that MXene-based hydrogels possess considerable potential for promoting chronic wound healing. In this review, we summarize the preparation and properties of MXene, and mainly focus on the applications of MXene-based hydrogels in chronic wound healing. The purpose of this review is to provide a reference for further study and promote the application of MXene-based hydrogels in clinical practice in the future.
2025, 36(7): 110443
doi: 10.1016/j.cclet.2024.110443
摘要:
With the global advancement of the circular economy, integrating reverse osmosis (RO) or forward osmosis (FO) with anaerobic membrane bioreactor (AnMBR) offers a promising approach to simultaneously generate high-grade reclaimed water, produce energy, and preserve valuable nutrients from municipal wastewater. However, the selectivity of these osmotic membranes towards ammonia nitrogen, a major component in municipal wastewater and anaerobic effluent, remains unsatisfactory due to its similar polarity and hydraulic radius to water molecules. Therefore, enhancing the ammonia nitrogen rejection of osmotic membranes is imperative to maximize the quality of reclaimed water and minimize the loss of ammonia nitrogen resources. Unfortunately, the current understanding of the mapping relationship between ammonia nitrogen transmembrane diffusion and the micro/nano-structure of osmotic membranes is not systematic, making precise optimization of the membranes challenging. Hence, this review comprehensively analyzed the diffusion behavior of ammonia nitrogen through osmotic membranes to lay the foundation for targeted regulation of membrane fine structure. Initially, the desire for ammonia/ammonium-rejecting membranes was highlighted by introducing current and promising osmotic membrane-based applications in municipal wastewater reclamation processes. Subsequently, the connection between the micro/nano-structure of osmotic membranes and the transmembrane diffusion behavior of ammonia nitrogen was explored by analyzing the effects of membrane characteristics on ammonia nitrogen transport using the DSPM-DE model. Finally, precise methods for modifying membranes to enhance ammonia nitrogen rejection were proposed. This review aims to offer theoretical insights guiding the development of RO and FO membranes with superior ammonia nitrogen rejection for efficient reclamation of municipal wastewater.
With the global advancement of the circular economy, integrating reverse osmosis (RO) or forward osmosis (FO) with anaerobic membrane bioreactor (AnMBR) offers a promising approach to simultaneously generate high-grade reclaimed water, produce energy, and preserve valuable nutrients from municipal wastewater. However, the selectivity of these osmotic membranes towards ammonia nitrogen, a major component in municipal wastewater and anaerobic effluent, remains unsatisfactory due to its similar polarity and hydraulic radius to water molecules. Therefore, enhancing the ammonia nitrogen rejection of osmotic membranes is imperative to maximize the quality of reclaimed water and minimize the loss of ammonia nitrogen resources. Unfortunately, the current understanding of the mapping relationship between ammonia nitrogen transmembrane diffusion and the micro/nano-structure of osmotic membranes is not systematic, making precise optimization of the membranes challenging. Hence, this review comprehensively analyzed the diffusion behavior of ammonia nitrogen through osmotic membranes to lay the foundation for targeted regulation of membrane fine structure. Initially, the desire for ammonia/ammonium-rejecting membranes was highlighted by introducing current and promising osmotic membrane-based applications in municipal wastewater reclamation processes. Subsequently, the connection between the micro/nano-structure of osmotic membranes and the transmembrane diffusion behavior of ammonia nitrogen was explored by analyzing the effects of membrane characteristics on ammonia nitrogen transport using the DSPM-DE model. Finally, precise methods for modifying membranes to enhance ammonia nitrogen rejection were proposed. This review aims to offer theoretical insights guiding the development of RO and FO membranes with superior ammonia nitrogen rejection for efficient reclamation of municipal wastewater.
2025, 36(7): 110447
doi: 10.1016/j.cclet.2024.110447
摘要:
Signal transducer and activator of transcription 3 (STAT3) is a member of the transcription factors involved in regulating many physiological and pathological processes, such as cell proliferation, angiogenesis and immune escape. STAT3 has been identified as a potential therapeutic target for various cancers. Although numerous STAT3 inhibitors have been discovered and optimized to directly inhibit STAT3 activity, they are not yet authorized for clinical use and only a few have entered clinical trials. Furthermore, several proteolysis-targeting chimera (PROTAC) molecules with STAT3 degrading effects have been developed. The event-driven action of PROTAC overcome the drawbacks of STAT3, a traditional undruggable target, and addressed possible resistance to small-molecule inhibitors by degrading the entire STAT3 protein. In this review, we presented a brief introduction to STAT3 and its functions in various cancers, and systematically overviewed the pharmacological effects of inhibitors targeting different domains of STAT3 in the last three years, the structural characterization of the main scaffold, the design strategies, and the pharmacological activities of the substituents. Also, the binding patterns and interactions of some inhibitors with STAT3 were analyzed in detail and the recent advances in STAT3 degraders are also summarized. We anticipate that this perspective will contribute to the design and optimize more novel effective and specific STAT3 inhibitors or degraders for carcinoma treatment.
Signal transducer and activator of transcription 3 (STAT3) is a member of the transcription factors involved in regulating many physiological and pathological processes, such as cell proliferation, angiogenesis and immune escape. STAT3 has been identified as a potential therapeutic target for various cancers. Although numerous STAT3 inhibitors have been discovered and optimized to directly inhibit STAT3 activity, they are not yet authorized for clinical use and only a few have entered clinical trials. Furthermore, several proteolysis-targeting chimera (PROTAC) molecules with STAT3 degrading effects have been developed. The event-driven action of PROTAC overcome the drawbacks of STAT3, a traditional undruggable target, and addressed possible resistance to small-molecule inhibitors by degrading the entire STAT3 protein. In this review, we presented a brief introduction to STAT3 and its functions in various cancers, and systematically overviewed the pharmacological effects of inhibitors targeting different domains of STAT3 in the last three years, the structural characterization of the main scaffold, the design strategies, and the pharmacological activities of the substituents. Also, the binding patterns and interactions of some inhibitors with STAT3 were analyzed in detail and the recent advances in STAT3 degraders are also summarized. We anticipate that this perspective will contribute to the design and optimize more novel effective and specific STAT3 inhibitors or degraders for carcinoma treatment.
2025, 36(7): 110451
doi: 10.1016/j.cclet.2024.110451
摘要:
Butyrylcholinesterase (BChE) is a pivotal enzyme that degrades the neurotransmitter acetylcholine, which is related to learning and memory, into choline and acetic acid. BChE activity is strongly associated with various diseases, including Alzheimer's disease, multiple sclerosis, diabetes, and lipid metabolism disorders. It also possesses pharmacological properties for combating cocaine addiction and detoxifying organophosphate poisoning. Given the significant importance of BChE in the biological and medical fields, detecting its activity and understanding its expression in the body are crucial for advancing related research. Herein, a brief review of recently reported specific fluorescence or chemiluminescence probes for quantifying and real-time monitoring BChE is provided. By utilizing unique recognition groups, these probes achieve highly selective identification of BChE and effectively resist interference from other biological factors. Probes demonstrate excellent performance in measuring BChE activity, screening BChE inhibitors, and locating BChE in cells and mice. These also offer strong technical support for early diagnosis, precise intervention, and effective treatment of diseases with pathological changes in BChE.
Butyrylcholinesterase (BChE) is a pivotal enzyme that degrades the neurotransmitter acetylcholine, which is related to learning and memory, into choline and acetic acid. BChE activity is strongly associated with various diseases, including Alzheimer's disease, multiple sclerosis, diabetes, and lipid metabolism disorders. It also possesses pharmacological properties for combating cocaine addiction and detoxifying organophosphate poisoning. Given the significant importance of BChE in the biological and medical fields, detecting its activity and understanding its expression in the body are crucial for advancing related research. Herein, a brief review of recently reported specific fluorescence or chemiluminescence probes for quantifying and real-time monitoring BChE is provided. By utilizing unique recognition groups, these probes achieve highly selective identification of BChE and effectively resist interference from other biological factors. Probes demonstrate excellent performance in measuring BChE activity, screening BChE inhibitors, and locating BChE in cells and mice. These also offer strong technical support for early diagnosis, precise intervention, and effective treatment of diseases with pathological changes in BChE.
2025, 36(7): 110492
doi: 10.1016/j.cclet.2024.110492
摘要:
Vascular stents play an important role in the minimally invasive treatment of vascular diseases, such as vascular stenosis, vascular aneurysm, vascular dissection and vascular atherosclerotic plaque disease. Bare metal stents were initially fabricated; however, the incidence of complications such as thrombosis, inflammation, restenosis, vascular injury, displacement and endoleakage is still high after implantation. To overcome these complications, several strategies for designing functional vascular stents have been carried out. Drug-eluting stents, biodegradable stents and bionic stents were manufactured and investigated. This review aims to comprehensively analyze the vascular diseases suitable for stent implantation treatment, tissue reactions after implantation, the materials and manufacturing techniques used to fabricate vascular stents, the various application scenarios in which they could be used to treat vascular lesions and the development process of vascular stents. Future development trends of vascular stents are expected to prioritize their performance, biocompatibility, and clinical accessibility. The design of vascular stents may be transformed or improved to better fulfill the rehabilitation requirements of vascular disease patients. Finally, various application scenarios may be used to treat vascular or even nonvascular diseases via endovascular access.
Vascular stents play an important role in the minimally invasive treatment of vascular diseases, such as vascular stenosis, vascular aneurysm, vascular dissection and vascular atherosclerotic plaque disease. Bare metal stents were initially fabricated; however, the incidence of complications such as thrombosis, inflammation, restenosis, vascular injury, displacement and endoleakage is still high after implantation. To overcome these complications, several strategies for designing functional vascular stents have been carried out. Drug-eluting stents, biodegradable stents and bionic stents were manufactured and investigated. This review aims to comprehensively analyze the vascular diseases suitable for stent implantation treatment, tissue reactions after implantation, the materials and manufacturing techniques used to fabricate vascular stents, the various application scenarios in which they could be used to treat vascular lesions and the development process of vascular stents. Future development trends of vascular stents are expected to prioritize their performance, biocompatibility, and clinical accessibility. The design of vascular stents may be transformed or improved to better fulfill the rehabilitation requirements of vascular disease patients. Finally, various application scenarios may be used to treat vascular or even nonvascular diseases via endovascular access.
2025, 36(7): 110506
doi: 10.1016/j.cclet.2024.110506
摘要:
The management of nitrogenous waste emissions presents significant environmental and health challenges. Efficient and sustainable upcycling strategies are needed to convert waste nitrogen compounds into valuable resources. Electrocatalysis has emerged as a promising solution for waste management, but several challenges remain, including the identification of suitable electrocatalysts and understanding the complex reaction mechanisms. In this review, we focus on the progress in electrocatalytic oxidized nitrogen waste upgrading and utilization, highlighting the application of advanced in situ/operando characterization techniques, including X-ray spectroscopy, scanning electrochemical microscopy and others. These techniques provide valuable insights into the structural and chemical properties of electrocatalysts as well as intermediates during electrochemical reactions, enabling a better understanding of reaction mechanisms and optimization of reaction conditions. The review explores the mechanisms of electrocatalytic upcycling of nitrogenous waste, including nitrate/nitrite reduction, nitric oxide reduction, and carbon dioxide and nitrate co-reduction reactions. Additionally, future research directions and development trends are discussed, offering a relevant guide for the development of sustainable electrocatalytic technologies for waste management and resource recovery.
The management of nitrogenous waste emissions presents significant environmental and health challenges. Efficient and sustainable upcycling strategies are needed to convert waste nitrogen compounds into valuable resources. Electrocatalysis has emerged as a promising solution for waste management, but several challenges remain, including the identification of suitable electrocatalysts and understanding the complex reaction mechanisms. In this review, we focus on the progress in electrocatalytic oxidized nitrogen waste upgrading and utilization, highlighting the application of advanced in situ/operando characterization techniques, including X-ray spectroscopy, scanning electrochemical microscopy and others. These techniques provide valuable insights into the structural and chemical properties of electrocatalysts as well as intermediates during electrochemical reactions, enabling a better understanding of reaction mechanisms and optimization of reaction conditions. The review explores the mechanisms of electrocatalytic upcycling of nitrogenous waste, including nitrate/nitrite reduction, nitric oxide reduction, and carbon dioxide and nitrate co-reduction reactions. Additionally, future research directions and development trends are discussed, offering a relevant guide for the development of sustainable electrocatalytic technologies for waste management and resource recovery.
2025, 36(7): 110507
doi: 10.1016/j.cclet.2024.110507
摘要:
Strand displacement-based DNA circuits have emerged as highly effective tools for molecular computation, serving purposes of amplification or decision-making. They are favored for their inherent occurrence and sensitivity to external conditions. However, achieving enhanced amplification or decision-making necessitates the incorporation of multiple strands, thereby increasing the risk of contamination. Recent advancements have led to the development of CRISPR-Cas-based DNA circuits. These systems aim to simplify the complexity associated with conventional circuits, mitigate contamination risks, and enable more substantial amplification or decision-making capabilities. Here, the review article centers on current strategies of CRISPR-Cas (Cas9, Cas12a, Cas13a) system-assisted circuits in amplification and decision-making, and assesses their tendencies and limitations in amplification circuits and decision-making circuits. Furthermore, we discuss the challenges of CRISPR-Cas in circuits and propose prospects that will contribute to constructing more efficient and diverse CRISPR-Cas-based DNA functional circuits.
Strand displacement-based DNA circuits have emerged as highly effective tools for molecular computation, serving purposes of amplification or decision-making. They are favored for their inherent occurrence and sensitivity to external conditions. However, achieving enhanced amplification or decision-making necessitates the incorporation of multiple strands, thereby increasing the risk of contamination. Recent advancements have led to the development of CRISPR-Cas-based DNA circuits. These systems aim to simplify the complexity associated with conventional circuits, mitigate contamination risks, and enable more substantial amplification or decision-making capabilities. Here, the review article centers on current strategies of CRISPR-Cas (Cas9, Cas12a, Cas13a) system-assisted circuits in amplification and decision-making, and assesses their tendencies and limitations in amplification circuits and decision-making circuits. Furthermore, we discuss the challenges of CRISPR-Cas in circuits and propose prospects that will contribute to constructing more efficient and diverse CRISPR-Cas-based DNA functional circuits.
2025, 36(7): 110675
doi: 10.1016/j.cclet.2024.110675
摘要:
Macrocyclic polyamines are excellent chelating agents with the advantage of forming highly stable complexes. They offer the flexibility to adjust the coordination environment through functionalization. making them valuable in numerous applications owing to their unique chemical and biological characteristics. This review summarizes the use of macrocyclic polyamines as carriers and molecular platforms of targeted drugs for medical applications. The significance and innovative design of these original approaches are dissected from the unique perspective of diverse mechanisms, such as iron depletion, metallo-β-lactamases inhibitors, intracellular ATP depletion, non-viral gene vector, DNA/RNA syntheses inhibitors and theranostics agent. Of interest are the metal complex of macrocyclic polyamines, which is usually a double-edged sword as dealing with endogenous macromolecular targets, especially DNA. These excellent cases will help to understand the typical mechanism in drug design based on macrocyclic polyamines, and achieve actual applications in medicine.
Macrocyclic polyamines are excellent chelating agents with the advantage of forming highly stable complexes. They offer the flexibility to adjust the coordination environment through functionalization. making them valuable in numerous applications owing to their unique chemical and biological characteristics. This review summarizes the use of macrocyclic polyamines as carriers and molecular platforms of targeted drugs for medical applications. The significance and innovative design of these original approaches are dissected from the unique perspective of diverse mechanisms, such as iron depletion, metallo-β-lactamases inhibitors, intracellular ATP depletion, non-viral gene vector, DNA/RNA syntheses inhibitors and theranostics agent. Of interest are the metal complex of macrocyclic polyamines, which is usually a double-edged sword as dealing with endogenous macromolecular targets, especially DNA. These excellent cases will help to understand the typical mechanism in drug design based on macrocyclic polyamines, and achieve actual applications in medicine.
2025, 36(7): 110678
doi: 10.1016/j.cclet.2024.110678
摘要:
Planar chiral cyclophanes are a type of structurally intriguing organic molecules, which have found increasingly applications in the field of biologically active compounds, asymmetric catalysis, and optically pure materials. As such, significant efforts in the development of new methods to build up enantioenriched cyclophanes in a precise manner have attracted increased attention in recent years. Among the plethora of reported synthetic strategies, catalytic enantioselective method has emerged as one of the most straightforward and efficient ways to deliver optically pure planar chiral cyclophanes. In this review, the recent progress in catalytic enantioselective reactions for the synthesis of planar chiral cyclophanes will be discussed, which would stimulate the research interest of chemists for the discovery of novel asymmetric strategies for the preparation of valuable and previously difficult-to-access chiral molecules.
Planar chiral cyclophanes are a type of structurally intriguing organic molecules, which have found increasingly applications in the field of biologically active compounds, asymmetric catalysis, and optically pure materials. As such, significant efforts in the development of new methods to build up enantioenriched cyclophanes in a precise manner have attracted increased attention in recent years. Among the plethora of reported synthetic strategies, catalytic enantioselective method has emerged as one of the most straightforward and efficient ways to deliver optically pure planar chiral cyclophanes. In this review, the recent progress in catalytic enantioselective reactions for the synthesis of planar chiral cyclophanes will be discussed, which would stimulate the research interest of chemists for the discovery of novel asymmetric strategies for the preparation of valuable and previously difficult-to-access chiral molecules.
2025, 36(7): 110777
doi: 10.1016/j.cclet.2024.110777
摘要:
Sonodynamic therapy (SDT) is a new non-invasive treatment method, which uses low-intensity ultrasound (US) to activate specific sonosensitizers (SNs) to produce reactive oxygen species (ROS) for therapeutic purposes. However, traditional sonosensitizers have the defects of low generation efficiency of ROS and single treatment mode. Therefore, designing sonosensitizers with high efficiency to generate ROS, high stability, and multimodal therapy is an excellent alternative to achieve effective, safe, and intelligent therapy. Heterojunction nanosonosensitizers (NSNs), as novel type of SNs, combine different materials through heterojunction structures to improve the efficiency of ROS generation. In this review, the classification of heterojunction NSNs, the preparation methods and characterization methods of heterojunction NSNs and the possible mechanisms for enhancing SDT were firstly presented, followed by an in-depth discussion of the application of heterojunction NSNs in the treatment of bacterial infections and tumors, with a special emphasis on synergistic enhancement of therapeutic efficacy of heterojunction SNs in combination with different therapeutic models such as gas therapy, immunotherapy and nanocatalytic therapy. Finally, the challenges and perspectives of such heterojunction SNs-supported SDT were outlined and highlighted to facilitate their clinical translation.
Sonodynamic therapy (SDT) is a new non-invasive treatment method, which uses low-intensity ultrasound (US) to activate specific sonosensitizers (SNs) to produce reactive oxygen species (ROS) for therapeutic purposes. However, traditional sonosensitizers have the defects of low generation efficiency of ROS and single treatment mode. Therefore, designing sonosensitizers with high efficiency to generate ROS, high stability, and multimodal therapy is an excellent alternative to achieve effective, safe, and intelligent therapy. Heterojunction nanosonosensitizers (NSNs), as novel type of SNs, combine different materials through heterojunction structures to improve the efficiency of ROS generation. In this review, the classification of heterojunction NSNs, the preparation methods and characterization methods of heterojunction NSNs and the possible mechanisms for enhancing SDT were firstly presented, followed by an in-depth discussion of the application of heterojunction NSNs in the treatment of bacterial infections and tumors, with a special emphasis on synergistic enhancement of therapeutic efficacy of heterojunction SNs in combination with different therapeutic models such as gas therapy, immunotherapy and nanocatalytic therapy. Finally, the challenges and perspectives of such heterojunction SNs-supported SDT were outlined and highlighted to facilitate their clinical translation.
2025, 36(7): 110784
doi: 10.1016/j.cclet.2024.110784
摘要:
Chromones serve as versatile heterocyclic scaffolds and are common core structural units in a variety of natural products and bioactive organic molecules. This area of research, at the forefront of organic synthesis, has seen remarkable progress in recent years. Among the various synthetic methodologies for accessing chromone scaffolds, the tandem annulation of o-hydroxyaryl enaminones has emerged as a robust and practical strategy. This approach, through direct vinyl CH bond functionalization of o-hydroxyaryl enaminones, enables the construction of structurally diverse chromones (including 3-substituted chromones, 2-substituted chromones, and 2,3-disubstituted chromones) and their derivatives since mid-2019. In this review, we highlight recent advances in the synthesis of various types of chromones and their derivatives, achieved through tandem direct vinyl CH activation and chromone annulation of o-hydroxyaryl enaminones.
Chromones serve as versatile heterocyclic scaffolds and are common core structural units in a variety of natural products and bioactive organic molecules. This area of research, at the forefront of organic synthesis, has seen remarkable progress in recent years. Among the various synthetic methodologies for accessing chromone scaffolds, the tandem annulation of o-hydroxyaryl enaminones has emerged as a robust and practical strategy. This approach, through direct vinyl CH bond functionalization of o-hydroxyaryl enaminones, enables the construction of structurally diverse chromones (including 3-substituted chromones, 2-substituted chromones, and 2,3-disubstituted chromones) and their derivatives since mid-2019. In this review, we highlight recent advances in the synthesis of various types of chromones and their derivatives, achieved through tandem direct vinyl CH activation and chromone annulation of o-hydroxyaryl enaminones.
2025, 36(7): 111056
doi: 10.1016/j.cclet.2025.111056
摘要:
Ammonia is a key industry raw material for fertilizers and the electro-reduction of N2 (NRR) can be served as a promising method. It is urgently needed to discover advanced catalysts while the lack of design principles still hinders the high-throughput screen of efficient candidates. Herein, we have provided an up-to-date review of NRR catalysts mainly on theoretical works and highlighted the latest achievements on descriptors, which can be served as valid guidance of optimal catalysts. The descriptors are classified with adsorption energy and the corresponding derived ones, which can screen the NRR catalysts from various aspects. Finally, the challenges and opportunities in the descriptor field are presented.
Ammonia is a key industry raw material for fertilizers and the electro-reduction of N2 (NRR) can be served as a promising method. It is urgently needed to discover advanced catalysts while the lack of design principles still hinders the high-throughput screen of efficient candidates. Herein, we have provided an up-to-date review of NRR catalysts mainly on theoretical works and highlighted the latest achievements on descriptors, which can be served as valid guidance of optimal catalysts. The descriptors are classified with adsorption energy and the corresponding derived ones, which can screen the NRR catalysts from various aspects. Finally, the challenges and opportunities in the descriptor field are presented.
2025, 36(7): 110500
doi: 10.1016/j.cclet.2024.110500
摘要:
Oral antiretroviral drugs have been a fundamental component of human immunodeficiency virus (HIV) treatment for over three decades, and their continuously improving safety and efficacy have directly contributed to reversing the initially devastating course of the HIV epidemic. Long-acting antiretroviral (ARV) regimens are necessary to sustain viral suppression in people living with HIV who express a strong desire to alleviate pill fatigue or avoid the potential stigma associated with daily oral regimens. The development of innovative long-acting ARVs remains an unmet requirement in the fields of HIV treatment and prevention. In this review, we provide an overview of lenacapavir, a first-in-class picomolar long-acting capsid inhibitor for HIV-1 that operates through multiple stages without any known cross-resistance to other existing antiretroviral drug classes.
Oral antiretroviral drugs have been a fundamental component of human immunodeficiency virus (HIV) treatment for over three decades, and their continuously improving safety and efficacy have directly contributed to reversing the initially devastating course of the HIV epidemic. Long-acting antiretroviral (ARV) regimens are necessary to sustain viral suppression in people living with HIV who express a strong desire to alleviate pill fatigue or avoid the potential stigma associated with daily oral regimens. The development of innovative long-acting ARVs remains an unmet requirement in the fields of HIV treatment and prevention. In this review, we provide an overview of lenacapavir, a first-in-class picomolar long-acting capsid inhibitor for HIV-1 that operates through multiple stages without any known cross-resistance to other existing antiretroviral drug classes.
2025, 36(7): 110986
doi: 10.1016/j.cclet.2025.110986
摘要:
2025, 36(7): 111039
doi: 10.1016/j.cclet.2025.111039
摘要:
2025, 36(7): 111054
doi: 10.1016/j.cclet.2025.111054
摘要:
2025, 36(7): 111070
doi: 10.1016/j.cclet.2025.111070
摘要:
2025, 36(7): 111221
doi: 10.1016/j.cclet.2025.111221
摘要:
2025, 36(5): 109726
doi: 10.1016/j.cclet.2024.109726
摘要:
Conventional hydrometallurgy recycling process for treating wasted lithium-ion batteries (LIBs) typically results in the consumption of large amounts of corrosive leachates. Recent research on reusable leachate is expected to significantly improve the economic and environmental benefits, but is usually limited to specific and unique chemical reactions which could only apply to one type of metal elements. Herein, we report the co-extraction of multiple metal elements can be extracted without adding precipitates by mixed crystal co-precipitation, which enables the reusability of the leachate. We show that an oxalic acid (OA): choline chloride (ChCl): ethylene glycol (EG) type DES leachate system can leach transition metals from wasted LiNixCoyMn1-x-yO2 (NCM) cathode materials with satisfactory efficiency (The time required for complete leaching at 120 ℃ is 1.5 h). The transition metals were then efficiently extracted (with a recovery efficiency of over 96% for all elements) by directly adding water without precipitants. Noteworthy, the leachate can be efficiently recovered by directly evaporating the added water. The successful realization of reusability of leachate for the synergistic extraction of multiple elements relies on the regulation of the mixed crystal co-precipitation coefficient, which is realized by rationally design the reaction condition (composition of leachate, temperature and time) and induces the extraction of originally soluble manganese element. Our strategy is expected to be generally applicable and highly competent for industrial applications.
Conventional hydrometallurgy recycling process for treating wasted lithium-ion batteries (LIBs) typically results in the consumption of large amounts of corrosive leachates. Recent research on reusable leachate is expected to significantly improve the economic and environmental benefits, but is usually limited to specific and unique chemical reactions which could only apply to one type of metal elements. Herein, we report the co-extraction of multiple metal elements can be extracted without adding precipitates by mixed crystal co-precipitation, which enables the reusability of the leachate. We show that an oxalic acid (OA): choline chloride (ChCl): ethylene glycol (EG) type DES leachate system can leach transition metals from wasted LiNixCoyMn1-x-yO2 (NCM) cathode materials with satisfactory efficiency (The time required for complete leaching at 120 ℃ is 1.5 h). The transition metals were then efficiently extracted (with a recovery efficiency of over 96% for all elements) by directly adding water without precipitants. Noteworthy, the leachate can be efficiently recovered by directly evaporating the added water. The successful realization of reusability of leachate for the synergistic extraction of multiple elements relies on the regulation of the mixed crystal co-precipitation coefficient, which is realized by rationally design the reaction condition (composition of leachate, temperature and time) and induces the extraction of originally soluble manganese element. Our strategy is expected to be generally applicable and highly competent for industrial applications.
2025, 36(5): 109853
doi: 10.1016/j.cclet.2024.109853
摘要:
Even the sulfur cathode in lithium-sulfur (Li-S) battery has the advantages of high theoretical energy density, wide source of raw materials, no pollution to the environment, and so on. It still suffers the sore points of easy electrode collapse due to large volume expansion during charge and discharge and low active materials utilization caused by the severe shuttle effect of lithium polysulfides (LiPSs). Therefore, in this work, ramie gum (RG) was extracted from ramie fiber degumming liquid and used as the functional binder to address the above problems and improve the Li-S battery's performance for the first time. Surprisingly, the sulfur cathode using RG binder illustrates a high initial capacity of 1152.2 mAh/g, and a reversible capacity of 644.6 mAh/g after 500 cycles at 0.5 C, far better than the sulfur cathode using polyvinylidene fluoride (PVDF) and sodium carboxymethyl cellulose (CMC) binder. More importantly, even if the active materials loading increased to as high as 4.30 mg/cm2, the area capacity is still around 3.1 mAh/cm2 after 200 cycles. Such excellent performances could be attributed to the abundant oxygen- and nitrogen-containing functional groups of RG that can effectively inhibit the shuttle effect of LiPSs, as well as the excellent viscosity and mechanical properties that can maintain electrode integrity during long-term charging/discharging. This work verifies the feasibility of RG as an eco-friendly and high-performance Li-S battery binder and provides a new idea for the utilization of agricultural biomass resources.
Even the sulfur cathode in lithium-sulfur (Li-S) battery has the advantages of high theoretical energy density, wide source of raw materials, no pollution to the environment, and so on. It still suffers the sore points of easy electrode collapse due to large volume expansion during charge and discharge and low active materials utilization caused by the severe shuttle effect of lithium polysulfides (LiPSs). Therefore, in this work, ramie gum (RG) was extracted from ramie fiber degumming liquid and used as the functional binder to address the above problems and improve the Li-S battery's performance for the first time. Surprisingly, the sulfur cathode using RG binder illustrates a high initial capacity of 1152.2 mAh/g, and a reversible capacity of 644.6 mAh/g after 500 cycles at 0.5 C, far better than the sulfur cathode using polyvinylidene fluoride (PVDF) and sodium carboxymethyl cellulose (CMC) binder. More importantly, even if the active materials loading increased to as high as 4.30 mg/cm2, the area capacity is still around 3.1 mAh/cm2 after 200 cycles. Such excellent performances could be attributed to the abundant oxygen- and nitrogen-containing functional groups of RG that can effectively inhibit the shuttle effect of LiPSs, as well as the excellent viscosity and mechanical properties that can maintain electrode integrity during long-term charging/discharging. This work verifies the feasibility of RG as an eco-friendly and high-performance Li-S battery binder and provides a new idea for the utilization of agricultural biomass resources.
2025, 36(5): 109870
doi: 10.1016/j.cclet.2024.109870
摘要:
Although lithium-ion batteries (LIBs) currently dominate a wide spectrum of energy storage applications, they face challenges such as fast cycle life decay and poor stability that hinder their further application. To address these limitations, element doping has emerged as a prevalent strategy to enhance the discharge capacity and extend the durability of Li-Ni-Co-Mn (LNCM) ternary compounds. This study utilized a machine learning-driven feature screening method to effectively pinpoint four key features crucially impacting the initial discharge capacity (IC) of Li-Ni-Co-Mn (LNCM) ternary cathode materials. These features were also proved highly predictive for the 50th cycle discharge capacity (EC). Additionally, the application of SHAP value analysis yielded an in-depth understanding of the interplay between these features and discharge performance. This insight offers valuable direction for future advancements in the development of LNCM cathode materials, effectively promoting this field toward greater efficiency and sustainability.
Although lithium-ion batteries (LIBs) currently dominate a wide spectrum of energy storage applications, they face challenges such as fast cycle life decay and poor stability that hinder their further application. To address these limitations, element doping has emerged as a prevalent strategy to enhance the discharge capacity and extend the durability of Li-Ni-Co-Mn (LNCM) ternary compounds. This study utilized a machine learning-driven feature screening method to effectively pinpoint four key features crucially impacting the initial discharge capacity (IC) of Li-Ni-Co-Mn (LNCM) ternary cathode materials. These features were also proved highly predictive for the 50th cycle discharge capacity (EC). Additionally, the application of SHAP value analysis yielded an in-depth understanding of the interplay between these features and discharge performance. This insight offers valuable direction for future advancements in the development of LNCM cathode materials, effectively promoting this field toward greater efficiency and sustainability.
2025, 36(5): 109873
doi: 10.1016/j.cclet.2024.109873
摘要:
In this work, the synthesis of uniform zeolitic imidazolate framework-coated Mo-glycerate spheres and their subsequent conversion into hierarchical architecture containing bimetallic selenides heterostructures and nitrogen-doped carbon shell are reported. Selenization temperature plays a significant role in determining the phases, morphology, and lithium-ion storage performance of the composite. Notably, the optimal electrode demonstrates an ultrahigh reversible capacity of 1298.2 mAh/g after 100 cycles at 0.2 A/g and an outstanding rate capability with the capacity still maintained 505.7 mAh/g after 300 cycles at 1.0 A/g, surpassing the calculated theoretical capacity according to individual component and most of the reported MoSe@C- or ZnSe@C-based anodes. Furthermore, ex-situ X-ray diffraction patterns reveal the combined conversion and alloying reaction mechanisms of the composite.
In this work, the synthesis of uniform zeolitic imidazolate framework-coated Mo-glycerate spheres and their subsequent conversion into hierarchical architecture containing bimetallic selenides heterostructures and nitrogen-doped carbon shell are reported. Selenization temperature plays a significant role in determining the phases, morphology, and lithium-ion storage performance of the composite. Notably, the optimal electrode demonstrates an ultrahigh reversible capacity of 1298.2 mAh/g after 100 cycles at 0.2 A/g and an outstanding rate capability with the capacity still maintained 505.7 mAh/g after 300 cycles at 1.0 A/g, surpassing the calculated theoretical capacity according to individual component and most of the reported MoSe@C- or ZnSe@C-based anodes. Furthermore, ex-situ X-ray diffraction patterns reveal the combined conversion and alloying reaction mechanisms of the composite.
2025, 36(5): 109919
doi: 10.1016/j.cclet.2024.109919
摘要:
Industrial high-current-density oxygen evolution catalyst is the key to accelerating the practical application of hydrogen energy. Herein, Co9S8/CoS heterojunctions were rationally encapsulated in S, N-codoped carbon ((Co9S8/CoS)@SNC) microleaf arrays, which are rooted on S-doped carbonized wood fibers (SCWF). Benefiting from the synergistic electronic interactions on heterointerfaces and the accelerated mass transfer by array structure, the obtained self-supporting (Co9S8/CoS)@SNC/SCWF electrode exhibits superior performance toward alkaline oxygen evolution reaction (OER) with an ultra-low overpotential of 274 mV at 1000 mA/cm2, a small Tafel slope of 48.84 mV/dec, and ultralong stability up to 100 h. Theoretical calculations show that interfacing Co9S8 with CoS can upshift the d-band center of the Co atoms and strengthen the interactions with oxygen intermediates, thereby favoring OER performance. Furthermore, the (Co9S8/CoS)@SNC/SCWF electrode shows outstanding rechargeability and stable cycle life in aqueous Zn-air batteries with a peak power density of 201.3 mW/cm2, exceeding the commercial RuO2 and Pt/C hybrid catalysts. This work presents a promising strategy for the design of high-current-density OER electrocatalysts from sustainable wood fiber resources, thus promoting their practical applications in the field of electrochemical energy storage and conversion.
Industrial high-current-density oxygen evolution catalyst is the key to accelerating the practical application of hydrogen energy. Herein, Co9S8/CoS heterojunctions were rationally encapsulated in S, N-codoped carbon ((Co9S8/CoS)@SNC) microleaf arrays, which are rooted on S-doped carbonized wood fibers (SCWF). Benefiting from the synergistic electronic interactions on heterointerfaces and the accelerated mass transfer by array structure, the obtained self-supporting (Co9S8/CoS)@SNC/SCWF electrode exhibits superior performance toward alkaline oxygen evolution reaction (OER) with an ultra-low overpotential of 274 mV at 1000 mA/cm2, a small Tafel slope of 48.84 mV/dec, and ultralong stability up to 100 h. Theoretical calculations show that interfacing Co9S8 with CoS can upshift the d-band center of the Co atoms and strengthen the interactions with oxygen intermediates, thereby favoring OER performance. Furthermore, the (Co9S8/CoS)@SNC/SCWF electrode shows outstanding rechargeability and stable cycle life in aqueous Zn-air batteries with a peak power density of 201.3 mW/cm2, exceeding the commercial RuO2 and Pt/C hybrid catalysts. This work presents a promising strategy for the design of high-current-density OER electrocatalysts from sustainable wood fiber resources, thus promoting their practical applications in the field of electrochemical energy storage and conversion.
2025, 36(5): 109920
doi: 10.1016/j.cclet.2024.109920
摘要:
Aqueous proton batteries (APBs) embody a compelling alternative in the realm of economical and reliable energy technologies by virtue of their distinctive "Grotthuss mechanism". Sustainable production and adjustable molecular structure make organic polymers a promising choice for APB electrodes. However, inadequate proton-storage redox capability currently hinders their practical implementation. To address this issue, we introduce a pioneering phenazine-conjugated polymer (PPZ), synthesized through a straightforward polymerization process, marking its debut in APB applications. The inclusion of N-heteroaromatic fused-ring in the extended π-conjugated framework not only prevents the dissolution of redox-active units but also refines the energy bandgap and electronic properties, endowing the PPZ polymer with both structural integrity and enhanced redox activity. Consequently, the PPZ polymer as an electrode material achieves a remarkable proton-storage capacity of 211.5 mAh/g, maintaining a notable capacity of 158.3 mAh/g even under a high rate of 8 A/g with a minimal capacity fade of merely 0.00226% per cycle. The rapid, stable and impressive redox behavior is further elucidated through in-situ techniques and theoretical calculations. Ultimately, we fabricate an APB device featuring satisfactory electrochemical attributes with an extraordinary longevity over 10,000 cycles, thereby affirming its auspicious potential for eminent applications.
Aqueous proton batteries (APBs) embody a compelling alternative in the realm of economical and reliable energy technologies by virtue of their distinctive "Grotthuss mechanism". Sustainable production and adjustable molecular structure make organic polymers a promising choice for APB electrodes. However, inadequate proton-storage redox capability currently hinders their practical implementation. To address this issue, we introduce a pioneering phenazine-conjugated polymer (PPZ), synthesized through a straightforward polymerization process, marking its debut in APB applications. The inclusion of N-heteroaromatic fused-ring in the extended π-conjugated framework not only prevents the dissolution of redox-active units but also refines the energy bandgap and electronic properties, endowing the PPZ polymer with both structural integrity and enhanced redox activity. Consequently, the PPZ polymer as an electrode material achieves a remarkable proton-storage capacity of 211.5 mAh/g, maintaining a notable capacity of 158.3 mAh/g even under a high rate of 8 A/g with a minimal capacity fade of merely 0.00226% per cycle. The rapid, stable and impressive redox behavior is further elucidated through in-situ techniques and theoretical calculations. Ultimately, we fabricate an APB device featuring satisfactory electrochemical attributes with an extraordinary longevity over 10,000 cycles, thereby affirming its auspicious potential for eminent applications.
2025, 36(5): 109935
doi: 10.1016/j.cclet.2024.109935
摘要:
Developing effective strategy for constructing the electrocatalysts enable tri-functional electrocatalytic activity of hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is the premise to achieve both the zinc-air battery (ZAB) and overall water splitting. Herein, we utilize density functional theory to calculate the cobalt nitride (CoxN, x = 1, 2, 4, 5.47) system, revealing that the Co5.47N maybe exhibits a tri-functional activity due to the diverse valence states and high-density d-electron state of Co site. Furthermore, the electron of Co site is further delocalized by the electronic compensation effect of vanadium nitride (VN), thus improving the intermediates absorption and electrocatalytic activity. Accordingly, the Co5.47N/VN heterojunction is designed and synthesized via an electrospinning and a subsequent pyrolysis route. As expected, it displays excellent HER, OER, and ORR activity in alkaline electrolyte, which can be applied to assemble ZAB with a high power density of 207 mW/cm2 and overall water splitting system only requires a lower voltage of 1.53 V to achieve 10 mA/cm2. The electron regulation effect of VN makes the Co valence state decrease in the reduction reaction whereas increase in the oxidization reaction as evidenced by quasi-operando XPS analyses. Importantly, two ZABs connected in series could drive overall water splitting, indicating the potential application in renewable energy technologies.
Developing effective strategy for constructing the electrocatalysts enable tri-functional electrocatalytic activity of hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is the premise to achieve both the zinc-air battery (ZAB) and overall water splitting. Herein, we utilize density functional theory to calculate the cobalt nitride (CoxN, x = 1, 2, 4, 5.47) system, revealing that the Co5.47N maybe exhibits a tri-functional activity due to the diverse valence states and high-density d-electron state of Co site. Furthermore, the electron of Co site is further delocalized by the electronic compensation effect of vanadium nitride (VN), thus improving the intermediates absorption and electrocatalytic activity. Accordingly, the Co5.47N/VN heterojunction is designed and synthesized via an electrospinning and a subsequent pyrolysis route. As expected, it displays excellent HER, OER, and ORR activity in alkaline electrolyte, which can be applied to assemble ZAB with a high power density of 207 mW/cm2 and overall water splitting system only requires a lower voltage of 1.53 V to achieve 10 mA/cm2. The electron regulation effect of VN makes the Co valence state decrease in the reduction reaction whereas increase in the oxidization reaction as evidenced by quasi-operando XPS analyses. Importantly, two ZABs connected in series could drive overall water splitting, indicating the potential application in renewable energy technologies.
2025, 36(5): 109936
doi: 10.1016/j.cclet.2024.109936
摘要:
Metal-organic frameworks (MOFs) provide great prospective in the photodegradation of pollutants. Nevertheless, the poor separation and recovery hamper their pilot- or industrial-scare applications because of their microcrystalline features. Herein, this challenge can be tackled by integrating Cu-MOFs into an alginate substrate to offer environmentally friendly, sustainable, facile separation, and high-performance MOF-based hydrogel photocatalysis platforms. The CuII-MOF 1 and CuI-MOF 2 were initially synthesized through a direct diffusion and single-crystal to single-crystal (SCSC) transformation method, respectively, and after the immobilization into alginate, more effective pollutant decontamination was achieved via the synergistic effect of the adsorption feature of hydrogel and in situ photodegradation of Cu-MOFs. Specifically, Cu-MOF-alginate composites present an improved and nearly completed Cr(VI) elimination at a short time of 15–25 min. Additionally, the congo red (CR) decolorization can be effectively enhanced in the presence of Cr(VI), and 1-alginate showed superior simultaneous decontamination efficiency of CR and Cr(VI) with 99% and 78%, respectively. Furthermore, Cu-MOF-alginate composites can maintain a high pollutant removal after over 10 continuous cycles (95% for Cr(VI) after 14 runs, and 90% for CR after 10 runs). Moreover, the Cr(VI)/CR degradation mechanism for Cu-MOF-alginate composite was investigated.
Metal-organic frameworks (MOFs) provide great prospective in the photodegradation of pollutants. Nevertheless, the poor separation and recovery hamper their pilot- or industrial-scare applications because of their microcrystalline features. Herein, this challenge can be tackled by integrating Cu-MOFs into an alginate substrate to offer environmentally friendly, sustainable, facile separation, and high-performance MOF-based hydrogel photocatalysis platforms. The CuII-MOF 1 and CuI-MOF 2 were initially synthesized through a direct diffusion and single-crystal to single-crystal (SCSC) transformation method, respectively, and after the immobilization into alginate, more effective pollutant decontamination was achieved via the synergistic effect of the adsorption feature of hydrogel and in situ photodegradation of Cu-MOFs. Specifically, Cu-MOF-alginate composites present an improved and nearly completed Cr(VI) elimination at a short time of 15–25 min. Additionally, the congo red (CR) decolorization can be effectively enhanced in the presence of Cr(VI), and 1-alginate showed superior simultaneous decontamination efficiency of CR and Cr(VI) with 99% and 78%, respectively. Furthermore, Cu-MOF-alginate composites can maintain a high pollutant removal after over 10 continuous cycles (95% for Cr(VI) after 14 runs, and 90% for CR after 10 runs). Moreover, the Cr(VI)/CR degradation mechanism for Cu-MOF-alginate composite was investigated.
2025, 36(5): 109937
doi: 10.1016/j.cclet.2024.109937
摘要:
Cu-based metal-organic frameworks (MOFs) are widely employed in CO2 reduction reactions (CO2RR). Mostly, the in-situ reconstructed derivatives such as Cu or Cu oxides during CO2RR are regarded as the catalytic active center for the formation of catalytic products. However, in many cases, the pristine MOFs still exist during the catalytic process, the key role of these pristine MOFs is often ignored in revealing the catalytic mechanism. Here, we designed two Cu(imidazole) with different coordination environments, namely CuN2 and Cu2N4 for CO2RR. The structures of the two MOFs were still remained after the catalytic reaction. We discovered that the pristine MOFs served as activation catalysts for converting CO2 into CO. Sequentially, the Cu-based derivatives, in the two cases, Cu(111) converted the CO into C2+ products. The CuN2 with more exposed Cu-N centers showed a higher FECO and a higher final FEC2+ than Cu2N4. This auto-tandem catalytic mechanism was supported by electrocatalytic performance, TPD-CO, HRTEM, SAED, XPS, in-situ XANES and XES and DFT computation. The auto-tandem catalytic mechanism provides a new route to design Cu-based MOF electrocatalysts for high product selectivity in CO2RR.
Cu-based metal-organic frameworks (MOFs) are widely employed in CO2 reduction reactions (CO2RR). Mostly, the in-situ reconstructed derivatives such as Cu or Cu oxides during CO2RR are regarded as the catalytic active center for the formation of catalytic products. However, in many cases, the pristine MOFs still exist during the catalytic process, the key role of these pristine MOFs is often ignored in revealing the catalytic mechanism. Here, we designed two Cu(imidazole) with different coordination environments, namely CuN2 and Cu2N4 for CO2RR. The structures of the two MOFs were still remained after the catalytic reaction. We discovered that the pristine MOFs served as activation catalysts for converting CO2 into CO. Sequentially, the Cu-based derivatives, in the two cases, Cu(111) converted the CO into C2+ products. The CuN2 with more exposed Cu-N centers showed a higher FECO and a higher final FEC2+ than Cu2N4. This auto-tandem catalytic mechanism was supported by electrocatalytic performance, TPD-CO, HRTEM, SAED, XPS, in-situ XANES and XES and DFT computation. The auto-tandem catalytic mechanism provides a new route to design Cu-based MOF electrocatalysts for high product selectivity in CO2RR.
2025, 36(5): 109939
doi: 10.1016/j.cclet.2024.109939
摘要:
Listeria monocytogenes (LM) is a dangerous foodborne pathogen for humans. One emerging and validated method of indirectly assessing LM in food is detecting 3-hydroxy-2-butanone (3H2B) gas. In this study, the synthesis of 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTMS) functionalized hierarchical hollow TiO2 nanospheres was achieved via precise controlling of solvothermal reaction temperature and post-grafting route. The sensors based on as-prepared materials exhibited excellent sensitivity (480 Hz@50 ppm), low detection limit (100 ppb), and outstanding selectivity. Moreover, the evaluation of LM with high sensitivity and specificity was achieved using the sensors. Such stable three-dimensional spheres, whose distinctive hierarchical and hollow nanostructure simultaneously improved both sensitivity and response/recovery speed dramatically, were spontaneously assembled by nanosheets. Meanwhile, the moderate loadings of AAPTMS significantly improved the selectivity of sensors. Then, the gas-sensing mechanism was explored by utilizing thermodynamic investigation, Gaussian 16 software, and in situ diffuse reflectance infrared transform spectroscopy, illustrating the weak chemisorption between the -NH- group and 3H2B molecules. These portable sensors are promising for real-time assessment of LM at room temperature, which will make a magnificent contribution to food safety.
Listeria monocytogenes (LM) is a dangerous foodborne pathogen for humans. One emerging and validated method of indirectly assessing LM in food is detecting 3-hydroxy-2-butanone (3H2B) gas. In this study, the synthesis of 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTMS) functionalized hierarchical hollow TiO2 nanospheres was achieved via precise controlling of solvothermal reaction temperature and post-grafting route. The sensors based on as-prepared materials exhibited excellent sensitivity (480 Hz@50 ppm), low detection limit (100 ppb), and outstanding selectivity. Moreover, the evaluation of LM with high sensitivity and specificity was achieved using the sensors. Such stable three-dimensional spheres, whose distinctive hierarchical and hollow nanostructure simultaneously improved both sensitivity and response/recovery speed dramatically, were spontaneously assembled by nanosheets. Meanwhile, the moderate loadings of AAPTMS significantly improved the selectivity of sensors. Then, the gas-sensing mechanism was explored by utilizing thermodynamic investigation, Gaussian 16 software, and in situ diffuse reflectance infrared transform spectroscopy, illustrating the weak chemisorption between the -NH- group and 3H2B molecules. These portable sensors are promising for real-time assessment of LM at room temperature, which will make a magnificent contribution to food safety.
2025, 36(5): 109940
doi: 10.1016/j.cclet.2024.109940
摘要:
Shape control of nickel sulfide (NiS2) catalysts is beneficial for boosting their catalytic performances, which is vital to their practical application as a class of advanced non-noble electro-catalysts. However, precisely controlling the formation kinetics and fabricate ultrathin NiS2 nanostructures still remains challenge. Herein, we provide an injection rate-mediated method to fabricate ultrathin NiS2 nanocages (HNCs) with hierarchical walls, high-density lattice defects and abundant grain boundaries (GBs). Through mechanism analysis, we find the injection rate determines the concentration of S2− in the steady state and thus control the growth pattern, leading to the formation of NiS2 HNCs at slow etching kinetics and NiCo PBA@NiS2 frames at fast etching kinetics, respectively. Benefiting from the ultrathin and hierarchical walls that minimize the mass transport restrictions, the high-density lattice defects and GBs that offer abundant unsaturated reaction sites, the NiS2 HNCs exhibit obviously enhanced electrocatalytic activity and stability toward OER, with overpotential of 255 mV to reach 10 mA/cm2 and a Tafel slope of 27.44 mV/dec, surpassing the performances of NiCo PBA@NiS2 frames and commercial RuO2.
Shape control of nickel sulfide (NiS2) catalysts is beneficial for boosting their catalytic performances, which is vital to their practical application as a class of advanced non-noble electro-catalysts. However, precisely controlling the formation kinetics and fabricate ultrathin NiS2 nanostructures still remains challenge. Herein, we provide an injection rate-mediated method to fabricate ultrathin NiS2 nanocages (HNCs) with hierarchical walls, high-density lattice defects and abundant grain boundaries (GBs). Through mechanism analysis, we find the injection rate determines the concentration of S2− in the steady state and thus control the growth pattern, leading to the formation of NiS2 HNCs at slow etching kinetics and NiCo PBA@NiS2 frames at fast etching kinetics, respectively. Benefiting from the ultrathin and hierarchical walls that minimize the mass transport restrictions, the high-density lattice defects and GBs that offer abundant unsaturated reaction sites, the NiS2 HNCs exhibit obviously enhanced electrocatalytic activity and stability toward OER, with overpotential of 255 mV to reach 10 mA/cm2 and a Tafel slope of 27.44 mV/dec, surpassing the performances of NiCo PBA@NiS2 frames and commercial RuO2.
2025, 36(5): 110015
doi: 10.1016/j.cclet.2024.110015
摘要:
Mn-based P2-type oxides are considered as promising cathodes for Na-ion batteries; however, they face significant challenges, including structural degradation when charged at high cutoff voltages and structural changes upon storing in a humid atmosphere. In response to these issues, we have designed an oxide with co-doping of Cu and Al which can balance both cost and structural stability. The redox reaction of Cu2+/3+ can provide certain charge compensation, and the introduction of Al can further suppress the Jahn-Teller effect of Mn, thereby achieving superior long-term cycling performance. The ex-situ XRD testing indicates that Cu/Al co-doping can effectively suppress the phase transition of P2-O2 at high voltage, thereby explaining the improvement in electrochemical performance. DFT calculations reveal a high chemical tolerance to moisture, with lower adsorption energy for H2O compared to pure Na0.67Cu0.25Mn0.75O2. A representative Na0.67Cu0.20Al0.05Mn0.75O2 cathode demonstrates impressive reversible capacities of 148.7 mAh/g at 0.2 C, along with a remarkable capacity retention of 79.1% (2 C, 500 cycles).
Mn-based P2-type oxides are considered as promising cathodes for Na-ion batteries; however, they face significant challenges, including structural degradation when charged at high cutoff voltages and structural changes upon storing in a humid atmosphere. In response to these issues, we have designed an oxide with co-doping of Cu and Al which can balance both cost and structural stability. The redox reaction of Cu2+/3+ can provide certain charge compensation, and the introduction of Al can further suppress the Jahn-Teller effect of Mn, thereby achieving superior long-term cycling performance. The ex-situ XRD testing indicates that Cu/Al co-doping can effectively suppress the phase transition of P2-O2 at high voltage, thereby explaining the improvement in electrochemical performance. DFT calculations reveal a high chemical tolerance to moisture, with lower adsorption energy for H2O compared to pure Na0.67Cu0.25Mn0.75O2. A representative Na0.67Cu0.20Al0.05Mn0.75O2 cathode demonstrates impressive reversible capacities of 148.7 mAh/g at 0.2 C, along with a remarkable capacity retention of 79.1% (2 C, 500 cycles).
2025, 36(5): 110034
doi: 10.1016/j.cclet.2024.110034
摘要:
Environmentally friendly slow-release fertilizers are highly desired in sustainable agriculture. Encapsulating fertilizers can routinely achieve controlled releasing performances but suffers from short-term effectiveness or environmental unfriendliness. In this work, a bio-derived shellac incorporated with poly-dodecyl trimethoxysilane (SL-PDTMS) capsule was developed for long-term controlled releasing urea. Due to enhanced hydrophobicity and thus water resistance, the SL-PDTMS encapsulated urea fertilizer (SPEU) demonstrated a long-term effectiveness of 60 d, compared with SL encapsulated urea fertilizer (SEU, 30 d) and pure urea fertilizer (U, 5 min). In addition, SPEU showed a broad pH tolerance from 5.0 to 9.0, covering most various soil pH conditions. In the pot experiments, promoted growth of maize seedlings was observed after applying SPEU, rendering it promising as a high-performance controlled-released fertilizer.
Environmentally friendly slow-release fertilizers are highly desired in sustainable agriculture. Encapsulating fertilizers can routinely achieve controlled releasing performances but suffers from short-term effectiveness or environmental unfriendliness. In this work, a bio-derived shellac incorporated with poly-dodecyl trimethoxysilane (SL-PDTMS) capsule was developed for long-term controlled releasing urea. Due to enhanced hydrophobicity and thus water resistance, the SL-PDTMS encapsulated urea fertilizer (SPEU) demonstrated a long-term effectiveness of 60 d, compared with SL encapsulated urea fertilizer (SEU, 30 d) and pure urea fertilizer (U, 5 min). In addition, SPEU showed a broad pH tolerance from 5.0 to 9.0, covering most various soil pH conditions. In the pot experiments, promoted growth of maize seedlings was observed after applying SPEU, rendering it promising as a high-performance controlled-released fertilizer.
2025, 36(5): 110043
doi: 10.1016/j.cclet.2024.110043
摘要:
Carbon monoxide (CO) is a crucial gaseous signaling molecule that regulates various physiological and pathological processes, and may exert an anti-inflammatory and protective role in drug-induced liver injury (DILI). Despite this, understanding the exact relationship between CO and the occurrence and development of DILI remains challenging. Hence, there is an urgent need to develop a reliable and robust tool for the rapid visual detection and assessment of CO in this context. Herein, we presented a novel near-infrared (NIR) fluorescent nanoprobe with aggregation-induced emission (AIE) properties and excited-state intramolecular proton transfer (ESIPT) characteristics for the detection and imaging of CO both in vitro and in vivo. Simultaneously, the nanoprobe enables self-assembly form nanoaggregates in aqueous media with high biocompatible, which can sense CO in situ through the conversion of yellow-to-red fluorescence facilitated aggregation-induced dual-color fluorescence. What is more, this nanoprobe shows ratiometric respond to CO, which demonstrates excellent stability, high sensitivity (with a detection limit of 12.5 nmol/L), and superior selectivity. Crucially, this nanoprobe enables the visual detection of exogenous and endogenous CO in living cells and tissues affected by DILI, offering a user-friendly tool for real-time visualization of CO in living system. Hence, it holds great promise in advancing our understanding of CO's role.
Carbon monoxide (CO) is a crucial gaseous signaling molecule that regulates various physiological and pathological processes, and may exert an anti-inflammatory and protective role in drug-induced liver injury (DILI). Despite this, understanding the exact relationship between CO and the occurrence and development of DILI remains challenging. Hence, there is an urgent need to develop a reliable and robust tool for the rapid visual detection and assessment of CO in this context. Herein, we presented a novel near-infrared (NIR) fluorescent nanoprobe with aggregation-induced emission (AIE) properties and excited-state intramolecular proton transfer (ESIPT) characteristics for the detection and imaging of CO both in vitro and in vivo. Simultaneously, the nanoprobe enables self-assembly form nanoaggregates in aqueous media with high biocompatible, which can sense CO in situ through the conversion of yellow-to-red fluorescence facilitated aggregation-induced dual-color fluorescence. What is more, this nanoprobe shows ratiometric respond to CO, which demonstrates excellent stability, high sensitivity (with a detection limit of 12.5 nmol/L), and superior selectivity. Crucially, this nanoprobe enables the visual detection of exogenous and endogenous CO in living cells and tissues affected by DILI, offering a user-friendly tool for real-time visualization of CO in living system. Hence, it holds great promise in advancing our understanding of CO's role.
2025, 36(5): 110045
doi: 10.1016/j.cclet.2024.110045
摘要:
This study presents an approach to enhanced cancer immunotherapy through the in situ synthesis of potassium permanganate (KMnO4) derived manganese dioxide (MnO2) micro/nano-adjuvants. Addressing the limitations of traditional immunotherapy due to patient variability and the complexity of the tumor microenvironment, our research establishes KMnO4 as a potent immunomodulator that enhances the efficacy of anti-programmed death-ligand 1 (αPD-L1) antibodies. The in situ synthesized MnO2 adjuvants in the tumor exhibit direct interactions with biological systems, leading to the reduction of MnO2 to Mn2+ within the tumor, and thereby improving the microenvironment for immune cell activity. Our in vitro and in vivo models demonstrate KMnO4’s capability to induce concentration-dependent cytotoxicity in tumor cells, triggering DNA damage and apoptosis. It also potentiates immunogenic cell death by upregulating calreticulin and high mobility group box 1 (HMGB1) on the cell surface. The combination of KMnO4 with αPD-L1 antibodies substantially inhibits tumor growth, promotes dendritic cell maturation, and enhances CD8+ T cell infiltration, resulting in a significant phenotypic shift in tumor-associated macrophages towards a pro-inflammatory M1 profile. Our findings advocate for further research into the long-term efficacy of KMnO4 and its application in diverse tumor models, emphasizing its potential to redefine immune checkpoint blockade therapy and offering a new vista in the fight against cancer.
This study presents an approach to enhanced cancer immunotherapy through the in situ synthesis of potassium permanganate (KMnO4) derived manganese dioxide (MnO2) micro/nano-adjuvants. Addressing the limitations of traditional immunotherapy due to patient variability and the complexity of the tumor microenvironment, our research establishes KMnO4 as a potent immunomodulator that enhances the efficacy of anti-programmed death-ligand 1 (αPD-L1) antibodies. The in situ synthesized MnO2 adjuvants in the tumor exhibit direct interactions with biological systems, leading to the reduction of MnO2 to Mn2+ within the tumor, and thereby improving the microenvironment for immune cell activity. Our in vitro and in vivo models demonstrate KMnO4’s capability to induce concentration-dependent cytotoxicity in tumor cells, triggering DNA damage and apoptosis. It also potentiates immunogenic cell death by upregulating calreticulin and high mobility group box 1 (HMGB1) on the cell surface. The combination of KMnO4 with αPD-L1 antibodies substantially inhibits tumor growth, promotes dendritic cell maturation, and enhances CD8+ T cell infiltration, resulting in a significant phenotypic shift in tumor-associated macrophages towards a pro-inflammatory M1 profile. Our findings advocate for further research into the long-term efficacy of KMnO4 and its application in diverse tumor models, emphasizing its potential to redefine immune checkpoint blockade therapy and offering a new vista in the fight against cancer.
2025, 36(5): 110053
doi: 10.1016/j.cclet.2024.110053
摘要:
Crucial for mediating inflammation and the perception of pain, the ion channel known as transient receptor potential ankyrin 1 (TRPA1) holds significant importance. It contributes to the increased production of cytokines in the inflammatory cells of cartilage affected by osteoarthritis and represents a promising target for the treatment of this condition. By leveraging the unique advantages of liposomes, a composite microsphere drug delivery system with stable structural properties and high adaptability can be developed, providing a new strategy for osteoarthritis (OA) drug therapy. The liposomes as drug reservoirs for TRPA1 inhibitors were loaded into hyaluronic acid methacrylate (HAMA) hydrogels to make hydrogel microspheres via microfluidic technology. An in vitro inflammatory chondrocyte model was established with interleukin-1β (IL-1β) to demonstrate HAMA@Lipo@HC's capabilities. A destabilization of the medial meniscus (DMM) mouse model was also created to evaluate the efficacy of intra-articular injections for treating OA. HAMA@Lipo@HC has a uniform particle-size distribution and is injectable. The drug encapsulation rate was 64.29% ± 2.58%, with a sustained release period of 28 days. Inhibition of TRPA1 via HC-030031 effectively alleviated IL-1β-induced chondrocyte inflammation and matrix degradation. In DMM model OA mice, microspheres showed good long-term sustained drug release properties, improved joint inflammation microenvironment, reduced articular cartilage damage and decreased mechanical nociceptive threshold. This research pioneers the creation of a drug delivery system tailored for delivery into the joint cavity, focusing on TRPA1 as a therapeutic target for osteoarthritis. Additionally, it offers a cutting-edge drug delivery platform aimed at addressing diseases linked to inflammation.
Crucial for mediating inflammation and the perception of pain, the ion channel known as transient receptor potential ankyrin 1 (TRPA1) holds significant importance. It contributes to the increased production of cytokines in the inflammatory cells of cartilage affected by osteoarthritis and represents a promising target for the treatment of this condition. By leveraging the unique advantages of liposomes, a composite microsphere drug delivery system with stable structural properties and high adaptability can be developed, providing a new strategy for osteoarthritis (OA) drug therapy. The liposomes as drug reservoirs for TRPA1 inhibitors were loaded into hyaluronic acid methacrylate (HAMA) hydrogels to make hydrogel microspheres via microfluidic technology. An in vitro inflammatory chondrocyte model was established with interleukin-1β (IL-1β) to demonstrate HAMA@Lipo@HC's capabilities. A destabilization of the medial meniscus (DMM) mouse model was also created to evaluate the efficacy of intra-articular injections for treating OA. HAMA@Lipo@HC has a uniform particle-size distribution and is injectable. The drug encapsulation rate was 64.29% ± 2.58%, with a sustained release period of 28 days. Inhibition of TRPA1 via HC-030031 effectively alleviated IL-1β-induced chondrocyte inflammation and matrix degradation. In DMM model OA mice, microspheres showed good long-term sustained drug release properties, improved joint inflammation microenvironment, reduced articular cartilage damage and decreased mechanical nociceptive threshold. This research pioneers the creation of a drug delivery system tailored for delivery into the joint cavity, focusing on TRPA1 as a therapeutic target for osteoarthritis. Additionally, it offers a cutting-edge drug delivery platform aimed at addressing diseases linked to inflammation.
2025, 36(5): 110067
doi: 10.1016/j.cclet.2024.110067
摘要:
Postoperative recurrence and metastasis are still the main challenges of cancer therapy. Tumor vaccines that induce potent and long-lasting immune activation have great potential for postoperative cancer therapy. However, the clinical effects of therapeutic tumor vaccines are unsatisfactory due to immune escape caused by the lack of immunogenicity after surgery and the local fibrosis barrier of the tumor which limits effector T cell infiltration. To overcome these challenges, we developed an injectable hydrogel-based tumor vaccine, RATG, which contains whole tumor cell lysates (TCL), Toll-like receptor (TLR) 7/8 agonist imiquimod (R837) and an antifibrotic drug ARV-825. TCL and R837 were loaded onto the hydrogel to achieve a powerful reservoir of antigens and adjuvants that induced potent and lasting immune activation. More importantly, ARV-825 could be slowly and sustainably released in the tumor resection cavity to downregulate α-smooth muscle actin (α-SMA) and collagen levels, disintegrate fibrosis barriers and promote T cell infiltration after immune activation to reduce immune escape. In addition, ARV-825 also directly acted on the remaining tumor cells to degrade bromodomain-containing protein 4 (BRD4) which is a critical epigenetic reader overexpressed in tumor cells, inhibiting tumor cell migration and invasion. Therefore, our injectable hydrogel created a powerful immune niche in postoperative tumor resection cavity, significantly enhancing the efficacy of tumor vaccines. Our strategy potently activates the immune system and disintegrates the fibrotic barrier of residual tumors with immune microenvironment remodeling in situ, showing anti-recurrence and anti-metastatic effects, and provides a new paradigm for postoperative treatment of tumors.
Postoperative recurrence and metastasis are still the main challenges of cancer therapy. Tumor vaccines that induce potent and long-lasting immune activation have great potential for postoperative cancer therapy. However, the clinical effects of therapeutic tumor vaccines are unsatisfactory due to immune escape caused by the lack of immunogenicity after surgery and the local fibrosis barrier of the tumor which limits effector T cell infiltration. To overcome these challenges, we developed an injectable hydrogel-based tumor vaccine, RATG, which contains whole tumor cell lysates (TCL), Toll-like receptor (TLR) 7/8 agonist imiquimod (R837) and an antifibrotic drug ARV-825. TCL and R837 were loaded onto the hydrogel to achieve a powerful reservoir of antigens and adjuvants that induced potent and lasting immune activation. More importantly, ARV-825 could be slowly and sustainably released in the tumor resection cavity to downregulate α-smooth muscle actin (α-SMA) and collagen levels, disintegrate fibrosis barriers and promote T cell infiltration after immune activation to reduce immune escape. In addition, ARV-825 also directly acted on the remaining tumor cells to degrade bromodomain-containing protein 4 (BRD4) which is a critical epigenetic reader overexpressed in tumor cells, inhibiting tumor cell migration and invasion. Therefore, our injectable hydrogel created a powerful immune niche in postoperative tumor resection cavity, significantly enhancing the efficacy of tumor vaccines. Our strategy potently activates the immune system and disintegrates the fibrotic barrier of residual tumors with immune microenvironment remodeling in situ, showing anti-recurrence and anti-metastatic effects, and provides a new paradigm for postoperative treatment of tumors.
2025, 36(5): 110069
doi: 10.1016/j.cclet.2024.110069
摘要:
Efficient electrocatalysts for oxygen reduction reaction (ORR) show significant importance for advancing the performance and affordability of proton exchange membrane fuel cells and other energy conversion devices. Herein, PtCo3 nanoalloys dispersed on a carbon black support, were prepared using ultrafast Joule heating method. By tuning the heating modes, such as high-temperature shock and heating for 2 s, two kinds of PtCo3 nanoalloys with varying crystallinities were obtained, referred to as PtCo3HTS (average size of 5.4 nm) and PtCo3HT-2 s (average size of 6.4 nm), respectively. Impressively, PtCo3HTS exhibited superior electrocatalytic ORR activity and stability (E1/2 = 0.897 V vs. RHE and 36 mV negative shift after 50, 000 cycles), outperforming PtCo3HT-2 s (E1/2 = 0.872 V and 16.2 mV negative shift), as well as the commercial Pt/C (20 wt%) catalyst (E1/2 = 0.847 V and 21.0 mV negative shift). The enhanced ORR performance of PtCo3HTS may be attributed to its low crystallinity, which results in an active local electronic structure and chemical state, as confirmed by X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) analyses. The ultrafast Joule heating method showed great potential for crystallinity engineering, offering a promising pathway to revolutionize the manufacturing of cost-effective and environmentally friendly catalysts for clean energy applications.
Efficient electrocatalysts for oxygen reduction reaction (ORR) show significant importance for advancing the performance and affordability of proton exchange membrane fuel cells and other energy conversion devices. Herein, PtCo3 nanoalloys dispersed on a carbon black support, were prepared using ultrafast Joule heating method. By tuning the heating modes, such as high-temperature shock and heating for 2 s, two kinds of PtCo3 nanoalloys with varying crystallinities were obtained, referred to as PtCo3HTS (average size of 5.4 nm) and PtCo3HT-2 s (average size of 6.4 nm), respectively. Impressively, PtCo3HTS exhibited superior electrocatalytic ORR activity and stability (E1/2 = 0.897 V vs. RHE and 36 mV negative shift after 50, 000 cycles), outperforming PtCo3HT-2 s (E1/2 = 0.872 V and 16.2 mV negative shift), as well as the commercial Pt/C (20 wt%) catalyst (E1/2 = 0.847 V and 21.0 mV negative shift). The enhanced ORR performance of PtCo3HTS may be attributed to its low crystallinity, which results in an active local electronic structure and chemical state, as confirmed by X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) analyses. The ultrafast Joule heating method showed great potential for crystallinity engineering, offering a promising pathway to revolutionize the manufacturing of cost-effective and environmentally friendly catalysts for clean energy applications.
2025, 36(5): 110073
doi: 10.1016/j.cclet.2024.110073
摘要:
Diseases associated with bacterial infection, especially those caused by gram-negative bacteria, have been posing a serious threat to human health. Photodynamic therapy based on aggregation-induced emission (AIE) photosensitizer have recently emerged and provided a promising approach for bacterial discrimination and efficient photodynamic antimicrobial applications. However, they often suffer from the shorter excitation wavelength and lower molar extinction coefficients in the visible region, severely limiting their further applications. Herein, three novel BF2-curcuminoid-based AIE photosensitizers, TBBC, TBC and TBBC-C8, have been rationally designed and successfully developed, in which OCH3- and OC8H17-substituted tetraphenylethene (TPE) groups serve as both electron donor (D) and AIE active moieties, BF2bdk group functions as electron acceptor (A), and styrene (or ethylene) group as π-bridge in this D-π-A-π-D system, respectively. As expected, these resulting BF2-curcuminoids presented solvent-dependent photophysical properties with large molar extinction coefficients in solutions and excellent AIE properties. Notably, TBBC showed an effective singlet oxygen generation efficiency thanks to the smaller singlet-triplet energy gap (ΔEST), and remarkable photostability under green light exposure at 530 nm (8.9 mW/cm2). More importantly, TBBC was demonstrated effectiveness in selective staining and photodynamic killing of Escherichia coli (E. coli) in vitro probably due to its optimal molecular size compared with TBC and TBBC-C8. Therefore, TBBC will have great potential as a novel AIE photosensitizer to apply in the discrimination and selective sterilization between Gram-positive and Gram-negative bacteria.
Diseases associated with bacterial infection, especially those caused by gram-negative bacteria, have been posing a serious threat to human health. Photodynamic therapy based on aggregation-induced emission (AIE) photosensitizer have recently emerged and provided a promising approach for bacterial discrimination and efficient photodynamic antimicrobial applications. However, they often suffer from the shorter excitation wavelength and lower molar extinction coefficients in the visible region, severely limiting their further applications. Herein, three novel BF2-curcuminoid-based AIE photosensitizers, TBBC, TBC and TBBC-C8, have been rationally designed and successfully developed, in which OCH3- and OC8H17-substituted tetraphenylethene (TPE) groups serve as both electron donor (D) and AIE active moieties, BF2bdk group functions as electron acceptor (A), and styrene (or ethylene) group as π-bridge in this D-π-A-π-D system, respectively. As expected, these resulting BF2-curcuminoids presented solvent-dependent photophysical properties with large molar extinction coefficients in solutions and excellent AIE properties. Notably, TBBC showed an effective singlet oxygen generation efficiency thanks to the smaller singlet-triplet energy gap (ΔEST), and remarkable photostability under green light exposure at 530 nm (8.9 mW/cm2). More importantly, TBBC was demonstrated effectiveness in selective staining and photodynamic killing of Escherichia coli (E. coli) in vitro probably due to its optimal molecular size compared with TBC and TBBC-C8. Therefore, TBBC will have great potential as a novel AIE photosensitizer to apply in the discrimination and selective sterilization between Gram-positive and Gram-negative bacteria.
2025, 36(5): 110082
doi: 10.1016/j.cclet.2024.110082
摘要:
Acute lung injury (ALI) is a serious clinical condition with a high mortality rate. Oxidative stress and inflammatory responses play pivotal roles in the pathogenesis of ALI. ONOO− is a key mediator that exacerbates oxidative damage and microvascular permeability in ALI. Accurate detection of ONOO− would facilitate early diagnosis and intervention in ALI. Near-infrared fluorescence (NIRF) probes offer new solutions due to their sensitivity, depth of tissue penetration, and imaging capabilities. However, the developed ONOO− fluorescent probes face problems such as interference from other reactive oxygen species and easy intracellular diffusion. To address these issues, we introduced an innovative self-immobilizing NIRF probe, DCI2F-OTf, which was capable of monitoring ONOO− in vitro and in vivo. Importantly, leveraging the high reactivity of the methylene quinone (QM) intermediate, DCI2F-OTf was able to covalently label proteins in the presence of ONOO−, enabling in situ imaging. In mice models of ALI, DCI2F-OTf enabled real-time imaging of ONOO− levels and found that ONOO− was tightly correlated with the progression of ALI. Our findings demonstrated that DCI2F-OTf was a promising chemical tool for the detection of ONOO−, which could help to gain insight into the pathogenesis of ALI and monitor treatment efficacy.
Acute lung injury (ALI) is a serious clinical condition with a high mortality rate. Oxidative stress and inflammatory responses play pivotal roles in the pathogenesis of ALI. ONOO− is a key mediator that exacerbates oxidative damage and microvascular permeability in ALI. Accurate detection of ONOO− would facilitate early diagnosis and intervention in ALI. Near-infrared fluorescence (NIRF) probes offer new solutions due to their sensitivity, depth of tissue penetration, and imaging capabilities. However, the developed ONOO− fluorescent probes face problems such as interference from other reactive oxygen species and easy intracellular diffusion. To address these issues, we introduced an innovative self-immobilizing NIRF probe, DCI2F-OTf, which was capable of monitoring ONOO− in vitro and in vivo. Importantly, leveraging the high reactivity of the methylene quinone (QM) intermediate, DCI2F-OTf was able to covalently label proteins in the presence of ONOO−, enabling in situ imaging. In mice models of ALI, DCI2F-OTf enabled real-time imaging of ONOO− levels and found that ONOO− was tightly correlated with the progression of ALI. Our findings demonstrated that DCI2F-OTf was a promising chemical tool for the detection of ONOO−, which could help to gain insight into the pathogenesis of ALI and monitor treatment efficacy.
2025, 36(5): 110084
doi: 10.1016/j.cclet.2024.110084
摘要:
Glioma is a severe malignant brain tumor marked by an exceedingly dire prognosis and elevated incidence of recurrence. The resilience of such tumors to chemotherapeutic agents, coupled with the formidable obstacle the blood-brain barrier (BBB) presents to most pharmacological interventions are major challenges in anti-glioma therapy. In an endeavor to surmount these impediments, we have synergized pH-sensitive nanoparticles carrying doxorubicin and apatinib to amplify the anti-neoplastic efficacy with cyclic arginine–glycine–aspartate acid (cRGD) modification. In this study, we found that the combination of doxorubicin (DOX) and apatinib (AP) showed a significant synergistic effect, achieved through cytotoxicity and induction of apoptosis, which might be due to the increased intracellular uptake of DOX following AP treatment. Besides, polycaprolactone-polyethylene glycol-cRGD (PCL-PEG-cRGD) drug carrier could cross the BBB by its targeting ability, and then deliver the drug to the glioma site via pH-responsive release, increasing the concentration of the drugs in the tumor. Meanwhile, DOX/AP-loaded PCL-PEG-cRGD nanoparticles effectively inhibited cell proliferation, enhanced glioma cell apoptosis, and retarded tumor growth in vivo. These results collectively identified DOX/AP-loaded PCL-PEG-cRGD nanoparticles as a promising therapeutic candidate for the treatment of glioma.
Glioma is a severe malignant brain tumor marked by an exceedingly dire prognosis and elevated incidence of recurrence. The resilience of such tumors to chemotherapeutic agents, coupled with the formidable obstacle the blood-brain barrier (BBB) presents to most pharmacological interventions are major challenges in anti-glioma therapy. In an endeavor to surmount these impediments, we have synergized pH-sensitive nanoparticles carrying doxorubicin and apatinib to amplify the anti-neoplastic efficacy with cyclic arginine–glycine–aspartate acid (cRGD) modification. In this study, we found that the combination of doxorubicin (DOX) and apatinib (AP) showed a significant synergistic effect, achieved through cytotoxicity and induction of apoptosis, which might be due to the increased intracellular uptake of DOX following AP treatment. Besides, polycaprolactone-polyethylene glycol-cRGD (PCL-PEG-cRGD) drug carrier could cross the BBB by its targeting ability, and then deliver the drug to the glioma site via pH-responsive release, increasing the concentration of the drugs in the tumor. Meanwhile, DOX/AP-loaded PCL-PEG-cRGD nanoparticles effectively inhibited cell proliferation, enhanced glioma cell apoptosis, and retarded tumor growth in vivo. These results collectively identified DOX/AP-loaded PCL-PEG-cRGD nanoparticles as a promising therapeutic candidate for the treatment of glioma.
2025, 36(5): 110097
doi: 10.1016/j.cclet.2024.110097
摘要:
Insufficient endogenous H2O2 for generation of hydroxyl radicals (•OH) has strikingly compromised anti-tumor benefits of ferroptosis. Herein, we develop a H2O2 self-supplying nanoparticle based on a pH-responsive lipopeptide C18-pHis10. Inspired by the coordinate pattern of hemoglobin binding heme, Fe2+ and tetrakis(4-carboxyphenyl)porphyrin (TCPP) were delicately encapsulated by formation of coordination compounds with His. Ascorbgyl palmitate (AscP) was also incorporated into the nanoparticles for generation of H2O2 by reduction 1O2 produced from TCPP, meanwhile prevented Fe2+ from being oxidized. The protonation of pHis in acidic endo-lysosome induced the breakage of Fe2+/His/TCPP coordinate interactions, leading to accelerated release of payloads and the following escape to cytoplasm. Upon laser irradiation, TCPP produces excessive 1O2 followed by conversion to H2O2 in the presence of AscP, which is further catalyzed to lethal •OH by Fe2+ via Fenton reaction. The self-supplying H2O2 was found to result significantly higher accumulation of lipid peroxides and more effective tumor inhibition. Overall, this work sheds new a light on H2O2 self-supplying strategy to enhance ferroptosis by taking advantage of 1O2 generated by photodynamic therapy (PDT).
Insufficient endogenous H2O2 for generation of hydroxyl radicals (•OH) has strikingly compromised anti-tumor benefits of ferroptosis. Herein, we develop a H2O2 self-supplying nanoparticle based on a pH-responsive lipopeptide C18-pHis10. Inspired by the coordinate pattern of hemoglobin binding heme, Fe2+ and tetrakis(4-carboxyphenyl)porphyrin (TCPP) were delicately encapsulated by formation of coordination compounds with His. Ascorbgyl palmitate (AscP) was also incorporated into the nanoparticles for generation of H2O2 by reduction 1O2 produced from TCPP, meanwhile prevented Fe2+ from being oxidized. The protonation of pHis in acidic endo-lysosome induced the breakage of Fe2+/His/TCPP coordinate interactions, leading to accelerated release of payloads and the following escape to cytoplasm. Upon laser irradiation, TCPP produces excessive 1O2 followed by conversion to H2O2 in the presence of AscP, which is further catalyzed to lethal •OH by Fe2+ via Fenton reaction. The self-supplying H2O2 was found to result significantly higher accumulation of lipid peroxides and more effective tumor inhibition. Overall, this work sheds new a light on H2O2 self-supplying strategy to enhance ferroptosis by taking advantage of 1O2 generated by photodynamic therapy (PDT).
2025, 36(5): 110098
doi: 10.1016/j.cclet.2024.110098
摘要:
D-D'-A type aza-borondipyrromethenes (aza-BODIPYs) were prepared by Suzuki cross-coupling reaction. Photothermal conversion efficiency of self-assemble aza-BODIPY-based nanoparticles (DA-azaBDP-NPs) with NIR-II emission (λem = 1065 nm) was 37.2% under near infrared (NIR) irradiation, and the outstanding cytotoxicity was triggered by coexistence of DA-azaBDP-NPs and the NIR irradiation, with the decrease of glioblastoma migration and the inhibition of glioblastoma proliferation. DA-azaBDP-NPs could promote glioblastoma autophagy and accelerate the process of cell death. The photothermal therapy (PTT) of DA-azaBDP-NPs can effectively induce glioblastoma death by apoptosis under the NIR irradiation, which is highly promising to be applied in vivo experiments of brain.
D-D'-A type aza-borondipyrromethenes (aza-BODIPYs) were prepared by Suzuki cross-coupling reaction. Photothermal conversion efficiency of self-assemble aza-BODIPY-based nanoparticles (DA-azaBDP-NPs) with NIR-II emission (λem = 1065 nm) was 37.2% under near infrared (NIR) irradiation, and the outstanding cytotoxicity was triggered by coexistence of DA-azaBDP-NPs and the NIR irradiation, with the decrease of glioblastoma migration and the inhibition of glioblastoma proliferation. DA-azaBDP-NPs could promote glioblastoma autophagy and accelerate the process of cell death. The photothermal therapy (PTT) of DA-azaBDP-NPs can effectively induce glioblastoma death by apoptosis under the NIR irradiation, which is highly promising to be applied in vivo experiments of brain.
2025, 36(5): 110105
doi: 10.1016/j.cclet.2024.110105
摘要:
Singlet oxygen (1O2), as the primary reactive oxygen species in photodynamic therapy, can effectively induce excessive oxidative stress to ablate tumors and kill germs in clinical treatment. However, monitoring endogenous 1O2 is greatly challenging due to its extremely short lifetime and high reactivity in biological condition. Herein, we report an ultra-high signal-to-ratio near-infrared chemiluminescent probe (DCM-Cy) for the precise detection of endogenous 1O2 during photodynamic therapy (PDT). The methoxy moiety was removed from enolether unit in DCM-Cy to suppress the potential self-photooxidation reaction, thus greatly eliminating the photoinduced background signals during PDT. Additionally, the compact cyclobutane modification of DCM-Cy resulted in a significant 6-fold increase in cell permeability compared to conventional adamantane-dioxane probes. Therefore, our "step-by-step" strategy for DCM-Cy addressed the limitations of traditional chemiluminescent (CL) probes for 1O2, enabling effectively tracking of endogenous 1O2 level changes in living cells, pathogenic bacteria and mice in PDT.
Singlet oxygen (1O2), as the primary reactive oxygen species in photodynamic therapy, can effectively induce excessive oxidative stress to ablate tumors and kill germs in clinical treatment. However, monitoring endogenous 1O2 is greatly challenging due to its extremely short lifetime and high reactivity in biological condition. Herein, we report an ultra-high signal-to-ratio near-infrared chemiluminescent probe (DCM-Cy) for the precise detection of endogenous 1O2 during photodynamic therapy (PDT). The methoxy moiety was removed from enolether unit in DCM-Cy to suppress the potential self-photooxidation reaction, thus greatly eliminating the photoinduced background signals during PDT. Additionally, the compact cyclobutane modification of DCM-Cy resulted in a significant 6-fold increase in cell permeability compared to conventional adamantane-dioxane probes. Therefore, our "step-by-step" strategy for DCM-Cy addressed the limitations of traditional chemiluminescent (CL) probes for 1O2, enabling effectively tracking of endogenous 1O2 level changes in living cells, pathogenic bacteria and mice in PDT.
2025, 36(5): 110106
doi: 10.1016/j.cclet.2024.110106
摘要:
Interstitial hypertension and extracellular matrix (ECM) barriers imposed by cancer-associated fibroblasts (CAFs) at the tumor site significantly impede the retention of intratumorally administered oncolytic viruses (OVs) as well as their efficacy in infecting and eradicating tumor cells. Herein, a stable, controllable, and easily prepared hydrogel was developed for employing a differential release strategy to deliver OVs. The oncolytic herpes simplex virus-2 (oH2) particles were loaded within sodium alginate (ALG), together with the small molecule drug PT-100 targeting CAFs. The rapid release of PT-100 functions as an anti-CAFs agent, reducing ECM, and alleviating interstitial pressure at the tumor site. Consequently, the delayed release of oH2 could more effectively invade and eradicate tumor cells while also facilitating enhanced infiltration of immune cells into the tumor microenvironment, thereby establishing an immunologically favorable milieu against tumors. This approach holds significant potential for achieving highly efficient oncolytic virus therapy with minimal toxicity, particularly in tumors rich in stromal components.
Interstitial hypertension and extracellular matrix (ECM) barriers imposed by cancer-associated fibroblasts (CAFs) at the tumor site significantly impede the retention of intratumorally administered oncolytic viruses (OVs) as well as their efficacy in infecting and eradicating tumor cells. Herein, a stable, controllable, and easily prepared hydrogel was developed for employing a differential release strategy to deliver OVs. The oncolytic herpes simplex virus-2 (oH2) particles were loaded within sodium alginate (ALG), together with the small molecule drug PT-100 targeting CAFs. The rapid release of PT-100 functions as an anti-CAFs agent, reducing ECM, and alleviating interstitial pressure at the tumor site. Consequently, the delayed release of oH2 could more effectively invade and eradicate tumor cells while also facilitating enhanced infiltration of immune cells into the tumor microenvironment, thereby establishing an immunologically favorable milieu against tumors. This approach holds significant potential for achieving highly efficient oncolytic virus therapy with minimal toxicity, particularly in tumors rich in stromal components.
2025, 36(5): 110116
doi: 10.1016/j.cclet.2024.110116
摘要:
Constructing multi-dimensional hydrogen bond (H-bond) regulated single-molecule systems with multi-emission remains a challenge. Herein, we report the design of a new excited-state intramolecular proton transfer (ESIPT) featured chromophore (HBT-DPI) that shows flexible emission tunability via the multi-dimensional regulation of intra- and intermolecular H-bonds. The feature of switchable intramolecular H-bonds is induced via incorporating several hydrogen bond acceptors and donors into one single HBT-DPI molecule, allowing the "turn on/off" of ESIPT process by forming isomers with distinct intramolecular H-bonds configurations. In response to different external H-bonding environments, the obtained four types of crystal/cocrystals vary in the contents of isomers and the molecular packing modes, which are mainly guided by the intermolecular H-bonds, exhibiting non-emissive features or emissions ranging from green to orange. Utilizing the feature of intermolecular H-bond guided molecular packing, we demonstrate the utility of this fluorescent material for visualizing hydrophobic/hydrophilic areas on large-scale heterogeneous surfaces of modified poly(1,1-difluoroethylene) (PVDF) membranes and quantitatively estimating the surface hydrophobicity, providing a new approach for hydrophobicity/hydrophilicity monitoring and measurement. Overall, this study represents a new design strategy for constructing multi-dimensional hydrogen bond regulated ESIPT-based fluorescent materials that enable multiple emissions and unique applications.
Constructing multi-dimensional hydrogen bond (H-bond) regulated single-molecule systems with multi-emission remains a challenge. Herein, we report the design of a new excited-state intramolecular proton transfer (ESIPT) featured chromophore (HBT-DPI) that shows flexible emission tunability via the multi-dimensional regulation of intra- and intermolecular H-bonds. The feature of switchable intramolecular H-bonds is induced via incorporating several hydrogen bond acceptors and donors into one single HBT-DPI molecule, allowing the "turn on/off" of ESIPT process by forming isomers with distinct intramolecular H-bonds configurations. In response to different external H-bonding environments, the obtained four types of crystal/cocrystals vary in the contents of isomers and the molecular packing modes, which are mainly guided by the intermolecular H-bonds, exhibiting non-emissive features or emissions ranging from green to orange. Utilizing the feature of intermolecular H-bond guided molecular packing, we demonstrate the utility of this fluorescent material for visualizing hydrophobic/hydrophilic areas on large-scale heterogeneous surfaces of modified poly(1,1-difluoroethylene) (PVDF) membranes and quantitatively estimating the surface hydrophobicity, providing a new approach for hydrophobicity/hydrophilicity monitoring and measurement. Overall, this study represents a new design strategy for constructing multi-dimensional hydrogen bond regulated ESIPT-based fluorescent materials that enable multiple emissions and unique applications.
2025, 36(5): 110119
doi: 10.1016/j.cclet.2024.110119
摘要:
Photodynamic therapy (PDT) has emerged as a promising approach for tumor treatment due to its non-invasiveness and high selectivity. However, the off-target activation of phototoxicity and the limited availability of tumor-specific biomarkers pose challenges for effective PDT. Here, we present the development of a novel ratiometric near-infrared-Ⅱ (NIR-Ⅱ) fluorescent organic nanoprobe, BTz-IC@IR1061, which responds specifically to hypochlorite (HClO) within tumors. This nanoprobe allows ratiometric fluorescence imaging to monitor and guide activated tumor PDT. BTz-IC@IR1061 nanoparticles were synthesized by codoping the small molecule dye BTz-IC, which generates reactive oxygen species (ROS), with the commercial dye IR1061. The presence of HClO selectively activates the fluorescence and photodynamic properties of BTz-IC while destroying IR1061, enabling controlled release of ROS for tumor therapy. We demonstrated the high selectivity of the nanoprobe for HClO, as well as its excellent photostability, photoacoustic imaging capability, and photothermal effects. Furthermore, in vivo studies revealed effective tumor targeting and remarkable tumor growth inhibition through tumor-activated PDT. Our findings highlight the potential of BTz-IC@IR1061 as a promising tool for tumor-specific PDT, providing new opportunities for precise and controlled cancer therapy.
Photodynamic therapy (PDT) has emerged as a promising approach for tumor treatment due to its non-invasiveness and high selectivity. However, the off-target activation of phototoxicity and the limited availability of tumor-specific biomarkers pose challenges for effective PDT. Here, we present the development of a novel ratiometric near-infrared-Ⅱ (NIR-Ⅱ) fluorescent organic nanoprobe, BTz-IC@IR1061, which responds specifically to hypochlorite (HClO) within tumors. This nanoprobe allows ratiometric fluorescence imaging to monitor and guide activated tumor PDT. BTz-IC@IR1061 nanoparticles were synthesized by codoping the small molecule dye BTz-IC, which generates reactive oxygen species (ROS), with the commercial dye IR1061. The presence of HClO selectively activates the fluorescence and photodynamic properties of BTz-IC while destroying IR1061, enabling controlled release of ROS for tumor therapy. We demonstrated the high selectivity of the nanoprobe for HClO, as well as its excellent photostability, photoacoustic imaging capability, and photothermal effects. Furthermore, in vivo studies revealed effective tumor targeting and remarkable tumor growth inhibition through tumor-activated PDT. Our findings highlight the potential of BTz-IC@IR1061 as a promising tool for tumor-specific PDT, providing new opportunities for precise and controlled cancer therapy.
2025, 36(5): 110128
doi: 10.1016/j.cclet.2024.110128
摘要:
The bioactive constituents found in natural products (NPs) are crucial in protein-ligand interactions and drug discovery. However, it is difficult to identify ligand molecules from complex NPs that specifically bind to target protein, which often requires time-consuming and labor-intensive processes such as isolation and enrichment. To address this issue, in this study we developed a method that combines ultra-high performance liquid chromatography-electrospray ionization-mass spectrometry (UHPLC-ESI-MS) with molecular dynamics (MD) simulation to identify and observe, rapidly and efficiently, the bioactive components in NPs that bind to specific protein target. In this method, a specific protein target was introduced online using a three-way valve to form a protein-ligand complex. The complex was then detected in real time using high-resolution MS to identify potential ligands. Based on our method, only 10 molecules from green tea (a representative natural product), including the commonly reported epigallocatechin gallate (EGCG) and epicatechin gallate (ECG), as well as the previously unreported eepicatechin (4β→8)-epigallocatechin 3-O-gallate (EC-EGCG) and eepiafzelechin 3-O-gallate-(4β→8)-epigallocatechin 3-O-gallate (EFG-EGCG), were screened out, which could form complexes with Aβ1–42 (a representative protein target), and could be potential ligands of Aβ1–42. Among of them, EC-EGCG demonstrated the highest binding free energy with Aβ1–42 (−68.54 ± 3.82 kcal/mol). On the other side, even though the caffeine had the highest signal among green tea extracts, it was not observed to form a complex with Aβ1–42. Compared to other methods such as affinity selection mass spectrometry (ASMS) and native MS, our method is easy to operate and interpret the data. Undoubtedly, it provides a new methodology for potential drug discovery in NPs, and will accelerate the research on screening ligands for specific proteins from complex NPs.
The bioactive constituents found in natural products (NPs) are crucial in protein-ligand interactions and drug discovery. However, it is difficult to identify ligand molecules from complex NPs that specifically bind to target protein, which often requires time-consuming and labor-intensive processes such as isolation and enrichment. To address this issue, in this study we developed a method that combines ultra-high performance liquid chromatography-electrospray ionization-mass spectrometry (UHPLC-ESI-MS) with molecular dynamics (MD) simulation to identify and observe, rapidly and efficiently, the bioactive components in NPs that bind to specific protein target. In this method, a specific protein target was introduced online using a three-way valve to form a protein-ligand complex. The complex was then detected in real time using high-resolution MS to identify potential ligands. Based on our method, only 10 molecules from green tea (a representative natural product), including the commonly reported epigallocatechin gallate (EGCG) and epicatechin gallate (ECG), as well as the previously unreported eepicatechin (4β→8)-epigallocatechin 3-O-gallate (EC-EGCG) and eepiafzelechin 3-O-gallate-(4β→8)-epigallocatechin 3-O-gallate (EFG-EGCG), were screened out, which could form complexes with Aβ1–42 (a representative protein target), and could be potential ligands of Aβ1–42. Among of them, EC-EGCG demonstrated the highest binding free energy with Aβ1–42 (−68.54 ± 3.82 kcal/mol). On the other side, even though the caffeine had the highest signal among green tea extracts, it was not observed to form a complex with Aβ1–42. Compared to other methods such as affinity selection mass spectrometry (ASMS) and native MS, our method is easy to operate and interpret the data. Undoubtedly, it provides a new methodology for potential drug discovery in NPs, and will accelerate the research on screening ligands for specific proteins from complex NPs.
2025, 36(5): 110130
doi: 10.1016/j.cclet.2024.110130
摘要:
The overuse of surfactants has made them well-known environmental pollutants. So far, it is still a challenge to simultaneously distinguish cationic, anionic, zwitterionic, nonionic surfactants and surfactants with similar structures based on traditional analytical techniques. We developed a high-throughput method for distinguishing various surfactants based on the adaptive emission profile as fingerprints (AEPF). The fluorescence response of the sensor was based on the interaction between surfactants and 1,3-diacetylpyrene (o-DAP) probe. The interaction affected the reversible conversion of free molecules and two aggregates in the solution, thereby changing the relative abundance and the fluorescence intensity ratio of two aggregates emitting different fluorescence. The o-DAP sensor can distinguish four types of surfactants (16 surfactants), especially surfactants of the same type with similar structures. The o-DAP sensor sensitively determined the critical micelle concentration (CMC) of 16 surfactants based on the interaction between o-DAP and surfactants. Additionally, the o-DAP sensor can detect and distinguish artificial vesicles made from different surfactants.
The overuse of surfactants has made them well-known environmental pollutants. So far, it is still a challenge to simultaneously distinguish cationic, anionic, zwitterionic, nonionic surfactants and surfactants with similar structures based on traditional analytical techniques. We developed a high-throughput method for distinguishing various surfactants based on the adaptive emission profile as fingerprints (AEPF). The fluorescence response of the sensor was based on the interaction between surfactants and 1,3-diacetylpyrene (o-DAP) probe. The interaction affected the reversible conversion of free molecules and two aggregates in the solution, thereby changing the relative abundance and the fluorescence intensity ratio of two aggregates emitting different fluorescence. The o-DAP sensor can distinguish four types of surfactants (16 surfactants), especially surfactants of the same type with similar structures. The o-DAP sensor sensitively determined the critical micelle concentration (CMC) of 16 surfactants based on the interaction between o-DAP and surfactants. Additionally, the o-DAP sensor can detect and distinguish artificial vesicles made from different surfactants.
2025, 36(5): 110133
doi: 10.1016/j.cclet.2024.110133
摘要:
Severe traumatic bone healing relies on the involvement of growth factors. However, excessive supplementation of growth factors can lead to ectopic ossification and inflammation. In this study, utilizing the neural regulatory mechanism of bone regeneration, we have developed a multifunctional three dimensions (3D) printed scaffold containing both vasoactive intestinal peptide (VIP) and nerve growth factor (NGF) as an effective new method for achieving bone defect regeneration. The scaffold is provided by a controlled biodegradable and biomechanically matched poly(lactide-ethylene glycol-trimethylene carbonate) (PLTG), providing long-term support for the bone healing cycle. Factor loading is provided by peptide fiber-reinforced biomimetic antimicrobial extracellular matrix (ECM) (B-ECM) hydrogels with different release kinetics, the hydrogel guides rapid bone growth and resists bacterial infection at the early stage of healing. Physical and chemical characterization indicates that the scaffold has good structural stability and mechanical properties, providing an ideal 3D microenvironment for bone reconstruction. In the skull defect model, compared to releasing VIP or NGF alone, this drug delivery system can simulate a natural healing cascade of controllable release factors, significantly accelerating nerve/vascular bone regeneration. In conclusion, this study provides a promising strategy for implanting materials to repair bone defects by utilizing neuroregulatory mechanisms during bone regeneration.
Severe traumatic bone healing relies on the involvement of growth factors. However, excessive supplementation of growth factors can lead to ectopic ossification and inflammation. In this study, utilizing the neural regulatory mechanism of bone regeneration, we have developed a multifunctional three dimensions (3D) printed scaffold containing both vasoactive intestinal peptide (VIP) and nerve growth factor (NGF) as an effective new method for achieving bone defect regeneration. The scaffold is provided by a controlled biodegradable and biomechanically matched poly(lactide-ethylene glycol-trimethylene carbonate) (PLTG), providing long-term support for the bone healing cycle. Factor loading is provided by peptide fiber-reinforced biomimetic antimicrobial extracellular matrix (ECM) (B-ECM) hydrogels with different release kinetics, the hydrogel guides rapid bone growth and resists bacterial infection at the early stage of healing. Physical and chemical characterization indicates that the scaffold has good structural stability and mechanical properties, providing an ideal 3D microenvironment for bone reconstruction. In the skull defect model, compared to releasing VIP or NGF alone, this drug delivery system can simulate a natural healing cascade of controllable release factors, significantly accelerating nerve/vascular bone regeneration. In conclusion, this study provides a promising strategy for implanting materials to repair bone defects by utilizing neuroregulatory mechanisms during bone regeneration.
2025, 36(5): 110135
doi: 10.1016/j.cclet.2024.110135
摘要:
Biomolecular condensates, also known as membraneless organelles, play a crucial role in cellular organization by concentrating or sequestering biomolecules. Despite their importance, synthetically mimicking these organelles using non-peptidic small organic molecules has posed a significant challenge. The present study reports the discovery of D008, a self-assembling small molecule that sequesters a unique subset of RNA-binding proteins. Analysis and screening of a comprehensive collection of approximately 1 million compounds in the Chinese National Compound Library (Shanghai) identified 44 self-assembling small molecules in aqueous solutions. Subsequent screening of the focused library, coupled with proteome analysis, led to the discovery of D008 as a small organic molecule with the ability to condensate a specific subset of RNA-binding proteins. In vitro experiments demonstrated that the D008-induced sequestration of RNA-binding proteins impeded mRNA translation. D008 may offer a unique opportunity for studying the condensations of RNA-binding proteins and for developing an unprecedented class of small molecules that control gene expression.
Biomolecular condensates, also known as membraneless organelles, play a crucial role in cellular organization by concentrating or sequestering biomolecules. Despite their importance, synthetically mimicking these organelles using non-peptidic small organic molecules has posed a significant challenge. The present study reports the discovery of D008, a self-assembling small molecule that sequesters a unique subset of RNA-binding proteins. Analysis and screening of a comprehensive collection of approximately 1 million compounds in the Chinese National Compound Library (Shanghai) identified 44 self-assembling small molecules in aqueous solutions. Subsequent screening of the focused library, coupled with proteome analysis, led to the discovery of D008 as a small organic molecule with the ability to condensate a specific subset of RNA-binding proteins. In vitro experiments demonstrated that the D008-induced sequestration of RNA-binding proteins impeded mRNA translation. D008 may offer a unique opportunity for studying the condensations of RNA-binding proteins and for developing an unprecedented class of small molecules that control gene expression.
2025, 36(5): 110140
doi: 10.1016/j.cclet.2024.110140
摘要:
Diabetic kidney disease (DKD) is recognized as a severe complication in the development of diabetes mellitus (DM), posing a significant burden for global health. Major characteristics of DKD kidneys include tubulointerstitial oxidative stress, inflammation, excessive extracellular matrix deposition, and progressing renal fibrosis. However, current treatment options are limited and cannot offer enough efficacy, thus urgently requiring novel therapeutic approaches. Tetrahedral framework nucleic acids (tFNAs) are a novel type of self-assembled DNA nanomaterial with excellent structural stability, biocompatibility, tailorable functionality, and regulatory effects on cellular behaviors. In this study, we established an in vitro high glucose (HG)-induced human renal tubular epithelial cells (HK-2 cells) pro-fibrogenic model and explored the antioxidative, anti-inflammatory, and antifibrotic capacity of tFNAs and the potential molecular mechanisms. tFNAs not only effectively alleviated oxidative stress through reactive oxygen species (ROS)-scavenging and activating the serine and threonine kinase (Akt)/nuclear factor erythroid 2-related factor 2 (Nrf2)/heme oxygenase-1 (HO-1) signaling pathway but also inhibited the production of pro-inflammatory factors such as tumor necrosis factor (TNF-α), interleukin-1β (IL-1β), and interleukin-6 (IL-6) in diabetic HK-2 cells. Additionally, tFNAs significantly downregulated the expression of Collagen I and α-smooth muscle actin (α-SMA), two representative biomarkers of pro-fibrogenic myofibroblasts in the renal tubular epithelial-mesenchymal transition (EMT). Furthermore, we found that tFNAs exerted this function by inhibiting the Wnt/β-catenin signaling pathway, preventing the occurrence of EMT and fibrosis. The findings of this study demonstrated that tFNAs are naturally endowed with great potential to prevent fibrosis progress in DKD kidneys and can be further combined with emerging pharmacotherapies, providing a secure and efficient drug delivery strategy for future DKD therapy.
Diabetic kidney disease (DKD) is recognized as a severe complication in the development of diabetes mellitus (DM), posing a significant burden for global health. Major characteristics of DKD kidneys include tubulointerstitial oxidative stress, inflammation, excessive extracellular matrix deposition, and progressing renal fibrosis. However, current treatment options are limited and cannot offer enough efficacy, thus urgently requiring novel therapeutic approaches. Tetrahedral framework nucleic acids (tFNAs) are a novel type of self-assembled DNA nanomaterial with excellent structural stability, biocompatibility, tailorable functionality, and regulatory effects on cellular behaviors. In this study, we established an in vitro high glucose (HG)-induced human renal tubular epithelial cells (HK-2 cells) pro-fibrogenic model and explored the antioxidative, anti-inflammatory, and antifibrotic capacity of tFNAs and the potential molecular mechanisms. tFNAs not only effectively alleviated oxidative stress through reactive oxygen species (ROS)-scavenging and activating the serine and threonine kinase (Akt)/nuclear factor erythroid 2-related factor 2 (Nrf2)/heme oxygenase-1 (HO-1) signaling pathway but also inhibited the production of pro-inflammatory factors such as tumor necrosis factor (TNF-α), interleukin-1β (IL-1β), and interleukin-6 (IL-6) in diabetic HK-2 cells. Additionally, tFNAs significantly downregulated the expression of Collagen I and α-smooth muscle actin (α-SMA), two representative biomarkers of pro-fibrogenic myofibroblasts in the renal tubular epithelial-mesenchymal transition (EMT). Furthermore, we found that tFNAs exerted this function by inhibiting the Wnt/β-catenin signaling pathway, preventing the occurrence of EMT and fibrosis. The findings of this study demonstrated that tFNAs are naturally endowed with great potential to prevent fibrosis progress in DKD kidneys and can be further combined with emerging pharmacotherapies, providing a secure and efficient drug delivery strategy for future DKD therapy.
2025, 36(5): 110141
doi: 10.1016/j.cclet.2024.110141
摘要:
A computer-assisted chemical investigation of an intriguing photoreaction of norditerpenoids (3‒7) has been first reported, leading to not only their biomimetic conversion, but also the generation of several new products with uncommon 4,14-dioxabicyclo[10.2.1]pentadecane scaffold (8, 9, 12‒14). In bioassay, compounds 10 and 15 exhibited significant stimulation of GLP-1 secretion. This study has given an insight for the application of computational methods on the late-stage skeleton transformation of complex natural products towards new bioactive compounds.
A computer-assisted chemical investigation of an intriguing photoreaction of norditerpenoids (3‒7) has been first reported, leading to not only their biomimetic conversion, but also the generation of several new products with uncommon 4,14-dioxabicyclo[10.2.1]pentadecane scaffold (8, 9, 12‒14). In bioassay, compounds 10 and 15 exhibited significant stimulation of GLP-1 secretion. This study has given an insight for the application of computational methods on the late-stage skeleton transformation of complex natural products towards new bioactive compounds.
2025, 36(5): 110146
doi: 10.1016/j.cclet.2024.110146
摘要:
Tumor blockade therapy inhibits tumor progression by cutting off essential supplies of nutrients, oxygen, and biomolecules from the surrounding microenvironments. Inspired by natural processes, tumor biomineralization has evolved due to its biocompatibility, self-reinforcing capability, and penetration-independent mechanism. However, the selective induction of tumor biomineralization using synthetic tools presents a significant challenge. Herein, a metabolic glycoengineering-assistant tumor biomineralization strategy was developed. Specifically, the azido group (N3) was introduced onto the cytomembrane by incubating tumor cells with glycose analog Ac4ManNAz. In addition, a bisphosphonate-containing polymer, dibenzocyclooctyne-poly(ethylene glycol)-alendronate (DBCO-PEG-ALN, DBPA) was synthesized, which attached to the tumor cell surface via "click chemistry" reaction between DBCO and N3. Subsequently, the bisphosphonate group on the cell surface chelated with positively charged ions in the microenvironments, triggering a consecutive process of biomineralization. This physical barrier significantly reduced tumor cell viability and mobility in a calcium ion concentration-dependent manner, suggesting its potential as an effective anti-tumor strategy for in vivo applications.
Tumor blockade therapy inhibits tumor progression by cutting off essential supplies of nutrients, oxygen, and biomolecules from the surrounding microenvironments. Inspired by natural processes, tumor biomineralization has evolved due to its biocompatibility, self-reinforcing capability, and penetration-independent mechanism. However, the selective induction of tumor biomineralization using synthetic tools presents a significant challenge. Herein, a metabolic glycoengineering-assistant tumor biomineralization strategy was developed. Specifically, the azido group (N3) was introduced onto the cytomembrane by incubating tumor cells with glycose analog Ac4ManNAz. In addition, a bisphosphonate-containing polymer, dibenzocyclooctyne-poly(ethylene glycol)-alendronate (DBCO-PEG-ALN, DBPA) was synthesized, which attached to the tumor cell surface via "click chemistry" reaction between DBCO and N3. Subsequently, the bisphosphonate group on the cell surface chelated with positively charged ions in the microenvironments, triggering a consecutive process of biomineralization. This physical barrier significantly reduced tumor cell viability and mobility in a calcium ion concentration-dependent manner, suggesting its potential as an effective anti-tumor strategy for in vivo applications.
2025, 36(5): 110147
doi: 10.1016/j.cclet.2024.110147
摘要:
The aggressive nature and high mortality rate of lung cancer underscore the imperative need for early diagnosis of the disease. Thus, aminopeptidase N (APN), a potential biomarker for lung cancer, should be thoroughly investigated in this context. This report describes the development of HA-apn, a novel near-infrared fluorescent probe, specifically engineered for the sensitive detection of endogenous APN. Characterized by its high selectivity, straightforward molecular architecture, and suitable optical properties, including a long-wavelength emission at 835 nm and a large Stokes shift of 285 nm, HA-apn had high efficacy in identifying overexpressed APN in tumor cells, which shows its potential in pinpointing malignancies. To further validate its applicability and effectiveness in facilitating the direct and enhanced visualization of pulmonary alterations, an in situ lung cancer mouse model was employed. Notably, HA-apn was applied for in vivo imaging of APN activity in the lung cancer mouse model receiving the probe through aerosol inhalation, and rapid and precise diagnostic results were achieved within 30 min post-administration. Overall, HA-apn can be applied as an effective, non-intrusive tool for the rapid and accurate detection of pulmonary conditions.
The aggressive nature and high mortality rate of lung cancer underscore the imperative need for early diagnosis of the disease. Thus, aminopeptidase N (APN), a potential biomarker for lung cancer, should be thoroughly investigated in this context. This report describes the development of HA-apn, a novel near-infrared fluorescent probe, specifically engineered for the sensitive detection of endogenous APN. Characterized by its high selectivity, straightforward molecular architecture, and suitable optical properties, including a long-wavelength emission at 835 nm and a large Stokes shift of 285 nm, HA-apn had high efficacy in identifying overexpressed APN in tumor cells, which shows its potential in pinpointing malignancies. To further validate its applicability and effectiveness in facilitating the direct and enhanced visualization of pulmonary alterations, an in situ lung cancer mouse model was employed. Notably, HA-apn was applied for in vivo imaging of APN activity in the lung cancer mouse model receiving the probe through aerosol inhalation, and rapid and precise diagnostic results were achieved within 30 min post-administration. Overall, HA-apn can be applied as an effective, non-intrusive tool for the rapid and accurate detection of pulmonary conditions.
2025, 36(5): 110149
doi: 10.1016/j.cclet.2024.110149
摘要:
[2+2]-Type cyclobutane derivatives comprise a large family of natural products with diverse molecular architectures. However, the structure elucidation of the cyclobutane ring, including its connection mode and stereochemistry, presents a significant challenge. Plumerubradins A–C (1–3), three novel iridoid glycoside [2+2] dimers featuring a highly functionalized cyclobutane core and multiple stereogenic centers, were isolated from the flowers of Plumeria rubra. Through biomimetic semisynthesis and chemical degradation of compounds 1–3, synthesis of phenylpropanoid-derived [2+2] dimers 7–10, combined with extensive spectroscopic analysis, single-crystal X-ray crystallography, and microcrystal electron diffraction experiments, the structures with absolute configurations of 1–3 were unequivocally elucidated. Furthermore, quantum mechanics-based 1H NMR iterative full spin analysis successfully established the correlations between the signal patterns of cyclobutane protons and the structural information of the cyclobutane ring in phenylpropanoid-derived [2+2] dimers, providing a diagnostic tool for the rapid structural elucidation of [2+2]-type cyclobutane derivatives.
[2+2]-Type cyclobutane derivatives comprise a large family of natural products with diverse molecular architectures. However, the structure elucidation of the cyclobutane ring, including its connection mode and stereochemistry, presents a significant challenge. Plumerubradins A–C (1–3), three novel iridoid glycoside [2+2] dimers featuring a highly functionalized cyclobutane core and multiple stereogenic centers, were isolated from the flowers of Plumeria rubra. Through biomimetic semisynthesis and chemical degradation of compounds 1–3, synthesis of phenylpropanoid-derived [2+2] dimers 7–10, combined with extensive spectroscopic analysis, single-crystal X-ray crystallography, and microcrystal electron diffraction experiments, the structures with absolute configurations of 1–3 were unequivocally elucidated. Furthermore, quantum mechanics-based 1H NMR iterative full spin analysis successfully established the correlations between the signal patterns of cyclobutane protons and the structural information of the cyclobutane ring in phenylpropanoid-derived [2+2] dimers, providing a diagnostic tool for the rapid structural elucidation of [2+2]-type cyclobutane derivatives.
2025, 36(5): 110166
doi: 10.1016/j.cclet.2024.110166
摘要:
Early recognition is key to improving the prognosis of ischemic stroke (IS), while available imaging methods tend to target events that have already undergone ischemia. A new method to detect early IS is urgently needed, as well as further study of its mechanisms. Viscosity and cysteine (Cys) levels of mitochondria have been associated with ferroptosis and IS. It is possible to identify IS and ferroptosis accurately and early by monitoring changes in mitochondrial Cys and viscosity simultaneously. In this work, a viscosity/Cys dual-responsive mitochondrial-targeted near-infrared (NIR) fluorescent probe (NVCP) was constructed for the precise tracking of IS using a two-dimensional design strategy. NVCP consists of a chromophore dyad containing diethylaminostyrene quinolinium rotor and chloro-sulfonylbenzoxadiazole (SBD-Cl) derivative with two easily distinguished emission bands (λem = 592 and 670 nm). NVCP performs the way of killing two birds with one stone, that is, the probe exhibits excellent selectivity and sensitivity for detecting viscosity and Cys in living cells with excellent biocompatibility and accurate mitochondrial targeting capability by dual channel imaging mode. In addition, NVCP recognized that the viscosity increases and Cys level decreases in cells when undergoing ferroptosis and oxygen-glucose deprivation (OGD) stress by confocal imaging, flow cytometry, and Western blot experiments. Treatment of ferroptosis inhibitors (ferrostatin-1 (Fer-1) and deferoxamine (DFO)) could reverse the variation tendency of viscosity and Cys. This is the first time that the relationship between ferroptosis and IS was identified through an analysis of Cys and viscosity. More importantly, the ischemic area was also instantly distinguished from normal tissues through fluorescence imaging of NVCP in vivo. The developed NIR dual-responsive probe NVCP toward viscosity and Cys could serve as a sensitive and reliable tool for tracking ferroptosis-related pathological processes during IS.
Early recognition is key to improving the prognosis of ischemic stroke (IS), while available imaging methods tend to target events that have already undergone ischemia. A new method to detect early IS is urgently needed, as well as further study of its mechanisms. Viscosity and cysteine (Cys) levels of mitochondria have been associated with ferroptosis and IS. It is possible to identify IS and ferroptosis accurately and early by monitoring changes in mitochondrial Cys and viscosity simultaneously. In this work, a viscosity/Cys dual-responsive mitochondrial-targeted near-infrared (NIR) fluorescent probe (NVCP) was constructed for the precise tracking of IS using a two-dimensional design strategy. NVCP consists of a chromophore dyad containing diethylaminostyrene quinolinium rotor and chloro-sulfonylbenzoxadiazole (SBD-Cl) derivative with two easily distinguished emission bands (λem = 592 and 670 nm). NVCP performs the way of killing two birds with one stone, that is, the probe exhibits excellent selectivity and sensitivity for detecting viscosity and Cys in living cells with excellent biocompatibility and accurate mitochondrial targeting capability by dual channel imaging mode. In addition, NVCP recognized that the viscosity increases and Cys level decreases in cells when undergoing ferroptosis and oxygen-glucose deprivation (OGD) stress by confocal imaging, flow cytometry, and Western blot experiments. Treatment of ferroptosis inhibitors (ferrostatin-1 (Fer-1) and deferoxamine (DFO)) could reverse the variation tendency of viscosity and Cys. This is the first time that the relationship between ferroptosis and IS was identified through an analysis of Cys and viscosity. More importantly, the ischemic area was also instantly distinguished from normal tissues through fluorescence imaging of NVCP in vivo. The developed NIR dual-responsive probe NVCP toward viscosity and Cys could serve as a sensitive and reliable tool for tracking ferroptosis-related pathological processes during IS.
2025, 36(5): 110168
doi: 10.1016/j.cclet.2024.110168
摘要:
Photodynamic therapy (PDT) has received much attention in recent years. However, traditional photosensitizers (PSs) applied in PDT usually suffer from aggregation-caused quenching (ACQ) effect in H2O, single and inefficient photochemical mechanism of action (MoA), poor cancer targeting ability, etc. In this work, two novel Ru(Ⅱ)-based aggregation-induced emission (AIE) agents (Ru1 and Ru2) were developed. Both complexes exhibited long triplet excited lifetimes and nearly 100% singlet oxygen quantum yields in H2O. In addition, Ru1 and Ru2 displayed potent photo-catalytic reduced nicotinamide adenine dinucleotide (NADH) oxidation activity with turnover frequency (TOF) values of about 1779 and 2000 h−1, respectively. Therefore, both Ru1 and Ru2 showed efficient PDT activity towards a series of cancer cells. Moreover, Ru2 was further loaded in bovine serum albumin (BSA) to enhance the tumor targeting ability in vivo, and the obtained Ru2@BSA could selectively accumulate in tumor tissues and effectively inhibit tumor growth on a 4T1 tumor-bearing mouse model. So far as we know, this work represents the first report about Ru(Ⅱ) AIE agents that possess high singlet oxygen quantum yields and also potent photo-catalytic NADH oxidation activity, and may provide new ideas for rational design of novel PSs with efficient PDT activity.
Photodynamic therapy (PDT) has received much attention in recent years. However, traditional photosensitizers (PSs) applied in PDT usually suffer from aggregation-caused quenching (ACQ) effect in H2O, single and inefficient photochemical mechanism of action (MoA), poor cancer targeting ability, etc. In this work, two novel Ru(Ⅱ)-based aggregation-induced emission (AIE) agents (Ru1 and Ru2) were developed. Both complexes exhibited long triplet excited lifetimes and nearly 100% singlet oxygen quantum yields in H2O. In addition, Ru1 and Ru2 displayed potent photo-catalytic reduced nicotinamide adenine dinucleotide (NADH) oxidation activity with turnover frequency (TOF) values of about 1779 and 2000 h−1, respectively. Therefore, both Ru1 and Ru2 showed efficient PDT activity towards a series of cancer cells. Moreover, Ru2 was further loaded in bovine serum albumin (BSA) to enhance the tumor targeting ability in vivo, and the obtained Ru2@BSA could selectively accumulate in tumor tissues and effectively inhibit tumor growth on a 4T1 tumor-bearing mouse model. So far as we know, this work represents the first report about Ru(Ⅱ) AIE agents that possess high singlet oxygen quantum yields and also potent photo-catalytic NADH oxidation activity, and may provide new ideas for rational design of novel PSs with efficient PDT activity.
2025, 36(5): 110178
doi: 10.1016/j.cclet.2024.110178
摘要:
Chemodynamic therapy (CDT), using Fenton agents to generate highly cytotoxic •OH from H2O2 has been demonstrated as a powerful anticancer method. However, the insufficient endogenous H2O2 in tumor cells greatly limited its therapeutic effect. Herein, we prepared a pH-responsive β-lapachone-loaded iron-polyphenol nanocomplex (LIPN) through a one-pot method. β-Lapachone in LIPN selectively enhanced H2O2 concentration in tumor cells, and ferrous ions cascadely generated abundant cytotoxic •OH. Therefore, LIPN with cascade amplification of reactive oxygen species (ROS) showed high chemodynamic cytotoxicity in tumor cells, efficiently improving the expression of damage-associated molecular patterns (DAMPs), and exerting strong immunogenic cell death (ICD). As a result, LIPN exhibited efficient tumor inhibition ability in 4T1 subcutaneous tumor model in vivo with great biocompatibility. Additionally, the infiltration of cytotoxic CD8+ T lymphocytes and inhibition of regulatory CD4+ FoxP3+ T lymphocytes in tumors demonstrated the activation of immunosuppressive tumor microenvironment by LIPN-induced ICD. Therefore, this work provided a new approach to enhance ICD of chemodynamic therapy through selective cascade amplification of ROS in cancer cells.
Chemodynamic therapy (CDT), using Fenton agents to generate highly cytotoxic •OH from H2O2 has been demonstrated as a powerful anticancer method. However, the insufficient endogenous H2O2 in tumor cells greatly limited its therapeutic effect. Herein, we prepared a pH-responsive β-lapachone-loaded iron-polyphenol nanocomplex (LIPN) through a one-pot method. β-Lapachone in LIPN selectively enhanced H2O2 concentration in tumor cells, and ferrous ions cascadely generated abundant cytotoxic •OH. Therefore, LIPN with cascade amplification of reactive oxygen species (ROS) showed high chemodynamic cytotoxicity in tumor cells, efficiently improving the expression of damage-associated molecular patterns (DAMPs), and exerting strong immunogenic cell death (ICD). As a result, LIPN exhibited efficient tumor inhibition ability in 4T1 subcutaneous tumor model in vivo with great biocompatibility. Additionally, the infiltration of cytotoxic CD8+ T lymphocytes and inhibition of regulatory CD4+ FoxP3+ T lymphocytes in tumors demonstrated the activation of immunosuppressive tumor microenvironment by LIPN-induced ICD. Therefore, this work provided a new approach to enhance ICD of chemodynamic therapy through selective cascade amplification of ROS in cancer cells.
2025, 36(5): 110179
doi: 10.1016/j.cclet.2024.110179
摘要:
The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants, with little attention to the involved selectivity which may correlate with toxicant residues. Herein, an electron localization strategy for specific O2 adsorption/activation enabled by photothermal/pyroelectric effect and in situ constructed active centers of single-atom Co and oxygen vacancy (Co-OV) on the Co/BiOCl-OV photocatalyst was developed for photocatalytic degradation of glyphosate (GLP) wastewater of high performance/selectivity. Under full-spectrum-light irradiation, a high GLP degradation rate of 99.8% with over 90% C‒P bond-breaking selectivity was achieved within 2 h, while effectively circumventing toxicant residues such as aminomethylphosphonic acid (AMPA). X-ray absorption spectroscopy and relevant characterizations expounded the tailored anchoring of Co single atoms onto the BiOCl-OV carrier and photothermal/pyroelectric effect. The oriented formation of more •O2− on Co/BiOCl-OV could be achieved with the Co-OV coupled center that had excellent O2 adsorption/activation capacity, as demonstrated by quantum calculations. The formed unique Co-OV active sites could largely decrease the C‒P bond-breaking energy barrier, thus greatly improving the selectivity toward the initial C‒P bond scission and the activity in subsequent conversion steps in the directional photocatalytic degradation of GLP. The electron localization strategy by in situ constructing the coupled active centers provides an efficient scheme and new insights for the low-toxic photodegradation of organic pollutants containing C‒X bonds.
The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants, with little attention to the involved selectivity which may correlate with toxicant residues. Herein, an electron localization strategy for specific O2 adsorption/activation enabled by photothermal/pyroelectric effect and in situ constructed active centers of single-atom Co and oxygen vacancy (Co-OV) on the Co/BiOCl-OV photocatalyst was developed for photocatalytic degradation of glyphosate (GLP) wastewater of high performance/selectivity. Under full-spectrum-light irradiation, a high GLP degradation rate of 99.8% with over 90% C‒P bond-breaking selectivity was achieved within 2 h, while effectively circumventing toxicant residues such as aminomethylphosphonic acid (AMPA). X-ray absorption spectroscopy and relevant characterizations expounded the tailored anchoring of Co single atoms onto the BiOCl-OV carrier and photothermal/pyroelectric effect. The oriented formation of more •O2− on Co/BiOCl-OV could be achieved with the Co-OV coupled center that had excellent O2 adsorption/activation capacity, as demonstrated by quantum calculations. The formed unique Co-OV active sites could largely decrease the C‒P bond-breaking energy barrier, thus greatly improving the selectivity toward the initial C‒P bond scission and the activity in subsequent conversion steps in the directional photocatalytic degradation of GLP. The electron localization strategy by in situ constructing the coupled active centers provides an efficient scheme and new insights for the low-toxic photodegradation of organic pollutants containing C‒X bonds.
2025, 36(5): 110183
doi: 10.1016/j.cclet.2024.110183
摘要:
Lipids serve as fundamental constituents of cell membranes and organelles. Recent studies have highlighted the significance of lipids as biomarkers in the diagnosis of breast cancer. Although liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) is widely employed for lipid analysis in complex samples, it suffers from limitations such as complexity and time-consuming procedures. In this study, we have developed dopamine-modified TiO2 nanoparticles (TiO2-DA) and applied the materials to assist the analysis of lipids by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The TiO2-DA can provide large specific surface area and acidic environment, well suited for lipid analysis. The method was initially validated using standard lipid molecules. Good sensitivity, reproducibility and quantification performance was observed. Then, the method was applied to the analysis of 90 serum samples from 30 patients with breast cancer, 30 patients with benign breast disease and 30 healthy controls. Five lipid molecules were identified as potential biomarkers for breast cancer. We constructed a classification model based on the MALDI-TOF MS signal of the 5 lipid molecules, and achieved high sensitivity, specificity and accuracy for the differentiation of breast cancer from benign breast disease and healthy control. We further collected another 60 serum samples from 20 healthy controls, 20 patients with benign breast disease and 20 patients with breast cancer for MALDI-TOF MS analysis to verify the accuracy of the classification model. This advancement holds great promise for the development of diagnostic models for other lipid metabolism-related diseases.
Lipids serve as fundamental constituents of cell membranes and organelles. Recent studies have highlighted the significance of lipids as biomarkers in the diagnosis of breast cancer. Although liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) is widely employed for lipid analysis in complex samples, it suffers from limitations such as complexity and time-consuming procedures. In this study, we have developed dopamine-modified TiO2 nanoparticles (TiO2-DA) and applied the materials to assist the analysis of lipids by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The TiO2-DA can provide large specific surface area and acidic environment, well suited for lipid analysis. The method was initially validated using standard lipid molecules. Good sensitivity, reproducibility and quantification performance was observed. Then, the method was applied to the analysis of 90 serum samples from 30 patients with breast cancer, 30 patients with benign breast disease and 30 healthy controls. Five lipid molecules were identified as potential biomarkers for breast cancer. We constructed a classification model based on the MALDI-TOF MS signal of the 5 lipid molecules, and achieved high sensitivity, specificity and accuracy for the differentiation of breast cancer from benign breast disease and healthy control. We further collected another 60 serum samples from 20 healthy controls, 20 patients with benign breast disease and 20 patients with breast cancer for MALDI-TOF MS analysis to verify the accuracy of the classification model. This advancement holds great promise for the development of diagnostic models for other lipid metabolism-related diseases.
2025, 36(5): 110190
doi: 10.1016/j.cclet.2024.110190
摘要:
Boron neutron capture therapy (BNCT) has emerged as a promising treatment for cancers, offering a unique approach to selectively target tumor cells while sparing healthy tissues. Despite its clinical utility, the widespread use of fructose-BPA (F-BPA) has been hampered by its limited ability to penetrate the blood-brain barrier (BBB) and potential risks for patients with certain complications such as diabetes, hyperuricemia, and gout, particularly with substantial dosages. Herein, a series of novel BPA derivatives were synthesized. After the primary screening, geniposide-BPA (G-BPA) and salidroside-BPA (S-BPA) exhibited high water solubility, low cytotoxicity and safe profiles for intravenous injection. Furthermore, both G-BPA and S-BPA had demonstrated superior efficacy in vitro against the 4T1 cell line compared with F-BPA. Notably, S-BPA displayed optimal BBB penetration capability, as evidenced by in vitro BBB models and glioblastoma models in vivo, surpassing all other BPA derivative candidates. Meanwhile, G-BPA also exhibited enhanced performance relative to the clinical drug F-BPA. In brief, G-BPA and S-BPA, as novel BPA derivatives, demonstrated notable safety profiles and remarkable boron delivery capabilities, thereby offering promising therapeutic options for BNCT in the clinic.
Boron neutron capture therapy (BNCT) has emerged as a promising treatment for cancers, offering a unique approach to selectively target tumor cells while sparing healthy tissues. Despite its clinical utility, the widespread use of fructose-BPA (F-BPA) has been hampered by its limited ability to penetrate the blood-brain barrier (BBB) and potential risks for patients with certain complications such as diabetes, hyperuricemia, and gout, particularly with substantial dosages. Herein, a series of novel BPA derivatives were synthesized. After the primary screening, geniposide-BPA (G-BPA) and salidroside-BPA (S-BPA) exhibited high water solubility, low cytotoxicity and safe profiles for intravenous injection. Furthermore, both G-BPA and S-BPA had demonstrated superior efficacy in vitro against the 4T1 cell line compared with F-BPA. Notably, S-BPA displayed optimal BBB penetration capability, as evidenced by in vitro BBB models and glioblastoma models in vivo, surpassing all other BPA derivative candidates. Meanwhile, G-BPA also exhibited enhanced performance relative to the clinical drug F-BPA. In brief, G-BPA and S-BPA, as novel BPA derivatives, demonstrated notable safety profiles and remarkable boron delivery capabilities, thereby offering promising therapeutic options for BNCT in the clinic.
2025, 36(5): 110191
doi: 10.1016/j.cclet.2024.110191
摘要:
Gallstones are a common disease worldwide, often leading to obstruction and inflammatory complications, which seriously affect the quality of life of patients. Research has shown that gallstone disease is associated with ferroptosis, lipid droplets (LDs), and abnormal levels of nitric oxide (NO). Fluorescent probes provide a sensitive and convenient method for detecting important substances in life systems and diseases. However, so far, no fluorescent probes for NO and LDs in gallstone disease have been reported. In this work, an effective ratiometric fluorescent probe LR-NH was designed for the detection of NO in LDs. With an anthracimide fluorophore and a secondary amine as a response site for NO, LR-NH exhibits high selectivity, sensitivity, and attractive ratiometric capability in detecting NO. Importantly, it can target LDs and shows excellent imaging ability for NO in cells and ferroptosis. Moreover, LR-NH can target the gallbladder and image NO in gallstone disease models, providing a unique and unprecedented tool for studying NO in LDs and gallbladder.
Gallstones are a common disease worldwide, often leading to obstruction and inflammatory complications, which seriously affect the quality of life of patients. Research has shown that gallstone disease is associated with ferroptosis, lipid droplets (LDs), and abnormal levels of nitric oxide (NO). Fluorescent probes provide a sensitive and convenient method for detecting important substances in life systems and diseases. However, so far, no fluorescent probes for NO and LDs in gallstone disease have been reported. In this work, an effective ratiometric fluorescent probe LR-NH was designed for the detection of NO in LDs. With an anthracimide fluorophore and a secondary amine as a response site for NO, LR-NH exhibits high selectivity, sensitivity, and attractive ratiometric capability in detecting NO. Importantly, it can target LDs and shows excellent imaging ability for NO in cells and ferroptosis. Moreover, LR-NH can target the gallbladder and image NO in gallstone disease models, providing a unique and unprecedented tool for studying NO in LDs and gallbladder.
2025, 36(5): 110192
doi: 10.1016/j.cclet.2024.110192
摘要:
Photocatalytic overall water splitting is a promising method for producing clean hydrogen energy, but faces challenges such as low light utilization efficiency and high charge carrier recombination rates. This study demonstrates that dielectric Mie resonance in TiO2 hollow nanoshells can enhance electric field intensity and increase light absorption through resonant energy transfer, compared to crushed TiO2 nanoparticles. The Mie resonance effect was confirmed through fluorescence spectra, photo-response current measurements, photocatalytic water splitting experiments, and Mie calculation. The incident electric-field amplitude was doubled in hollow nanoshells, allowing for increased light trapping. Additionally, the spatially separated Pt and RuO2 cocatalysts on the inner and outer surfaces facilitated the separation of photoinduced electrons and holes. Pt@TiO2@RuO2 hollow nanoshells exhibited superior photocatalytic water splitting performance, with a stable H2 generation rate of 50.1 µmol g−1 h−1 and O2 evolution rate of 25.1 µmol g−1 h−1, outperforming other nanostructures such as TiO2, Pt@TiO2, and TiO2@RuO2 hollow nanoshells. This study suggests that dielectric Mie resonance and spatially-separated cocatalysts offer a new approach to simultaneously enhance light absorption and charge carrier transfer in photocatalysis.
Photocatalytic overall water splitting is a promising method for producing clean hydrogen energy, but faces challenges such as low light utilization efficiency and high charge carrier recombination rates. This study demonstrates that dielectric Mie resonance in TiO2 hollow nanoshells can enhance electric field intensity and increase light absorption through resonant energy transfer, compared to crushed TiO2 nanoparticles. The Mie resonance effect was confirmed through fluorescence spectra, photo-response current measurements, photocatalytic water splitting experiments, and Mie calculation. The incident electric-field amplitude was doubled in hollow nanoshells, allowing for increased light trapping. Additionally, the spatially separated Pt and RuO2 cocatalysts on the inner and outer surfaces facilitated the separation of photoinduced electrons and holes. Pt@TiO2@RuO2 hollow nanoshells exhibited superior photocatalytic water splitting performance, with a stable H2 generation rate of 50.1 µmol g−1 h−1 and O2 evolution rate of 25.1 µmol g−1 h−1, outperforming other nanostructures such as TiO2, Pt@TiO2, and TiO2@RuO2 hollow nanoshells. This study suggests that dielectric Mie resonance and spatially-separated cocatalysts offer a new approach to simultaneously enhance light absorption and charge carrier transfer in photocatalysis.
2025, 36(5): 110195
doi: 10.1016/j.cclet.2024.110195
摘要:
Traditional Pt/C electrode materials are prone to corrosion and detachment during H2S detection, leading to a decrease in fuel cell-type sensor performance. Here, a high-performance H2S sensor based on Pt loaded Ti3C2 electrode material with -O/-OH terminal groups was designed and prepared. Experimental tests showed that the Pt/Ti3C2 sensor has good sensitivity (0.162 µA/ppm) and a very low detection limit to H2S (10 ppb). After 90 days of stability testing, the response of the Pt/Ti3C2 sensor shows a smaller decrease of 2% compared to that of the Pt/C sensor (22.9%). Meanwhile, the sensor also has high selectivity and repeatability. The density functional theory (DFT) calculation combined with the experiment results revealed that the improved H2S sensing mechanism is attributed to the fact that the strong interaction between Pt and Ti3C2 via the Pt-O-Ti bonding can reduce the formation energy of Pt and Ti3C2, ultimately prolonging the sensor’s service life. Furthermore, the catalytic property of Pt can decrease the adsorption energy and dissociation barrier of H2S on Pt/Ti3C2 surface, greatly enhance the ability to generate protons and effectively transfer charges, realizing good sensitivity and high selectivity of the sensor. The sensor works at room temperature, making it very promising in the field of H2S detection in future.
Traditional Pt/C electrode materials are prone to corrosion and detachment during H2S detection, leading to a decrease in fuel cell-type sensor performance. Here, a high-performance H2S sensor based on Pt loaded Ti3C2 electrode material with -O/-OH terminal groups was designed and prepared. Experimental tests showed that the Pt/Ti3C2 sensor has good sensitivity (0.162 µA/ppm) and a very low detection limit to H2S (10 ppb). After 90 days of stability testing, the response of the Pt/Ti3C2 sensor shows a smaller decrease of 2% compared to that of the Pt/C sensor (22.9%). Meanwhile, the sensor also has high selectivity and repeatability. The density functional theory (DFT) calculation combined with the experiment results revealed that the improved H2S sensing mechanism is attributed to the fact that the strong interaction between Pt and Ti3C2 via the Pt-O-Ti bonding can reduce the formation energy of Pt and Ti3C2, ultimately prolonging the sensor’s service life. Furthermore, the catalytic property of Pt can decrease the adsorption energy and dissociation barrier of H2S on Pt/Ti3C2 surface, greatly enhance the ability to generate protons and effectively transfer charges, realizing good sensitivity and high selectivity of the sensor. The sensor works at room temperature, making it very promising in the field of H2S detection in future.
2025, 36(5): 110196
doi: 10.1016/j.cclet.2024.110196
摘要:
The addition of cold flow improvers (CFIs) is considered as the optimum strategy to improve the cold flow properties (CFPs) of diesel fuels, but this strategy is always limited by the required large dosage. To obtain low-dosage and high-efficiency CFIs for diesel, 1,2,3,6-tetrahydrophthalic anhydride (THPA) was introduced as a third and polar monomer to enhance the depressive effects of alkyl methacrylate-trans anethole copolymers (C14MC-TA). The terpolymers of alkyl methacrylate-trans anethole-1,2,3,6-tetrahydrophthalic anhydride (C14MC-TA-THPA) were synthesized and compared with the binary copolymers of C14MC-TA and alkyl methacrylate-1,2,3,6-tetrahydrophthalic anhydride (C14MC-THPA). Results showed that C14MC -THPA achieved the best depressive effects on the cold filter plugging point (CFPP) and solid point (SP) by 11 ℃ and 16 ℃ at a dosage of 1250 mg/L and monomer ratio of 6:1, while 1500 mg/L C14MC-TA (1:1) reached the optimal depressive effects on the CFPP and SP by 12 ℃ and 18 ℃. THPA introduction significantly improved the depressive effects of C14MC-TA. Lower dosages of C14MC-TA-THPA in diesel exerted better improvement effects on the CFPP and SP than that of C14MC-TA and C14MC-THPA. When the monomer ratio and dosage were 6:0.6:0.4 and 1000 mg/L, the improvement effect of C14MC-TA-THPA on diesel reached the optimum level, and the CFPP and SP were reduced by 13 ℃ and 19 ℃, respectively. A 3D nonlinear surface diagram fitted by a mathematical model was also used for the first time to better understand the relationships of monomer ratios, dosages, and depressive effects of CFIs in diesel. Surface analysis results showed that C14MC-TA-THPA achieved the optimum depressive effects at a monomer ratio of 6:0.66:0.34 and dosage of 1000 mg/L, and the CFPP and SP decreased by 14 ℃ and 19 ℃, respectively. The predicted results were consistent with the actual ones. Additionally, the improvement mechanism of these copolymers in diesel was also explored.
The addition of cold flow improvers (CFIs) is considered as the optimum strategy to improve the cold flow properties (CFPs) of diesel fuels, but this strategy is always limited by the required large dosage. To obtain low-dosage and high-efficiency CFIs for diesel, 1,2,3,6-tetrahydrophthalic anhydride (THPA) was introduced as a third and polar monomer to enhance the depressive effects of alkyl methacrylate-trans anethole copolymers (C14MC-TA). The terpolymers of alkyl methacrylate-trans anethole-1,2,3,6-tetrahydrophthalic anhydride (C14MC-TA-THPA) were synthesized and compared with the binary copolymers of C14MC-TA and alkyl methacrylate-1,2,3,6-tetrahydrophthalic anhydride (C14MC-THPA). Results showed that C14MC -THPA achieved the best depressive effects on the cold filter plugging point (CFPP) and solid point (SP) by 11 ℃ and 16 ℃ at a dosage of 1250 mg/L and monomer ratio of 6:1, while 1500 mg/L C14MC-TA (1:1) reached the optimal depressive effects on the CFPP and SP by 12 ℃ and 18 ℃. THPA introduction significantly improved the depressive effects of C14MC-TA. Lower dosages of C14MC-TA-THPA in diesel exerted better improvement effects on the CFPP and SP than that of C14MC-TA and C14MC-THPA. When the monomer ratio and dosage were 6:0.6:0.4 and 1000 mg/L, the improvement effect of C14MC-TA-THPA on diesel reached the optimum level, and the CFPP and SP were reduced by 13 ℃ and 19 ℃, respectively. A 3D nonlinear surface diagram fitted by a mathematical model was also used for the first time to better understand the relationships of monomer ratios, dosages, and depressive effects of CFIs in diesel. Surface analysis results showed that C14MC-TA-THPA achieved the optimum depressive effects at a monomer ratio of 6:0.66:0.34 and dosage of 1000 mg/L, and the CFPP and SP decreased by 14 ℃ and 19 ℃, respectively. The predicted results were consistent with the actual ones. Additionally, the improvement mechanism of these copolymers in diesel was also explored.
2025, 36(5): 110200
doi: 10.1016/j.cclet.2024.110200
摘要:
Simultaneous degradation and detoxification during pharmaceutical and personal care product removal are important for water treatment. In this study, sodium niobate nanocubes decorated with graphitic carbon nitride (NbNC/g-C3N4) were fabricated to achieve the efficient photocatalytic degradation and detoxification of ciprofloxacin (CIP) under simulated solar light. NaNbO3 nanocubes were in-situ transformed from Na2Nb2O6·H2O via thermal dehydration at the interface of g-C3N4. The optimized NbNC/g-C3N4–1 was a type-Ⅰ heterojunction, which showed a high conduction band (CB) level of −1.68 eV, leading to the efficient transfer of photogenerated electrons to O2 to produce primary reactive species, •O2−. Density functional theory (DFT) calculations of the density of states indicated that C 2p and Nb 3d contributed to the CB, and 0.37 e– transferred from NaNbO3 to g-C3N4 in NbNC/g-C3N4 based on the Mulliken population analysis of the built-in electric field intensity. NbNC/g-C3N4–1 had 3.3- and 2.3-fold of CIP degradation rate constants (k1 = 0.173 min−1) compared with those of pristine g-C3N4 and NaNbO3, respectively. In addition, N24, N19, and C5 in CIP with a high Fukui index were reactive sites for electrophilic attack by •O2−, resulting in the defluorination and ring-opening of the piperazine moiety of the dominant degradation pathways. Intermediate/product identification, integrated with computational toxicity evaluation, further indicated a substantial detoxification effect during CIP degradation in the photocatalysis system.
Simultaneous degradation and detoxification during pharmaceutical and personal care product removal are important for water treatment. In this study, sodium niobate nanocubes decorated with graphitic carbon nitride (NbNC/g-C3N4) were fabricated to achieve the efficient photocatalytic degradation and detoxification of ciprofloxacin (CIP) under simulated solar light. NaNbO3 nanocubes were in-situ transformed from Na2Nb2O6·H2O via thermal dehydration at the interface of g-C3N4. The optimized NbNC/g-C3N4–1 was a type-Ⅰ heterojunction, which showed a high conduction band (CB) level of −1.68 eV, leading to the efficient transfer of photogenerated electrons to O2 to produce primary reactive species, •O2−. Density functional theory (DFT) calculations of the density of states indicated that C 2p and Nb 3d contributed to the CB, and 0.37 e– transferred from NaNbO3 to g-C3N4 in NbNC/g-C3N4 based on the Mulliken population analysis of the built-in electric field intensity. NbNC/g-C3N4–1 had 3.3- and 2.3-fold of CIP degradation rate constants (k1 = 0.173 min−1) compared with those of pristine g-C3N4 and NaNbO3, respectively. In addition, N24, N19, and C5 in CIP with a high Fukui index were reactive sites for electrophilic attack by •O2−, resulting in the defluorination and ring-opening of the piperazine moiety of the dominant degradation pathways. Intermediate/product identification, integrated with computational toxicity evaluation, further indicated a substantial detoxification effect during CIP degradation in the photocatalysis system.
2025, 36(5): 110201
doi: 10.1016/j.cclet.2024.110201
摘要:
Rational tuning of crystallographic surface and metal doping were effective to enhance the catalytic performance of metal organic frameworks, but limited work has been explored for achieving modulation of crystal facets and metal doping in a single system. MIL-68(In) was promising for photocatalytic applications due to its low toxicity and excellent photoresponsivity. However, its catalytic activity was constrained by severe carrier recombination and a lack of active sites. Herein, increased (001) facet ratio and active sites exposure were simultaneously realized by cobalt doping in MIL-68(In) through a one-pot solvothermal strategy. Optimized MIL-68(In/Co)-2.5 exhibited remarkable catalytic performance in comparison with pristine MIL-68(In) and other MIL-68(In/Co). The reaction kinetic constant and degradation efficiency of MIL-68(In/Co) were approximately twice and 17% higher than the pristine MIL-68(In) in 36 min reaction, respectively. Density functional theory calculations revealed that Co dopant could modulate the orientation of MIL-68(In) facets, facilitate the exchange of electrons and reduce the adsorption energy of peroxymonosulfate (PMS). This work provides a novel pathway for improvement of In-based MOFs in PMS/vis system, it also promotes the profound comprehension of the correlation between crystal facet regulation and catalytic activation in the PMS/vis system.
Rational tuning of crystallographic surface and metal doping were effective to enhance the catalytic performance of metal organic frameworks, but limited work has been explored for achieving modulation of crystal facets and metal doping in a single system. MIL-68(In) was promising for photocatalytic applications due to its low toxicity and excellent photoresponsivity. However, its catalytic activity was constrained by severe carrier recombination and a lack of active sites. Herein, increased (001) facet ratio and active sites exposure were simultaneously realized by cobalt doping in MIL-68(In) through a one-pot solvothermal strategy. Optimized MIL-68(In/Co)-2.5 exhibited remarkable catalytic performance in comparison with pristine MIL-68(In) and other MIL-68(In/Co). The reaction kinetic constant and degradation efficiency of MIL-68(In/Co) were approximately twice and 17% higher than the pristine MIL-68(In) in 36 min reaction, respectively. Density functional theory calculations revealed that Co dopant could modulate the orientation of MIL-68(In) facets, facilitate the exchange of electrons and reduce the adsorption energy of peroxymonosulfate (PMS). This work provides a novel pathway for improvement of In-based MOFs in PMS/vis system, it also promotes the profound comprehension of the correlation between crystal facet regulation and catalytic activation in the PMS/vis system.
2025, 36(5): 110202
doi: 10.1016/j.cclet.2024.110202
摘要:
As antibiotic pollutants cannot be incompletely removed by conventional wastewater treatment plants, ultraviolet (UV) based advanced oxidation processes (AOPs) such as UV/persulfate (UV/PS) and UV/chlorine are increasingly concerned for the effective removal of antibiotics from wastewaters. However, the specific mechanisms involving degradation kinetics and transformation mechanisms are not well elucidated. Here we report a detailed examination of SO4•−/Cl•-mediated degradation kinetics, products, and toxicities of sulfathiazole (ST), sarafloxacin (SAR), and lomefloxacin (LOM) in the two processes. Both SO4•−/Cl•-mediated transformation kinetics were found to be dependent on pH (P < 0.05), which was attributed to the disparate reactivities of their individual dissociated forms. Based on competition kinetic experiments and matrix calculations, the cationic forms (H2ST+, H2SAR+, and H2LOM+) were more highly reactive towards SO4•− in most cases, while the neutral forms (e.g., HSAR0 and HLOM0) reacted the fastest with Cl• for the most of the antibiotics tested. Based on the identification of 31 key intermediates using tandem mass spectrometry, these reactions generated different products, of which the majority still retained the core chemical structure of the parent compounds. The corresponding diverse transformation pathways were proposed, involving S−N breaking, hydroxylation, defluorination, and chlorination reactions. Furthermore, the toxicity changes of their reaction solutions as well as the toxicity of each intermediate were evaluated by the vibrio fischeri and ECOSAR model, respectively. Many primary by-products were proven to be more toxic than the parent chemicals, raising the wider issue of extended potency for these compounds with regards to their ecotoxicity. These results have implications for assessing the degradative fate and risk of these chemicals during the AOPs.
As antibiotic pollutants cannot be incompletely removed by conventional wastewater treatment plants, ultraviolet (UV) based advanced oxidation processes (AOPs) such as UV/persulfate (UV/PS) and UV/chlorine are increasingly concerned for the effective removal of antibiotics from wastewaters. However, the specific mechanisms involving degradation kinetics and transformation mechanisms are not well elucidated. Here we report a detailed examination of SO4•−/Cl•-mediated degradation kinetics, products, and toxicities of sulfathiazole (ST), sarafloxacin (SAR), and lomefloxacin (LOM) in the two processes. Both SO4•−/Cl•-mediated transformation kinetics were found to be dependent on pH (P < 0.05), which was attributed to the disparate reactivities of their individual dissociated forms. Based on competition kinetic experiments and matrix calculations, the cationic forms (H2ST+, H2SAR+, and H2LOM+) were more highly reactive towards SO4•− in most cases, while the neutral forms (e.g., HSAR0 and HLOM0) reacted the fastest with Cl• for the most of the antibiotics tested. Based on the identification of 31 key intermediates using tandem mass spectrometry, these reactions generated different products, of which the majority still retained the core chemical structure of the parent compounds. The corresponding diverse transformation pathways were proposed, involving S−N breaking, hydroxylation, defluorination, and chlorination reactions. Furthermore, the toxicity changes of their reaction solutions as well as the toxicity of each intermediate were evaluated by the vibrio fischeri and ECOSAR model, respectively. Many primary by-products were proven to be more toxic than the parent chemicals, raising the wider issue of extended potency for these compounds with regards to their ecotoxicity. These results have implications for assessing the degradative fate and risk of these chemicals during the AOPs.
2025, 36(5): 110203
doi: 10.1016/j.cclet.2024.110203
摘要:
Recent advances in drug development and bioactive molecules that covalently target lysine residues have shown substantial progress. Both reversible and irreversible covalent inhibitors are developed for targeting lysine residues. The identification of protein targets and binding sites of these lysine-targeting molecules in the whole proteome is crucial to understand their proteome-wide selectivity. For covalent inhibitors, the pull down-based methods including activity-based protein profiling (ABPP) are commonly used to profile their target proteins. For covalent reversible inhibitors, it is not easy to pull down the potential protein targets as the captured proteins may get off beads because of the reversible manner. Here, we report a pair of isotope-labelled click-free probes to competitively identify the protein targets of lysine-targeting covalent reversible small molecules. This pair of isotopic probes consists of a lysine-reactive warhead, a desthiobiotin moiety and isotopicable linker. This integrated probe could eliminate the background proteins induced by the click chemistry during the pull-down process. To demonstrate the feasibility of our newly-developed probes for the protein target identification, we selected the natural product Gossypol in that we proved for the first time that it could modify the lysine residue in a covalent reversible manner. Finally, we confirmed that this pair of integrated probes can be used in a competitive manner to precisely identify the protein target as well as binding sites of Gossypol. Interestingly, pretreatment of Gossypol could stop the antibody from recognizing Gossypol-binding proteins. Together, our isotope-labeled click-free probes could be used for whole-proteome profiling of lysine-targeting covalent reversible small molecules.
Recent advances in drug development and bioactive molecules that covalently target lysine residues have shown substantial progress. Both reversible and irreversible covalent inhibitors are developed for targeting lysine residues. The identification of protein targets and binding sites of these lysine-targeting molecules in the whole proteome is crucial to understand their proteome-wide selectivity. For covalent inhibitors, the pull down-based methods including activity-based protein profiling (ABPP) are commonly used to profile their target proteins. For covalent reversible inhibitors, it is not easy to pull down the potential protein targets as the captured proteins may get off beads because of the reversible manner. Here, we report a pair of isotope-labelled click-free probes to competitively identify the protein targets of lysine-targeting covalent reversible small molecules. This pair of isotopic probes consists of a lysine-reactive warhead, a desthiobiotin moiety and isotopicable linker. This integrated probe could eliminate the background proteins induced by the click chemistry during the pull-down process. To demonstrate the feasibility of our newly-developed probes for the protein target identification, we selected the natural product Gossypol in that we proved for the first time that it could modify the lysine residue in a covalent reversible manner. Finally, we confirmed that this pair of integrated probes can be used in a competitive manner to precisely identify the protein target as well as binding sites of Gossypol. Interestingly, pretreatment of Gossypol could stop the antibody from recognizing Gossypol-binding proteins. Together, our isotope-labeled click-free probes could be used for whole-proteome profiling of lysine-targeting covalent reversible small molecules.
2025, 36(5): 110206
doi: 10.1016/j.cclet.2024.110206
摘要:
The selective conversion of CO2 and NH3 into valuable nitriles presents significant potential for CO2 utilization. In this study, we exploited the synergistic interplay between silicon and fluoride to augment the nickel-catalyzed reductive cyanation of aryl pseudohalides containing silyl groups, utilizing CO2 and NH3 as the CN source. Our methodology exhibited exceptional compatibility with diverse functional groups, such as alcohols, ketones, ethers, esters, nitriles, olefins, pyridines, and quinolines, among others, as demonstrated by the successful synthesis of 58 different nitriles. Notably, we achieved high yields in the preparation of bifunctionalized molecules, including intermediates for perampanel, derived from o-silylaryl triflates, which are well-known as aryne precursors. Remarkably, no degradation of substrates or formation of aryne intermediates were observed. Mechanistic studies imply that the formation of penta-coordinated silyl isocyanate intermediates is crucial for the key C–C coupling step and the presence of vicinal silyl group in the substrate is beneficial to further make this step kinetically favorable.
The selective conversion of CO2 and NH3 into valuable nitriles presents significant potential for CO2 utilization. In this study, we exploited the synergistic interplay between silicon and fluoride to augment the nickel-catalyzed reductive cyanation of aryl pseudohalides containing silyl groups, utilizing CO2 and NH3 as the CN source. Our methodology exhibited exceptional compatibility with diverse functional groups, such as alcohols, ketones, ethers, esters, nitriles, olefins, pyridines, and quinolines, among others, as demonstrated by the successful synthesis of 58 different nitriles. Notably, we achieved high yields in the preparation of bifunctionalized molecules, including intermediates for perampanel, derived from o-silylaryl triflates, which are well-known as aryne precursors. Remarkably, no degradation of substrates or formation of aryne intermediates were observed. Mechanistic studies imply that the formation of penta-coordinated silyl isocyanate intermediates is crucial for the key C–C coupling step and the presence of vicinal silyl group in the substrate is beneficial to further make this step kinetically favorable.
2025, 36(5): 110207
doi: 10.1016/j.cclet.2024.110207
摘要:
The development of general and practical strategies toward the construction of medium-sized rings is still challenging in organic synthesis, especially for the multiple stereocenters control of substituted groups on the ring owing to the long distance between groups. Thus, stereoselective synthesis of multi-substituted ten-membered rings is attractive. Herein, a rapid assembly of various highly substituted ten-membered nitrogen heterocycles between two 1,3-dipoles through a tandem [3 + 3] cycloaddition/aza-Claisen rearrangement of N-vinyl-α,β-unsaturated nitrones and aza-oxyallyl or oxyallyl cations are disclosed. Products containing two or multiple stereocenters could be obtained in up to 96% yield with high regioselectivity and diastereoselectivity. Selective N-O bond cleavages of ten-membered nitrogen heterocycles lead to various novel 5,6,6-perifused benzofurans, bicyclo[4.4.0] or bicyclo[5.3.0] skeletons containing three or multiple continuous stereocenters in good yields and high diastereoselectivity. Biological tests show that the obtained ten-membered N-heterocycles and bicyclo[4.4.0] skeletons inhibited nitric oxide generation in LPS-stimulated RAW264.7 cells and might serve as good anti-inflammatory agents.
The development of general and practical strategies toward the construction of medium-sized rings is still challenging in organic synthesis, especially for the multiple stereocenters control of substituted groups on the ring owing to the long distance between groups. Thus, stereoselective synthesis of multi-substituted ten-membered rings is attractive. Herein, a rapid assembly of various highly substituted ten-membered nitrogen heterocycles between two 1,3-dipoles through a tandem [3 + 3] cycloaddition/aza-Claisen rearrangement of N-vinyl-α,β-unsaturated nitrones and aza-oxyallyl or oxyallyl cations are disclosed. Products containing two or multiple stereocenters could be obtained in up to 96% yield with high regioselectivity and diastereoselectivity. Selective N-O bond cleavages of ten-membered nitrogen heterocycles lead to various novel 5,6,6-perifused benzofurans, bicyclo[4.4.0] or bicyclo[5.3.0] skeletons containing three or multiple continuous stereocenters in good yields and high diastereoselectivity. Biological tests show that the obtained ten-membered N-heterocycles and bicyclo[4.4.0] skeletons inhibited nitric oxide generation in LPS-stimulated RAW264.7 cells and might serve as good anti-inflammatory agents.
2025, 36(5): 110209
doi: 10.1016/j.cclet.2024.110209
摘要:
Algal copper uptake (i.e., Cu bioavailability) in the euphotic zone plays a vital role in algal photosynthesis and respiration, affecting the primary productivity and the source and sink of atmospheric carbon. Algal Cu uptake is controlled by natural dissolved organic Cu (DOCu) speciation (i.e., complexed with the dissolved organic matter) that conventionally could be tested by model prediction or molecular-level characterizations in the lab, while DOCu uptake are hardly directly assessed. Thus, the new chemistry-biology insight into the mechanisms of the Cu uptake process in algae is urgent. The DOCu speciation transformation (organic DOCu to free Cu(Ⅱ) ions), enzymatic reduction-induced valence change (reduction of free Cu(Ⅱ) to Cu(Ⅰ) ions), and algal Cu uptake at the algae-water interface are imitated. Herein, an intelligent system with DOCu colorimetric sensor is developed for real-time monitoring of newly generated Cu(Ⅰ) ions. Deep learning with whole sample image-based characterization and powerful feature extraction capabilities facilitates colorimetric measurement. In this context, the Cu bioavailability with 7 kinds of organic ligands (e.g., amino acids, organic acids, carbohydrates) can be predicted by the mimetic intelligent biosensor within 15.0 min, i.e., the DOCu uptake and speciation is successfully predicted and streamlined by the biomimetic approach.
Algal copper uptake (i.e., Cu bioavailability) in the euphotic zone plays a vital role in algal photosynthesis and respiration, affecting the primary productivity and the source and sink of atmospheric carbon. Algal Cu uptake is controlled by natural dissolved organic Cu (DOCu) speciation (i.e., complexed with the dissolved organic matter) that conventionally could be tested by model prediction or molecular-level characterizations in the lab, while DOCu uptake are hardly directly assessed. Thus, the new chemistry-biology insight into the mechanisms of the Cu uptake process in algae is urgent. The DOCu speciation transformation (organic DOCu to free Cu(Ⅱ) ions), enzymatic reduction-induced valence change (reduction of free Cu(Ⅱ) to Cu(Ⅰ) ions), and algal Cu uptake at the algae-water interface are imitated. Herein, an intelligent system with DOCu colorimetric sensor is developed for real-time monitoring of newly generated Cu(Ⅰ) ions. Deep learning with whole sample image-based characterization and powerful feature extraction capabilities facilitates colorimetric measurement. In this context, the Cu bioavailability with 7 kinds of organic ligands (e.g., amino acids, organic acids, carbohydrates) can be predicted by the mimetic intelligent biosensor within 15.0 min, i.e., the DOCu uptake and speciation is successfully predicted and streamlined by the biomimetic approach.
2025, 36(5): 110213
doi: 10.1016/j.cclet.2024.110213
摘要:
Bridged bicyclic cores have been recognized as valuable bioisosteres of benzene ring, which are of great value in medicinal chemistry. However, the development of fluorinated bicyclic skeletons, which encompass two privileged elements widely acknowledged for fine tuning the working effect of target molecules, are far less common. Herein, we present a general and practical synthesis of gem–difluorobicyclo[2.1.1]hexanes (diF-BCHs) from readily available difluorinated hexa-1,5-dienes through energy transfer photocatalysis. By taking advantage of an efficient Cope rearrangement, the preparation of both constitutional isomers of diF-BCHs is readily achieved under identical conditions. The operational simplicity, mild conditions and wide scope further highlight the potential application of this protocol. Moreover, computational studies indicated a positive effect of fluorine atoms in lowering either the triplet or FMO energies of the hexa-1,5-diene substrates, thus promoting the present photoinduced [2 + 2] cycloaddition.
Bridged bicyclic cores have been recognized as valuable bioisosteres of benzene ring, which are of great value in medicinal chemistry. However, the development of fluorinated bicyclic skeletons, which encompass two privileged elements widely acknowledged for fine tuning the working effect of target molecules, are far less common. Herein, we present a general and practical synthesis of gem–difluorobicyclo[2.1.1]hexanes (diF-BCHs) from readily available difluorinated hexa-1,5-dienes through energy transfer photocatalysis. By taking advantage of an efficient Cope rearrangement, the preparation of both constitutional isomers of diF-BCHs is readily achieved under identical conditions. The operational simplicity, mild conditions and wide scope further highlight the potential application of this protocol. Moreover, computational studies indicated a positive effect of fluorine atoms in lowering either the triplet or FMO energies of the hexa-1,5-diene substrates, thus promoting the present photoinduced [2 + 2] cycloaddition.
2025, 36(5): 110227
doi: 10.1016/j.cclet.2024.110227
摘要:
Combining cytotoxic drugs with tumor microenvironment (TME) modulator agents is an effective strategy to enhance anti-tumor effects. In this study, two natural anti-tumor active ingredients celastrol (CEL) and glycyrrhetinic acid (GA) were combined for tumor treatment. In order to ensure the precise co-delivery and controllable synchronous release of combined drugs to tumors, it is necessary to construct a suitable nano-drug delivery platform. Based on this, we coupled hyaluronic acid (HA) with CEL by amide reaction to obtain an amphiphilic polymer prodrug HA-SS-CEL, and GA was spontaneously loaded into polymer micelles by self-assembly to obtain G/HSSC-M. G/HSSC-M has ideal size distribution, redox-responsive synchronous drug release, enhanced tumor cell internalization and in vivo tumor targeting. Compared with free drugs, the construction of multifunctional polymer micelles makes G/HSSC-M show better anticancer effect at the same concentration, and can significantly inhibit the proliferation and migration of HepG2 and 4T1 cells. In the in vivo experiments, G/HSSC-M achieved a tumor inhibition rate as high as 75.12% in H22 tumor-bearing mice. The mechanism included regulation of M1/M2 macrophage polarization, inhibition of Janus kinase 1/signal transducer and activator of transcription 3 (JAK1/STAT3) signaling pathway, and remodeling of tumor blood vessels. Therefore, the development of prodrug micelles co-loaded with CEL and GA provides a promising drug co-delivery strategy for combined cancer therapy.
Combining cytotoxic drugs with tumor microenvironment (TME) modulator agents is an effective strategy to enhance anti-tumor effects. In this study, two natural anti-tumor active ingredients celastrol (CEL) and glycyrrhetinic acid (GA) were combined for tumor treatment. In order to ensure the precise co-delivery and controllable synchronous release of combined drugs to tumors, it is necessary to construct a suitable nano-drug delivery platform. Based on this, we coupled hyaluronic acid (HA) with CEL by amide reaction to obtain an amphiphilic polymer prodrug HA-SS-CEL, and GA was spontaneously loaded into polymer micelles by self-assembly to obtain G/HSSC-M. G/HSSC-M has ideal size distribution, redox-responsive synchronous drug release, enhanced tumor cell internalization and in vivo tumor targeting. Compared with free drugs, the construction of multifunctional polymer micelles makes G/HSSC-M show better anticancer effect at the same concentration, and can significantly inhibit the proliferation and migration of HepG2 and 4T1 cells. In the in vivo experiments, G/HSSC-M achieved a tumor inhibition rate as high as 75.12% in H22 tumor-bearing mice. The mechanism included regulation of M1/M2 macrophage polarization, inhibition of Janus kinase 1/signal transducer and activator of transcription 3 (JAK1/STAT3) signaling pathway, and remodeling of tumor blood vessels. Therefore, the development of prodrug micelles co-loaded with CEL and GA provides a promising drug co-delivery strategy for combined cancer therapy.
2025, 36(5): 110230
doi: 10.1016/j.cclet.2024.110230
摘要:
Self-assembled prodrug nanomedicine has emerged as an advanced platform for antitumor therapy, mainly comprise drug modules, response modules and modification modules. However, existing studies usually compare the differences between single types of modification modules, neglecting the impact of steric-hindrance effect caused by chemical structure. Herein, single-tailed modification module with low-steric-hindrance effect and two-tailed modification module with high-steric-hindrance effect were selected to construct paclitaxel prodrugs (P-LAC18 and P-BAC18), and the in-depth insights of the steric-hindrance effect on prodrug nanoassemblies were explored. Notably, the size stability of the two-tailed prodrugs was enhanced due to improved intermolecular interactions and steric hindrance. Single-tailed prodrug nanoassemblies were more susceptible to attack by redox agents, showing faster drug release and stronger antitumor efficacy, but with poorer safety. In contrast, two-tailed prodrug nanoassemblies exhibited significant advantages in terms of pharmacokinetics, tumor accumulation and safety due to the good size stability, thus ensuring equivalent antitumor efficacy at tolerance dose. These findings highlighted the critical role of steric-hindrance effect of the modification module in regulating the structure-activity relationship of prodrug nanoassemblies and proposed new perspectives into the precise design of self-assembled prodrugs for high-performance cancer therapeutics.
Self-assembled prodrug nanomedicine has emerged as an advanced platform for antitumor therapy, mainly comprise drug modules, response modules and modification modules. However, existing studies usually compare the differences between single types of modification modules, neglecting the impact of steric-hindrance effect caused by chemical structure. Herein, single-tailed modification module with low-steric-hindrance effect and two-tailed modification module with high-steric-hindrance effect were selected to construct paclitaxel prodrugs (P-LAC18 and P-BAC18), and the in-depth insights of the steric-hindrance effect on prodrug nanoassemblies were explored. Notably, the size stability of the two-tailed prodrugs was enhanced due to improved intermolecular interactions and steric hindrance. Single-tailed prodrug nanoassemblies were more susceptible to attack by redox agents, showing faster drug release and stronger antitumor efficacy, but with poorer safety. In contrast, two-tailed prodrug nanoassemblies exhibited significant advantages in terms of pharmacokinetics, tumor accumulation and safety due to the good size stability, thus ensuring equivalent antitumor efficacy at tolerance dose. These findings highlighted the critical role of steric-hindrance effect of the modification module in regulating the structure-activity relationship of prodrug nanoassemblies and proposed new perspectives into the precise design of self-assembled prodrugs for high-performance cancer therapeutics.
2025, 36(5): 110231
doi: 10.1016/j.cclet.2024.110231
摘要:
The chemo-, regio-, and enantio-controlled synthesis of P-chiral phosphines in a general and efficient manner remains a significant synthetic challenge. In this study, a Pd-catalyzed hydrofunctionalization is developed for the highly selective synthesis of P-stereogenic alkenylphosphinates and alkenylphosphine oxides via conjugate addition of enynes. Notably, this methodology is suitable for both phosphine oxide and phosphinate nucleophiles, providing a versatile approach for the construction of diverse P-chiral organophosphosphorus compound.
The chemo-, regio-, and enantio-controlled synthesis of P-chiral phosphines in a general and efficient manner remains a significant synthetic challenge. In this study, a Pd-catalyzed hydrofunctionalization is developed for the highly selective synthesis of P-stereogenic alkenylphosphinates and alkenylphosphine oxides via conjugate addition of enynes. Notably, this methodology is suitable for both phosphine oxide and phosphinate nucleophiles, providing a versatile approach for the construction of diverse P-chiral organophosphosphorus compound.
2025, 36(5): 110237
doi: 10.1016/j.cclet.2024.110237
摘要:
Traditional electrospray ionization tandem mass spectrometry (ESI-MSn) has been a powerful tool in diverse research areas, however, it faces great limitations in the study of protein-small molecule interactions. In this article, the state-of-the-art temperature-controlled electrospray ionization tandem mass spectrometry (TC-ESI-MSn) is applied to investigate interactions between ubiquitin and two flavonol molecules, respectively. The combination of collision-induced dissociation (CID) and MS solution-melting experiments facilitates the understanding of flavonol-protein interactions in a new dimension across varying temperature ranges. While structural changes of proteins disturbed by small molecules are unseen in ESI-MSn, TC-ESI-MSn allows a simultaneous assessment of the stability of the complex in both gas and liquid phases under various temperature conditions, meanwhile investigating the impact on the protein’s structure and tracking changes in thermodynamic data, and the characteristics of structural intermediates.
Traditional electrospray ionization tandem mass spectrometry (ESI-MSn) has been a powerful tool in diverse research areas, however, it faces great limitations in the study of protein-small molecule interactions. In this article, the state-of-the-art temperature-controlled electrospray ionization tandem mass spectrometry (TC-ESI-MSn) is applied to investigate interactions between ubiquitin and two flavonol molecules, respectively. The combination of collision-induced dissociation (CID) and MS solution-melting experiments facilitates the understanding of flavonol-protein interactions in a new dimension across varying temperature ranges. While structural changes of proteins disturbed by small molecules are unseen in ESI-MSn, TC-ESI-MSn allows a simultaneous assessment of the stability of the complex in both gas and liquid phases under various temperature conditions, meanwhile investigating the impact on the protein’s structure and tracking changes in thermodynamic data, and the characteristics of structural intermediates.
2025, 36(5): 110238
doi: 10.1016/j.cclet.2024.110238
摘要:
Neutrophil extracellular traps (NETs) formation (NETosis), is a crucial immune system mechanism mediated by neutrophils, measuring the capacity to induce NETosis is proposed as a clinical biomarker indicating the severity of COVID-19 and long COVID. Azvudine (FNC), has shown efficacy in treating SARS-CoV-2 infection and potential for alleviating inflammation. However, the molecular mechanism underlying its anti-inflammatory effects has not been extensively investigated. Therefore, a series of experiments were conducted on SARS-CoV-2 infected rhesus macaques (RMs) to investigate the anti-inflammatory effects of FNC. The experiments involved HE staining, mass spectrometry-based proteomics, validation experiments conducted in vivo using RMs tissues and in vitro differentiation of HL-60 cells. Additionally, interaction investigations were carried out utilizing LiP-MS, CETSA, Co-IP along with molecular docking. The results demonstrated that FNC treatment effectively alleviated neutrophil infiltration and attenuated inflammatory injury following infection. In addition to exhibiting antiviral effects, FNC treatment exhibited a reduction in inflammation-associated proteins and pathways such as myeloperoxidase (MPO) and the formation of NETs, respectively. Validation experiments confirmed the impact of FNC on regulating NETs formation, interaction experiments suggested that MPO may serves as a therapeutic target. The multifaceted properties of FNC, including its antiviral and anti-inflammatory characteristics, highlight the therapeutic potential in diseases associated with NETosis, particularly those involving concurrent SARS-CoV-2 infection, providing insights for drug development targeting MPO and NETosis-associated diseases.
Neutrophil extracellular traps (NETs) formation (NETosis), is a crucial immune system mechanism mediated by neutrophils, measuring the capacity to induce NETosis is proposed as a clinical biomarker indicating the severity of COVID-19 and long COVID. Azvudine (FNC), has shown efficacy in treating SARS-CoV-2 infection and potential for alleviating inflammation. However, the molecular mechanism underlying its anti-inflammatory effects has not been extensively investigated. Therefore, a series of experiments were conducted on SARS-CoV-2 infected rhesus macaques (RMs) to investigate the anti-inflammatory effects of FNC. The experiments involved HE staining, mass spectrometry-based proteomics, validation experiments conducted in vivo using RMs tissues and in vitro differentiation of HL-60 cells. Additionally, interaction investigations were carried out utilizing LiP-MS, CETSA, Co-IP along with molecular docking. The results demonstrated that FNC treatment effectively alleviated neutrophil infiltration and attenuated inflammatory injury following infection. In addition to exhibiting antiviral effects, FNC treatment exhibited a reduction in inflammation-associated proteins and pathways such as myeloperoxidase (MPO) and the formation of NETs, respectively. Validation experiments confirmed the impact of FNC on regulating NETs formation, interaction experiments suggested that MPO may serves as a therapeutic target. The multifaceted properties of FNC, including its antiviral and anti-inflammatory characteristics, highlight the therapeutic potential in diseases associated with NETosis, particularly those involving concurrent SARS-CoV-2 infection, providing insights for drug development targeting MPO and NETosis-associated diseases.
2025, 36(5): 110239
doi: 10.1016/j.cclet.2024.110239
摘要:
Here we present a highly efficient protocol utilizing nickel-hydride hydrogen atom transfer catalysis for the regio- and enantioselective hydrofluorination of internal alkenes. This method efficiently assembles a wide array of enantioenriched β-fluoro amides with excellent regio- and enantioselectivity from internal unactivated alkenes. Mechanistic investigations suggest that this transformation proceeds via a NiH-hydrogen atom transfer to alkene, followed by a stereoselective fluorine atom transfer process. The weak coordination effect of the tethered amide group is identified as a crucial factor governing the observed regio- and enantioselectivity.
Here we present a highly efficient protocol utilizing nickel-hydride hydrogen atom transfer catalysis for the regio- and enantioselective hydrofluorination of internal alkenes. This method efficiently assembles a wide array of enantioenriched β-fluoro amides with excellent regio- and enantioselectivity from internal unactivated alkenes. Mechanistic investigations suggest that this transformation proceeds via a NiH-hydrogen atom transfer to alkene, followed by a stereoselective fluorine atom transfer process. The weak coordination effect of the tethered amide group is identified as a crucial factor governing the observed regio- and enantioselectivity.
2025, 36(5): 110240
doi: 10.1016/j.cclet.2024.110240
摘要:
Nanoplastics exhibit greater environmental biotoxicity than microplastics and can be ingested by humans through major routes such as tap water, bottled water and other drinking water. Nanoplastics present a challenge for air flotation due to their minute particle size, negative surface potential, and similar density to water. This study employed dodecyltrimethylammonium chloride (DTAC) as a modifier to improve conventional air flotation, which significantly enhanced the removal of polystyrene nanoplastics (PSNPs). Conventional air flotation removed only 3.09% of PSNPs, while air flotation modified by dodecyltrimethylammonium chloride (DTAC-modified air flotation) increased the removal of PSNPs to 98.05%. The analysis of the DTAC-modified air flotation mechanism was conducted using a combination of instruments, including a zeta potential analyzer, contact angle meter, laser particle size meter, high definition camera, scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and Fourier transform infrared spectrometer (FTIR). The results indicated that the incorporation of DTAC reversed the electrostatic repulsion between bubbles and PSNPs to electrostatic attraction, significantly enhancing the hydrophobic force in the system. This, in turn, improved the collision adhesion effect between bubbles and PSNPs. The experimental results indicated that even when the flotation time was reduced to 7 min, the DTAC-modified air flotation still achieved a high removal rate of 96.26%. Furthermore, changes in aeration, pH, and ionic strength did not significantly affect the performance of the modified air flotation for the removal of PSNPs. The removal rate of PSNPs in all three water bodies exceeded 95%. The DTAC-modified air flotation has excellent resistance to interference from complex conditions and shows great potential for practical application.
Nanoplastics exhibit greater environmental biotoxicity than microplastics and can be ingested by humans through major routes such as tap water, bottled water and other drinking water. Nanoplastics present a challenge for air flotation due to their minute particle size, negative surface potential, and similar density to water. This study employed dodecyltrimethylammonium chloride (DTAC) as a modifier to improve conventional air flotation, which significantly enhanced the removal of polystyrene nanoplastics (PSNPs). Conventional air flotation removed only 3.09% of PSNPs, while air flotation modified by dodecyltrimethylammonium chloride (DTAC-modified air flotation) increased the removal of PSNPs to 98.05%. The analysis of the DTAC-modified air flotation mechanism was conducted using a combination of instruments, including a zeta potential analyzer, contact angle meter, laser particle size meter, high definition camera, scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and Fourier transform infrared spectrometer (FTIR). The results indicated that the incorporation of DTAC reversed the electrostatic repulsion between bubbles and PSNPs to electrostatic attraction, significantly enhancing the hydrophobic force in the system. This, in turn, improved the collision adhesion effect between bubbles and PSNPs. The experimental results indicated that even when the flotation time was reduced to 7 min, the DTAC-modified air flotation still achieved a high removal rate of 96.26%. Furthermore, changes in aeration, pH, and ionic strength did not significantly affect the performance of the modified air flotation for the removal of PSNPs. The removal rate of PSNPs in all three water bodies exceeded 95%. The DTAC-modified air flotation has excellent resistance to interference from complex conditions and shows great potential for practical application.
2025, 36(5): 110241
doi: 10.1016/j.cclet.2024.110241
摘要:
Hyperglycemia resulting from diabetes mellitus (DM) exacerbates osteoporosis and fractures, damaging bone regeneration due to impaired healing capacity. Stem cell therapy offers the potential for bone repair, accelerating the healing of bone defects by introducing stem cells with osteogenic differentiation ability. Dental follicle stem cells (DFSCs) are a newly emerging type of dental stem cells that not only have the potential for multipotent differentiation but also hold easy accessibility and can stand long-term storage. However, DM-associated oxidative stress and inflammation elevate the risk of DFSCs dysfunction and apoptosis, diminishing stem cell therapy efficacy. Recent nanomaterial advances, particularly in DNA nanostructures like tetrahedral framework nucleic acids (tFNAs), have been promising candidates for modulating cellular behaviors. Accumulating experiments have shown that tFNAs' cell proliferation and migration-promoting ability and induce osteogenic differentiation of stem cells. Meanwhile, tFNAs can scavenge reactive oxygen species (ROS) and downregulate the secretion of inflammatory factors by inhibiting various inflammation-related signaling pathways. Here, we applied tFNAs to modify DFSCs and observed enhanced osteogenic differentiation alongside ROS scavenging and anti-inflammatory effects mediated by suppressing the ROS/mitogen-activated protein kinases (MAPKs)/nuclear factor kappa-B (NF-κB) signaling pathway. This intervention reduced stem cell apoptosis, bolstering stem cell therapy efficacy in DM. Our study establishes a simple yet potent tFNAs-DFSCs system, offering potential as a bone repair agent for future DM treatment.
Hyperglycemia resulting from diabetes mellitus (DM) exacerbates osteoporosis and fractures, damaging bone regeneration due to impaired healing capacity. Stem cell therapy offers the potential for bone repair, accelerating the healing of bone defects by introducing stem cells with osteogenic differentiation ability. Dental follicle stem cells (DFSCs) are a newly emerging type of dental stem cells that not only have the potential for multipotent differentiation but also hold easy accessibility and can stand long-term storage. However, DM-associated oxidative stress and inflammation elevate the risk of DFSCs dysfunction and apoptosis, diminishing stem cell therapy efficacy. Recent nanomaterial advances, particularly in DNA nanostructures like tetrahedral framework nucleic acids (tFNAs), have been promising candidates for modulating cellular behaviors. Accumulating experiments have shown that tFNAs' cell proliferation and migration-promoting ability and induce osteogenic differentiation of stem cells. Meanwhile, tFNAs can scavenge reactive oxygen species (ROS) and downregulate the secretion of inflammatory factors by inhibiting various inflammation-related signaling pathways. Here, we applied tFNAs to modify DFSCs and observed enhanced osteogenic differentiation alongside ROS scavenging and anti-inflammatory effects mediated by suppressing the ROS/mitogen-activated protein kinases (MAPKs)/nuclear factor kappa-B (NF-κB) signaling pathway. This intervention reduced stem cell apoptosis, bolstering stem cell therapy efficacy in DM. Our study establishes a simple yet potent tFNAs-DFSCs system, offering potential as a bone repair agent for future DM treatment.
2025, 36(5): 110243
doi: 10.1016/j.cclet.2024.110243
摘要:
The asymmetric addition of aromatic organometallic compounds to the carbonyl group (C-3) of isatins, catalyzed by transition metals, has emerged as a remarkably efficient method for the synthesis of chiral 3-hydroxyoxindoles. Here, an exceptionally enantioselective approach was developed for the first time to achieve a catalytic NHK reaction of isatins with aromatic halides (both aryl and heteroaryl). Utilizing chiral cobalt complexes as catalysts, and the presence of a diboron reagent B2nep2 as both a reducing agent and determinant in enantiocontrol, has resulted in the triumphantly achieved synthesis of enantioenriched products. Compared to reported strategies, this approach exhibits remarkable compatibility with substrates bearing sensitive functional groups, such as halides and borate esters, while also eliminating the need for organometallic reagents as required in previous strategies. Through experimental investigations, the presence of aryl-cobalt species during the addition process was confirmed, rather than in-situ generation of an arylboron reagent. Furthermore, the successful attainment of the R absolute configuration through aryl addition was demonstrated.
The asymmetric addition of aromatic organometallic compounds to the carbonyl group (C-3) of isatins, catalyzed by transition metals, has emerged as a remarkably efficient method for the synthesis of chiral 3-hydroxyoxindoles. Here, an exceptionally enantioselective approach was developed for the first time to achieve a catalytic NHK reaction of isatins with aromatic halides (both aryl and heteroaryl). Utilizing chiral cobalt complexes as catalysts, and the presence of a diboron reagent B2nep2 as both a reducing agent and determinant in enantiocontrol, has resulted in the triumphantly achieved synthesis of enantioenriched products. Compared to reported strategies, this approach exhibits remarkable compatibility with substrates bearing sensitive functional groups, such as halides and borate esters, while also eliminating the need for organometallic reagents as required in previous strategies. Through experimental investigations, the presence of aryl-cobalt species during the addition process was confirmed, rather than in-situ generation of an arylboron reagent. Furthermore, the successful attainment of the R absolute configuration through aryl addition was demonstrated.
2025, 36(5): 110244
doi: 10.1016/j.cclet.2024.110244
摘要:
Humic acid (HA), as a represent of natural organic matter widely existing in water body, dose harm to water quality and human health; however, it was commonly treated as an environmental background substance while not targeted contaminant in advanced oxidation processes (AOPs). Herein, we investigated the removal of HA in the alkali-activated biochar (KBC)/peroxymonosulfate (PMS) system. The modification of the original biochar (BC) resulted in an increased adsorption capacity and catalytic activity due to the introduction of more micropores, mesopores, and oxygen-containing functional groups, particularly carbonyl groups. Mechanistic insights indicated that HA is primarily chemically adsorbed on the KBC surface, while singlet oxygen (1O2) produced by the PMS decomposition served as the major reactive species for the degradation of HA. An underlying synergistic adsorption and oxidation mechanism involving a local high concentration reaction region around the KBC interface was then proposed. This work not only provides a cost-effective solution for the elimination of HA but also advances our understanding of the nonradical oxidation at the biochar interface.
Humic acid (HA), as a represent of natural organic matter widely existing in water body, dose harm to water quality and human health; however, it was commonly treated as an environmental background substance while not targeted contaminant in advanced oxidation processes (AOPs). Herein, we investigated the removal of HA in the alkali-activated biochar (KBC)/peroxymonosulfate (PMS) system. The modification of the original biochar (BC) resulted in an increased adsorption capacity and catalytic activity due to the introduction of more micropores, mesopores, and oxygen-containing functional groups, particularly carbonyl groups. Mechanistic insights indicated that HA is primarily chemically adsorbed on the KBC surface, while singlet oxygen (1O2) produced by the PMS decomposition served as the major reactive species for the degradation of HA. An underlying synergistic adsorption and oxidation mechanism involving a local high concentration reaction region around the KBC interface was then proposed. This work not only provides a cost-effective solution for the elimination of HA but also advances our understanding of the nonradical oxidation at the biochar interface.
2025, 36(5): 110249
doi: 10.1016/j.cclet.2024.110249
摘要:
Nanobelts are a rapidly developing family of macrocycles with appealing features. However, their host-guest chemistry is currently limited to the recognition of fullerenes via π–π interactions. Herein, we report two heteroatom-bridged [8]cyclophenoxathiin nanobelts ([8]CP-Me and [8]CP) encapsulate corannulene (Cora) to form bowl-in-bowl supramolecular structures stabilized mainly through CH–π interactions in solid-state. The convex surface of corannulene is oriented towards the cavity due to geometry complementarity. The complex Cora⊂[8]CP exhibits a unique 2:2 capsule-like structure in crystal packing, in which corannulene adopts a concave-to-concave assembling fashion. This work enriches the molecular recognition of nanobelts and demonstrates that CH–π interactions can act as the main driving force for nanobelts host-guest complexes.
Nanobelts are a rapidly developing family of macrocycles with appealing features. However, their host-guest chemistry is currently limited to the recognition of fullerenes via π–π interactions. Herein, we report two heteroatom-bridged [8]cyclophenoxathiin nanobelts ([8]CP-Me and [8]CP) encapsulate corannulene (Cora) to form bowl-in-bowl supramolecular structures stabilized mainly through CH–π interactions in solid-state. The convex surface of corannulene is oriented towards the cavity due to geometry complementarity. The complex Cora⊂[8]CP exhibits a unique 2:2 capsule-like structure in crystal packing, in which corannulene adopts a concave-to-concave assembling fashion. This work enriches the molecular recognition of nanobelts and demonstrates that CH–π interactions can act as the main driving force for nanobelts host-guest complexes.
2025, 36(5): 110253
doi: 10.1016/j.cclet.2024.110253
摘要:
The radical difunctionalization of alkenes with sulfonyl bifunctional represents a powerful and straightforward approach to access functionalized alkane derivatives. However, both the mechanistic activation mode and the substrate scopes of this type of radical difunctionalizations are still limited. We demonstrate herein a modular photoredox strategy for the difunctionalization of alkenes, employing arylsulfonyl acetate as the bifunctional reagent. This approach involves a radical addition/Smiles rearrangement cascade process, offering a robust alternative for the synthesis of valuable γ,γ-diaryl and γ-aryl esters. A complementary oxidative bifunctional reagents activation mode is identified to govern the radical cascade reactions, facilitating the simultaneous incorporation of aryl and carboxylate-bearing alkyl groups into the alkenes with excellent diastereoselectivity. Noteworthy features of this method include mild reaction conditions, organophotocatalysis, high atom- and step-economy, excellent functional group compatibility and great structural diversity.
The radical difunctionalization of alkenes with sulfonyl bifunctional represents a powerful and straightforward approach to access functionalized alkane derivatives. However, both the mechanistic activation mode and the substrate scopes of this type of radical difunctionalizations are still limited. We demonstrate herein a modular photoredox strategy for the difunctionalization of alkenes, employing arylsulfonyl acetate as the bifunctional reagent. This approach involves a radical addition/Smiles rearrangement cascade process, offering a robust alternative for the synthesis of valuable γ,γ-diaryl and γ-aryl esters. A complementary oxidative bifunctional reagents activation mode is identified to govern the radical cascade reactions, facilitating the simultaneous incorporation of aryl and carboxylate-bearing alkyl groups into the alkenes with excellent diastereoselectivity. Noteworthy features of this method include mild reaction conditions, organophotocatalysis, high atom- and step-economy, excellent functional group compatibility and great structural diversity.
2025, 36(5): 110258
doi: 10.1016/j.cclet.2024.110258
摘要:
The continuous mutation and rapid spread of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) have led to the ineffectiveness of many antiviral drugs targeting the original strain. To keep pace with the virus' evolutionary speed, there is a crucial need for the development of rapid, cost-effective, and efficient inhibitor screening methods. In this study, we created a novel approach based on fluorescence resonance energy transfer (FRET) technology for in vitro detection of inhibitors targeting the interaction between the SARS-CoV-2 spike protein RBD (s-RBD) and the virus receptor angiotensin-converting enzyme 2 (ACE2). Utilizing crystallographic insights into the s-RBD/ACE2 interaction, we modified ACE2 by fusing SNAP tag to its N-terminus (resulting in SA740) and Halo tag to s-RBD’s C-terminus (producing R525H and R541H), thereby ensuring the proximity (< 10 nm) of labeled FRET dyes. We found that relative to the R541H fusion protein, R525H exhibited higher FRET efficiency, which attributed to the shortened distance between FRET dyes due to the truncation of s-RBD. Utilizing the sensitive FRET effect between SA740 and R525H, we evaluated its efficacy in detecting inhibitors of SARS-CoV-2 entry in solution and live cells. Ultimately, this FRET-based detection method was demonstrated high sensitivity, rapidity, and simplicity in solution and held promise for high-throughput screening of SARS-CoV-2 inhibitors.
The continuous mutation and rapid spread of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) have led to the ineffectiveness of many antiviral drugs targeting the original strain. To keep pace with the virus' evolutionary speed, there is a crucial need for the development of rapid, cost-effective, and efficient inhibitor screening methods. In this study, we created a novel approach based on fluorescence resonance energy transfer (FRET) technology for in vitro detection of inhibitors targeting the interaction between the SARS-CoV-2 spike protein RBD (s-RBD) and the virus receptor angiotensin-converting enzyme 2 (ACE2). Utilizing crystallographic insights into the s-RBD/ACE2 interaction, we modified ACE2 by fusing SNAP tag to its N-terminus (resulting in SA740) and Halo tag to s-RBD’s C-terminus (producing R525H and R541H), thereby ensuring the proximity (< 10 nm) of labeled FRET dyes. We found that relative to the R541H fusion protein, R525H exhibited higher FRET efficiency, which attributed to the shortened distance between FRET dyes due to the truncation of s-RBD. Utilizing the sensitive FRET effect between SA740 and R525H, we evaluated its efficacy in detecting inhibitors of SARS-CoV-2 entry in solution and live cells. Ultimately, this FRET-based detection method was demonstrated high sensitivity, rapidity, and simplicity in solution and held promise for high-throughput screening of SARS-CoV-2 inhibitors.
2025, 36(5): 110260
doi: 10.1016/j.cclet.2024.110260
摘要:
Perovskite oxides have been widely applied as an effective catalyst in heterogeneous catalysis. However, the rational design of active catalysts has been restricted by the lack of understanding of the electronic structure. The correlations between surface properties and bulk electronic structure have been ignored. Herein, a simple handler of LaFeO3 with diluted HNO3 was employed to tune the electronic structure and catalytic properties. Experimental analysis and theoretical calculations elucidate that acid etching could raise the Fe valence and enhance Fe–O covalency in the octahedral structure, thereby lessening charge transfer energy. Enhanced Fe–O covalency could lower oxygen vacancy formation energy and enhance oxygen mobility. In-situ DRIFTS results indicated the inherent adsorption capability of Toluene and CO molecules has been greatly improved owing to higher Fe–O covalency. As compared, the catalysts after acid etching exhibited higher catalytic activity, and the T90 had a great reduction of 45 and 58 ℃ for toluene and CO oxidation, respectively. A deeper understanding of electronic structure in perovskite oxides may inspire the design of high-performance catalysts.
Perovskite oxides have been widely applied as an effective catalyst in heterogeneous catalysis. However, the rational design of active catalysts has been restricted by the lack of understanding of the electronic structure. The correlations between surface properties and bulk electronic structure have been ignored. Herein, a simple handler of LaFeO3 with diluted HNO3 was employed to tune the electronic structure and catalytic properties. Experimental analysis and theoretical calculations elucidate that acid etching could raise the Fe valence and enhance Fe–O covalency in the octahedral structure, thereby lessening charge transfer energy. Enhanced Fe–O covalency could lower oxygen vacancy formation energy and enhance oxygen mobility. In-situ DRIFTS results indicated the inherent adsorption capability of Toluene and CO molecules has been greatly improved owing to higher Fe–O covalency. As compared, the catalysts after acid etching exhibited higher catalytic activity, and the T90 had a great reduction of 45 and 58 ℃ for toluene and CO oxidation, respectively. A deeper understanding of electronic structure in perovskite oxides may inspire the design of high-performance catalysts.
2025, 36(5): 110282
doi: 10.1016/j.cclet.2024.110282
摘要:
As a renovator in the field of gene editing, CRISPR-Cas9 has demonstrated immense potential for advancing next-generation gene therapy owing to its simplicity and precision. However, this potential faces significant challenges primarily stemming from the difficulty in efficiently delivering large-sized genome editing system (including Cas9 protein and sgRNA) into targeted cells and spatiotemporally controlling their activity in vitro and in vivo. Therefore, the development of CRISPR/Cas9 nanovectors that integrate high loading capacity, efficient encapsulation and spatiotemporally-controlled release is highly desirable. Herein, we have engineered a near-infrared (NIR) light-activated upconversion-DNA nanocapsule for the remote control of CRISPR-Cas9 genome editing. The light-responsive upconversion-DNA nanocapsules consist of macroporous silica (mSiO2) coated upconversion nanoparticles (UCNPs) and photocleavable o-nitrobenzyl-phosphate-modified DNA shells. The UCNPs act as a "nanotransducers" to convert NIR light (980 nm) into local ultraviolet light, thereby facilitating the cleavage of photosensitive DNA nanocapsules and enabling on-demand release of CRISPR-Cas9 encapsuled in the macroporous silica. Furthermore, by formulating a sgRNA targeted to a tumor gene (polo-like kinase-1, PLK-1), the CRISPR-Cas9 loaded UCNP-DNA nanocapsules (crUCNP-DNA nanocapsules) have effectively suppressed the proliferation of tumor cells through NIR light-activated gene editing both in vitro and in vivo. Overall, this UCNP-DNA nanocapsule holds tremendous potential for CRISPR-Cas9 delivery and remote-controlled gene editing in deep tissues, as well as the treatment of diverse diseases.
As a renovator in the field of gene editing, CRISPR-Cas9 has demonstrated immense potential for advancing next-generation gene therapy owing to its simplicity and precision. However, this potential faces significant challenges primarily stemming from the difficulty in efficiently delivering large-sized genome editing system (including Cas9 protein and sgRNA) into targeted cells and spatiotemporally controlling their activity in vitro and in vivo. Therefore, the development of CRISPR/Cas9 nanovectors that integrate high loading capacity, efficient encapsulation and spatiotemporally-controlled release is highly desirable. Herein, we have engineered a near-infrared (NIR) light-activated upconversion-DNA nanocapsule for the remote control of CRISPR-Cas9 genome editing. The light-responsive upconversion-DNA nanocapsules consist of macroporous silica (mSiO2) coated upconversion nanoparticles (UCNPs) and photocleavable o-nitrobenzyl-phosphate-modified DNA shells. The UCNPs act as a "nanotransducers" to convert NIR light (980 nm) into local ultraviolet light, thereby facilitating the cleavage of photosensitive DNA nanocapsules and enabling on-demand release of CRISPR-Cas9 encapsuled in the macroporous silica. Furthermore, by formulating a sgRNA targeted to a tumor gene (polo-like kinase-1, PLK-1), the CRISPR-Cas9 loaded UCNP-DNA nanocapsules (crUCNP-DNA nanocapsules) have effectively suppressed the proliferation of tumor cells through NIR light-activated gene editing both in vitro and in vivo. Overall, this UCNP-DNA nanocapsule holds tremendous potential for CRISPR-Cas9 delivery and remote-controlled gene editing in deep tissues, as well as the treatment of diverse diseases.
2025, 36(5): 110291
doi: 10.1016/j.cclet.2024.110291
摘要:
Metal hydrides serve as crucial intermediates in many chemical processes, facilitating the utilization of hydrogen resources. Traditionally, three-centre metal hydrides have been viewed as less reactive due to their multi-stabilization effects. However, recent discoveries show the "three-centre four-electron" (3c-4e) bridging hydride bond exhibits significant activity in boryl transition metal systems. This research employs computational techniques to explore the factors that influence the formation of the 3c-4e bridging hydride, focusing on boryl 3d non-noble transition metals ranging from chromium (Cr) to nickel (Ni). By analyzing bond distances and bond orders, the study sheds light on the electronic and structural characteristics of the B-H-M bridging hydride. It reveals a clear link between the metal centre's redox properties and the emergence of bridging hydrides. Specifically, metal centres like Cr and Co, which have lower oxidation states and electronegativity, are more inclined to form active 3c-4e bridging hydrides. These insights, derived from computational analyses, offer valuable guidelines for the development of active 3c-4e bridging metal hydrides, thereby contributing to the advancement of new hydrogen transformation catalysts.
Metal hydrides serve as crucial intermediates in many chemical processes, facilitating the utilization of hydrogen resources. Traditionally, three-centre metal hydrides have been viewed as less reactive due to their multi-stabilization effects. However, recent discoveries show the "three-centre four-electron" (3c-4e) bridging hydride bond exhibits significant activity in boryl transition metal systems. This research employs computational techniques to explore the factors that influence the formation of the 3c-4e bridging hydride, focusing on boryl 3d non-noble transition metals ranging from chromium (Cr) to nickel (Ni). By analyzing bond distances and bond orders, the study sheds light on the electronic and structural characteristics of the B-H-M bridging hydride. It reveals a clear link between the metal centre's redox properties and the emergence of bridging hydrides. Specifically, metal centres like Cr and Co, which have lower oxidation states and electronegativity, are more inclined to form active 3c-4e bridging hydrides. These insights, derived from computational analyses, offer valuable guidelines for the development of active 3c-4e bridging metal hydrides, thereby contributing to the advancement of new hydrogen transformation catalysts.
2025, 36(5): 110293
doi: 10.1016/j.cclet.2024.110293
摘要:
Singlet oxygen (1O2), as an electrophilic oxidant, is essential for the selective water decontamination of pollutants from water. Herein, we showcase a high-performing electrocatalytic filtration system composed of carbon nanotubes functionalized with CoFe alloy nanoparticles (CoFeCNT) to selectively facilitate the electrochemical activation of O2 to 1O2. Benefiting from the prominently featured bimetal active sites of CoFeCNT, nearly complete production of 1O2 is achieved by the electrocatalytic activation of O2. Additionally, the proposed system exhibits a consistent pollutant removal efficiency > 90% in a flow-through reactor over 48 h of continuous operation without a noticeable decline in performance, highlighting the dependable stability of the system for practical applications. The flow-through configuration demonstrates a striking 8-fold enhancement in tetracycline oxidation compared to a conventional batch reactor. This work provides a molecular level understanding of the oxygen reduction reaction, showing promising potential for the selective removal of emerging organic contaminants from water.
Singlet oxygen (1O2), as an electrophilic oxidant, is essential for the selective water decontamination of pollutants from water. Herein, we showcase a high-performing electrocatalytic filtration system composed of carbon nanotubes functionalized with CoFe alloy nanoparticles (CoFeCNT) to selectively facilitate the electrochemical activation of O2 to 1O2. Benefiting from the prominently featured bimetal active sites of CoFeCNT, nearly complete production of 1O2 is achieved by the electrocatalytic activation of O2. Additionally, the proposed system exhibits a consistent pollutant removal efficiency > 90% in a flow-through reactor over 48 h of continuous operation without a noticeable decline in performance, highlighting the dependable stability of the system for practical applications. The flow-through configuration demonstrates a striking 8-fold enhancement in tetracycline oxidation compared to a conventional batch reactor. This work provides a molecular level understanding of the oxygen reduction reaction, showing promising potential for the selective removal of emerging organic contaminants from water.
2025, 36(5): 110295
doi: 10.1016/j.cclet.2024.110295
摘要:
Developing a high-efficiency catalyst with both superior low-temperature activity and good N2 selectivity is still challenging for the NH3 selective catalytic reduction (SCR) of NOx from mobile sources. Herein, we demonstrate the improved low-temperature activity and N2 selectivity by regulating the redox and acidic properties of MnCe oxides supported on etched ZSM-5 supports. The etched ZSM-5 enables the highly dispersed state of MnCeOx species and strong interaction between Mn and Ce species, which promotes the reduction of CeO2, facilitates electron transfer from Mn to Ce, and generates more Mn4+ and Ce3+ species. The strong redox capacity contributes to forming the reactive nitrate species and -NH2 species from oxidative dehydrogenation of NH3. Moreover, the adsorbed NH3 and -NH2 species are the reactive intermediates that promote the formation of N2. This work demonstrates an effective strategy to enhance the low-temperature activity and N2 selectivity of SCR catalysts, contributing to the NOx control for the low-temperature exhaust gas during the cold-start of diesel vehicles.
Developing a high-efficiency catalyst with both superior low-temperature activity and good N2 selectivity is still challenging for the NH3 selective catalytic reduction (SCR) of NOx from mobile sources. Herein, we demonstrate the improved low-temperature activity and N2 selectivity by regulating the redox and acidic properties of MnCe oxides supported on etched ZSM-5 supports. The etched ZSM-5 enables the highly dispersed state of MnCeOx species and strong interaction between Mn and Ce species, which promotes the reduction of CeO2, facilitates electron transfer from Mn to Ce, and generates more Mn4+ and Ce3+ species. The strong redox capacity contributes to forming the reactive nitrate species and -NH2 species from oxidative dehydrogenation of NH3. Moreover, the adsorbed NH3 and -NH2 species are the reactive intermediates that promote the formation of N2. This work demonstrates an effective strategy to enhance the low-temperature activity and N2 selectivity of SCR catalysts, contributing to the NOx control for the low-temperature exhaust gas during the cold-start of diesel vehicles.
2025, 36(5): 110306
doi: 10.1016/j.cclet.2024.110306
摘要:
The intrinsic clustering behavior and kinetically sluggish conversion process of lithium polysulfides seriously limit the electrochemical reversibility of sulfur redox reactions in lithium-sulfur (Li-S) batteries. Here, we introduce molybdenum pentachloride (MoCl5) into the electrolyte which could coordinate with lithium polysulfides and inhibit their intrinsic clustering behavior, subsequently serving as an improved mediator with the bi-functional catalytic effect for Li2S deposition and activation. Moreover, the coordination bonding and accelerated conversion reaction can also greatly suppress the dissolution and shuttling of polysulfides. Consequently, such polysulfide complexes enable the Li-S coin cell to exhibit good long-term cycling stability with a capacity decay of 0.078% per cycle after 400 cycles at 2 C, and excellent rate performance with a discharge capacity of 589 mAh/g at 4 C. An area capacity of 3.94 mAh/cm2 is also achieved with a high sulfur loading of 4.5 mg/cm2 at 0.2 C. Even at -20 ℃, the modified cell maintains standard discharge plateaus with low overpotential, delivering a high capacity of 741 mAh/g at 0.2 C after 80 cycles. The low-cost and convenient MoCl5 additive opens a new avenue for the effective regulation of polysulfides and significant enhancement in sulfur redox conversion.
The intrinsic clustering behavior and kinetically sluggish conversion process of lithium polysulfides seriously limit the electrochemical reversibility of sulfur redox reactions in lithium-sulfur (Li-S) batteries. Here, we introduce molybdenum pentachloride (MoCl5) into the electrolyte which could coordinate with lithium polysulfides and inhibit their intrinsic clustering behavior, subsequently serving as an improved mediator with the bi-functional catalytic effect for Li2S deposition and activation. Moreover, the coordination bonding and accelerated conversion reaction can also greatly suppress the dissolution and shuttling of polysulfides. Consequently, such polysulfide complexes enable the Li-S coin cell to exhibit good long-term cycling stability with a capacity decay of 0.078% per cycle after 400 cycles at 2 C, and excellent rate performance with a discharge capacity of 589 mAh/g at 4 C. An area capacity of 3.94 mAh/cm2 is also achieved with a high sulfur loading of 4.5 mg/cm2 at 0.2 C. Even at -20 ℃, the modified cell maintains standard discharge plateaus with low overpotential, delivering a high capacity of 741 mAh/g at 0.2 C after 80 cycles. The low-cost and convenient MoCl5 additive opens a new avenue for the effective regulation of polysulfides and significant enhancement in sulfur redox conversion.
2025, 36(5): 110310
doi: 10.1016/j.cclet.2024.110310
摘要:
An electronic circular dichroism (ECD)-based chiroptical sensing method has been developed for β- and γ-chiral primary amines via a C–H activation reaction. With the addition of Pd(OAc)2, the flexible remote chiral primary amine fragment in the bidentate ligand intermediate was fixed to form a cyclopalladium complex, producing an intense ECD response. The correlation between the sign of Cotton effects and the absolute configuration of substrates was proposed, together with theoretical verification using time-dependent density functional theory (TDDFT). Chiroptical sensing of an important drug raw material was performed to provide rapid and accurate information on the absolute optical purity. This work introduces an alternative perspective of C–H activation reaction as well as a feasible chiroptical sensing method of remote chiral amines.
An electronic circular dichroism (ECD)-based chiroptical sensing method has been developed for β- and γ-chiral primary amines via a C–H activation reaction. With the addition of Pd(OAc)2, the flexible remote chiral primary amine fragment in the bidentate ligand intermediate was fixed to form a cyclopalladium complex, producing an intense ECD response. The correlation between the sign of Cotton effects and the absolute configuration of substrates was proposed, together with theoretical verification using time-dependent density functional theory (TDDFT). Chiroptical sensing of an important drug raw material was performed to provide rapid and accurate information on the absolute optical purity. This work introduces an alternative perspective of C–H activation reaction as well as a feasible chiroptical sensing method of remote chiral amines.
2025, 36(5): 110311
doi: 10.1016/j.cclet.2024.110311
摘要:
Achieving artificial simulations of multi-step energy transfer processes and conversions in nature remains a challenge. In this study, we present a three-step sequential energy transfer process, which was constructed through host-guest interactions between a piperazine derivative (PPE-BPI) with aggregation-induced emission (AIE) and cucurbit[7]uril (CB[7]) in water to serve as ideal energy donors. To achieve multi-step sequential energy transfer, we employ three distinct fluorescent dyes Eosin B (EsB), Sulforhodamine 101 (SR101), and Cyanine 5 (Cy5) as energy acceptors. The PPE-PBI-2CB[7]+EsB+SR101+Cy5 system demonstrates a highly efficient three-step sequential energy transfer mechanism, starting with PPE-PBI-2CB[7] and transferring energy successively to EsB, SR101, and finally to Cy5, with remarkable energy transfer efficiencies. More interestingly, with the progressive transfer of energy in the multi-step energy transfer system, the generation efficiency of superoxide anion radical (O2•–) increased gradually, which can be used as photocatalysts for selectively photooxidation of N-phenyltetrahydroisoquinoline in an aqueous medium with a high yield of 86% after irradiation for 18 h. This study offers a valuable investigation into the simulation of multi-step energy transfer processes and transformations in the natural world, paving the way for further research in the field.
Achieving artificial simulations of multi-step energy transfer processes and conversions in nature remains a challenge. In this study, we present a three-step sequential energy transfer process, which was constructed through host-guest interactions between a piperazine derivative (PPE-BPI) with aggregation-induced emission (AIE) and cucurbit[7]uril (CB[7]) in water to serve as ideal energy donors. To achieve multi-step sequential energy transfer, we employ three distinct fluorescent dyes Eosin B (EsB), Sulforhodamine 101 (SR101), and Cyanine 5 (Cy5) as energy acceptors. The PPE-PBI-2CB[7]+EsB+SR101+Cy5 system demonstrates a highly efficient three-step sequential energy transfer mechanism, starting with PPE-PBI-2CB[7] and transferring energy successively to EsB, SR101, and finally to Cy5, with remarkable energy transfer efficiencies. More interestingly, with the progressive transfer of energy in the multi-step energy transfer system, the generation efficiency of superoxide anion radical (O2•–) increased gradually, which can be used as photocatalysts for selectively photooxidation of N-phenyltetrahydroisoquinoline in an aqueous medium with a high yield of 86% after irradiation for 18 h. This study offers a valuable investigation into the simulation of multi-step energy transfer processes and transformations in the natural world, paving the way for further research in the field.
2025, 36(5): 110312
doi: 10.1016/j.cclet.2024.110312
摘要:
A sp2 carbon-conjugated covalent organic framework (BDATN) was modified through γ-ray radiation reduction and subsequent acidification with hydrochloric acid to yield a novel functional COF (named rBDATN-HCl) for Cr(VI) removal. The morphology and structure of rBDATN-HCl were analyzed and identified by SEM, FTIR, XRD and solid-state 13C NMR. It is found that the active functional groups, such as hydroxyl and amide, were introduced into BDATN after radiation reduction and acidification. The prepared rBDATN-HCl demonstrates a photocatalytic reduction removal rate of Cr(VI) above 99% after 60 min of illumination with a solid-liquid ratio of 0.5 mg/mL, showing outstanding performance, which is attributed to the increase of dispersibility and adsorption sites of rBDATN-HCl. In comparison to the cBDATN-HCl synthesized with chemical reduction, rBDATN-HCl exhibits a better photoreduction performance for Cr(VI), demonstrating the advantages of radiation preparation of rBDATN-HCl. It is expected that more functionalized sp2 carbon-conjugated COFs could be obtained by this radiation-induced reduction strategy.
A sp2 carbon-conjugated covalent organic framework (BDATN) was modified through γ-ray radiation reduction and subsequent acidification with hydrochloric acid to yield a novel functional COF (named rBDATN-HCl) for Cr(VI) removal. The morphology and structure of rBDATN-HCl were analyzed and identified by SEM, FTIR, XRD and solid-state 13C NMR. It is found that the active functional groups, such as hydroxyl and amide, were introduced into BDATN after radiation reduction and acidification. The prepared rBDATN-HCl demonstrates a photocatalytic reduction removal rate of Cr(VI) above 99% after 60 min of illumination with a solid-liquid ratio of 0.5 mg/mL, showing outstanding performance, which is attributed to the increase of dispersibility and adsorption sites of rBDATN-HCl. In comparison to the cBDATN-HCl synthesized with chemical reduction, rBDATN-HCl exhibits a better photoreduction performance for Cr(VI), demonstrating the advantages of radiation preparation of rBDATN-HCl. It is expected that more functionalized sp2 carbon-conjugated COFs could be obtained by this radiation-induced reduction strategy.
2025, 36(5): 110334
doi: 10.1016/j.cclet.2024.110334
摘要:
An unprecedented 2,3-arylacylation reaction of allenes with aryl iodides and aldehydes was developed by resorting to Pd/NHC synergetic catalysis. It is the first time that allene was introduced into transition metal and NHC synergetic catalysis, which demonstrated a versatile three-component reaction pattern, thus enabling two C-C bonds forged regioselectively in the reaction. The important reaction intermediates were successfully captured and characterized by HRMS analysis, and the migrative insertion of allene to the Ph-Pd species was identified as the reaction rate-limiting step by kinetic experiments.
An unprecedented 2,3-arylacylation reaction of allenes with aryl iodides and aldehydes was developed by resorting to Pd/NHC synergetic catalysis. It is the first time that allene was introduced into transition metal and NHC synergetic catalysis, which demonstrated a versatile three-component reaction pattern, thus enabling two C-C bonds forged regioselectively in the reaction. The important reaction intermediates were successfully captured and characterized by HRMS analysis, and the migrative insertion of allene to the Ph-Pd species was identified as the reaction rate-limiting step by kinetic experiments.
2025, 36(5): 110432
doi: 10.1016/j.cclet.2024.110432
摘要:
Chirality, ubiquitous in living matter, plays vital roles in a series of physiological processes. The clarification of the multiple functions of chirality in bioapplications may provide innovative methodologies for engineering anti-tumor agents. Nevertheless, the related research has been rarely explored. In this study, the chiral supramolecular l/d-cysteine (Cys)-Zn2+-indocyanine green (ICG) nanoparticles were constructed through the coordination interaction between l/d-Cys and Zn2+, followed by the encapsulation of ICG. Experimental findings revealed that the d-Cys-Zn2+-ICG exhibited 17.31 times higher binding affinity toward phospholipid-composed liposomes compared to l-Cys-Zn2+-ICG. Furthermore, driven by chirality-specific interaction, a 2.07 folds greater cellular internalization of d-Cys-Zn2+-ICG than l-Cys-Zn2+-ICG was demonstrated. Additionally, the triple-level chirality-dependent photothermal, photodynamic and Zn2+ releasing anti-tumor effects of l/d Cys-Zn2+-ICG in vitro were verified. As a result, the d-formed nanoparticles achieved 1.93 times higher anti-tumor efficiency than the l-formed ones. The triple-level chirality-mediated anti-tumor effect highlighted in this study underscores the enormous potential of chirality in biomedicine and holds substantial significance in improving cancer therapeutic efficacy.
Chirality, ubiquitous in living matter, plays vital roles in a series of physiological processes. The clarification of the multiple functions of chirality in bioapplications may provide innovative methodologies for engineering anti-tumor agents. Nevertheless, the related research has been rarely explored. In this study, the chiral supramolecular l/d-cysteine (Cys)-Zn2+-indocyanine green (ICG) nanoparticles were constructed through the coordination interaction between l/d-Cys and Zn2+, followed by the encapsulation of ICG. Experimental findings revealed that the d-Cys-Zn2+-ICG exhibited 17.31 times higher binding affinity toward phospholipid-composed liposomes compared to l-Cys-Zn2+-ICG. Furthermore, driven by chirality-specific interaction, a 2.07 folds greater cellular internalization of d-Cys-Zn2+-ICG than l-Cys-Zn2+-ICG was demonstrated. Additionally, the triple-level chirality-dependent photothermal, photodynamic and Zn2+ releasing anti-tumor effects of l/d Cys-Zn2+-ICG in vitro were verified. As a result, the d-formed nanoparticles achieved 1.93 times higher anti-tumor efficiency than the l-formed ones. The triple-level chirality-mediated anti-tumor effect highlighted in this study underscores the enormous potential of chirality in biomedicine and holds substantial significance in improving cancer therapeutic efficacy.
2025, 36(5): 110437
doi: 10.1016/j.cclet.2024.110437
摘要:
Ferroptosis in combination with immune therapy emerges as a promising approach for cancer therapy. Herein, dual-responsive metal-polyphenol coordinated nanomedicines were developed for pH/glutathione (GSH)-responsive synergistic ferroptosis and immunotherapy. Our innovative strategy involves the development of a manganese-polyphenol coordinated nanostructure, leveraging the biocompatibility of bovine serum albumin (BSA) as a template to encapsulate the anticancer drug sorafenib. The tumor microenvironment (pH/GSH) prompts the disassembly of MnO2 and epigallocatechin gallate (EGCG), thereby releases the anticancer payload. Concurrently, MnO2 acts to deplete intracellular GSH, which in turn suppresses glutathione peroxidase activity, leading to an accumulation of lipid peroxides with cell ferroptosis. Additionally, the release of Mn2+ ions bolster the cyclic guanosine monophosphlic acid (GMP)-adenosine monophosphlic acid (AMP) synthase-stimulator of interferon gene (cGAS-STING) pathway, which, in conjunction with the immunogenic cell death (ICD) effect induced by tumor cell apoptosis, significantly promotes dendritic cell (DC) maturation and enhances the presentation of tumor antigens. This successively ignites a robust innate and adaptive immune response. Both in vitro and in vivo experiments have demonstrated that the concurrent administration of ferroptosis-inducing and immune-stimulating therapies can significantly inhibit tumor growth.
Ferroptosis in combination with immune therapy emerges as a promising approach for cancer therapy. Herein, dual-responsive metal-polyphenol coordinated nanomedicines were developed for pH/glutathione (GSH)-responsive synergistic ferroptosis and immunotherapy. Our innovative strategy involves the development of a manganese-polyphenol coordinated nanostructure, leveraging the biocompatibility of bovine serum albumin (BSA) as a template to encapsulate the anticancer drug sorafenib. The tumor microenvironment (pH/GSH) prompts the disassembly of MnO2 and epigallocatechin gallate (EGCG), thereby releases the anticancer payload. Concurrently, MnO2 acts to deplete intracellular GSH, which in turn suppresses glutathione peroxidase activity, leading to an accumulation of lipid peroxides with cell ferroptosis. Additionally, the release of Mn2+ ions bolster the cyclic guanosine monophosphlic acid (GMP)-adenosine monophosphlic acid (AMP) synthase-stimulator of interferon gene (cGAS-STING) pathway, which, in conjunction with the immunogenic cell death (ICD) effect induced by tumor cell apoptosis, significantly promotes dendritic cell (DC) maturation and enhances the presentation of tumor antigens. This successively ignites a robust innate and adaptive immune response. Both in vitro and in vivo experiments have demonstrated that the concurrent administration of ferroptosis-inducing and immune-stimulating therapies can significantly inhibit tumor growth.
2025, 36(5): 110508
doi: 10.1016/j.cclet.2024.110508
摘要:
Candida albicans is one of the most common pathogens causing invasive fungal infections, with a mortality rate of up to 20%–50%. Amphotericin B (AmB), a biopharmaceutics classification system (BCS) IV drug, significantly inhibits Candida albicans. AmB is primarily administered via oral and intravenous infusion, but severe infusion adverse effects, nephrotoxicity, and potential hepatotoxicity limit its clinical application. Deep eutectic solvents (DESs), with excellent solubilization ability and skin permeability, are attractive for transdermal delivery. Herein, we used DESs to deliver AmB for antifungal therapy transdermally. We first prepared and characterized DESs with different stoichiometric ratios of choline (Ch) and geranate (Ge). DESs increased the solubility of AmB by a thousand-fold. In vitro and in vivo, skin permeation studies indicated that DES1:2 (Ch and Ge in 1:2 ratio) had the most outstanding penetration and delivered fluorescence dye to the dermis layer. Then, DES1:2-AmB was prepared and in vitro antifungal tests demonstrated that DES1:2-AmB had superior antifungal effects compared to AmB and DES1:2. Furthermore, DES1:2-AmB was skin-irritating and biocompatible. In conclusion, DES-AmB provides a new and effective therapeutic solution for fungal infections.
Candida albicans is one of the most common pathogens causing invasive fungal infections, with a mortality rate of up to 20%–50%. Amphotericin B (AmB), a biopharmaceutics classification system (BCS) IV drug, significantly inhibits Candida albicans. AmB is primarily administered via oral and intravenous infusion, but severe infusion adverse effects, nephrotoxicity, and potential hepatotoxicity limit its clinical application. Deep eutectic solvents (DESs), with excellent solubilization ability and skin permeability, are attractive for transdermal delivery. Herein, we used DESs to deliver AmB for antifungal therapy transdermally. We first prepared and characterized DESs with different stoichiometric ratios of choline (Ch) and geranate (Ge). DESs increased the solubility of AmB by a thousand-fold. In vitro and in vivo, skin permeation studies indicated that DES1:2 (Ch and Ge in 1:2 ratio) had the most outstanding penetration and delivered fluorescence dye to the dermis layer. Then, DES1:2-AmB was prepared and in vitro antifungal tests demonstrated that DES1:2-AmB had superior antifungal effects compared to AmB and DES1:2. Furthermore, DES1:2-AmB was skin-irritating and biocompatible. In conclusion, DES-AmB provides a new and effective therapeutic solution for fungal infections.
2025, 36(5): 110561
doi: 10.1016/j.cclet.2024.110561
摘要:
Nanochannel technology based on ionic current rectification has emerged as a powerful tool for the detection of biomolecules owing to unique advantages. Nevertheless, existing nanochannel sensors mainly focus on the detection of targets in solution or inside the cells, moreover, they only have a single function, greatly limiting their application. Herein, we fabricated SuperDNA self-assembled conical nanochannel, which was clamped in the middle of self-made device for two functions: Online detecting living cells released TNF-α and studying intercellular communication. Polyethylene terephthalate (PET) membrane incubated tumor associated macrophages and tumor cells was rolled up and inserted into the left and right chamber of the device, respectively. Through monitoring the ion current change in the nanochannel, tumor associated macrophages released TNF-α could be in situ and noninvasive detected with a detection limit of 0.23 pg/mL. Furthermore, the secreted TNF-α induced epithelial-mesenchymal transformation of tumor cells in the right chamber was also studied. The presented strategy displayed outstanding performance and multi-function, providing a promising platform for in situ non-destructive detection of cell secretions and related intercellular communication analysis.
Nanochannel technology based on ionic current rectification has emerged as a powerful tool for the detection of biomolecules owing to unique advantages. Nevertheless, existing nanochannel sensors mainly focus on the detection of targets in solution or inside the cells, moreover, they only have a single function, greatly limiting their application. Herein, we fabricated SuperDNA self-assembled conical nanochannel, which was clamped in the middle of self-made device for two functions: Online detecting living cells released TNF-α and studying intercellular communication. Polyethylene terephthalate (PET) membrane incubated tumor associated macrophages and tumor cells was rolled up and inserted into the left and right chamber of the device, respectively. Through monitoring the ion current change in the nanochannel, tumor associated macrophages released TNF-α could be in situ and noninvasive detected with a detection limit of 0.23 pg/mL. Furthermore, the secreted TNF-α induced epithelial-mesenchymal transformation of tumor cells in the right chamber was also studied. The presented strategy displayed outstanding performance and multi-function, providing a promising platform for in situ non-destructive detection of cell secretions and related intercellular communication analysis.
2025, 36(5): 110629
doi: 10.1016/j.cclet.2024.110629
摘要:
Room-temperature phosphorescence (RTP) materials exhibiting long emission lifetimes have gained increasing attention owing to their potential applications in encryption, anti-counterfeiting, and sensing. However, most polymers exhibit a short RTP lifetime (<1 s) because of their unstable triplet excitons. Herein, a new strategy of polymer chain stabilized phosphorescence (PCSP), which yields a new kind of RTP polymers with an ultralong lifetime and a sensitive oxygen response, has been reported. The rigid polymer chains of poly(methyl mathacrylate) (PMMA) immobilize the emitter molecules through multiple interactions between them, giving rise to efficient RTP. Meanwhile, the loosely-packed amorphous polymer chains allow oxygen to diffuse inside, endowing the doped polymers with oxygen sensitivity. Flexible and transparent polymer films exhibited an impressive ultralong RTP lifetime of 2.57 s at room temperature in vacuum, which was among the best performance of PMMA. Intriguingly, their RTP was rapidly quenched in the presence of oxygen. Furthermore, RTP microparticles with a diameter of 1.63 µm were synthesized using in situ dispersion polymerization technique. Finally, oxygen sensors for quick, visual, and quantitative oxygen detection were developed based on the RTP microparticles through phosphorescence lifetime and image analysis. With distinctive advantages such as an ultralong lifetime, oxygen sensitivity, ease of fabrication, and cost-effectiveness, PCSP opens a new avenue to sensitive materials for oxygen detection.
Room-temperature phosphorescence (RTP) materials exhibiting long emission lifetimes have gained increasing attention owing to their potential applications in encryption, anti-counterfeiting, and sensing. However, most polymers exhibit a short RTP lifetime (<1 s) because of their unstable triplet excitons. Herein, a new strategy of polymer chain stabilized phosphorescence (PCSP), which yields a new kind of RTP polymers with an ultralong lifetime and a sensitive oxygen response, has been reported. The rigid polymer chains of poly(methyl mathacrylate) (PMMA) immobilize the emitter molecules through multiple interactions between them, giving rise to efficient RTP. Meanwhile, the loosely-packed amorphous polymer chains allow oxygen to diffuse inside, endowing the doped polymers with oxygen sensitivity. Flexible and transparent polymer films exhibited an impressive ultralong RTP lifetime of 2.57 s at room temperature in vacuum, which was among the best performance of PMMA. Intriguingly, their RTP was rapidly quenched in the presence of oxygen. Furthermore, RTP microparticles with a diameter of 1.63 µm were synthesized using in situ dispersion polymerization technique. Finally, oxygen sensors for quick, visual, and quantitative oxygen detection were developed based on the RTP microparticles through phosphorescence lifetime and image analysis. With distinctive advantages such as an ultralong lifetime, oxygen sensitivity, ease of fabrication, and cost-effectiveness, PCSP opens a new avenue to sensitive materials for oxygen detection.
2025, 36(5): 110663
doi: 10.1016/j.cclet.2024.110663
摘要:
Transition metal cobalt exhibits strong activation capabilities for alkanes, however, the instability of Co sites leads to sintering and coke deposition, resulting in rapid deactivation. Hierarchical zeolites, with their diverse pore structures and high surface areas, are used to effectively anchor metals and enhance coke tolerance. Herein, a post-treatment method using an alkaline solution was employed to synthesize meso-microporous zeolite supports, which were subsequently loaded with Co species for propane dehydrogenation catalyst. The results indicate that the application of NaOH, an inorganic base, produces supports with a larger mesopore volume and more abundant hydroxyl nests compared to TPAOH, an organic base. UV–vis, Raman, and XPS analyses reveal that Co in the 0.5Co/SN-1–0.05 catalyst is mainly in the form of tetrahedral Co2+, which effectively activates CH bonds. In contrast, the 0.5Co/S-1 catalyst contains mainly Co3O4 species. Co2+ supported on hierarchical zeolites shows better propane conversion (58.6%) and propylene selectivity (>96%) compared to pure silica zeolites. Coke characterization indicates that hierarchical zeolites accumulate more coke, but it is mostly in the form of easily removable disordered carbon. The mesopores in the microporous zeolite support help disperse the active Co metal and facilitate coke removal during dehydrogenation, effectively preventing deactivation from sintering and coke coverage.
Transition metal cobalt exhibits strong activation capabilities for alkanes, however, the instability of Co sites leads to sintering and coke deposition, resulting in rapid deactivation. Hierarchical zeolites, with their diverse pore structures and high surface areas, are used to effectively anchor metals and enhance coke tolerance. Herein, a post-treatment method using an alkaline solution was employed to synthesize meso-microporous zeolite supports, which were subsequently loaded with Co species for propane dehydrogenation catalyst. The results indicate that the application of NaOH, an inorganic base, produces supports with a larger mesopore volume and more abundant hydroxyl nests compared to TPAOH, an organic base. UV–vis, Raman, and XPS analyses reveal that Co in the 0.5Co/SN-1–0.05 catalyst is mainly in the form of tetrahedral Co2+, which effectively activates CH bonds. In contrast, the 0.5Co/S-1 catalyst contains mainly Co3O4 species. Co2+ supported on hierarchical zeolites shows better propane conversion (58.6%) and propylene selectivity (>96%) compared to pure silica zeolites. Coke characterization indicates that hierarchical zeolites accumulate more coke, but it is mostly in the form of easily removable disordered carbon. The mesopores in the microporous zeolite support help disperse the active Co metal and facilitate coke removal during dehydrogenation, effectively preventing deactivation from sintering and coke coverage.
2025, 36(5): 110672
doi: 10.1016/j.cclet.2024.110672
摘要:
On-demand droplet manipulation plays a critical role in microfluidics, bio/chemical detection and micro-reactions. Acoustic droplet manipulation has emerged as a promising technique due to its non-contact nature, biocompatibility and precision, circumventing the complexities associated with other methods requiring surface or droplet pretreatment. Despite their promise, existing methods for acoustic droplet manipulation often involve complex hardware setups and difficulty for controlling individual droplet amidst multiple ones. Here we fabricate simple yet effective acoustic tweezers for in-surface and out-of-surface droplet manipulation. It is found that droplets can be transported on the superhydrophobic surfaces when the acoustic radiation force surpasses the friction force. Using a two-axis acoustic tweezer, droplets can be maneuvered along arbitrarily programmed paths on the surfaces. By introducing multiple labyrinthine structures on the superhydrophobic surface, individual droplet manipulation is realized by constraining the unselected droplets in the labyrinthine structures. In addition, a three-axis acoustic tweezer is developed for manipulating droplets in three-dimensional space. Potential applications of the acoustic tweezers for micro-reaction, bio-assay and chemical analysis are also demonstrated.
On-demand droplet manipulation plays a critical role in microfluidics, bio/chemical detection and micro-reactions. Acoustic droplet manipulation has emerged as a promising technique due to its non-contact nature, biocompatibility and precision, circumventing the complexities associated with other methods requiring surface or droplet pretreatment. Despite their promise, existing methods for acoustic droplet manipulation often involve complex hardware setups and difficulty for controlling individual droplet amidst multiple ones. Here we fabricate simple yet effective acoustic tweezers for in-surface and out-of-surface droplet manipulation. It is found that droplets can be transported on the superhydrophobic surfaces when the acoustic radiation force surpasses the friction force. Using a two-axis acoustic tweezer, droplets can be maneuvered along arbitrarily programmed paths on the surfaces. By introducing multiple labyrinthine structures on the superhydrophobic surface, individual droplet manipulation is realized by constraining the unselected droplets in the labyrinthine structures. In addition, a three-axis acoustic tweezer is developed for manipulating droplets in three-dimensional space. Potential applications of the acoustic tweezers for micro-reaction, bio-assay and chemical analysis are also demonstrated.
2025, 36(5): 110699
doi: 10.1016/j.cclet.2024.110699
摘要:
Generally, gaining fundamental insights into chain processes during the combustion of flame-retardant polymers relies on the qualitative and quantitative characterization of key chain carriers. However, polymer combustion processes based on conventional solid-fuel combustion strategies, due to the high coupling of pyrolysis, combustion, soot formation and oxidation, exhibit relatively high complexity and poor flame stability, and lead to a huge obstacle to the use of optical diagnostics. Herein, a spatial-confinement combustion strategy, which can produce a special staged flame with multi-jets secondary wave, is devised to provide a highly decoupled combustion environment. Glowing soot particles are therefore decoupled from main chemiluminescence region and confined to the flame tip to provide a well-controlled, optical-thin test environment for combustion diagnostic. Based on this strategy, a multi-nozzle-separation (MNS) burner is designed and fabricated, and the combustion processes associated with four model compounds, PVC, PS, PP/TBBA blends and PP/RP blends are investigated by spontaneous spectral diagnosis, and the chemiluminescence fingerprint of key diatomic/triatomic intermediates (such as OH, CH, C2, ClO, Br2, and PHO) are clearly observed. This encouraging result means that the strategy of spatial-confinement combustion we proposed shows promising prospect in many subjects associated with combustion chain regulation, such as efficient design of flame retardants.
Generally, gaining fundamental insights into chain processes during the combustion of flame-retardant polymers relies on the qualitative and quantitative characterization of key chain carriers. However, polymer combustion processes based on conventional solid-fuel combustion strategies, due to the high coupling of pyrolysis, combustion, soot formation and oxidation, exhibit relatively high complexity and poor flame stability, and lead to a huge obstacle to the use of optical diagnostics. Herein, a spatial-confinement combustion strategy, which can produce a special staged flame with multi-jets secondary wave, is devised to provide a highly decoupled combustion environment. Glowing soot particles are therefore decoupled from main chemiluminescence region and confined to the flame tip to provide a well-controlled, optical-thin test environment for combustion diagnostic. Based on this strategy, a multi-nozzle-separation (MNS) burner is designed and fabricated, and the combustion processes associated with four model compounds, PVC, PS, PP/TBBA blends and PP/RP blends are investigated by spontaneous spectral diagnosis, and the chemiluminescence fingerprint of key diatomic/triatomic intermediates (such as OH, CH, C2, ClO, Br2, and PHO) are clearly observed. This encouraging result means that the strategy of spatial-confinement combustion we proposed shows promising prospect in many subjects associated with combustion chain regulation, such as efficient design of flame retardants.
2025, 36(5): 110700
doi: 10.1016/j.cclet.2024.110700
摘要:
Heterocyclic compounds play an important role in organic hole transport materials (HTMs) for perovskite solar cells (PSCs). Herein, a series of linear D-π-D HTMs (OCBz, S-CBz, SO2-CBz) with different dibenzo-heterocycles core (dibenzofuran, dibenzothiophene, dibenzothiophene sulfone) were designed and synthesized, and their applications in PSCs were investigated. The intrinsic properties (CV, UV–vis, hole mobility and conductivity) were systematically investigated, demonstrating that all three materials are suitable HTMs for planar n-i-p type PSCs. Benefiting from the excellent hole mobility and conductivity, good film forming ability, and outstanding charge extraction and transport capability of S-CBz, FAPbI3-based PSCs using S-CBz as HTM achieved a PCE of 25.0%, which is superior to that of Spiro-OMeTAD-based PSCs fabricated under the same conditions (23.9%). Furthermore, due to the interaction between S and Pb2+, S-CBz-based PSC devices exhibited improved stability. This work demonstrates that dibenzothiophene-based architectures are promising candidates for high-performance HTMs in perovskite solar cell architectures.
Heterocyclic compounds play an important role in organic hole transport materials (HTMs) for perovskite solar cells (PSCs). Herein, a series of linear D-π-D HTMs (OCBz, S-CBz, SO2-CBz) with different dibenzo-heterocycles core (dibenzofuran, dibenzothiophene, dibenzothiophene sulfone) were designed and synthesized, and their applications in PSCs were investigated. The intrinsic properties (CV, UV–vis, hole mobility and conductivity) were systematically investigated, demonstrating that all three materials are suitable HTMs for planar n-i-p type PSCs. Benefiting from the excellent hole mobility and conductivity, good film forming ability, and outstanding charge extraction and transport capability of S-CBz, FAPbI3-based PSCs using S-CBz as HTM achieved a PCE of 25.0%, which is superior to that of Spiro-OMeTAD-based PSCs fabricated under the same conditions (23.9%). Furthermore, due to the interaction between S and Pb2+, S-CBz-based PSC devices exhibited improved stability. This work demonstrates that dibenzothiophene-based architectures are promising candidates for high-performance HTMs in perovskite solar cell architectures.
2025, 36(5): 110719
doi: 10.1016/j.cclet.2024.110719
摘要:
Crystalized CeO2 structures were typically considered potential photocatalysts due to their great capacity to alter the active sites’ size and ability to absorb light. However, the controllable fabrication of well-defined hierarchical structures of CeO2 with high reactive facets is significant and challenging. Herein, a series of CeO2 supports including hierarchical flower-like (F-CeO2), ball-like (B-CeO2), cube-like (CCeO2), and rod-like CeO2(R-CeO2) supports were prepared by hydrothermal method (B-CeO2, R-CeO2 and CCeO2) or ice-bath method (F-CeO2) respectively. V atoms were selected as the active atoms and loaded on these supports. Their structure-activity relationship in photo-assisted thermal propane dehydrogenation (PTPDH) was investigated systematically. The samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N2 adsorption-desorption isotherms, and Fourier transform infrared spectrum. Results show that R-CeO2 support exhibits the biggest surface area thus achieving the best dispersion of VOx species. UV–vis spectrum and photoluminescence spectrum indicate that V/F-CeO2 has the best light adsorption property and V/R-CeO2 has the best carrier migration capacity. The activity tests demonstrate that the V/R-CeO2 has the largest net growth rate and the V/F-CeO2 has the biggest relative growth ratio. Furthermore, the non-thermal effect was confirmed by the kinetic method, which lowers the propane reaction orders, selectively promoting the first C–H bond activation. The light radiation TPSR experiment confirmed this point. DFT calculations show a good linear relationship between the energy barrier and the exchanged electron number. It inspires the design of high-reactive facets for boosting the intrinsic activity of the C–H bond in photo-assisted thermal chemical processes.
Crystalized CeO2 structures were typically considered potential photocatalysts due to their great capacity to alter the active sites’ size and ability to absorb light. However, the controllable fabrication of well-defined hierarchical structures of CeO2 with high reactive facets is significant and challenging. Herein, a series of CeO2 supports including hierarchical flower-like (F-CeO2), ball-like (B-CeO2), cube-like (CCeO2), and rod-like CeO2(R-CeO2) supports were prepared by hydrothermal method (B-CeO2, R-CeO2 and CCeO2) or ice-bath method (F-CeO2) respectively. V atoms were selected as the active atoms and loaded on these supports. Their structure-activity relationship in photo-assisted thermal propane dehydrogenation (PTPDH) was investigated systematically. The samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N2 adsorption-desorption isotherms, and Fourier transform infrared spectrum. Results show that R-CeO2 support exhibits the biggest surface area thus achieving the best dispersion of VOx species. UV–vis spectrum and photoluminescence spectrum indicate that V/F-CeO2 has the best light adsorption property and V/R-CeO2 has the best carrier migration capacity. The activity tests demonstrate that the V/R-CeO2 has the largest net growth rate and the V/F-CeO2 has the biggest relative growth ratio. Furthermore, the non-thermal effect was confirmed by the kinetic method, which lowers the propane reaction orders, selectively promoting the first C–H bond activation. The light radiation TPSR experiment confirmed this point. DFT calculations show a good linear relationship between the energy barrier and the exchanged electron number. It inspires the design of high-reactive facets for boosting the intrinsic activity of the C–H bond in photo-assisted thermal chemical processes.
2025, 36(5): 110724
doi: 10.1016/j.cclet.2024.110724
摘要:
To get large dissymmetric factor (glum) of organic circularly polarized luminescence (CPL) materials is still a great challenge. Although helical chirality and planar chirality are usual efficient access to enhancement of CPL, they are not combined together to boost CPL. Here, a new tetraphenylethylene (TPE) tetracycle acid helicate bearing both helical chirality and planar chirality was designed and synthesized. Uniquely, synergy of the helical chirality and planar chirality was used to boost CPL signals both in solution and in helical self-assemblies. In the presence of octadecylamine, the TPE helicate could form helical nanofibers that emitted strong CPL signals with an absolute glum value up to 0.237. Exceptionally, followed by addition of para-phenylenediamine, the glum value was successively increased to 0.387 due to formation of bigger helical nanofibers. Compared with that of TPE helicate itself, the CPL signal of the self-assemblies was not only magnified by 104-fold but also inversed, which was very rare result for CPL-active materials. Surprisingly, the interaction of TPE helicate with xylylenediamine even gave a gel, which was transformed into suspension by shaking. Unexpectedly, the suspension showed 40-fold stronger CPL signals than the gel with signal direction inversion each other. Using synergy of the helical chirality and planar chirality to significantly boost CPL intensity provides a new strategy in preparation of organic CPL materials having very large glum value.
To get large dissymmetric factor (glum) of organic circularly polarized luminescence (CPL) materials is still a great challenge. Although helical chirality and planar chirality are usual efficient access to enhancement of CPL, they are not combined together to boost CPL. Here, a new tetraphenylethylene (TPE) tetracycle acid helicate bearing both helical chirality and planar chirality was designed and synthesized. Uniquely, synergy of the helical chirality and planar chirality was used to boost CPL signals both in solution and in helical self-assemblies. In the presence of octadecylamine, the TPE helicate could form helical nanofibers that emitted strong CPL signals with an absolute glum value up to 0.237. Exceptionally, followed by addition of para-phenylenediamine, the glum value was successively increased to 0.387 due to formation of bigger helical nanofibers. Compared with that of TPE helicate itself, the CPL signal of the self-assemblies was not only magnified by 104-fold but also inversed, which was very rare result for CPL-active materials. Surprisingly, the interaction of TPE helicate with xylylenediamine even gave a gel, which was transformed into suspension by shaking. Unexpectedly, the suspension showed 40-fold stronger CPL signals than the gel with signal direction inversion each other. Using synergy of the helical chirality and planar chirality to significantly boost CPL intensity provides a new strategy in preparation of organic CPL materials having very large glum value.
2025, 36(5): 110760
doi: 10.1016/j.cclet.2024.110760
摘要:
Triphenylamine (TPA) is the most promising donor fragment for the construction of long-wavelength thermally activated delayed fluorescence (TADF) emitters owing to its suitable dihedral angle that could enhance radiative decay to compete with the serious non-radiative decay. However, the moderate electron-donating capacity of TPA seriously limits the selection of acceptor for constructing long-wavelength TADF emitters with narrow bandgaps. To address this issue, in this work, the peripheral benzene of TPA was replaced with 1,4-benzodioxane and anisole to obtain two new electron-donating units N-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-N-phenyl-2,3-dihydrobenzo[b][1,4]dioxin-6-amine (TPADBO, −5.02 eV) and 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline (TPAMO, −5.00 eV), which possess much shallower highest occupied molecule orbital (HOMO) energy levels than the prototype TPA (−5.33 eV). Based on TPA and the modified TPA donor fragments, three TADF emitters were designed and synthesized, namely Py-TPA, Py-TPADBO and Py-TPAMO, with the same acceptor fragment 12-(2,6-diisopropylphenyl)pyrido[2′,3′:5,6]pyrazino[2,3-f][1,10]phenanthroline (Py). Among them, Py-TPAMO exhibits the highest photoluminescence quantum yield of 78.4% and the smallest singlet-triplet energy gap, which is because the introduction of anisole does not cause significant molecule deformation for the excited Py-TPAMO. And Py-TPAMO-based OLEDs successfully realize a maximum external quantum efficiency of 25.5% with the emission peak at 605 nm. This work provides a series of candidate of donor fragments for the development of efficient long-wavelength TADF emitters.
Triphenylamine (TPA) is the most promising donor fragment for the construction of long-wavelength thermally activated delayed fluorescence (TADF) emitters owing to its suitable dihedral angle that could enhance radiative decay to compete with the serious non-radiative decay. However, the moderate electron-donating capacity of TPA seriously limits the selection of acceptor for constructing long-wavelength TADF emitters with narrow bandgaps. To address this issue, in this work, the peripheral benzene of TPA was replaced with 1,4-benzodioxane and anisole to obtain two new electron-donating units N-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-N-phenyl-2,3-dihydrobenzo[b][1,4]dioxin-6-amine (TPADBO, −5.02 eV) and 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline (TPAMO, −5.00 eV), which possess much shallower highest occupied molecule orbital (HOMO) energy levels than the prototype TPA (−5.33 eV). Based on TPA and the modified TPA donor fragments, three TADF emitters were designed and synthesized, namely Py-TPA, Py-TPADBO and Py-TPAMO, with the same acceptor fragment 12-(2,6-diisopropylphenyl)pyrido[2′,3′:5,6]pyrazino[2,3-f][1,10]phenanthroline (Py). Among them, Py-TPAMO exhibits the highest photoluminescence quantum yield of 78.4% and the smallest singlet-triplet energy gap, which is because the introduction of anisole does not cause significant molecule deformation for the excited Py-TPAMO. And Py-TPAMO-based OLEDs successfully realize a maximum external quantum efficiency of 25.5% with the emission peak at 605 nm. This work provides a series of candidate of donor fragments for the development of efficient long-wavelength TADF emitters.
2025, 36(5): 110762
doi: 10.1016/j.cclet.2024.110762
摘要:
A series of “half-sandwich” bis(imino)pyridyl iron complexes with a substituted 8-(p-X-phenyl)naphthylamine (X = OMe, Me, CF3) was designed and synthesized by combining weak π-π interaction with steric and electronic tunings. The weak noncovalent π-π interaction as well as the steric and electronic effects of bis(imino)pyridyl iron complexes were identified by experimental analyses and calculations. The roles of weak π-π interaction, steric bulk, and electronic tuning on the ethylene polymerization performance of bis(imino)pyridyl iron catalysts were studied in detail. The combination of π-π interaction with steric and electronic tunings can access to thermally stable bis(imino)pyridyl iron at 130 ℃.
A series of “half-sandwich” bis(imino)pyridyl iron complexes with a substituted 8-(p-X-phenyl)naphthylamine (X = OMe, Me, CF3) was designed and synthesized by combining weak π-π interaction with steric and electronic tunings. The weak noncovalent π-π interaction as well as the steric and electronic effects of bis(imino)pyridyl iron complexes were identified by experimental analyses and calculations. The roles of weak π-π interaction, steric bulk, and electronic tuning on the ethylene polymerization performance of bis(imino)pyridyl iron catalysts were studied in detail. The combination of π-π interaction with steric and electronic tunings can access to thermally stable bis(imino)pyridyl iron at 130 ℃.
2025, 36(5): 110765
doi: 10.1016/j.cclet.2024.110765
摘要:
Metal ions trigger Fenton/Fenton-like reactions, generating highly toxic hydroxyl radicals (•OH) for chemodynamic therapy (CDT), which is crucial in inducing lethal oxidative DNA damage and subsequent cell apoptosis. However, tumor cells can counteract this damage through repair pathways, particularly MutT homolog 1 (MTH1) protein attenuation of oxidative DNA damage. Suppression of MTH1 can enhance CDT efficacy, therefore, orderly integrating Fenton/Fenton-like agents with an MTH1 inhibitor is expected to significantly augment CDT effectiveness. Carrier-free CuTH@CD, self-assembled through the supramolecular orchestration of γ-cyclodextrin (γ-CD) with Cu2+ and the MTH1 inhibitor TH588, effectively overcoming tumor resistance by greatly amplifying oxidative damage capability. Without additional carriers and mediated by multiple supramolecular regulatory effects, CuTH@CD enables high drug loading content, stability, and uniform size distribution. Upon internalization by tumor cells, CuTH@CD invalidates repair pathways through Cu2+-mediated glutathione (GSH) depletion and TH588-mediated MTH1 inhibition. Meanwhile, both generated Cu+ ions and existing ones within the nanoassembly initiate a Fenton-like reaction, leading to the accumulation of •OH. This strategy enhances CDT efficiency with minimal side effects, improving oxidative damage potency and advancing self-delivery nanoplatforms for developing effective chemodynamic tumor therapies.
Metal ions trigger Fenton/Fenton-like reactions, generating highly toxic hydroxyl radicals (•OH) for chemodynamic therapy (CDT), which is crucial in inducing lethal oxidative DNA damage and subsequent cell apoptosis. However, tumor cells can counteract this damage through repair pathways, particularly MutT homolog 1 (MTH1) protein attenuation of oxidative DNA damage. Suppression of MTH1 can enhance CDT efficacy, therefore, orderly integrating Fenton/Fenton-like agents with an MTH1 inhibitor is expected to significantly augment CDT effectiveness. Carrier-free CuTH@CD, self-assembled through the supramolecular orchestration of γ-cyclodextrin (γ-CD) with Cu2+ and the MTH1 inhibitor TH588, effectively overcoming tumor resistance by greatly amplifying oxidative damage capability. Without additional carriers and mediated by multiple supramolecular regulatory effects, CuTH@CD enables high drug loading content, stability, and uniform size distribution. Upon internalization by tumor cells, CuTH@CD invalidates repair pathways through Cu2+-mediated glutathione (GSH) depletion and TH588-mediated MTH1 inhibition. Meanwhile, both generated Cu+ ions and existing ones within the nanoassembly initiate a Fenton-like reaction, leading to the accumulation of •OH. This strategy enhances CDT efficiency with minimal side effects, improving oxidative damage potency and advancing self-delivery nanoplatforms for developing effective chemodynamic tumor therapies.
2025, 36(5): 109871
doi: 10.1016/j.cclet.2024.109871
摘要:
Green synthesis of drugs is of paramount importance for current public health and a prerequisite to new drugs exploiting. Nowadays, novel strategies of disease diagnosis and therapies are in blooming development as remarkable advances have been achieved which are all highly depended on drug development. Under the current requirements to high production capacity and novel synthesis methods of drugs, green synthesis based on strategies with different ways of empowering, advanced catalysts and unique reaction equipment are attracting huge attention and of great challenging. Higher quality products and environmentally friendly synthesis conditions are becoming more and more important for manufacturing process which has new requirements for catalyst materials and synthesis processes. Polyoxometalates (POMs) are class of transition metals-oxygen clusters with precise molecular structures and superior physicochemical properties which have made longstanding and important applications upon research community of functional materials, catalysis and medicine. In this review, the recent advances of polyoxometalates based strategies for green synthesis of drugs are summarized including POMs based catalysts, alternative reaction equipment based novel synthesis protocols. The significance of POMs to pharmaceutical and industrial field is highlighted and the related perspective for future development are well discussed.
Green synthesis of drugs is of paramount importance for current public health and a prerequisite to new drugs exploiting. Nowadays, novel strategies of disease diagnosis and therapies are in blooming development as remarkable advances have been achieved which are all highly depended on drug development. Under the current requirements to high production capacity and novel synthesis methods of drugs, green synthesis based on strategies with different ways of empowering, advanced catalysts and unique reaction equipment are attracting huge attention and of great challenging. Higher quality products and environmentally friendly synthesis conditions are becoming more and more important for manufacturing process which has new requirements for catalyst materials and synthesis processes. Polyoxometalates (POMs) are class of transition metals-oxygen clusters with precise molecular structures and superior physicochemical properties which have made longstanding and important applications upon research community of functional materials, catalysis and medicine. In this review, the recent advances of polyoxometalates based strategies for green synthesis of drugs are summarized including POMs based catalysts, alternative reaction equipment based novel synthesis protocols. The significance of POMs to pharmaceutical and industrial field is highlighted and the related perspective for future development are well discussed.
2025, 36(5): 109898
doi: 10.1016/j.cclet.2024.109898
摘要:
Two-dimensional (2D) transition metal sulfides (TMDs) are emerging and highly well received 2D materials, which are considered as an ideal 2D platform for studying various electronic properties and potential applications due to their chemical diversity. Converting 2D TMDs into one-dimensional (1D) TMDs nanotubes can not only retain some advantages of 2D nanosheets but also providing a unique direction to explore the novel properties of TMDs materials in the 1D limit. However, the controllable preparation of high-quality nanotubes remains a major challenge. It is very necessary to review the advanced development of one-dimensional transition metal dichalcogenide nanotubes from preparation to application. Here, we first summarize a series of bottom-up synthesis methods of 1D TMDs, such as template growth and metal catalyzed method. Then, top-down synthesis methods are summarized, which included self-curing and stacking of TMDs nanosheets. In addition, we discuss some key applications that utilize the properties of 1D-TMDs nanotubes in the areas of catalyst preparation, energy storage, and electronic devices. Last but not least, we prospect the preparation methods of high-quality 1D-TMDs nanotubes, which will lay a foundation for the synthesis of high-performance optoelectronic devices, catalysts, and energy storage components
Two-dimensional (2D) transition metal sulfides (TMDs) are emerging and highly well received 2D materials, which are considered as an ideal 2D platform for studying various electronic properties and potential applications due to their chemical diversity. Converting 2D TMDs into one-dimensional (1D) TMDs nanotubes can not only retain some advantages of 2D nanosheets but also providing a unique direction to explore the novel properties of TMDs materials in the 1D limit. However, the controllable preparation of high-quality nanotubes remains a major challenge. It is very necessary to review the advanced development of one-dimensional transition metal dichalcogenide nanotubes from preparation to application. Here, we first summarize a series of bottom-up synthesis methods of 1D TMDs, such as template growth and metal catalyzed method. Then, top-down synthesis methods are summarized, which included self-curing and stacking of TMDs nanosheets. In addition, we discuss some key applications that utilize the properties of 1D-TMDs nanotubes in the areas of catalyst preparation, energy storage, and electronic devices. Last but not least, we prospect the preparation methods of high-quality 1D-TMDs nanotubes, which will lay a foundation for the synthesis of high-performance optoelectronic devices, catalysts, and energy storage components
Iridium-based catalysts for oxygen evolution reaction in proton exchange membrane water electrolysis
2025, 36(5): 109906
doi: 10.1016/j.cclet.2024.109906
摘要:
Proton exchange membrane water electrolysis (PEMWE) is a favorable technology for producing high-purity hydrogen under high current density using intermittent renewable energy. The performance of PEMWE is largely determined by the oxygen evolution reaction (OER), a sluggish four-electron reaction with a high reaction barrier. Nowadays, iridium (Ir)-based catalysts are the catalysts of choice for OER due to their excellent activity and durability in acidic solution. However, its high price and unsatisfactory electrochemical performance severely restrict the PEMWE’s practical application. In this review, we initiate by introducing the current OER reaction mechanisms, namely adsorbate evolution mechanism and lattice oxygen mechanism, with degradation mechanisms discussed. Optimized strategies in the preparation of advanced Ir-based catalysts are further introduced, with merits and potential problems also discussed. The parameters that determine the performance of PEMWE are then introduced, with unsolved issues and related outlooks summarized in the end.
Proton exchange membrane water electrolysis (PEMWE) is a favorable technology for producing high-purity hydrogen under high current density using intermittent renewable energy. The performance of PEMWE is largely determined by the oxygen evolution reaction (OER), a sluggish four-electron reaction with a high reaction barrier. Nowadays, iridium (Ir)-based catalysts are the catalysts of choice for OER due to their excellent activity and durability in acidic solution. However, its high price and unsatisfactory electrochemical performance severely restrict the PEMWE’s practical application. In this review, we initiate by introducing the current OER reaction mechanisms, namely adsorbate evolution mechanism and lattice oxygen mechanism, with degradation mechanisms discussed. Optimized strategies in the preparation of advanced Ir-based catalysts are further introduced, with merits and potential problems also discussed. The parameters that determine the performance of PEMWE are then introduced, with unsolved issues and related outlooks summarized in the end.
2025, 36(5): 109938
doi: 10.1016/j.cclet.2024.109938
摘要:
Solid-state electrolytes (SSEs), as the core component within the next generation of key energy storage technologies - solid-state lithium batteries (SSLBs) - are significantly leading the development of future energy storage systems. Among the numerous types of SSEs, inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12 (LLZO) crystallized with the cubic Ia3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity, wide electrochemical voltage window, high shear modulus, and excellent chemical stability with electrodes. However, no SSEs possess all the properties necessary for SSLBs, thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement. Hence, this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration, Li vacancy concentration, Li carrier concentration and mobility, Li occupancy at available sites, lattice constant, triangle bottleneck size, oxygen vacancy defects, and Li-O bonding interactions. Furthermore, the general illustration of structures and fundamental features being crucial to chemical stability is examined, including Li concentration, Li-site occupation behavior, and Li-O bonding interactions. Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures, revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions. We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors, thus assisting in promoting the rapid development of alternative green and sustainable technologies.
Solid-state electrolytes (SSEs), as the core component within the next generation of key energy storage technologies - solid-state lithium batteries (SSLBs) - are significantly leading the development of future energy storage systems. Among the numerous types of SSEs, inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12 (LLZO) crystallized with the cubic Ia3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity, wide electrochemical voltage window, high shear modulus, and excellent chemical stability with electrodes. However, no SSEs possess all the properties necessary for SSLBs, thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement. Hence, this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration, Li vacancy concentration, Li carrier concentration and mobility, Li occupancy at available sites, lattice constant, triangle bottleneck size, oxygen vacancy defects, and Li-O bonding interactions. Furthermore, the general illustration of structures and fundamental features being crucial to chemical stability is examined, including Li concentration, Li-site occupation behavior, and Li-O bonding interactions. Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures, revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions. We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors, thus assisting in promoting the rapid development of alternative green and sustainable technologies.
2025, 36(5): 110059
doi: 10.1016/j.cclet.2024.110059
摘要:
Lateral flow immunoassay (LFIA), a rapid detection technique noted for simplicity and economy, has showcased indispensable applicability in diverse domains such as disease screening, food safety, and environmental monitoring. Nevertheless, challenges still exist in detecting ultra-low concentration analytes due to the inherent sensitivity limitations of LFIA. Recently, significant advances have been achieved by integrating enzyme activity probes and transforming LFIA into a highly sensitive tool for rapidly detecting trace analyte concentrations. Specifically, modifying natural enzymes or engineered nanozymes allows them to function as immune probes, directly catalyzing the production of signal molecules or indirectly initiating enzyme activity. Therefore, the signal intensity and detection sensitivity of LFIA are markedly elevated. The present review undertakes a comprehensive examination of pertinent research literature, offering a systematic analysis of recently proposed enzyme-based signal amplification strategies. By way of comparative assessment, the merits and demerits of current approaches are delineated, along with the identification of research avenues that still need to be explored. It is anticipated that this critical overview will garner considerable attention within the biomedical and materials science communities, providing valuable direction and insight toward the advancement of high-performance LFIA technologies.
Lateral flow immunoassay (LFIA), a rapid detection technique noted for simplicity and economy, has showcased indispensable applicability in diverse domains such as disease screening, food safety, and environmental monitoring. Nevertheless, challenges still exist in detecting ultra-low concentration analytes due to the inherent sensitivity limitations of LFIA. Recently, significant advances have been achieved by integrating enzyme activity probes and transforming LFIA into a highly sensitive tool for rapidly detecting trace analyte concentrations. Specifically, modifying natural enzymes or engineered nanozymes allows them to function as immune probes, directly catalyzing the production of signal molecules or indirectly initiating enzyme activity. Therefore, the signal intensity and detection sensitivity of LFIA are markedly elevated. The present review undertakes a comprehensive examination of pertinent research literature, offering a systematic analysis of recently proposed enzyme-based signal amplification strategies. By way of comparative assessment, the merits and demerits of current approaches are delineated, along with the identification of research avenues that still need to be explored. It is anticipated that this critical overview will garner considerable attention within the biomedical and materials science communities, providing valuable direction and insight toward the advancement of high-performance LFIA technologies.
2025, 36(5): 110072
doi: 10.1016/j.cclet.2024.110072
摘要:
Designing advanced hydrogels with controlled mechanical properties, drug delivery manner and multifunctional properties will be beneficial for biomedical applications. However, the further development of hydrogel is limited due to its poor mechanical property and structural diversity. Hydrogels combined with polymeric micelles to obtain micelle-hydrogel composites have been designed for synergistic enhancement of each original properties. Incorporation polymeric micelles into hydrogel networks can not only enhance the mechanical property of hydrogel, but also expand the functionality of hydrogel. Recent advances in polymeric micelle-hydrogel composites are herein reviewed with a focus on three typical micelle incorporation methods. In this review, we will also highlight some emerging biomedical applications in developing micelle-hydrogel composite with multiple functionalities. In addition, further development and application prospects of the micelle-hydrogels composites have also been addressed.
Designing advanced hydrogels with controlled mechanical properties, drug delivery manner and multifunctional properties will be beneficial for biomedical applications. However, the further development of hydrogel is limited due to its poor mechanical property and structural diversity. Hydrogels combined with polymeric micelles to obtain micelle-hydrogel composites have been designed for synergistic enhancement of each original properties. Incorporation polymeric micelles into hydrogel networks can not only enhance the mechanical property of hydrogel, but also expand the functionality of hydrogel. Recent advances in polymeric micelle-hydrogel composites are herein reviewed with a focus on three typical micelle incorporation methods. In this review, we will also highlight some emerging biomedical applications in developing micelle-hydrogel composite with multiple functionalities. In addition, further development and application prospects of the micelle-hydrogels composites have also been addressed.
2025, 36(5): 110126
doi: 10.1016/j.cclet.2024.110126
摘要:
Chemical modification of native peptides and proteins is a versatile strategy to facilitate late-stage diversification for functional studies. Among the proteogenic amino acids, lysine is extensively involved in post-translational modifications and the binding of ligands to target proteins, making its selective modification attractive. However, lysine’s high natural abundance and solvent accessibility, as well as its relatively low reactivity to cysteine, necessitate addressing chemoselectivity and regioselectivity for the Lys modification of native proteins. Although Lys chemoselective modification methods have been well developed, achieving site-selective modification of a specific Lys residue remains a great challenge. In this review, we discussed the challenges of Lys selective modification, presented recent examples of Lys chemoselective modification, and summarized the currently known methods and strategies for Lys site-selective modification. We also included an outlook on potential solutions for Lys site-selective labeling and its potential applications in chemical biology and drug development.
Chemical modification of native peptides and proteins is a versatile strategy to facilitate late-stage diversification for functional studies. Among the proteogenic amino acids, lysine is extensively involved in post-translational modifications and the binding of ligands to target proteins, making its selective modification attractive. However, lysine’s high natural abundance and solvent accessibility, as well as its relatively low reactivity to cysteine, necessitate addressing chemoselectivity and regioselectivity for the Lys modification of native proteins. Although Lys chemoselective modification methods have been well developed, achieving site-selective modification of a specific Lys residue remains a great challenge. In this review, we discussed the challenges of Lys selective modification, presented recent examples of Lys chemoselective modification, and summarized the currently known methods and strategies for Lys site-selective modification. We also included an outlook on potential solutions for Lys site-selective labeling and its potential applications in chemical biology and drug development.
2025, 36(5): 110226
doi: 10.1016/j.cclet.2024.110226
摘要:
The heritage preservation is of great intractability to the conservators as each kind of heritage material has unique and diverse requirements on temperature, humidity and air cleanliness. It is promising for metal-organic frameworks (MOFs), the multifunctional environment remediation materials, to be applied in heritage environmental protection. The advantages of MOFs lie in their multifunction like adsorption, photocatalysis, sterilization, as well as the controllable structure and properties that could be flexibly adjusted as demands, helping the heritage against various environmental threats. Thereby, the applications and the corresponding mechanisms of MOFs in cultural heritage preservation were reviewed in this work, including harmful gas adsorption, surface waterproofing, particulate matters (PM) removal, anti-bacterial and humidity control of environment. Finally, the selection principles and precautions of MOFs in heritage preservation were discussed, aiming to provide a forward-looking direction for the selection and application of MOFs.
The heritage preservation is of great intractability to the conservators as each kind of heritage material has unique and diverse requirements on temperature, humidity and air cleanliness. It is promising for metal-organic frameworks (MOFs), the multifunctional environment remediation materials, to be applied in heritage environmental protection. The advantages of MOFs lie in their multifunction like adsorption, photocatalysis, sterilization, as well as the controllable structure and properties that could be flexibly adjusted as demands, helping the heritage against various environmental threats. Thereby, the applications and the corresponding mechanisms of MOFs in cultural heritage preservation were reviewed in this work, including harmful gas adsorption, surface waterproofing, particulate matters (PM) removal, anti-bacterial and humidity control of environment. Finally, the selection principles and precautions of MOFs in heritage preservation were discussed, aiming to provide a forward-looking direction for the selection and application of MOFs.
2025, 36(5): 110277
doi: 10.1016/j.cclet.2024.110277
摘要:
As a versatile and environmentally benign oxidant, hydrogen peroxide (H2O2) is highly desired in sanitation, disinfection, environmental remediation, and the chemical industry. Compared with the conventional anthraquinone process, the electrosynthesis of H2O2 through the two-electron oxygen reduction reaction (2e− ORR) is an efficient, competitive, and promising avenue. Electrocatalysts and devices are two core factors in 2e− ORR, but the design principles of catalysts for different pH conditions and the development trends of relevant synthesis devices remain unclear. To this end, this review adopts a multiscale perspective to summarize recent advancements in the design principles, catalytic mechanisms, and application prospects of 2e− ORR catalysts, with a particular focus on the influence of pH conditions, aiming at providing guidance for the selective design of advanced 2e− ORR catalysts for highly-efficient H2O2 production. Moreover, in response to diverse on-site application demands, we elaborate on the evolution of H2O2 electrosynthesis devices, from rotating ring-disk electrodes and H-type cells to diverse flow-type cells. We elaborate on their characteristics and shortcomings, which can be beneficial for their further upgrades and customized applications. These insights may inspire the rational design of innovative catalysts and devices with high performance and wide serviceability for large-scale implementations.
As a versatile and environmentally benign oxidant, hydrogen peroxide (H2O2) is highly desired in sanitation, disinfection, environmental remediation, and the chemical industry. Compared with the conventional anthraquinone process, the electrosynthesis of H2O2 through the two-electron oxygen reduction reaction (2e− ORR) is an efficient, competitive, and promising avenue. Electrocatalysts and devices are two core factors in 2e− ORR, but the design principles of catalysts for different pH conditions and the development trends of relevant synthesis devices remain unclear. To this end, this review adopts a multiscale perspective to summarize recent advancements in the design principles, catalytic mechanisms, and application prospects of 2e− ORR catalysts, with a particular focus on the influence of pH conditions, aiming at providing guidance for the selective design of advanced 2e− ORR catalysts for highly-efficient H2O2 production. Moreover, in response to diverse on-site application demands, we elaborate on the evolution of H2O2 electrosynthesis devices, from rotating ring-disk electrodes and H-type cells to diverse flow-type cells. We elaborate on their characteristics and shortcomings, which can be beneficial for their further upgrades and customized applications. These insights may inspire the rational design of innovative catalysts and devices with high performance and wide serviceability for large-scale implementations.
2025, 36(5): 110284
doi: 10.1016/j.cclet.2024.110284
摘要:
Developing efficient, non-toxic, and low-cost emitters is a key issue in promoting the applications of electrochemiluminescence (ECL). Among varied ECL emitters, polymeric emitters are attracting dramatically increasing interest due to tunable structure, large surface area, brilliant transfer capability, and sustainable raw materials. In this review, we present a general overview of recent advances in developing polymeric luminophores, including their structural and synthetic methodologies. Methods rooted in straightforward unique structural modulation have been comprehensively summarized, aiming at enhancing the efficiency of ECL along with the underlying kinetic mechanisms. Moreover, as several conjugated polymers were just discovered in recent years, promising prospects and perspectives have also been deliberated. The insight of this review may provide a new avenue for helping develop advanced conjugated polymer ECL emitters and decode ECL applications.
Developing efficient, non-toxic, and low-cost emitters is a key issue in promoting the applications of electrochemiluminescence (ECL). Among varied ECL emitters, polymeric emitters are attracting dramatically increasing interest due to tunable structure, large surface area, brilliant transfer capability, and sustainable raw materials. In this review, we present a general overview of recent advances in developing polymeric luminophores, including their structural and synthetic methodologies. Methods rooted in straightforward unique structural modulation have been comprehensively summarized, aiming at enhancing the efficiency of ECL along with the underlying kinetic mechanisms. Moreover, as several conjugated polymers were just discovered in recent years, promising prospects and perspectives have also been deliberated. The insight of this review may provide a new avenue for helping develop advanced conjugated polymer ECL emitters and decode ECL applications.
2025, 36(5): 110423
doi: 10.1016/j.cclet.2024.110423
摘要:
As a novel two-dimensional (2D) material, MXenes are anticipated to have a significant impact on future aqueous energy storage and conversion technologies owing to their unique intrinsic laminar structure and exceptional physicochemical properties. Nevertheless, the fabrication and utilization of functional MXene-based devices face formidable challenges due to their susceptibility to oxidative degradation in aqueous solutions. This review begins with an outline of various preparation techniques for MXenes and their implications for structure and surface chemistry. Subsequently, the controversial oxidation mechanisms are discussed, followed by a summary of currently employed oxidation characterization techniques. Additionally, the factors influencing MXene oxidation are then introduced, encompassing chemical composition (types of M, X elements, layer numbers, terminations, and defects) as well as environment (atmosphere, temperature, light, potential, solution pH, free water and O2 content). The review then shifts its focus to strategies aiming to prevent or delay MXene oxidation, thereby expanding the applicability of MXenes in complex environments. Finally, the challenges and prospects within this rapidly-growing research field are presented to promote further advancements of MXenes in aqueous storage systems.
As a novel two-dimensional (2D) material, MXenes are anticipated to have a significant impact on future aqueous energy storage and conversion technologies owing to their unique intrinsic laminar structure and exceptional physicochemical properties. Nevertheless, the fabrication and utilization of functional MXene-based devices face formidable challenges due to their susceptibility to oxidative degradation in aqueous solutions. This review begins with an outline of various preparation techniques for MXenes and their implications for structure and surface chemistry. Subsequently, the controversial oxidation mechanisms are discussed, followed by a summary of currently employed oxidation characterization techniques. Additionally, the factors influencing MXene oxidation are then introduced, encompassing chemical composition (types of M, X elements, layer numbers, terminations, and defects) as well as environment (atmosphere, temperature, light, potential, solution pH, free water and O2 content). The review then shifts its focus to strategies aiming to prevent or delay MXene oxidation, thereby expanding the applicability of MXenes in complex environments. Finally, the challenges and prospects within this rapidly-growing research field are presented to promote further advancements of MXenes in aqueous storage systems.
2025, 36(5): 110503
doi: 10.1016/j.cclet.2024.110503
摘要:
Homogeneous C–H and C–X borylation via transition-metal-catalysis have undergone rapid development in the past decades and become one of the most practical methods for the synthesis of organoboron compounds. However, the catalysts employed in homogeneous catalysis are generally expensive, sensitive, and difficult to separate from the reaction mixture and reuse. With the rapid development of heterogeneous catalysis, heterogeneous C–H and C–X borylation have emerged as highly efficient and sustainable approaches towards the synthesis of organoboron compounds. This review aims to highlight the recent advances in the synthesis of organoboron compounds employing heterogeneous C–H and C–X borylation strategies. We endeavor to shed light on new perspectives and inspire further research and applications in this emerging area.
Homogeneous C–H and C–X borylation via transition-metal-catalysis have undergone rapid development in the past decades and become one of the most practical methods for the synthesis of organoboron compounds. However, the catalysts employed in homogeneous catalysis are generally expensive, sensitive, and difficult to separate from the reaction mixture and reuse. With the rapid development of heterogeneous catalysis, heterogeneous C–H and C–X borylation have emerged as highly efficient and sustainable approaches towards the synthesis of organoboron compounds. This review aims to highlight the recent advances in the synthesis of organoboron compounds employing heterogeneous C–H and C–X borylation strategies. We endeavor to shed light on new perspectives and inspire further research and applications in this emerging area.
2025, 36(5): 110521
doi: 10.1016/j.cclet.2024.110521
摘要:
The enantioselective separation of racemate, particularly those containing C(sp3)-H bonds knowns for their high bond dissociation energies and significant polarity, presents a significant challenge in pharmaceutical synthesis. Recent advances have witnessed the fusion of photocatalysis with hydrogen atom transfer (HAT) methodologies, marking a notable trend in synthesis of chiral molecules. This technique uses the excitation of a catalyst to activate substrates, enabling the selective isomerization of chiral centers containing C(sp3) configurations. This process distinctively facilitates the direct activation of the C(sp3)-H bond in targeted reagents. This review systematically discusses the photocatalytic isomerization of various chiral molecule featuring C(sp3)-H centers, capable of undergoing deracemization through two primary HAT mechanisms: direct and indirect pathways. From the perspective of synthetic organic chemistry, this field has progressed towards the development of isomerization strategies for molecules that incorporate an activating group at the α-position adjacent to the C(sp3) chiral center. Moreover, it covers methodologies applicable to molecules characterized by specific C-C and C-S bond configurations. The integration of photocatalysis with HAT technology thus provides valuable strategies for the synthesis of enantiopure compounds with enhanced selectivity and efficiency.
The enantioselective separation of racemate, particularly those containing C(sp3)-H bonds knowns for their high bond dissociation energies and significant polarity, presents a significant challenge in pharmaceutical synthesis. Recent advances have witnessed the fusion of photocatalysis with hydrogen atom transfer (HAT) methodologies, marking a notable trend in synthesis of chiral molecules. This technique uses the excitation of a catalyst to activate substrates, enabling the selective isomerization of chiral centers containing C(sp3) configurations. This process distinctively facilitates the direct activation of the C(sp3)-H bond in targeted reagents. This review systematically discusses the photocatalytic isomerization of various chiral molecule featuring C(sp3)-H centers, capable of undergoing deracemization through two primary HAT mechanisms: direct and indirect pathways. From the perspective of synthetic organic chemistry, this field has progressed towards the development of isomerization strategies for molecules that incorporate an activating group at the α-position adjacent to the C(sp3) chiral center. Moreover, it covers methodologies applicable to molecules characterized by specific C-C and C-S bond configurations. The integration of photocatalysis with HAT technology thus provides valuable strategies for the synthesis of enantiopure compounds with enhanced selectivity and efficiency.
2025, 36(5): 110529
doi: 10.1016/j.cclet.2024.110529
摘要:
Utilizing transporter-mediated drug delivery to achieve effective oral absorption emerges as a promising strategy. Researchers have been concentrated on discovering solutions to the issues of low solubility and poor permeability of insoluble drugs, whereas, current reports have revealed that drug transporter proteins are abundantly expressed in the mucosa of intestinal epithelial cells, and that their mediated drug absorption effectively improved the bioavailability of orally administered drugs. There are two main categories based on the transporter mechanism, which include the family of ATP-binding cassette (ABC) transporters with efflux effects that reduce drug bioavailability and the family of solute carriers (SLC) transporters with uptake effects that promote drug absorption, respectively. Thus, we review studies of intestinal transporter-mediated delivery of drugs to enhance oral absorption, including the types of intestinal transporters, distribution characteristics, and strategies for enhancing oral absorption using transporter-mediated drug delivery systems are summarized, with the aim of providing important theoretical references for the development of intestinal-targeted delivery system.
Utilizing transporter-mediated drug delivery to achieve effective oral absorption emerges as a promising strategy. Researchers have been concentrated on discovering solutions to the issues of low solubility and poor permeability of insoluble drugs, whereas, current reports have revealed that drug transporter proteins are abundantly expressed in the mucosa of intestinal epithelial cells, and that their mediated drug absorption effectively improved the bioavailability of orally administered drugs. There are two main categories based on the transporter mechanism, which include the family of ATP-binding cassette (ABC) transporters with efflux effects that reduce drug bioavailability and the family of solute carriers (SLC) transporters with uptake effects that promote drug absorption, respectively. Thus, we review studies of intestinal transporter-mediated delivery of drugs to enhance oral absorption, including the types of intestinal transporters, distribution characteristics, and strategies for enhancing oral absorption using transporter-mediated drug delivery systems are summarized, with the aim of providing important theoretical references for the development of intestinal-targeted delivery system.
2025, 36(5): 110618
doi: 10.1016/j.cclet.2024.110618
摘要:
Carbon dots (CDs) are an emerging class of zero-dimensional carbon nano optical materials that are as promising candidates for various applications. Through the exploration of scientific researchers, the optical band gap of CDs has been continuously regulated and red-shifted from the initial blue-violet light to longer wavelengths. In recent years, CDs with near-infrared (NIR) absorption/emission have been gradually reported. Because NIR light has deeper penetration and lower scattering and is invisible to the human eye, it has great application prospects in the fields of biological imaging and treatment, information encryption, optical communications, etc. Although there are a few reviews on deep red to NIR CDs, they only focus on the single biomedical direction. There is still a lack of comprehensive reviews focusing on NIR (≥700 nm) absorption and luminescent CDs and their multifunctional applications. Based on our research group’s findings on NIR CDs, this review summarizes recent advancements in their preparation strategies and applications, points out the current shortcomings and challenges, and anticipates future development trajectories.
Carbon dots (CDs) are an emerging class of zero-dimensional carbon nano optical materials that are as promising candidates for various applications. Through the exploration of scientific researchers, the optical band gap of CDs has been continuously regulated and red-shifted from the initial blue-violet light to longer wavelengths. In recent years, CDs with near-infrared (NIR) absorption/emission have been gradually reported. Because NIR light has deeper penetration and lower scattering and is invisible to the human eye, it has great application prospects in the fields of biological imaging and treatment, information encryption, optical communications, etc. Although there are a few reviews on deep red to NIR CDs, they only focus on the single biomedical direction. There is still a lack of comprehensive reviews focusing on NIR (≥700 nm) absorption and luminescent CDs and their multifunctional applications. Based on our research group’s findings on NIR CDs, this review summarizes recent advancements in their preparation strategies and applications, points out the current shortcomings and challenges, and anticipates future development trajectories.
2025, 36(5): 110628
doi: 10.1016/j.cclet.2024.110628
摘要:
Polycyclic compounds are widely found in natural products and drug molecules with important biological activities, which attracted the attention of many chemists. Phosphine-catalyzed nucleophilic addition is one of the most powerful tools for the construction of various cyclic compounds with the advantages of atom economy, mild reaction conditions and simplicity of operation. Allenolates, Morita−Baylis−Hillman (MBH) alcohols and their derivatives (MBHADs), electron-deficient olefins and alkynes are very efficient substrates in phosphine mediated annulations, which formed many phosphonium species such as β-phosphonium enolates, β-phosphonium dienolates and vinyl phosphonium ylides as intermediates. This review describes the reactivities of these phosphonium zwitterions and summarizes the synthesis of polycycle compounds through phosphine-mediated intramolecular and intermolecular sequential annulations. Thus, a systematic summary of the research process based on the phosphine-mediated sequential annulations of allenolates, MBH alcohols and MBHADs, electron-deficient olefins and alkynes are presented in Chapters 2–6, respectively.
Polycyclic compounds are widely found in natural products and drug molecules with important biological activities, which attracted the attention of many chemists. Phosphine-catalyzed nucleophilic addition is one of the most powerful tools for the construction of various cyclic compounds with the advantages of atom economy, mild reaction conditions and simplicity of operation. Allenolates, Morita−Baylis−Hillman (MBH) alcohols and their derivatives (MBHADs), electron-deficient olefins and alkynes are very efficient substrates in phosphine mediated annulations, which formed many phosphonium species such as β-phosphonium enolates, β-phosphonium dienolates and vinyl phosphonium ylides as intermediates. This review describes the reactivities of these phosphonium zwitterions and summarizes the synthesis of polycycle compounds through phosphine-mediated intramolecular and intermolecular sequential annulations. Thus, a systematic summary of the research process based on the phosphine-mediated sequential annulations of allenolates, MBH alcohols and MBHADs, electron-deficient olefins and alkynes are presented in Chapters 2–6, respectively.
2025, 36(5): 110764
doi: 10.1016/j.cclet.2024.110764
摘要:
2025, 36(5): 110869
doi: 10.1016/j.cclet.2025.110869
摘要:
2025, 36(5): 110936
doi: 10.1016/j.cclet.2025.110936
摘要:
