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2025 Volume 36 Issue 7
2025, 36(7): 109775
doi: 10.1016/j.cclet.2024.109775
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
2025, 36(7): 111039
doi: 10.1016/j.cclet.2025.111039
Abstract:
2025, 36(7): 111054
doi: 10.1016/j.cclet.2025.111054
Abstract:
2025, 36(7): 111070
doi: 10.1016/j.cclet.2025.111070
Abstract:
2025, 36(7): 111221
doi: 10.1016/j.cclet.2025.111221
Abstract:
