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Chinese Chemical Letters
Chinese Chemical Letters
主管 : 中国科学技术协会
刊期 : 月刊主编 : 钱旭红
语种 : 英文主办 : 中国化学会、中国医学科学院药物研究所
ISSN : 1001-8417 CN : 11-2710/O6本刊创办于1990年7月，是由中国化学会主办，中国医学科学院药物研究所承办的核心期刊。本刊由著名化学家梁晓天院士任主编，其内容涵盖化学研究的各个领域，及时报道我国化学界各个研究领域的最新进展及世界上一些化学研究的热点问题。本刊自1993年起为SCI、CA、日本科技文献速报等收录，2000年美国化学文摘引用中国期刊频次中位列第四。展开 > - 影响因子: 6.779
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Synthesis of a new ratiometric emission Ca2+ indicator for in vivo bioimaging
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Synthesis of a water-soluble macromolecular light stabilizer containing hindered amine structures
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Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation
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Superiority of poly(L-lactic acid) microspheres as dermal fillers
2025, 36(2): 109586
doi: 10.1016/j.cclet.2024.109586
摘要:
We propose and investigate a novel stable two-dimensional (2D) AlO2 with anomalous stoichiometric ratios based on first-principles calculation. 2D AlO2 has metallic properties. It possesses the rare in-plane and out-of-plane negative Poisson's ratio (NPR) phenomenon, originating from its special sawtooth-like structure. The absolute value of the NPR decreases as the number of layers increases. The adsorption of volatile organic compounds (VOCs) including CH2O, C2H3Cl and C6H6 by AlO2 exhibit small adsorption distance, large adsorption energy, large charge transfer and significant density of states (DOS) changes, indicating the presence of strong interactions. The desorption time of each gas molecule on the AlO2 surface is also evaluated, and the results further suggest that the desorption of VOCs can be controlled by changing the temperature to achieve the recycling of AlO2. These interesting properties make 2D AlO2 a promising material for electronic, mechanical and sensing applications for VOCs.
We propose and investigate a novel stable two-dimensional (2D) AlO2 with anomalous stoichiometric ratios based on first-principles calculation. 2D AlO2 has metallic properties. It possesses the rare in-plane and out-of-plane negative Poisson's ratio (NPR) phenomenon, originating from its special sawtooth-like structure. The absolute value of the NPR decreases as the number of layers increases. The adsorption of volatile organic compounds (VOCs) including CH2O, C2H3Cl and C6H6 by AlO2 exhibit small adsorption distance, large adsorption energy, large charge transfer and significant density of states (DOS) changes, indicating the presence of strong interactions. The desorption time of each gas molecule on the AlO2 surface is also evaluated, and the results further suggest that the desorption of VOCs can be controlled by changing the temperature to achieve the recycling of AlO2. These interesting properties make 2D AlO2 a promising material for electronic, mechanical and sensing applications for VOCs.
2025, 36(2): 109587
doi: 10.1016/j.cclet.2024.109587
摘要:
Defects at the grain boundaries (GBs) of perovskite film highly restrict both the efficiency and stability of perovskite solar cells (PSCs). Herein, organic small molecules of butanedioic acid (BA) and acetylenedicarboxylic acid (AA), containing two carbonyl (C=O) groups and different core-units, were incorporated into perovskite as additives for PSCs application. Thanks to the strong coordination interaction between CO group and under-coordinated Pb2+, the additives can effectively passivate film defects and regulate the perovskite crystallization, yielding high-quality perovskite films with lower defect densities. More importantly, the additives can efficiently regulate the charge transport behaviors in PSCs. Benefiting from the defects passivation and the regulation of charge carrier dynamics, the BA and AA-treaded PSCs show the power conversion efficiencies of 21.52% and 20.50%, which are higher than that of the control device (19.41%). Besides, the optimal devices exhibit a remarkable enhanced long-term stability and moisture tolerance compared to the pristine devices. Furthermore, the transient absorption spectrum reveals the mechanism of enhanced photovoltaic performances, attributing to the improvement of charge transport capability at the perovskite/Spiro-OMeTAD interfaces. This work affords a promising strategy to improve the efficiency and stability of PSCs through regulating the charge-carrier dynamic process in perovskite film.
Defects at the grain boundaries (GBs) of perovskite film highly restrict both the efficiency and stability of perovskite solar cells (PSCs). Herein, organic small molecules of butanedioic acid (BA) and acetylenedicarboxylic acid (AA), containing two carbonyl (C=O) groups and different core-units, were incorporated into perovskite as additives for PSCs application. Thanks to the strong coordination interaction between CO group and under-coordinated Pb2+, the additives can effectively passivate film defects and regulate the perovskite crystallization, yielding high-quality perovskite films with lower defect densities. More importantly, the additives can efficiently regulate the charge transport behaviors in PSCs. Benefiting from the defects passivation and the regulation of charge carrier dynamics, the BA and AA-treaded PSCs show the power conversion efficiencies of 21.52% and 20.50%, which are higher than that of the control device (19.41%). Besides, the optimal devices exhibit a remarkable enhanced long-term stability and moisture tolerance compared to the pristine devices. Furthermore, the transient absorption spectrum reveals the mechanism of enhanced photovoltaic performances, attributing to the improvement of charge transport capability at the perovskite/Spiro-OMeTAD interfaces. This work affords a promising strategy to improve the efficiency and stability of PSCs through regulating the charge-carrier dynamic process in perovskite film.
2025, 36(2): 109600
doi: 10.1016/j.cclet.2024.109600
摘要:
Two CoⅡ-based complexes, {[Co(dps)2(N3)2]·H2O} (1) and [Co(dps)2(N3)2] (2), show a 1D chain and a 3D network, respectively. The central CoⅡ ions in the complexes have the same coordination environment with the [Co(dps)4(N3)2] unit. Although the differences in crystal parameters are nearly negligible, their magnetic properties are very different. AC susceptibility data show that 1 behaves as a typical field-induced single-ion magnet (SIM) with the out-of-phase (χM'') signals, while 2 shows ac signals of χM'' without peaks even under applied dc filed within our measurement window. Far-IR magneto-spectra (FIRMS) show strong spin-phonon couplings at 0 T in 2, likely making the magnetic relaxation in 2 fast, while the couplings are negligible in 1. Small spin-phonon coupling in 1 likely leads to slower magnetic relaxation, making 1 a SIM. The difference in the properties is due to the structural rigidity of 2 in its 3D network, leading to stronger spin-phonon coupling. Combined high-field EPR (HF-EPR) and FIRMS studies give spin-Hamiltonian parameters, including D = 64.0(9) cm-1, E = 15.7(2) cm-1 for 1 and D = 80.0(2) cm-1, E = 19.0(1) cm-1 for 2.
Two CoⅡ-based complexes, {[Co(dps)2(N3)2]·H2O} (1) and [Co(dps)2(N3)2] (2), show a 1D chain and a 3D network, respectively. The central CoⅡ ions in the complexes have the same coordination environment with the [Co(dps)4(N3)2] unit. Although the differences in crystal parameters are nearly negligible, their magnetic properties are very different. AC susceptibility data show that 1 behaves as a typical field-induced single-ion magnet (SIM) with the out-of-phase (χM'') signals, while 2 shows ac signals of χM'' without peaks even under applied dc filed within our measurement window. Far-IR magneto-spectra (FIRMS) show strong spin-phonon couplings at 0 T in 2, likely making the magnetic relaxation in 2 fast, while the couplings are negligible in 1. Small spin-phonon coupling in 1 likely leads to slower magnetic relaxation, making 1 a SIM. The difference in the properties is due to the structural rigidity of 2 in its 3D network, leading to stronger spin-phonon coupling. Combined high-field EPR (HF-EPR) and FIRMS studies give spin-Hamiltonian parameters, including D = 64.0(9) cm-1, E = 15.7(2) cm-1 for 1 and D = 80.0(2) cm-1, E = 19.0(1) cm-1 for 2.
2025, 36(2): 109621
doi: 10.1016/j.cclet.2024.109621
摘要:
Dion–Jacobson (DJ) phase hybrid perovskites have been proven to improve the photovoltaic performance of the devices due to its unique structure. At present, some DJ hybrid perovskites have been reported and used for photodetection filed, but most of them are based on lead-bromide systems, which is not conducive to construct broadband photodetection devices due to the limitation of intrinsic absorption. Herein, we constructed a bilayered DJ hybrid perovskite (3AMPY)(EA)Pb2I7 (3AMPY2+ is 3-(aminomethyl)pyridinium, EA+ is ethylammonium) using an aromatic spacer, which exhibit large current on/off ratios of ~104 under 520 and 637 nm illumination. In particular, the single crystal device based on (3AMPY)(EA)Pb2I7 shows a distinguished detectivity of 7.4 × 1012 Jones and a high responsivity of 0.89 A/W under 637 nm illumination. Such finding not only enriches the quantities of DJ hybrid perovskites, but also provides useful assistance for constructing high-performance optoelectronic device in the future.
Dion–Jacobson (DJ) phase hybrid perovskites have been proven to improve the photovoltaic performance of the devices due to its unique structure. At present, some DJ hybrid perovskites have been reported and used for photodetection filed, but most of them are based on lead-bromide systems, which is not conducive to construct broadband photodetection devices due to the limitation of intrinsic absorption. Herein, we constructed a bilayered DJ hybrid perovskite (3AMPY)(EA)Pb2I7 (3AMPY2+ is 3-(aminomethyl)pyridinium, EA+ is ethylammonium) using an aromatic spacer, which exhibit large current on/off ratios of ~104 under 520 and 637 nm illumination. In particular, the single crystal device based on (3AMPY)(EA)Pb2I7 shows a distinguished detectivity of 7.4 × 1012 Jones and a high responsivity of 0.89 A/W under 637 nm illumination. Such finding not only enriches the quantities of DJ hybrid perovskites, but also provides useful assistance for constructing high-performance optoelectronic device in the future.
2025, 36(2): 109630
doi: 10.1016/j.cclet.2024.109630
摘要:
Atomically dispersed Cu-based single-metal-site catalysts (Cu-N-C) have emerged as a frontier for electrocatalytic oxygen reduction reactions (ORR) because they can effectively optimize the d-band center of the Cu active site and provide appropriate adsorption/desorption energy for oxygen-containing intermediates. Metal-organic frameworks (MOFs) show excellent prospects in many fields because of their structural regularity and designability, but their direct use for electrocatalysis has been rarely reported due to the low intrinsic conductivity. Here, a MOF material (Cu-TCNQ) with highly regular single-atom copper active centers was successfully prepared using a solution chemical reaction method. Subsequently, Cu-TCNQ and graphene oxide (GO) were directly self-assembled to form a Cu-TCNQ/GO composite, which improved the conductivity of the catalyst while maintained the atomically precise controllability. The resistivity of the Cu-TCNQ/GO decreased by three orders of magnitude (1663.6–2.7 W/cm) compared with pure Cu-TCNQ. The half-wave potential was as high as 0.92 V in 0.1 mol/L KOH, even better than that of commercial 20% Pt/C. In alkaline polymer electrolyte fuel cells (APEFCs), the open-circuit voltage and power density of Cu-TCNQ/GO electrode reached 0.95 V and 320 mW/cm2, respectively, which suggests that Cu-TCNQ/GO has a good potential for application as a cathode ORR catalyst.
Atomically dispersed Cu-based single-metal-site catalysts (Cu-N-C) have emerged as a frontier for electrocatalytic oxygen reduction reactions (ORR) because they can effectively optimize the d-band center of the Cu active site and provide appropriate adsorption/desorption energy for oxygen-containing intermediates. Metal-organic frameworks (MOFs) show excellent prospects in many fields because of their structural regularity and designability, but their direct use for electrocatalysis has been rarely reported due to the low intrinsic conductivity. Here, a MOF material (Cu-TCNQ) with highly regular single-atom copper active centers was successfully prepared using a solution chemical reaction method. Subsequently, Cu-TCNQ and graphene oxide (GO) were directly self-assembled to form a Cu-TCNQ/GO composite, which improved the conductivity of the catalyst while maintained the atomically precise controllability. The resistivity of the Cu-TCNQ/GO decreased by three orders of magnitude (1663.6–2.7 W/cm) compared with pure Cu-TCNQ. The half-wave potential was as high as 0.92 V in 0.1 mol/L KOH, even better than that of commercial 20% Pt/C. In alkaline polymer electrolyte fuel cells (APEFCs), the open-circuit voltage and power density of Cu-TCNQ/GO electrode reached 0.95 V and 320 mW/cm2, respectively, which suggests that Cu-TCNQ/GO has a good potential for application as a cathode ORR catalyst.
2025, 36(2): 109640
doi: 10.1016/j.cclet.2024.109640
摘要:
The three-way catalyst (TWC), as a promising approach to control automobile exhaust emission, has been widely studied and applied. However, it still suffers from the high light-off temperature and poor stability. Herein, we synthesized a multicomponent catalyst Rh/Cu-CeSn by using Cu metal doping to modify the Ce-based solid solution, which exhibited good TWC catalytic performance: the light-off temperatures for CO, NO, and C3H6 conversion are 172 ℃, 266 ℃, and 193 ℃, respectively. Moreover, the catalyst still maintained good activity after 12 h of the continuous reaction under high-temperature conditions. The experiments and mechanism studies reveal that due to the redox pair Cu+/Cu2+, the Cu incorporation can effectively inhibit the Rh transition to the oxidation state and greatly enhance the catalytic activity and stability. This work provides a viable strategy for precise characteristic modulation of composite oxide supports during the fabrication of noble metal-based catalysts, which significantly reduces environmental pollution from energy applications.
The three-way catalyst (TWC), as a promising approach to control automobile exhaust emission, has been widely studied and applied. However, it still suffers from the high light-off temperature and poor stability. Herein, we synthesized a multicomponent catalyst Rh/Cu-CeSn by using Cu metal doping to modify the Ce-based solid solution, which exhibited good TWC catalytic performance: the light-off temperatures for CO, NO, and C3H6 conversion are 172 ℃, 266 ℃, and 193 ℃, respectively. Moreover, the catalyst still maintained good activity after 12 h of the continuous reaction under high-temperature conditions. The experiments and mechanism studies reveal that due to the redox pair Cu+/Cu2+, the Cu incorporation can effectively inhibit the Rh transition to the oxidation state and greatly enhance the catalytic activity and stability. This work provides a viable strategy for precise characteristic modulation of composite oxide supports during the fabrication of noble metal-based catalysts, which significantly reduces environmental pollution from energy applications.
2025, 36(2): 109641
doi: 10.1016/j.cclet.2024.109641
摘要:
Rare–earth supramolecular compounds, such as lanthanide organic polyhedrons (LOPs), are of particular interest due to their many possible applications in various fields. Here we report the first syntheses of Ln4(L•+)4–type (Ln, lanthanides; L•+, radical ligand) radical–bridged lanthanide organic tetrahedrons by self–assembly of face–capping triphenylamine (TPA)–cored radical ligand with different lanthanide ions. Remarkable coordination enhanced radical stability has been observed, with half–life times (t1/2) for L1•+, La4(L1•+)4, Eu4(L1•+)4, Gd4(L1•+)4, Tb4(L1•+)4 and Lu4(L1•+)4 estimated to be 53 min, 482 min, 624 min, 1248 min, 822 min and 347 min, respectively. The TPA radical in Ln4(L1•+)4 containing paramagnetic Ln ions (Ln = EuⅢ, GdⅢ and TbⅢ) is observed to be more stable than that in Ln4(L1•+)4 (Ln = LaⅢ and LuⅢ) constructed by diamagnetic Ln ions. This difference in radical stability is possibly due to the magnetic interactions between paramagnetic LnⅢ ions and L1•+ ligands, as confirmed by electron paramagnetic resonance (EPR) in La4(L)4 (L = L1 and L1•+) and Tb4(L)4 (L = L1 and L1•+), and magnetic susceptibility measurements in Tb4(L)4 (L = L1 and L1•+). Our study reveals the coordination of radical ligands with lanthanide ions can improve the radical stability, which is crucial for their applications.
Rare–earth supramolecular compounds, such as lanthanide organic polyhedrons (LOPs), are of particular interest due to their many possible applications in various fields. Here we report the first syntheses of Ln4(L•+)4–type (Ln, lanthanides; L•+, radical ligand) radical–bridged lanthanide organic tetrahedrons by self–assembly of face–capping triphenylamine (TPA)–cored radical ligand with different lanthanide ions. Remarkable coordination enhanced radical stability has been observed, with half–life times (t1/2) for L1•+, La4(L1•+)4, Eu4(L1•+)4, Gd4(L1•+)4, Tb4(L1•+)4 and Lu4(L1•+)4 estimated to be 53 min, 482 min, 624 min, 1248 min, 822 min and 347 min, respectively. The TPA radical in Ln4(L1•+)4 containing paramagnetic Ln ions (Ln = EuⅢ, GdⅢ and TbⅢ) is observed to be more stable than that in Ln4(L1•+)4 (Ln = LaⅢ and LuⅢ) constructed by diamagnetic Ln ions. This difference in radical stability is possibly due to the magnetic interactions between paramagnetic LnⅢ ions and L1•+ ligands, as confirmed by electron paramagnetic resonance (EPR) in La4(L)4 (L = L1 and L1•+) and Tb4(L)4 (L = L1 and L1•+), and magnetic susceptibility measurements in Tb4(L)4 (L = L1 and L1•+). Our study reveals the coordination of radical ligands with lanthanide ions can improve the radical stability, which is crucial for their applications.
2025, 36(2): 109643
doi: 10.1016/j.cclet.2024.109643
摘要:
Na3V2(PO4)3 (NVP) is regarded as alternative cathode material for sodium-ion batteries (SIBs) due to its potential high-rate performance and pronounced long-term cycle stability. However, electronic conductivity and tap density are difficult to be balanced. Herein, we report that high-temperature shock (HTS) can prepare "single crystalline like" NVP which combines high-rate capability with high tap density together into one with the assistance of carbon framework and large particle. Thus, high reversible capacity of 110 mAh/g at 0.1 C with 89.9% capacity retention after 1600 cycles at 1 C and specific capacity of 83.5 mAh/g at 50 C rate has been exhibited. This study provides a novel strategy to guide the production of high tap density, and rate performance polyanionic cathode materials.
Na3V2(PO4)3 (NVP) is regarded as alternative cathode material for sodium-ion batteries (SIBs) due to its potential high-rate performance and pronounced long-term cycle stability. However, electronic conductivity and tap density are difficult to be balanced. Herein, we report that high-temperature shock (HTS) can prepare "single crystalline like" NVP which combines high-rate capability with high tap density together into one with the assistance of carbon framework and large particle. Thus, high reversible capacity of 110 mAh/g at 0.1 C with 89.9% capacity retention after 1600 cycles at 1 C and specific capacity of 83.5 mAh/g at 50 C rate has been exhibited. This study provides a novel strategy to guide the production of high tap density, and rate performance polyanionic cathode materials.
2025, 36(2): 109675
doi: 10.1016/j.cclet.2024.109675
摘要:
A pseudocapacitance dominated anode material assembled from Li3VO4 nanocrystals encapsulated in the interlayers of N-doped graphene has been developed via a facile 2D nanospace confined strategy for lithium ion capacitors (LICs). In this contribution, the N-doped graphene synthesized by a faicle solid state reaction using C3N4 nanosheets as template and glucose as carbon source provides sufficient 2D nanospace for the confined and homogeneous growth of Li3VO4 at the nanoscale, and simultaneously efficiently anchors each nanobuilding block inside the interlayers, thus realizing the utilizaiton of full potential of active components. The so-formed 3D hybrids not only ensure intimate electronic coupling between active materials and N-doped graphene, but also realize robust structure integrity. Owing to these unique advantages, the resulting hybrids show pseudocapacitance dominated lithium storage behaviors with capacitive contributions of over 90% at both low and high current rates. The LVO@C@NG delivers reversible capacities of 206 mAh/g at 10 A/g, capacity retention of 92.7% after 1000 cycles at 2 A/g, and a high energy density of 113.6 Wh/kg at 231.8 W/kg for LICs.
A pseudocapacitance dominated anode material assembled from Li3VO4 nanocrystals encapsulated in the interlayers of N-doped graphene has been developed via a facile 2D nanospace confined strategy for lithium ion capacitors (LICs). In this contribution, the N-doped graphene synthesized by a faicle solid state reaction using C3N4 nanosheets as template and glucose as carbon source provides sufficient 2D nanospace for the confined and homogeneous growth of Li3VO4 at the nanoscale, and simultaneously efficiently anchors each nanobuilding block inside the interlayers, thus realizing the utilizaiton of full potential of active components. The so-formed 3D hybrids not only ensure intimate electronic coupling between active materials and N-doped graphene, but also realize robust structure integrity. Owing to these unique advantages, the resulting hybrids show pseudocapacitance dominated lithium storage behaviors with capacitive contributions of over 90% at both low and high current rates. The LVO@C@NG delivers reversible capacities of 206 mAh/g at 10 A/g, capacity retention of 92.7% after 1000 cycles at 2 A/g, and a high energy density of 113.6 Wh/kg at 231.8 W/kg for LICs.
2025, 36(2): 109678
doi: 10.1016/j.cclet.2024.109678
摘要:
In this work, we employed a ring-opening strategy to develop a series of novel N-benzyl arylamide derivatives as tubulin polymerization inhibitors. Notably, 13n (MY-1388) exhibited remarkable antiproliferative potency on fifteen human cancer cell lines, with half maximal inhibitory concentration (IC50) values ranging from 8 nmol/L to 48 nmol/L. Furthermore, 13n effectively suppressed tubulin polymerization by targeting the colchicine-binding site (IC50 = 0.62 µmol/L). 13n also exhibited significant inhibition of cell colony formation, as well as displayed potent effects on inducing G2/M phase cell cycle arrest and promoting apoptosis. Importantly, 13n exhibited enhanced and adequate liver microsomal stability in human and rat liver microsomes, and also exhibited a moderate half-life (T1/2 = 0.938 h) in vivo. Meanwhile, 13n demonstrated effective antitumor effects in vivo in suppressing tumor growth in the MGC-803 xenograft model (tumor growth inhibition (TGI) value was 76.4% at the dosage of 30 mg kg−1 day−1) with a good safety profile. Collectively, these results revealed that 13n represents a promising tubulin polymerization inhibitor that deserves further investigation for its efficacy in treating gastric cancers.
In this work, we employed a ring-opening strategy to develop a series of novel N-benzyl arylamide derivatives as tubulin polymerization inhibitors. Notably, 13n (MY-1388) exhibited remarkable antiproliferative potency on fifteen human cancer cell lines, with half maximal inhibitory concentration (IC50) values ranging from 8 nmol/L to 48 nmol/L. Furthermore, 13n effectively suppressed tubulin polymerization by targeting the colchicine-binding site (IC50 = 0.62 µmol/L). 13n also exhibited significant inhibition of cell colony formation, as well as displayed potent effects on inducing G2/M phase cell cycle arrest and promoting apoptosis. Importantly, 13n exhibited enhanced and adequate liver microsomal stability in human and rat liver microsomes, and also exhibited a moderate half-life (T1/2 = 0.938 h) in vivo. Meanwhile, 13n demonstrated effective antitumor effects in vivo in suppressing tumor growth in the MGC-803 xenograft model (tumor growth inhibition (TGI) value was 76.4% at the dosage of 30 mg kg−1 day−1) with a good safety profile. Collectively, these results revealed that 13n represents a promising tubulin polymerization inhibitor that deserves further investigation for its efficacy in treating gastric cancers.
2025, 36(2): 109721
doi: 10.1016/j.cclet.2024.109721
摘要:
In chemical science, the vertical ionization potential (VIP) is a crucial metric for understanding the electronegativity, hardness and softness of chemical material systems as well as the electronic structure and stability of molecules. Ever since the last century, the model chemistry composite methods have witnessed tremendous developments in computing the thermodynamic properties as well as the barrier heights. However, their performance in realm of the vertical electron processes of molecular systems has been rarely explored. In this study, we for the first time benchmarked the model chemistry composite methods (e.g., CBS-QB3, G4 and W1BD) in comparison with the commonly used Koopmans's theorem (KT), electron propagator theory (e.g., OVGF, D2, P3 and P3+) and CCSD(T) methods in calculating the VIP for up to 613 molecular systems with available experimental measurements. The large-scale test calculations strongly showed that the CBS-QB3 model chemistry composite technique can be well recommended to calculate VIP from the perspectives of accuracy, economy and applicability. Notably, the VIP values of up to 7 molecules were identified to have the absolute errors of larger than 0.3 eV at all calculation levels, which have strong hints that their VIP experimental values should be re-investigated.
In chemical science, the vertical ionization potential (VIP) is a crucial metric for understanding the electronegativity, hardness and softness of chemical material systems as well as the electronic structure and stability of molecules. Ever since the last century, the model chemistry composite methods have witnessed tremendous developments in computing the thermodynamic properties as well as the barrier heights. However, their performance in realm of the vertical electron processes of molecular systems has been rarely explored. In this study, we for the first time benchmarked the model chemistry composite methods (e.g., CBS-QB3, G4 and W1BD) in comparison with the commonly used Koopmans's theorem (KT), electron propagator theory (e.g., OVGF, D2, P3 and P3+) and CCSD(T) methods in calculating the VIP for up to 613 molecular systems with available experimental measurements. The large-scale test calculations strongly showed that the CBS-QB3 model chemistry composite technique can be well recommended to calculate VIP from the perspectives of accuracy, economy and applicability. Notably, the VIP values of up to 7 molecules were identified to have the absolute errors of larger than 0.3 eV at all calculation levels, which have strong hints that their VIP experimental values should be re-investigated.
2025, 36(2): 109734
doi: 10.1016/j.cclet.2024.109734
摘要:
It is of great significance to find safe and effective radiosensitizers. A primary investigation has been made on fisetin’s modification of radiation effect, but its radiosensitization and related mechanisms still need to be deeply clarified. Furthermore, fisetin with high hydrophobicity is difficult to dissolve in water, severely limiting its research and application. In this study, we fabricated a safe and soluble radiosensitizer fisetin micelle for precisely enhancing radiotherapy by inhibiting platelet-derived growth factor receptor-β (PDGFRβ)/signal transducer and activator of transcription 1 (STAT1)/signal transducer and activator of transcription 3 (STAT3)/B cell lymphoma 2 (Bcl-2) signaling pathway in the tumor. Systematic and detailed studies were performed to verify its radiosensitization effect in vitro and in vivo. On the cellular level, fisetin micelles selectively increased the radiosensitivity of tumor cells (CT26 and 4T1 cells) and had little effect on the sensitivity of normal mouse cells (L929 cells) to radiation. In the mouse models of colon and breast cancers, fisetin micelles showed an efficient radiosensitization capacity without apparent toxicity. Additionally, we first found that fisetin micelles played a radiotherapy sensitization role by inhibiting the PDGFRβ/STAT1/STAT3/Bcl-2 pathway activity. In general, this work not only confirmed that fisetin micelles precisely exhibit a radiosensitization effect in vitro and in vivo, but also profoundly explored its mechanisms underlying, to provide a theoretical and experimental basis for the clinical application of fisetin micelles.
It is of great significance to find safe and effective radiosensitizers. A primary investigation has been made on fisetin’s modification of radiation effect, but its radiosensitization and related mechanisms still need to be deeply clarified. Furthermore, fisetin with high hydrophobicity is difficult to dissolve in water, severely limiting its research and application. In this study, we fabricated a safe and soluble radiosensitizer fisetin micelle for precisely enhancing radiotherapy by inhibiting platelet-derived growth factor receptor-β (PDGFRβ)/signal transducer and activator of transcription 1 (STAT1)/signal transducer and activator of transcription 3 (STAT3)/B cell lymphoma 2 (Bcl-2) signaling pathway in the tumor. Systematic and detailed studies were performed to verify its radiosensitization effect in vitro and in vivo. On the cellular level, fisetin micelles selectively increased the radiosensitivity of tumor cells (CT26 and 4T1 cells) and had little effect on the sensitivity of normal mouse cells (L929 cells) to radiation. In the mouse models of colon and breast cancers, fisetin micelles showed an efficient radiosensitization capacity without apparent toxicity. Additionally, we first found that fisetin micelles played a radiotherapy sensitization role by inhibiting the PDGFRβ/STAT1/STAT3/Bcl-2 pathway activity. In general, this work not only confirmed that fisetin micelles precisely exhibit a radiosensitization effect in vitro and in vivo, but also profoundly explored its mechanisms underlying, to provide a theoretical and experimental basis for the clinical application of fisetin micelles.
2025, 36(2): 109746
doi: 10.1016/j.cclet.2024.109746
摘要:
Planktonic bacteria adhere and subsequently form biofilms on implantable medical devices can cause severe infections that have become the major types of hospital-acquired infections. Traditional coatings for the implants are frequently lack of long-term antifouling and bactericidal activities. It is still a big challenge to simultaneously improve the antifouling and bactericidal activities of the coatings. Herein, we report that mixed-charge glycopolypeptide coatings are of long-term antibacterial activities to efficiently inhibit the biofilm growth. The glycosylation of mixed-charge polypeptides has led to a significant improvement of both antifouling and bactericidal activities. The cooperative effect of the saccharide residues and mixed-charge residues improved the resistance of the polypeptide coatings against protein adsorption. The saccharide and L-glutamic acid (E) residues collectively enhanced the bacterial membrane-disruption of cationic L-lysine (K) residues, leading to potent bactericidal activity. Meanwhile, the glycopolypeptide coatings showed superior biocompatibility, long-term antibiofilm and anti-infection properties in two types of mouse subcutaneous infection models and one type of mouse urinary tract infection model. This work provides a new strategy to achieve antibacterial coatings with long-term activities for preventing implantable medical device associated infections.
Planktonic bacteria adhere and subsequently form biofilms on implantable medical devices can cause severe infections that have become the major types of hospital-acquired infections. Traditional coatings for the implants are frequently lack of long-term antifouling and bactericidal activities. It is still a big challenge to simultaneously improve the antifouling and bactericidal activities of the coatings. Herein, we report that mixed-charge glycopolypeptide coatings are of long-term antibacterial activities to efficiently inhibit the biofilm growth. The glycosylation of mixed-charge polypeptides has led to a significant improvement of both antifouling and bactericidal activities. The cooperative effect of the saccharide residues and mixed-charge residues improved the resistance of the polypeptide coatings against protein adsorption. The saccharide and L-glutamic acid (E) residues collectively enhanced the bacterial membrane-disruption of cationic L-lysine (K) residues, leading to potent bactericidal activity. Meanwhile, the glycopolypeptide coatings showed superior biocompatibility, long-term antibiofilm and anti-infection properties in two types of mouse subcutaneous infection models and one type of mouse urinary tract infection model. This work provides a new strategy to achieve antibacterial coatings with long-term activities for preventing implantable medical device associated infections.
2025, 36(2): 109751
doi: 10.1016/j.cclet.2024.109751
摘要:
The preparation of immobilized enzyme with excellent performance is one of the difficulties that restrict the application of enzyme catalysis technology. Here, Candida rugosa lipase (CRL) was firstly adsorbed on the surface of magnetic zeolitic imidazolate framework-8 (ZIF-8) nanospheres, which was further encapsulated with a mesoporous SiO2 nano-membrane formed by tetraethyl orthosilicate (TEOS) polycondensation. Consequently, lipase could be firmly immobilized on carrier surface by physical binding rather than chemical binding, which did not damage the active conformation of enzyme. There were mesopores on the silica nano-membrane, which could improve the accessibility of enzyme and its apparent catalytic activity. Moreover, silica membrane encapsulation could also improve the stability of enzyme, suggesting an effective enzyme immobilization strategy. It showed that TEOS amount and the encapsulation time had significant effects on the thickness of silica membrane and the enzyme activity. The analysis in enzyme activity and protein secondary structure showed that lipase encapsulated in silica membrane retained the active conformation to the greatest extent. Compared with the adsorbed lipase, the encapsulated lipase increased its thermostability by 3 times and resistance to chemical denaturants by 7 times. The relative enzyme activity remained around 80% after 8 repetitions, while the adsorbed lipase only remained at 7.3%.
The preparation of immobilized enzyme with excellent performance is one of the difficulties that restrict the application of enzyme catalysis technology. Here, Candida rugosa lipase (CRL) was firstly adsorbed on the surface of magnetic zeolitic imidazolate framework-8 (ZIF-8) nanospheres, which was further encapsulated with a mesoporous SiO2 nano-membrane formed by tetraethyl orthosilicate (TEOS) polycondensation. Consequently, lipase could be firmly immobilized on carrier surface by physical binding rather than chemical binding, which did not damage the active conformation of enzyme. There were mesopores on the silica nano-membrane, which could improve the accessibility of enzyme and its apparent catalytic activity. Moreover, silica membrane encapsulation could also improve the stability of enzyme, suggesting an effective enzyme immobilization strategy. It showed that TEOS amount and the encapsulation time had significant effects on the thickness of silica membrane and the enzyme activity. The analysis in enzyme activity and protein secondary structure showed that lipase encapsulated in silica membrane retained the active conformation to the greatest extent. Compared with the adsorbed lipase, the encapsulated lipase increased its thermostability by 3 times and resistance to chemical denaturants by 7 times. The relative enzyme activity remained around 80% after 8 repetitions, while the adsorbed lipase only remained at 7.3%.
2025, 36(2): 109762
doi: 10.1016/j.cclet.2024.109762
摘要:
Skins expose to kinds of risk factors for damage, such as the hormone drugs, skin care products and ultraviolet radiation, which is accompanied by the production of excessive reactive oxygen species (ROS) and eventually leads to hypertrichosis. This skin disease is not aesthetically pleasing and even causes psychological and spiritual problems such as inferiority, anxiety and irritability. Current therapies are limited and often unsatisfactory, such as pharmacological and physical therapies, which have adverse effects and cause the irreversible destruction of hair follicles. Gold nanoclusters have good biocompatibility and their biosynthesis in vivo is responsive to oxidative stress microenvironment (OSM), which could be a safe and effective drug for ROS-induced skin injury. In our study, we demonstrated that zero valence fluorescent gold nanoclusters (FGNCs) were in situ biosynthesized in the plucking-induced damaged skin but not in the normal skin after the administration of gold precursors (+3), while FGNCs inhibited hair follicle regeneration by negatively regulating nuclear transcription factor kappa B (NFκB)-mediated inflammatory response signaling pathway (NFκB/tumor necrosis factor-α (TNF-α) axis). This OSM-responsive in situ biosynthesis method is facile and safe and holds great promise for curing hypertrichosis associated with skin dermatitis and injury.
Skins expose to kinds of risk factors for damage, such as the hormone drugs, skin care products and ultraviolet radiation, which is accompanied by the production of excessive reactive oxygen species (ROS) and eventually leads to hypertrichosis. This skin disease is not aesthetically pleasing and even causes psychological and spiritual problems such as inferiority, anxiety and irritability. Current therapies are limited and often unsatisfactory, such as pharmacological and physical therapies, which have adverse effects and cause the irreversible destruction of hair follicles. Gold nanoclusters have good biocompatibility and their biosynthesis in vivo is responsive to oxidative stress microenvironment (OSM), which could be a safe and effective drug for ROS-induced skin injury. In our study, we demonstrated that zero valence fluorescent gold nanoclusters (FGNCs) were in situ biosynthesized in the plucking-induced damaged skin but not in the normal skin after the administration of gold precursors (+3), while FGNCs inhibited hair follicle regeneration by negatively regulating nuclear transcription factor kappa B (NFκB)-mediated inflammatory response signaling pathway (NFκB/tumor necrosis factor-α (TNF-α) axis). This OSM-responsive in situ biosynthesis method is facile and safe and holds great promise for curing hypertrichosis associated with skin dermatitis and injury.
2025, 36(2): 109765
doi: 10.1016/j.cclet.2024.109765
摘要:
Prostate cancer (PCa) is characterized by high incidence and propensity for easy metastasis, presenting significant challenges in clinical diagnosis and treatment. Tumor microenvironment (TME)-responsive nanomaterials provide a promising prospect for imaging-guided precision therapy. Considering that tumor-derived alkaline phosphatase (ALP) is over-expressed in metastatic PCa, it makes a great chance to develop a theranostics system with ALP responsive in the TME. Herein, an ALP-responsive aggregation-induced emission luminogens (AIEgens) nanoprobe AMNF self-assembly was designed for enhancing the diagnosis and treatment of metastatic PCa. The nanoprobe exhibited self-aggregation in the presence of ALP resulted in aggregation-induced fluorescence, and enhanced accumulation and prolonged retention period at the tumor site. In terms of detection, the fluorescence (FL)/computed tomography (CT)/magnetic resonance (MR) multi-mode imaging effect of nanoprobe was significantly improved post-aggregation, enabling precise diagnosis through the amalgamation of multiple imaging modes. Enhanced CT/MR imaging can achieve assist preoperative tumor diagnosis, and enhanced FL imaging technology can achieve "intraoperative visual navigation", showing its potential application value in clinical tumor detection and surgical guidance. In terms of treatment, AMNF showed strong absorption in the near infrared region after aggregation, which improved the photothermal treatment effect. Overall, our work developed an effective aggregation-enhanced theranostic strategy for ALP-related cancers.
Prostate cancer (PCa) is characterized by high incidence and propensity for easy metastasis, presenting significant challenges in clinical diagnosis and treatment. Tumor microenvironment (TME)-responsive nanomaterials provide a promising prospect for imaging-guided precision therapy. Considering that tumor-derived alkaline phosphatase (ALP) is over-expressed in metastatic PCa, it makes a great chance to develop a theranostics system with ALP responsive in the TME. Herein, an ALP-responsive aggregation-induced emission luminogens (AIEgens) nanoprobe AMNF self-assembly was designed for enhancing the diagnosis and treatment of metastatic PCa. The nanoprobe exhibited self-aggregation in the presence of ALP resulted in aggregation-induced fluorescence, and enhanced accumulation and prolonged retention period at the tumor site. In terms of detection, the fluorescence (FL)/computed tomography (CT)/magnetic resonance (MR) multi-mode imaging effect of nanoprobe was significantly improved post-aggregation, enabling precise diagnosis through the amalgamation of multiple imaging modes. Enhanced CT/MR imaging can achieve assist preoperative tumor diagnosis, and enhanced FL imaging technology can achieve "intraoperative visual navigation", showing its potential application value in clinical tumor detection and surgical guidance. In terms of treatment, AMNF showed strong absorption in the near infrared region after aggregation, which improved the photothermal treatment effect. Overall, our work developed an effective aggregation-enhanced theranostic strategy for ALP-related cancers.
2025, 36(2): 109769
doi: 10.1016/j.cclet.2024.109769
摘要:
A phenylphenothiazine anchored Tb(Ⅲ)-cyclen complex PTP-Cy-Tb for hypochlorite ion (ClO−) detection has been designed and prepared. PTP-Cy-Tb shows a weak Tb-based emission with AIE-characteristics in aqueous solutions. After addition of ClO−, the fluorescence of PTP-Cy-Tb gives a large enhancement for oxidization the thioether to sulfoxide group. The detection limit of PTP-Cy-Tb toward ClO− is as low as 8.85 nmol/L. The sensing mechanism was detailedly investigated by time of flight mass spectrometer (TOF-MS), Fourier transform infrared spectroscopy (FT-IR) and density functional theory (DFT) calculation. In addition, PTP-Cy-Tb has been successfully used for on-site and real-time detection of ClO− in real water samples by using the smartphone-based visualization method and test strips.
A phenylphenothiazine anchored Tb(Ⅲ)-cyclen complex PTP-Cy-Tb for hypochlorite ion (ClO−) detection has been designed and prepared. PTP-Cy-Tb shows a weak Tb-based emission with AIE-characteristics in aqueous solutions. After addition of ClO−, the fluorescence of PTP-Cy-Tb gives a large enhancement for oxidization the thioether to sulfoxide group. The detection limit of PTP-Cy-Tb toward ClO− is as low as 8.85 nmol/L. The sensing mechanism was detailedly investigated by time of flight mass spectrometer (TOF-MS), Fourier transform infrared spectroscopy (FT-IR) and density functional theory (DFT) calculation. In addition, PTP-Cy-Tb has been successfully used for on-site and real-time detection of ClO− in real water samples by using the smartphone-based visualization method and test strips.
2025, 36(2): 109776
doi: 10.1016/j.cclet.2024.109776
摘要:
Solid-state batteries (SSBs) with high-capacity Si anodes have been regarded as one of the most promising candidates to meet the large scale energy storage and electrical vehicles due to its intrinsic safety and potential high energy density. However, Si suffers from poor electrical conductivity and huge volume change and particles fracture during lithiaiotn and delithiation, which induces low practical energy density. In addition, the SSBs are often operated at high temperature due to the poor physical contact and huge resistance between Si and solid-state electrolyte (SSE). To improve the bulk electronic/ionic conductivity of Si and its interfacial compatibility with SSE, herein, a binder free and self-supporting Si/C film was developed. The monolithic carbon not only enhance the electric conductivity but also release huge stress during lithiation and delithiation. In addition, paired with the flexible and soft poly(vinylidene fluoride)-co-hexafluoropropylene (PVDF-HFP) and Li1.3Al0.3Ti1.7(PO4)3 (LATP) solid-state electrolyte, a LiF-rich and electrochemical stable solid-electrolyte interphase (SEI) layer is in-situ engineered. The fast bulk and interfacial ionic transportation as well as the mechanical integrity of MSi enable high performance SSBs at room temperature. As a result, high specific capacity of 2137 mAh/g with an initial Coulombic efficiency of 83.2% is obtained at a rate of 0.5 A/g. Even at a high rate of 3 A/g, the specific capacity is 1793 mAh/g. At a rate of 1 A/g, the Si/C anode delivers a long cycling performance over 500 cycles while maintains a capacity of 1135 mAh/g. This work provides a new strategy that combines charge transfer kinetics and interfacial chemistry design toward high energy density Si-based SSBs.
Solid-state batteries (SSBs) with high-capacity Si anodes have been regarded as one of the most promising candidates to meet the large scale energy storage and electrical vehicles due to its intrinsic safety and potential high energy density. However, Si suffers from poor electrical conductivity and huge volume change and particles fracture during lithiaiotn and delithiation, which induces low practical energy density. In addition, the SSBs are often operated at high temperature due to the poor physical contact and huge resistance between Si and solid-state electrolyte (SSE). To improve the bulk electronic/ionic conductivity of Si and its interfacial compatibility with SSE, herein, a binder free and self-supporting Si/C film was developed. The monolithic carbon not only enhance the electric conductivity but also release huge stress during lithiation and delithiation. In addition, paired with the flexible and soft poly(vinylidene fluoride)-co-hexafluoropropylene (PVDF-HFP) and Li1.3Al0.3Ti1.7(PO4)3 (LATP) solid-state electrolyte, a LiF-rich and electrochemical stable solid-electrolyte interphase (SEI) layer is in-situ engineered. The fast bulk and interfacial ionic transportation as well as the mechanical integrity of MSi enable high performance SSBs at room temperature. As a result, high specific capacity of 2137 mAh/g with an initial Coulombic efficiency of 83.2% is obtained at a rate of 0.5 A/g. Even at a high rate of 3 A/g, the specific capacity is 1793 mAh/g. At a rate of 1 A/g, the Si/C anode delivers a long cycling performance over 500 cycles while maintains a capacity of 1135 mAh/g. This work provides a new strategy that combines charge transfer kinetics and interfacial chemistry design toward high energy density Si-based SSBs.
2025, 36(2): 109784
doi: 10.1016/j.cclet.2024.109784
摘要:
Imaging detection of interlinked dual proteases is imperative for precise tumor imaging, which remains challenging due to limited modification position of specific substrate and possible steric hindrance. Herein, we have developed a unimolecular chemiluminescent probe (LGP-CL) tandemly activated by two proteases interlinked with liver cancer to achieve precise tumor imaging. Probe LGP-CL consists of a phenoxy-dioxetane scaffold caged by a tripeptide substrate (LGP, leucine-glycine-proline) as the sensing layer, which can be cleaved sequentially by aminopeptidase N (APN) and dipeptidyl peptidase Ⅳ (DPPIV) to turn on a strong chemiluminescent signal, and silenced by specific inhibitor of each enzyme, which accounts for an integrated logic gate (AND, OR and INHIBIT). The successful cleavage of dual proteases on the metabolic site depends on the proper structure of the tripeptide substrate, as confirmed by two probes design. Probe LGP-CL (LGP as the substrate) enables the excellent "dual-lock-dual-key" fit with a 382-fold enhancement of chemiluminescent emission while no obvious signal is observed by using GPL-CL (GPL as the substrate). By virtue of its rapid response (several minutes), high sensitivity and good cell viability, probe LGP-CL has been utilized to evaluate upregulated levels of proteases in vitro and in living systems, especially to distinguish liver tumor cells (HepG2) from others (LO2, MCF-7, MCF-10a and RAW264.7). Overall, the newly developed CL probe may facilitate rapid investigation into the role played by proteases in liver diseases, enabling timely selection appropriate treatment. Therefore, our work not only sheds light on the rational design of optical probes for dual protease imaging, but provides a promising tool for clinical diagnosis and even drug discovery.
Imaging detection of interlinked dual proteases is imperative for precise tumor imaging, which remains challenging due to limited modification position of specific substrate and possible steric hindrance. Herein, we have developed a unimolecular chemiluminescent probe (LGP-CL) tandemly activated by two proteases interlinked with liver cancer to achieve precise tumor imaging. Probe LGP-CL consists of a phenoxy-dioxetane scaffold caged by a tripeptide substrate (LGP, leucine-glycine-proline) as the sensing layer, which can be cleaved sequentially by aminopeptidase N (APN) and dipeptidyl peptidase Ⅳ (DPPIV) to turn on a strong chemiluminescent signal, and silenced by specific inhibitor of each enzyme, which accounts for an integrated logic gate (AND, OR and INHIBIT). The successful cleavage of dual proteases on the metabolic site depends on the proper structure of the tripeptide substrate, as confirmed by two probes design. Probe LGP-CL (LGP as the substrate) enables the excellent "dual-lock-dual-key" fit with a 382-fold enhancement of chemiluminescent emission while no obvious signal is observed by using GPL-CL (GPL as the substrate). By virtue of its rapid response (several minutes), high sensitivity and good cell viability, probe LGP-CL has been utilized to evaluate upregulated levels of proteases in vitro and in living systems, especially to distinguish liver tumor cells (HepG2) from others (LO2, MCF-7, MCF-10a and RAW264.7). Overall, the newly developed CL probe may facilitate rapid investigation into the role played by proteases in liver diseases, enabling timely selection appropriate treatment. Therefore, our work not only sheds light on the rational design of optical probes for dual protease imaging, but provides a promising tool for clinical diagnosis and even drug discovery.
2025, 36(2): 109816
doi: 10.1016/j.cclet.2024.109816
摘要:
The first total synthesis of (+)-taberdicatine B and (+)-tabernabovine B has been accomplished in 10 steps with 26.9% overall yield and 15 steps with 7.3% overall yield, respectively. The prominent features of this efficient synthetic strategy include the following: (1) (+)-Taberdicatine B and (+)-tabernabovine B were accessed from common advanced intermediates by varying the substituents; (2) A one-pot asymmetric bromocyclization/hydrolysis was explored to assemble HPI skeleton; (3) Dieckmann condensation to form β-keto ester for the assembly of seven-membered ring; (4) An ester reduction/amide semireduction/cyclization sequence was applied to form the cage-like framework.
The first total synthesis of (+)-taberdicatine B and (+)-tabernabovine B has been accomplished in 10 steps with 26.9% overall yield and 15 steps with 7.3% overall yield, respectively. The prominent features of this efficient synthetic strategy include the following: (1) (+)-Taberdicatine B and (+)-tabernabovine B were accessed from common advanced intermediates by varying the substituents; (2) A one-pot asymmetric bromocyclization/hydrolysis was explored to assemble HPI skeleton; (3) Dieckmann condensation to form β-keto ester for the assembly of seven-membered ring; (4) An ester reduction/amide semireduction/cyclization sequence was applied to form the cage-like framework.
2025, 36(2): 109819
doi: 10.1016/j.cclet.2024.109819
摘要:
Diabetic wound healing is often complicated due to bacterial infections that intensify inflammation. Employing hydrogel dressings with inherent antibacterial properties can significantly reduce reliance on antibiotics for treating infected wounds in diabetics. Traditional hydrogels typically rely on the infiltration of bacteria into their porous structure to manifest antibacterial effects. However, this infiltration process is not only prolonged but can also exacerbate inflammation, further delaying the healing of the wound. Thus, promptly capturing and eliminating bacteria is crucial for enhancing the antibacterial efficiency of the hydrogel. In this context, we present a multifunctional hydrogel dressing, termed SIP, designed to tackle drug-resistant bacterial infections in diabetic wounds. This dressing integrates ionic liquid functional groups into a sericin-based matrix: phenylboronic acid for the immobilization of bacteria and imidazole for their subsequent annihilation. Expectedly, the SIP system demonstrates potent antibacterial activity against methicillin-resistant Staphylococcus aureus, verified through in vitro and in vivo experiments. As a result, SIP emerges as a promising candidate in the realm of hydrogel dressings with innate antibacterial properties, showcasing considerable potential for addressing diabetic wounds plagued by drug-resistant bacterial infections.
Diabetic wound healing is often complicated due to bacterial infections that intensify inflammation. Employing hydrogel dressings with inherent antibacterial properties can significantly reduce reliance on antibiotics for treating infected wounds in diabetics. Traditional hydrogels typically rely on the infiltration of bacteria into their porous structure to manifest antibacterial effects. However, this infiltration process is not only prolonged but can also exacerbate inflammation, further delaying the healing of the wound. Thus, promptly capturing and eliminating bacteria is crucial for enhancing the antibacterial efficiency of the hydrogel. In this context, we present a multifunctional hydrogel dressing, termed SIP, designed to tackle drug-resistant bacterial infections in diabetic wounds. This dressing integrates ionic liquid functional groups into a sericin-based matrix: phenylboronic acid for the immobilization of bacteria and imidazole for their subsequent annihilation. Expectedly, the SIP system demonstrates potent antibacterial activity against methicillin-resistant Staphylococcus aureus, verified through in vitro and in vivo experiments. As a result, SIP emerges as a promising candidate in the realm of hydrogel dressings with innate antibacterial properties, showcasing considerable potential for addressing diabetic wounds plagued by drug-resistant bacterial infections.
2025, 36(2): 109854
doi: 10.1016/j.cclet.2024.109854
摘要:
Cholelithiasis affects approximately 10%-20% of the adult population globally. And cholesterol accumulation and nucleation of cholesterol crystals are commonly recognized as the primary process in the initiation and progression of gallstones. Hydroxypropyl-β-cyclodextrin (HPCD) is a supramolecular host compound that can solubilize cholesterol, potentially serving as a preventative or therapeutic agent for cholelithiasis. However, we found that the administration of HPCD treatment did not impede the formation of gallstones in mice, mainly attributed to the pre-complexation of its cavity during the transition process. Here we synthesized a prodrug of HPCD and prepared a HPCD nanoparticle (HPCD-NP), which can be transported efficiently to the gallbladder through the hepatobiliary system following an intravenous injection. In the bile, the HPCD-NP degraded into free HPCD, bound to cholesterol crystals and gallstones within the gallbladder and effectively increased cholesterol solubilization, leading to gallstones regression. Given the established safety of both HPCD and cyclodextrin-based nanoparticles in numerous animal and human studies, HPCD-NP shows considerable promise for the prevention and treatment of human cholelithiasis.
Cholelithiasis affects approximately 10%-20% of the adult population globally. And cholesterol accumulation and nucleation of cholesterol crystals are commonly recognized as the primary process in the initiation and progression of gallstones. Hydroxypropyl-β-cyclodextrin (HPCD) is a supramolecular host compound that can solubilize cholesterol, potentially serving as a preventative or therapeutic agent for cholelithiasis. However, we found that the administration of HPCD treatment did not impede the formation of gallstones in mice, mainly attributed to the pre-complexation of its cavity during the transition process. Here we synthesized a prodrug of HPCD and prepared a HPCD nanoparticle (HPCD-NP), which can be transported efficiently to the gallbladder through the hepatobiliary system following an intravenous injection. In the bile, the HPCD-NP degraded into free HPCD, bound to cholesterol crystals and gallstones within the gallbladder and effectively increased cholesterol solubilization, leading to gallstones regression. Given the established safety of both HPCD and cyclodextrin-based nanoparticles in numerous animal and human studies, HPCD-NP shows considerable promise for the prevention and treatment of human cholelithiasis.
2025, 36(2): 109860
doi: 10.1016/j.cclet.2024.109860
摘要:
In this study, a simple and effective ratiometric fluorescence method has been developed for carbaryl detection, utilizing red emissive carbon dots (R-CDs). The underlying principle of this proposed strategy relies on the rapid hydrolysis of carbaryl under an alkaline condition and production of 1-naphthol with blue-emission at 462 nm. Furthermore, the as-synthesized R-CDs (Em. 677 nm), serve as a reference, enhancing the visual tracking of carbaryl through the transformation of fluorescent color from red to blue. The concentration of carbaryl exhibits a commendable linear correlation with the ratio of fluorescence intensity, ranging from 0 to 20 µg/mL (R2 = 0.9989) with a low detection limit of 0.52 ng/mL. Additionally, the described methodology can be used for the enzyme-free visual assay of carbaryl, even in the presence of other carbamate pesticides and metal ions, in tap water and lake water samples with excellent accuracy (spiked recoveries, 94%–106.1%), high precision (relative standard deviation (RSD) ≤ 2.42), and remarkable selectivity. This fast and highly sensitive naked-eye ratiometric sensor holds immense promise for carbaryl detection in intricate environments and food safety fields.
In this study, a simple and effective ratiometric fluorescence method has been developed for carbaryl detection, utilizing red emissive carbon dots (R-CDs). The underlying principle of this proposed strategy relies on the rapid hydrolysis of carbaryl under an alkaline condition and production of 1-naphthol with blue-emission at 462 nm. Furthermore, the as-synthesized R-CDs (Em. 677 nm), serve as a reference, enhancing the visual tracking of carbaryl through the transformation of fluorescent color from red to blue. The concentration of carbaryl exhibits a commendable linear correlation with the ratio of fluorescence intensity, ranging from 0 to 20 µg/mL (R2 = 0.9989) with a low detection limit of 0.52 ng/mL. Additionally, the described methodology can be used for the enzyme-free visual assay of carbaryl, even in the presence of other carbamate pesticides and metal ions, in tap water and lake water samples with excellent accuracy (spiked recoveries, 94%–106.1%), high precision (relative standard deviation (RSD) ≤ 2.42), and remarkable selectivity. This fast and highly sensitive naked-eye ratiometric sensor holds immense promise for carbaryl detection in intricate environments and food safety fields.
2025, 36(2): 109865
doi: 10.1016/j.cclet.2024.109865
摘要:
Chiral coordination molecular cages/capsules with discrete nanoconfined chiral cavities demonstrate significant potential applications across various fields. In this study, we utilized Tröger's base as the building block to design and synthesize two pairs of enantiopure ligands. These ligands were then self-assembled with Pd(Ⅱ) ions through chiral self-sorting coordination, resulting in the formation of two pairs of homochiral M2L4-type coordination molecular capsules. Notably, due to differences in the substitution positions on the Tröger's base, these two pairs of enantiomeric coordination molecular capsules exhibited distinct levels of cavity closures, cavity sizes, and host-guest recognition properties. This research offers valuable insights into the construction of novel chiral molecular capsules and the regulation of confined cavities.
Chiral coordination molecular cages/capsules with discrete nanoconfined chiral cavities demonstrate significant potential applications across various fields. In this study, we utilized Tröger's base as the building block to design and synthesize two pairs of enantiopure ligands. These ligands were then self-assembled with Pd(Ⅱ) ions through chiral self-sorting coordination, resulting in the formation of two pairs of homochiral M2L4-type coordination molecular capsules. Notably, due to differences in the substitution positions on the Tröger's base, these two pairs of enantiomeric coordination molecular capsules exhibited distinct levels of cavity closures, cavity sizes, and host-guest recognition properties. This research offers valuable insights into the construction of novel chiral molecular capsules and the regulation of confined cavities.
2025, 36(2): 109866
doi: 10.1016/j.cclet.2024.109866
摘要:
Late-stage modification of complex molecules via site-selective hydrodefluorination is a challenging endeavor. The selective activation of carbon-fluorine (C–F) bonds in the presence of multiple C–F bonds is of importance in organic synthesis and drug discovery. Herein, we describe the activation of C-F bonds via multiphoton photoredox catalysis to selectively produces a series of hydrodefluorinated compounds by simply tuning the reaction conditions. Moreover, this protocol was successfully applied to the late-stage functionalization of different drug-derivatives and the corresponding mono-, di-, and tri-defluorinated products were obtained in good to excellent yields. A detailed mechanistic investigation provides insight into the unprecedented hydrodefluorination pathway.
Late-stage modification of complex molecules via site-selective hydrodefluorination is a challenging endeavor. The selective activation of carbon-fluorine (C–F) bonds in the presence of multiple C–F bonds is of importance in organic synthesis and drug discovery. Herein, we describe the activation of C-F bonds via multiphoton photoredox catalysis to selectively produces a series of hydrodefluorinated compounds by simply tuning the reaction conditions. Moreover, this protocol was successfully applied to the late-stage functionalization of different drug-derivatives and the corresponding mono-, di-, and tri-defluorinated products were obtained in good to excellent yields. A detailed mechanistic investigation provides insight into the unprecedented hydrodefluorination pathway.
2025, 36(2): 109876
doi: 10.1016/j.cclet.2024.109876
摘要:
Colorectal cancer (CRC) is one of the most prevalent malignant tumors worldwide, exhibiting high morbidity and mortality. Lack of efficient tools for early diagnosis and surgical resection guidance of CRC have been a serious threat to the long-term survival rate of the CRC patients. Recent studies have shown that relative higher viscosity was presented in tumor cells compared to that in normal cells, leading to viscosity as a potential biomarker for CRC. Herein, we reported the development of a series of novel viscosity-sensitive and mitochondria-specific fluorescent probes (HTB, HTI, and HTP) for CRC detection. Among them, HTB showed high sensitivity, minimal background interference, low cytotoxicity, and significant viscous response capability, making it an ideal tool for distinguishing colorectal tumor cells from normal cells. Importantly, we have successfully utilized HTB to visualize in a CRC-cells-derived xenograft (CDX) model, enriching its medical imaging capacity, which laid a foundation for further clinical translational application.
Colorectal cancer (CRC) is one of the most prevalent malignant tumors worldwide, exhibiting high morbidity and mortality. Lack of efficient tools for early diagnosis and surgical resection guidance of CRC have been a serious threat to the long-term survival rate of the CRC patients. Recent studies have shown that relative higher viscosity was presented in tumor cells compared to that in normal cells, leading to viscosity as a potential biomarker for CRC. Herein, we reported the development of a series of novel viscosity-sensitive and mitochondria-specific fluorescent probes (HTB, HTI, and HTP) for CRC detection. Among them, HTB showed high sensitivity, minimal background interference, low cytotoxicity, and significant viscous response capability, making it an ideal tool for distinguishing colorectal tumor cells from normal cells. Importantly, we have successfully utilized HTB to visualize in a CRC-cells-derived xenograft (CDX) model, enriching its medical imaging capacity, which laid a foundation for further clinical translational application.
2025, 36(2): 109878
doi: 10.1016/j.cclet.2024.109878
摘要:
Nor-seco-cucurbit[10]uril (ns-CB[10]) is a kinetic product with unique structure. The single bridged methylene in its structure makes the molecular cavity of ns-CB[10] more deformable when compared to ordinary cucurbit[n]uril, reducing its structural stability. Repeated experiments showed that ns-CB[10] gradually cracks in an acidic solution and changes the specificity of cucurbit[5]uril (CB[5]) and cucurbit[8]uril (CB[8]) under more robust acidic solutions and when heated. A series of experiments were designed to study the transformation behavior of ns-CB[10]. It was found that the concentration of ns-CB[10] was correlated with the content distribution of CB[5] and CB[8]. This study explores the influencing factors and mechanisms of the transformation of ns-CB[10] to CB[5] and CB[8]. The results are of great significance for the application of ns-CB[10], understanding the formation mechanism of cucurbit[n]urils. Furthermore, it provides a new pathway for synthesizing new cucurbit[n]urils.
Nor-seco-cucurbit[10]uril (ns-CB[10]) is a kinetic product with unique structure. The single bridged methylene in its structure makes the molecular cavity of ns-CB[10] more deformable when compared to ordinary cucurbit[n]uril, reducing its structural stability. Repeated experiments showed that ns-CB[10] gradually cracks in an acidic solution and changes the specificity of cucurbit[5]uril (CB[5]) and cucurbit[8]uril (CB[8]) under more robust acidic solutions and when heated. A series of experiments were designed to study the transformation behavior of ns-CB[10]. It was found that the concentration of ns-CB[10] was correlated with the content distribution of CB[5] and CB[8]. This study explores the influencing factors and mechanisms of the transformation of ns-CB[10] to CB[5] and CB[8]. The results are of great significance for the application of ns-CB[10], understanding the formation mechanism of cucurbit[n]urils. Furthermore, it provides a new pathway for synthesizing new cucurbit[n]urils.
2025, 36(2): 109880
doi: 10.1016/j.cclet.2024.109880
摘要:
The first synthesis of flavanostilbenes with a 2-cyclohepten-1-one core was carried out by applying an effective strategy in three steps from abundant polymerized flavanol resources. A key regio- and stereoselective Cu-mediated [5 + 2] cycloaddition/decarboxylation cascade was explored and applied without the use of protecting groups, and water as an environmentally friendly solvent contributed to the cascade. The intramolecular [5 + 2] cycloaddition mechanism, involving oxidation and dearomatization of the flavanol unit as a diene, was proposed and supported by the synthesis of the intermediate. The regioselectivity of the cyclization was found to be dependent on the substitution effects of the stilbene units by the exploration of substrate scope.
The first synthesis of flavanostilbenes with a 2-cyclohepten-1-one core was carried out by applying an effective strategy in three steps from abundant polymerized flavanol resources. A key regio- and stereoselective Cu-mediated [5 + 2] cycloaddition/decarboxylation cascade was explored and applied without the use of protecting groups, and water as an environmentally friendly solvent contributed to the cascade. The intramolecular [5 + 2] cycloaddition mechanism, involving oxidation and dearomatization of the flavanol unit as a diene, was proposed and supported by the synthesis of the intermediate. The regioselectivity of the cyclization was found to be dependent on the substitution effects of the stilbene units by the exploration of substrate scope.
2025, 36(2): 109895
doi: 10.1016/j.cclet.2024.109895
摘要:
Gold-catalyzed amination reactions based on azides via α-imino gold carbene intermediates have attracted extensive attention in the past decades because this methodology leads to the facile and efficient construction of synthetically useful N-containing molecules, especially valuable N-heterocycles. However, successful examples of intermolecular generation of α-imino gold carbenes by using azides as amination reagents are rarely explored probably due to the weak nucleophilicity of azides. Herein, we disclose an efficient gold-catalyzed intermolecular aminative cyclopropanation of ynamides with the allyl azides, enabling flexible synthesis of a wide range of valuable 3-azabicyclo[3.1.0]hex-2-ene derivatives in good to excellent yields with excellent diastereoselectivities. Importantly, this protocol represents the first use of allyl azide as an efficient amination reagent in gold-catalyzed alkyne amination reactions.
Gold-catalyzed amination reactions based on azides via α-imino gold carbene intermediates have attracted extensive attention in the past decades because this methodology leads to the facile and efficient construction of synthetically useful N-containing molecules, especially valuable N-heterocycles. However, successful examples of intermolecular generation of α-imino gold carbenes by using azides as amination reagents are rarely explored probably due to the weak nucleophilicity of azides. Herein, we disclose an efficient gold-catalyzed intermolecular aminative cyclopropanation of ynamides with the allyl azides, enabling flexible synthesis of a wide range of valuable 3-azabicyclo[3.1.0]hex-2-ene derivatives in good to excellent yields with excellent diastereoselectivities. Importantly, this protocol represents the first use of allyl azide as an efficient amination reagent in gold-catalyzed alkyne amination reactions.
2025, 36(2): 109901
doi: 10.1016/j.cclet.2024.109901
摘要:
Metal-organic frameworks (MOFs) attract broad interests in mercury (Hg) ion adsorption field, while unreasonable distribution of active groups commonly restricts their utilization efficiency. In this work, we constructed a new MOF (TYUST-6) with dense thiol-rich traps in the 1D pore wall. This accessible channel and rational distribution of thiols allow the smooth diffusion of Hg ions and thereby result in a high Langmuir adsorption capacity of 1347.6 mg/g, almost reaching the theoretical maximum (1444.3 mg/g). Adsorption equilibrium needs 10 and 30 min at the initial concentrations of 10 and 100 mg/L, respectively. Common co-existing ions and solution pH show almost negligible interferences on the adsorption, and adsorbent regeneration can be well achieved. Combining experimental characterizations and theoretical calculations, the thiol groups in the pore wall are proved to be the dominant interaction sites. Thus, this work reports a novel high-capacity adsorbent for Hg2+, and proposes a feasible guideline for designing effective adsorbents.
Metal-organic frameworks (MOFs) attract broad interests in mercury (Hg) ion adsorption field, while unreasonable distribution of active groups commonly restricts their utilization efficiency. In this work, we constructed a new MOF (TYUST-6) with dense thiol-rich traps in the 1D pore wall. This accessible channel and rational distribution of thiols allow the smooth diffusion of Hg ions and thereby result in a high Langmuir adsorption capacity of 1347.6 mg/g, almost reaching the theoretical maximum (1444.3 mg/g). Adsorption equilibrium needs 10 and 30 min at the initial concentrations of 10 and 100 mg/L, respectively. Common co-existing ions and solution pH show almost negligible interferences on the adsorption, and adsorbent regeneration can be well achieved. Combining experimental characterizations and theoretical calculations, the thiol groups in the pore wall are proved to be the dominant interaction sites. Thus, this work reports a novel high-capacity adsorbent for Hg2+, and proposes a feasible guideline for designing effective adsorbents.
2025, 36(2): 109908
doi: 10.1016/j.cclet.2024.109908
摘要:
The interaction between nanoparticles (NPs) and pollutants affects their bioavailability and toxicity. However, the processes by which NPs and pollutants change in vivo have rarely been explored. Here, using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP–MS), we found that both nanoplastics and ZnO NPs caused more Cd to accumulate in zebrafish larvae, but with distinct pathways. Nanoplastics could adsorb Cd2+ and transfer it into the larvae through the "Trojan horse" effect. The coexposure of nanoplastics and Cd2+ caused Cd to accumulate in the abdomen where the nanoplastics were located without dissociation, showing a lower toxic effect than Cd2+ exposure alone. ZnO NPs weakly adsorbed Cd2+, but they increased the Zn and Cd contents in larvae by enhancing the expression of metal transporters. The coexposure of ZnO and Cd2+ evenly distributed Cd in the larvae, revealing a more severe toxic effect than Cd2+ exposure alone. Our results demonstrated the changing bioavailability and toxicity of Cd induced by different NPs. This also shows the vital role LA-ICP-MS plays in revealing the relationship between toxicity and bioavailability. In addition, the long-term effect of bioavailability on heavy metal toxicity and nanosafety deserves further investigation.
The interaction between nanoparticles (NPs) and pollutants affects their bioavailability and toxicity. However, the processes by which NPs and pollutants change in vivo have rarely been explored. Here, using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP–MS), we found that both nanoplastics and ZnO NPs caused more Cd to accumulate in zebrafish larvae, but with distinct pathways. Nanoplastics could adsorb Cd2+ and transfer it into the larvae through the "Trojan horse" effect. The coexposure of nanoplastics and Cd2+ caused Cd to accumulate in the abdomen where the nanoplastics were located without dissociation, showing a lower toxic effect than Cd2+ exposure alone. ZnO NPs weakly adsorbed Cd2+, but they increased the Zn and Cd contents in larvae by enhancing the expression of metal transporters. The coexposure of ZnO and Cd2+ evenly distributed Cd in the larvae, revealing a more severe toxic effect than Cd2+ exposure alone. Our results demonstrated the changing bioavailability and toxicity of Cd induced by different NPs. This also shows the vital role LA-ICP-MS plays in revealing the relationship between toxicity and bioavailability. In addition, the long-term effect of bioavailability on heavy metal toxicity and nanosafety deserves further investigation.
2025, 36(2): 109910
doi: 10.1016/j.cclet.2024.109910
摘要:
Photodynamic therapy (PDT) presents a promising avenue in cancer treatment. Erlotinib, an FDA-approved anticancer drug targeting epidermal growth factor receptor (EGFR), has shown effectiveness in normalizing tumor vasculature across various tumors, thereby promoting tumor oxygenation and facilitating PDT. In this work, erlotinib was conjugated with a near-infrared (NIR) photosensitizer, benzo[a]phenoselenazinium, yielding three EGFR-targeted PDT agents (NBSe-nC-Er). These newly synthesized photosensitizers demonstrate specificity in binding to EGFR, thereby enhancing their accumulation in cancer cells and tumors, and consequently improving the efficiency of both PDT and chemotherapy. Additionally, the NIR fluorescence emitted by the photosensitizer allows for imaging-guided therapy, offering a non-invasive means of monitoring treatment progress. The distinctive properties of the three-in-one photosensitizer render it an ideal candidate for precise tumor treatment, overcoming the limitations of conventional therapies.
Photodynamic therapy (PDT) presents a promising avenue in cancer treatment. Erlotinib, an FDA-approved anticancer drug targeting epidermal growth factor receptor (EGFR), has shown effectiveness in normalizing tumor vasculature across various tumors, thereby promoting tumor oxygenation and facilitating PDT. In this work, erlotinib was conjugated with a near-infrared (NIR) photosensitizer, benzo[a]phenoselenazinium, yielding three EGFR-targeted PDT agents (NBSe-nC-Er). These newly synthesized photosensitizers demonstrate specificity in binding to EGFR, thereby enhancing their accumulation in cancer cells and tumors, and consequently improving the efficiency of both PDT and chemotherapy. Additionally, the NIR fluorescence emitted by the photosensitizer allows for imaging-guided therapy, offering a non-invasive means of monitoring treatment progress. The distinctive properties of the three-in-one photosensitizer render it an ideal candidate for precise tumor treatment, overcoming the limitations of conventional therapies.
2025, 36(2): 109911
doi: 10.1016/j.cclet.2024.109911
摘要:
Wearable flexible sensor devices have the characteristics of lightweight and miniaturization. Currently, power supply and detection components limit the portability of wearable flexible sensor devices. Meanwhile, conventional liquid electrolytes are unsuitable for the integration of sensing devices. To address these constraints, wearable biofuel cells and flexible electrochromic displays have been introduced, which can improve integration with other devices, safety, and color-coded display data. Meanwhile, electrode chips prepared through screen printing technology can further improve portability. In this work, a wearable sensor device with screen-printed chips was constructed and used for non-invasive detection of glucose. Agarose gel electrolytes doped with PDA-CNTs were prepared, and the mechanical strength and moisture retention were significantly improved compared with traditional gel electrolytes. Glucose in interstitial fluid was non-invasive extracted to the skin surface using reverse iontophoresis. As a biofuel for wearable biofuel cells, glucose drives self-powered sensor and electrochromic display to produce color change, allowing for visually measurement of glucose levels in body fluids. Accurate detection results can be visualized by reading the RGB value with a cell phone.
Wearable flexible sensor devices have the characteristics of lightweight and miniaturization. Currently, power supply and detection components limit the portability of wearable flexible sensor devices. Meanwhile, conventional liquid electrolytes are unsuitable for the integration of sensing devices. To address these constraints, wearable biofuel cells and flexible electrochromic displays have been introduced, which can improve integration with other devices, safety, and color-coded display data. Meanwhile, electrode chips prepared through screen printing technology can further improve portability. In this work, a wearable sensor device with screen-printed chips was constructed and used for non-invasive detection of glucose. Agarose gel electrolytes doped with PDA-CNTs were prepared, and the mechanical strength and moisture retention were significantly improved compared with traditional gel electrolytes. Glucose in interstitial fluid was non-invasive extracted to the skin surface using reverse iontophoresis. As a biofuel for wearable biofuel cells, glucose drives self-powered sensor and electrochromic display to produce color change, allowing for visually measurement of glucose levels in body fluids. Accurate detection results can be visualized by reading the RGB value with a cell phone.
2025, 36(2): 109923
doi: 10.1016/j.cclet.2024.109923
摘要:
Environment-sensitive fluorescent probes are commonly utilized in various fields, including fluorescence sensing and imaging. This paper describes the synthesis and photophysical properties of a novel class of solvatochromic fluorophores that incorporate biisoindolylidene as the core backbone. This study investigates the structure-property relationships of these newly developed fluorophores. The central biisoindolylidene acts as an efficient electron acceptor, and by modifying the aryl ring substituent at the 3,3′ position, the photophysical properties of the fluorophores can be significantly enhanced, particularly in terms of photoluminescence quantum efficiency. Furthermore, when an electron-donor group replaces the aryl ring at the 3,3′ position, intriguing solvatochromic behavior is observed. This leads to a red-shift in the maximum emission wavelength and an increase in the Stokes shift with increasing solvent polarity. In solvent dimethyl sulfoxide (DMSO), the maximum emission wavelength can reach up to 750 nm, with a Stokes shift of approximately 150 nm. Finally, the potential application of the fluorophore in the detection of volatile acids is explored in a preliminary manner.
Environment-sensitive fluorescent probes are commonly utilized in various fields, including fluorescence sensing and imaging. This paper describes the synthesis and photophysical properties of a novel class of solvatochromic fluorophores that incorporate biisoindolylidene as the core backbone. This study investigates the structure-property relationships of these newly developed fluorophores. The central biisoindolylidene acts as an efficient electron acceptor, and by modifying the aryl ring substituent at the 3,3′ position, the photophysical properties of the fluorophores can be significantly enhanced, particularly in terms of photoluminescence quantum efficiency. Furthermore, when an electron-donor group replaces the aryl ring at the 3,3′ position, intriguing solvatochromic behavior is observed. This leads to a red-shift in the maximum emission wavelength and an increase in the Stokes shift with increasing solvent polarity. In solvent dimethyl sulfoxide (DMSO), the maximum emission wavelength can reach up to 750 nm, with a Stokes shift of approximately 150 nm. Finally, the potential application of the fluorophore in the detection of volatile acids is explored in a preliminary manner.
2025, 36(2): 109930
doi: 10.1016/j.cclet.2024.109930
摘要:
The extracellular vesicles show great potential as a noninvasive biomarker for the early detection of cancer. Hence, there is an urgent requirement to create biosensors that are time-saving, simple, and easily scalable in order to accomplish rapid, sensitive, and quantitative detection of extracellular vesicles. In this study, we present a self-propelled DNA walker powered by endonuclease Nt.BbvCI, which enables the development of a "signal on" sensing platform for the rapid and highly sensitive detection of extracellular vesicles. The DNA motor employed tracks made of streptavidin magnetic beads, which consisted of substrate strands labeled with fluorescein and motor strands locked by aptamers. The aptamer recognition of the target protein on extracellular vesicles unlocked the motor strand, initiating the DNA motor process. After replacing the optimal buffer solution containing the endonuclease Nt.BbvCI, the motor strands autonomously moved along the streptavidin magnetic beads track, continuously releasing fluorescent molecules and producing detectable fluorescence signals. Under optimal conditions, the detection range was from 2×104 particles/mL to 2×109 particles/mL, with a detection limit of 2.9×103 particles/mL, demonstrating excellent selectivity. This method has demonstrated good selectivity in different tumor-derived extracellular vesicles and performs well in complex biological samples. The ability to effectively analyze surface proteins of extracellular vesicles in a short period of time gives our DNA walker a tremendous potential for developing simple and cost-effective clinical diagnostic devices.
The extracellular vesicles show great potential as a noninvasive biomarker for the early detection of cancer. Hence, there is an urgent requirement to create biosensors that are time-saving, simple, and easily scalable in order to accomplish rapid, sensitive, and quantitative detection of extracellular vesicles. In this study, we present a self-propelled DNA walker powered by endonuclease Nt.BbvCI, which enables the development of a "signal on" sensing platform for the rapid and highly sensitive detection of extracellular vesicles. The DNA motor employed tracks made of streptavidin magnetic beads, which consisted of substrate strands labeled with fluorescein and motor strands locked by aptamers. The aptamer recognition of the target protein on extracellular vesicles unlocked the motor strand, initiating the DNA motor process. After replacing the optimal buffer solution containing the endonuclease Nt.BbvCI, the motor strands autonomously moved along the streptavidin magnetic beads track, continuously releasing fluorescent molecules and producing detectable fluorescence signals. Under optimal conditions, the detection range was from 2×104 particles/mL to 2×109 particles/mL, with a detection limit of 2.9×103 particles/mL, demonstrating excellent selectivity. This method has demonstrated good selectivity in different tumor-derived extracellular vesicles and performs well in complex biological samples. The ability to effectively analyze surface proteins of extracellular vesicles in a short period of time gives our DNA walker a tremendous potential for developing simple and cost-effective clinical diagnostic devices.
2025, 36(2): 109931
doi: 10.1016/j.cclet.2024.109931
摘要:
The interface modulation significantly affects the photocatalytic performances of supported metal phthalocyanines (MPc)-based systems. Herein, ZnPc was loaded on nanosized Au-modified TiO2 nanosheets (Au-T) to obtain wide-spectrum ZnPc/Au-T photocatalysts. Compared with large Au NP (8 nm)-mediated ZnPc/Au-T photocatalyst, ultrasmall Au NP (3 nm)-mediated one shows advantageous photoactivity, achieving 3- and 10-fold CO2 conversion rates compared with reference ZnPc/T and pristine TiO2 nanosheets, respectively. Employing monochromatic beam-assisted surface photovoltage and photocurrent action, etc., the introduction of ultrasmall Au NPs more effectively facilitates intrinsic interfacial charge transfer. Moreover, ZnPc molecules are found more dispersed with the existence of small Au NPs hence exposing abundant Zn2+sites as the catalytic center for CO2 reduction. This work provides a feasible design strategy and renewed recognition for supported MPc-based photocatalyst systems.
The interface modulation significantly affects the photocatalytic performances of supported metal phthalocyanines (MPc)-based systems. Herein, ZnPc was loaded on nanosized Au-modified TiO2 nanosheets (Au-T) to obtain wide-spectrum ZnPc/Au-T photocatalysts. Compared with large Au NP (8 nm)-mediated ZnPc/Au-T photocatalyst, ultrasmall Au NP (3 nm)-mediated one shows advantageous photoactivity, achieving 3- and 10-fold CO2 conversion rates compared with reference ZnPc/T and pristine TiO2 nanosheets, respectively. Employing monochromatic beam-assisted surface photovoltage and photocurrent action, etc., the introduction of ultrasmall Au NPs more effectively facilitates intrinsic interfacial charge transfer. Moreover, ZnPc molecules are found more dispersed with the existence of small Au NPs hence exposing abundant Zn2+sites as the catalytic center for CO2 reduction. This work provides a feasible design strategy and renewed recognition for supported MPc-based photocatalyst systems.
2025, 36(2): 109958
doi: 10.1016/j.cclet.2024.109958
摘要:
In this work, an effective catalyst of Cu/MnOOH has been successfully constructed for electrochemical nitrate reduction reaction (eNO3RR) for synthesis of ammonia (NH3) under ambient conditions. The substrate of MnOOH plays an important role on the size and electronic structure of Cu nanoparticles, where Cu has the ultrafine size of 2.2 nm and positive shift of its valence states, which in turn causes the increased number of Cu active sites and enhanced intrinsic activity of every active site. As a result, this catalyst realizes an excellent catalytic performance on eNO3RR with the maximal NH3 Faraday efficiency (FE) (96.8%) and the highest yield rate (55.51 mg h−1 cm−2) at a large NH3 partial current density of 700 mA/cm2, which could help to promote the industrialization of NH3 production under ambient conditions.
In this work, an effective catalyst of Cu/MnOOH has been successfully constructed for electrochemical nitrate reduction reaction (eNO3RR) for synthesis of ammonia (NH3) under ambient conditions. The substrate of MnOOH plays an important role on the size and electronic structure of Cu nanoparticles, where Cu has the ultrafine size of 2.2 nm and positive shift of its valence states, which in turn causes the increased number of Cu active sites and enhanced intrinsic activity of every active site. As a result, this catalyst realizes an excellent catalytic performance on eNO3RR with the maximal NH3 Faraday efficiency (FE) (96.8%) and the highest yield rate (55.51 mg h−1 cm−2) at a large NH3 partial current density of 700 mA/cm2, which could help to promote the industrialization of NH3 production under ambient conditions.
2025, 36(2): 109959
doi: 10.1016/j.cclet.2024.109959
摘要:
The complexity of living environment system demands higher requirements for the sensitivity and selectivity of the probe. Therefore, it is of great importance to develop a universal strategy for high-performance probe optimization. Herein, we propose a novel “Enrichment-enhanced Detection” strategy and use carbon dots-dopamine detection system as a representative model to evaluate its feasibility. The composite probe carbon dots (CDs)-encapsulated in glycol-chitosan (GC) (i.e., CDs@GC) was obtained by simply mixing GC and CDs through noncovalent interactions, including electrostatic interactions and hydrogen bonding. Dopamine (DA) could be detected through internal filter effect (IFE)-induced quenching of CDs. In the case of CDs@GC, noncovalent interactions (electrostatic interactions) between GC and the formed quinone (oxide of DA) could selectively extract and enrich the local concentration of DA, thus effectively improving the sensitivity and selectivity of the sensing system. The nanosensor had a low detection limit of 3.7 nmol/L, which was a 12-fold sensitivity improvement compared to the bare CDs probes with similar fluorescent profiles, proving the feasibility of the “Enrichment-enhanced Detection” strategy. Further, to examine this theory in real case, we designed a highly portable sensing platform to realize visual determination of DA. Overall, our work introduces a new strategy for accurately detecting DA and provides valuable insights for the universal design and optimization of superior nanoprobes.
The complexity of living environment system demands higher requirements for the sensitivity and selectivity of the probe. Therefore, it is of great importance to develop a universal strategy for high-performance probe optimization. Herein, we propose a novel “Enrichment-enhanced Detection” strategy and use carbon dots-dopamine detection system as a representative model to evaluate its feasibility. The composite probe carbon dots (CDs)-encapsulated in glycol-chitosan (GC) (i.e., CDs@GC) was obtained by simply mixing GC and CDs through noncovalent interactions, including electrostatic interactions and hydrogen bonding. Dopamine (DA) could be detected through internal filter effect (IFE)-induced quenching of CDs. In the case of CDs@GC, noncovalent interactions (electrostatic interactions) between GC and the formed quinone (oxide of DA) could selectively extract and enrich the local concentration of DA, thus effectively improving the sensitivity and selectivity of the sensing system. The nanosensor had a low detection limit of 3.7 nmol/L, which was a 12-fold sensitivity improvement compared to the bare CDs probes with similar fluorescent profiles, proving the feasibility of the “Enrichment-enhanced Detection” strategy. Further, to examine this theory in real case, we designed a highly portable sensing platform to realize visual determination of DA. Overall, our work introduces a new strategy for accurately detecting DA and provides valuable insights for the universal design and optimization of superior nanoprobes.
2025, 36(2): 109962
doi: 10.1016/j.cclet.2024.109962
摘要:
Revealing the factors that affect the vibrational frequency of Stark probe at interface is a pre-requirement for evaluating the absolute interfacial electric field. Here using surface-enhanced infrared absorption (SEIRA) spectroscopy, attenuated total reflection (ATR) spectroscopy and molecular dynamics (MD), we reveal the assembled CN at gold nanofilm exhibits a reduced Stark tuning rate (STR) referring to the vibrational frequency shift in response to electric field comparing with the bulk which was regulated by the electron transfer between S and Au. These findings lead to a deeper understanding of the vibrational Stark effect at the interface and provide guidance for improving the interface electric field theory.
Revealing the factors that affect the vibrational frequency of Stark probe at interface is a pre-requirement for evaluating the absolute interfacial electric field. Here using surface-enhanced infrared absorption (SEIRA) spectroscopy, attenuated total reflection (ATR) spectroscopy and molecular dynamics (MD), we reveal the assembled CN at gold nanofilm exhibits a reduced Stark tuning rate (STR) referring to the vibrational frequency shift in response to electric field comparing with the bulk which was regulated by the electron transfer between S and Au. These findings lead to a deeper understanding of the vibrational Stark effect at the interface and provide guidance for improving the interface electric field theory.
2025, 36(2): 109969
doi: 10.1016/j.cclet.2024.109969
摘要:
Efficient selective adsorption and separation using porous frameworks are critical in many industrial processes, where adsorption energy and dynamic diffusion rate are predominant factors governing selectivity. They are highly susceptible to framework charge, which plays a significant role in selective adsorption. Currently, ionic porous frameworks can be divided into two types. One of them is composed of a charged backbone and counter ions. The framework with zwitterionic channels is another type. It is composed of regular and alternating arrangements of cationic and anionic building units. Herein, we report a hydrogen-bonded ionic framework (HIF) of {(CN3H6)2[Ti(μ2O)(SO4)2]}n with 1D channel exhibits unique adsorption selectivity for Ar against N2 and CO2. Density functional theory (DFT) results suggest that CO2 cannot be adsorbed by HIF at the experimental temperature due to a positive adsorption free energy. In addition, due to a relatively large diffusion barrier at 77 K, N2 molecules hardly diffuse in HIF channels, while Ar has a negligible diffusion barrier. The unique net positively-charged space in the channel is the key to the unusual phenomena, based on DFT simulations and structural analysis. The findings in this work proposes the new adsorption mechanism and provides unique perspective for special separation applications, such as isotope and noble gasses separations.
Efficient selective adsorption and separation using porous frameworks are critical in many industrial processes, where adsorption energy and dynamic diffusion rate are predominant factors governing selectivity. They are highly susceptible to framework charge, which plays a significant role in selective adsorption. Currently, ionic porous frameworks can be divided into two types. One of them is composed of a charged backbone and counter ions. The framework with zwitterionic channels is another type. It is composed of regular and alternating arrangements of cationic and anionic building units. Herein, we report a hydrogen-bonded ionic framework (HIF) of {(CN3H6)2[Ti(μ2O)(SO4)2]}n with 1D channel exhibits unique adsorption selectivity for Ar against N2 and CO2. Density functional theory (DFT) results suggest that CO2 cannot be adsorbed by HIF at the experimental temperature due to a positive adsorption free energy. In addition, due to a relatively large diffusion barrier at 77 K, N2 molecules hardly diffuse in HIF channels, while Ar has a negligible diffusion barrier. The unique net positively-charged space in the channel is the key to the unusual phenomena, based on DFT simulations and structural analysis. The findings in this work proposes the new adsorption mechanism and provides unique perspective for special separation applications, such as isotope and noble gasses separations.
2025, 36(2): 109970
doi: 10.1016/j.cclet.2024.109970
摘要:
Synergy strategy of photocatalysts and polymer resins are promising technology for marine antifouling. However, it is still a main challenge to obtain a green, safe, and efficient antifouling coatings. Herein, carbon (graphene or CNT) modified TiO2 photocatalyst was synthesized via hydrothermal and annealing process and has successfully applied in acrylate fluoroboron polymer (ABFP) composite coating. Morphology and chemical composition were detailed characterized. The graphene or CNT acted as a bridge with supplemental spatial structures (petal gaps, entanglement) and new functional groups (CO, CTiO, etc.) on TiO2 particle. Carbon nanotube (CNT) modified TiO2-ABFP coatings (BTCP) achieved excellent antibacterial and anti-diatom adhesion rate of 89.3%–96.70% and 99.00%–99.50%, which was 1.84–4.94-fold more than that of the single ABFP. CNT or graphene served as electronic bridges was considered as the crucial mechanism, which significantly improved the light absorption range and capacity, conductivity, and photoelectric response of TiO2, and further accelerated the generation and transfer of free radicals to the surface of BTCP or FTGP. Moreover, the improvement of catalyst activity synergizes with the smooth surface, hydrophilicity, and slow hydrolysis of composite coatings, achieved long-term and efficient antifouling performance. This work provides a new insight into the modification of TiO2 and antifouling mechanism of polymer coating.
Synergy strategy of photocatalysts and polymer resins are promising technology for marine antifouling. However, it is still a main challenge to obtain a green, safe, and efficient antifouling coatings. Herein, carbon (graphene or CNT) modified TiO2 photocatalyst was synthesized via hydrothermal and annealing process and has successfully applied in acrylate fluoroboron polymer (ABFP) composite coating. Morphology and chemical composition were detailed characterized. The graphene or CNT acted as a bridge with supplemental spatial structures (petal gaps, entanglement) and new functional groups (CO, CTiO, etc.) on TiO2 particle. Carbon nanotube (CNT) modified TiO2-ABFP coatings (BTCP) achieved excellent antibacterial and anti-diatom adhesion rate of 89.3%–96.70% and 99.00%–99.50%, which was 1.84–4.94-fold more than that of the single ABFP. CNT or graphene served as electronic bridges was considered as the crucial mechanism, which significantly improved the light absorption range and capacity, conductivity, and photoelectric response of TiO2, and further accelerated the generation and transfer of free radicals to the surface of BTCP or FTGP. Moreover, the improvement of catalyst activity synergizes with the smooth surface, hydrophilicity, and slow hydrolysis of composite coatings, achieved long-term and efficient antifouling performance. This work provides a new insight into the modification of TiO2 and antifouling mechanism of polymer coating.
2025, 36(2): 109984
doi: 10.1016/j.cclet.2024.109984
摘要:
Photocatalytic H2 production from water splitting is a promising candidate for solving the increasing energy crisis and environmental issues. Herein we report a novel g-C3N4/AgInS S-scheme heterojunction photocatalyst for water splitting into stoichiometric H2 and H2O2 under visible light. The catalyst was prepared by depositing 3D bimetallic sulfide (AgInS) nanotubes onto 2D g-C3N4 nanosheets. Owing to the special 3D-on-2D configuration, the photogenerated carriers could be rapidly transferred and effectively separated through the abundant interfacial heterostructures to avoid recombination, and therefore excellent performance for visible light-driven water splitting could be obtained, with a 24-h H2 evolution rate up to 237 µmol g−1 h−1. Furthermore, suitable band alignment enables simultaneous H2 and H2O2 production in a 1:1 stoichiometric ratio. H2 and H2O2 were evolved on the conduction band of g-C3N4 and on the valance band of AgInS, respectively. The novel 3D-on-2D configuration for heterojunction construction proposed in this work provided alternative research ideas toward photocatalytic reaction.
Photocatalytic H2 production from water splitting is a promising candidate for solving the increasing energy crisis and environmental issues. Herein we report a novel g-C3N4/AgInS S-scheme heterojunction photocatalyst for water splitting into stoichiometric H2 and H2O2 under visible light. The catalyst was prepared by depositing 3D bimetallic sulfide (AgInS) nanotubes onto 2D g-C3N4 nanosheets. Owing to the special 3D-on-2D configuration, the photogenerated carriers could be rapidly transferred and effectively separated through the abundant interfacial heterostructures to avoid recombination, and therefore excellent performance for visible light-driven water splitting could be obtained, with a 24-h H2 evolution rate up to 237 µmol g−1 h−1. Furthermore, suitable band alignment enables simultaneous H2 and H2O2 production in a 1:1 stoichiometric ratio. H2 and H2O2 were evolved on the conduction band of g-C3N4 and on the valance band of AgInS, respectively. The novel 3D-on-2D configuration for heterojunction construction proposed in this work provided alternative research ideas toward photocatalytic reaction.
2025, 36(2): 109992
doi: 10.1016/j.cclet.2024.109992
摘要:
A visible light-promoted fast photochemical Wolff rearrangement was developed toward synthesis of α-substituted amides in continuous flow with the use of a photochemical oscillatory flow reactor (POFR). The control experiment indicates that a fast process of the Wolff rearrangement (<40 s) is involved. Notably, this protocol does not require excess use of any reactants, and the resulting α-substituted amides could be isolated by recrystallization in good to excellent yields.
A visible light-promoted fast photochemical Wolff rearrangement was developed toward synthesis of α-substituted amides in continuous flow with the use of a photochemical oscillatory flow reactor (POFR). The control experiment indicates that a fast process of the Wolff rearrangement (<40 s) is involved. Notably, this protocol does not require excess use of any reactants, and the resulting α-substituted amides could be isolated by recrystallization in good to excellent yields.
2025, 36(2): 110013
doi: 10.1016/j.cclet.2024.110013
摘要:
The quest for efficient and durable catalysts using abundant resources has garnered significant interest in the field of bifunctional oxygen electrocatalysis. In this contribution, we have designed a FeN4 or CoN4 embedded graphene-based bilayer as active layer and TMC3 or TMN3 doped graphene as supporting layer, named as FeN4/TMC3 or FeN4/TMN3 and CoN4/TMC3 or CoN4/TMN3, wherein TM strands for transition metal. Based on density functional theory calculations, our results demonstrate that the interaction formed between dual metal atoms in the bilayer interspace leads to the coordination environment altered from flat four-coordination to spatial five-coordination, further stabilizing the bilayer structure and impairing its affinity toward the O-containing intermediates. According to thermodynamic analysis, the bilayers of CoN4/CoN3, FeN4/FeC3, FeN4/CoC3, FeN4/NiC3, FeN4/ZnC3, FeN4/FeN3, FeN4/CrN3 and FeN4/ZnN3 are attractively promising for bifunctional oxygen electrocatalysis due to the small overpotential difference Δη between oxygen reduction and oxygen evolution that are less than 1 V. Density functional theory calculations combined with machine learning analysis directly identify the key role played by the inter-binding formed between bilayers, that boosts catalytic activity, which establishes a predictable framework for a fast screen for graphene-based bilayer vertical heterojunction. This work opens up a new path for designing the efficient electrocatalysts via modification of coordination environment.
The quest for efficient and durable catalysts using abundant resources has garnered significant interest in the field of bifunctional oxygen electrocatalysis. In this contribution, we have designed a FeN4 or CoN4 embedded graphene-based bilayer as active layer and TMC3 or TMN3 doped graphene as supporting layer, named as FeN4/TMC3 or FeN4/TMN3 and CoN4/TMC3 or CoN4/TMN3, wherein TM strands for transition metal. Based on density functional theory calculations, our results demonstrate that the interaction formed between dual metal atoms in the bilayer interspace leads to the coordination environment altered from flat four-coordination to spatial five-coordination, further stabilizing the bilayer structure and impairing its affinity toward the O-containing intermediates. According to thermodynamic analysis, the bilayers of CoN4/CoN3, FeN4/FeC3, FeN4/CoC3, FeN4/NiC3, FeN4/ZnC3, FeN4/FeN3, FeN4/CrN3 and FeN4/ZnN3 are attractively promising for bifunctional oxygen electrocatalysis due to the small overpotential difference Δη between oxygen reduction and oxygen evolution that are less than 1 V. Density functional theory calculations combined with machine learning analysis directly identify the key role played by the inter-binding formed between bilayers, that boosts catalytic activity, which establishes a predictable framework for a fast screen for graphene-based bilayer vertical heterojunction. This work opens up a new path for designing the efficient electrocatalysts via modification of coordination environment.
2025, 36(2): 110035
doi: 10.1016/j.cclet.2024.110035
摘要:
The nano-MOF-303 synthesized by microwave method exhibited efficient adsorption capacity (232 mg/g) toward Ag+, in which the adsorption behaviors were fitted by the pseudo-second-order kinetic and the Freundlich isotherm model. The outstanding Ag+ sorption ability of nano-MOF-303 could be contributed to electrostatic interactions, weak coordination interaction of Ag-N, and AgCl precipitates originating from the stored Cl− in nano-MOF-303. Besides the adsorbent regeneration, the formed Ag/AgCl onto nano-MOF-303 could produce Ag/AgCl/MOF-303 as a photocatalyst for sulfamethoxazole degradation under visible light. In this work, both the adsorption and photocatalysis mechanisms were clarified, which might provide insight to develop more effective adsorbents for mining the critical resource from the wastewater.
The nano-MOF-303 synthesized by microwave method exhibited efficient adsorption capacity (232 mg/g) toward Ag+, in which the adsorption behaviors were fitted by the pseudo-second-order kinetic and the Freundlich isotherm model. The outstanding Ag+ sorption ability of nano-MOF-303 could be contributed to electrostatic interactions, weak coordination interaction of Ag-N, and AgCl precipitates originating from the stored Cl− in nano-MOF-303. Besides the adsorbent regeneration, the formed Ag/AgCl onto nano-MOF-303 could produce Ag/AgCl/MOF-303 as a photocatalyst for sulfamethoxazole degradation under visible light. In this work, both the adsorption and photocatalysis mechanisms were clarified, which might provide insight to develop more effective adsorbents for mining the critical resource from the wastewater.
2025, 36(2): 110077
doi: 10.1016/j.cclet.2024.110077
摘要:
Accurate determination of lung cancer margins at the molecular level is of great significance to determine the optimal extent of resection during surgical operation and reduce the risk of postoperative recurrence. In this study, internal extractive electrospray ionization mass spectrometry (iEESI-MS) was used to trace potential molecular tumor margins in lung cancer tissue. Molecular differential model for the determination of lung cancer tumor margin was established via partial least-squares discriminant analysis (PLS-DA) of iEESI-MS data collected from lung tissue pieces within cancer tumor area and iEESI-MS data collected from lung tissue pieces outside cancer tumor area. Proof-of-concept data demonstrate that the developed molecular differential model yields ca. 1–2 mm wider potential molecular tumor margin of a lung cancer compared to the conventional histological analysis, showing promising potential of iEESI-MS to increase the accuracy of tumor margins determination and lower risk of lung cancer postoperative recurrence. Furthermore, our results revealed that creatine and taurine showed positive correlations with lung cancer.
Accurate determination of lung cancer margins at the molecular level is of great significance to determine the optimal extent of resection during surgical operation and reduce the risk of postoperative recurrence. In this study, internal extractive electrospray ionization mass spectrometry (iEESI-MS) was used to trace potential molecular tumor margins in lung cancer tissue. Molecular differential model for the determination of lung cancer tumor margin was established via partial least-squares discriminant analysis (PLS-DA) of iEESI-MS data collected from lung tissue pieces within cancer tumor area and iEESI-MS data collected from lung tissue pieces outside cancer tumor area. Proof-of-concept data demonstrate that the developed molecular differential model yields ca. 1–2 mm wider potential molecular tumor margin of a lung cancer compared to the conventional histological analysis, showing promising potential of iEESI-MS to increase the accuracy of tumor margins determination and lower risk of lung cancer postoperative recurrence. Furthermore, our results revealed that creatine and taurine showed positive correlations with lung cancer.
2025, 36(2): 110118
doi: 10.1016/j.cclet.2024.110118
摘要:
It is well known that cationic polymers have excellent antimicrobial capacity accompanied with high biotoxicity, to reduce biotoxicity needs to decrease the number of cationic groups on polymers, which will influence antimicrobial activity. It is necessary to design a cationic polymer mimic natural antimicrobial peptide with excellent antibacterial activity and low toxicity to solve the above dilemma. Here, we designed and prepared a series of cationic poly(β-amino ester)s (PBAEs) with different cationic contents, and introducing hydrophobic alkyl chain to adjust the balance between antimicrobial activity and biotoxicity to obtain an ideal antimicrobial polymer. The optimum one of synthesized PBAE (hydrophilic cationic monomer: hydrophobic monomer = 5:5) was screened by testing cytotoxicity and minimum inhibitory concentration (MIC), which can effectively kill S. aureus and E. coli with PBAE concentration of 15 µg/mL by a spread plate bacteriostatic method and dead and alive staining test. The way of PBAE killing bacterial was destroying the membrane like natural antimicrobial peptide observed by scanning electron microscopy (SEM). In addition, PBAE did not exhibit hemolysis and cytotoxicity. In particular, from the result of animal tests, the PBAE was able to promote healing of infected wounds from removing mature S. aureus and E. coli on the surface of infected wound. As a result, our work offers a viable approach for designing antimicrobial materials, highlighting the significant potential of PBAE polymers in the field of biomedical materials.
It is well known that cationic polymers have excellent antimicrobial capacity accompanied with high biotoxicity, to reduce biotoxicity needs to decrease the number of cationic groups on polymers, which will influence antimicrobial activity. It is necessary to design a cationic polymer mimic natural antimicrobial peptide with excellent antibacterial activity and low toxicity to solve the above dilemma. Here, we designed and prepared a series of cationic poly(β-amino ester)s (PBAEs) with different cationic contents, and introducing hydrophobic alkyl chain to adjust the balance between antimicrobial activity and biotoxicity to obtain an ideal antimicrobial polymer. The optimum one of synthesized PBAE (hydrophilic cationic monomer: hydrophobic monomer = 5:5) was screened by testing cytotoxicity and minimum inhibitory concentration (MIC), which can effectively kill S. aureus and E. coli with PBAE concentration of 15 µg/mL by a spread plate bacteriostatic method and dead and alive staining test. The way of PBAE killing bacterial was destroying the membrane like natural antimicrobial peptide observed by scanning electron microscopy (SEM). In addition, PBAE did not exhibit hemolysis and cytotoxicity. In particular, from the result of animal tests, the PBAE was able to promote healing of infected wounds from removing mature S. aureus and E. coli on the surface of infected wound. As a result, our work offers a viable approach for designing antimicrobial materials, highlighting the significant potential of PBAE polymers in the field of biomedical materials.
2025, 36(2): 110124
doi: 10.1016/j.cclet.2024.110124
摘要:
This work develops a protein imprinted nanosphere with varied recognition specificity for bovine serum albumin (BSA) and lysozyme (Lyz) under different UV light through a gradient dual crosslinked imprinting strategy (i.e., covalent crosslinking and dynamic reversible crosslinking). The imprinting cavities are initially constructed using irreversible covalent crosslinking to specifically recognize BSA, and then the coumarin residues in the imprinting cavities are crosslinked under 365 nm UV light to further imprint Lyz, because Lyz has smaller size than BSA. Since the photo-crosslinking of coumarin is a reversible reaction, the imprinting cavities of Lyz can be de-crosslinked under 254 nm UV light and restore the imprinting cavities of BSA. Moreover, the N-isopropyl acrylamide (NIPAM) and pyrrolidine residues copolymerized in the polymeric surface of the nanospheres are temperature- and pH-responsive respectively. Therefore, the protein rebinding and release behaviors of the nanospheres are controlled by external temperature and pH. As a result, the materials can selectively separate BSA from real bovine whole blood and Lyz from egg white under different UV light. This study may provide a new strategy for construction of protein imprinted materials with tunable specificity for different proteins.
This work develops a protein imprinted nanosphere with varied recognition specificity for bovine serum albumin (BSA) and lysozyme (Lyz) under different UV light through a gradient dual crosslinked imprinting strategy (i.e., covalent crosslinking and dynamic reversible crosslinking). The imprinting cavities are initially constructed using irreversible covalent crosslinking to specifically recognize BSA, and then the coumarin residues in the imprinting cavities are crosslinked under 365 nm UV light to further imprint Lyz, because Lyz has smaller size than BSA. Since the photo-crosslinking of coumarin is a reversible reaction, the imprinting cavities of Lyz can be de-crosslinked under 254 nm UV light and restore the imprinting cavities of BSA. Moreover, the N-isopropyl acrylamide (NIPAM) and pyrrolidine residues copolymerized in the polymeric surface of the nanospheres are temperature- and pH-responsive respectively. Therefore, the protein rebinding and release behaviors of the nanospheres are controlled by external temperature and pH. As a result, the materials can selectively separate BSA from real bovine whole blood and Lyz from egg white under different UV light. This study may provide a new strategy for construction of protein imprinted materials with tunable specificity for different proteins.
2025, 36(2): 110167
doi: 10.1016/j.cclet.2024.110167
摘要:
Pyridyl-based ketones and 1, 6-diketones are both attractive and invaluable scaffolds which play pivotal roles in the construction and structural modification of a plethora of synthetically paramount natural products, pharmaceuticals, organic materials and fine chemicals. In this context, we herein demonstrate an unprecedented, robust and generally applicable synthetically strategy to deliver these two crucial ketone frameworks via visible-light-induced ring-opening coupling reactions of cycloalcohols with vinylazaarenes and enones, respectively. A plausible mechanism involves the selective β-C-C bond cleavage of cycloalcohols enabled by proton-coupled electron transfer and ensuing Giese-type addition followed by single electron reduction and protonation. The synthetic methodology exhibits broad substrate scope, excellent functional group compatibility as well as operational simplicity and environmental friendliness.
Pyridyl-based ketones and 1, 6-diketones are both attractive and invaluable scaffolds which play pivotal roles in the construction and structural modification of a plethora of synthetically paramount natural products, pharmaceuticals, organic materials and fine chemicals. In this context, we herein demonstrate an unprecedented, robust and generally applicable synthetically strategy to deliver these two crucial ketone frameworks via visible-light-induced ring-opening coupling reactions of cycloalcohols with vinylazaarenes and enones, respectively. A plausible mechanism involves the selective β-C-C bond cleavage of cycloalcohols enabled by proton-coupled electron transfer and ensuing Giese-type addition followed by single electron reduction and protonation. The synthetic methodology exhibits broad substrate scope, excellent functional group compatibility as well as operational simplicity and environmental friendliness.
2025, 36(2): 110211
doi: 10.1016/j.cclet.2024.110211
摘要:
Acute lung injury (ALI) was characterized by excessive reactive oxygen species (ROS) levels and inflammatory response in the lung. Scavenging ROS could inhibit the excessive inflammatory response, further treating ALI. Herein, we designed a novel nanozyme (P@Co) comprised of polydopamine (PDA) nanoparticles (NPs) loading with ultra-small Co, combining with near infrared (NIR) irradiation, which could efficiently scavenge intracellular ROS and suppress inflammatory responses against ALI. For lipopolysaccharide (LPS) induced macrophages, P@Co + NIR presented excellent antioxidant and anti-inflammatory capacities through lowering intracellular ROS levels, decreasing the expression levels of interleukin-6 (IL-6) and tumor necrosis factor-α (TNF-α) as well as inducing macrophage M2 directional polarization. Significantly, it displayed the outstanding activities of lowering acute lung inflammation, relieving diffuse alveolar damage, and up-regulating heat shock protein 70 (HSP70) expression, resulting in synergistic enhanced ALI therapy effect. It offers a novel strategy for the clinical treatment of ROS related diseases.
Acute lung injury (ALI) was characterized by excessive reactive oxygen species (ROS) levels and inflammatory response in the lung. Scavenging ROS could inhibit the excessive inflammatory response, further treating ALI. Herein, we designed a novel nanozyme (P@Co) comprised of polydopamine (PDA) nanoparticles (NPs) loading with ultra-small Co, combining with near infrared (NIR) irradiation, which could efficiently scavenge intracellular ROS and suppress inflammatory responses against ALI. For lipopolysaccharide (LPS) induced macrophages, P@Co + NIR presented excellent antioxidant and anti-inflammatory capacities through lowering intracellular ROS levels, decreasing the expression levels of interleukin-6 (IL-6) and tumor necrosis factor-α (TNF-α) as well as inducing macrophage M2 directional polarization. Significantly, it displayed the outstanding activities of lowering acute lung inflammation, relieving diffuse alveolar damage, and up-regulating heat shock protein 70 (HSP70) expression, resulting in synergistic enhanced ALI therapy effect. It offers a novel strategy for the clinical treatment of ROS related diseases.
2025, 36(2): 110248
doi: 10.1016/j.cclet.2024.110248
摘要:
Ln-containing polyoxoniobates (PONbs) have appealing applications in luminescence, information encryption and magnetic fields, but the synthesis of PONbs containing high-nuclearity Ln-O clusters is challenging due to the easy hydrolysis of Ln3+ ions in alkaline environments. In this paper, we are able to integrate CO32− and high-nuclearity Ln-O clusters into PONb to construct an inorganic giant Eu19-embedded PONb H49K16Na13(H2O)63[Eu21O2(OH)7(H2O)5(Nb7O22)10(Nb2O6)2(CO3)18]·91H2O (1), which contains the highest nuclearity Eu-O clusters and the largest number of Eu3+ ions among PONbs. In addition, the film that was prepared by mixing 1 with gelatin and glycerol, exhibits reversible luminescence switching behavior under acid/alkali stimulation and has been used to create a fluorescence-encoded information approach. This work paves a feasible strategy for the construction of high-nuclearity Ln-O cluster-containing PONbs and the expansion of the application of Ln-containing PONbs in information encryption.
Ln-containing polyoxoniobates (PONbs) have appealing applications in luminescence, information encryption and magnetic fields, but the synthesis of PONbs containing high-nuclearity Ln-O clusters is challenging due to the easy hydrolysis of Ln3+ ions in alkaline environments. In this paper, we are able to integrate CO32− and high-nuclearity Ln-O clusters into PONb to construct an inorganic giant Eu19-embedded PONb H49K16Na13(H2O)63[Eu21O2(OH)7(H2O)5(Nb7O22)10(Nb2O6)2(CO3)18]·91H2O (1), which contains the highest nuclearity Eu-O clusters and the largest number of Eu3+ ions among PONbs. In addition, the film that was prepared by mixing 1 with gelatin and glycerol, exhibits reversible luminescence switching behavior under acid/alkali stimulation and has been used to create a fluorescence-encoded information approach. This work paves a feasible strategy for the construction of high-nuclearity Ln-O cluster-containing PONbs and the expansion of the application of Ln-containing PONbs in information encryption.
2025, 36(2): 110250
doi: 10.1016/j.cclet.2024.110250
摘要:
The development of innovative and sustainable catalytic strategies for organic synthesis is a pivotal aspect of advancing material science and chemical engineering. This research presents a new catalytic method for the aminoacylation of N-sulfonyl ketimines by utilizing a potassium-doped graphite-like carbon nitride (g-C3N4) framework. This method not only enhances the catalytic efficiency and broadens the light absorption spectrum of g-C3N4 but also significantly reduces the recombination rate of electron-hole pairs, thereby increasing the reaction yield and selectivity. Importantly, our approach facilitates the synthesis of aminoacylated N-heterocycles, expanding the applicability of potassium-modified g-C3N4 in photocatalytic organic synthesis. A notable accomplishment of this study is the unprecedented generation of carbamoyl radicals via heterogeneous photocatalysis, which can be easily recycled after reaction. This advancement highlights the capability of potassium-doped g-C3N4 (namely K-CN) as an advanced heterogeneous photocatalyst for the formation of complex organic compounds.
The development of innovative and sustainable catalytic strategies for organic synthesis is a pivotal aspect of advancing material science and chemical engineering. This research presents a new catalytic method for the aminoacylation of N-sulfonyl ketimines by utilizing a potassium-doped graphite-like carbon nitride (g-C3N4) framework. This method not only enhances the catalytic efficiency and broadens the light absorption spectrum of g-C3N4 but also significantly reduces the recombination rate of electron-hole pairs, thereby increasing the reaction yield and selectivity. Importantly, our approach facilitates the synthesis of aminoacylated N-heterocycles, expanding the applicability of potassium-modified g-C3N4 in photocatalytic organic synthesis. A notable accomplishment of this study is the unprecedented generation of carbamoyl radicals via heterogeneous photocatalysis, which can be easily recycled after reaction. This advancement highlights the capability of potassium-doped g-C3N4 (namely K-CN) as an advanced heterogeneous photocatalyst for the formation of complex organic compounds.
2025, 36(2): 110255
doi: 10.1016/j.cclet.2024.110255
摘要:
Nitrogen-doping of carbon support (N-C) for platinum (Pt) nanoparticles to form Pt/N-C catalyst represents an effective strategy to promote the electrocatalysis of cathodic oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. For fundamental understanding, clearly identifying the metal-support effect on enhancement mechanisms of ORR electrocatalysis is definitely needed. In this work, the impact of Pt-support interaction via interfacial Pt-N coordination on electrocatalytic ORR activity and stability in Pt/N-C catalyst is deeply studied through structural/compositional characterizations, electrochemical measurements and theoretical DFT-calculations/AIMD-simulations. The resulting Pt/N-C catalyst exhibits a superior electrocatalytic performance compared to the commercial Pt/C catalyst in both half-cell and H2-O2 fuel cell. Experimental and theoretical results reveal that the interfacial Pt-N coordination enables electron transfer from N-C support to Pt nanoparticles, which can weaken the adsorption strength of oxygen intermediates on Pt surface to improve ORR activity and induce the strong Pt-support interaction to enhance electrochemical stability.
Nitrogen-doping of carbon support (N-C) for platinum (Pt) nanoparticles to form Pt/N-C catalyst represents an effective strategy to promote the electrocatalysis of cathodic oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. For fundamental understanding, clearly identifying the metal-support effect on enhancement mechanisms of ORR electrocatalysis is definitely needed. In this work, the impact of Pt-support interaction via interfacial Pt-N coordination on electrocatalytic ORR activity and stability in Pt/N-C catalyst is deeply studied through structural/compositional characterizations, electrochemical measurements and theoretical DFT-calculations/AIMD-simulations. The resulting Pt/N-C catalyst exhibits a superior electrocatalytic performance compared to the commercial Pt/C catalyst in both half-cell and H2-O2 fuel cell. Experimental and theoretical results reveal that the interfacial Pt-N coordination enables electron transfer from N-C support to Pt nanoparticles, which can weaken the adsorption strength of oxygen intermediates on Pt surface to improve ORR activity and induce the strong Pt-support interaction to enhance electrochemical stability.
2025, 36(2): 110256
doi: 10.1016/j.cclet.2024.110256
摘要:
Birefringent crystals play an irreplaceable role in optical systems by adjusting the polarization state of light in optical devices. This work successfully synthesized a new thiophosphate phase of β-Pb3P2S8 through the high-temperature solid-state spontaneous crystallization method. Different from the cubic α-Pb3P2S8, the β-Pb3P2S8 crystallizes in the orthorhombic Pbcn space group. Notably, β-Pb3P2S8 shows a large band gap of 2.37 eV in lead-based chalcogenides, wide infrared transparent window (2.5−15 µm), and excellent thermal stability. Importantly, the experimental birefringence shows the largest value of 0.26@550 nm in chalcogenides, even larger than the commercialized oxide materials. The Barder charge analysis result indicates that the exceptional birefringence effect is mainly from the Pb2+ and S2− in the [PbSn] polyhedrons. Meanwhile, the parallelly arranged polyhedral layers could improve the structural anisotropic. Therefore, this work supports a new method for designing chalcogenides with exceptional birefringence effect in the infrared region.
Birefringent crystals play an irreplaceable role in optical systems by adjusting the polarization state of light in optical devices. This work successfully synthesized a new thiophosphate phase of β-Pb3P2S8 through the high-temperature solid-state spontaneous crystallization method. Different from the cubic α-Pb3P2S8, the β-Pb3P2S8 crystallizes in the orthorhombic Pbcn space group. Notably, β-Pb3P2S8 shows a large band gap of 2.37 eV in lead-based chalcogenides, wide infrared transparent window (2.5−15 µm), and excellent thermal stability. Importantly, the experimental birefringence shows the largest value of 0.26@550 nm in chalcogenides, even larger than the commercialized oxide materials. The Barder charge analysis result indicates that the exceptional birefringence effect is mainly from the Pb2+ and S2− in the [PbSn] polyhedrons. Meanwhile, the parallelly arranged polyhedral layers could improve the structural anisotropic. Therefore, this work supports a new method for designing chalcogenides with exceptional birefringence effect in the infrared region.
2025, 36(2): 110273
doi: 10.1016/j.cclet.2024.110273
摘要:
Developing a heterostructure for alloying-based anode for sodium-ion batteries (SIBs) is an efficient solution to accommodate volume change upon sodiation/desodiation and boost sodium storage since it combines the merits of each component. Herein, we report a metallic and microphone-like Sn-Zn0.9Mn0.1O heterostructure via an in-situ Mn doping strategy. Based on theoretical calculations and experimental results, the introduction of Mn into ZnO (a small amount of Mn also diffuses into the Sn lattice) can not only enhance intrinsic electronic conductivity but also reduce the Na+ diffusion barrier inside the Sn phase. When evaluated as anode for SIBs, the obtained heterostructures show a high reversible capacity of 395.1 mAh/g at 0.1 A/g, rate capability of 332 mAh/g at 5 A/g, and capacity retention of almost 100% after 850 cycles at 5 A/g, indicating its great potential for high-power application of SIBs.
Developing a heterostructure for alloying-based anode for sodium-ion batteries (SIBs) is an efficient solution to accommodate volume change upon sodiation/desodiation and boost sodium storage since it combines the merits of each component. Herein, we report a metallic and microphone-like Sn-Zn0.9Mn0.1O heterostructure via an in-situ Mn doping strategy. Based on theoretical calculations and experimental results, the introduction of Mn into ZnO (a small amount of Mn also diffuses into the Sn lattice) can not only enhance intrinsic electronic conductivity but also reduce the Na+ diffusion barrier inside the Sn phase. When evaluated as anode for SIBs, the obtained heterostructures show a high reversible capacity of 395.1 mAh/g at 0.1 A/g, rate capability of 332 mAh/g at 5 A/g, and capacity retention of almost 100% after 850 cycles at 5 A/g, indicating its great potential for high-power application of SIBs.
2025, 36(2): 110278
doi: 10.1016/j.cclet.2024.110278
摘要:
A series of heteronuclear yttrium-nickel monoxide carbonyl complexes YNiO(CO)n− (n = 1–5) were generated in a pulsed-laser vaporization source and characterized by mass-selected photoelectron velocity-map spectroscopy combined with theoretical calculations. CO ligand-mediated reactivity in CO oxidation of yttrium-nickel monoxide carbonyl complexes was experimentally and theoretically identified. During the consecutive CO adsorption, a μ2-O linear structure was most favorable for YNiO(CO)n− (n = 1, 2), then a structure in which the terminal O was bonded to the Y atom became favored for YNiO(CO)3−, and finally a structure bearing a CO2 moiety was most favorable for YNiO(CO)n− (n = 4, 5). Theoretical calculations indicated that the Ni atom acted as an electron acceptor and accumulated electron density at n ≤ 3, and then served as an electron donor along with the Y atom to contribute electron density in the rearrangement that accompanied CO oxidation at n > 3.
A series of heteronuclear yttrium-nickel monoxide carbonyl complexes YNiO(CO)n− (n = 1–5) were generated in a pulsed-laser vaporization source and characterized by mass-selected photoelectron velocity-map spectroscopy combined with theoretical calculations. CO ligand-mediated reactivity in CO oxidation of yttrium-nickel monoxide carbonyl complexes was experimentally and theoretically identified. During the consecutive CO adsorption, a μ2-O linear structure was most favorable for YNiO(CO)n− (n = 1, 2), then a structure in which the terminal O was bonded to the Y atom became favored for YNiO(CO)3−, and finally a structure bearing a CO2 moiety was most favorable for YNiO(CO)n− (n = 4, 5). Theoretical calculations indicated that the Ni atom acted as an electron acceptor and accumulated electron density at n ≤ 3, and then served as an electron donor along with the Y atom to contribute electron density in the rearrangement that accompanied CO oxidation at n > 3.
2025, 36(2): 110292
doi: 10.1016/j.cclet.2024.110292
摘要:
Preparing free-base porphyrinoid radicals that can function as coordination ligands is a challenging task. Here we report the synthesis of a stable, free-base benzocorrole (BC) radical containing only two inner NH protons via a retro-Diels-Alder conversion. The radical character of BC was fully supported by crystallographic analysis, spectroscopic evidence, and theoretical calculations. This neutral radical ligand allowed easy insertion of Zn(Ⅱ), Ga(Ⅲ), and Pd(Ⅱ) ions to produce radical complexes. All these radicals exhibited luminescence-on responses under weak reducing atmosphere, corresponding to the conversion to their aromatic anions. The red fluorescence was observed for BC and its Zn(Ⅱ) and Ga(Ⅲ) complexes, and the near-infrared phosphorescence (> 900 nm) was detected for Pd(Ⅱ) complex at room temperature. Furthermore, Ga(Ⅲ) corrole exhibited a variation in fluorescence in response to axial coordination. Our findings provide a promising radical platform for coordination and developing novel functional materials with switchable spin and emission.
Preparing free-base porphyrinoid radicals that can function as coordination ligands is a challenging task. Here we report the synthesis of a stable, free-base benzocorrole (BC) radical containing only two inner NH protons via a retro-Diels-Alder conversion. The radical character of BC was fully supported by crystallographic analysis, spectroscopic evidence, and theoretical calculations. This neutral radical ligand allowed easy insertion of Zn(Ⅱ), Ga(Ⅲ), and Pd(Ⅱ) ions to produce radical complexes. All these radicals exhibited luminescence-on responses under weak reducing atmosphere, corresponding to the conversion to their aromatic anions. The red fluorescence was observed for BC and its Zn(Ⅱ) and Ga(Ⅲ) complexes, and the near-infrared phosphorescence (> 900 nm) was detected for Pd(Ⅱ) complex at room temperature. Furthermore, Ga(Ⅲ) corrole exhibited a variation in fluorescence in response to axial coordination. Our findings provide a promising radical platform for coordination and developing novel functional materials with switchable spin and emission.
2025, 36(2): 110296
doi: 10.1016/j.cclet.2024.110296
摘要:
Sensitization of metal-centered forbidden transitions is of great significance. Solid MnⅡ-based phosphors with d-d forbidden transition sensitized by CeⅢ with d-f allowed transition are promising light conversion materials, but the energy transfer mechanism in CeⅢ-MnⅡ is still in dispute for the uncertainty of distances between metal centers. Herein, for the first time, we explored the energy transfer mechanism in two well-designed luminescent heteronuclear complexes with clear crystal structures, i.e., Ce-N8-Mn and Ce-N2O6-Mn (N8 = 1,4,7,10,13,16,21,24-octaazabicyclo[8.8.8]hexacosane; N2O6 = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane). Short distances between metal centers facilitate efficient energy transfer from CeⅢ to MnⅡ in both complexes, resulting in high photoluminescence quantum yield up to unity. After systematic study of the two heteronuclear complexes as well as two reference complexes Ce(N8)Br3 and Ce(N2O6)Br3, we concluded that dipole-quadrupole interaction is the dominant energy transfer mechanism in the heteronuclear complexes.
Sensitization of metal-centered forbidden transitions is of great significance. Solid MnⅡ-based phosphors with d-d forbidden transition sensitized by CeⅢ with d-f allowed transition are promising light conversion materials, but the energy transfer mechanism in CeⅢ-MnⅡ is still in dispute for the uncertainty of distances between metal centers. Herein, for the first time, we explored the energy transfer mechanism in two well-designed luminescent heteronuclear complexes with clear crystal structures, i.e., Ce-N8-Mn and Ce-N2O6-Mn (N8 = 1,4,7,10,13,16,21,24-octaazabicyclo[8.8.8]hexacosane; N2O6 = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane). Short distances between metal centers facilitate efficient energy transfer from CeⅢ to MnⅡ in both complexes, resulting in high photoluminescence quantum yield up to unity. After systematic study of the two heteronuclear complexes as well as two reference complexes Ce(N8)Br3 and Ce(N2O6)Br3, we concluded that dipole-quadrupole interaction is the dominant energy transfer mechanism in the heteronuclear complexes.
2025, 36(2): 110298
doi: 10.1016/j.cclet.2024.110298
摘要:
In this paper, low-temperature dielectric-blocked discharge plasma (DBD) was employed for the first time to treat silica-doped H4PMo11VO40 (HPAV) catalysts (DBD(Ar/x)-MF-Catal) and apply them in the catalytic methacrolein (MAL) selective oxidation to produce methacrylic acid (MAA). This work investigates in detail the controllable regulation of the concentration of oxidation states on silica-doped HPAV catalysts by adjusting the DBD discharge with controlled changes in voltage, current, treatment time, and treatment medium. It reports the intrinsic correlation between oxidation states and MAL oxidation performance. The research results indicated that the catalytic performance was related to the presence of oxygen vacancies and oxygen species (VO2+), and are the main reason for the selective oxidation of MAL to MAA. Besides, the generation of oxygen vacancies and VO2+ altered localized electrons, which resulted in the easier activation of O2. Theoretical calculations of DFT also proved the formation mechanism of oxygen vacancies and VO2+ and electron properties on high-performance polymers, which elucidated the intrinsic influence of catalyst components. The DBD(Ar/10)-MF-Catal catalysts with suitable VO2+ and oxygen vacancy concentrations exhibited the highest catalytic performance with 90% MAL conversion and 70% MAA selectivity and showed good stability (500 h).
In this paper, low-temperature dielectric-blocked discharge plasma (DBD) was employed for the first time to treat silica-doped H4PMo11VO40 (HPAV) catalysts (DBD(Ar/x)-MF-Catal) and apply them in the catalytic methacrolein (MAL) selective oxidation to produce methacrylic acid (MAA). This work investigates in detail the controllable regulation of the concentration of oxidation states on silica-doped HPAV catalysts by adjusting the DBD discharge with controlled changes in voltage, current, treatment time, and treatment medium. It reports the intrinsic correlation between oxidation states and MAL oxidation performance. The research results indicated that the catalytic performance was related to the presence of oxygen vacancies and oxygen species (VO2+), and are the main reason for the selective oxidation of MAL to MAA. Besides, the generation of oxygen vacancies and VO2+ altered localized electrons, which resulted in the easier activation of O2. Theoretical calculations of DFT also proved the formation mechanism of oxygen vacancies and VO2+ and electron properties on high-performance polymers, which elucidated the intrinsic influence of catalyst components. The DBD(Ar/10)-MF-Catal catalysts with suitable VO2+ and oxygen vacancy concentrations exhibited the highest catalytic performance with 90% MAL conversion and 70% MAA selectivity and showed good stability (500 h).
2025, 36(2): 110344
doi: 10.1016/j.cclet.2024.110344
摘要:
Lithium-ion batteries (LiBs) with high energy density have gained significant popularity in smart grids and portable electronics. LiMn1-xFexPO4 (LMFP) is considered a leading candidate for the cathode, with the potential to combine the low cost of LiFePO4 (LFP) with the high theoretical energy density of LiMnPO4 (LMP). However, quantitative investigation of the intricate coupling between the Fe/Mn ratio and the resulting energy density is challenging due to the parametric complexity. It is crucial to develop a universal approach for the rapid construction of multi-parameter mapping. In this work, we propose an active learning-guided high-throughput workflow for quantitatively predicting the Fe/Mn ratio and the energy density mapping of LMFP. An optimal composition (LiMn0.66Fe0.34PO4) was effectively screened from 81 cathode materials via only 5 samples. Model-guided electrochemical analysis revealed a nonlinear relationship between the Fe/Mn ratio and electrochemical properties, including ion mobility and impedance, elucidating the quantitative chemical composition-energy density map of LMFP. The results demonstrated the efficacy of the method in high-throughput screening of LiBs cathode materials.
Lithium-ion batteries (LiBs) with high energy density have gained significant popularity in smart grids and portable electronics. LiMn1-xFexPO4 (LMFP) is considered a leading candidate for the cathode, with the potential to combine the low cost of LiFePO4 (LFP) with the high theoretical energy density of LiMnPO4 (LMP). However, quantitative investigation of the intricate coupling between the Fe/Mn ratio and the resulting energy density is challenging due to the parametric complexity. It is crucial to develop a universal approach for the rapid construction of multi-parameter mapping. In this work, we propose an active learning-guided high-throughput workflow for quantitatively predicting the Fe/Mn ratio and the energy density mapping of LMFP. An optimal composition (LiMn0.66Fe0.34PO4) was effectively screened from 81 cathode materials via only 5 samples. Model-guided electrochemical analysis revealed a nonlinear relationship between the Fe/Mn ratio and electrochemical properties, including ion mobility and impedance, elucidating the quantitative chemical composition-energy density map of LMFP. The results demonstrated the efficacy of the method in high-throughput screening of LiBs cathode materials.
2025, 36(2): 110353
doi: 10.1016/j.cclet.2024.110353
摘要:
Herein, an alkyne-terminated acid/base responsive amphiphilic [2]rotaxane shuttle was synthesized, and then modified onto the glass surface through "click" reaction. The XPS N 1s spectrum and contact-angle measurement were performed to prove the successful immobilization. The amphiphilic [2]rotaxane functionalized surface presented controllable wettability responding to external acid-base stimuli. This bistable rotaxane modified material system promoted the practical application of molecular machines.
Herein, an alkyne-terminated acid/base responsive amphiphilic [2]rotaxane shuttle was synthesized, and then modified onto the glass surface through "click" reaction. The XPS N 1s spectrum and contact-angle measurement were performed to prove the successful immobilization. The amphiphilic [2]rotaxane functionalized surface presented controllable wettability responding to external acid-base stimuli. This bistable rotaxane modified material system promoted the practical application of molecular machines.
2025, 36(2): 110396
doi: 10.1016/j.cclet.2024.110396
摘要:
Herein, we fabricate an embedding structure at the interface between Pt nanoparticles (NPs) and CeO2-{100} nanocubes with surface defect sites (CeO2-SDS) through quenching and gas bubbling-assisted membrane reduction methods. The in-situ substitution of Pt NPs for atomic-layer Ce lattice significantly increases the amount of reactive oxygen species from 133.68 µmol/g to 199.44 µmol/g. As a result, the distinctive geometric structure of Pt/CeO2-SDS catalyst substantially improves the catalytic activity and stability for soot oxidation compared with the catalyst with no quenching process, i.e., its T50 and TOF values are 332 ℃ and 2.915 h-1, respectively. Combined with the results of experimental investigations and density functional theory calculations, it is unveiled that the unique embedding structure of Pt/CeO2-SDS catalyst can facilitate significantly electron transfer from Pt to the CeO2-{100} support, and induce the formation of interfacial [Ce-Ox-Pt2] bond chains, which plays a crucial role in enhancing the key step of soot oxidation through the dual activation of surface lattice oxygen and molecular O2. Such a fundamental revelation of the interfacial electronic transmission and corresponding modification strategy contributes a novel opportunity to develop high-efficient and stable noble metal catalysts at the atomic level.
Herein, we fabricate an embedding structure at the interface between Pt nanoparticles (NPs) and CeO2-{100} nanocubes with surface defect sites (CeO2-SDS) through quenching and gas bubbling-assisted membrane reduction methods. The in-situ substitution of Pt NPs for atomic-layer Ce lattice significantly increases the amount of reactive oxygen species from 133.68 µmol/g to 199.44 µmol/g. As a result, the distinctive geometric structure of Pt/CeO2-SDS catalyst substantially improves the catalytic activity and stability for soot oxidation compared with the catalyst with no quenching process, i.e., its T50 and TOF values are 332 ℃ and 2.915 h-1, respectively. Combined with the results of experimental investigations and density functional theory calculations, it is unveiled that the unique embedding structure of Pt/CeO2-SDS catalyst can facilitate significantly electron transfer from Pt to the CeO2-{100} support, and induce the formation of interfacial [Ce-Ox-Pt2] bond chains, which plays a crucial role in enhancing the key step of soot oxidation through the dual activation of surface lattice oxygen and molecular O2. Such a fundamental revelation of the interfacial electronic transmission and corresponding modification strategy contributes a novel opportunity to develop high-efficient and stable noble metal catalysts at the atomic level.
2025, 36(2): 110426
doi: 10.1016/j.cclet.2024.110426
摘要:
Carbon dots (CDs), due to their low cost, high stability, and high luminous efficiency, have emerged as an excellent material for the emissive layer in next-generation electroluminescent light-emitting diodes (ELEDs). However, improving the efficiency of fluorescent CDs-based ELEDs remains challenging, primarily because it is difficult to utilize triplet excitons in the electroluminescence process. Therefore, enhancing the exciton utilization efficiency of CDs during electroluminescence is crucial. Based on this, we exploited the characteristic large exciton binding energy commonly found in CDs to develop exciton-emitting CDs. These CDs facilitate the radiative recombination of excitons during electroluminescence, thereby improving the electroluminescent efficiency. By rationally selecting precursors, we developed high quantum efficiency CDs and subsequently constructed CDs-based ELEDs. The blue-light device exhibited an external quantum efficiency of over 4%. This study introduces a novel design concept for CDs, providing a new strategy for developing high-performance blue ELEDs based on CDs.
Carbon dots (CDs), due to their low cost, high stability, and high luminous efficiency, have emerged as an excellent material for the emissive layer in next-generation electroluminescent light-emitting diodes (ELEDs). However, improving the efficiency of fluorescent CDs-based ELEDs remains challenging, primarily because it is difficult to utilize triplet excitons in the electroluminescence process. Therefore, enhancing the exciton utilization efficiency of CDs during electroluminescence is crucial. Based on this, we exploited the characteristic large exciton binding energy commonly found in CDs to develop exciton-emitting CDs. These CDs facilitate the radiative recombination of excitons during electroluminescence, thereby improving the electroluminescent efficiency. By rationally selecting precursors, we developed high quantum efficiency CDs and subsequently constructed CDs-based ELEDs. The blue-light device exhibited an external quantum efficiency of over 4%. This study introduces a novel design concept for CDs, providing a new strategy for developing high-performance blue ELEDs based on CDs.
2025, 36(2): 110428
doi: 10.1016/j.cclet.2024.110428
摘要:
Excessive Fe3+ ion concentrations in wastewater pose a long-standing threat to human health. Achieving low-cost, high-efficiency quantification of Fe3+ ion concentration in unknown solutions can guide environmental management decisions and optimize water treatment processes. In this study, by leveraging the rapid, real-time detection capabilities of nanopores and the specific chemical binding affinity of tannic acid to Fe3+, a linear relationship between the ion current and Fe3+ ion concentration was established. Utilizing this linear relationship, quantification of Fe3+ ion concentration in unknown solutions was achieved. Furthermore, ethylenediaminetetraacetic acid disodium salt was employed to displace Fe3+ from the nanopores, allowing them to be restored to their initial conditions and reused for Fe3+ ion quantification. The reusable bioinspired nanopores remain functional over 330 days of storage. This recycling capability and the long-term stability of the nanopores contribute to a significant reduction in costs. This study provides a strategy for the quantification of unknown Fe3+ concentration using nanopores, with potential applications in environmental assessment, health monitoring, and so forth.
Excessive Fe3+ ion concentrations in wastewater pose a long-standing threat to human health. Achieving low-cost, high-efficiency quantification of Fe3+ ion concentration in unknown solutions can guide environmental management decisions and optimize water treatment processes. In this study, by leveraging the rapid, real-time detection capabilities of nanopores and the specific chemical binding affinity of tannic acid to Fe3+, a linear relationship between the ion current and Fe3+ ion concentration was established. Utilizing this linear relationship, quantification of Fe3+ ion concentration in unknown solutions was achieved. Furthermore, ethylenediaminetetraacetic acid disodium salt was employed to displace Fe3+ from the nanopores, allowing them to be restored to their initial conditions and reused for Fe3+ ion quantification. The reusable bioinspired nanopores remain functional over 330 days of storage. This recycling capability and the long-term stability of the nanopores contribute to a significant reduction in costs. This study provides a strategy for the quantification of unknown Fe3+ concentration using nanopores, with potential applications in environmental assessment, health monitoring, and so forth.
2025, 36(2): 110430
doi: 10.1016/j.cclet.2024.110430
摘要:
Optimizing the interfacial quality of halide perovskites heterojunction to promote the photogenerated charge separation is of great significance in photocatalytic reactions. However, the delicately regulation of interfacial structure and properties of halide perovskites hybrid is still a big challenge owing to the growth uncontrollability and incompatibility between different constituents. Here we use BiOBr nanosheets as the start-template to in situ epitaxially grow Cs3Bi2Br9 nanosheets by “cosharing” Bi and Br atoms strategy for designing a 2D/2D Cs3Bi2Br9/BiOBr heterojunction. Systematic studies show that the epitaxial heterojunction can optimize the synergistic effect of BiOBr and Cs3Bi2Br9 via the formation of tight-contact interfaces, strong interfacial electronic coupling and charge redistribution, which can not only drive the Z-scheme charge transfer mechanism to greatly promote the spatial separation of electron-hole pairs, but also modulate the interfacial electronic structure to facilitate the adsorption and activation of toluene molecules. The heterojunction exhibited 62.3 and 2.4-fold photoactivity improvement for toluene oxidation to benzaldehyde than parental BiOBr and Cs3Bi2Br9, respectively. This study not only proposed a novel dual atom-bridge protocol to engineer high-quality perovskite heterojunctions, but also uncovered the potential of heterojunction in promoting electron-hole separation as well as the application in photocatalytic organic synthesis.
Optimizing the interfacial quality of halide perovskites heterojunction to promote the photogenerated charge separation is of great significance in photocatalytic reactions. However, the delicately regulation of interfacial structure and properties of halide perovskites hybrid is still a big challenge owing to the growth uncontrollability and incompatibility between different constituents. Here we use BiOBr nanosheets as the start-template to in situ epitaxially grow Cs3Bi2Br9 nanosheets by “cosharing” Bi and Br atoms strategy for designing a 2D/2D Cs3Bi2Br9/BiOBr heterojunction. Systematic studies show that the epitaxial heterojunction can optimize the synergistic effect of BiOBr and Cs3Bi2Br9 via the formation of tight-contact interfaces, strong interfacial electronic coupling and charge redistribution, which can not only drive the Z-scheme charge transfer mechanism to greatly promote the spatial separation of electron-hole pairs, but also modulate the interfacial electronic structure to facilitate the adsorption and activation of toluene molecules. The heterojunction exhibited 62.3 and 2.4-fold photoactivity improvement for toluene oxidation to benzaldehyde than parental BiOBr and Cs3Bi2Br9, respectively. This study not only proposed a novel dual atom-bridge protocol to engineer high-quality perovskite heterojunctions, but also uncovered the potential of heterojunction in promoting electron-hole separation as well as the application in photocatalytic organic synthesis.
2025, 36(2): 110431
doi: 10.1016/j.cclet.2024.110431
摘要:
Core-shell colloidal particles with a polymer layer have broad applications in different areas. Herein, we developed a two-step method combining aqueous surface-initiated photoinduced polymerization-induced self-assembly and photoinduced seeded reversible addition-fragmentation chain transfer (RAFT) polymerization to prepare a diverse set of core-shell colloidal particles with a well-defined polymer layer. Chemical compositions, structures, and thicknesses of polymer layers could be conveniently regulated by using different types of monomers and feed [monomer]/[chain transfer agent] ratios during seeded RAFT polymerization.
Core-shell colloidal particles with a polymer layer have broad applications in different areas. Herein, we developed a two-step method combining aqueous surface-initiated photoinduced polymerization-induced self-assembly and photoinduced seeded reversible addition-fragmentation chain transfer (RAFT) polymerization to prepare a diverse set of core-shell colloidal particles with a well-defined polymer layer. Chemical compositions, structures, and thicknesses of polymer layers could be conveniently regulated by using different types of monomers and feed [monomer]/[chain transfer agent] ratios during seeded RAFT polymerization.
2025, 36(2): 110439
doi: 10.1016/j.cclet.2024.110439
摘要:
Solar-induced water oxidation reaction (WOR) for oxygen evolution is a critical step in the transformation of Earth’s atmosphere from a reducing to an oxidation one during its primordial stages. WOR is also associated with important reduction reactions, such as oxygen reduction reaction (ORR), which leads to the production of hydrogen peroxide (H2O2). These transitions are instrumental in the emergence and evolution of life. In this study, transition metals were loaded onto nitrogen-doped carbon (NDC) prepared under the primitive Earth’s atmospheric conditions. These metal-loaded NDC samples were found to catalyze both WOR and ORR under light illumination. The chemical pathways initiated by the pristine and metal-loaded NDC were investigated. This study provides valuable insights into potential mechanisms relevant to the early evolution of our planet.
Solar-induced water oxidation reaction (WOR) for oxygen evolution is a critical step in the transformation of Earth’s atmosphere from a reducing to an oxidation one during its primordial stages. WOR is also associated with important reduction reactions, such as oxygen reduction reaction (ORR), which leads to the production of hydrogen peroxide (H2O2). These transitions are instrumental in the emergence and evolution of life. In this study, transition metals were loaded onto nitrogen-doped carbon (NDC) prepared under the primitive Earth’s atmospheric conditions. These metal-loaded NDC samples were found to catalyze both WOR and ORR under light illumination. The chemical pathways initiated by the pristine and metal-loaded NDC were investigated. This study provides valuable insights into potential mechanisms relevant to the early evolution of our planet.
2025, 36(2): 110444
doi: 10.1016/j.cclet.2024.110444
摘要:
Propane dehydrogenation (PDH) is a vital industrial process for producing propene, utilizing primarily Cr-based or Pt-based catalysts. These catalysts often suffer from challenges such as the toxicity of Cr, the high costs of noble metals like Pt, and deactivation issues due to sintering or coke formation at elevated temperatures. We introduce an exceptional Ru-based catalyst, Ru nanoparticles anchored on a nitrogen-doped carbon matrix (Ru@NC), which achieves a propane conversion rate of 32.2% and a propene selectivity of 93.1% at 550 ℃, with minimal coke deposition and a low deactivation rate of 0.0065 h−1. Characterizations using techniques like TEM and XPS, along with carefully-designed controlled experiments, reveal that the notable performance of Ru@NC stems from the modified electronic state of Ru by nitrogen dopant and the microporous nature of the matrix, positioning it as a top contender among state-of-the-art PDH catalysts.
Propane dehydrogenation (PDH) is a vital industrial process for producing propene, utilizing primarily Cr-based or Pt-based catalysts. These catalysts often suffer from challenges such as the toxicity of Cr, the high costs of noble metals like Pt, and deactivation issues due to sintering or coke formation at elevated temperatures. We introduce an exceptional Ru-based catalyst, Ru nanoparticles anchored on a nitrogen-doped carbon matrix (Ru@NC), which achieves a propane conversion rate of 32.2% and a propene selectivity of 93.1% at 550 ℃, with minimal coke deposition and a low deactivation rate of 0.0065 h−1. Characterizations using techniques like TEM and XPS, along with carefully-designed controlled experiments, reveal that the notable performance of Ru@NC stems from the modified electronic state of Ru by nitrogen dopant and the microporous nature of the matrix, positioning it as a top contender among state-of-the-art PDH catalysts.
2025, 36(2): 110449
doi: 10.1016/j.cclet.2024.110449
摘要:
With the impact of energy crisis and environmental problems, it is urgent to develop green sustainable energy. Osmotic energy stored in the salinity difference between seawater and river water is one of the sustainable, abundant, and renewable energy. However, the membranes used to capture osmotic energy by reverse electrodialysis (RED) always suffer from low ion selectivity, low stability and low power. Hydrogels with three-dimensional (3D) networks have shown great potential for ion transportation and energy conversion. In this work, based on the homogeneity and porosity characteristics of acrylamide (AM) hydrogel, as well as the remarkable stability and abundant negative charge of 3-sulfopropyl acrylate potassium salt (SPAK), a high-performance AM/SPAK cation-selective hydrogel membrane was successfully developed for harvesting osmotic energy. Compared to AM hydrogels, utilizing AM/SPAK as a monomer mixture greatly facilitated the preparation of homogeneous polymers, exhibiting a porous structure, exceptional ion selectivity, and remarkable stability. A maximum output power density of 13.73 W/m2 was achieved at a 50-fold NaCl concentration gradient, exceeding the commercial requirement of 5 W/m2. This work broadens the idea for the construction and application of composite hydrogel in high efficiency osmotic energy conversion.
With the impact of energy crisis and environmental problems, it is urgent to develop green sustainable energy. Osmotic energy stored in the salinity difference between seawater and river water is one of the sustainable, abundant, and renewable energy. However, the membranes used to capture osmotic energy by reverse electrodialysis (RED) always suffer from low ion selectivity, low stability and low power. Hydrogels with three-dimensional (3D) networks have shown great potential for ion transportation and energy conversion. In this work, based on the homogeneity and porosity characteristics of acrylamide (AM) hydrogel, as well as the remarkable stability and abundant negative charge of 3-sulfopropyl acrylate potassium salt (SPAK), a high-performance AM/SPAK cation-selective hydrogel membrane was successfully developed for harvesting osmotic energy. Compared to AM hydrogels, utilizing AM/SPAK as a monomer mixture greatly facilitated the preparation of homogeneous polymers, exhibiting a porous structure, exceptional ion selectivity, and remarkable stability. A maximum output power density of 13.73 W/m2 was achieved at a 50-fold NaCl concentration gradient, exceeding the commercial requirement of 5 W/m2. This work broadens the idea for the construction and application of composite hydrogel in high efficiency osmotic energy conversion.
2025, 36(2): 110467
doi: 10.1016/j.cclet.2024.110467
摘要:
Improving the surface atoms utilization efficiency of catalysts is extremely important for large-scale H2 production by electrochemical water splitting, but it remains a great challenge. Herein, we reported two kinds of MoO3-polyoxometalate hybrid nanobelt superstructures (MoO3-POM HNSs, POM= PW12O40 and SiW12O40) using a simple hydrothermal method. Such superstructure with highly uniform nanoparticles as building blocks can expose more surface atoms and emanate increased specific surface area. The incorporated POMs generated abundant oxygen vacancies, improved the electronic mobility, and modulated the surface electronic structure of MoO3, allowing to optimize the H* adsorption/desorption and dehydrogenation kinetics of catalyst. Notably, the as-prepared MoO3-PW12O40 HNSs electrodes not only displayed the low overpotentials of 108 mV at 10 mA/cm2 current density in 0.5 mol/L H2SO4 electrolyte but also displayed excellent long-term stability. The hydrogen evolution reaction (HER) performance of MoO3-POM superstructures is significantly better than that of corresponding bulk materials MoO3@PW12O40 and MoO3@SiW12O40, and the overpotentials are about 8.3 and 4.9 times lower than that of single MoO3. This work opens an avenue for designing highly surface-exposed catalysts for electrocatalytic H2 production and other electrochemical applications.
Improving the surface atoms utilization efficiency of catalysts is extremely important for large-scale H2 production by electrochemical water splitting, but it remains a great challenge. Herein, we reported two kinds of MoO3-polyoxometalate hybrid nanobelt superstructures (MoO3-POM HNSs, POM= PW12O40 and SiW12O40) using a simple hydrothermal method. Such superstructure with highly uniform nanoparticles as building blocks can expose more surface atoms and emanate increased specific surface area. The incorporated POMs generated abundant oxygen vacancies, improved the electronic mobility, and modulated the surface electronic structure of MoO3, allowing to optimize the H* adsorption/desorption and dehydrogenation kinetics of catalyst. Notably, the as-prepared MoO3-PW12O40 HNSs electrodes not only displayed the low overpotentials of 108 mV at 10 mA/cm2 current density in 0.5 mol/L H2SO4 electrolyte but also displayed excellent long-term stability. The hydrogen evolution reaction (HER) performance of MoO3-POM superstructures is significantly better than that of corresponding bulk materials MoO3@PW12O40 and MoO3@SiW12O40, and the overpotentials are about 8.3 and 4.9 times lower than that of single MoO3. This work opens an avenue for designing highly surface-exposed catalysts for electrocatalytic H2 production and other electrochemical applications.
2025, 36(2): 110468
doi: 10.1016/j.cclet.2024.110468
摘要:
The considerable hazard posed by periprosthetic joint infections underlines the urgent need for the rapid advancement of in-situ drug delivery systems within joint materials. However, the pursuit of sustained antibacterial efficacy remains a formidable challenge. In this context, we proposed a novel strategy that leverages swelling and erosion mechanisms to facilitate drug release of drug-loaded ultrahigh molecular weight polyethylene (UHMWPE), thereby ensuring its long-lasting antibacterial performance. Polyethylene oxide (PEO), a hydrophilic polymer with fast hydrating ability and high swelling capacity, was incorporated in UHMWPE alongside the antibacterial tea polyphenol (epigallocatechin gallate, EGCG as representative). The swelling of PEO enhanced water infiltration into the matrix, while the erosion of PEO balanced the release of the encapsulated EGCG, resulting in a steady release. The behavior was supported by the EGCG release profiles and the corresponding fitted release kinetic models. As demonstrated by segmented antibacterial assessments, the antibacterial efficiency was enhanced 2 to 3 times in the PEO/EGCG/UHMWPE composite compared to that of EGCG/UHMWPE. Additionally, the PEO/EGCG/UHMWPE composite exhibited favorable biocompatibility and mechanical performance, making it a potential candidate for the development of drug-releasing joint implants to combat prosthetic bacterial infections.
The considerable hazard posed by periprosthetic joint infections underlines the urgent need for the rapid advancement of in-situ drug delivery systems within joint materials. However, the pursuit of sustained antibacterial efficacy remains a formidable challenge. In this context, we proposed a novel strategy that leverages swelling and erosion mechanisms to facilitate drug release of drug-loaded ultrahigh molecular weight polyethylene (UHMWPE), thereby ensuring its long-lasting antibacterial performance. Polyethylene oxide (PEO), a hydrophilic polymer with fast hydrating ability and high swelling capacity, was incorporated in UHMWPE alongside the antibacterial tea polyphenol (epigallocatechin gallate, EGCG as representative). The swelling of PEO enhanced water infiltration into the matrix, while the erosion of PEO balanced the release of the encapsulated EGCG, resulting in a steady release. The behavior was supported by the EGCG release profiles and the corresponding fitted release kinetic models. As demonstrated by segmented antibacterial assessments, the antibacterial efficiency was enhanced 2 to 3 times in the PEO/EGCG/UHMWPE composite compared to that of EGCG/UHMWPE. Additionally, the PEO/EGCG/UHMWPE composite exhibited favorable biocompatibility and mechanical performance, making it a potential candidate for the development of drug-releasing joint implants to combat prosthetic bacterial infections.
2025, 36(2): 110497
doi: 10.1016/j.cclet.2024.110497
摘要:
White light illumination is essential in daily life, however, the substantial amount of blue light it contains can damage human eyes. Therefore, it is important to block this high-energy blue light to protect visual health. In this study, yellow-emitting carbon dots (CDs) with a quantum yield exceeding 94% were synthesized using citric acid and urea. These CDs effectively absorb blue light. By incorporating them into polystyrene, multiple films termed CDs-based blue light blocking films (CBFs) were developed, each offering different levels of blue light absorption. These CBFs exhibited excellent transparency and efficient blue light filtering capabilities. This study highlights the potential of high quantum yield CDs, which specifically absorb blue light, as foundational materials for developing light-blocking solutions against high-energy short-wavelength light.
White light illumination is essential in daily life, however, the substantial amount of blue light it contains can damage human eyes. Therefore, it is important to block this high-energy blue light to protect visual health. In this study, yellow-emitting carbon dots (CDs) with a quantum yield exceeding 94% were synthesized using citric acid and urea. These CDs effectively absorb blue light. By incorporating them into polystyrene, multiple films termed CDs-based blue light blocking films (CBFs) were developed, each offering different levels of blue light absorption. These CBFs exhibited excellent transparency and efficient blue light filtering capabilities. This study highlights the potential of high quantum yield CDs, which specifically absorb blue light, as foundational materials for developing light-blocking solutions against high-energy short-wavelength light.
2025, 36(2): 110510
doi: 10.1016/j.cclet.2024.110510
摘要:
In this study, we proposed a novel and efficient way to strengthen polyvinyl alcohol (PVA) fiber using graphene quantum dots (GQDs). PVA molecular chains were grafted onto the surface of GQDs through Friedel-Crafts alkylation reaction to obtain functionalized GQDs (f-GQDs), and PVA/f-GQDs composite fiber was successfully prepared by wet spinning and post-treatment. The tensile strength and Young’s modulus of the composite fiber reached up to 1229.24 MPa and 35.36 GPa which were approximately twice and 4 times those of the pure PVA fiber, respectively. Moreover, the composite fiber was demonstrated excellent resistance to solvents. In addition, the PVA/f-GQDs composite fiber showed intense and uniform cyan fluorescence, meanwhile, it could maintain stable solid-state fluorescence in acid and alkali solutions and particularly after long-term immersion in water (1 month). This study proposes a promising route for obtaining high-performance conventional fibers with some new functions.
In this study, we proposed a novel and efficient way to strengthen polyvinyl alcohol (PVA) fiber using graphene quantum dots (GQDs). PVA molecular chains were grafted onto the surface of GQDs through Friedel-Crafts alkylation reaction to obtain functionalized GQDs (f-GQDs), and PVA/f-GQDs composite fiber was successfully prepared by wet spinning and post-treatment. The tensile strength and Young’s modulus of the composite fiber reached up to 1229.24 MPa and 35.36 GPa which were approximately twice and 4 times those of the pure PVA fiber, respectively. Moreover, the composite fiber was demonstrated excellent resistance to solvents. In addition, the PVA/f-GQDs composite fiber showed intense and uniform cyan fluorescence, meanwhile, it could maintain stable solid-state fluorescence in acid and alkali solutions and particularly after long-term immersion in water (1 month). This study proposes a promising route for obtaining high-performance conventional fibers with some new functions.
2025, 36(2): 110549
doi: 10.1016/j.cclet.2024.110549
摘要:
Herein, the Cu(Ⅲ) synthesized from copper plating effluent was developed for the first time to evaluate the onsite degradation performance of heavy metal complexes in the wastewater, thus achieving the purpose of "treating waste with waste". The results indicated that synthetic Cu(Ⅲ) presented the excellent decomplexation performance for Cu(Ⅱ)/Ni(Ⅱ)-organic complexes. The removal efficiency of Cu(Ⅱ)/Ni(Ⅱ)-EDTA significantly increased with increasing Cu(Ⅲ) dosage, and the degradation of Cu(Ⅱ)/Ni(Ⅱ)-EDTA by synthetic Cu(Ⅲ) system displayed highly pH-dependent reactivity. The radical quencher experiments confirmed that Cu(Ⅲ) direct oxidation were mainly involved in the degradation of Cu(Ⅱ)-EDTA. Additionally, the continuous decarboxylation process was proven to be the main degradation pathway of Cu(Ⅱ)-EDTA in Cu(Ⅲ) system. The coexisting substances (SO42−, Cl− and fulvic acids) showed little impacts at low level for the removal of Cu(Ⅱ)/Ni(Ⅱ)-EDTA, while retarded the degradation of Cu(Ⅱ)-EDTA slightly at high level, which features high selective oxidation. Encouragingly, it was also effective to remove Cu(Ⅱ)/Ni(Ⅱ)-EDTA from in treating actual Cu/Ni-containing wastewater through synthetic Cu(Ⅲ) treatment.
Herein, the Cu(Ⅲ) synthesized from copper plating effluent was developed for the first time to evaluate the onsite degradation performance of heavy metal complexes in the wastewater, thus achieving the purpose of "treating waste with waste". The results indicated that synthetic Cu(Ⅲ) presented the excellent decomplexation performance for Cu(Ⅱ)/Ni(Ⅱ)-organic complexes. The removal efficiency of Cu(Ⅱ)/Ni(Ⅱ)-EDTA significantly increased with increasing Cu(Ⅲ) dosage, and the degradation of Cu(Ⅱ)/Ni(Ⅱ)-EDTA by synthetic Cu(Ⅲ) system displayed highly pH-dependent reactivity. The radical quencher experiments confirmed that Cu(Ⅲ) direct oxidation were mainly involved in the degradation of Cu(Ⅱ)-EDTA. Additionally, the continuous decarboxylation process was proven to be the main degradation pathway of Cu(Ⅱ)-EDTA in Cu(Ⅲ) system. The coexisting substances (SO42−, Cl− and fulvic acids) showed little impacts at low level for the removal of Cu(Ⅱ)/Ni(Ⅱ)-EDTA, while retarded the degradation of Cu(Ⅱ)-EDTA slightly at high level, which features high selective oxidation. Encouragingly, it was also effective to remove Cu(Ⅱ)/Ni(Ⅱ)-EDTA from in treating actual Cu/Ni-containing wastewater through synthetic Cu(Ⅲ) treatment.
2025, 36(2): 110568
doi: 10.1016/j.cclet.2024.110568
摘要:
The first example of Nd@C3N4-photoredox/chlorine dual catalyzed alkylation with unactivated alkanes as the alkyl sources has been developed, which allows for the synthesis of various 4-alkylated cyclic sulfonyl ketimines. In this process, chlorine functions as both a redox and hydrogen atom transfer catalyst. The synergism of the reversible Nd2+/Nd3+ and Cl¯/Cl˙ redox pairs significantly enhances overall photocatalytic efficiency. The in vitro anticancer activity of 4-alkylated products was evaluated by using the CCK8 assay against both human choroidal melanoma (MUM-2B) and lung cancer (A549) cell. Compound 3da showed approximately triple the potency of 5-fluorouracil.
The first example of Nd@C3N4-photoredox/chlorine dual catalyzed alkylation with unactivated alkanes as the alkyl sources has been developed, which allows for the synthesis of various 4-alkylated cyclic sulfonyl ketimines. In this process, chlorine functions as both a redox and hydrogen atom transfer catalyst. The synergism of the reversible Nd2+/Nd3+ and Cl¯/Cl˙ redox pairs significantly enhances overall photocatalytic efficiency. The in vitro anticancer activity of 4-alkylated products was evaluated by using the CCK8 assay against both human choroidal melanoma (MUM-2B) and lung cancer (A549) cell. Compound 3da showed approximately triple the potency of 5-fluorouracil.
2025, 36(2): 110579
doi: 10.1016/j.cclet.2024.110579
摘要:
The photoinduced ligand-to-metal charge transfer (LMCT) process has been extensively investigated, however, the recovery of photocatalysts has remained a persistent challenge in the field. In light of this issue, a novel approach involving the development of iron-based ionic liquids as photocatalysts has been pursued for the first time, with the goal of simultaneously facilitating the LMCT process and addressing the issue of photocatalyst recovery. Remarkably, the iron-based ionic liquid 1-butyl-3-methylimidazolium tetrachloroferrate (C4mim-FeCl4) demonstrates exceptional recyclability and stability for the photocatalytic hydroacylation of olefins. This study will pave the way for new approaches to photocatalytic organic synthesis using ionic liquids as recyclable photocatalysts.
The photoinduced ligand-to-metal charge transfer (LMCT) process has been extensively investigated, however, the recovery of photocatalysts has remained a persistent challenge in the field. In light of this issue, a novel approach involving the development of iron-based ionic liquids as photocatalysts has been pursued for the first time, with the goal of simultaneously facilitating the LMCT process and addressing the issue of photocatalyst recovery. Remarkably, the iron-based ionic liquid 1-butyl-3-methylimidazolium tetrachloroferrate (C4mim-FeCl4) demonstrates exceptional recyclability and stability for the photocatalytic hydroacylation of olefins. This study will pave the way for new approaches to photocatalytic organic synthesis using ionic liquids as recyclable photocatalysts.
2025, 36(2): 109589
doi: 10.1016/j.cclet.2024.109589
摘要:
Lithium metal is one of the most promising anodes for lithium batteries because of their high theoretical specific capacity and the low electrochemical potential. However, the commercialization of lithium metal anodes (LMAs) is facing significant obstacles, such as uncontrolled lithium dendrite growth and unstable solid electrolyte interface, leading to inferior Coulombic efficiency, unsatisfactory cycling stability and even serious safety issues. Introducing low-cost natural clay-based materials (NCBMs) in LMAs is deemed as one of the most effective methods to solve aforementioned issues. These NCBMs have received considerable attention for stabilizing LMAs due to their unique structure, large specific surface areas, abundant surface groups, high mechanical strength, excellent thermal stability, and environmental friendliness. Considering the rapidly growing research enthusiasm for this topic in the last several years, here, we review the recent progress on the application of NCBMs in stable and dendrite-free LMAs. The different structures and modification methods of natural clays are first summarized. In addition, the relationship between their modification methods and nano/microstructures, as well as their impact on the electrochemical properties of LMAs are systematically discussed. Finally, the current challenges and opportunities for application of NCBMs in stable LMAs are also proposed to facilitate their further development.
Lithium metal is one of the most promising anodes for lithium batteries because of their high theoretical specific capacity and the low electrochemical potential. However, the commercialization of lithium metal anodes (LMAs) is facing significant obstacles, such as uncontrolled lithium dendrite growth and unstable solid electrolyte interface, leading to inferior Coulombic efficiency, unsatisfactory cycling stability and even serious safety issues. Introducing low-cost natural clay-based materials (NCBMs) in LMAs is deemed as one of the most effective methods to solve aforementioned issues. These NCBMs have received considerable attention for stabilizing LMAs due to their unique structure, large specific surface areas, abundant surface groups, high mechanical strength, excellent thermal stability, and environmental friendliness. Considering the rapidly growing research enthusiasm for this topic in the last several years, here, we review the recent progress on the application of NCBMs in stable and dendrite-free LMAs. The different structures and modification methods of natural clays are first summarized. In addition, the relationship between their modification methods and nano/microstructures, as well as their impact on the electrochemical properties of LMAs are systematically discussed. Finally, the current challenges and opportunities for application of NCBMs in stable LMAs are also proposed to facilitate their further development.
2025, 36(2): 109841
doi: 10.1016/j.cclet.2024.109841
摘要:
Various chemical irrigants and drugs have been employed for intra-canal disinfection in root canal therapy (RCT). However, due to the complexity of root canal anatomy, many drugs still exhibit poor penetrability and antibiotic resistance, leading to suboptimal treatment outcomes. Thus, it is challenging to remove the organic biofilms from root canals. In recent years, light-responsive therapy, with deeper tissue penetration than traditional treatments, has emerged as an effective RCT modality. Herein, this review summarizes the recent development of light-responsive nanomaterials for biofilm removal in RCT. The light-responsive nanomaterials and the corresponding therapeutic methods in RCT, including photodynamic therapy (PDT), photothermal therapy (PTT), and laser-activated therapy, are highlighted. Finally, the challenges that light-responsive nanomaterials and treatment modalities will encounter to conquer the biofilm in future RCT are discussed. This review is believed to significantly accelerate the future development of light-responsive nanomaterials for RCT from bench to bedside.
Various chemical irrigants and drugs have been employed for intra-canal disinfection in root canal therapy (RCT). However, due to the complexity of root canal anatomy, many drugs still exhibit poor penetrability and antibiotic resistance, leading to suboptimal treatment outcomes. Thus, it is challenging to remove the organic biofilms from root canals. In recent years, light-responsive therapy, with deeper tissue penetration than traditional treatments, has emerged as an effective RCT modality. Herein, this review summarizes the recent development of light-responsive nanomaterials for biofilm removal in RCT. The light-responsive nanomaterials and the corresponding therapeutic methods in RCT, including photodynamic therapy (PDT), photothermal therapy (PTT), and laser-activated therapy, are highlighted. Finally, the challenges that light-responsive nanomaterials and treatment modalities will encounter to conquer the biofilm in future RCT are discussed. This review is believed to significantly accelerate the future development of light-responsive nanomaterials for RCT from bench to bedside.
2025, 36(2): 109867
doi: 10.1016/j.cclet.2024.109867
摘要:
Excited-state intramolecular proton-transfer (ESIPT) based fluorescence probes are particularly attractive due to their unique properties including environmental sensitivity, a large Stokes shift, and potential for ratiometric sensing. In general, ESIPT-based fluorophore incorporates an intramolecular hydrogen bonding interaction between a hydrogen bond donor (–OH and NH2 are common) and a hydrogen bond acceptor (C=N and C=O). More, protection–deprotection of hydroxyl group as hydrogen bond donor could induce an off-on switch of ESIPT-based emission. Therefore, protection–deprotection of hydroxyl group has been the widely used strategy to design fluorescent probes, where the potential key issue is selecting a protective group that can specifically leave in the presence of the target analyte. In this review, we mainly summarize the specific protecting groups (sites) and deprotection mechanisms for biologically important species (including reactive sulfur species (RSS), reactive oxygen species (ROS), enzymes, etc.), and analyze the advantages and disadvantages of different protection mechanisms from some aspects including probe stability, selectivity, response rate and assay system, etc. Based on the aforementioned, we further point out the current challenges and the potential future direction for developing ESIPT-based probes.
Excited-state intramolecular proton-transfer (ESIPT) based fluorescence probes are particularly attractive due to their unique properties including environmental sensitivity, a large Stokes shift, and potential for ratiometric sensing. In general, ESIPT-based fluorophore incorporates an intramolecular hydrogen bonding interaction between a hydrogen bond donor (–OH and NH2 are common) and a hydrogen bond acceptor (C=N and C=O). More, protection–deprotection of hydroxyl group as hydrogen bond donor could induce an off-on switch of ESIPT-based emission. Therefore, protection–deprotection of hydroxyl group has been the widely used strategy to design fluorescent probes, where the potential key issue is selecting a protective group that can specifically leave in the presence of the target analyte. In this review, we mainly summarize the specific protecting groups (sites) and deprotection mechanisms for biologically important species (including reactive sulfur species (RSS), reactive oxygen species (ROS), enzymes, etc.), and analyze the advantages and disadvantages of different protection mechanisms from some aspects including probe stability, selectivity, response rate and assay system, etc. Based on the aforementioned, we further point out the current challenges and the potential future direction for developing ESIPT-based probes.
2025, 36(2): 109924
doi: 10.1016/j.cclet.2024.109924
摘要:
Ultrasensitive detection of nucleic acids is of great significance for precision medicine. Digital polymerase chain reaction (dPCR) is the most sensitive method but requires sophisticated and expensive instruments and a long reaction time. Digital PCR-free technologies, which mean the digital assay not relying on thermal cycling to amplify the signal for quantitative detection of nucleic acids at the single-molecule level, include the digital isothermal amplification techniques (dIATs) and the digital clustered regularly interspaced short palindromic repeats (CRISPR) technologies. They combine the advantages of dPCR and IATs, which could be fast and simple, enabling absolute quantification of nucleic acids at a single-molecule level with minimum instrument, representing the next-generation molecular diagnostic technology. Herein, we systematically summarized the strategies and applications of various dIATs, including the digital loop-mediated isothermal amplification (dLAMP), the digital recombinase polymerase amplification (dRPA), the digital rolling circle amplification (dRCA), the digital nucleic acid sequence-based amplification (dNASBA) and the digital multiple displacement amplification (dMDA), and evaluated the pros and cons of each method. The emerging digital CRISPR technologies, including the detection mechanism of CRISPR and the various strategies for signal amplification, are also introduced comprehensively in this review. The current challenges as well as the future perspectives of the digital PCR-free technology were discussed.
Ultrasensitive detection of nucleic acids is of great significance for precision medicine. Digital polymerase chain reaction (dPCR) is the most sensitive method but requires sophisticated and expensive instruments and a long reaction time. Digital PCR-free technologies, which mean the digital assay not relying on thermal cycling to amplify the signal for quantitative detection of nucleic acids at the single-molecule level, include the digital isothermal amplification techniques (dIATs) and the digital clustered regularly interspaced short palindromic repeats (CRISPR) technologies. They combine the advantages of dPCR and IATs, which could be fast and simple, enabling absolute quantification of nucleic acids at a single-molecule level with minimum instrument, representing the next-generation molecular diagnostic technology. Herein, we systematically summarized the strategies and applications of various dIATs, including the digital loop-mediated isothermal amplification (dLAMP), the digital recombinase polymerase amplification (dRPA), the digital rolling circle amplification (dRCA), the digital nucleic acid sequence-based amplification (dNASBA) and the digital multiple displacement amplification (dMDA), and evaluated the pros and cons of each method. The emerging digital CRISPR technologies, including the detection mechanism of CRISPR and the various strategies for signal amplification, are also introduced comprehensively in this review. The current challenges as well as the future perspectives of the digital PCR-free technology were discussed.
2025, 36(2): 109957
doi: 10.1016/j.cclet.2024.109957
摘要:
Innovative anti-cancer therapies that activate the immune system show promise in combating cancers resistant to conventional treatments. Photodynamic therapy (PDT) is one such treatment, which not only directly eliminates tumor cells but also functions as an in situ tumor vaccine by enhancing tumor immunogenicity and triggering anti-tumor immune responses through immunogenic cell death (ICD). However, the effectiveness of PDT in enhancing immune responses is influenced by factors, such as photosensitizers and the tumor microenvironment, particularly hypoxia. Current clinically used PDT heavily relies on oxygen (O2) availability and can be limited by tumor hypoxia. Additionally, the tumor immunosuppressive microenvironment induced by hypoxia affects the anti-tumor immunity of tumor-infiltrating effector T cells. Meanwhile, the immunosuppressive myeloid-lineage cells are recruited to the hypoxic tumor tissue and exhibit higher immunosuppressive capabilities under hypoxia conditions. Consequently, numerous strategies have been developed to modulate tumor hypoxia or to create hypoxia-compatible PDT, aiming to reduce the effects of tumor hypoxia on PDT-driven immunotherapy. This review investigates these strategies, including approaches to alleviate, exploit, and disregard tumor hypoxia within the context of PDT/immunotherapy. It also emphasizes the role of advanced nanomedicine and its benefits in these strategies, while outlining current challenges and future prospects in the field.
Innovative anti-cancer therapies that activate the immune system show promise in combating cancers resistant to conventional treatments. Photodynamic therapy (PDT) is one such treatment, which not only directly eliminates tumor cells but also functions as an in situ tumor vaccine by enhancing tumor immunogenicity and triggering anti-tumor immune responses through immunogenic cell death (ICD). However, the effectiveness of PDT in enhancing immune responses is influenced by factors, such as photosensitizers and the tumor microenvironment, particularly hypoxia. Current clinically used PDT heavily relies on oxygen (O2) availability and can be limited by tumor hypoxia. Additionally, the tumor immunosuppressive microenvironment induced by hypoxia affects the anti-tumor immunity of tumor-infiltrating effector T cells. Meanwhile, the immunosuppressive myeloid-lineage cells are recruited to the hypoxic tumor tissue and exhibit higher immunosuppressive capabilities under hypoxia conditions. Consequently, numerous strategies have been developed to modulate tumor hypoxia or to create hypoxia-compatible PDT, aiming to reduce the effects of tumor hypoxia on PDT-driven immunotherapy. This review investigates these strategies, including approaches to alleviate, exploit, and disregard tumor hypoxia within the context of PDT/immunotherapy. It also emphasizes the role of advanced nanomedicine and its benefits in these strategies, while outlining current challenges and future prospects in the field.
2025, 36(2): 109960
doi: 10.1016/j.cclet.2024.109960
摘要:
Current research primarily focuses on emerging organic pollutants, with limited attention to emerging inorganic pollutants (EIPs). However, due to advances in detection technology and the escalating environmental and health challenges posed by pollution, there is a growing interest in treating waters contaminated with EIPs. This paper explores biochar characteristics and modification methods, encompassing physical, chemical, and biological approaches for adsorbing EIPs. It offers a comprehensive review of research advancements in employing biochar for EIPs remediation in water, outlines the adsorption mechanisms of EIPs by biochar, and presents an environmental and economic analysis. It can be concluded that using biochar for the adsorption of EIPs in wastewater exhibits promising potential. Nonetheless, it is noteworthy that certain EIPs like Au(Ⅲ), Rh(Ⅲ), Ir(Ⅲ), Ru(Ⅲ), Os(Ⅲ), Sc(Ⅲ), and Y(Ⅲ), have not been extensively investigated regarding their adsorption onto biochar. This comprehensive review will catalyze further inquiry into the biochar-based adsorption of EIPs, addressing current research deficiencies and advancing the practical implementation of biochar as a potent substrate for EIP removal from wastewater streams.
Current research primarily focuses on emerging organic pollutants, with limited attention to emerging inorganic pollutants (EIPs). However, due to advances in detection technology and the escalating environmental and health challenges posed by pollution, there is a growing interest in treating waters contaminated with EIPs. This paper explores biochar characteristics and modification methods, encompassing physical, chemical, and biological approaches for adsorbing EIPs. It offers a comprehensive review of research advancements in employing biochar for EIPs remediation in water, outlines the adsorption mechanisms of EIPs by biochar, and presents an environmental and economic analysis. It can be concluded that using biochar for the adsorption of EIPs in wastewater exhibits promising potential. Nonetheless, it is noteworthy that certain EIPs like Au(Ⅲ), Rh(Ⅲ), Ir(Ⅲ), Ru(Ⅲ), Os(Ⅲ), Sc(Ⅲ), and Y(Ⅲ), have not been extensively investigated regarding their adsorption onto biochar. This comprehensive review will catalyze further inquiry into the biochar-based adsorption of EIPs, addressing current research deficiencies and advancing the practical implementation of biochar as a potent substrate for EIP removal from wastewater streams.
2025, 36(2): 109961
doi: 10.1016/j.cclet.2024.109961
摘要:
Carbon dioxide photocatalytic reduction (CO2-PR) is an efficient method for controlling CO2 emissions and generating cleaner energy while mitigating global warming. Tungsten oxides (WxOy) have attracted considerable attention for CO2-PR due to their excellent spectral absorbance. However, comprehensive reviews are lacking on the use of WxOy for CO2-PR. Therefore, this review provides a detailed summary of t research progress made with WxOy-based catalysts in CO2-PR. It also explains the fundamental principles of CO2-PR and evaluates key performance indicators that affect the activity of WxOy-based photocatalysts, including yield, selectivity, stability, and apparent quantum yield. Additionally, this review explores opportunities for synthesizing high-performance WxOy-based photocatalysts and highlights their potential for the green preparation of C1/C2 products through CO2-PR. These innovative strategies aim to address the challenges and pressures associated with energy and environmental issues, particularly by enhancing artificial photosynthesis efficiency.
Carbon dioxide photocatalytic reduction (CO2-PR) is an efficient method for controlling CO2 emissions and generating cleaner energy while mitigating global warming. Tungsten oxides (WxOy) have attracted considerable attention for CO2-PR due to their excellent spectral absorbance. However, comprehensive reviews are lacking on the use of WxOy for CO2-PR. Therefore, this review provides a detailed summary of t research progress made with WxOy-based catalysts in CO2-PR. It also explains the fundamental principles of CO2-PR and evaluates key performance indicators that affect the activity of WxOy-based photocatalysts, including yield, selectivity, stability, and apparent quantum yield. Additionally, this review explores opportunities for synthesizing high-performance WxOy-based photocatalysts and highlights their potential for the green preparation of C1/C2 products through CO2-PR. These innovative strategies aim to address the challenges and pressures associated with energy and environmental issues, particularly by enhancing artificial photosynthesis efficiency.
2025, 36(2): 110225
doi: 10.1016/j.cclet.2024.110225
摘要:
In recent years, biopharmaceuticals have witnessed remarkable advancements, transforming the landscape of therapeutic interventions. Biopharmaceuticals encompassing therapeutics generated through cutting-edge biotechnological methods have shown promising therapeutic outcomes. However, their clinical success hinges significantly on overcoming drug delivery challenges related to stability, intracellular delivery, immunogenicity, and pharmacokinetic properties. Herein, we provide an overview of various marketed macromolecules, including nucleic acids, and immunotherapeutic agents such as cytokines and monoclonal antibodies, as well as other therapeutic peptides/proteins like enzymes, hormones, and coagulation factors. Our primary focus is on elucidating the delivery challenges associated with these macromolecules and highlighting the pivotal role played by drug delivery platforms in the development of currently marketed products, offering valuable insights for both scientific research and the pharmaceutical industry.
In recent years, biopharmaceuticals have witnessed remarkable advancements, transforming the landscape of therapeutic interventions. Biopharmaceuticals encompassing therapeutics generated through cutting-edge biotechnological methods have shown promising therapeutic outcomes. However, their clinical success hinges significantly on overcoming drug delivery challenges related to stability, intracellular delivery, immunogenicity, and pharmacokinetic properties. Herein, we provide an overview of various marketed macromolecules, including nucleic acids, and immunotherapeutic agents such as cytokines and monoclonal antibodies, as well as other therapeutic peptides/proteins like enzymes, hormones, and coagulation factors. Our primary focus is on elucidating the delivery challenges associated with these macromolecules and highlighting the pivotal role played by drug delivery platforms in the development of currently marketed products, offering valuable insights for both scientific research and the pharmaceutical industry.
2025, 36(2): 110389
doi: 10.1016/j.cclet.2024.110389
摘要:
The detrimental phase transformations of sodium layered transition metal oxides (NaxTMO2) during desodiation/sodiation seriously suppress their practical applications for sodium ion batteries (SIBs). Undoubtedly, comprehensively investigating of the dynamic crystal structure evolutions of NaxTMO2 associating with Na ions extraction/intercalation and then deeply understanding of the relationships between electrochemical performances and phase structures drawing support from advanced characterization techniques are indispensable. In-situ high-energy X-ray diffraction (HEXRD), a powerful technology to distinguish the crystal structure of electrode materials, has been widely used to identify the phase evolutions of NaxTMO2 and then profoundly revealed the electrochemical reaction processes. In this review, we begin with the descriptions of synchrotron characterization techniques and then present the advantages of synchrotron X-ray diffraction (XRD) over conventional XRD in detail. The optimizations of structural stability and electrochemical properties for P2-, O3-, and P2/O3-type NaxTMO2 cathodes through single/dual-site substitution, high-entropy design, phase composition regulation, and surface engineering are summarized. The dynamic crystal structure evolutions of NaxTMO2 polytypes during Na ion extraction/intercalation as well as corresponding structural enhancement mechanisms characterizing by means of HEXRD are concluded. The interior relationships between structure/component of NaxTMO2 polytypes and their electrochemical properties are discussed. Finally, we look forward the research directions and issues in the route to improve the electrochemical properties of NaxTMO2 cathodes for SIBs in the future and the combined utilizations of multiple characterization techniques. This review will provide significant guidelines for rational designs of high-performance NaxTMO2 cathodes.
The detrimental phase transformations of sodium layered transition metal oxides (NaxTMO2) during desodiation/sodiation seriously suppress their practical applications for sodium ion batteries (SIBs). Undoubtedly, comprehensively investigating of the dynamic crystal structure evolutions of NaxTMO2 associating with Na ions extraction/intercalation and then deeply understanding of the relationships between electrochemical performances and phase structures drawing support from advanced characterization techniques are indispensable. In-situ high-energy X-ray diffraction (HEXRD), a powerful technology to distinguish the crystal structure of electrode materials, has been widely used to identify the phase evolutions of NaxTMO2 and then profoundly revealed the electrochemical reaction processes. In this review, we begin with the descriptions of synchrotron characterization techniques and then present the advantages of synchrotron X-ray diffraction (XRD) over conventional XRD in detail. The optimizations of structural stability and electrochemical properties for P2-, O3-, and P2/O3-type NaxTMO2 cathodes through single/dual-site substitution, high-entropy design, phase composition regulation, and surface engineering are summarized. The dynamic crystal structure evolutions of NaxTMO2 polytypes during Na ion extraction/intercalation as well as corresponding structural enhancement mechanisms characterizing by means of HEXRD are concluded. The interior relationships between structure/component of NaxTMO2 polytypes and their electrochemical properties are discussed. Finally, we look forward the research directions and issues in the route to improve the electrochemical properties of NaxTMO2 cathodes for SIBs in the future and the combined utilizations of multiple characterization techniques. This review will provide significant guidelines for rational designs of high-performance NaxTMO2 cathodes.
2025, 36(2): 110469
doi: 10.1016/j.cclet.2024.110469
摘要:
Semi-heterogeneous photocatalysis has emerged as a powerful and productive platform in organic chemistry, which provides mild and eco-friendly conditions for a diverse range of bond-forming reactions. The synergy of homogeneous catalysts and heterogeneous catalysts inherits their main advantages, such as higher activities, easy separation and superior recyclability. In this review, we summarize the recent advances in recyclable semi-heterogenous protocols for the light promoted bond-forming reactions and identify directions for future research according to the different photocatalysts/metal/redox catalysts involved. Notably, this review is not a comprehensive description of reported literature but aim to highlight and illustrate key concepts, strategies, reaction model, reaction conditions and mechanisms.
Semi-heterogeneous photocatalysis has emerged as a powerful and productive platform in organic chemistry, which provides mild and eco-friendly conditions for a diverse range of bond-forming reactions. The synergy of homogeneous catalysts and heterogeneous catalysts inherits their main advantages, such as higher activities, easy separation and superior recyclability. In this review, we summarize the recent advances in recyclable semi-heterogenous protocols for the light promoted bond-forming reactions and identify directions for future research according to the different photocatalysts/metal/redox catalysts involved. Notably, this review is not a comprehensive description of reported literature but aim to highlight and illustrate key concepts, strategies, reaction model, reaction conditions and mechanisms.
2025, 36(2): 110501
doi: 10.1016/j.cclet.2024.110501
摘要:
Up to now, numerous emerging methods of cancer treatment including chemodynamic therapy, photothermal therapy, photodynamic therapy, sonodynamic therapy, immunotherapy and chemotherapy have rapidly entered a new stage of development. However, the single treatment mode is often constrained by the complex tumor microenvironment. Recently, the nanomaterials and nanomedicine have emerged as promising avenues to overcome the limitation in cancer theranostics. Especially, metal-organic frameworks (MOFs) have gained considerable interests in cancer therapy because of their customizable morphologies, easy functionalization, large specific surface area, and good biocompatibility. Among these MOFs, iron-based MOFs (Fe-MOFs) are particularly promising for cancer treatment due to their properties as nano-photosensitizers, peroxidase-like activity, bioimaging contrast capabilities, and biodegradability. Utilizing their structural regularity and synthetic tunability, Fe-MOFs can be engineered to incorporate organic molecules or other inorganic nanoparticles, thereby creating multifunctional nanoplatforms for single or combined theranostic modes. Herein, the minireview focuses on the recent advancements of the Fe-MOFs-based nanoplatforms for self-enhanced imaging and treatment at tumor sites. Furthermore, the clinical research development of Fe-MOFs-based nanoplatforms is discussed, addressing key challenges and innovations for the future. Our review aims to provide novice researchers with a foundational understanding of advanced cancer theranostic modes and promote their clinical applications through the modification of Fe-MOFs.
Up to now, numerous emerging methods of cancer treatment including chemodynamic therapy, photothermal therapy, photodynamic therapy, sonodynamic therapy, immunotherapy and chemotherapy have rapidly entered a new stage of development. However, the single treatment mode is often constrained by the complex tumor microenvironment. Recently, the nanomaterials and nanomedicine have emerged as promising avenues to overcome the limitation in cancer theranostics. Especially, metal-organic frameworks (MOFs) have gained considerable interests in cancer therapy because of their customizable morphologies, easy functionalization, large specific surface area, and good biocompatibility. Among these MOFs, iron-based MOFs (Fe-MOFs) are particularly promising for cancer treatment due to their properties as nano-photosensitizers, peroxidase-like activity, bioimaging contrast capabilities, and biodegradability. Utilizing their structural regularity and synthetic tunability, Fe-MOFs can be engineered to incorporate organic molecules or other inorganic nanoparticles, thereby creating multifunctional nanoplatforms for single or combined theranostic modes. Herein, the minireview focuses on the recent advancements of the Fe-MOFs-based nanoplatforms for self-enhanced imaging and treatment at tumor sites. Furthermore, the clinical research development of Fe-MOFs-based nanoplatforms is discussed, addressing key challenges and innovations for the future. Our review aims to provide novice researchers with a foundational understanding of advanced cancer theranostic modes and promote their clinical applications through the modification of Fe-MOFs.
2025, 36(2): 110407
doi: 10.1016/j.cclet.2024.110407
摘要:
2025, 36(2): 110417
doi: 10.1016/j.cclet.2024.110417
摘要:
2025, 36(2): 110523
doi: 10.1016/j.cclet.2024.110523
摘要:
2025, 36(2): 110616
doi: 10.1016/j.cclet.2024.110616
摘要:
2025, 36(1): 109530
doi: 10.1016/j.cclet.2024.109530
摘要:
Multiple switchable physical channels within one material or device, encompassing optical, electrical, thermal, and mechanical pathways, can enable multifunctionality in mechanical-thermal-opto-electronic applications. Achieving integrated encryption and enhanced performance in storage and sensing presents a formidable challenge in the synthesis and functionality of new materials. In an effort to overcome the complexities associated with these multiple physical functions, this study investigates the large-size crystal of DPACdCl4 (DPA = diisopropylammonium), revealing significant features in rare multi-channel switches. This compound demonstrates the ability to switch between "OFF/0" and "ON/1" states in the mechanical-thermal-opto-electronic channels. Consequently, DPACdCl4 possesses four switchable physical channels, characterized by a higher phase transition temperature of 440.7 K and a competitive piezoelectric coefficient of 46 pC/N. Furthermore, solid-state NMR analysis indicates that thermally activated molecular vibrations significantly contribute to its multifunctional switching capabilities.
Multiple switchable physical channels within one material or device, encompassing optical, electrical, thermal, and mechanical pathways, can enable multifunctionality in mechanical-thermal-opto-electronic applications. Achieving integrated encryption and enhanced performance in storage and sensing presents a formidable challenge in the synthesis and functionality of new materials. In an effort to overcome the complexities associated with these multiple physical functions, this study investigates the large-size crystal of DPACdCl4 (DPA = diisopropylammonium), revealing significant features in rare multi-channel switches. This compound demonstrates the ability to switch between "OFF/0" and "ON/1" states in the mechanical-thermal-opto-electronic channels. Consequently, DPACdCl4 possesses four switchable physical channels, characterized by a higher phase transition temperature of 440.7 K and a competitive piezoelectric coefficient of 46 pC/N. Furthermore, solid-state NMR analysis indicates that thermally activated molecular vibrations significantly contribute to its multifunctional switching capabilities.
2025, 36(1): 109551
doi: 10.1016/j.cclet.2024.109551
摘要:
α-MnO2 is a potential positive electrode material for aqueous zinc-ion batteries, but its electrochemical performance of zinc storage requires further improvement. In this paper, potassium ion-doped manganese dioxide nanoscrolls (KMnO2) with oxygen vacancy were synthesized by a one-step hydrothermal method. It was observed that the electrochemical specific capacity was 250.9 mAh/g at a current density of 0.2 C, which was better than the existing commercial α-MnO2. At a high current of 1 C, these batteries demonstrate improved cycle stability. Synchrotron radiation and other experiments as well as DFT theoretical calculations provided additional evidence that K doping was efficient in regulating the metal bond type and the mean charge regulation of covalent bonds with oxygen atoms in MnO2. When MnO and MnK bonds are present, KMnO2 showed outstanding adsorption of Zn2+ and further enhanced the Zn2+ embedding process. Simultaneously, oxygen defects caused by doping boosted the development of the nanoscroll structure, leading to an increase in active sites available for electrochemical reactions and subsequently enhancing the electrical conductivity of α-MnO2. This study exhibits the potential of optimizing materials based on manganese with the introduction of a potassium doping strategy, resulting in improved performance for aquatic zinc-ion batteries, and presents novel perspectives for related research.
α-MnO2 is a potential positive electrode material for aqueous zinc-ion batteries, but its electrochemical performance of zinc storage requires further improvement. In this paper, potassium ion-doped manganese dioxide nanoscrolls (KMnO2) with oxygen vacancy were synthesized by a one-step hydrothermal method. It was observed that the electrochemical specific capacity was 250.9 mAh/g at a current density of 0.2 C, which was better than the existing commercial α-MnO2. At a high current of 1 C, these batteries demonstrate improved cycle stability. Synchrotron radiation and other experiments as well as DFT theoretical calculations provided additional evidence that K doping was efficient in regulating the metal bond type and the mean charge regulation of covalent bonds with oxygen atoms in MnO2. When MnO and MnK bonds are present, KMnO2 showed outstanding adsorption of Zn2+ and further enhanced the Zn2+ embedding process. Simultaneously, oxygen defects caused by doping boosted the development of the nanoscroll structure, leading to an increase in active sites available for electrochemical reactions and subsequently enhancing the electrical conductivity of α-MnO2. This study exhibits the potential of optimizing materials based on manganese with the introduction of a potassium doping strategy, resulting in improved performance for aquatic zinc-ion batteries, and presents novel perspectives for related research.
2025, 36(1): 109555
doi: 10.1016/j.cclet.2024.109555
摘要:
Leveraging the interplay between the metal component and the supporting material represents a cornerstone strategy for augmenting electrocatalytic efficiency, e.g., electrocatalytic CO2 reduction reaction (CO2RR). Herein, we employ freestanding porous carbon fibers (PCNF) as an efficacious and stable support for the uniformly distributed SnO2 nanoparticles (SnO2PCNF), thereby capitalizing on the synergistic support effect that arises from their strong interaction. On one hand, the interaction between the SnO2 nanoparticles and the carbon support optimizes the electronic configuration of the active centers. This interaction leads to a noteworthy shift of the d-band center toward stronger intermediate adsorption energy, consequently lowering the energy barrier associated with CO2 reduction. As a result, the SnO2PCNF realizes a remarkable CO2RR performance with excellent selectivity towards formate (98.1%). On the other hand, the porous carbon fibers enable the uniform and stable dispersion of SnO2 nanoparticles, and this superior porous structure of carbon supports can also facilitate the exposure of the SnO2 nanoparticles on the reaction interface to a great extent. Consequently, adequate contact between active sites, reactants, and electrolytes can significantly increase the metal utilization, eventually bringing forth a remarkable 7.09 A/mg mass activity. This work might provide a useful idea for improving the utilization rate of metals in numerous electrocatalytic reactions.
Leveraging the interplay between the metal component and the supporting material represents a cornerstone strategy for augmenting electrocatalytic efficiency, e.g., electrocatalytic CO2 reduction reaction (CO2RR). Herein, we employ freestanding porous carbon fibers (PCNF) as an efficacious and stable support for the uniformly distributed SnO2 nanoparticles (SnO2PCNF), thereby capitalizing on the synergistic support effect that arises from their strong interaction. On one hand, the interaction between the SnO2 nanoparticles and the carbon support optimizes the electronic configuration of the active centers. This interaction leads to a noteworthy shift of the d-band center toward stronger intermediate adsorption energy, consequently lowering the energy barrier associated with CO2 reduction. As a result, the SnO2PCNF realizes a remarkable CO2RR performance with excellent selectivity towards formate (98.1%). On the other hand, the porous carbon fibers enable the uniform and stable dispersion of SnO2 nanoparticles, and this superior porous structure of carbon supports can also facilitate the exposure of the SnO2 nanoparticles on the reaction interface to a great extent. Consequently, adequate contact between active sites, reactants, and electrolytes can significantly increase the metal utilization, eventually bringing forth a remarkable 7.09 A/mg mass activity. This work might provide a useful idea for improving the utilization rate of metals in numerous electrocatalytic reactions.
Diluent modified weakly solvating electrolyte for fast-charging high-voltage lithium metal batteries
2025, 36(1): 109556
doi: 10.1016/j.cclet.2024.109556
摘要:
Weakly solvating electrolyte (WSE) demonstrates superior compatibility with lithium (Li) metal batteries (LMBs). However, its application in fast-charging high-voltage LMBs is challenging. Here, we propose a diluent modified WSE for fast-charging high-voltage LMBs, which is formed by adding diluent of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) into the tetrahydropyran (THP) based WSE. A relatively loose solvation structure is formed due to the formation of weak hydrogen bond between TTE and THP, which accelerates the de-solvation kinetics of Li+. Besides, more anions are involved in solvation structure in the presence of TTE, yielding inorganic-rich interphases with improved stability. Li (30 µm)LiNi0.5 Co0.2Mn0.3O2 (4.1 mAh/cm2) batteries with the TTE modified WSE retain over 64% capacity retention after 175 cycles under high rate of 3 C and high-voltage of 4.5 V, much better than that with pure THP based WSE. This work points out that the combination of diluent with weakly solvating solvent is a promising approach to develop high performance electrolytes for fast-charging high-voltage LMBs.
Weakly solvating electrolyte (WSE) demonstrates superior compatibility with lithium (Li) metal batteries (LMBs). However, its application in fast-charging high-voltage LMBs is challenging. Here, we propose a diluent modified WSE for fast-charging high-voltage LMBs, which is formed by adding diluent of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) into the tetrahydropyran (THP) based WSE. A relatively loose solvation structure is formed due to the formation of weak hydrogen bond between TTE and THP, which accelerates the de-solvation kinetics of Li+. Besides, more anions are involved in solvation structure in the presence of TTE, yielding inorganic-rich interphases with improved stability. Li (30 µm)LiNi0.5 Co0.2Mn0.3O2 (4.1 mAh/cm2) batteries with the TTE modified WSE retain over 64% capacity retention after 175 cycles under high rate of 3 C and high-voltage of 4.5 V, much better than that with pure THP based WSE. This work points out that the combination of diluent with weakly solvating solvent is a promising approach to develop high performance electrolytes for fast-charging high-voltage LMBs.
2025, 36(1): 109559
doi: 10.1016/j.cclet.2024.109559
摘要:
Customized design of well-defined cathode structures with abundant adsorption sites and rapid diffusion dynamics, holds great promise in filling capacity gap of carbonaceous cathodes towards high-performance Zn-ion hybrid supercapacitors (ZHC). Herein, we fabricate a series of dynamics-oriented hierarchical porous carbons derived from the unique organic-inorganic interpenetrating polymer networks. The interpenetrating polymer networks are obtained through physically knitting polyferric chloride (PFC) network into the highly crosslinked resorcinol-formaldehyde (RF) network. Instead of covalent bonding, physical interpenetrating force in such RF-PFC networks efficiently relieves the RF skeleton shrinkage upon pyrolysis. Meanwhile, the in-situ PFC network sacrifices as a structure-directing agent to suppress the macrophase separation, and correspondingly 3D hierarchical porous structure with plentiful ion-diffusion channels (pore volume of 1.35 cm3/g) is generated in the representative HPC4 via nanospace occupation and swelling effect. Further removal of Fe fillers leaves behind a large accessible specific surface area of 1550 m2/g for enhanced Zn-ion adsorption. When used as the cathode for ZHC, HPC4 demonstrates a remarkable electrochemical performance with a specific capacity of 215.1 mAh/g at 0.5 A/g and a high Zn2+ ion diffusion coefficient of 11.1 × 10−18 cm2/s. The ZHC device yields 117.0 Wh/kg energy output at a power density of 272.1 W/kg, coupled with good cycle lifespan (100,000 cycles@10 A/g). This work inspires innovative insights to accelerate Zn diffusion dynamics by structure elaboration towards high-capacity cathode materials.
Customized design of well-defined cathode structures with abundant adsorption sites and rapid diffusion dynamics, holds great promise in filling capacity gap of carbonaceous cathodes towards high-performance Zn-ion hybrid supercapacitors (ZHC). Herein, we fabricate a series of dynamics-oriented hierarchical porous carbons derived from the unique organic-inorganic interpenetrating polymer networks. The interpenetrating polymer networks are obtained through physically knitting polyferric chloride (PFC) network into the highly crosslinked resorcinol-formaldehyde (RF) network. Instead of covalent bonding, physical interpenetrating force in such RF-PFC networks efficiently relieves the RF skeleton shrinkage upon pyrolysis. Meanwhile, the in-situ PFC network sacrifices as a structure-directing agent to suppress the macrophase separation, and correspondingly 3D hierarchical porous structure with plentiful ion-diffusion channels (pore volume of 1.35 cm3/g) is generated in the representative HPC4 via nanospace occupation and swelling effect. Further removal of Fe fillers leaves behind a large accessible specific surface area of 1550 m2/g for enhanced Zn-ion adsorption. When used as the cathode for ZHC, HPC4 demonstrates a remarkable electrochemical performance with a specific capacity of 215.1 mAh/g at 0.5 A/g and a high Zn2+ ion diffusion coefficient of 11.1 × 10−18 cm2/s. The ZHC device yields 117.0 Wh/kg energy output at a power density of 272.1 W/kg, coupled with good cycle lifespan (100,000 cycles@10 A/g). This work inspires innovative insights to accelerate Zn diffusion dynamics by structure elaboration towards high-capacity cathode materials.
2025, 36(1): 109566
doi: 10.1016/j.cclet.2024.109566
摘要:
Hydrogen, as a cheap, clean, and cost-effective secondary energy source, performs an essential role in optimizing today’s energy structure. Magnesium hydride (MgH2) represents an attractive hydrogen carrier for storage and transportation, however, the kinetic behavior and operating temperature remain undesirable. In this work, a dual-phase multi-site alloy (MsA) anchored on carbon substrates was designed, and its superior catalytic effects on the hydrogen storage properties of MgH2 were reported. Mechanism analysis identified that multi-site FeNi3/NiCu nanoalloys synergistically served as intrinsic drivers for the striking de/hydrogenation performance of the MgH2−MsA systems. Concretely, the unique multi-metallic site structure attached to the surface of MgH2 provided substantial reversible channels and accessible active sites conducive to the adsorption, activation, and nucleation of H atoms. In addition, the coupling system formed by FeNi3 and NiCu dual-phase alloys further enhanced the reactivity between Mg/MgH2 and H atoms. Hence, the onset dehydrogenation temperature of MgH2 + 5 wt% MsA was reduced to 195 ℃ and the hydrogen desorption apparent activation energy was reduced to 83.6 kJ/mol. 5.08 wt% H2 could be released at 250 ℃ in 20 min, reaching a high dehydrogenation rate of 0.254 wt% H2/min, yet that for MgH2 at a higher temperature of 335 ℃ was only 0.145 wt% H2/min. Then, the dehydrogenated MgH2−MsA sample could absorb hydrogen from room temperature (30 ℃) and charge 3.93 wt% H2 at 100 ℃ within 20 min under 3.0 MPa H2 pressure. Benefiting from carbon substrates, the 5 wt% MsA doped-MgH2 could still maintain 6.36 wt% hydrogen capacity after 20 cycles. In conclusion, this work provides experimental rationale and new insights for the design of efficient catalysts for magnesium-based solid-state hydrogen storage materials.
Hydrogen, as a cheap, clean, and cost-effective secondary energy source, performs an essential role in optimizing today’s energy structure. Magnesium hydride (MgH2) represents an attractive hydrogen carrier for storage and transportation, however, the kinetic behavior and operating temperature remain undesirable. In this work, a dual-phase multi-site alloy (MsA) anchored on carbon substrates was designed, and its superior catalytic effects on the hydrogen storage properties of MgH2 were reported. Mechanism analysis identified that multi-site FeNi3/NiCu nanoalloys synergistically served as intrinsic drivers for the striking de/hydrogenation performance of the MgH2−MsA systems. Concretely, the unique multi-metallic site structure attached to the surface of MgH2 provided substantial reversible channels and accessible active sites conducive to the adsorption, activation, and nucleation of H atoms. In addition, the coupling system formed by FeNi3 and NiCu dual-phase alloys further enhanced the reactivity between Mg/MgH2 and H atoms. Hence, the onset dehydrogenation temperature of MgH2 + 5 wt% MsA was reduced to 195 ℃ and the hydrogen desorption apparent activation energy was reduced to 83.6 kJ/mol. 5.08 wt% H2 could be released at 250 ℃ in 20 min, reaching a high dehydrogenation rate of 0.254 wt% H2/min, yet that for MgH2 at a higher temperature of 335 ℃ was only 0.145 wt% H2/min. Then, the dehydrogenated MgH2−MsA sample could absorb hydrogen from room temperature (30 ℃) and charge 3.93 wt% H2 at 100 ℃ within 20 min under 3.0 MPa H2 pressure. Benefiting from carbon substrates, the 5 wt% MsA doped-MgH2 could still maintain 6.36 wt% hydrogen capacity after 20 cycles. In conclusion, this work provides experimental rationale and new insights for the design of efficient catalysts for magnesium-based solid-state hydrogen storage materials.
2025, 36(1): 109568
doi: 10.1016/j.cclet.2024.109568
摘要:
All-solid-state Li batteries (ASSLBs) using solid electrolytes (SEs) have gained significant attention in recent years considering the safety issue and their high energy density. Despite these advantages, the commercialization of ASSLBs still faces challenges regarding the electrolyte/electrodes interfaces and growth of Li dendrites. Elemental doping is an effective and direct method to enhance the performance of SEs. Here, we report an Al-F co-doping strategy to improve the overall properties including ion conductivity, high voltage stability, and cathode and anode compatibility. Particularly, the Al-F co-doping enables the formation of a thin Li-Al alloy layer and fluoride interphases, thereby constructing a relatively stable interface and promoting uniform Li deposition. The similar merits of Al-F co-doping are also revealed in the Li-argyrodite series. ASSLBs assembled with these optimized electrolytes gain good electrochemical performance, demonstrating the universality of Al-F co-doping towards advanced SEs.
All-solid-state Li batteries (ASSLBs) using solid electrolytes (SEs) have gained significant attention in recent years considering the safety issue and their high energy density. Despite these advantages, the commercialization of ASSLBs still faces challenges regarding the electrolyte/electrodes interfaces and growth of Li dendrites. Elemental doping is an effective and direct method to enhance the performance of SEs. Here, we report an Al-F co-doping strategy to improve the overall properties including ion conductivity, high voltage stability, and cathode and anode compatibility. Particularly, the Al-F co-doping enables the formation of a thin Li-Al alloy layer and fluoride interphases, thereby constructing a relatively stable interface and promoting uniform Li deposition. The similar merits of Al-F co-doping are also revealed in the Li-argyrodite series. ASSLBs assembled with these optimized electrolytes gain good electrochemical performance, demonstrating the universality of Al-F co-doping towards advanced SEs.
2025, 36(1): 109569
doi: 10.1016/j.cclet.2024.109569
摘要:
The oxygen reduction reaction (ORR) is a crucial process in Zn-air systems, and the catalyst plays a significant role in this reaction. However, reported catalysts often suffer from poor durability and stability during the ORR process. Herein, we synthesized La-Fe bimetallic nanoparticles encapsulated in a N-doped porous carbon dodecahedron (La-Fe/NC) originated from ZIF-8 by a simple direct carbonization. The La-Fe/NC catalyst had a numerous mesopores and dendritic outer layer generated by carbon nanotubes (CNTs), forming a high conductivity network that helped to optimize electron transfer and mass transport in the ORR process. The effect of different doping transition metals and metal ratios on the ORR activity of Zn-air batteries was investigated. In alkaline media, the La-Fe/NC showed the highest ORR catalytic activity, with a half-wave potential (E1/2) of 0.879 V (vs. RHE, Pt/C 0.845 V). After 5000 cycles, the E1/2 of the La-Fe/NC catalyst only decreased by 7 mV, and its performance in stability tests and methanol tolerance tests was superior to Pt/C. When used as the air electrode in a Zn-air battery, the La-Fe/NC catalyst demonstrated an excellent specific capacity of 755 mAh/g and a peak power density of 179.8 mW/cm2. The results provide important insights for the development of high-performance Zn-air batteries and new directions for the design of ORR catalysts.
The oxygen reduction reaction (ORR) is a crucial process in Zn-air systems, and the catalyst plays a significant role in this reaction. However, reported catalysts often suffer from poor durability and stability during the ORR process. Herein, we synthesized La-Fe bimetallic nanoparticles encapsulated in a N-doped porous carbon dodecahedron (La-Fe/NC) originated from ZIF-8 by a simple direct carbonization. The La-Fe/NC catalyst had a numerous mesopores and dendritic outer layer generated by carbon nanotubes (CNTs), forming a high conductivity network that helped to optimize electron transfer and mass transport in the ORR process. The effect of different doping transition metals and metal ratios on the ORR activity of Zn-air batteries was investigated. In alkaline media, the La-Fe/NC showed the highest ORR catalytic activity, with a half-wave potential (E1/2) of 0.879 V (vs. RHE, Pt/C 0.845 V). After 5000 cycles, the E1/2 of the La-Fe/NC catalyst only decreased by 7 mV, and its performance in stability tests and methanol tolerance tests was superior to Pt/C. When used as the air electrode in a Zn-air battery, the La-Fe/NC catalyst demonstrated an excellent specific capacity of 755 mAh/g and a peak power density of 179.8 mW/cm2. The results provide important insights for the development of high-performance Zn-air batteries and new directions for the design of ORR catalysts.
2025, 36(1): 109588
doi: 10.1016/j.cclet.2024.109588
摘要:
Designing highly active electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution and reduction reactions (OER and ORR) is pivotal to renewable energy technology. Herein, based on density functional theory (DFT) calculations, we systematically investigate the catalytic activity of iron-nitrogen-carbon based covalent organic frameworks (COF) monolayers with axially coordinated ligands (denotes as FeN4-X@COF, X refers to axial ligand, X = -SCN, -I, -H, -SH, -NO2, -Br, -ClO, -Cl, -HCO3, -NO, -ClO2, -OH, -CN and -F). The calculated results demonstrate that all the catalysts possess good thermodynamic and electrochemical stabilities. The different ligands axially ligated to the Fe active center could induce changes in the charge of the Fe center, which further regulates the interaction strength between intermediates and catalysts that governs the catalytic activity. Importantly, FeN4-SH@COF and FeN4OH@COF are efficient bifunctional catalysts for HER and OER, FeN4OH@COF and FeN4-I@COF are promising bifunctional catalysts for OER and ORR. These findings not only reveal promising bifunctional HER/OER and OER/ORR catalysts but also provide theoretical guidance for designing optimum iron-nitrogen-carbon based catalysts.
Designing highly active electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution and reduction reactions (OER and ORR) is pivotal to renewable energy technology. Herein, based on density functional theory (DFT) calculations, we systematically investigate the catalytic activity of iron-nitrogen-carbon based covalent organic frameworks (COF) monolayers with axially coordinated ligands (denotes as FeN4-X@COF, X refers to axial ligand, X = -SCN, -I, -H, -SH, -NO2, -Br, -ClO, -Cl, -HCO3, -NO, -ClO2, -OH, -CN and -F). The calculated results demonstrate that all the catalysts possess good thermodynamic and electrochemical stabilities. The different ligands axially ligated to the Fe active center could induce changes in the charge of the Fe center, which further regulates the interaction strength between intermediates and catalysts that governs the catalytic activity. Importantly, FeN4-SH@COF and FeN4OH@COF are efficient bifunctional catalysts for HER and OER, FeN4OH@COF and FeN4-I@COF are promising bifunctional catalysts for OER and ORR. These findings not only reveal promising bifunctional HER/OER and OER/ORR catalysts but also provide theoretical guidance for designing optimum iron-nitrogen-carbon based catalysts.
2025, 36(1): 109590
doi: 10.1016/j.cclet.2024.109590
摘要:
The metal ion batteries have gained widespread attention for wearable electronics due to their competitive energy density and long cycling life. Exploring the advanced anode materials is significant for next generation energy storage systems. However, severe electrode volume changes and sluggish redox kinetics are the critical problems for lithium/potassium ion batteries (LIBs/PIBs) towards large-scale applications. Herein, we prepare a novel anode material, which consists of reduced graphene oxide wrapping one-dimensional (1D) N-doped porous carbon nanotube with cobalt phosphoselenide (CoPSe) nanoparticles embedded inside them (rGO@CoPSe/NC). Benefited from the dual carbon decorations and ultrafine nanoparticles structure, it achieves a reversible capacity of 245 mAh/g at 5 A/g after 2000 cycles for LIBs and 215 mAh/g at 1 A/g after 500 cycles for PIBs. The pseudocapacitance and GITT measurements are used to investigate the electrochemical kinetics of rGO@CoPSe/NC for LIBs. In addition, the lithium ion full cell also shows good electrochemical performance when paired with high capacity LiNi0.8Co0.1Mn0.1O2 cathode. This work provides a feasible electrode design strategy for high-efficiency metal ion batteries based on multidimensional nanoarchitecture engineering and composition tailoring.
The metal ion batteries have gained widespread attention for wearable electronics due to their competitive energy density and long cycling life. Exploring the advanced anode materials is significant for next generation energy storage systems. However, severe electrode volume changes and sluggish redox kinetics are the critical problems for lithium/potassium ion batteries (LIBs/PIBs) towards large-scale applications. Herein, we prepare a novel anode material, which consists of reduced graphene oxide wrapping one-dimensional (1D) N-doped porous carbon nanotube with cobalt phosphoselenide (CoPSe) nanoparticles embedded inside them (rGO@CoPSe/NC). Benefited from the dual carbon decorations and ultrafine nanoparticles structure, it achieves a reversible capacity of 245 mAh/g at 5 A/g after 2000 cycles for LIBs and 215 mAh/g at 1 A/g after 500 cycles for PIBs. The pseudocapacitance and GITT measurements are used to investigate the electrochemical kinetics of rGO@CoPSe/NC for LIBs. In addition, the lithium ion full cell also shows good electrochemical performance when paired with high capacity LiNi0.8Co0.1Mn0.1O2 cathode. This work provides a feasible electrode design strategy for high-efficiency metal ion batteries based on multidimensional nanoarchitecture engineering and composition tailoring.
2025, 36(1): 109596
doi: 10.1016/j.cclet.2024.109596
摘要:
Pure near-infrared (NIR) phosphorescent materials with emission peak larger than 700 nm are of great significance for the development of optoelectronics and biomedicine. We have designed and synthesized two new B-embedded pure near-infrared (NIR)-emitting iridium complexes (Ir(Bpiq)2acac and Ir(Bpiq)2dpm) with peaks greater than 720 nm. More importantly, they exhibit very narrow phosphorescent emission with full width at half maximum (FWHM) of only about 50 nm (0.12 eV), resulting in a high NIR content (> 90%) in their spectrum. In view of better optical property and solubility, the complex Ir(Bpiq)2dpm was used as the emitting layer of a solution-processed OLED device, and achieved good maximum external quantum efficiency (EQE) (2.8%) peaking at 728 nm. This research provides an important strategy for the design of narrowband NIR-emitting phosphorescent iridium complexes and their optoelectronic applications.
Pure near-infrared (NIR) phosphorescent materials with emission peak larger than 700 nm are of great significance for the development of optoelectronics and biomedicine. We have designed and synthesized two new B-embedded pure near-infrared (NIR)-emitting iridium complexes (Ir(Bpiq)2acac and Ir(Bpiq)2dpm) with peaks greater than 720 nm. More importantly, they exhibit very narrow phosphorescent emission with full width at half maximum (FWHM) of only about 50 nm (0.12 eV), resulting in a high NIR content (> 90%) in their spectrum. In view of better optical property and solubility, the complex Ir(Bpiq)2dpm was used as the emitting layer of a solution-processed OLED device, and achieved good maximum external quantum efficiency (EQE) (2.8%) peaking at 728 nm. This research provides an important strategy for the design of narrowband NIR-emitting phosphorescent iridium complexes and their optoelectronic applications.
2025, 36(1): 109597
doi: 10.1016/j.cclet.2024.109597
摘要:
Exploring transition metal sulfide electrocatalysts with high-efficiency for hydrogen evolution reaction (HER) is essential to produce H2 fuel through water splitting. Herein, novel nickel tungsten sulfide heterojunction (NiS-WS2) with a nanowoven ball-like structure were directed synthetized by a facile hydrothermal method. The hierarchical NiS-WS2 exhibited excellent HER activity with a relatively small overpotential of 142 and 137 mV at 10 mA/cm2 in 0.5 mol/L H2SO4 and 1 mol/L KOH, which is much better than that of single NiS and WS2. The impressive performance of NiS-WS2 heterojunction is owed to the collective synergy of special morphological and more exposed active sites between the crystal interfacial of NiS and WS2. In addition, the hierarchical NiS-WS2 can facilitate the transport of charge/mass by optimized electronic structure, which further improves the HER activity of electrocatalysts. These outcomes provide a simple method to prospect towards the design and application of heterostructures as efficient electrocatalysts, shedding some light on the development of functional materials in energy chemistry.
Exploring transition metal sulfide electrocatalysts with high-efficiency for hydrogen evolution reaction (HER) is essential to produce H2 fuel through water splitting. Herein, novel nickel tungsten sulfide heterojunction (NiS-WS2) with a nanowoven ball-like structure were directed synthetized by a facile hydrothermal method. The hierarchical NiS-WS2 exhibited excellent HER activity with a relatively small overpotential of 142 and 137 mV at 10 mA/cm2 in 0.5 mol/L H2SO4 and 1 mol/L KOH, which is much better than that of single NiS and WS2. The impressive performance of NiS-WS2 heterojunction is owed to the collective synergy of special morphological and more exposed active sites between the crystal interfacial of NiS and WS2. In addition, the hierarchical NiS-WS2 can facilitate the transport of charge/mass by optimized electronic structure, which further improves the HER activity of electrocatalysts. These outcomes provide a simple method to prospect towards the design and application of heterostructures as efficient electrocatalysts, shedding some light on the development of functional materials in energy chemistry.
2025, 36(1): 109650
doi: 10.1016/j.cclet.2024.109650
摘要:
Phosphorus-based anode is a promising anode for sodium-ion batteries (SIBs) due to its high specific capacity, however, suffers from poor electronic conductivity and unfavorable electrochemical reversibility. Incorporating metals such as copper (Cu) into phosphorus has been demonstrated to not only improve the electronic conductivity but also accommodate the volume change during cycling, yet the underline sodiation mechanism is not clear. Herein, take a copper phosphide and reduced graphene oxide (CuP2/C) composite as an example, which delivers a high reversible capacity of > 900 mAh/g. Interestingly, it is revealed that the native oxidation PO components of the CuP2/C composite show higher electrochemical reversibility than the bulk CuP2, based on a quantitative analysis of high-resolution solid-state 31P NMR, ex-situ XPS and synchrotron X-ray diffraction characterization techniques. The sodiation products Na3PO4 and Na4P2O7 derived from PO could react with Na-P alloys and regenerate to PO during charge process, which probably accounts for the high reversible capacity of the CuP2/C anode. The findings also illustrate that the phosphorus transforms into nanocrystalline Na3P and NaP alloys, which laterally shows crystallization-amorphization evolution process during cycling.
Phosphorus-based anode is a promising anode for sodium-ion batteries (SIBs) due to its high specific capacity, however, suffers from poor electronic conductivity and unfavorable electrochemical reversibility. Incorporating metals such as copper (Cu) into phosphorus has been demonstrated to not only improve the electronic conductivity but also accommodate the volume change during cycling, yet the underline sodiation mechanism is not clear. Herein, take a copper phosphide and reduced graphene oxide (CuP2/C) composite as an example, which delivers a high reversible capacity of > 900 mAh/g. Interestingly, it is revealed that the native oxidation PO components of the CuP2/C composite show higher electrochemical reversibility than the bulk CuP2, based on a quantitative analysis of high-resolution solid-state 31P NMR, ex-situ XPS and synchrotron X-ray diffraction characterization techniques. The sodiation products Na3PO4 and Na4P2O7 derived from PO could react with Na-P alloys and regenerate to PO during charge process, which probably accounts for the high reversible capacity of the CuP2/C anode. The findings also illustrate that the phosphorus transforms into nanocrystalline Na3P and NaP alloys, which laterally shows crystallization-amorphization evolution process during cycling.
2025, 36(1): 109669
doi: 10.1016/j.cclet.2024.109669
摘要:
High-efficient rubber antioxidants for enhanced heat resistance without compromising mechanical properties remain an enormous and long-term challenge for the rubber industry. Herein, we employed the in-situ growth of Ce-doped Co-metal-organic framework (CeCo-MOF) in dendritic mesoporous organosilica nanoparticles (DMONs@CeCo-MOF, denoted as DCCM) to prepare a novel antioxidant that exhibit outstanding thermal stability. Dendritic mesoporous organosilica nanoparticles (DMONs) effectively alleviated the incompatibility of CeCo-MOF in the polymer matrix, and the effective scavenging of free radicals was attributed to the various oxidation states of metal ions in CeCo-MOF. Surprising, by adding only 0.5 phr (parts per hundred of rubber) of DMONs@CeCo-MOF to silicone rubber, (SR), the retention rate of tensile strength increased from 37.3% to 61.6% after aging 72 h at 250 ℃, and the retention rate of elongation at break of DCCM/SR1 composites reached 68%, which was 5.43 times of SR. The strategy of anchoring MOFs on the surface of silica also provides a viable method for preparing effective compound functionalized rubber antioxidant.
High-efficient rubber antioxidants for enhanced heat resistance without compromising mechanical properties remain an enormous and long-term challenge for the rubber industry. Herein, we employed the in-situ growth of Ce-doped Co-metal-organic framework (CeCo-MOF) in dendritic mesoporous organosilica nanoparticles (DMONs@CeCo-MOF, denoted as DCCM) to prepare a novel antioxidant that exhibit outstanding thermal stability. Dendritic mesoporous organosilica nanoparticles (DMONs) effectively alleviated the incompatibility of CeCo-MOF in the polymer matrix, and the effective scavenging of free radicals was attributed to the various oxidation states of metal ions in CeCo-MOF. Surprising, by adding only 0.5 phr (parts per hundred of rubber) of DMONs@CeCo-MOF to silicone rubber, (SR), the retention rate of tensile strength increased from 37.3% to 61.6% after aging 72 h at 250 ℃, and the retention rate of elongation at break of DCCM/SR1 composites reached 68%, which was 5.43 times of SR. The strategy of anchoring MOFs on the surface of silica also provides a viable method for preparing effective compound functionalized rubber antioxidant.
2025, 36(1): 109731
doi: 10.1016/j.cclet.2024.109731
摘要:
Selective separation of amino acids and proteins is crucial in various areas of research, including proteomics, protein structure and function studies, protein purification and drug development, and biosensing and biodetection. A nanocomposite film is formed by combining layer-by-layer self-assembled gold nanospheres (AuNPs) driven by cucurbit[7]uril (CB[7]) and polymethyl methacrylate (PMMA) film. Due to the host-guest interactions, the selective transmission of L-tryptophan in the nanocomposite film is confirmed by the current-voltage measurements using a picoammeter. Furthermore, by adjusting the particle size of AuNPs to increase channel size, lysozyme containing multiple tryptophan residues can selectively pass through the nanocomposite film, indicating the high versatility and adaptability of the nanocomposite film. This study will provide a new direction for the selective separation of amino acids and proteins.
Selective separation of amino acids and proteins is crucial in various areas of research, including proteomics, protein structure and function studies, protein purification and drug development, and biosensing and biodetection. A nanocomposite film is formed by combining layer-by-layer self-assembled gold nanospheres (AuNPs) driven by cucurbit[7]uril (CB[7]) and polymethyl methacrylate (PMMA) film. Due to the host-guest interactions, the selective transmission of L-tryptophan in the nanocomposite film is confirmed by the current-voltage measurements using a picoammeter. Furthermore, by adjusting the particle size of AuNPs to increase channel size, lysozyme containing multiple tryptophan residues can selectively pass through the nanocomposite film, indicating the high versatility and adaptability of the nanocomposite film. This study will provide a new direction for the selective separation of amino acids and proteins.
2025, 36(1): 109733
doi: 10.1016/j.cclet.2024.109733
摘要:
The self-assembled nanoparticles (SAN) formed during the decoction process of traditional Chinese medicine (TCM) exhibit non-uniform particle sizes and a tendency for aggregation. Our group found that the pH-driven method can improve the self-assembly phenomenon of Herpetospermum caudigerum Wall., and the SAN exhibited uniform particle size and demonstrated good stability. In this paper, we analyzed the interactions between the main active compound, herpetrione (Her), and its main carrier, Herpetospermum caudigerum Wall. polysaccharide (HCWP), along with their self-assembly mechanisms under different pH values. The binding constants of Her and HCWP increase with rising pH, leading to the formation of Her-HCWP SAN with a smaller particle size, higher zeta potential, and improved thermal stability. While the contributions of hydrogen bonding and electrostatic attraction to the formation of Her-HCWP SAN increase with rising pH, the hydrophobic force consistently plays a dominant role. This study enhances our scientific understanding of the self-assembly phenomenon of TCM improved by pH driven method.
The self-assembled nanoparticles (SAN) formed during the decoction process of traditional Chinese medicine (TCM) exhibit non-uniform particle sizes and a tendency for aggregation. Our group found that the pH-driven method can improve the self-assembly phenomenon of Herpetospermum caudigerum Wall., and the SAN exhibited uniform particle size and demonstrated good stability. In this paper, we analyzed the interactions between the main active compound, herpetrione (Her), and its main carrier, Herpetospermum caudigerum Wall. polysaccharide (HCWP), along with their self-assembly mechanisms under different pH values. The binding constants of Her and HCWP increase with rising pH, leading to the formation of Her-HCWP SAN with a smaller particle size, higher zeta potential, and improved thermal stability. While the contributions of hydrogen bonding and electrostatic attraction to the formation of Her-HCWP SAN increase with rising pH, the hydrophobic force consistently plays a dominant role. This study enhances our scientific understanding of the self-assembly phenomenon of TCM improved by pH driven method.
2025, 36(1): 109744
doi: 10.1016/j.cclet.2024.109744
摘要:
A supramolecular assembly composed of perylene diimide derivative (PDI-nm) and nor-seco-cucurbit[10]uril (ns-Q[10]) was designed. The excellent host-guest interaction between PDI-nm and ns-Q[10] prevented the aggregation-caused quenching (ACQ) effect of PDI-nm, resulting in a luminescent assembly. The addition of spermine to the PDI-nm/ns-Q[10] assembly restored the ACQ of PDI-nm due to the competitive binding of spermine to ns-Q[10], which released PDI-nm. The assembly based on this principle showed ultra-high sensitivity for the detection of spermine with a detection limit as low as 7.84 × 10−7 mol/L in aqueous solution and 3.69 × 10−7 mol/L in plasma solution. Moreover, an artificial light-harvesting system based on this assembly was proposed, benefiting from its good luminescent performance. Nile red (NiR) functioned as an acceptor loaded into assembly, and a highly efficient energy transfer process occurred from PDI-nm/ns-Q[10] to NiR, with an efficiency up to 87%.
A supramolecular assembly composed of perylene diimide derivative (PDI-nm) and nor-seco-cucurbit[10]uril (ns-Q[10]) was designed. The excellent host-guest interaction between PDI-nm and ns-Q[10] prevented the aggregation-caused quenching (ACQ) effect of PDI-nm, resulting in a luminescent assembly. The addition of spermine to the PDI-nm/ns-Q[10] assembly restored the ACQ of PDI-nm due to the competitive binding of spermine to ns-Q[10], which released PDI-nm. The assembly based on this principle showed ultra-high sensitivity for the detection of spermine with a detection limit as low as 7.84 × 10−7 mol/L in aqueous solution and 3.69 × 10−7 mol/L in plasma solution. Moreover, an artificial light-harvesting system based on this assembly was proposed, benefiting from its good luminescent performance. Nile red (NiR) functioned as an acceptor loaded into assembly, and a highly efficient energy transfer process occurred from PDI-nm/ns-Q[10] to NiR, with an efficiency up to 87%.
2025, 36(1): 109747
doi: 10.1016/j.cclet.2024.109747
摘要:
Triflumezopyrim (TFM) is a novel mesoionic pyrido[1,2-α]pyrimidinones insecticide, which acts on nicotinic acetylcholine receptors (nAChRs) and has no cross-resistance with other insecticides. Herein, we firstly developed a new continuous flow approach to synthesis 2-[3-(trifluoromethyl)phenyl]malonic acid, a key intermate of TFM, coupling with esterification, condensation, and hydrolysis. All three-step reactions were optimized and transformed into a continuous synthesis mode by three micro reaction units. Compared with the batch mode, the total reaction time and overall separation yield were improved from more than 12 h and 60% to 18 min and 73.38%, respectively. The solvent consumption and waste emission were significantly reduced, which also provides an eco-friendly and efficient potential tool for the development and production of mesoionic pyrido[1,2-α]pyrimidinones insecticide.
Triflumezopyrim (TFM) is a novel mesoionic pyrido[1,2-α]pyrimidinones insecticide, which acts on nicotinic acetylcholine receptors (nAChRs) and has no cross-resistance with other insecticides. Herein, we firstly developed a new continuous flow approach to synthesis 2-[3-(trifluoromethyl)phenyl]malonic acid, a key intermate of TFM, coupling with esterification, condensation, and hydrolysis. All three-step reactions were optimized and transformed into a continuous synthesis mode by three micro reaction units. Compared with the batch mode, the total reaction time and overall separation yield were improved from more than 12 h and 60% to 18 min and 73.38%, respectively. The solvent consumption and waste emission were significantly reduced, which also provides an eco-friendly and efficient potential tool for the development and production of mesoionic pyrido[1,2-α]pyrimidinones insecticide.
2025, 36(1): 109748
doi: 10.1016/j.cclet.2024.109748
摘要:
Ag2CO3-promoted dehydroxymethylative fluorination of aliphatic alcohols has been achieved with Selectfluor as both oxidant and fluorine source. The reaction involves β-fragmentation of primary alkoxy radicals, followed by the fluorination of the resulting C-centered radical intermediates. The transformation proceeds under mild reaction conditions and exhibits a broad substrate scope, thus opening up a new entrance to the synthesis of fluorinated constructs including α-fluoroimides and 1-fluoroalkyl benzoates as well as secondary and tertiary alkyl fluorides like versatile 2-fluoro-2-alkyl 1,3-propandiol derivatives. The divergent functionalization of the obtained α-fluoroimides enables an efficient access to amine derivatives through C–F bond activation under the action of BF3·OEt2.
Ag2CO3-promoted dehydroxymethylative fluorination of aliphatic alcohols has been achieved with Selectfluor as both oxidant and fluorine source. The reaction involves β-fragmentation of primary alkoxy radicals, followed by the fluorination of the resulting C-centered radical intermediates. The transformation proceeds under mild reaction conditions and exhibits a broad substrate scope, thus opening up a new entrance to the synthesis of fluorinated constructs including α-fluoroimides and 1-fluoroalkyl benzoates as well as secondary and tertiary alkyl fluorides like versatile 2-fluoro-2-alkyl 1,3-propandiol derivatives. The divergent functionalization of the obtained α-fluoroimides enables an efficient access to amine derivatives through C–F bond activation under the action of BF3·OEt2.
2025, 36(1): 109752
doi: 10.1016/j.cclet.2024.109752
摘要:
Osteoarthritis (OA) is the most prevalent joint disease and icariin is a promising drug for its treatment. However, the clinical use of icariin is hindered by poor water solubility, low bioavailability, and non-specific release and biological distribution. Herein, sulfonated azocalix[4]arene (SAC4A) with enhanced water solubility, recognition capacity, and designed responsiveness was used to improve the efficiency of icariin for OA therapy. SAC4A, a macrocycle with well-defined molecular weight and structure, could encapsulate and enhance water solubility of various drugs. In addition, SAC4A enables hypoxia-responsive release of loaded drug. Compared with icariin treatment, supramolecular complex icariin@SAC4A significantly relieved OA symptoms of rats, including more regular bone morphology and structure, and lower degree of cartilage damage. Moreover, the supramolecular formulation demonstrated various advantages, including easy preparation, hypoxia-triggered release, and small size that conducive to drug penetration.
Osteoarthritis (OA) is the most prevalent joint disease and icariin is a promising drug for its treatment. However, the clinical use of icariin is hindered by poor water solubility, low bioavailability, and non-specific release and biological distribution. Herein, sulfonated azocalix[4]arene (SAC4A) with enhanced water solubility, recognition capacity, and designed responsiveness was used to improve the efficiency of icariin for OA therapy. SAC4A, a macrocycle with well-defined molecular weight and structure, could encapsulate and enhance water solubility of various drugs. In addition, SAC4A enables hypoxia-responsive release of loaded drug. Compared with icariin treatment, supramolecular complex icariin@SAC4A significantly relieved OA symptoms of rats, including more regular bone morphology and structure, and lower degree of cartilage damage. Moreover, the supramolecular formulation demonstrated various advantages, including easy preparation, hypoxia-triggered release, and small size that conducive to drug penetration.
2025, 36(1): 109755
doi: 10.1016/j.cclet.2024.109755
摘要:
A transition-metal- and oxidant-free amination/cyclization reaction to access 1,2,4-triazolo[1,5-a]pyridines was realized in water by using amino diphenylphosphinate as amino source. A broad array of readily accessible N-(pyridyl)amides could be converted into the products featuring a diverse set of functional groups. The sustainable methodology was successfully applied to the late-stage functionalization of natural products and drugs.
A transition-metal- and oxidant-free amination/cyclization reaction to access 1,2,4-triazolo[1,5-a]pyridines was realized in water by using amino diphenylphosphinate as amino source. A broad array of readily accessible N-(pyridyl)amides could be converted into the products featuring a diverse set of functional groups. The sustainable methodology was successfully applied to the late-stage functionalization of natural products and drugs.
2025, 36(1): 109760
doi: 10.1016/j.cclet.2024.109760
摘要:
Controlled synthesis of two-dimensional covalent organic frameworks (2D COFs), including stoichiometric and sub-stoichiometric variations, is a topic of growing interest due to its potential in gas separation applications. In this study, we successfully synthesized three distinct 2D COFs by carefully adjusting solvent compositions and monomer ratios during the synthesis of [4 + 4] type COFs. These included a stoichiometric [4 + 4] type COF and two sub-stoichiometric [4 + 2] type COFs, featuring unreacted amino or formyl groups. The resulting COFs exhibit different gas adsorption and separation properties. Specifically, sub-stoichiometric COF-DA with residual amino groups shows comparable adsorption capacity for C2H2, C2H4, and CO2 to stoichiometric COF-DAPy. In contrast, sub-stoichiometric COF-Py with residual formyl groups displays enhanced adsorption selectivity for C2H2/C2H4 and C2H2/CO2 separation, with the C2H2/C2H4 selectivity being the highest among reported COFs, attributed to increased pore polarity resulting from the presence of formyl groups. This study not only offers an additional example of sub-stoichiometric COF synthesis but also advocates for further exploration of sub-stoichiometric COF materials, particularly in the field of gas adsorption and separation.
Controlled synthesis of two-dimensional covalent organic frameworks (2D COFs), including stoichiometric and sub-stoichiometric variations, is a topic of growing interest due to its potential in gas separation applications. In this study, we successfully synthesized three distinct 2D COFs by carefully adjusting solvent compositions and monomer ratios during the synthesis of [4 + 4] type COFs. These included a stoichiometric [4 + 4] type COF and two sub-stoichiometric [4 + 2] type COFs, featuring unreacted amino or formyl groups. The resulting COFs exhibit different gas adsorption and separation properties. Specifically, sub-stoichiometric COF-DA with residual amino groups shows comparable adsorption capacity for C2H2, C2H4, and CO2 to stoichiometric COF-DAPy. In contrast, sub-stoichiometric COF-Py with residual formyl groups displays enhanced adsorption selectivity for C2H2/C2H4 and C2H2/CO2 separation, with the C2H2/C2H4 selectivity being the highest among reported COFs, attributed to increased pore polarity resulting from the presence of formyl groups. This study not only offers an additional example of sub-stoichiometric COF synthesis but also advocates for further exploration of sub-stoichiometric COF materials, particularly in the field of gas adsorption and separation.
2025, 36(1): 109763
doi: 10.1016/j.cclet.2024.109763
摘要:
Immunotherapy offers significant potential but is often hampered by the immunosuppressive environment in oral squamous cell carcinoma (OSCC). To address this, we propose an enhanced immunotherapeutic strategy that revitalizes the tumor immune microenvironment (TIME) in OSCC by integrating upconversion-based photodynamic therapy (PDT) with chemotherapy. Using a red blood cell membrane-inspired biomimetic nanoplatform, our approach concurrently delivers chlorin e6@upconversion nanoparticles (Ce6@UCNP) and doxorubicin (DOX). By leveraging fluorescence resonance energy transfer (FRET) for 980 nm to 660 nm upconversion excitation, we address challenges such as limited tissue penetration and tissue damage, as well as nanoplatform issues including immunogenicity and targeting inaccuracy Our integrated approach enhances PDT and chemotherapy with the goal of transforming immunologically "cold" tumors into "hot" ones through a cascaded therapy, thereby revitalizing the tumor immune microenvironment in OSCC.
Immunotherapy offers significant potential but is often hampered by the immunosuppressive environment in oral squamous cell carcinoma (OSCC). To address this, we propose an enhanced immunotherapeutic strategy that revitalizes the tumor immune microenvironment (TIME) in OSCC by integrating upconversion-based photodynamic therapy (PDT) with chemotherapy. Using a red blood cell membrane-inspired biomimetic nanoplatform, our approach concurrently delivers chlorin e6@upconversion nanoparticles (Ce6@UCNP) and doxorubicin (DOX). By leveraging fluorescence resonance energy transfer (FRET) for 980 nm to 660 nm upconversion excitation, we address challenges such as limited tissue penetration and tissue damage, as well as nanoplatform issues including immunogenicity and targeting inaccuracy Our integrated approach enhances PDT and chemotherapy with the goal of transforming immunologically "cold" tumors into "hot" ones through a cascaded therapy, thereby revitalizing the tumor immune microenvironment in OSCC.
2025, 36(1): 109778
doi: 10.1016/j.cclet.2024.109778
摘要:
Intracellular redox homeostasis is of indispensable importance in pathophysiology. In order to maintain the balance of the redox state within the cell, reactive oxygen species (ROS) and reactive sulfur species (RSS) react and transform with each other, and their levels also directly reflect the degree of oxidative stress and disease. Hypochlorous acid (HClO) and cysteine (Cys) usually co-exist in organisms, interacting with each other in many important physiological processes and synergistically maintaining the dynamic redox balance in the body. To understand the relevance and pathophysiological effects of these two signaling molecules in oxidative stress, unique fluorescence imaging tools are required. Herein, we designed and developed a dual-channel fluorescent probe HP, for the individual and continuous detection of HClO and Cys. This probe could simultaneously monitor the changes in the concentrations of HClO and Cys in cells, and was characterized by a fast response, high sensitivity and high selectivity, especially compared with glutathione (GSH) and homocysteine (Hcy), the probe had a good specificity for Cys. Importantly, probe HP successfully observed dynamic changes in HClO- and Cys-mediated redox status in the oxygen-glucose deprivation/reperfusion (OGD/R) model of HeLa cells and dynamically monitored fluctuations in endogenous HClO levels in lipopolysaccharides (LPS)-induced peritonitis mice.
Intracellular redox homeostasis is of indispensable importance in pathophysiology. In order to maintain the balance of the redox state within the cell, reactive oxygen species (ROS) and reactive sulfur species (RSS) react and transform with each other, and their levels also directly reflect the degree of oxidative stress and disease. Hypochlorous acid (HClO) and cysteine (Cys) usually co-exist in organisms, interacting with each other in many important physiological processes and synergistically maintaining the dynamic redox balance in the body. To understand the relevance and pathophysiological effects of these two signaling molecules in oxidative stress, unique fluorescence imaging tools are required. Herein, we designed and developed a dual-channel fluorescent probe HP, for the individual and continuous detection of HClO and Cys. This probe could simultaneously monitor the changes in the concentrations of HClO and Cys in cells, and was characterized by a fast response, high sensitivity and high selectivity, especially compared with glutathione (GSH) and homocysteine (Hcy), the probe had a good specificity for Cys. Importantly, probe HP successfully observed dynamic changes in HClO- and Cys-mediated redox status in the oxygen-glucose deprivation/reperfusion (OGD/R) model of HeLa cells and dynamically monitored fluctuations in endogenous HClO levels in lipopolysaccharides (LPS)-induced peritonitis mice.
2025, 36(1): 109781
doi: 10.1016/j.cclet.2024.109781
摘要:
Herein, we report the dynamic kinetic resolution asymmetric acylation of γ-hydroxy-γ-perfluoroalkyl butenolides/phthalides catalyzed by amino acid-derived bifunctional organocatalysts, and a series of ketals were obtained in high yields (up to 95%) and excellent enantioselectivities (up to 99%). In terms of synthetic utility, the reaction can be performed on a gram scale, and the product can be converted into potential biological nucleoside analog.
Herein, we report the dynamic kinetic resolution asymmetric acylation of γ-hydroxy-γ-perfluoroalkyl butenolides/phthalides catalyzed by amino acid-derived bifunctional organocatalysts, and a series of ketals were obtained in high yields (up to 95%) and excellent enantioselectivities (up to 99%). In terms of synthetic utility, the reaction can be performed on a gram scale, and the product can be converted into potential biological nucleoside analog.
2025, 36(1): 109785
doi: 10.1016/j.cclet.2024.109785
摘要:
Aflatoxins B1 (AFB1) contamination in agro-food holds great threaten to human and animal health. Conventional test strips for rapid AFB1 visualized monitoring remains challenged by improvement of sensitivity and matrix interference resistance. In this case, we developed a portable electrochemiluminescence (ECL) imaging test strip with dual-signal outputs for AFB1 quantification in corn samples. Ru-PEI@SiO2@Au nanospheres were synthesized for bonding with anti-AFB1 antibody and then colorimetrical signal-reported on test line through the capillary flow at strips. Meanwhile, ECL imaging signal of the constructed carbon-ink-based working electrode on polyvinyl chloride substrate of strips was exported under an applied potential of 1.25 V. The whole ECL test strips not only endowed convenient colorimetric responses but guaranteed quick-witted ECL image distinguishment even at extremely low AFB1 content. The detection limit of this ECL imaging-integrated mode was 10-fold lower than that of only colorimetric mode. Furthermore, satisfactory selectivity, reliability and practicability of the as-proposed ECL test strips were demonstrated. This work offered a promising platform for on-site, accurate and sensitive detection of pollutants in foods.
Aflatoxins B1 (AFB1) contamination in agro-food holds great threaten to human and animal health. Conventional test strips for rapid AFB1 visualized monitoring remains challenged by improvement of sensitivity and matrix interference resistance. In this case, we developed a portable electrochemiluminescence (ECL) imaging test strip with dual-signal outputs for AFB1 quantification in corn samples. Ru-PEI@SiO2@Au nanospheres were synthesized for bonding with anti-AFB1 antibody and then colorimetrical signal-reported on test line through the capillary flow at strips. Meanwhile, ECL imaging signal of the constructed carbon-ink-based working electrode on polyvinyl chloride substrate of strips was exported under an applied potential of 1.25 V. The whole ECL test strips not only endowed convenient colorimetric responses but guaranteed quick-witted ECL image distinguishment even at extremely low AFB1 content. The detection limit of this ECL imaging-integrated mode was 10-fold lower than that of only colorimetric mode. Furthermore, satisfactory selectivity, reliability and practicability of the as-proposed ECL test strips were demonstrated. This work offered a promising platform for on-site, accurate and sensitive detection of pollutants in foods.
"Superimposed" spectral characteristics of fluorophores arising from cross-conjugation hybridization
2025, 36(1): 109786
doi: 10.1016/j.cclet.2024.109786
摘要:
The demand for enhanced optical properties in advanced fluorescence technologies has driven research into the structure-property relationship of fluorophores. In this paper, we use naphthalene fluorophores NaDC-Aze and PhDO-Aze as a case study to emphasize the pivotal role of cross conjugation in tuning the optical structure-property relationship. NaDC-Aze and PhDO-Aze, formed by hybridizing two distinct conjugated systems in a single naphthalene molecule, exhibit spectral characteristics from both conjugated systems. Experimental data and theoretical calculations demonstrate the coexistence of two electron-delocalization systems in a cross-conjugation manner in both NaDC-Aze and PhDO-Aze. The cross-conjugation fluorophores exhibit high brightness, large Stokes shift, and a broad absorption wavelength range by combining distinct spectral properties from its parent fluorophores. These spectral properties will be advantageous for certain applications (i.e., panchromatic absorption in organic solar cells, and fluorophores compatible with a wide range of excitation wavelengths).
The demand for enhanced optical properties in advanced fluorescence technologies has driven research into the structure-property relationship of fluorophores. In this paper, we use naphthalene fluorophores NaDC-Aze and PhDO-Aze as a case study to emphasize the pivotal role of cross conjugation in tuning the optical structure-property relationship. NaDC-Aze and PhDO-Aze, formed by hybridizing two distinct conjugated systems in a single naphthalene molecule, exhibit spectral characteristics from both conjugated systems. Experimental data and theoretical calculations demonstrate the coexistence of two electron-delocalization systems in a cross-conjugation manner in both NaDC-Aze and PhDO-Aze. The cross-conjugation fluorophores exhibit high brightness, large Stokes shift, and a broad absorption wavelength range by combining distinct spectral properties from its parent fluorophores. These spectral properties will be advantageous for certain applications (i.e., panchromatic absorption in organic solar cells, and fluorophores compatible with a wide range of excitation wavelengths).
2025, 36(1): 109790
doi: 10.1016/j.cclet.2024.109790
摘要:
An N-heterocyclic carbene (NHC) catalyzed enantioselective cyclisation and trifluoromethylation of olefins with cinnamaldehydes via radical relay cross-coupling in the presence of Togni reagent is reported and δ-lactones tolerated with stereogenic centers at β- and γ-positions are obtained in moderate to high yields and with high enantioselectivities. Further computational studies explain that the radical cross-coupling step is the key to determining the enantioselectivity. Energy analysis of key transition states and intermediates also provides a reasonable explanation for the difficulty of diastereoselective control. DFT calculations also reveal that the hydrogen-bonding interaction plays a vital role in the promotion of this chemistry.
An N-heterocyclic carbene (NHC) catalyzed enantioselective cyclisation and trifluoromethylation of olefins with cinnamaldehydes via radical relay cross-coupling in the presence of Togni reagent is reported and δ-lactones tolerated with stereogenic centers at β- and γ-positions are obtained in moderate to high yields and with high enantioselectivities. Further computational studies explain that the radical cross-coupling step is the key to determining the enantioselectivity. Energy analysis of key transition states and intermediates also provides a reasonable explanation for the difficulty of diastereoselective control. DFT calculations also reveal that the hydrogen-bonding interaction plays a vital role in the promotion of this chemistry.
2025, 36(1): 109798
doi: 10.1016/j.cclet.2024.109798
摘要:
PBQ [1-(4-chlorophenyl)-3-(pyridin-3-yl)urea], an enormous potent molluscicide, showed excellent Pomacea canaliculata (P. canaliculata) control activity and low toxicity for other aquatic organisms, but its snail-killing mechanisms are still not fully understood. We employed an optical method to elucidate PBQ action via a novel fluorescent viscosity probe, NCV. As the viscosity in the test solutions increased, compared with that in pure ethanol, a 54-fold fluorescence intensity enhancement of NCV was observed in 310 cP of 90% glycerol. Furthermore, NCV successfully exhibited a selective fluorescence response towards monensin-induced cellular viscosity changes in HepG2 cells. The liver, stomach, and foot plantar of the tested snails were frozen and sectioned for fluorescent imaging experiments after the treatment with different PBQ concentrations over various times. A significant fluorescent increase in the snail's liver was observed upon exposure to 0.75 mg/L PBQ for 72 h, which highlighted an increase in viscosity. Hematoxylin and eosin (HE) staining further supported PBQ-induced liver damage with a viscosity increase in P. canaliculata. Our study provides a new rapid optical visualization method to study the killing mechanisms of PBQ and may help discover new chemicals that control snail populations.
PBQ [1-(4-chlorophenyl)-3-(pyridin-3-yl)urea], an enormous potent molluscicide, showed excellent Pomacea canaliculata (P. canaliculata) control activity and low toxicity for other aquatic organisms, but its snail-killing mechanisms are still not fully understood. We employed an optical method to elucidate PBQ action via a novel fluorescent viscosity probe, NCV. As the viscosity in the test solutions increased, compared with that in pure ethanol, a 54-fold fluorescence intensity enhancement of NCV was observed in 310 cP of 90% glycerol. Furthermore, NCV successfully exhibited a selective fluorescence response towards monensin-induced cellular viscosity changes in HepG2 cells. The liver, stomach, and foot plantar of the tested snails were frozen and sectioned for fluorescent imaging experiments after the treatment with different PBQ concentrations over various times. A significant fluorescent increase in the snail's liver was observed upon exposure to 0.75 mg/L PBQ for 72 h, which highlighted an increase in viscosity. Hematoxylin and eosin (HE) staining further supported PBQ-induced liver damage with a viscosity increase in P. canaliculata. Our study provides a new rapid optical visualization method to study the killing mechanisms of PBQ and may help discover new chemicals that control snail populations.
2025, 36(1): 109799
doi: 10.1016/j.cclet.2024.109799
摘要:
The first-ever synthesis of the unknown furo[2′,3′:4,5]pyrimido[1,2-b]indazole skeleton was demonstrated based on the undiscovered tetra-functionalization of enaminones, with simple substrates and reaction conditions. The key to realizing this process lies in the multiple trapping of the in situ generated ketenimine cation by the 3-aminoindazole, which results in the formation of four new chemical bonds and two new rings in one pot. Moreover, the products of this new reaction were found to exhibit aggregation-induced emission (AIE) without modification.
The first-ever synthesis of the unknown furo[2′,3′:4,5]pyrimido[1,2-b]indazole skeleton was demonstrated based on the undiscovered tetra-functionalization of enaminones, with simple substrates and reaction conditions. The key to realizing this process lies in the multiple trapping of the in situ generated ketenimine cation by the 3-aminoindazole, which results in the formation of four new chemical bonds and two new rings in one pot. Moreover, the products of this new reaction were found to exhibit aggregation-induced emission (AIE) without modification.
2025, 36(1): 109811
doi: 10.1016/j.cclet.2024.109811
摘要:
Pyrrolobenzoxazines are a rare terpene-amino acid family of natural products with potent biological activities. Here, we reported the full biosynthetic pathway of paeciloxazine (1), a typical pyrrolobenzoxazine, with significant insecticidal activity. Base on heterologous expression, chemical complement experiment, and in vitro biochemical assays, we demonstrated the sesquiterpene portion of 1 derived from discontinuously oxidations of amorphdiene, in which P450 monooxygenase PaxH catalyzed a cascade of hydroxylation and epoxidation, while two flavin dependent monooxygenases are involved in the transformation of the esterified tryptophan into a pyrrolobenzoxazine core. Furthermore, a total of 15 compounds were generated through heterologous expression, of which 13, 17 and 20 showed potential antiepileptic activity. This study fully elucidated the biosynthetic pathway of paeciloxazine (1) and showed the diversity and complexity of constructing natural products by organisms.
Pyrrolobenzoxazines are a rare terpene-amino acid family of natural products with potent biological activities. Here, we reported the full biosynthetic pathway of paeciloxazine (1), a typical pyrrolobenzoxazine, with significant insecticidal activity. Base on heterologous expression, chemical complement experiment, and in vitro biochemical assays, we demonstrated the sesquiterpene portion of 1 derived from discontinuously oxidations of amorphdiene, in which P450 monooxygenase PaxH catalyzed a cascade of hydroxylation and epoxidation, while two flavin dependent monooxygenases are involved in the transformation of the esterified tryptophan into a pyrrolobenzoxazine core. Furthermore, a total of 15 compounds were generated through heterologous expression, of which 13, 17 and 20 showed potential antiepileptic activity. This study fully elucidated the biosynthetic pathway of paeciloxazine (1) and showed the diversity and complexity of constructing natural products by organisms.
2025, 36(1): 109817
doi: 10.1016/j.cclet.2024.109817
摘要:
Carbonyl compounds are abundant in nature and represent a substantial portion of biomass resources. Despite significant recent progress in homo-coupling of carbonyl compounds, achieving their deoxy-functionalization homo-coupling remains a highly intricate challenge. Herein, we report an entirely novel reaction paradigm: the trifluoromethylative homo-coupling of carbonyl compounds via hydrazones, which enables the formation of three C(sp3)–C(sp3) bonds in a single step. This method provides a new pathway for synthesizing trifluoromethylative coupling product which has unique applications in both fields of medical and material sciences. Mechanistic investigations have unveiled that the formation of a trifluoromethyl-substituted benzyl radical plays a pivotal role as a key intermediate in this reaction.
Carbonyl compounds are abundant in nature and represent a substantial portion of biomass resources. Despite significant recent progress in homo-coupling of carbonyl compounds, achieving their deoxy-functionalization homo-coupling remains a highly intricate challenge. Herein, we report an entirely novel reaction paradigm: the trifluoromethylative homo-coupling of carbonyl compounds via hydrazones, which enables the formation of three C(sp3)–C(sp3) bonds in a single step. This method provides a new pathway for synthesizing trifluoromethylative coupling product which has unique applications in both fields of medical and material sciences. Mechanistic investigations have unveiled that the formation of a trifluoromethyl-substituted benzyl radical plays a pivotal role as a key intermediate in this reaction.
2025, 36(1): 109818
doi: 10.1016/j.cclet.2024.109818
摘要:
The preparation, functionalization, and investigations in host-guest properties of high-level pillararene macrocycles have long been a big challenge because of the lack of efficient synthetic methods. Herein, a novel type of pillararene derivative, namely desymmetrized pillar[8]arene (DP[8]A), has been successfully synthesized via a facile two-step strategy with high yield. Compared with its pillar[8]arene counterpart, DP[8]A is composed of four alkoxy-substituted benzene units and four bare benzene rings. Single crystal analysis has been performed in order to unveil the molecular conformation and packing mode of DP[8]A, which indicated that DP[8]A possesses a unique chair-like structure and much smaller steric hindrance. Density functional theory (DFT) calculations and electrostatic potential map suggested the inhomogeneous electronic distribution in the DP[8]A cavity. Water-soluble carboxylate-modified DP[8]A, that is, CDP[8]A, was also prepared to investigate the host-guest properties in aqueous solution with methyl viologen (MV), where the binding constant and morphologies of the formed host-guest complexes have been studied. In all, this new version of eight-membered pillararene derivative might potentially serve as a powerful macrocycle candidate for further applications in supramolecular chemistry.
The preparation, functionalization, and investigations in host-guest properties of high-level pillararene macrocycles have long been a big challenge because of the lack of efficient synthetic methods. Herein, a novel type of pillararene derivative, namely desymmetrized pillar[8]arene (DP[8]A), has been successfully synthesized via a facile two-step strategy with high yield. Compared with its pillar[8]arene counterpart, DP[8]A is composed of four alkoxy-substituted benzene units and four bare benzene rings. Single crystal analysis has been performed in order to unveil the molecular conformation and packing mode of DP[8]A, which indicated that DP[8]A possesses a unique chair-like structure and much smaller steric hindrance. Density functional theory (DFT) calculations and electrostatic potential map suggested the inhomogeneous electronic distribution in the DP[8]A cavity. Water-soluble carboxylate-modified DP[8]A, that is, CDP[8]A, was also prepared to investigate the host-guest properties in aqueous solution with methyl viologen (MV), where the binding constant and morphologies of the formed host-guest complexes have been studied. In all, this new version of eight-membered pillararene derivative might potentially serve as a powerful macrocycle candidate for further applications in supramolecular chemistry.
2025, 36(1): 109834
doi: 10.1016/j.cclet.2024.109834
摘要:
Fluorescence lateral flow immunoassay (LFA) has emerged as a powerful tool for rapid screening of various biomarkers owing to its simplicity, sensitivity and flexibility. It is noteworthy that fluorescent probe mainly determines the analytical performance of LFA. Due to the emission and excitation wavelengths are located in the visible region, most fluorophores are inevitably subject to light scattering and background autofluorescence. Herein, we reported a novel LFA sensor based on the second near-infrared (NIR-Ⅱ) fluorescent probe with excellent anti-interference capability. The designed NIR-Ⅱ probe was the Nd3+ and Yb3+ doped rare earth nanoparticles (RENPs) by employing Nd3+ as energy donor and Yb3+ as energy acceptor, which of the donor-acceptor energy transfer (ET) efficiency reached up to 80.7%. Meanwhile, relying on the convenient and effective encapsulation strategy of poly(lactic-co-glycolic acid) (PLGA) microspheres to RENPs, the surface functionalized NIR-Ⅱ probe (RE@PLGA) was obtained for subsequent bioconjugation. Benefiting from the optical advantages of NIR-Ⅱ probe, this proposed NIR-Ⅱ LFA displayed a good linear relationship ranging from 7 ng/mL to 200 ng/mL for the detection of α-fetoprotein (AFP), an important biomarker of hepatocellular carcinoma (HCC). The limit of detection (LOD) was determined as low as 3.0 ng/mL, which was of 8.3 times lower than clinical cutoff value. It is promising that LFA sensor based on this efficient RENPs probe provides new opportunities for high sensitive detection of various biomarkers in biological samples.
Fluorescence lateral flow immunoassay (LFA) has emerged as a powerful tool for rapid screening of various biomarkers owing to its simplicity, sensitivity and flexibility. It is noteworthy that fluorescent probe mainly determines the analytical performance of LFA. Due to the emission and excitation wavelengths are located in the visible region, most fluorophores are inevitably subject to light scattering and background autofluorescence. Herein, we reported a novel LFA sensor based on the second near-infrared (NIR-Ⅱ) fluorescent probe with excellent anti-interference capability. The designed NIR-Ⅱ probe was the Nd3+ and Yb3+ doped rare earth nanoparticles (RENPs) by employing Nd3+ as energy donor and Yb3+ as energy acceptor, which of the donor-acceptor energy transfer (ET) efficiency reached up to 80.7%. Meanwhile, relying on the convenient and effective encapsulation strategy of poly(lactic-co-glycolic acid) (PLGA) microspheres to RENPs, the surface functionalized NIR-Ⅱ probe (RE@PLGA) was obtained for subsequent bioconjugation. Benefiting from the optical advantages of NIR-Ⅱ probe, this proposed NIR-Ⅱ LFA displayed a good linear relationship ranging from 7 ng/mL to 200 ng/mL for the detection of α-fetoprotein (AFP), an important biomarker of hepatocellular carcinoma (HCC). The limit of detection (LOD) was determined as low as 3.0 ng/mL, which was of 8.3 times lower than clinical cutoff value. It is promising that LFA sensor based on this efficient RENPs probe provides new opportunities for high sensitive detection of various biomarkers in biological samples.
2025, 36(1): 109839
doi: 10.1016/j.cclet.2024.109839
摘要:
Heterodimerization in RTKs is of vital importance in the RTK signaling and cell functions. Heterodimerization between RTKs can result in diversity of downstream signals, increasing the ability of cells to respond to external experiments. Traditional RTKs heterodimerization always occur in the same families and is lack of agonists to activate the heterodimeric RTKs signaling pathway. Herein, we developed the DNA agonist based on bivalent aptamers for the heterodimerized RTKs of different families, AF/AM-1, which could simultaneously activate FGFR1 and c-Met signaling. It is the first agonist that realizing the heterodimerization and activation of FGFR1 and c-Met, two different RTK families. The activation of FGFR1/c-Met heterodimer result in the down-stream signals transduction, such as the phosphorylation of Akt and Erk, inducing the cell migration and proliferation. The DNA agonist for RTK heterodimer of different families would have potential applications in the fields of biomedicine.
Heterodimerization in RTKs is of vital importance in the RTK signaling and cell functions. Heterodimerization between RTKs can result in diversity of downstream signals, increasing the ability of cells to respond to external experiments. Traditional RTKs heterodimerization always occur in the same families and is lack of agonists to activate the heterodimeric RTKs signaling pathway. Herein, we developed the DNA agonist based on bivalent aptamers for the heterodimerized RTKs of different families, AF/AM-1, which could simultaneously activate FGFR1 and c-Met signaling. It is the first agonist that realizing the heterodimerization and activation of FGFR1 and c-Met, two different RTK families. The activation of FGFR1/c-Met heterodimer result in the down-stream signals transduction, such as the phosphorylation of Akt and Erk, inducing the cell migration and proliferation. The DNA agonist for RTK heterodimer of different families would have potential applications in the fields of biomedicine.
2025, 36(1): 109840
doi: 10.1016/j.cclet.2024.109840
摘要:
Vascular disrupting agents (VDAs) can destroy tumor vasculature and lead to tumor ischemia and hypoxia, resulting in tumor necrosis. However, VDAs are easy to induce the upregulation of genes that are associated with cancer cell drug resistance and angiogenesis in tumor cells. Hypoxia-activated chemotherapy will be an ideal supplement to VDAs therapy since it can help to fully utilize the ischemia and hypoxia induced by VDAs to realize a synergistic antitumor therapeutic outcome. Here, we design a liposome whose surface is modified with a tumor-homing peptide Cys-Arg-Glu-Lys-Ala (CREKA, which can specifically target tumor vessels and stroma) and whose aqueous cavity and lipid bilayer are loaded by a hypoxia-activatable drug banoxantrone dihydrochloride (AQ4N) and a VDA combretastatin A4 (CA4), respectively. CA4 can selectively target vascular endothelial cells and destroy the tumor blood vessels, which will cause the rapid inhibition of blood flow in tumor and enhance the hypoxia in the tumor region. As a consequence, AQ4N can exert its boosted cytotoxicity under the enhanced hypoxic environment. The as-prepared liposome with a uniform particle size exhibits good stability and high cancer cell killing efficacy in vitro. In addition, in vivo experiments confirm the excellent tumor-targeting/accumulation, tumor vasculature-damaging, and tumor inhibition effects of the liposome. This work develops a liposomal which can achieve safe and effective tumor suppression without external stimulus excitation by only single injection, and is expected to benefit the future development of effective antitumor liposomal drugs.
Vascular disrupting agents (VDAs) can destroy tumor vasculature and lead to tumor ischemia and hypoxia, resulting in tumor necrosis. However, VDAs are easy to induce the upregulation of genes that are associated with cancer cell drug resistance and angiogenesis in tumor cells. Hypoxia-activated chemotherapy will be an ideal supplement to VDAs therapy since it can help to fully utilize the ischemia and hypoxia induced by VDAs to realize a synergistic antitumor therapeutic outcome. Here, we design a liposome whose surface is modified with a tumor-homing peptide Cys-Arg-Glu-Lys-Ala (CREKA, which can specifically target tumor vessels and stroma) and whose aqueous cavity and lipid bilayer are loaded by a hypoxia-activatable drug banoxantrone dihydrochloride (AQ4N) and a VDA combretastatin A4 (CA4), respectively. CA4 can selectively target vascular endothelial cells and destroy the tumor blood vessels, which will cause the rapid inhibition of blood flow in tumor and enhance the hypoxia in the tumor region. As a consequence, AQ4N can exert its boosted cytotoxicity under the enhanced hypoxic environment. The as-prepared liposome with a uniform particle size exhibits good stability and high cancer cell killing efficacy in vitro. In addition, in vivo experiments confirm the excellent tumor-targeting/accumulation, tumor vasculature-damaging, and tumor inhibition effects of the liposome. This work develops a liposomal which can achieve safe and effective tumor suppression without external stimulus excitation by only single injection, and is expected to benefit the future development of effective antitumor liposomal drugs.
2025, 36(1): 109842
doi: 10.1016/j.cclet.2024.109842
摘要:
Axially chiral binaphthol have achieved great success in asymmetric catalysis. Compared to α-binaphthol, axially chiral aryl-β-naphthol are far less reported. Here, we report a method of asymmetric catalysis to construct β-naphthol with up to 99% yield, 95.5:4.5 enantiomeric ratio, using alkynyl esters as precursors and chiral phosphonic acid (CPA)/Lewis acid as catalysts. Key steps involve oxygen transfer and de novo arene formation to set up the chiral axis. Moreover, this methodology provides a versatile platform for structurally divergent synthesis of atroposelective β-naphthol analogs, which are widely found in bioactive molecules and asymmetric catalysts.
Axially chiral binaphthol have achieved great success in asymmetric catalysis. Compared to α-binaphthol, axially chiral aryl-β-naphthol are far less reported. Here, we report a method of asymmetric catalysis to construct β-naphthol with up to 99% yield, 95.5:4.5 enantiomeric ratio, using alkynyl esters as precursors and chiral phosphonic acid (CPA)/Lewis acid as catalysts. Key steps involve oxygen transfer and de novo arene formation to set up the chiral axis. Moreover, this methodology provides a versatile platform for structurally divergent synthesis of atroposelective β-naphthol analogs, which are widely found in bioactive molecules and asymmetric catalysts.
2025, 36(1): 109844
doi: 10.1016/j.cclet.2024.109844
摘要:
Macrophages undergo dynamic transitions between M1 and M2 states, exerting profound influences on both inflammatory and regenerative processes. The biocompatible and wound-healing properties of decellularized amniotic membrane (dAM) make it a subject of exploration for its potential impact on the anti-inflammatory response of macrophages. Experimental findings unequivocally demonstrate that dAM promotes anti-inflammatory M2 polarization of macrophage, with its cytokine-rich content posited as a potential mediator. The application of RNA sequencing unveils differential gene expression, implicating the hypoxia inducible factor-1α (HIF-1α) signaling pathway in this intricate interplay. Subsequent investigation further demonstrates that dAM facilitates anti-inflammatory M2 polarization of macrophage through the upregulation of epidermal growth factor (EGF), which, in turn, activates the phosphatidylinositol 3-kinase (PI3K)/protein kinase B (AKT) pathway and stabilizes HIF-1α. This cascade results in a noteworthy augmentation of anti-inflammatory gene expression. This study significantly contributes to advancing our comprehension of dAM's immunomodulatory role in tissue repair, thereby suggesting promising therapeutic potential.
Macrophages undergo dynamic transitions between M1 and M2 states, exerting profound influences on both inflammatory and regenerative processes. The biocompatible and wound-healing properties of decellularized amniotic membrane (dAM) make it a subject of exploration for its potential impact on the anti-inflammatory response of macrophages. Experimental findings unequivocally demonstrate that dAM promotes anti-inflammatory M2 polarization of macrophage, with its cytokine-rich content posited as a potential mediator. The application of RNA sequencing unveils differential gene expression, implicating the hypoxia inducible factor-1α (HIF-1α) signaling pathway in this intricate interplay. Subsequent investigation further demonstrates that dAM facilitates anti-inflammatory M2 polarization of macrophage through the upregulation of epidermal growth factor (EGF), which, in turn, activates the phosphatidylinositol 3-kinase (PI3K)/protein kinase B (AKT) pathway and stabilizes HIF-1α. This cascade results in a noteworthy augmentation of anti-inflammatory gene expression. This study significantly contributes to advancing our comprehension of dAM's immunomodulatory role in tissue repair, thereby suggesting promising therapeutic potential.
2025, 36(1): 109848
doi: 10.1016/j.cclet.2024.109848
摘要:
Nanomaterials provide an ideal platform for biomolecular display due to their dimensions approach the molecular scale, facilitating binding behavior akin to that observed in solution-based processes. DNA nanoprobes hold great promise as miniature detectives capable of detecting miRNAs within cells. However, current nanoprobes face a challenge in achieving the required precision for accurate miRNA detection, particularly within the intricate confines of the cellular microenvironment, due to interference with biological autofluorescence, off-target effects, and a lack of spatiotemporal control. Here, we have designed a dual-stimuli responsive DNA tracker, synergistically utilizing specific intracellular cues and external triggers, which enables spatiotemporal-controlled and precise detection and imaging of miRNAs "on demand". The tracker, which combines zeolitic imidazolate framework-67 (ZIF-67) and unique hairpin DNA structures, effectively anchored onto the ZIF-67 through electrostatic interactions, remains in a dormant state until activated by abundant cellular ATP, resulting in the release of the hairpin structures that include a PC linker incorporated into the loop region. Subsequent irradiation triggers specific recognition of the target miRNA. The newly developed HP-PC-BT@ZIF-67 tracker demonstrates precise spatiotemporal miRNA detection and exhibits excellent biocompatibility, enabling specific miRNA recognition "on demand" within cancer cells. This research presents a reliable miRNA imaging platform in the intricate cellular environment, opening up the possibilities for precise biomedical analysis and disease diagnosis.
Nanomaterials provide an ideal platform for biomolecular display due to their dimensions approach the molecular scale, facilitating binding behavior akin to that observed in solution-based processes. DNA nanoprobes hold great promise as miniature detectives capable of detecting miRNAs within cells. However, current nanoprobes face a challenge in achieving the required precision for accurate miRNA detection, particularly within the intricate confines of the cellular microenvironment, due to interference with biological autofluorescence, off-target effects, and a lack of spatiotemporal control. Here, we have designed a dual-stimuli responsive DNA tracker, synergistically utilizing specific intracellular cues and external triggers, which enables spatiotemporal-controlled and precise detection and imaging of miRNAs "on demand". The tracker, which combines zeolitic imidazolate framework-67 (ZIF-67) and unique hairpin DNA structures, effectively anchored onto the ZIF-67 through electrostatic interactions, remains in a dormant state until activated by abundant cellular ATP, resulting in the release of the hairpin structures that include a PC linker incorporated into the loop region. Subsequent irradiation triggers specific recognition of the target miRNA. The newly developed HP-PC-BT@ZIF-67 tracker demonstrates precise spatiotemporal miRNA detection and exhibits excellent biocompatibility, enabling specific miRNA recognition "on demand" within cancer cells. This research presents a reliable miRNA imaging platform in the intricate cellular environment, opening up the possibilities for precise biomedical analysis and disease diagnosis.
2025, 36(1): 109857
doi: 10.1016/j.cclet.2024.109857
摘要:
Early diagnosis and accurate boundary delineation are the key steps of tumor precision medicine. Circulating tumor cells (CTCs) detection of liquid biopsy can provide abundant information for early diagnosis of cancer. High detection specificity and good enrichment features are two key factors for CTCs accurate identification in peripheral blood sample. For this purpose, iron oxide (IO)-based surface-enhanced Raman scattering (SERS) bioprobes with good biocompatibility, high detection sensitivity, remarkable detection specificity, and good enrichment efficiency, were developed for detecting different types of CTCs. Magnetic SERS bioprobes combined with programmed death ligand-1 (PD-L1) antibody are regarded as an effective way to boost the targeting ability and detection specificity, benefiting for accurately capturing and identifying rare CTCs. Four types of CTCs with different PD-L1 expression were accurately distinguished among white blood cells via high-resolution SERS mapping images and stable Raman signals. Subsequently, CTCs blood samples obtained from the triple negative breast cancer patients were also successfully recognized compared to that of health people, indicating IO@AR@PDA-aPD-L1 SERS bioprobe possessed great potential for CTCs detection in liquid biopsy. Additionally, IO-based bioprobe exhibited excellent dual-modal imaging abilities of high-resolution SERS imaging mode and microimaging magnetic resonance imaging mode. These two highly complementary imaging modes endowed IO-based bioprobes unrivalled capacity in tumor boundary differentiation, supporting tumor accurate resection and precise surgery. To our best knowledge, this is the first time that biocompatible IO-based SERS bioprobes without noble metal element were reported not only for CTCs accurate detection, but also for precise tumor boundary delineation, showing great advantages in tumor diagnosis and treatment.
Early diagnosis and accurate boundary delineation are the key steps of tumor precision medicine. Circulating tumor cells (CTCs) detection of liquid biopsy can provide abundant information for early diagnosis of cancer. High detection specificity and good enrichment features are two key factors for CTCs accurate identification in peripheral blood sample. For this purpose, iron oxide (IO)-based surface-enhanced Raman scattering (SERS) bioprobes with good biocompatibility, high detection sensitivity, remarkable detection specificity, and good enrichment efficiency, were developed for detecting different types of CTCs. Magnetic SERS bioprobes combined with programmed death ligand-1 (PD-L1) antibody are regarded as an effective way to boost the targeting ability and detection specificity, benefiting for accurately capturing and identifying rare CTCs. Four types of CTCs with different PD-L1 expression were accurately distinguished among white blood cells via high-resolution SERS mapping images and stable Raman signals. Subsequently, CTCs blood samples obtained from the triple negative breast cancer patients were also successfully recognized compared to that of health people, indicating IO@AR@PDA-aPD-L1 SERS bioprobe possessed great potential for CTCs detection in liquid biopsy. Additionally, IO-based bioprobe exhibited excellent dual-modal imaging abilities of high-resolution SERS imaging mode and microimaging magnetic resonance imaging mode. These two highly complementary imaging modes endowed IO-based bioprobes unrivalled capacity in tumor boundary differentiation, supporting tumor accurate resection and precise surgery. To our best knowledge, this is the first time that biocompatible IO-based SERS bioprobes without noble metal element were reported not only for CTCs accurate detection, but also for precise tumor boundary delineation, showing great advantages in tumor diagnosis and treatment.
2025, 36(1): 109882
doi: 10.1016/j.cclet.2024.109882
摘要:
The contamination of water resources by phenolic compounds (PCs) presents a significant environmental hazard, necessitating the development of novel materials and methodologies for effective mitigation. In this study, a metallic copper-doped zeolitic imidazolate framework was pyrolyzed and designated as Cu-NC-20 for the activation of peroxymonosulfate (PMS) to degrade phenol (PE). Cu-NC-20 could effectively address the issue of metal agglomeration while simultaneously diminishing copper dissolution during the activation of PMS reactions. The Cu-NC-20 catalyst exhibited a rapid degradation rate for PE across a broad pH range (3–9) and demonstrated high tolerance towards coexisting ions. According to scavenger experiments and electron paramagnetic resonance analysis, singlet oxygen (1O2) and high-valent copper-oxo (Cu(Ⅲ)) were the predominant reactive oxygen species, indicating that the system was nonradical-dominated during the degradation process. The quantitative structure-activity relationship (QSAR) between the oxidation rate constants of various substituted phenols and Hammett constants was established. It indicated that the Cu-NC-20/PMS system had the optimal oxidation rate constant with σ− correlation and exhibited a typical electrophilic reaction pattern. This study provides a comprehensive understanding of the heterogeneous activation process for the selective removal of phenolic compounds.
The contamination of water resources by phenolic compounds (PCs) presents a significant environmental hazard, necessitating the development of novel materials and methodologies for effective mitigation. In this study, a metallic copper-doped zeolitic imidazolate framework was pyrolyzed and designated as Cu-NC-20 for the activation of peroxymonosulfate (PMS) to degrade phenol (PE). Cu-NC-20 could effectively address the issue of metal agglomeration while simultaneously diminishing copper dissolution during the activation of PMS reactions. The Cu-NC-20 catalyst exhibited a rapid degradation rate for PE across a broad pH range (3–9) and demonstrated high tolerance towards coexisting ions. According to scavenger experiments and electron paramagnetic resonance analysis, singlet oxygen (1O2) and high-valent copper-oxo (Cu(Ⅲ)) were the predominant reactive oxygen species, indicating that the system was nonradical-dominated during the degradation process. The quantitative structure-activity relationship (QSAR) between the oxidation rate constants of various substituted phenols and Hammett constants was established. It indicated that the Cu-NC-20/PMS system had the optimal oxidation rate constant with σ− correlation and exhibited a typical electrophilic reaction pattern. This study provides a comprehensive understanding of the heterogeneous activation process for the selective removal of phenolic compounds.
2025, 36(1): 109883
doi: 10.1016/j.cclet.2024.109883
摘要:
Membrane distillation (MD) has gained extensive attention for treating highly saline wastewater. However, membrane scaling during the MD process has hindered the rapid development of this technology. Current approaches to mitigate scaling in membrane distillation focus primarily on achieving enhanced hydrophobicity and even superhydrophobicity via utilizing fluorinated fibrous membrane or introducing perfluorosilane modification. Considering the environmental hazards posed by fluorinated compounds, it is highly desirable to develop non-fluorinated membranes with enhanced anti-scaling properties for effective membrane distillation. In this study, we present a non-fluorinated liquid-like MD membrane with exceptional anti-scaling performance. This membrane was facilely fabricated by grafting linear polydimethylsiloxane (LPDMS) onto a hydrophilic polyether sulfone (PES) membrane pre-coated with the intermediate layers of polydopamine and silica (denoted as LPDMS-PES). Remarkably, LPDMS-PES manifested a drastically improved scaling resistance in continuous MD tests than its perfluorinated counterpart, i.e., 1H,1H,2H,2H-perfluorooctyltrichlorosilane-modified PES membrane (PFOS-PES), in both heterogeneous nucleation-dominated and crystal deposition-dominated scaling processes, despite the latter having a smaller surface energy. LPDMS-PES demonstrated a reduction of crystal accumulation of approximately 85% for NaCl and 73% for CaSO4 in the heterogeneous nucleation-dominated scaling process compared to PFOS-PES. Additionally, in the crystal deposition-dominated scaling process LPDMS-PES exhibited a reduction of about 70% in scale accumulation. These results explicitly evidenced the great potential of the liquid-like membrane to minimize scaling in membrane distillation by inhibiting both scale nucleation and adhesion onto the membrane. We believe the findings of this study have important implications for the design of high-performance MD membranes, particularly in the quest for environmentally sustainable alternatives to perfluorinated materials.
Membrane distillation (MD) has gained extensive attention for treating highly saline wastewater. However, membrane scaling during the MD process has hindered the rapid development of this technology. Current approaches to mitigate scaling in membrane distillation focus primarily on achieving enhanced hydrophobicity and even superhydrophobicity via utilizing fluorinated fibrous membrane or introducing perfluorosilane modification. Considering the environmental hazards posed by fluorinated compounds, it is highly desirable to develop non-fluorinated membranes with enhanced anti-scaling properties for effective membrane distillation. In this study, we present a non-fluorinated liquid-like MD membrane with exceptional anti-scaling performance. This membrane was facilely fabricated by grafting linear polydimethylsiloxane (LPDMS) onto a hydrophilic polyether sulfone (PES) membrane pre-coated with the intermediate layers of polydopamine and silica (denoted as LPDMS-PES). Remarkably, LPDMS-PES manifested a drastically improved scaling resistance in continuous MD tests than its perfluorinated counterpart, i.e., 1H,1H,2H,2H-perfluorooctyltrichlorosilane-modified PES membrane (PFOS-PES), in both heterogeneous nucleation-dominated and crystal deposition-dominated scaling processes, despite the latter having a smaller surface energy. LPDMS-PES demonstrated a reduction of crystal accumulation of approximately 85% for NaCl and 73% for CaSO4 in the heterogeneous nucleation-dominated scaling process compared to PFOS-PES. Additionally, in the crystal deposition-dominated scaling process LPDMS-PES exhibited a reduction of about 70% in scale accumulation. These results explicitly evidenced the great potential of the liquid-like membrane to minimize scaling in membrane distillation by inhibiting both scale nucleation and adhesion onto the membrane. We believe the findings of this study have important implications for the design of high-performance MD membranes, particularly in the quest for environmentally sustainable alternatives to perfluorinated materials.
2025, 36(1): 109884
doi: 10.1016/j.cclet.2024.109884
摘要:
Deep learning neural network incorporating surface enhancement Raman scattering technique (SERS) is becoming as a powerful tool for the precise classifications and diagnosis of bacterial infections. However, the large amount of sample requirement and time-consuming sample collection severely hinder its applications. We herein propose a spectral concatenation strategy for residual neural network using non-specific and specific SERS spectra for the training data augmentation, which is accessible to acquiring larger training dataset with same number of SERS spectra or same size of training dataset with fewer SERS spectra, compared with pure non-specific SERS spectra. With this strategy, the training loss exhibit rapid convergence, and an average accuracy up to 100% in bacteria classifications was achieved with 50 SERS spectra for each kind of bacterium; even reduced to 20 SERS spectra per kind of bacterium, classification accuracy is still > 95%, demonstrating marked advantage over the results without spectra concatenation. This method can markedly improve the classification accuracy under fewer samples and reduce the data collection workload, and can evidently enhance the performance when used in different machine learning models with high generalization ability. Therefore, this strategy is beneficial for rapid and accurate bacteria classifications with residual neural network.
Deep learning neural network incorporating surface enhancement Raman scattering technique (SERS) is becoming as a powerful tool for the precise classifications and diagnosis of bacterial infections. However, the large amount of sample requirement and time-consuming sample collection severely hinder its applications. We herein propose a spectral concatenation strategy for residual neural network using non-specific and specific SERS spectra for the training data augmentation, which is accessible to acquiring larger training dataset with same number of SERS spectra or same size of training dataset with fewer SERS spectra, compared with pure non-specific SERS spectra. With this strategy, the training loss exhibit rapid convergence, and an average accuracy up to 100% in bacteria classifications was achieved with 50 SERS spectra for each kind of bacterium; even reduced to 20 SERS spectra per kind of bacterium, classification accuracy is still > 95%, demonstrating marked advantage over the results without spectra concatenation. This method can markedly improve the classification accuracy under fewer samples and reduce the data collection workload, and can evidently enhance the performance when used in different machine learning models with high generalization ability. Therefore, this strategy is beneficial for rapid and accurate bacteria classifications with residual neural network.
2025, 36(1): 109885
doi: 10.1016/j.cclet.2024.109885
摘要:
Inactivation of carbon-based transition metal catalysts, which was caused by electron loss, limited their application in advanced oxidation processes. Therefore, Co and TiO2 double-loaded carbon nanofiber material (Co@CNFs-TiO2) was synthesized in this study. Photocatalytic and chemical catalytic systems were synergized efficiently. Tetracycline was eliminated within 15 min. The degradation rate remained above 90% after five cycles, and the 50% promotion proved the high stability of Co@CNFs-TiO2. The main reactive oxygen species in this system were sulfate radicals, whereas Co and TiO2 represented the active sites of the catalytic reaction. Electrons generated from TiO2 during the photocatalytic process were transferred to Co, which promoted the Co(Ⅲ)/Co(Ⅱ) cycle and maintained Co in a low-valence state, thereby stimulating the generation of sulfate radicals. In this study, the effective regulation of reactive oxygen species in the reaction system was realized. The results provided a guidance for in situ electron replenishment and regeneration of carbon-based transition metal catalysts, which will expand the practical application of advanced oxidation processes.
Inactivation of carbon-based transition metal catalysts, which was caused by electron loss, limited their application in advanced oxidation processes. Therefore, Co and TiO2 double-loaded carbon nanofiber material (Co@CNFs-TiO2) was synthesized in this study. Photocatalytic and chemical catalytic systems were synergized efficiently. Tetracycline was eliminated within 15 min. The degradation rate remained above 90% after five cycles, and the 50% promotion proved the high stability of Co@CNFs-TiO2. The main reactive oxygen species in this system were sulfate radicals, whereas Co and TiO2 represented the active sites of the catalytic reaction. Electrons generated from TiO2 during the photocatalytic process were transferred to Co, which promoted the Co(Ⅲ)/Co(Ⅱ) cycle and maintained Co in a low-valence state, thereby stimulating the generation of sulfate radicals. In this study, the effective regulation of reactive oxygen species in the reaction system was realized. The results provided a guidance for in situ electron replenishment and regeneration of carbon-based transition metal catalysts, which will expand the practical application of advanced oxidation processes.
2025, 36(1): 109889
doi: 10.1016/j.cclet.2024.109889
摘要:
An ionic liquid assisted hydrogel modified silica was synthesized using a one-pot polymerization and physical coating technique and subsequently applied to mixed-mode liquid chromatography. Analytical techniques, including Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and elemental analysis, etc., confirmed the successful prepared of this innovative stationary phase. The unique combination of amide, long alkyl chain, and imidazole ring in the hydrogel coating enables the stationary phase to function effectively in hydrophilic/reversed-phase/ion exchange liquid chromatography. Notably, the stationary phase exhibited superior separation performance owing to the synergistic effect of the ionic liquid and hydrogel. This was particularly evident when analyzing various analytes such as organic acids, nucleosides/bases, polycyclic aromatic hydrocarbons (PAHs) and anions. Furthermore, under our operating conditions, an excellent column efficiency of 53, 642.9 plates/m was achieved for theobromine. In summary, we have proposed a straightforward strategy to enhance the separation performance of hydrogel coatings in liquid chromatography, thereby broadening the potential applications of hydrogels in the field of separation.
An ionic liquid assisted hydrogel modified silica was synthesized using a one-pot polymerization and physical coating technique and subsequently applied to mixed-mode liquid chromatography. Analytical techniques, including Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and elemental analysis, etc., confirmed the successful prepared of this innovative stationary phase. The unique combination of amide, long alkyl chain, and imidazole ring in the hydrogel coating enables the stationary phase to function effectively in hydrophilic/reversed-phase/ion exchange liquid chromatography. Notably, the stationary phase exhibited superior separation performance owing to the synergistic effect of the ionic liquid and hydrogel. This was particularly evident when analyzing various analytes such as organic acids, nucleosides/bases, polycyclic aromatic hydrocarbons (PAHs) and anions. Furthermore, under our operating conditions, an excellent column efficiency of 53, 642.9 plates/m was achieved for theobromine. In summary, we have proposed a straightforward strategy to enhance the separation performance of hydrogel coatings in liquid chromatography, thereby broadening the potential applications of hydrogels in the field of separation.
2025, 36(1): 109896
doi: 10.1016/j.cclet.2024.109896
摘要:
Selenium is one of the important trace elements in the human body. Its deficiency will directly affect human health. With people's attention to health, the content of selenium in food has gradually attracted attention. However, detecting selenium compounds in complex samples remains a challenge. In this work, we built an online heating-reaction device. This device combines the electrospray extraction ionization mass spectrometry (EESI-MS) with the heating reaction device, which can simultaneously detect various selenium compounds in complex liquid samples. Under acidic conditions, the sample was heated and catalyzed by a heating reaction device, so that the SeO32− and O-phenylenediamine (OPD) could generate 1,3-dihydro-2,1,3-benzoselenadiazole. Based on the above reactions, we can detect organic selenium, inorganic selenium and other compounds in liquid samples by organic mass spectrometry. In this experiment, we determined the content of three forms of selenium: selenomethionine (SeMet), l-selenocystine (SeCys(2)), and sodium selenite. The calibration curves for SeMet, SeCys(2), and sodium selenite showed strong linearity within a range of 0.50–50.00 µg/L. The limits of detection (LOD) for the three compounds were 0.22, 0.27, and 0.41 µg/L, respectively. The limits of quantification (LOQ) were 0.68, 0.81, and 1.23 µg/L, respectively. Spiked recoveries at three levels ranged from 98.8% to 106.1%. In addition, this method can simultaneously detect three selenium compounds and three other specific chemical components in tea infusion samples, providing a rapid and efficient method for identifying tea quality.
Selenium is one of the important trace elements in the human body. Its deficiency will directly affect human health. With people's attention to health, the content of selenium in food has gradually attracted attention. However, detecting selenium compounds in complex samples remains a challenge. In this work, we built an online heating-reaction device. This device combines the electrospray extraction ionization mass spectrometry (EESI-MS) with the heating reaction device, which can simultaneously detect various selenium compounds in complex liquid samples. Under acidic conditions, the sample was heated and catalyzed by a heating reaction device, so that the SeO32− and O-phenylenediamine (OPD) could generate 1,3-dihydro-2,1,3-benzoselenadiazole. Based on the above reactions, we can detect organic selenium, inorganic selenium and other compounds in liquid samples by organic mass spectrometry. In this experiment, we determined the content of three forms of selenium: selenomethionine (SeMet), l-selenocystine (SeCys(2)), and sodium selenite. The calibration curves for SeMet, SeCys(2), and sodium selenite showed strong linearity within a range of 0.50–50.00 µg/L. The limits of detection (LOD) for the three compounds were 0.22, 0.27, and 0.41 µg/L, respectively. The limits of quantification (LOQ) were 0.68, 0.81, and 1.23 µg/L, respectively. Spiked recoveries at three levels ranged from 98.8% to 106.1%. In addition, this method can simultaneously detect three selenium compounds and three other specific chemical components in tea infusion samples, providing a rapid and efficient method for identifying tea quality.
2025, 36(1): 109928
doi: 10.1016/j.cclet.2024.109928
摘要:
Catalytic oxidation of soot is of great importance for emission control on diesel vehicles. In this work, a highly active Cs/Co/Ce-Sn catalyst was investigated for soot oxidation, and it was unexpectedly found that high-temperature calcination greatly improved the activity of the catalyst. When the calcination temperature was increased from 500 ℃ to 750 ℃, T50 decreased from 456.9 ℃ to 389.8 ℃ in a NO/O2/H2O/N2 atmosphere. Characterization results revealed that high-temperature calcination can promote the ability to transfer negative charge density from Cs to other metal cations in Cs/Co/Ce-Sn, which will facilitate the production of more oxygen defects and the generation of more surface-active oxygen species. Surface-active oxygen species are beneficial to the oxidation of NO to NO2, leading to the high yield of NO2 exploitation. Therefore, the Cs/Co/Ce-Sn catalyst calcined at 750 ℃ demonstrated higher activity than that calcined at 500 ℃. This work provides a pathway to prepare high efficiency catalysts for the removal of soot and significant insight into the effects of calcination on soot oxidation catalysts.
Catalytic oxidation of soot is of great importance for emission control on diesel vehicles. In this work, a highly active Cs/Co/Ce-Sn catalyst was investigated for soot oxidation, and it was unexpectedly found that high-temperature calcination greatly improved the activity of the catalyst. When the calcination temperature was increased from 500 ℃ to 750 ℃, T50 decreased from 456.9 ℃ to 389.8 ℃ in a NO/O2/H2O/N2 atmosphere. Characterization results revealed that high-temperature calcination can promote the ability to transfer negative charge density from Cs to other metal cations in Cs/Co/Ce-Sn, which will facilitate the production of more oxygen defects and the generation of more surface-active oxygen species. Surface-active oxygen species are beneficial to the oxidation of NO to NO2, leading to the high yield of NO2 exploitation. Therefore, the Cs/Co/Ce-Sn catalyst calcined at 750 ℃ demonstrated higher activity than that calcined at 500 ℃. This work provides a pathway to prepare high efficiency catalysts for the removal of soot and significant insight into the effects of calcination on soot oxidation catalysts.
2025, 36(1): 109934
doi: 10.1016/j.cclet.2024.109934
摘要:
Zirconium-based metal-organic cages (Zr-MOCs) typically exhibit high stability, but their structural and application reports are scarce due to stringent crystallization conditions. We have successfully fluorinated the classical Zr-MOCs (ZrT-3) for the first time, obtaining the fluorinated MOCs (ZrT-3-F). Notably, ZrT-3-F not only inherits the high stability of its parent structure, but also acts as a catalyst for the effective oxidation of benzyl thioether for the first time. The reaction can reach a conversion rate of 99% in 6 h, and the selectivity reaches 95%, which far exceeds the non-fluorinated ZrT-3. This work proves that the specific functionalization of the classical Zr-MOCs can further expand their application potential, such as catalysis.
Zirconium-based metal-organic cages (Zr-MOCs) typically exhibit high stability, but their structural and application reports are scarce due to stringent crystallization conditions. We have successfully fluorinated the classical Zr-MOCs (ZrT-3) for the first time, obtaining the fluorinated MOCs (ZrT-3-F). Notably, ZrT-3-F not only inherits the high stability of its parent structure, but also acts as a catalyst for the effective oxidation of benzyl thioether for the first time. The reaction can reach a conversion rate of 99% in 6 h, and the selectivity reaches 95%, which far exceeds the non-fluorinated ZrT-3. This work proves that the specific functionalization of the classical Zr-MOCs can further expand their application potential, such as catalysis.
2025, 36(1): 109985
doi: 10.1016/j.cclet.2024.109985
摘要:
Metal-organic frameworks (MOFs) with superior physicochemical properties have great potential for applications in chromatographic separation. However, currently popular methods for the synthesis of MOF-based silica composite materials usually require the use of harmful organic solvents and long-term high-temperature sealing reactions. In order to respond to the needs of green chromatography, it is urgent to develop a new green organic-solvent-free strategy for the synthesis of MOF@SiO2 composites. MIP-202 is a zirconium-MOF constructed from zirconium ion and l-aspartic acid, which features green synthesis as well as good hydrolytic stability and chemical stability. In this paper, SiO2-NH2 was first prepared in a hydrophilic deep eutectic solvent, and then an amino acid-based MOF material (MIP-202) was modified on the surface of the SiO2-NH2 in an aqueous solution to obtain a MIP-202@SiO2 composite material. The multi-mode separation performance of MIP-202@SiO2 as a promising liquid chromatographic stationary phase was particularly evaluated and the separation mechanisms were discussed. The MIP-202@SiO2 column exhibited excellent separation ability for aromatic positional isomers. In addition, chiral enantiomers and hydrophilic analytes were also satisfactorily detected and separated. This work provides a new approach for the facile synthesis of MOF-based liquid chromatographic separation material by using green deep eutectic solvent and water as the reaction media.
Metal-organic frameworks (MOFs) with superior physicochemical properties have great potential for applications in chromatographic separation. However, currently popular methods for the synthesis of MOF-based silica composite materials usually require the use of harmful organic solvents and long-term high-temperature sealing reactions. In order to respond to the needs of green chromatography, it is urgent to develop a new green organic-solvent-free strategy for the synthesis of MOF@SiO2 composites. MIP-202 is a zirconium-MOF constructed from zirconium ion and l-aspartic acid, which features green synthesis as well as good hydrolytic stability and chemical stability. In this paper, SiO2-NH2 was first prepared in a hydrophilic deep eutectic solvent, and then an amino acid-based MOF material (MIP-202) was modified on the surface of the SiO2-NH2 in an aqueous solution to obtain a MIP-202@SiO2 composite material. The multi-mode separation performance of MIP-202@SiO2 as a promising liquid chromatographic stationary phase was particularly evaluated and the separation mechanisms were discussed. The MIP-202@SiO2 column exhibited excellent separation ability for aromatic positional isomers. In addition, chiral enantiomers and hydrophilic analytes were also satisfactorily detected and separated. This work provides a new approach for the facile synthesis of MOF-based liquid chromatographic separation material by using green deep eutectic solvent and water as the reaction media.
2025, 36(1): 110047
doi: 10.1016/j.cclet.2024.110047
摘要:
Recently circularly polarized luminescence (CPL) materials have attracted significant interest. Introducing reversible dynamic property to these materials has been a key focus in cutting-edge fields, such as in high-level information encryption. Here, we provided a novel and general strategy involving handedness-selective filtration and ground-state chiral self-recovery (CSR) in double film system to address this issue. Based on this strategy, we achieved CPL switch through the reversible modulation of ground-state chirality including absorption and scattering circular dichroism (CD) signals over the full UV-visible wavelength range (365-700 nm) in a single azobenzene polymer (PAzo) film. More importantly, by flexibly changing the type of fluorescent films, it is convenient to achieve general excited-state CSR, that is reversible switching of full-color including ideal white (CIE coordinate (0.33, 0.33)), as well as room-temperature phosphorescent CPL. All these CPL signals without almost any intensity decay after three cycles of on-and-off switching. Experimental results indicated that the trans-cis isomerization and ordered rearrangement of azobenzene units in PAzo film were the fundamental reasons for realizing CPL switching. Finally, based on this system we achieved dynamic visual encryption and decryption process including multiple decryption methods. This study provides an effective method for constructing a universally applicable chiroptical switch in excited state.
Recently circularly polarized luminescence (CPL) materials have attracted significant interest. Introducing reversible dynamic property to these materials has been a key focus in cutting-edge fields, such as in high-level information encryption. Here, we provided a novel and general strategy involving handedness-selective filtration and ground-state chiral self-recovery (CSR) in double film system to address this issue. Based on this strategy, we achieved CPL switch through the reversible modulation of ground-state chirality including absorption and scattering circular dichroism (CD) signals over the full UV-visible wavelength range (365-700 nm) in a single azobenzene polymer (PAzo) film. More importantly, by flexibly changing the type of fluorescent films, it is convenient to achieve general excited-state CSR, that is reversible switching of full-color including ideal white (CIE coordinate (0.33, 0.33)), as well as room-temperature phosphorescent CPL. All these CPL signals without almost any intensity decay after three cycles of on-and-off switching. Experimental results indicated that the trans-cis isomerization and ordered rearrangement of azobenzene units in PAzo film were the fundamental reasons for realizing CPL switching. Finally, based on this system we achieved dynamic visual encryption and decryption process including multiple decryption methods. This study provides an effective method for constructing a universally applicable chiroptical switch in excited state.
2025, 36(1): 110083
doi: 10.1016/j.cclet.2024.110083
摘要:
Chloroform is a common and excellent solvent for preparing high-efficient organic solar cells (OSCs), however, it is toxic and poisonable chemical. In comparisons, deuterated chloroform (DC) is less toxic and costly, and particularly, it is non-poisonable chemical. In this paper, we use DC to replace ultra-dry chloroform (UC) as the processing solvent for preparation of active layers of organic solar cells. First, we selected PM6:BTP-eC9 as the basic binary and counted 100 solar cells' data, from which comparable device performance were obtained with use of DC and UC. Interestingly, DC showed better reproducibility, superior storage under a nitrogen atmosphere and a little better performance than UC. Both DC and UC gave rise of comparable hole and electron mobilities and similar charge recombination losses. Second, we based PM6:Y6 and D18-Cl: Y6 as the binaries and similar effects were obtained from both UC and DC when counting 30 devices for each binary. Third, the universality of the use of DC for preparing high-efficient OSCs were again checked with several binary and ternary systems. In all, this study demonstrate that DC can replace UC for use in the field of OSCs.
Chloroform is a common and excellent solvent for preparing high-efficient organic solar cells (OSCs), however, it is toxic and poisonable chemical. In comparisons, deuterated chloroform (DC) is less toxic and costly, and particularly, it is non-poisonable chemical. In this paper, we use DC to replace ultra-dry chloroform (UC) as the processing solvent for preparation of active layers of organic solar cells. First, we selected PM6:BTP-eC9 as the basic binary and counted 100 solar cells' data, from which comparable device performance were obtained with use of DC and UC. Interestingly, DC showed better reproducibility, superior storage under a nitrogen atmosphere and a little better performance than UC. Both DC and UC gave rise of comparable hole and electron mobilities and similar charge recombination losses. Second, we based PM6:Y6 and D18-Cl: Y6 as the binaries and similar effects were obtained from both UC and DC when counting 30 devices for each binary. Third, the universality of the use of DC for preparing high-efficient OSCs were again checked with several binary and ternary systems. In all, this study demonstrate that DC can replace UC for use in the field of OSCs.
2025, 36(1): 110099
doi: 10.1016/j.cclet.2024.110099
摘要:
Metal complexes hold significant promise in tumor diagnosis and treatment. However, their potential applications in photodynamic therapy (PDT) are hindered by issues such as poor photostability, low yield of reactive oxygen species (ROS), and aggregation-induced ROS quenching. To address these challenges, we present a molecular self-assembly strategy utilizing aggregation-induced emission (AIE) conjugates for metal complexes. As a proof of concept, we synthesized a mitochondrial-targeting cyclometalated Ir(III) photosensitizer Ir-TPE. This approach significantly enhances the photodynamic effect while mitigating the dark toxicity associated with AIE groups. Ir-TPE readily self-assembles into nanoaggregates in aqueous solution, leading to a significant production of ROS upon light irradiation. Photoirradiated Ir-TPE triggers multiple modes of death by excessively accumulating ROS in the mitochondria, resulting in mitochondrial DNA damage. This damage can lead to ferroptosis and autophagy, two forms of cell death that are highly cytotoxic to cancer cells. The aggregation-enhanced photodynamic effect of Ir-TPE significantly enhances the production of ROS, leading to a more pronounced cytotoxic effect. In vitro and in vivo experiments demonstrate this aggregation-enhanced PDT approach achieves effective in situ tumor eradication. This study not only addresses the limitations of metal complexes in terms of low ROS production due to aggregation but also highlights the potential of this strategy for enhancing ROS production in PDT.
Metal complexes hold significant promise in tumor diagnosis and treatment. However, their potential applications in photodynamic therapy (PDT) are hindered by issues such as poor photostability, low yield of reactive oxygen species (ROS), and aggregation-induced ROS quenching. To address these challenges, we present a molecular self-assembly strategy utilizing aggregation-induced emission (AIE) conjugates for metal complexes. As a proof of concept, we synthesized a mitochondrial-targeting cyclometalated Ir(III) photosensitizer Ir-TPE. This approach significantly enhances the photodynamic effect while mitigating the dark toxicity associated with AIE groups. Ir-TPE readily self-assembles into nanoaggregates in aqueous solution, leading to a significant production of ROS upon light irradiation. Photoirradiated Ir-TPE triggers multiple modes of death by excessively accumulating ROS in the mitochondria, resulting in mitochondrial DNA damage. This damage can lead to ferroptosis and autophagy, two forms of cell death that are highly cytotoxic to cancer cells. The aggregation-enhanced photodynamic effect of Ir-TPE significantly enhances the production of ROS, leading to a more pronounced cytotoxic effect. In vitro and in vivo experiments demonstrate this aggregation-enhanced PDT approach achieves effective in situ tumor eradication. This study not only addresses the limitations of metal complexes in terms of low ROS production due to aggregation but also highlights the potential of this strategy for enhancing ROS production in PDT.
2025, 36(1): 110123
doi: 10.1016/j.cclet.2024.110123
摘要:
In our work, polymorphism strategy has been successfully applied to tune up chromism and luminescence properties of viologen-based materials. Two polymorphs of viologen-based complexes of α-CdBr2(PHSQ)2(H2O)2 (1) and β-CdBr2(PHSQ)2(H2O)2 (2) (PHSQ = N-(4-sulfophenyl)-4,4′-bipyridinium) were synthesized by changing the solvent. They can both respond to UV light and electricity in the manner of chromism visible to the naked eye and the coloration states have good reversibility, through which an inkless erasable printing model has been established. But the coloration contrast of 1 is higher compared to 2. Meanwhile, they both exhibit photoluminescence properties and the intensity of 1 is twice that of 2, which is accompanied by photoquenching upon continuous UV light irradiation. The only divergence of disordered/ordered O atoms in the two crystalline compounds leads to significantly different chromic and luminescent properties. Further explorations simultaneously demonstrate that the different chromic performance between 1 and 2 should attribute to the alteration of stimulus-induced (light/ electricity) electron transfer channels caused by the ordered/disordered O atoms in the complexes, which is achieved through CH···O and OH···O interactions to change crystal arrangement and structural rigidity, thus affect luminescent properties.
In our work, polymorphism strategy has been successfully applied to tune up chromism and luminescence properties of viologen-based materials. Two polymorphs of viologen-based complexes of α-CdBr2(PHSQ)2(H2O)2 (1) and β-CdBr2(PHSQ)2(H2O)2 (2) (PHSQ = N-(4-sulfophenyl)-4,4′-bipyridinium) were synthesized by changing the solvent. They can both respond to UV light and electricity in the manner of chromism visible to the naked eye and the coloration states have good reversibility, through which an inkless erasable printing model has been established. But the coloration contrast of 1 is higher compared to 2. Meanwhile, they both exhibit photoluminescence properties and the intensity of 1 is twice that of 2, which is accompanied by photoquenching upon continuous UV light irradiation. The only divergence of disordered/ordered O atoms in the two crystalline compounds leads to significantly different chromic and luminescent properties. Further explorations simultaneously demonstrate that the different chromic performance between 1 and 2 should attribute to the alteration of stimulus-induced (light/ electricity) electron transfer channels caused by the ordered/disordered O atoms in the complexes, which is achieved through CH···O and OH···O interactions to change crystal arrangement and structural rigidity, thus affect luminescent properties.
2025, 36(1): 110169
doi: 10.1016/j.cclet.2024.110169
摘要:
Quantitative determination of tetracycline (TC) in environment and foods is of great importance, as excessive residues might have negative effects on human health and environmental risks. Herein, a self-powered molecularly imprinted photoelectrochemical (PEC) sensor based on the ZnO/C photoanode and the Fe-doped CuBi2O4 (CBFO) photocathode is developed for the sensitive detection of TC. The photocathodic current can be amplified by the efficient electron transfer caused by the Fermi energy level gap between the photoanode and photocathode. Furthermore, molecularly imprinted polymers (MIPs) at photocathode can selectivity identify the TC templates and thus improve the specificity. Under the optimal conditions, the sensor has a linear range of 10‒2–1.0 × 105 nmol/L, and a limit of detection (LOD) of 0.007 nmol/L (S/N = 3). More crucially, the milk sample detection is carried out using the as-prepared sensor, and the outcome is satisfactory. The research gives us a novel sensing platform for quick and accurate antibiotic (like TC) in environment and food monitoring.
Quantitative determination of tetracycline (TC) in environment and foods is of great importance, as excessive residues might have negative effects on human health and environmental risks. Herein, a self-powered molecularly imprinted photoelectrochemical (PEC) sensor based on the ZnO/C photoanode and the Fe-doped CuBi2O4 (CBFO) photocathode is developed for the sensitive detection of TC. The photocathodic current can be amplified by the efficient electron transfer caused by the Fermi energy level gap between the photoanode and photocathode. Furthermore, molecularly imprinted polymers (MIPs) at photocathode can selectivity identify the TC templates and thus improve the specificity. Under the optimal conditions, the sensor has a linear range of 10‒2–1.0 × 105 nmol/L, and a limit of detection (LOD) of 0.007 nmol/L (S/N = 3). More crucially, the milk sample detection is carried out using the as-prepared sensor, and the outcome is satisfactory. The research gives us a novel sensing platform for quick and accurate antibiotic (like TC) in environment and food monitoring.
2025, 36(1): 110174
doi: 10.1016/j.cclet.2024.110174
摘要:
Diradicaloid polycyclic hydrocarbons (PHs) own unique open-shell electronic structures and exhibit potential utility in the fields of organic electronics and spintronics. Herein, we disclose precise fusion of B/O-heterocycles onto PHs for control over their electronic structures and diradical properties. We designed and synthesized four B/O-containing diradicaloid isomers that feature the fluoreno[3,2-b]fluorene and fluoreno[2,1-a]fluorene π-skeletons, respectively. The precise B/O-heterocycle fusion modes along with the changed conjugation patterns lead to their modulated electronic structures and properties, such as diradical and aromatic structures, energy levels and band gaps, as well as magnetic, electrochemical and photophysical properties. Notably, the mode A may decrease the open-shell extent, whereas the mode B can enhance the diradical nature, leading to their well-tuned diradical characters in the range of 0.46‒0.70. Moreover, the mode A stabilizes the LUMOs and the mode B obviously increases the HOMO levels, which are remarkably contributed by the B and O atoms, respectively, further giving rise to the decreased band gaps and redshifted absorptions. This study clearly illustrates the electronic effects of B/O-heterocycle fusion on PHs and gains insight into B/O-type organic diradicaloids. These findings will provide an important guideline for the design of more fascinating heteroatom-containing diradicaloids.
Diradicaloid polycyclic hydrocarbons (PHs) own unique open-shell electronic structures and exhibit potential utility in the fields of organic electronics and spintronics. Herein, we disclose precise fusion of B/O-heterocycles onto PHs for control over their electronic structures and diradical properties. We designed and synthesized four B/O-containing diradicaloid isomers that feature the fluoreno[3,2-b]fluorene and fluoreno[2,1-a]fluorene π-skeletons, respectively. The precise B/O-heterocycle fusion modes along with the changed conjugation patterns lead to their modulated electronic structures and properties, such as diradical and aromatic structures, energy levels and band gaps, as well as magnetic, electrochemical and photophysical properties. Notably, the mode A may decrease the open-shell extent, whereas the mode B can enhance the diradical nature, leading to their well-tuned diradical characters in the range of 0.46‒0.70. Moreover, the mode A stabilizes the LUMOs and the mode B obviously increases the HOMO levels, which are remarkably contributed by the B and O atoms, respectively, further giving rise to the decreased band gaps and redshifted absorptions. This study clearly illustrates the electronic effects of B/O-heterocycle fusion on PHs and gains insight into B/O-type organic diradicaloids. These findings will provide an important guideline for the design of more fascinating heteroatom-containing diradicaloids.
2025, 36(1): 110175
doi: 10.1016/j.cclet.2024.110175
摘要:
Copper (Cu) is widely used in the electrochemical carbon dioxide reduction reaction (ECO2RR) for efficient methane (CH4) product. However, the morphology and valence of Cu-based catalysts are usually unstable under reaction conditions. In this work, we prepared Ce-doped MOF-199 precursor (Ce/HKUST-1) and further obtained nanoparticle electrocatalyst Ce/CuOx-NPs by cyclic voltammetry (CV) pretreatment. The Faradic efficiency of methane () maintains above 62% within a broad potential window of 350 mV and the maximum reaches 67.4% with a partial current density of 293 mA/cm2 at −1.6 V vs. a reversible hydrogen electrode. Catalyst characterization and theoretical calculations revealed that the unique electronic structure and large ionic radius of Cerium (Ce) not only promoted the generation of key intermediate *CO but also lowered energy barrier of the *CO to *CHO step. This study provides a novel and efficient catalyst for methane production in ECO2RR and offers profound insights into constructing high performance Cu-based catalysts.
Copper (Cu) is widely used in the electrochemical carbon dioxide reduction reaction (ECO2RR) for efficient methane (CH4) product. However, the morphology and valence of Cu-based catalysts are usually unstable under reaction conditions. In this work, we prepared Ce-doped MOF-199 precursor (Ce/HKUST-1) and further obtained nanoparticle electrocatalyst Ce/CuOx-NPs by cyclic voltammetry (CV) pretreatment. The Faradic efficiency of methane () maintains above 62% within a broad potential window of 350 mV and the maximum reaches 67.4% with a partial current density of 293 mA/cm2 at −1.6 V vs. a reversible hydrogen electrode. Catalyst characterization and theoretical calculations revealed that the unique electronic structure and large ionic radius of Cerium (Ce) not only promoted the generation of key intermediate *CO but also lowered energy barrier of the *CO to *CHO step. This study provides a novel and efficient catalyst for methane production in ECO2RR and offers profound insights into constructing high performance Cu-based catalysts.
2025, 36(1): 110204
doi: 10.1016/j.cclet.2024.110204
摘要:
Membrane electrode assembly (MEA) is widely considered to be the most promising type of electrolyzer for the practical application of electrochemical CO2 reduction reaction (CO2RR). In MEAs, a square-shaped cross-section in the flow channel is normally adopted, the configuration optimization of which could potentially enhance the performance of the electrolyzer. This paper describes the numerical simulation study on the impact of the flow-channel cross-section shapes in the MEA electrolyzer for CO2RR. The results show that wide flow channels with low heights are beneficial to the CO2RR by providing a uniform flow field of CO2, especially at high current densities. Moreover, the larger the electrolyzer, the more significant the effect is. This study provides a theoretical basis for the design of high-performance MEA electrolyzers for CO2RR.
Membrane electrode assembly (MEA) is widely considered to be the most promising type of electrolyzer for the practical application of electrochemical CO2 reduction reaction (CO2RR). In MEAs, a square-shaped cross-section in the flow channel is normally adopted, the configuration optimization of which could potentially enhance the performance of the electrolyzer. This paper describes the numerical simulation study on the impact of the flow-channel cross-section shapes in the MEA electrolyzer for CO2RR. The results show that wide flow channels with low heights are beneficial to the CO2RR by providing a uniform flow field of CO2, especially at high current densities. Moreover, the larger the electrolyzer, the more significant the effect is. This study provides a theoretical basis for the design of high-performance MEA electrolyzers for CO2RR.
2025, 36(1): 110222
doi: 10.1016/j.cclet.2024.110222
摘要:
Highly toxic phosgene, diethyl chlorophosphate (DCP) and volatile acyl chlorides endanger our life and public security. To achieve facile sensing and discrimination of multiple target analytes, herein, we presented a single fluorescent probe (BDP-CHD) for high-throughput screening of phosgene, DCP and volatile acyl chlorides. The probe underwent a covalent cascade reaction with phosgene to form boron dipyrromethene (BODIPY) with bright green fluorescence. By contrast, DCP, diphosgene and acyl chlorides can covalently assembled with the probe, giving rise to strong blue fluorescence. The probe has demonstrated high-throughput detection capability, high sensitivity, fast response (within 3 s) and parts per trillion (ppt) level detection limit. Furthermore, a portable platform based on BDP-CHD was constructed, which has achieved high-throughput discrimination of 16 analytes through linear discriminant analysis (LDA). Moreover, a smartphone adaptable RGB recognition pattern was established for the quantitative detection of multi-analytes. Therefore, this portable fluorescence sensing platform can serve as a versatile tool for rapid and high-throughput detection of toxic phosgene, DCP and volatile acyl chlorides. The proposed "one for more" strategy simplifies multi-target discrimination procedures and holds great promise for various sensing applications.
Highly toxic phosgene, diethyl chlorophosphate (DCP) and volatile acyl chlorides endanger our life and public security. To achieve facile sensing and discrimination of multiple target analytes, herein, we presented a single fluorescent probe (BDP-CHD) for high-throughput screening of phosgene, DCP and volatile acyl chlorides. The probe underwent a covalent cascade reaction with phosgene to form boron dipyrromethene (BODIPY) with bright green fluorescence. By contrast, DCP, diphosgene and acyl chlorides can covalently assembled with the probe, giving rise to strong blue fluorescence. The probe has demonstrated high-throughput detection capability, high sensitivity, fast response (within 3 s) and parts per trillion (ppt) level detection limit. Furthermore, a portable platform based on BDP-CHD was constructed, which has achieved high-throughput discrimination of 16 analytes through linear discriminant analysis (LDA). Moreover, a smartphone adaptable RGB recognition pattern was established for the quantitative detection of multi-analytes. Therefore, this portable fluorescence sensing platform can serve as a versatile tool for rapid and high-throughput detection of toxic phosgene, DCP and volatile acyl chlorides. The proposed "one for more" strategy simplifies multi-target discrimination procedures and holds great promise for various sensing applications.
2025, 36(1): 110223
doi: 10.1016/j.cclet.2024.110223
摘要:
The dysbiosis of oral microbiota contributes to diseases such as periodontitis and certain cancers by triggering the host inflammatory response. Developing methods for the immediate and sensitive identification of oral microorganism is crucial for the rapid diagnosis and early interventions of associated diseases. Traditional methods for microbial detection primarily include the plate culturing, polymerase chain reaction and enzyme-linked immunosorbent assay, which are either time-consuming or laborious. Herein, we reported a persistent luminescence-encoded multiple-channel optical sensing array and achieved the rapid and accurate identification of oral-derived microorganisms. Our results demonstrate that electrostatic attractions and hydrophobic-hydrophobic interactions dominate the binding of the persistent luminescent nanoprobes to oral microorganisms and the microbial identification process can be finished within 30 min. Specifically, a total of 7 oral-derived microorganisms demonstrate their own response patterns and were differentiated by linear discriminant analysis (LDA) with the accuracy up to 100% both in the solution and artificial saliva samples. Moreover, the persistent luminescence encoded array sensor could also discern the microorganism mixtures with the accuracy up to 100%. The proposed persistent luminescence encoding sensor arrays in this work might offer new ideas for rapid and accurate oral-derived microorganism detection, and provide new ways for disease diagnosis associated with microbial metabolism.
The dysbiosis of oral microbiota contributes to diseases such as periodontitis and certain cancers by triggering the host inflammatory response. Developing methods for the immediate and sensitive identification of oral microorganism is crucial for the rapid diagnosis and early interventions of associated diseases. Traditional methods for microbial detection primarily include the plate culturing, polymerase chain reaction and enzyme-linked immunosorbent assay, which are either time-consuming or laborious. Herein, we reported a persistent luminescence-encoded multiple-channel optical sensing array and achieved the rapid and accurate identification of oral-derived microorganisms. Our results demonstrate that electrostatic attractions and hydrophobic-hydrophobic interactions dominate the binding of the persistent luminescent nanoprobes to oral microorganisms and the microbial identification process can be finished within 30 min. Specifically, a total of 7 oral-derived microorganisms demonstrate their own response patterns and were differentiated by linear discriminant analysis (LDA) with the accuracy up to 100% both in the solution and artificial saliva samples. Moreover, the persistent luminescence encoded array sensor could also discern the microorganism mixtures with the accuracy up to 100%. The proposed persistent luminescence encoding sensor arrays in this work might offer new ideas for rapid and accurate oral-derived microorganism detection, and provide new ways for disease diagnosis associated with microbial metabolism.
2025, 36(1): 110232
doi: 10.1016/j.cclet.2024.110232
摘要:
Rational design of viable routes to obtain efficient and stable oxygen evolution reaction (OER) electrocatalysts remains challenging, especially under industrial conditions. Here, we provide a solvent-steam assisted corrosion engineering strategy to directly fabricate high-entropy NiFe-LDH with spatially resolved structural order. Ammonium fluoride in methanol steam enables the formation of nanosheets while Fe3+ effectively enhances their adhesion to the semi-sacrificial nickel-iron foam (NFF), thereby conjuring up a NiFe-LDH@NFF catalyst that exhibits remarkable adaptability to robust electrochemical activation yet with excellent stability. Comprehensive measurements reveal the in-situ formation of high-valance metal oxyhydroxide and the enhancement of adsorption-desorption process. Under the industrial condition (6 mol/L KOH, 60 ℃), the NiFe-LDH@NFF exhibits excellent activity of 50 mA/cm2 at 1.55 V and high durability of over 120 h at 200 mA/cm2. We anticipate that the steam assisted strategy could promote the development of efficient non-precious electrocatalysts for hydrogen energy.
Rational design of viable routes to obtain efficient and stable oxygen evolution reaction (OER) electrocatalysts remains challenging, especially under industrial conditions. Here, we provide a solvent-steam assisted corrosion engineering strategy to directly fabricate high-entropy NiFe-LDH with spatially resolved structural order. Ammonium fluoride in methanol steam enables the formation of nanosheets while Fe3+ effectively enhances their adhesion to the semi-sacrificial nickel-iron foam (NFF), thereby conjuring up a NiFe-LDH@NFF catalyst that exhibits remarkable adaptability to robust electrochemical activation yet with excellent stability. Comprehensive measurements reveal the in-situ formation of high-valance metal oxyhydroxide and the enhancement of adsorption-desorption process. Under the industrial condition (6 mol/L KOH, 60 ℃), the NiFe-LDH@NFF exhibits excellent activity of 50 mA/cm2 at 1.55 V and high durability of over 120 h at 200 mA/cm2. We anticipate that the steam assisted strategy could promote the development of efficient non-precious electrocatalysts for hydrogen energy.
2025, 36(1): 110233
doi: 10.1016/j.cclet.2024.110233
摘要:
Benzotriazole (BTA)-based A2-A1-D-A1-A2 type wide-bandgap (WBG) non-fullerene acceptors (NFAs) have shown promising potential in indoor photovoltaic, and in-depth investigation of their structure-property relationship is of great significance. Herein, we explored the chlorination effect of the side chain on the terminals. We introduced Cl atoms into the benzyl side chains in parent BTA5 to synthesize two NFAs, BTA5-Cl with mono-chlorinated benzyl groups and BTA5-2Cl containing bi-chlorinated benzyl groups. We chose D18-Cl with deep-energy levels and strong crystallinity to pair with these three acceptors, affording high photovoltage and photocurrent. With the stepwise chlorination, the open-circuit voltage (VOC) values decrease from 1.28, 1.22, to 1.20 V, while the corresponding power conversion efficiencies (PCEs) improve from 5.07%, 9.15%, to 10.96%. Compared with BTA5-based OSCs, introducing Cl atoms downshifts the energy levels and slightly increases the non-radiative energy loss (0.14 < 0.17 < 0.19 eV), resulting in a sequential decrease in VOC. However, more chlorine atom replacements produce more effective exciton dissociation, higher charge transfer, and balanced carrier mobility in the blend films, ultimately achieving better PCEs. This work indicates that chlorination of the benzyl group on the terminals can improve the device's performance, implying good application potential in indoor photovoltaics.
Benzotriazole (BTA)-based A2-A1-D-A1-A2 type wide-bandgap (WBG) non-fullerene acceptors (NFAs) have shown promising potential in indoor photovoltaic, and in-depth investigation of their structure-property relationship is of great significance. Herein, we explored the chlorination effect of the side chain on the terminals. We introduced Cl atoms into the benzyl side chains in parent BTA5 to synthesize two NFAs, BTA5-Cl with mono-chlorinated benzyl groups and BTA5-2Cl containing bi-chlorinated benzyl groups. We chose D18-Cl with deep-energy levels and strong crystallinity to pair with these three acceptors, affording high photovoltage and photocurrent. With the stepwise chlorination, the open-circuit voltage (VOC) values decrease from 1.28, 1.22, to 1.20 V, while the corresponding power conversion efficiencies (PCEs) improve from 5.07%, 9.15%, to 10.96%. Compared with BTA5-based OSCs, introducing Cl atoms downshifts the energy levels and slightly increases the non-radiative energy loss (0.14 < 0.17 < 0.19 eV), resulting in a sequential decrease in VOC. However, more chlorine atom replacements produce more effective exciton dissociation, higher charge transfer, and balanced carrier mobility in the blend films, ultimately achieving better PCEs. This work indicates that chlorination of the benzyl group on the terminals can improve the device's performance, implying good application potential in indoor photovoltaics.
2025, 36(1): 110235
doi: 10.1016/j.cclet.2024.110235
摘要:
The high conductivity of electrocatalyst can eliminate the Schottky energy barrier at the interface of heterogeneous phases during an electrocatalytic reaction and accelerate the rapid electron transfer to the catalytic active center. Therefore, the electronic conductivity is a vital parameter for oxygen reduction reaction (ORR). Covalent triazine frameworks (CTFs) have shown great potential application as electrocatalysts in ORR with a merit of the diverse building blocks. However, the intrinsic low conductivity and high impedance of CTFs could be significant setbacks in electrocatalytic application. Herein, CTFs were constructed by introducing F and N co-modification for efficient 2e− ORR. Compared with the pristine CTF, the co-presence of F, N could increase the conductivity obviously by 1000-fold. As a result, F-N-CTF exhibits enhanced catalytic performance of H2O2 generation and selectivity towards reaction pathways. This work reveals the importance of conductivity optimization for CTFs and provides guidance for designing high conductivity non-metallic organic semiconductor catalysts for 2e− ORR.
The high conductivity of electrocatalyst can eliminate the Schottky energy barrier at the interface of heterogeneous phases during an electrocatalytic reaction and accelerate the rapid electron transfer to the catalytic active center. Therefore, the electronic conductivity is a vital parameter for oxygen reduction reaction (ORR). Covalent triazine frameworks (CTFs) have shown great potential application as electrocatalysts in ORR with a merit of the diverse building blocks. However, the intrinsic low conductivity and high impedance of CTFs could be significant setbacks in electrocatalytic application. Herein, CTFs were constructed by introducing F and N co-modification for efficient 2e− ORR. Compared with the pristine CTF, the co-presence of F, N could increase the conductivity obviously by 1000-fold. As a result, F-N-CTF exhibits enhanced catalytic performance of H2O2 generation and selectivity towards reaction pathways. This work reveals the importance of conductivity optimization for CTFs and provides guidance for designing high conductivity non-metallic organic semiconductor catalysts for 2e− ORR.
2025, 36(1): 110236
doi: 10.1016/j.cclet.2024.110236
摘要:
The synthesis of polyurethanes (PUs) from the reaction of low molecular weight poly(ethylene carbonate) diol (PECD) is rarely investigated. This work reports a novel PU with excellent mechanical properties from the solution polymerization of 4,4′-diphenylmethane diisocyanate (MDI) with PECD that was derived from the copolymerization of carbon dioxide (CO2) and ethylene oxide (EO). The tensile strength, the elongation at break and 300% constant tensile strength of the PECD-PU were up to 66 ± 2 MPa, 880% ± 50% and 13 MPa, respectively, higher than the control PUs from the reaction of MDI with commercial polyethers or polyesters. The PECD-PU with high CO2 carbonate content exhibited good solvent resistance and chemical stability. Of importance, the mechanical properties and chemical resistance of PECD-PU were significantly enhanced with the increasing content of CO2, i.e., the carbonate unit in PECD. This work provides comprehensive properties of PECD-derived PUs, indicating that PECD is a competitive precursor for the preparation of PU and has broad application prospects.
The synthesis of polyurethanes (PUs) from the reaction of low molecular weight poly(ethylene carbonate) diol (PECD) is rarely investigated. This work reports a novel PU with excellent mechanical properties from the solution polymerization of 4,4′-diphenylmethane diisocyanate (MDI) with PECD that was derived from the copolymerization of carbon dioxide (CO2) and ethylene oxide (EO). The tensile strength, the elongation at break and 300% constant tensile strength of the PECD-PU were up to 66 ± 2 MPa, 880% ± 50% and 13 MPa, respectively, higher than the control PUs from the reaction of MDI with commercial polyethers or polyesters. The PECD-PU with high CO2 carbonate content exhibited good solvent resistance and chemical stability. Of importance, the mechanical properties and chemical resistance of PECD-PU were significantly enhanced with the increasing content of CO2, i.e., the carbonate unit in PECD. This work provides comprehensive properties of PECD-derived PUs, indicating that PECD is a competitive precursor for the preparation of PU and has broad application prospects.
2025, 36(1): 110279
doi: 10.1016/j.cclet.2024.110279
摘要:
Atomically precise metal nanoclusters (NCs) have been deemed as a new generation of metal nanomaterials in the field of solar energy conversion due to their unique atomic stacking manner, quantum confinement effects, light-harvesting capability and multitude of active sites. Nonetheless, wide-spread application of monometallic NCs is blocked by the ultrashort carrier lifespan, uncontrollable charge transport pathway, and light-induced poor stability, impeding the construction of robust and stable metal NC-based photosystems. Herein, we report the fabrication of stable alloy (Au1-xPtx) NCs photosystem, for which tailor-made negatively charged l-glutathione (GSH)-capped Au1-xPtx NCs as the building blocks are controllably deposited on the BiVO4 (BVO) by a self-assembly approach for steering enhanced light absorption and interfacial charge transfer over alloy NCs-based photoanodes (Au1-xPtx/BVO). The self-assembled Au1-xPtx/BVO composite photoanode exhibits the significantly enhanced photoelectrochemical water oxidation performances compared with pristine BVO and Aux/BVO photoanodes, which is caused by the Pt atom doping into the Aux NCs for elevating photosensitivity and boosting the stability. The synergy of Au and Pt atoms in alloy NCs protects the gold core from rapid oxidation, improving the photostability and accelerating the surface charge transfer kinetics. Our work would significantly inspire ongoing interest in unlocking the charge transport characteristics of atomically precise alloy NCs for solar energy conversion.
Atomically precise metal nanoclusters (NCs) have been deemed as a new generation of metal nanomaterials in the field of solar energy conversion due to their unique atomic stacking manner, quantum confinement effects, light-harvesting capability and multitude of active sites. Nonetheless, wide-spread application of monometallic NCs is blocked by the ultrashort carrier lifespan, uncontrollable charge transport pathway, and light-induced poor stability, impeding the construction of robust and stable metal NC-based photosystems. Herein, we report the fabrication of stable alloy (Au1-xPtx) NCs photosystem, for which tailor-made negatively charged l-glutathione (GSH)-capped Au1-xPtx NCs as the building blocks are controllably deposited on the BiVO4 (BVO) by a self-assembly approach for steering enhanced light absorption and interfacial charge transfer over alloy NCs-based photoanodes (Au1-xPtx/BVO). The self-assembled Au1-xPtx/BVO composite photoanode exhibits the significantly enhanced photoelectrochemical water oxidation performances compared with pristine BVO and Aux/BVO photoanodes, which is caused by the Pt atom doping into the Aux NCs for elevating photosensitivity and boosting the stability. The synergy of Au and Pt atoms in alloy NCs protects the gold core from rapid oxidation, improving the photostability and accelerating the surface charge transfer kinetics. Our work would significantly inspire ongoing interest in unlocking the charge transport characteristics of atomically precise alloy NCs for solar energy conversion.
2025, 36(1): 110288
doi: 10.1016/j.cclet.2024.110288
摘要:
Photocatalytic overall pure water splitting is a promising method for generating green hydrogen energy under mild conditions. However, this process is often hindered by sluggish electron-hole separation and transport. To address this, a step-scheme (S-scheme) B-doped N-deficient C3N4/O-doped C3N5 (BN-C3N4/O-C3N5) heterojunction with interfacial B-O bonds has been constructed. Utilizing Pt and Co(OH)2 as co-catalysts, BN-C3N4/O-C3N5 S-scheme heterojunction demonstrates significantly enhanced photocatalytic activity for overall pure water splitting under visible light, achieving H2 and O2 evolution rates of 40.12 and 19.62 µmol/h, respectively. Systematic characterizations and experiments revealed the performance-enhancing effects of the enhanced built-in electric field and the interfacial B-O bonding. Firstly, the strengthened built-in electric field provides sufficient force for rapid interfacial electron transport. Secondly, by reducing the transport energy barrier and transfer distance, the interfacial B-O bonds facilitate rapid recombination of electrons and holes with relatively low redox potential via the S-scheme charge-transfer route, leaving the high-potential electrons and holes available for H+ reduction and OH− oxidation reactions. Overall, the photocatalytic efficiency of BN-C3N4/O-C3N5 S-scheme heterojunction was significantly improved, making it a promising approach for green hydrogen production through overall pure water splitting.
Photocatalytic overall pure water splitting is a promising method for generating green hydrogen energy under mild conditions. However, this process is often hindered by sluggish electron-hole separation and transport. To address this, a step-scheme (S-scheme) B-doped N-deficient C3N4/O-doped C3N5 (BN-C3N4/O-C3N5) heterojunction with interfacial B-O bonds has been constructed. Utilizing Pt and Co(OH)2 as co-catalysts, BN-C3N4/O-C3N5 S-scheme heterojunction demonstrates significantly enhanced photocatalytic activity for overall pure water splitting under visible light, achieving H2 and O2 evolution rates of 40.12 and 19.62 µmol/h, respectively. Systematic characterizations and experiments revealed the performance-enhancing effects of the enhanced built-in electric field and the interfacial B-O bonding. Firstly, the strengthened built-in electric field provides sufficient force for rapid interfacial electron transport. Secondly, by reducing the transport energy barrier and transfer distance, the interfacial B-O bonds facilitate rapid recombination of electrons and holes with relatively low redox potential via the S-scheme charge-transfer route, leaving the high-potential electrons and holes available for H+ reduction and OH− oxidation reactions. Overall, the photocatalytic efficiency of BN-C3N4/O-C3N5 S-scheme heterojunction was significantly improved, making it a promising approach for green hydrogen production through overall pure water splitting.
2025, 36(1): 110289
doi: 10.1016/j.cclet.2024.110289
摘要:
Precise tumor targeting and therapy is a major trend in cancer treatment. Herein, we designed a tumor acidic microenvironment activatable drug loaded DNA nanostructure, in which, we made a clever use of the sequences of AS1411 and i-motif, which can partially hybridize, and designed a simple while robust DNA d-strand nanostructure, in which, i-motif sequence was designed to regulate the binding ability of the AS1411 aptamer to target tumor. In the normal physiological environment, i-motif inhibits the targeting ability of AS1411. In the acidic tumor microenvironment, i-motif forms a quadruplex conformation and dissociates from AS1411, restoring the targeting ability of AS1411. Only when acidic condition and tumor cell receptor are present, this nanostructure can be internalized by the tumor cells. Moreover, the structure change of this nanostructure can realize the release of loaded drug. This drug loaded A-I-Duplex DNA structure showed cancer cell and spheroid targeting and inhibition ability, which is promising in the clinical cancer therapy.
Precise tumor targeting and therapy is a major trend in cancer treatment. Herein, we designed a tumor acidic microenvironment activatable drug loaded DNA nanostructure, in which, we made a clever use of the sequences of AS1411 and i-motif, which can partially hybridize, and designed a simple while robust DNA d-strand nanostructure, in which, i-motif sequence was designed to regulate the binding ability of the AS1411 aptamer to target tumor. In the normal physiological environment, i-motif inhibits the targeting ability of AS1411. In the acidic tumor microenvironment, i-motif forms a quadruplex conformation and dissociates from AS1411, restoring the targeting ability of AS1411. Only when acidic condition and tumor cell receptor are present, this nanostructure can be internalized by the tumor cells. Moreover, the structure change of this nanostructure can realize the release of loaded drug. This drug loaded A-I-Duplex DNA structure showed cancer cell and spheroid targeting and inhibition ability, which is promising in the clinical cancer therapy.
2025, 36(1): 110299
doi: 10.1016/j.cclet.2024.110299
摘要:
In this work, we developed plasmonic photocatalyst composed of CuPd alloy nanoparticles supported on TiN, the optimized Cu3Pd2/TiN catalyst shows excellent conversion (> 96%) and selectivity (> 99%) for Heck reaction at 50 ℃ under visible light irradiation. By in-situ spectroscopic investigations, we find that visible light excitation could achieve stable metallic Cu species on the surface of CuPd alloy nanoparticles, thereby eliminating the inevitable surface oxides of Cu based catalyst. The in-situ formed metallic Cu species under irradiation take advantage of the strong interactions of Cu with visible light, and manifest in the localized surface plasmon resonances (LSPR) photoexcitation. Visible light excitation could further promote the charge transfer between catalytic Pd component and the support TiN, resulting in electron-rich Pd sites on CuPd/TiN. Moreover, light excitation on CuPd/TiN generates strong chemisorption of iodobenzene and styrene, favoring the activation of reactants for Heck reaction. DFT calculations suggest that electron-rich CuPd sites ideally lower the activation energy barrier for the coupling reaction. This work provides valuable insights for mechanistic understanding of plasmonic photocatalysis.
In this work, we developed plasmonic photocatalyst composed of CuPd alloy nanoparticles supported on TiN, the optimized Cu3Pd2/TiN catalyst shows excellent conversion (> 96%) and selectivity (> 99%) for Heck reaction at 50 ℃ under visible light irradiation. By in-situ spectroscopic investigations, we find that visible light excitation could achieve stable metallic Cu species on the surface of CuPd alloy nanoparticles, thereby eliminating the inevitable surface oxides of Cu based catalyst. The in-situ formed metallic Cu species under irradiation take advantage of the strong interactions of Cu with visible light, and manifest in the localized surface plasmon resonances (LSPR) photoexcitation. Visible light excitation could further promote the charge transfer between catalytic Pd component and the support TiN, resulting in electron-rich Pd sites on CuPd/TiN. Moreover, light excitation on CuPd/TiN generates strong chemisorption of iodobenzene and styrene, favoring the activation of reactants for Heck reaction. DFT calculations suggest that electron-rich CuPd sites ideally lower the activation energy barrier for the coupling reaction. This work provides valuable insights for mechanistic understanding of plasmonic photocatalysis.
2025, 36(1): 110313
doi: 10.1016/j.cclet.2024.110313
摘要:
In-situ enhanced bioreduction by functional materials is a cost-effective technology to remove chlorinated hydrocarbons in groundwater. Herein, a novel polydopamine (PDA)-modified biochar (BC)-based composite containing nanoscale zero-valent iron (nZVI) and poly-l-lactic acid (PLLA) (PB-PDA-Fe) was synthesized to enhance the removal of 1,1,1-trichloroethane (1,1,1-TCA) in simulated groundwater with actual site sediments. Its impact on functional microbial community structure in system was also investigated. The typical characterizations revealed uniform dispersion of PLA and nZVI particles on the BC surface, being smoother after PDA coating. The composite exhibited a significantly higher performance on 1,1,1-TCA removal (82.38%, initial concentration 100 mg/L) than Fe-PDA and PB-PDA treatments. The diversity and richness of the microbial community in the composite treatment consistently decreased during incubation due to a synergistic effect between PLLA-BC and nZVI. Desulfitobaterium, Pedobacter, Sphaerochaeta, Shewanella, and Clostridium were identified as enriched genera by the composite through DNA-stable isotope probing (DNA-SIP), playing a crucial role in the bioreductive dechlorination process. All the above results demonstrate that this novel composite selectively enhances the activity of microorganisms with extracellular respiration functions to efficiently dechlorinate 1,1,1-TCA. These findings could contribute to understanding the responsive microbial community by carbon-iron composites and expedite the application of in-situ enhanced bioreduction for effective remediation of chlorinated hydrocarbon-contaminated groundwater.
In-situ enhanced bioreduction by functional materials is a cost-effective technology to remove chlorinated hydrocarbons in groundwater. Herein, a novel polydopamine (PDA)-modified biochar (BC)-based composite containing nanoscale zero-valent iron (nZVI) and poly-l-lactic acid (PLLA) (PB-PDA-Fe) was synthesized to enhance the removal of 1,1,1-trichloroethane (1,1,1-TCA) in simulated groundwater with actual site sediments. Its impact on functional microbial community structure in system was also investigated. The typical characterizations revealed uniform dispersion of PLA and nZVI particles on the BC surface, being smoother after PDA coating. The composite exhibited a significantly higher performance on 1,1,1-TCA removal (82.38%, initial concentration 100 mg/L) than Fe-PDA and PB-PDA treatments. The diversity and richness of the microbial community in the composite treatment consistently decreased during incubation due to a synergistic effect between PLLA-BC and nZVI. Desulfitobaterium, Pedobacter, Sphaerochaeta, Shewanella, and Clostridium were identified as enriched genera by the composite through DNA-stable isotope probing (DNA-SIP), playing a crucial role in the bioreductive dechlorination process. All the above results demonstrate that this novel composite selectively enhances the activity of microorganisms with extracellular respiration functions to efficiently dechlorinate 1,1,1-TCA. These findings could contribute to understanding the responsive microbial community by carbon-iron composites and expedite the application of in-situ enhanced bioreduction for effective remediation of chlorinated hydrocarbon-contaminated groundwater.
2025, 36(1): 110314
doi: 10.1016/j.cclet.2024.110314
摘要:
Disulfidptosis, a novel mechanism of programmed cell death through the disruption of tumor metabolic symbiosis (TMS), has showed tremendous potential in cancer therapy. However, the efficacy of disulfidptosis is limited by poor permeability of drugs in solid tumors. Herein, hydrogen sulfide (H2S) and near-infrared (NIR) light-driven nanomotors (denoted as HGPP) have been constructed to efficiently penetrate tumors and induce disulfidptosis. HGPP demonstrate glutathione (GSH)-responsive release of H2S, which combined with NIR light-induced photothermal effect drive HGPP movement to facilitate deep tumor penetration. The released H2S induces tumor acidosis and disrupts TMS, where disulfide accumulation following cell starvation leads to disulfidptosis. In addition, HGPP induce hepatoma specific cellular uptake and catalyze the conversion of glucose and oxygen to produce hydrogen peroxide (H2O2), leading to glucose starvation. Overall, this study has developed a multifunctional Janus nanomotor that provides a novel strategy for disulfidptosis-based solid tumor therapy.
Disulfidptosis, a novel mechanism of programmed cell death through the disruption of tumor metabolic symbiosis (TMS), has showed tremendous potential in cancer therapy. However, the efficacy of disulfidptosis is limited by poor permeability of drugs in solid tumors. Herein, hydrogen sulfide (H2S) and near-infrared (NIR) light-driven nanomotors (denoted as HGPP) have been constructed to efficiently penetrate tumors and induce disulfidptosis. HGPP demonstrate glutathione (GSH)-responsive release of H2S, which combined with NIR light-induced photothermal effect drive HGPP movement to facilitate deep tumor penetration. The released H2S induces tumor acidosis and disrupts TMS, where disulfide accumulation following cell starvation leads to disulfidptosis. In addition, HGPP induce hepatoma specific cellular uptake and catalyze the conversion of glucose and oxygen to produce hydrogen peroxide (H2O2), leading to glucose starvation. Overall, this study has developed a multifunctional Janus nanomotor that provides a novel strategy for disulfidptosis-based solid tumor therapy.
2025, 36(1): 110351
doi: 10.1016/j.cclet.2024.110351
摘要:
Gastric Carcinoma (GC) is a highly fatal malignant tumor with a poor prognosis. Its elevated mortality rates are primarily due to its proclivity for late-stage metastasis. Exploring the metabolic interactions between tumor microenvironment and the systemic bloodstream could help to clearly understand the mechanisms and identify precise biomarkers of tumor growth, proliferation, and metastasis. In this study, an integrative approach that combines plasma metabolomics with mass spectrometry imaging of tumor tissue was developed to investigate the global metabolic landscape of GC tumorigenesis and metastasis. The results showed that the oxidized glutathione to glutathione ratio (GSSH/GSH) became increased in non-distal metastatic GC (M0), which means an accumulation of oxidative stress in tumor tissues. Furthermore, it was found that the peroxidation of polyunsaturated fatty acids, such as 9,10-EpOMe, 9-HOTrE, etc., were accelerated in both plasma and tumor tissues of distal metastatic GC (M1). These changes were further confirmed the potential effect of CYP2E1 and GGT1 in metastatic potential of GC by mass spectrometry imaging (MSI) and immunohistochemistry (IHC). Collectively, our findings reveal the integrated multidimensional metabolomics approach is a clinical useful method to unravel the blood-tumor metabolic crosstalk, illuminate reprogrammed metabolic networks, and provide reliable circulating biomarkers.
Gastric Carcinoma (GC) is a highly fatal malignant tumor with a poor prognosis. Its elevated mortality rates are primarily due to its proclivity for late-stage metastasis. Exploring the metabolic interactions between tumor microenvironment and the systemic bloodstream could help to clearly understand the mechanisms and identify precise biomarkers of tumor growth, proliferation, and metastasis. In this study, an integrative approach that combines plasma metabolomics with mass spectrometry imaging of tumor tissue was developed to investigate the global metabolic landscape of GC tumorigenesis and metastasis. The results showed that the oxidized glutathione to glutathione ratio (GSSH/GSH) became increased in non-distal metastatic GC (M0), which means an accumulation of oxidative stress in tumor tissues. Furthermore, it was found that the peroxidation of polyunsaturated fatty acids, such as 9,10-EpOMe, 9-HOTrE, etc., were accelerated in both plasma and tumor tissues of distal metastatic GC (M1). These changes were further confirmed the potential effect of CYP2E1 and GGT1 in metastatic potential of GC by mass spectrometry imaging (MSI) and immunohistochemistry (IHC). Collectively, our findings reveal the integrated multidimensional metabolomics approach is a clinical useful method to unravel the blood-tumor metabolic crosstalk, illuminate reprogrammed metabolic networks, and provide reliable circulating biomarkers.
2025, 36(1): 110385
doi: 10.1016/j.cclet.2024.110385
摘要:
Ethylene carbonate (EC) is the conventional and promising solvent to achieve high energy lithium metal battery. However, the innate low energy level of lowest unoccupied molecular orbital (LUMO) in EC makes it incompatible with lithium metal, causing uncontrolled lithium growth and low Coulombic efficiency (CE). Herein, we introduced bis(2,2,2-trifluoroethyl) carbonate (TFEC), a carbonate with a strong electron-withdrawing effect (-CF3), which enhances the stability of EC at electrode interface by reducing ion-dipole interactions between Li+ and EC. As the interaction between Li and EC weakens, TFEC and more PF6− anions coordinate with Li+, promoting the formation of contact ion pairs (CIPs) and aggregates (AGGs), thereby increasing the inorganic composition within the solid electrolyte interphase. Additionally, the distinct solvated sheath structure favors the decomposition of fluorinated solvents and PF6− anions, forming inorganic-rich electrode-electrolyte interfaces (SEI and CEI), thereby ensuring high stability for both the Li anode and high-voltage cathode. Hence, when applied in the full-cell LiLiMn0.8Fe0.2PO4, it displays consistent cycling performance, exhibiting minimal capacity decay with a retention rate of 62.5% after 800 cycles, substantially surpassing that of cells using base electrolytes (29.8%).
Ethylene carbonate (EC) is the conventional and promising solvent to achieve high energy lithium metal battery. However, the innate low energy level of lowest unoccupied molecular orbital (LUMO) in EC makes it incompatible with lithium metal, causing uncontrolled lithium growth and low Coulombic efficiency (CE). Herein, we introduced bis(2,2,2-trifluoroethyl) carbonate (TFEC), a carbonate with a strong electron-withdrawing effect (-CF3), which enhances the stability of EC at electrode interface by reducing ion-dipole interactions between Li+ and EC. As the interaction between Li and EC weakens, TFEC and more PF6− anions coordinate with Li+, promoting the formation of contact ion pairs (CIPs) and aggregates (AGGs), thereby increasing the inorganic composition within the solid electrolyte interphase. Additionally, the distinct solvated sheath structure favors the decomposition of fluorinated solvents and PF6− anions, forming inorganic-rich electrode-electrolyte interfaces (SEI and CEI), thereby ensuring high stability for both the Li anode and high-voltage cathode. Hence, when applied in the full-cell LiLiMn0.8Fe0.2PO4, it displays consistent cycling performance, exhibiting minimal capacity decay with a retention rate of 62.5% after 800 cycles, substantially surpassing that of cells using base electrolytes (29.8%).
2025, 36(1): 110452
doi: 10.1016/j.cclet.2024.110452
摘要:
Flexible energy storage devices have been paid much attention and adapts to apply in various fields. Benefiting from the active sites of boron (B) and phosphorus (P) doping materials, co-doped carbon materials are widely used in energy storage devices for the enhanced electrochemical performance. Herein, B and P co-doped flexible carbon nanofibers with nitrogen-rich (B-P/NC) are investigated with electrospinning for sodium-ion battery. The flexible of binderless B-P/NC with annealing of 600 ℃ (B-P/NC-600) exhibits the remarkable performance for the robust capacity of 200 mAh/g at 0.1 A/g after 500 cycles and a durable reversible capacity of 160 mAh/g even at 1 A/g after 12, 000 cycles, exhibiting the equally commendable stability of flexible B-P/NC-600. In addition, B-P/NC-600 delivers the reversible capacity of 265 mAh/g with the test temperature of 60 ℃. More importantly, the flexible B-P/NC-600 is fabricated as anode for the whole battery, delivering the capacity of 90 mAh/g at 1 A/g after 200 cycles. Meanwhile, theoretical calculation further verified that boron and phosphorus co-doping can improve the adsorption capacity of nitrogen carbon materials. The favorable performance of flexible B-P/NC-600 can be ascribed to the nitrogen-rich carbon nanofibers with three-dimensional network matrix for the more active site of boron and phosphorus co-doping. Our work paves the way for the improvement of flexible anodes and wide-operating temperature of sodium-ion batteries by doping approach of much heteroatom.
Flexible energy storage devices have been paid much attention and adapts to apply in various fields. Benefiting from the active sites of boron (B) and phosphorus (P) doping materials, co-doped carbon materials are widely used in energy storage devices for the enhanced electrochemical performance. Herein, B and P co-doped flexible carbon nanofibers with nitrogen-rich (B-P/NC) are investigated with electrospinning for sodium-ion battery. The flexible of binderless B-P/NC with annealing of 600 ℃ (B-P/NC-600) exhibits the remarkable performance for the robust capacity of 200 mAh/g at 0.1 A/g after 500 cycles and a durable reversible capacity of 160 mAh/g even at 1 A/g after 12, 000 cycles, exhibiting the equally commendable stability of flexible B-P/NC-600. In addition, B-P/NC-600 delivers the reversible capacity of 265 mAh/g with the test temperature of 60 ℃. More importantly, the flexible B-P/NC-600 is fabricated as anode for the whole battery, delivering the capacity of 90 mAh/g at 1 A/g after 200 cycles. Meanwhile, theoretical calculation further verified that boron and phosphorus co-doping can improve the adsorption capacity of nitrogen carbon materials. The favorable performance of flexible B-P/NC-600 can be ascribed to the nitrogen-rich carbon nanofibers with three-dimensional network matrix for the more active site of boron and phosphorus co-doping. Our work paves the way for the improvement of flexible anodes and wide-operating temperature of sodium-ion batteries by doping approach of much heteroatom.
2025, 36(1): 110491
doi: 10.1016/j.cclet.2024.110491
摘要:
Herein, vacancy engineering is utilized reasonably to explore molybdenum tungsten oxide nanowires (W4MoO3 NWs) rich in O-vacancies as an advanced electrochemical nitrogen reduction reaction (eNRR) electrocatalyst, realizing further enhancement of NRR performance. In 0.1 mol/L Na2SO4, W4MoO3 NWs rich in O vacancies (CTAB-D-W4MoO3) achieve a large NH3 yield of 60.77 µg h-1 mg-1cat. at -0.70 V vs. RHE and a high faradaic efficiency of 56.42% at -0.60 V, much superior to the W4MoO3 NWs deficient in oxygen vacancies (20.26 µg h-1 mg-1cat. and 17.1% at -0.70 V vs. RHE). Meanwhile, W4MoO3 NWs rich in O-vacancies also show high electrochemical stability. Density functional theory (DFT) calculations present that O vacancies in CTAB-D-W4MoO3 reduce the energy barrier formed by the intermediate of *N-NH, facilitate the activation and further hydrogenation of *N-N, promote the NRR process, and improve NRR activity.
Herein, vacancy engineering is utilized reasonably to explore molybdenum tungsten oxide nanowires (W4MoO3 NWs) rich in O-vacancies as an advanced electrochemical nitrogen reduction reaction (eNRR) electrocatalyst, realizing further enhancement of NRR performance. In 0.1 mol/L Na2SO4, W4MoO3 NWs rich in O vacancies (CTAB-D-W4MoO3) achieve a large NH3 yield of 60.77 µg h-1 mg-1cat. at -0.70 V vs. RHE and a high faradaic efficiency of 56.42% at -0.60 V, much superior to the W4MoO3 NWs deficient in oxygen vacancies (20.26 µg h-1 mg-1cat. and 17.1% at -0.70 V vs. RHE). Meanwhile, W4MoO3 NWs rich in O-vacancies also show high electrochemical stability. Density functional theory (DFT) calculations present that O vacancies in CTAB-D-W4MoO3 reduce the energy barrier formed by the intermediate of *N-NH, facilitate the activation and further hydrogenation of *N-N, promote the NRR process, and improve NRR activity.
2025, 36(1): 109557
doi: 10.1016/j.cclet.2024.109557
摘要:
Available online Alkaline water electrolysis (AWE) is a prominent technique for obtaining a sustainable hydrogen source and effectively managing the energy infrastructure. Noble metal-based electrocatalysts, owing to their exceptional hydrogen binding energy, exhibit remarkable catalytic activity and long-term stability in the hydrogen evolution reaction (HER). However, the restricted accessibility and exorbitant cost of noble-metal materials pose obstacles to their extensive adoption in industrial contexts. This review investigates strategies aimed at reducing the dependence on noble-metal electrocatalysts and developing a cost-effective alkaline HER catalyst, while considering the principles of sustainable development. The initial discussion covers the fundamental principle of HER, followed by an overview of prevalent techniques for synthesizing catalysts based on noble metals, along with a thorough examination of recent advancements. The subsequent discussion focuses on the strategies employed to improve noble metal-based catalysts, including enhancing the intrinsic activity at active sites and increasing the quantity of active sites. Ultimately, this investigation concludes by examining the present state and future direction of research in the field of electrocatalysis for the HER.
Available online Alkaline water electrolysis (AWE) is a prominent technique for obtaining a sustainable hydrogen source and effectively managing the energy infrastructure. Noble metal-based electrocatalysts, owing to their exceptional hydrogen binding energy, exhibit remarkable catalytic activity and long-term stability in the hydrogen evolution reaction (HER). However, the restricted accessibility and exorbitant cost of noble-metal materials pose obstacles to their extensive adoption in industrial contexts. This review investigates strategies aimed at reducing the dependence on noble-metal electrocatalysts and developing a cost-effective alkaline HER catalyst, while considering the principles of sustainable development. The initial discussion covers the fundamental principle of HER, followed by an overview of prevalent techniques for synthesizing catalysts based on noble metals, along with a thorough examination of recent advancements. The subsequent discussion focuses on the strategies employed to improve noble metal-based catalysts, including enhancing the intrinsic activity at active sites and increasing the quantity of active sites. Ultimately, this investigation concludes by examining the present state and future direction of research in the field of electrocatalysis for the HER.
2025, 36(1): 109684
doi: 10.1016/j.cclet.2024.109684
摘要:
As the global population ages, osteoporotic bone fractures leading to bone defects are increasingly becoming a significant challenge in the field of public health. Treating this disease faces many challenges, especially in the context of an imbalance between osteoblast and osteoclast activities. Therefore, the development of new biomaterials has become the key. This article reviews various design strategies and their advantages and disadvantages for biomaterials aimed at osteoporotic bone defects. Overall, current research progress indicates that innovative design, functionalization, and targeting of materials can significantly enhance bone regeneration under osteoporotic conditions. By comprehensively considering biocompatibility, mechanical properties, and bioactivity, these biomaterials can be further optimized, offering a range of choices and strategies for the repair of osteoporotic bone defects.
As the global population ages, osteoporotic bone fractures leading to bone defects are increasingly becoming a significant challenge in the field of public health. Treating this disease faces many challenges, especially in the context of an imbalance between osteoblast and osteoclast activities. Therefore, the development of new biomaterials has become the key. This article reviews various design strategies and their advantages and disadvantages for biomaterials aimed at osteoporotic bone defects. Overall, current research progress indicates that innovative design, functionalization, and targeting of materials can significantly enhance bone regeneration under osteoporotic conditions. By comprehensively considering biocompatibility, mechanical properties, and bioactivity, these biomaterials can be further optimized, offering a range of choices and strategies for the repair of osteoporotic bone defects.
2025, 36(1): 109724
doi: 10.1016/j.cclet.2024.109724
摘要:
Despite ongoing advancements in cancer treatment, the emergence of primary and acquired resistance poses a significant challenge for both traditional chemotherapy and immune checkpoint blockade therapies. The demand for targeted therapeutics for multidrug-resistant cancer is more important than ever. Peptides, as emerging alternatives to current anticancer drugs, offer exquisite versatility in facilitating the design of novel oncology drugs, with the core superiorities of good biocompatibility and a low tendency to induce drug resistance. This review comprehensively introduces the pharmacological mechanisms of peptide-based drugs and strategies for overcoming multidrug resistance (MDR) in cancers, including inducing cell membrane lysis, targeting organelles, activating anticancer immune responses, enhancing drug uptake, targeting ATP-binding cassette (ABC) transporters, and targeting B-cell lymphoma-2 (BCL-2) family proteins. Additionally, the current clinical applications of representative peptides in combating MDR cancers and their potential directions for medicinal chemistry research have been thoroughly discussed. This review offers essential insights into the novel treatment approaches for MDR cancers and highlights the trends and perspectives in this field.
Despite ongoing advancements in cancer treatment, the emergence of primary and acquired resistance poses a significant challenge for both traditional chemotherapy and immune checkpoint blockade therapies. The demand for targeted therapeutics for multidrug-resistant cancer is more important than ever. Peptides, as emerging alternatives to current anticancer drugs, offer exquisite versatility in facilitating the design of novel oncology drugs, with the core superiorities of good biocompatibility and a low tendency to induce drug resistance. This review comprehensively introduces the pharmacological mechanisms of peptide-based drugs and strategies for overcoming multidrug resistance (MDR) in cancers, including inducing cell membrane lysis, targeting organelles, activating anticancer immune responses, enhancing drug uptake, targeting ATP-binding cassette (ABC) transporters, and targeting B-cell lymphoma-2 (BCL-2) family proteins. Additionally, the current clinical applications of representative peptides in combating MDR cancers and their potential directions for medicinal chemistry research have been thoroughly discussed. This review offers essential insights into the novel treatment approaches for MDR cancers and highlights the trends and perspectives in this field.
2025, 36(1): 109766
doi: 10.1016/j.cclet.2024.109766
摘要:
The treatment of skin wounds, especially chronic wounds, remains a critical clinical challenge and places a heavy burden on patients and healthcare systems. In recent years, the engineering strategy of using biomaterial-assisted exosomes has emerged as a powerful tool for skin repair. Compared to treatments such as debridement and regular dressing changes, the design of biomaterial-assisted exosomes not only maintains the bioactivity of exosomes at the wound site but also provides an appropriate microenvironment for the repair of complex tissues, thereby accelerating wound healing. This review systematically introduces the general characteristics of exosomes and their functions in skin wound healing, highlights recent advances in classification of natural exosomes and engineering methods which enriching their functions in intercellular communication. Then, various emerging and innovative approaches based on biomaterials delivery of exosomes are comprehensively discussed. The review seeks to bring an in-depth understanding of bioactive dressings based on exosomes therapeutic strategies, aiming to facilitate new clinical application value.
The treatment of skin wounds, especially chronic wounds, remains a critical clinical challenge and places a heavy burden on patients and healthcare systems. In recent years, the engineering strategy of using biomaterial-assisted exosomes has emerged as a powerful tool for skin repair. Compared to treatments such as debridement and regular dressing changes, the design of biomaterial-assisted exosomes not only maintains the bioactivity of exosomes at the wound site but also provides an appropriate microenvironment for the repair of complex tissues, thereby accelerating wound healing. This review systematically introduces the general characteristics of exosomes and their functions in skin wound healing, highlights recent advances in classification of natural exosomes and engineering methods which enriching their functions in intercellular communication. Then, various emerging and innovative approaches based on biomaterials delivery of exosomes are comprehensively discussed. The review seeks to bring an in-depth understanding of bioactive dressings based on exosomes therapeutic strategies, aiming to facilitate new clinical application value.
2025, 36(1): 109836
doi: 10.1016/j.cclet.2024.109836
摘要:
As more and more studies have shown that lipid molecules play an important role in the whole biology, in-depth analysis of lipid structure has become particularly important in lipidomics. Mass spectrometry (MS), as the preferred tool for lipid analysis, has greatly promoted the development of this field. However, the existing MS methods still face many difficulties in the in-depth or even comprehensive analysis of lipid structure. In this review, we discuss recent advances in MS methods based on double bond-specific chemistries for the resolving of C=C location and geometry isomers of lipids. This progress has greatly advanced the lipidomics analysis to a deeper structural level and facilitated the development of structural lipid biology.
As more and more studies have shown that lipid molecules play an important role in the whole biology, in-depth analysis of lipid structure has become particularly important in lipidomics. Mass spectrometry (MS), as the preferred tool for lipid analysis, has greatly promoted the development of this field. However, the existing MS methods still face many difficulties in the in-depth or even comprehensive analysis of lipid structure. In this review, we discuss recent advances in MS methods based on double bond-specific chemistries for the resolving of C=C location and geometry isomers of lipids. This progress has greatly advanced the lipidomics analysis to a deeper structural level and facilitated the development of structural lipid biology.
2025, 36(1): 109855
doi: 10.1016/j.cclet.2024.109855
摘要:
Piperidine is a crucial pharmacophore and a special scaffold in the realm of drug discovery. Its flexibility increases the molecule's capability to bind to the receptor. The piperidine-containing compounds are distinguished by their remarkable activity, and are increasingly becoming a vital category of pesticides. In this review, the research progress of piperidines in the discovery of pesticides was updated according to their active characteristics. The structure-activity relationships (SARs), and mechanisms of action of piperidine-containing compounds were also discussed. This article is meant to enable readers to quickly understand piperidines, while providing ideas for creating piperidines with novel structures and unique mechanisms of action.
Piperidine is a crucial pharmacophore and a special scaffold in the realm of drug discovery. Its flexibility increases the molecule's capability to bind to the receptor. The piperidine-containing compounds are distinguished by their remarkable activity, and are increasingly becoming a vital category of pesticides. In this review, the research progress of piperidines in the discovery of pesticides was updated according to their active characteristics. The structure-activity relationships (SARs), and mechanisms of action of piperidine-containing compounds were also discussed. This article is meant to enable readers to quickly understand piperidines, while providing ideas for creating piperidines with novel structures and unique mechanisms of action.
2025, 36(1): 109861
doi: 10.1016/j.cclet.2024.109861
摘要:
Poly(butylene adipate-terephthalate) (PBAT), as one of the most common and promising biodegradable plastics, has been widely used in agriculture, packaging, and other industries due to its strong biodegradability properties. It is well known that PBAT suffers a series of natural weathering, mechanical wear, hydrolysis, photochemical transformation, and other abiotic degradation processes before being biodegraded. Therefore, it is particularly important to understand the role of abiotic degradation in the life cycle of PBAT. Since the abiotic degradation of PBAT has not been systematically summarized, this review aims to summarize the mechanisms and main factors of the three major abiotic degradation pathways (hydrolysis, photochemical transformation, and thermochemical degradation) of PBAT. It was found that all of them preferentially destroy the chemical bonds with higher energy (especially C-O and C=O) of PBAT, which eventually leads to the shortening of the polymer chain and then leads to reduction in molecular weight. The main factors affecting these abiotic degradations are closely related to the energy or PBAT structure. These findings provide important theoretical and practical guidance for identifying effective methods for PBAT waste management and proposing advanced schemes to regulate the degradation rate of PBAT.
Poly(butylene adipate-terephthalate) (PBAT), as one of the most common and promising biodegradable plastics, has been widely used in agriculture, packaging, and other industries due to its strong biodegradability properties. It is well known that PBAT suffers a series of natural weathering, mechanical wear, hydrolysis, photochemical transformation, and other abiotic degradation processes before being biodegraded. Therefore, it is particularly important to understand the role of abiotic degradation in the life cycle of PBAT. Since the abiotic degradation of PBAT has not been systematically summarized, this review aims to summarize the mechanisms and main factors of the three major abiotic degradation pathways (hydrolysis, photochemical transformation, and thermochemical degradation) of PBAT. It was found that all of them preferentially destroy the chemical bonds with higher energy (especially C-O and C=O) of PBAT, which eventually leads to the shortening of the polymer chain and then leads to reduction in molecular weight. The main factors affecting these abiotic degradations are closely related to the energy or PBAT structure. These findings provide important theoretical and practical guidance for identifying effective methods for PBAT waste management and proposing advanced schemes to regulate the degradation rate of PBAT.
2025, 36(1): 109955
doi: 10.1016/j.cclet.2024.109955
摘要:
This review covers the structures of diterpenoids, including chain (72), monocyclic (9), labdane-type (67), clerodane-type (127) abietane-type (716), ent-kaurane-type (89), grayanane-type (331), ingenane-type (55), tigliane-type (154), daphnane-type (237), and aconitine-type diterpene alkaloids (265) with rich biological activities reported in 2013–2023. And the drugs in clinical use or under clinical investigation of diterpenoids and leading compounds were summarized.
This review covers the structures of diterpenoids, including chain (72), monocyclic (9), labdane-type (67), clerodane-type (127) abietane-type (716), ent-kaurane-type (89), grayanane-type (331), ingenane-type (55), tigliane-type (154), daphnane-type (237), and aconitine-type diterpene alkaloids (265) with rich biological activities reported in 2013–2023. And the drugs in clinical use or under clinical investigation of diterpenoids and leading compounds were summarized.
2025, 36(1): 109995
doi: 10.1016/j.cclet.2024.109995
摘要:
The rapid development of microfluidic technology has led to the evolution of microdroplets from simple emulsion structures to complex multilayered and multicompartmental configurations. These advancements have endowed microdroplets with the capability to contain multiple compartments that remain isolated from one another, enabling them to carry different molecules of interest. Consequently, researchers can now investigate intricate spatially confined chemical reactions and signal transduction pathways within subcellular organelles. Moreover, modern microdroplets often possess excellent optical transparency, allowing fluorescently labelled, multi-layered, and compartmental droplets to provide detailed insights through real-time, in situ, and dynamic fluorescence imaging. Hence, this review systematically summarizes current methodologies for preparing multicomponent microdroplets and their applications, particularly focusing on fluorescent microdroplets. Additionally, it discusses existing critical challenges and outlines future research directions. By offering a comprehensive overview of the preparation methods and applications of fluorescent microdroplets, this review aims to stimulate the interest of researchers and foster their utilization in more complex and biomimetic environments.
The rapid development of microfluidic technology has led to the evolution of microdroplets from simple emulsion structures to complex multilayered and multicompartmental configurations. These advancements have endowed microdroplets with the capability to contain multiple compartments that remain isolated from one another, enabling them to carry different molecules of interest. Consequently, researchers can now investigate intricate spatially confined chemical reactions and signal transduction pathways within subcellular organelles. Moreover, modern microdroplets often possess excellent optical transparency, allowing fluorescently labelled, multi-layered, and compartmental droplets to provide detailed insights through real-time, in situ, and dynamic fluorescence imaging. Hence, this review systematically summarizes current methodologies for preparing multicomponent microdroplets and their applications, particularly focusing on fluorescent microdroplets. Additionally, it discusses existing critical challenges and outlines future research directions. By offering a comprehensive overview of the preparation methods and applications of fluorescent microdroplets, this review aims to stimulate the interest of researchers and foster their utilization in more complex and biomimetic environments.
2025, 36(1): 109998
doi: 10.1016/j.cclet.2024.109998
摘要:
Photocatalytic CO2 reduction reaction (CO2RR) is one of the promising strategies for sustainably producing solar fuels. The precise identification of catalytic sites and the enhancement of photocatalytic CO2 conversion is imperative yet quite challenging. This critical review summarizes recent advances in porous photo-responsive polymers, including covalent organic frameworks (COFs), covalent triazine frameworks (CTFs), and conjugated microporous polymers (CMPs), those can be rationally designed from the molecular level for visible-light-driven photocatalytic CO2 reduction. Additionally, special emphasis is placed on how the well-defined active sites on these polymers can influence their properties and photocatalytic performance. The precise regulation and control of microenvironments and electronic properties of metal active centers are crucial for boosting catalytic efficiency and selectivity, as well as for the design of better photocatalysts for CO2 reduction.
Photocatalytic CO2 reduction reaction (CO2RR) is one of the promising strategies for sustainably producing solar fuels. The precise identification of catalytic sites and the enhancement of photocatalytic CO2 conversion is imperative yet quite challenging. This critical review summarizes recent advances in porous photo-responsive polymers, including covalent organic frameworks (COFs), covalent triazine frameworks (CTFs), and conjugated microporous polymers (CMPs), those can be rationally designed from the molecular level for visible-light-driven photocatalytic CO2 reduction. Additionally, special emphasis is placed on how the well-defined active sites on these polymers can influence their properties and photocatalytic performance. The precise regulation and control of microenvironments and electronic properties of metal active centers are crucial for boosting catalytic efficiency and selectivity, as well as for the design of better photocatalysts for CO2 reduction.
2025, 36(1): 110100
doi: 10.1016/j.cclet.2024.110100
摘要:
Surface with well-defined components and structures possesses unique electronic, magnetic, optical and chemical properties. As a result, surface chemistry research plays a crucial role in various fields such as catalysis, energy, materials, quantum, and microelectronics. Surface science mainly investigates the correspondence between surface property and functionality. Scanning probe microscopy (SPM) techniques are important tools to characterize surface properties because of the capability of atomic-scale imaging, spectroscopy and manipulation at the single-atom level. In this review, we summarize recent advances in surface electronic, magnetic and optical properties characterized mainly by SPM-based methods. We focus on elucidating the π-magnetism in graphene-based nanostructures, construction of spin qubits on surfaces, topology properties of surface organic structures, STM-based light emission, tip-enhanced Raman spectroscopy and integration of machine learning in SPM studies.
Surface with well-defined components and structures possesses unique electronic, magnetic, optical and chemical properties. As a result, surface chemistry research plays a crucial role in various fields such as catalysis, energy, materials, quantum, and microelectronics. Surface science mainly investigates the correspondence between surface property and functionality. Scanning probe microscopy (SPM) techniques are important tools to characterize surface properties because of the capability of atomic-scale imaging, spectroscopy and manipulation at the single-atom level. In this review, we summarize recent advances in surface electronic, magnetic and optical properties characterized mainly by SPM-based methods. We focus on elucidating the π-magnetism in graphene-based nanostructures, construction of spin qubits on surfaces, topology properties of surface organic structures, STM-based light emission, tip-enhanced Raman spectroscopy and integration of machine learning in SPM studies.
2025, 36(1): 110117
doi: 10.1016/j.cclet.2024.110117
摘要:
Organic pollutants are harmful and toxic chemical substances that adversely threaten human health and the living environment all over the world. More and more studies have been investigating the relationship between low level of human exposure of organic compounds and various internal diseases. For the sake of assessing disease risk due to organic compounds contact in a particular location, it is imperative for relevant government departments to make a human health risk assessment in view of the organic pollutants’ bioavailability and their dosage-response correlations. It is inevitable to make use of an efficient method to detect organic pollutants, which is significant for public health and safety. Fluorescent assays based on carbon dots thus would provide a very plausible candidate method. After consulting a large number of literatures, we offer a comprehensive review of the sensing applications of carbon dots for organic pollutants.
Organic pollutants are harmful and toxic chemical substances that adversely threaten human health and the living environment all over the world. More and more studies have been investigating the relationship between low level of human exposure of organic compounds and various internal diseases. For the sake of assessing disease risk due to organic compounds contact in a particular location, it is imperative for relevant government departments to make a human health risk assessment in view of the organic pollutants’ bioavailability and their dosage-response correlations. It is inevitable to make use of an efficient method to detect organic pollutants, which is significant for public health and safety. Fluorescent assays based on carbon dots thus would provide a very plausible candidate method. After consulting a large number of literatures, we offer a comprehensive review of the sensing applications of carbon dots for organic pollutants.
2025, 36(1): 110142
doi: 10.1016/j.cclet.2024.110142
摘要:
Photocatalysis is widely regarded as a highly promising sustainable technique for addressing the challenges posed by environmental pollution and energy provision. In recent years, metal-loaded MOFs has become a rising star within the domain of photocatalysis due to its high specific surface area and porosity, adjustable structure, diverse and abundant catalytic components, which has exhibited excellent photocatalytic activity and exhibit great potential in a range of disciplines. In this paper, the principles for evaluating the photocatalytic performance of MOFs-based materials were firstly introduced, and some typical examples were also listed accordingly. Along with this, particular emphasis is paid to the main factors affecting the photocatalytic performance of metal-loaded MOFs. Then the synthesis and design strategies of MOFs loaded metal entities of varying sizes (single atoms, nanoclusters, and nanoparticles), and their applications in photocatalytic CO2 reduction, hydrogen production, photooxidation and photocatalytic hydrogenation were summarized and discussed. Finally, the opportunities and challenges faced in this kind of MOFs-based composites were analyzed from different perspectives. This report is expected to help researchers design and develop high-performance MOFs-based photocatalytic materials.
Photocatalysis is widely regarded as a highly promising sustainable technique for addressing the challenges posed by environmental pollution and energy provision. In recent years, metal-loaded MOFs has become a rising star within the domain of photocatalysis due to its high specific surface area and porosity, adjustable structure, diverse and abundant catalytic components, which has exhibited excellent photocatalytic activity and exhibit great potential in a range of disciplines. In this paper, the principles for evaluating the photocatalytic performance of MOFs-based materials were firstly introduced, and some typical examples were also listed accordingly. Along with this, particular emphasis is paid to the main factors affecting the photocatalytic performance of metal-loaded MOFs. Then the synthesis and design strategies of MOFs loaded metal entities of varying sizes (single atoms, nanoclusters, and nanoparticles), and their applications in photocatalytic CO2 reduction, hydrogen production, photooxidation and photocatalytic hydrogenation were summarized and discussed. Finally, the opportunities and challenges faced in this kind of MOFs-based composites were analyzed from different perspectives. This report is expected to help researchers design and develop high-performance MOFs-based photocatalytic materials.
2025, 36(1): 110234
doi: 10.1016/j.cclet.2024.110234
摘要:
Photocatalytic technology harnesses solar energy to facilitate chemical transformations, presenting significant potential in energy generation and environmental remediation. However, the conventional O2 evolution process is hindered by high reaction barriers and inefficiencies, which limit its widespread application. Therefore, exploring novel photocatalytic coupling strategies to replace water oxidation has become a key route to enhance the efficiency of H2 production. In this review, organic pollutants removal and the valorization of organics as substitutes for water oxidation coupling strategies for photocatalytic H2 production are comprehensively summarized. These strategies not only circumvent the high reaction barriers associated with O2 evolution to enhance the H2 production but also aid in the removing of organic pollutants or synthesis of value-added chemicals. We also present future research directions and underscore the significance of advanced catalyst design, in-depth analysis of reaction mechanisms, and systematic optimization strategies in realizing an efficient and sustainable photocatalytic process. This guidance is anticipated to provide theoretical and practical new insights for the future development of photocatalytic coupling reactions, fostering further explorations in the realm of renewable energy and environmental governance.
Photocatalytic technology harnesses solar energy to facilitate chemical transformations, presenting significant potential in energy generation and environmental remediation. However, the conventional O2 evolution process is hindered by high reaction barriers and inefficiencies, which limit its widespread application. Therefore, exploring novel photocatalytic coupling strategies to replace water oxidation has become a key route to enhance the efficiency of H2 production. In this review, organic pollutants removal and the valorization of organics as substitutes for water oxidation coupling strategies for photocatalytic H2 production are comprehensively summarized. These strategies not only circumvent the high reaction barriers associated with O2 evolution to enhance the H2 production but also aid in the removing of organic pollutants or synthesis of value-added chemicals. We also present future research directions and underscore the significance of advanced catalyst design, in-depth analysis of reaction mechanisms, and systematic optimization strategies in realizing an efficient and sustainable photocatalytic process. This guidance is anticipated to provide theoretical and practical new insights for the future development of photocatalytic coupling reactions, fostering further explorations in the realm of renewable energy and environmental governance.
2025, 36(1): 110368
doi: 10.1016/j.cclet.2024.110368
摘要:
As battery technology evolves and demand for efficient energy storage solutions, aqueous zinc ion batteries (AZIBs) have garnered significant attention due to their safety and environmental benefits. However, the stability of cathode materials under high-voltage conditions remains a critical challenge in improving its energy density. This review systematically explores the failure mechanisms of high-voltage cathode materials in AZIBs, including hydrogen evolution reaction, phase transformation and dissolution phenomena. To address these challenges, we propose a range of advanced strategies aimed at improving the stability of cathode materials. These strategies include surface coating and doping techniques designed to fortify the surface properties and structure integrity of the cathode materials under high-voltage conditions. Additionally, we emphasize the importance of designing antioxidant electrolytes, with a focus on understanding and optimizing electrolyte decomposition mechanisms. The review also highlights the significance of modifying conductive agents and employing innovative separators to further enhance the stability of AZIBs. By integrating these cutting-edge approaches, this review anticipates substantial advancements in the stability of high-voltage cathode materials, paving the way for the broader application and development of AZIBs in energy storage.
As battery technology evolves and demand for efficient energy storage solutions, aqueous zinc ion batteries (AZIBs) have garnered significant attention due to their safety and environmental benefits. However, the stability of cathode materials under high-voltage conditions remains a critical challenge in improving its energy density. This review systematically explores the failure mechanisms of high-voltage cathode materials in AZIBs, including hydrogen evolution reaction, phase transformation and dissolution phenomena. To address these challenges, we propose a range of advanced strategies aimed at improving the stability of cathode materials. These strategies include surface coating and doping techniques designed to fortify the surface properties and structure integrity of the cathode materials under high-voltage conditions. Additionally, we emphasize the importance of designing antioxidant electrolytes, with a focus on understanding and optimizing electrolyte decomposition mechanisms. The review also highlights the significance of modifying conductive agents and employing innovative separators to further enhance the stability of AZIBs. By integrating these cutting-edge approaches, this review anticipates substantial advancements in the stability of high-voltage cathode materials, paving the way for the broader application and development of AZIBs in energy storage.
2025, 36(1): 110457
doi: 10.1016/j.cclet.2024.110457
摘要:
Photocatalytic hydrogen peroxide (H2O2) production has been considered as a promising strategy for H2O2 synthesis due to its environmentally friendly. Among various photocatalysts, carbon nitride-based materials are excellent candidates for H2O2 production because of their excellent visible-light response, low cost and high stability. In this review, we summarize in detail the research progress on the photocatalytic production of H2O2 by carbon nitride. First, we summarize the basic principles of photocatalysis and photocatalytic H2O2 production. Second, the classification and modification methods of carbon-nitride-based materials are discussed, including morphology modulation, noble metal loading, defect control, heterojunction regulation, molecular structure engineering and elemental doping. Finally, the different in-situ applications of H2O2 via photosynthesis were discussed, including disinfection and antibiotic resistant genes degradation, organic pollutants degradation, medical applications and fine chemical synthesis. This review brings great promise for in-situ H2O2 photosynthesis, which is expected to serve as a key component in future applications.
Photocatalytic hydrogen peroxide (H2O2) production has been considered as a promising strategy for H2O2 synthesis due to its environmentally friendly. Among various photocatalysts, carbon nitride-based materials are excellent candidates for H2O2 production because of their excellent visible-light response, low cost and high stability. In this review, we summarize in detail the research progress on the photocatalytic production of H2O2 by carbon nitride. First, we summarize the basic principles of photocatalysis and photocatalytic H2O2 production. Second, the classification and modification methods of carbon-nitride-based materials are discussed, including morphology modulation, noble metal loading, defect control, heterojunction regulation, molecular structure engineering and elemental doping. Finally, the different in-situ applications of H2O2 via photosynthesis were discussed, including disinfection and antibiotic resistant genes degradation, organic pollutants degradation, medical applications and fine chemical synthesis. This review brings great promise for in-situ H2O2 photosynthesis, which is expected to serve as a key component in future applications.
2025, 36(1): 110378
doi: 10.1016/j.cclet.2024.110378
摘要:
2025, 36(1): 110384
doi: 10.1016/j.cclet.2024.110384
摘要:
2025, 36(1): 110446
doi: 10.1016/j.cclet.2024.110446
摘要:
