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The first issue is scheduled to be published in Dec. 2018.
Call for Papers
CCS Chemistry is the flagship general journal for the cutting edge and fundamental research in the areas of chemica research facing global audiences published by Chinese Chemical Society. We call for excellent papers cover but not limited to synthetic chemistry, catalysis & surface chemistry, chemical theory and mechanism, chemical metrology, materials & energy chemistry, environmental chemistry, chemical biology, chemical engineering and industrial chemistry. Professional arrangement ensures that all papers can be reviewed and published online quickly and efficiently (one or two weeks).
Contact information:
Dr. Hao Linxiao, haolinxiao@iccas.ac.cn; +86-10-82449177-888
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2025, 36(2): 109586
doi: 10.1016/j.cclet.2024.109586
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
2025, 36(2): 110417
doi: 10.1016/j.cclet.2024.110417
Abstract:
2025, 36(2): 110523
doi: 10.1016/j.cclet.2024.110523
Abstract:
2025, 36(2): 110616
doi: 10.1016/j.cclet.2024.110616
Abstract: