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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(4): 109713
doi: 10.1016/j.cclet.2024.109713
Abstract:
Developing high-efficient and low-loading Pt based catalyst is significant for the electrocatalytic pH-universal hydrogen evolution reaction (HER). Herein, the molybdenum carbide nanoparticles supported on the polyhedral N-doped carbon nanotube skeleton (MoC/NCT) composite has been synthesized by a pyrolysis of polyacid organo-metallic phosphate framework precursor. Then, only 2.15 wt% Pt are loaded on the MoC/NCT to form Pt-MoC/NCT catalyst, which performs superior HER activity and stability in entire pH range. Specially, the overpotentials of 22 and 74 mV are respectively attained at 10 mA/cm2 in 1.0 mol/L KOH and 0.5 mol/L H2SO4 electrolytes, approaching or even exceeding commercial Pt/C. More importantly, it can be used as excellent catalyst for efficient hydrogen production at 0–14 pH range. Density functional theory (DFT) calculations demonstrate that the interaction between MoC and Pt leads to the electron redistribution at the corresponding interfaces and the downward shift of the d-band centers, thus optimizing H* adsorption and desorption for promoting the HER activity. Besides, the unique three-dimensional network structure is conductive to the transmission of mass and electrons. In the application of both alkaline and acidic electrolysers, only 1.52 V voltage of solar panel can drive a hydrogen production current density of 10 mA/cm2.
Developing high-efficient and low-loading Pt based catalyst is significant for the electrocatalytic pH-universal hydrogen evolution reaction (HER). Herein, the molybdenum carbide nanoparticles supported on the polyhedral N-doped carbon nanotube skeleton (MoC/NCT) composite has been synthesized by a pyrolysis of polyacid organo-metallic phosphate framework precursor. Then, only 2.15 wt% Pt are loaded on the MoC/NCT to form Pt-MoC/NCT catalyst, which performs superior HER activity and stability in entire pH range. Specially, the overpotentials of 22 and 74 mV are respectively attained at 10 mA/cm2 in 1.0 mol/L KOH and 0.5 mol/L H2SO4 electrolytes, approaching or even exceeding commercial Pt/C. More importantly, it can be used as excellent catalyst for efficient hydrogen production at 0–14 pH range. Density functional theory (DFT) calculations demonstrate that the interaction between MoC and Pt leads to the electron redistribution at the corresponding interfaces and the downward shift of the d-band centers, thus optimizing H* adsorption and desorption for promoting the HER activity. Besides, the unique three-dimensional network structure is conductive to the transmission of mass and electrons. In the application of both alkaline and acidic electrolysers, only 1.52 V voltage of solar panel can drive a hydrogen production current density of 10 mA/cm2.
2025, 36(4): 109714
doi: 10.1016/j.cclet.2024.109714
Abstract:
PVDF-based nanocomposites have gained significant focus in capacitors for their excellent dielectric strength, its multi-scale structural inhomogeneity is the bottleneck for improving the energy storage performance. Here, the composite components are optimized by the matrix modification, BST (Ba0.6Sr0.4TiO3) ceramic fibrillation and surface coating. A series of PVDF/polymethyl methacrylate/lysozyme@BST nanofibers with continuous gradient distribution (PF-M/mBST nf-g) are prepared by the concentration gradient-biaxial high-speed electrospinning. The finite element simulation and experiment results indicate that the continuous gradient structure is favorable for the microstructure and inhomogeneity of the electric field distribution, significantly increasing the breakdown strength (Eb) and the permittivity (εr), as well as effectively suppressing the interfacial injected charge and leakage current. As a result, the energy storage density (Ue) of 23.1 J/cm3 at 600 MV/m with the charge-discharge efficiency (η) of 71% is achieved compared to PF-M (5.6 J/cm3@350 MV/m, 65%). The exciting energy storage performance based on the well-designed PF-M/mBST nf-g provides important information for the development and application of polymer nanocomposite dielectrics.
PVDF-based nanocomposites have gained significant focus in capacitors for their excellent dielectric strength, its multi-scale structural inhomogeneity is the bottleneck for improving the energy storage performance. Here, the composite components are optimized by the matrix modification, BST (Ba0.6Sr0.4TiO3) ceramic fibrillation and surface coating. A series of PVDF/polymethyl methacrylate/lysozyme@BST nanofibers with continuous gradient distribution (PF-M/mBST nf-g) are prepared by the concentration gradient-biaxial high-speed electrospinning. The finite element simulation and experiment results indicate that the continuous gradient structure is favorable for the microstructure and inhomogeneity of the electric field distribution, significantly increasing the breakdown strength (Eb) and the permittivity (εr), as well as effectively suppressing the interfacial injected charge and leakage current. As a result, the energy storage density (Ue) of 23.1 J/cm3 at 600 MV/m with the charge-discharge efficiency (η) of 71% is achieved compared to PF-M (5.6 J/cm3@350 MV/m, 65%). The exciting energy storage performance based on the well-designed PF-M/mBST nf-g provides important information for the development and application of polymer nanocomposite dielectrics.
2025, 36(4): 109716
doi: 10.1016/j.cclet.2024.109716
Abstract:
Selective oxidation of olefin to epoxides is an important reaction in industry, however, developing heterogeneous catalysts to achieve the effective catalysis for this reaction under O2 atmosphere at room temperature is challenging but highly desired. In this work, two novel 2D cobalt metal-organic complexes, namely [Co(L)(5-HIP)]·2H2O (Co-MOC-1) and [Co(L)(BTEC)0.5]·H2O (Co-MOC-2) (L = (E)-4,4′-(ethene-1,2-diyl)bis(N-(pyridin-3-yl)benzamide; 5-H2HIP = 5-hydroxyisophthalic acid; H4BTEC = pyromellitic acid) were designed and synthesized through hydrothermal method, which exhibited different metal coordination modes (4-coordinate and 5-coordinate, respectively) and 2D layer structures directed by different carboxylates co-ligands. Two Co-MOCs can serve as heterogeneous catalysts for the selective oxidation of olefins to epoxides at room temperature using O2 as oxidant. Furthermore, a higher catalysis activity of Co-MOC-1 than Co-MOC-2 (96.7% vs. 90.2% yield of 1,2-epoxycyclooctane) was observed, which may be attributed to the coordination unsaturated Co centers, the less coordination number and larger interlayer spacing of Co-MOC-1.
Selective oxidation of olefin to epoxides is an important reaction in industry, however, developing heterogeneous catalysts to achieve the effective catalysis for this reaction under O2 atmosphere at room temperature is challenging but highly desired. In this work, two novel 2D cobalt metal-organic complexes, namely [Co(L)(5-HIP)]·2H2O (Co-MOC-1) and [Co(L)(BTEC)0.5]·H2O (Co-MOC-2) (L = (E)-4,4′-(ethene-1,2-diyl)bis(N-(pyridin-3-yl)benzamide; 5-H2HIP = 5-hydroxyisophthalic acid; H4BTEC = pyromellitic acid) were designed and synthesized through hydrothermal method, which exhibited different metal coordination modes (4-coordinate and 5-coordinate, respectively) and 2D layer structures directed by different carboxylates co-ligands. Two Co-MOCs can serve as heterogeneous catalysts for the selective oxidation of olefins to epoxides at room temperature using O2 as oxidant. Furthermore, a higher catalysis activity of Co-MOC-1 than Co-MOC-2 (96.7% vs. 90.2% yield of 1,2-epoxycyclooctane) was observed, which may be attributed to the coordination unsaturated Co centers, the less coordination number and larger interlayer spacing of Co-MOC-1.
2025, 36(4): 109720
doi: 10.1016/j.cclet.2024.109720
Abstract:
Metal-organic framework (MOF) has been widely applied in photocatalysis, which is significant for addressing energy crises and environmental issues. Based on density functional theory calculations, the performances of Cu-BTC, a copper-based MOF, and its derivatives CuTM-BTC via the substitution of transition metal (TM) elements at the Cu site for photocatalytic overall water splitting (POWS) have been studied. POWS of Cu-BTC suffers from the sluggish hydrogen evolution reaction due to the large overpotential of 2.02 V and limited solar utilization due to a wide HOMO-LUMO gap of 4.11 eV. Via TM substitution, the HOMO-LUMO gap narrows but still satisfies the redox potentials when taken 3d-TM of Cr, Fe, Co or Ni, 4d-TM of Rh or Pd, or 5d-TM of Re or Pt into consideration, benefiting for the light absorption. Furthermore, Cr and Re could serve as active sites for hydrogen evolution with remarkably lowered overpotentials of 0.79 V and 0.28 V, respectively; similarly, oxygen evolution activities could be enhanced by Fe, Co and Rh because of their reduced overpotentials which are less than 0.5 V. Therefore, our findings pave guidance for designing Cu-BTC derivatives in overall water splitting.
Metal-organic framework (MOF) has been widely applied in photocatalysis, which is significant for addressing energy crises and environmental issues. Based on density functional theory calculations, the performances of Cu-BTC, a copper-based MOF, and its derivatives CuTM-BTC via the substitution of transition metal (TM) elements at the Cu site for photocatalytic overall water splitting (POWS) have been studied. POWS of Cu-BTC suffers from the sluggish hydrogen evolution reaction due to the large overpotential of 2.02 V and limited solar utilization due to a wide HOMO-LUMO gap of 4.11 eV. Via TM substitution, the HOMO-LUMO gap narrows but still satisfies the redox potentials when taken 3d-TM of Cr, Fe, Co or Ni, 4d-TM of Rh or Pd, or 5d-TM of Re or Pt into consideration, benefiting for the light absorption. Furthermore, Cr and Re could serve as active sites for hydrogen evolution with remarkably lowered overpotentials of 0.79 V and 0.28 V, respectively; similarly, oxygen evolution activities could be enhanced by Fe, Co and Rh because of their reduced overpotentials which are less than 0.5 V. Therefore, our findings pave guidance for designing Cu-BTC derivatives in overall water splitting.
2025, 36(4): 109730
doi: 10.1016/j.cclet.2024.109730
Abstract:
Sulfates are always promising short-wave ultraviolet (UV) nonlinear optical (NLO) candidates, if their birefringence could be greatly improved. Here, in terms of the insufficient birefringence, the unity of heteroleptic tetrahedral groups and triangular ones was proposed and implemented. Thus, a new semi-organic crystal, [C(NH2)3]S3O6 (G2S3O6), was obtained, which is composed of [S3O6]2− and [C(NH2)3]+ groups. It exhibits excellent optical properties with a short absorption cutoff edge of 218 nm, a strong NLO response of 1.4 × KH2PO4, and more especially, a large birefringence of 0.097@546 nm. This birefringence leap makes the G2S3O6 crystal achieve a phase-matching behavior under a 532 nm laser. Thus, the synergy of [S3O6]2− and [C(NH2)3]+ groups results in excellent optical performances. This finding opens a new horizon for exploring novel UV NLO crystals.
Sulfates are always promising short-wave ultraviolet (UV) nonlinear optical (NLO) candidates, if their birefringence could be greatly improved. Here, in terms of the insufficient birefringence, the unity of heteroleptic tetrahedral groups and triangular ones was proposed and implemented. Thus, a new semi-organic crystal, [C(NH2)3]S3O6 (G2S3O6), was obtained, which is composed of [S3O6]2− and [C(NH2)3]+ groups. It exhibits excellent optical properties with a short absorption cutoff edge of 218 nm, a strong NLO response of 1.4 × KH2PO4, and more especially, a large birefringence of 0.097@546 nm. This birefringence leap makes the G2S3O6 crystal achieve a phase-matching behavior under a 532 nm laser. Thus, the synergy of [S3O6]2− and [C(NH2)3]+ groups results in excellent optical performances. This finding opens a new horizon for exploring novel UV NLO crystals.
2025, 36(4): 109738
doi: 10.1016/j.cclet.2024.109738
Abstract:
Carbon materials are considered as prospective anode candidates for potassium ion batteries (PIBs). However, the low-rate capability is hampered by slow K+ diffusion kinetics and obstructed electron transport of carbon-based anodes. In this work, calcium d-gluconate derived mesoporous carbon nanosheets (CGC) were interpenetrated into the architecture of reduced graphene oxides (RGO) to form the composites of two-dimensional (2D)/2D graphene/mesoporous carbon nanosheets (RGO@CGC). CGC as a rigid skeleton can prevent the graphene layers from restacking and maintain the structural stability of the 2D/2D carbon composites of RGO@CGC. The mesopores in CGC can shorten the path of ion diffusion and facilitate the penetration of electrolytes. RGO possesses the high surface-to-volume ratio and superior electron transport capability in the honeycomb-like 2D network consisting of sp2-hybridized carbon atoms. Especially, the π-π stacking interaction between CGC and RGO enhances stable composite structure formation, expedites interlayer-electron transfer, and establishes three-dimensional (3D) ion transportation pathways. Owing to these unique structure, RGO@CGC exhibits fast and stable potassium storage capability. Furthermore, the effects of binders and electrolytes on the electrochemical performance of RGO@CGC were investigated. Finally, Prussian blue was synthesized as a positive electrode to explore the possibility of RGO@CGC as a full battery application.
Carbon materials are considered as prospective anode candidates for potassium ion batteries (PIBs). However, the low-rate capability is hampered by slow K+ diffusion kinetics and obstructed electron transport of carbon-based anodes. In this work, calcium d-gluconate derived mesoporous carbon nanosheets (CGC) were interpenetrated into the architecture of reduced graphene oxides (RGO) to form the composites of two-dimensional (2D)/2D graphene/mesoporous carbon nanosheets (RGO@CGC). CGC as a rigid skeleton can prevent the graphene layers from restacking and maintain the structural stability of the 2D/2D carbon composites of RGO@CGC. The mesopores in CGC can shorten the path of ion diffusion and facilitate the penetration of electrolytes. RGO possesses the high surface-to-volume ratio and superior electron transport capability in the honeycomb-like 2D network consisting of sp2-hybridized carbon atoms. Especially, the π-π stacking interaction between CGC and RGO enhances stable composite structure formation, expedites interlayer-electron transfer, and establishes three-dimensional (3D) ion transportation pathways. Owing to these unique structure, RGO@CGC exhibits fast and stable potassium storage capability. Furthermore, the effects of binders and electrolytes on the electrochemical performance of RGO@CGC were investigated. Finally, Prussian blue was synthesized as a positive electrode to explore the possibility of RGO@CGC as a full battery application.
2025, 36(4): 109739
doi: 10.1016/j.cclet.2024.109739
Abstract:
Two dimensional (2D) materials based on boron and carbon have attracted wide attention due to their unique properties. BC compounds have rich active sites and diverse chemical coordination, showing great potential in optoelectronic applications. However, due to the limitation of calculation and experimental conditions, it is still a challenging task to predict new 2D BC monolayer materials. Specifically, we utilized Crystal Diffusion Variational Autoencoder (CDVAE) and pre-trained Materials Graph Neural Network with 3-Body Interactions (M3GNet) model to generate novel and stable BCP materials. Each crystal structure was treated as a high-dimensional vector, where the encoder extracted lattice information and element coordinates, mapping the high-dimensional data into a low-dimensional latent space. The decoder then reconstructed the latent representation back into the original data space. Additionally, our designed attribute predictor network combined the advantages of dilated convolutions and residual connections, effectively increasing the model's receptive field and learning capacity while maintaining relatively low parameter count and computational complexity. By progressively increasing the dilation rate, the model can capture features at different scales. We used the DFT data set of about 1600 BCP monolayer materials to train the diffusion model, and combined with the pre-trained M3GNet model to screen the best candidate structure. Finally, we used DFT calculations to confirm the stability of the candidate structure. The results show that the combination of generative deep learning model and attribute prediction model can help accelerate the discovery and research of new 2D materials, and provide effective methods for exploring the inverse design of new two-dimensional materials.
Two dimensional (2D) materials based on boron and carbon have attracted wide attention due to their unique properties. BC compounds have rich active sites and diverse chemical coordination, showing great potential in optoelectronic applications. However, due to the limitation of calculation and experimental conditions, it is still a challenging task to predict new 2D BC monolayer materials. Specifically, we utilized Crystal Diffusion Variational Autoencoder (CDVAE) and pre-trained Materials Graph Neural Network with 3-Body Interactions (M3GNet) model to generate novel and stable BCP materials. Each crystal structure was treated as a high-dimensional vector, where the encoder extracted lattice information and element coordinates, mapping the high-dimensional data into a low-dimensional latent space. The decoder then reconstructed the latent representation back into the original data space. Additionally, our designed attribute predictor network combined the advantages of dilated convolutions and residual connections, effectively increasing the model's receptive field and learning capacity while maintaining relatively low parameter count and computational complexity. By progressively increasing the dilation rate, the model can capture features at different scales. We used the DFT data set of about 1600 BCP monolayer materials to train the diffusion model, and combined with the pre-trained M3GNet model to screen the best candidate structure. Finally, we used DFT calculations to confirm the stability of the candidate structure. The results show that the combination of generative deep learning model and attribute prediction model can help accelerate the discovery and research of new 2D materials, and provide effective methods for exploring the inverse design of new two-dimensional materials.
2025, 36(4): 109740
doi: 10.1016/j.cclet.2024.109740
Abstract:
Enhancement of the nonlinear optical (NLO) output power of lasers requires urgent development of an NLO crystal with a significant second-harmonic generation (SHG) response and sufficient birefringence for phase-matching capability; however, simultaneously optimizing these two key parameters remains a great challenge. In contrast to traditional single-anion units, the stereochemically-active lone pair Sb3+ ion is coordinated by S2− and I− ions to yield the mixed-anionic SbSI chalcohalide that can enhance hyperpolarizability and anisotropic polarizability concurrently. As anticipated, SbSI exhibited the largest SHG response (5.7 × AgGaS2@1.91 µm) among phase-matching Sb-based sulfides, the favorable laser-induced damage threshold (LIDT, 2.3 × AgGaS2@2.09 µm), and the giant calculated birefringence (0.62@1.91 µm). Structural analysis and computational simulations indicate that the highly polarizable mixed anion determine the enormous SHG response and birefringence.
Enhancement of the nonlinear optical (NLO) output power of lasers requires urgent development of an NLO crystal with a significant second-harmonic generation (SHG) response and sufficient birefringence for phase-matching capability; however, simultaneously optimizing these two key parameters remains a great challenge. In contrast to traditional single-anion units, the stereochemically-active lone pair Sb3+ ion is coordinated by S2− and I− ions to yield the mixed-anionic SbSI chalcohalide that can enhance hyperpolarizability and anisotropic polarizability concurrently. As anticipated, SbSI exhibited the largest SHG response (5.7 × AgGaS2@1.91 µm) among phase-matching Sb-based sulfides, the favorable laser-induced damage threshold (LIDT, 2.3 × AgGaS2@2.09 µm), and the giant calculated birefringence (0.62@1.91 µm). Structural analysis and computational simulations indicate that the highly polarizable mixed anion determine the enormous SHG response and birefringence.
2025, 36(4): 109770
doi: 10.1016/j.cclet.2024.109770
Abstract:
Metallabenzenes, a type of aromatic compound that includes metal atoms, have opened up new avenues for creating materials with unique properties. A distinctive feature of metallabenzenes is the significant deviation of their metal atoms from the planar configuration of the C5 ring, a phenomenon that paradoxically enhances their aromatic character. In this investigation, we propose that this counterintuitive increase in aromaticity upon geometric distortion is governed by the interactions of frontier orbitals in the σ-space. This insight not only corroborates the previously suggested role of σ-space orbitals in inducing geometric non-planarity in metallabenzenes but also underscores their pivotal contribution to the compounds' enhanced aromaticity. As a result, this work broadens the scope of the σ-control mechanism, highlighting its usefulness for the rational design of functional metalla-aromatic materials.
Metallabenzenes, a type of aromatic compound that includes metal atoms, have opened up new avenues for creating materials with unique properties. A distinctive feature of metallabenzenes is the significant deviation of their metal atoms from the planar configuration of the C5 ring, a phenomenon that paradoxically enhances their aromatic character. In this investigation, we propose that this counterintuitive increase in aromaticity upon geometric distortion is governed by the interactions of frontier orbitals in the σ-space. This insight not only corroborates the previously suggested role of σ-space orbitals in inducing geometric non-planarity in metallabenzenes but also underscores their pivotal contribution to the compounds' enhanced aromaticity. As a result, this work broadens the scope of the σ-control mechanism, highlighting its usefulness for the rational design of functional metalla-aromatic materials.
2025, 36(4): 109771
doi: 10.1016/j.cclet.2024.109771
Abstract:
The Fenton method is an effective technology for the removal of organic materials from wastewater. In this work, an induced catalyst Fe3O4 was synthesized by a hydrothermal method, and the modulation of the chemical composition of Fe3O4 crystals was achieved under the microwave shock method with the same effect as that of calcination treatment. Fe3O4 catalyst for the removal of the dye Rhodamine B (RhB) from polluted wastewater under microwave (MW), H2O2 system. The results showed that Fe3O4 nanomicrospheres prepared by microwave shock exhibited superior catalytic activity under the conditions of 500 W, 0.4 mol/L H2O2 and10 mg/L RhB, and the removal rate of RhB reached 98.5% after 10 min. The Fe3O4 catalysts also exhibited good stability and degradation efficiency. Electron paramagnetic resonance experiments confirmed that •OH plays a major role in the rapid degradation of RhB. Under microwave action, the catalyst produces electron-hole pairs, in which the holes react with OH− produced by water ionisation to form •OH, and the microwave-treated Fe3O4 produces more active species. Fe3+ and Fe2+ serve as microwave catalytic activity centers and Fenton catalytic activity centers, respectively. This research demonstrates that optimizing the Fe2+/Fe3+ ratio significantly enhances the degradation efficiency of RhB. This study presents novel views regarding the mechanism of microwave synergistic catalyst-induced Fenton.
The Fenton method is an effective technology for the removal of organic materials from wastewater. In this work, an induced catalyst Fe3O4 was synthesized by a hydrothermal method, and the modulation of the chemical composition of Fe3O4 crystals was achieved under the microwave shock method with the same effect as that of calcination treatment. Fe3O4 catalyst for the removal of the dye Rhodamine B (RhB) from polluted wastewater under microwave (MW), H2O2 system. The results showed that Fe3O4 nanomicrospheres prepared by microwave shock exhibited superior catalytic activity under the conditions of 500 W, 0.4 mol/L H2O2 and10 mg/L RhB, and the removal rate of RhB reached 98.5% after 10 min. The Fe3O4 catalysts also exhibited good stability and degradation efficiency. Electron paramagnetic resonance experiments confirmed that •OH plays a major role in the rapid degradation of RhB. Under microwave action, the catalyst produces electron-hole pairs, in which the holes react with OH− produced by water ionisation to form •OH, and the microwave-treated Fe3O4 produces more active species. Fe3+ and Fe2+ serve as microwave catalytic activity centers and Fenton catalytic activity centers, respectively. This research demonstrates that optimizing the Fe2+/Fe3+ ratio significantly enhances the degradation efficiency of RhB. This study presents novel views regarding the mechanism of microwave synergistic catalyst-induced Fenton.
2025, 36(4): 109773
doi: 10.1016/j.cclet.2024.109773
Abstract:
Fluoride-based electrolyte exhibits extraordinarily high oxidative stability in high-voltage lithium metal batteries (h-LMBs) due to the inherent low highest occupied molecular orbital (HOMO) of fluorinated solvents. However, such fascinating properties do not bring long-term cyclability of h-LMBs. One of critical challenges is the interface instability in contacting with the Li metal anode, as fluorinated solvents are highly susceptible to exceptionally reductive metallic Li attributed to its low lowest unoccupied molecular orbital (LUMO), which leads to significant consumption of the fluorinated components upon cycling. Herein, attenuating reductive decomposition of fluorinated electrolytes is proposed to circumvent rapid electrolyte consumption. Specifically, the vinylene carbonate (VC) is selected to tame the reduction decomposition by preferentially forming protective layer on the Li anode. This work, experimentally and computationally, demonstrates the importance of pre-passivation of Li metal anodes at high voltage to attenuate the decomposition of fluoroethylene carbonate (FEC). It is expected to enrich the understanding of how VC attenuate the reactivity of FEC, thereby extending the cycle life of fluorinated electrolytes in high-voltage Li-metal batteries.
Fluoride-based electrolyte exhibits extraordinarily high oxidative stability in high-voltage lithium metal batteries (h-LMBs) due to the inherent low highest occupied molecular orbital (HOMO) of fluorinated solvents. However, such fascinating properties do not bring long-term cyclability of h-LMBs. One of critical challenges is the interface instability in contacting with the Li metal anode, as fluorinated solvents are highly susceptible to exceptionally reductive metallic Li attributed to its low lowest unoccupied molecular orbital (LUMO), which leads to significant consumption of the fluorinated components upon cycling. Herein, attenuating reductive decomposition of fluorinated electrolytes is proposed to circumvent rapid electrolyte consumption. Specifically, the vinylene carbonate (VC) is selected to tame the reduction decomposition by preferentially forming protective layer on the Li anode. This work, experimentally and computationally, demonstrates the importance of pre-passivation of Li metal anodes at high voltage to attenuate the decomposition of fluoroethylene carbonate (FEC). It is expected to enrich the understanding of how VC attenuate the reactivity of FEC, thereby extending the cycle life of fluorinated electrolytes in high-voltage Li-metal batteries.
2025, 36(4): 109774
doi: 10.1016/j.cclet.2024.109774
Abstract:
Constructing high-performance electrocatalysts for oxygen evolution reaction (OER) using a simple and economical strategy is considerably meaningful yet still challenging. Herein, Co(OH)2/Mo2TiC2Tx (where T represents the surface functional groups, -O, -OH and -F) hetero-nanosheets were facilely prepared by the in situ topochemical transformation at room temperature towards efficient OER. The integrity of Co(OH)2 nanosheets and Mo2TiC2Tx nanosheets affords interfacial coupling to optimize the electronic structures of Co and Mo ions, which endows the high electron transfer efficiency and rapid reaction kinetics. As a result, the Co(OH)2/Mo2TiC2Tx hetero-nanosheets exhibit excellent OER performances with low overpotentials of 283 mV on glass-carbon electrode, and 227 mV on nickel foam at 10 mA/cm2. Furthermore, the decent anti-alkali ability underpins superior operational stability exceeding 100 h, demonstrating grand potential in practical applications. This work provides a new insight for the synthesis of efficient and cost-effective two-dimensional (2D) material-based electrocatalysts.
Constructing high-performance electrocatalysts for oxygen evolution reaction (OER) using a simple and economical strategy is considerably meaningful yet still challenging. Herein, Co(OH)2/Mo2TiC2Tx (where T represents the surface functional groups, -O, -OH and -F) hetero-nanosheets were facilely prepared by the in situ topochemical transformation at room temperature towards efficient OER. The integrity of Co(OH)2 nanosheets and Mo2TiC2Tx nanosheets affords interfacial coupling to optimize the electronic structures of Co and Mo ions, which endows the high electron transfer efficiency and rapid reaction kinetics. As a result, the Co(OH)2/Mo2TiC2Tx hetero-nanosheets exhibit excellent OER performances with low overpotentials of 283 mV on glass-carbon electrode, and 227 mV on nickel foam at 10 mA/cm2. Furthermore, the decent anti-alkali ability underpins superior operational stability exceeding 100 h, demonstrating grand potential in practical applications. This work provides a new insight for the synthesis of efficient and cost-effective two-dimensional (2D) material-based electrocatalysts.
2025, 36(4): 109793
doi: 10.1016/j.cclet.2024.109793
Abstract:
Exploring the intrinsic reasons for the dynamic reconstruction of catalysts during electrocatalytic reactions and their impact on activity enhancement still face severe challenges. Herein, the bifunctional catalyst Ru/V-CoO/CP with doping strategy and heterostructure was synthesized for overall water splitting. The Ru/V-CoO exhibits excellent activity for HER and OER with low overpotentials of 49, 147 mV at a current density of 10 mA/cm2 in 1.0 mol/L KOH, respectively. The assembled electrolytic cell just needs voltages of 1.47 and 1.71 V to achieve 10 and 350 mA/cm2 current density under the same conditions and delivers an outstanding stability for over 100 h, which is far superior to the commercial RuO2Pt/C cell. Experimental and theoretical results indicate that the doping of V species and the formation of heterostructures lead to charge redistribution. More importantly, the leaching of V species induces electron transfer form Co to O and then Ru through the Co-O-Ru electron bridge, optimizes the adsorption strength of the key intermediate, thereby reducing the free energy barrier of the rate-determining step and improving catalytic activity. This work proposes an effective strategy of using cation dissolution to induce electron transfer through the electron bridge and thus regulate the electronic structure of catalysts, providing new ideas for the design and development of efficient and stable electrocatalysts.
Exploring the intrinsic reasons for the dynamic reconstruction of catalysts during electrocatalytic reactions and their impact on activity enhancement still face severe challenges. Herein, the bifunctional catalyst Ru/V-CoO/CP with doping strategy and heterostructure was synthesized for overall water splitting. The Ru/V-CoO exhibits excellent activity for HER and OER with low overpotentials of 49, 147 mV at a current density of 10 mA/cm2 in 1.0 mol/L KOH, respectively. The assembled electrolytic cell just needs voltages of 1.47 and 1.71 V to achieve 10 and 350 mA/cm2 current density under the same conditions and delivers an outstanding stability for over 100 h, which is far superior to the commercial RuO2Pt/C cell. Experimental and theoretical results indicate that the doping of V species and the formation of heterostructures lead to charge redistribution. More importantly, the leaching of V species induces electron transfer form Co to O and then Ru through the Co-O-Ru electron bridge, optimizes the adsorption strength of the key intermediate, thereby reducing the free energy barrier of the rate-determining step and improving catalytic activity. This work proposes an effective strategy of using cation dissolution to induce electron transfer through the electron bridge and thus regulate the electronic structure of catalysts, providing new ideas for the design and development of efficient and stable electrocatalysts.
2025, 36(4): 109794
doi: 10.1016/j.cclet.2024.109794
Abstract:
Natural hydraulic lime (NHL) has garnered increasing attention for its sustainable and suitable performance in the field of historical building restoration. However, the prolonged hardening time and sluggish hydration rate of NHL influence the workability, strength development, and durability of construction structures in which it is used. In this study, nano-metakaolin (NMK) was applied as a highly reactive supplementary cementitious material (SCM) for NHL-based mortars to enhance their properties with various ratios. Meanwhile, the effects of NMK and its related enhancement mechanism on the physical properties and chemical structures of NHL composites were systematically investigated, mainly involving the modifications in their microstructure, chemical composition, and C-S-H structure. Results demonstrated that NMK-modified samples showed distinct and superior properties to pure NHL sample, such as shorter initial/final setting times (15.1%–49.1%, 27.1%–50.0%), and higher compactness (67.8%–81.4%, 38.1%–44.8%), lower shrinkage (25.0%–56.3%, 12.5%–25.0%), enhanced compressive strength (404.5%–546.0%, 180.8%–354.1%) and flexural strength (227.5%–351.1%, 59.9%–125.7%) for both early and late curing times (7 and 28 days). The inclusion of NMK not only acts as a fine filler, but also promotes NHL's hydrate rate by its super high pozzolanic activity, thus optimizing the pore structures and increasing the content and the average silicate chain length of hydration gel in NHL. Overall, this study can contribute to a deeper understanding of the enhancement mechanism of NMK on the physical properties and chemical structures of NHL from a meso/microscopic perspective, with a view to broadening NHL's potential applications.
Natural hydraulic lime (NHL) has garnered increasing attention for its sustainable and suitable performance in the field of historical building restoration. However, the prolonged hardening time and sluggish hydration rate of NHL influence the workability, strength development, and durability of construction structures in which it is used. In this study, nano-metakaolin (NMK) was applied as a highly reactive supplementary cementitious material (SCM) for NHL-based mortars to enhance their properties with various ratios. Meanwhile, the effects of NMK and its related enhancement mechanism on the physical properties and chemical structures of NHL composites were systematically investigated, mainly involving the modifications in their microstructure, chemical composition, and C-S-H structure. Results demonstrated that NMK-modified samples showed distinct and superior properties to pure NHL sample, such as shorter initial/final setting times (15.1%–49.1%, 27.1%–50.0%), and higher compactness (67.8%–81.4%, 38.1%–44.8%), lower shrinkage (25.0%–56.3%, 12.5%–25.0%), enhanced compressive strength (404.5%–546.0%, 180.8%–354.1%) and flexural strength (227.5%–351.1%, 59.9%–125.7%) for both early and late curing times (7 and 28 days). The inclusion of NMK not only acts as a fine filler, but also promotes NHL's hydrate rate by its super high pozzolanic activity, thus optimizing the pore structures and increasing the content and the average silicate chain length of hydration gel in NHL. Overall, this study can contribute to a deeper understanding of the enhancement mechanism of NMK on the physical properties and chemical structures of NHL from a meso/microscopic perspective, with a view to broadening NHL's potential applications.
2025, 36(4): 109795
doi: 10.1016/j.cclet.2024.109795
Abstract:
Polyphosphazene with phenoxy or 4-ester phenoxy as pendent groups are demonstrated as both ligands and host matrices for CsPbBr3 perovskite nanocrystals (NCs). These polymers produced flexible nanocomposite films with excellent NCs dispersion, optical transparency and stability in various extreme conditions. Both films remained stable even after 30 days of air storage. CsPbBr3/poly[bis(phenoxy phosphazene)] (PBPP) delivered better air and light stability, and CsPbBr3/poly[bis(4-esterphenoxy)phosphazene] (PBEPP) exhibited superior water and heat resistance. CsPbBr3/PBEPP showed a greater increase in fluorescence intensity under 365 nm UV light and demonstrated a 10% luminescence increase after 96 h of water immersion and even at high temperature (150 ℃). These findings thus provide new insight into flexible luminescent CsPbBr3 films with high stability in optoelectronic applications.
Polyphosphazene with phenoxy or 4-ester phenoxy as pendent groups are demonstrated as both ligands and host matrices for CsPbBr3 perovskite nanocrystals (NCs). These polymers produced flexible nanocomposite films with excellent NCs dispersion, optical transparency and stability in various extreme conditions. Both films remained stable even after 30 days of air storage. CsPbBr3/poly[bis(phenoxy phosphazene)] (PBPP) delivered better air and light stability, and CsPbBr3/poly[bis(4-esterphenoxy)phosphazene] (PBEPP) exhibited superior water and heat resistance. CsPbBr3/PBEPP showed a greater increase in fluorescence intensity under 365 nm UV light and demonstrated a 10% luminescence increase after 96 h of water immersion and even at high temperature (150 ℃). These findings thus provide new insight into flexible luminescent CsPbBr3 films with high stability in optoelectronic applications.
2025, 36(4): 109796
doi: 10.1016/j.cclet.2024.109796
Abstract:
Metal phosphosulfides have been recognized as advanced anode materials for sodium/potassium ion batteries due to their high theoretical capacities and the incorporation of the advantage of metal sulfides and phosphates. However, they also suffer from the shortcomings of frustrating cycling stability due to the large volume expansion and unsatisfactory electrical conductivity. Herein, hexapod cobalt phosphosulfide nanodots based nanorods encapsulating into N, P, and S hetero-atoms tri-doped carbon framework (CoP/CoS2@NPSC) have been triumphantly designed and synthesized. The six nanorods constructed hexapod framework and multi-atom doped carbon matrix not only provides more active sites, but also contribute to maintain the structure integrity from avoiding the agglomeration of internal CoP and CoS2 nanodots. The synergistic effect between CoP and CoS2 components, as well as the CoP/CoS2 and the NPSC carbon framework can improve the electrochemical conductivity. Besides, the kinetics analysis demonstrated that N/P/S tri-doping could greatly increase the interlayer distance and introduce enough active sites, which effectively facilitate the transport, adsorption, insertion and diffusion of Na+ and K+. CoP/CoS2@NPSC demonstrated excellent electrochemical properties and battery performances including excellent cycle stability with 404.63 mAh/g at 5.0 A/g around 700 cycles for SIBs and 115.33 mAh/g at 5.0 A/g around 800 cycles for PIBs. This presented strategy establishes a novel and adaptable method for the integration of doped carbon with metal phosphosulfide and guides a new research approach and direction for secondary batteries electrode materials.
Metal phosphosulfides have been recognized as advanced anode materials for sodium/potassium ion batteries due to their high theoretical capacities and the incorporation of the advantage of metal sulfides and phosphates. However, they also suffer from the shortcomings of frustrating cycling stability due to the large volume expansion and unsatisfactory electrical conductivity. Herein, hexapod cobalt phosphosulfide nanodots based nanorods encapsulating into N, P, and S hetero-atoms tri-doped carbon framework (CoP/CoS2@NPSC) have been triumphantly designed and synthesized. The six nanorods constructed hexapod framework and multi-atom doped carbon matrix not only provides more active sites, but also contribute to maintain the structure integrity from avoiding the agglomeration of internal CoP and CoS2 nanodots. The synergistic effect between CoP and CoS2 components, as well as the CoP/CoS2 and the NPSC carbon framework can improve the electrochemical conductivity. Besides, the kinetics analysis demonstrated that N/P/S tri-doping could greatly increase the interlayer distance and introduce enough active sites, which effectively facilitate the transport, adsorption, insertion and diffusion of Na+ and K+. CoP/CoS2@NPSC demonstrated excellent electrochemical properties and battery performances including excellent cycle stability with 404.63 mAh/g at 5.0 A/g around 700 cycles for SIBs and 115.33 mAh/g at 5.0 A/g around 800 cycles for PIBs. This presented strategy establishes a novel and adaptable method for the integration of doped carbon with metal phosphosulfide and guides a new research approach and direction for secondary batteries electrode materials.
2025, 36(4): 109797
doi: 10.1016/j.cclet.2024.109797
Abstract:
Electrocatalytic reduction of NO (NORR) is an effective method for NH3 synthesis, due to low bonding energy of NO bond. In this work, we have investigated many CrS2 based catalysts, including pristine CrS2, CrS2 with one S vacancy (v-CrS2), and Ti doped CrS2 (Ti@CrS2). The results have shown that the pristine CrS2 exhibits inert character for NO activation. However, v-CrS2 and Ti@CrS2 can exhibit enhanced interaction with NO, due to increased charge transfer between NO and substrates (0.52–0.75 e) and enhanced adsorption energies of NO on the catalysts (-0.96~-1.64 eV), compared to the situation of CrS2 (0.065 e/-0.30 eV). From the free energy profiles of NO electro-reduction to NH3, we can see that the v-CrS2 and Ti@CrS2 all exhibit ultralow limiting potentials of -0.03~-0.47 V, following both *NOH and *NHO mechanisms. Therefore, introducing vacancy and doping are all promising modification strategies for NORR catalysts. The results have provided a new idea for the search of catalysts for efficient electrocatalytic reduction of NO.
Electrocatalytic reduction of NO (NORR) is an effective method for NH3 synthesis, due to low bonding energy of NO bond. In this work, we have investigated many CrS2 based catalysts, including pristine CrS2, CrS2 with one S vacancy (v-CrS2), and Ti doped CrS2 (Ti@CrS2). The results have shown that the pristine CrS2 exhibits inert character for NO activation. However, v-CrS2 and Ti@CrS2 can exhibit enhanced interaction with NO, due to increased charge transfer between NO and substrates (0.52–0.75 e) and enhanced adsorption energies of NO on the catalysts (-0.96~-1.64 eV), compared to the situation of CrS2 (0.065 e/-0.30 eV). From the free energy profiles of NO electro-reduction to NH3, we can see that the v-CrS2 and Ti@CrS2 all exhibit ultralow limiting potentials of -0.03~-0.47 V, following both *NOH and *NHO mechanisms. Therefore, introducing vacancy and doping are all promising modification strategies for NORR catalysts. The results have provided a new idea for the search of catalysts for efficient electrocatalytic reduction of NO.
2025, 36(4): 109800
doi: 10.1016/j.cclet.2024.109800
Abstract:
Self-trapping excitons (STEs) emission in metal halides has been a matter of interest, correlating with the strength of electron-phonon coupling in the lattice, which are usually caused by ions with ns2 electronic structure. In this work, Sb3+/Te4+ ions doped Zn-based halide single crystals (SCs) with two STEs emissions have been synthesized and the possibility of its anti-counterfeiting application was explored. Further, the relationship between the strength of electron-phonon coupling and photoluminescence quantum yields (PLQYs) for STEs in a series of metal halides has been studied. And the semi-empirical range of the Huang-Rhys factors (S) for metal halides with excellent photoluminescence (PL) property has been summarized. This work provides ideas for further research into the relationship between luminescence performance and electron-phonon coupling of metal halides, and also provides a reference for designing the metal halides with high PLQYs.
Self-trapping excitons (STEs) emission in metal halides has been a matter of interest, correlating with the strength of electron-phonon coupling in the lattice, which are usually caused by ions with ns2 electronic structure. In this work, Sb3+/Te4+ ions doped Zn-based halide single crystals (SCs) with two STEs emissions have been synthesized and the possibility of its anti-counterfeiting application was explored. Further, the relationship between the strength of electron-phonon coupling and photoluminescence quantum yields (PLQYs) for STEs in a series of metal halides has been studied. And the semi-empirical range of the Huang-Rhys factors (S) for metal halides with excellent photoluminescence (PL) property has been summarized. This work provides ideas for further research into the relationship between luminescence performance and electron-phonon coupling of metal halides, and also provides a reference for designing the metal halides with high PLQYs.
2025, 36(4): 109801
doi: 10.1016/j.cclet.2024.109801
Abstract:
In the field of lithium-ion battery cathode materials, lithium-rich layered oxide materials have garnered significant attention due to their exceptional discharge specific capacity and high operating voltage. However, their limitations in terms of cycling stability and rate capability remain major impediments to their wider application. In this study, an innovative approach was employed by simultaneously utilizing the acidic and oxidative properties of phosphomolybdic acid to generate a spinel structure and in-situ coating of a conductive polymer (polypyrrole) on the surface of lithium-rich layered oxide materials. This strategy aimed to mitigate structural degradation during charge-discharge cycles, enhance the ionic/electronic conductivity, and suppress side reactions. Experimental results demonstrated that after 200 cycles at a current density of 1 C, the modified sample exhibited a discharge specific capacity of 193.4 mAh/g, with an improved capacity retention rate of 83.3% and a minimal voltage decay of only 0.27 V. These findings provide compelling support for the development and application of next-generation high-performance lithium-ion batteries.
In the field of lithium-ion battery cathode materials, lithium-rich layered oxide materials have garnered significant attention due to their exceptional discharge specific capacity and high operating voltage. However, their limitations in terms of cycling stability and rate capability remain major impediments to their wider application. In this study, an innovative approach was employed by simultaneously utilizing the acidic and oxidative properties of phosphomolybdic acid to generate a spinel structure and in-situ coating of a conductive polymer (polypyrrole) on the surface of lithium-rich layered oxide materials. This strategy aimed to mitigate structural degradation during charge-discharge cycles, enhance the ionic/electronic conductivity, and suppress side reactions. Experimental results demonstrated that after 200 cycles at a current density of 1 C, the modified sample exhibited a discharge specific capacity of 193.4 mAh/g, with an improved capacity retention rate of 83.3% and a minimal voltage decay of only 0.27 V. These findings provide compelling support for the development and application of next-generation high-performance lithium-ion batteries.
2025, 36(4): 109815
doi: 10.1016/j.cclet.2024.109815
Abstract:
Unstable electrode/electrolyte interfaces and heterogeneous Zn deposition would reduce the Coulombic efficiency and cycle life of Zn metal batteries (ZMBs). Applying water-in-salt (WIS) electrolytes has proven to be an effective strategy to address the above issues. However, an understanding of the reaction mechanisms on the Zn anode at nanoscale is still elusive. Here we utilize in situ atomic force microscopy to visualize the solid electrolyte interphase (SEI) formation and Zn deposition/dissolution processes in WIS electrolyte and construct relationships between interfacial behavior and electrochemical performance. The formation processes, chemical properties, and structure of the on-site formed SEI are deeply explored. The SEI with a “plum-pudding” model can guide uniform Zn deposition and reversible dissolution. Mechanistic understanding of the interfacial evolution of the SEI layer and Zn deposition/dissolution has been achieved and will benefit the structural optimization and interfacial engineering of ZMBs.
Unstable electrode/electrolyte interfaces and heterogeneous Zn deposition would reduce the Coulombic efficiency and cycle life of Zn metal batteries (ZMBs). Applying water-in-salt (WIS) electrolytes has proven to be an effective strategy to address the above issues. However, an understanding of the reaction mechanisms on the Zn anode at nanoscale is still elusive. Here we utilize in situ atomic force microscopy to visualize the solid electrolyte interphase (SEI) formation and Zn deposition/dissolution processes in WIS electrolyte and construct relationships between interfacial behavior and electrochemical performance. The formation processes, chemical properties, and structure of the on-site formed SEI are deeply explored. The SEI with a “plum-pudding” model can guide uniform Zn deposition and reversible dissolution. Mechanistic understanding of the interfacial evolution of the SEI layer and Zn deposition/dissolution has been achieved and will benefit the structural optimization and interfacial engineering of ZMBs.
2025, 36(4): 109845
doi: 10.1016/j.cclet.2024.109845
Abstract:
Mo2N has been identified as a highly promising carrier for electrocatalysis. However, its complex synthesis method, use of toxic gases, and serious effects on supported noble metals catalyst during high-temperature sintering processes have seriously affected its hydrogen evolution reaction (HER) activity and stability. Here, we report an efficient strategy for synthesizing Mo2N using the high temperature shock (HTS) method in just 1.67 s, while also uniformly loading Ru onto Mo2N nanosheets. The HTS enables the homogeneous dispersion of the noble metal Ru, leading to an increased electrocatalytic activity, along with a strong charge transfer between Mo2N and Ru. Ru/Mo2N exhibited an overpotential of 66 mV at 10 mA/cm2 in 1 mol/L KOH. In the evaluation of catalytic activity, Ru/Mo2N demonstrates superiority over commercial Pt/C catalysts in terms of mass activity (1.71 A/mgRu vs. 0.91 A/mgPt at 200 mV) and turnover frequency (1.41 s−1 vs. 0.18 s−1 at 100 mV). This result provides a rational and effective pathway for the preparation of efficient electrocatalysts.
Mo2N has been identified as a highly promising carrier for electrocatalysis. However, its complex synthesis method, use of toxic gases, and serious effects on supported noble metals catalyst during high-temperature sintering processes have seriously affected its hydrogen evolution reaction (HER) activity and stability. Here, we report an efficient strategy for synthesizing Mo2N using the high temperature shock (HTS) method in just 1.67 s, while also uniformly loading Ru onto Mo2N nanosheets. The HTS enables the homogeneous dispersion of the noble metal Ru, leading to an increased electrocatalytic activity, along with a strong charge transfer between Mo2N and Ru. Ru/Mo2N exhibited an overpotential of 66 mV at 10 mA/cm2 in 1 mol/L KOH. In the evaluation of catalytic activity, Ru/Mo2N demonstrates superiority over commercial Pt/C catalysts in terms of mass activity (1.71 A/mgRu vs. 0.91 A/mgPt at 200 mV) and turnover frequency (1.41 s−1 vs. 0.18 s−1 at 100 mV). This result provides a rational and effective pathway for the preparation of efficient electrocatalysts.
2025, 36(4): 109913
doi: 10.1016/j.cclet.2024.109913
Abstract:
Prostaglandin E2 (PGE2) serves as the ultimate mediator of fever induced by inflammatory factors. In contrast to cyclooxygenase inhibitors that suppress arachidonic acid metabolism, antipyretic herbs possess a well-established clinical history in effectively managing fever. However, the specific mechanisms underlying their efficacy remain unclear. Following the screening for lead compounds that inhibit PGE2 from antipyretic herbs, alkynylated active molecule probes were designed and synthesized to track and identify potential targets. The target investigation revealed that three antipyretic compounds, namely cinnamaldehyde, 2,4-decadienal, and perillaldehyde, containing α,β-unsaturated aldehyde groups irreversibly targeted the microsomal PGES1-TM4 helix (mPGES1-TM4) at Ser139. This specific interaction effectually inhibited PGE2 production in the cerebral vasculature, leading to exert potent antipyretic effects. α,β-Unsaturated aldehydes targeting mPGES1-TM4 offer a new approach for antipyretic effects with significant potential for various applications.
Prostaglandin E2 (PGE2) serves as the ultimate mediator of fever induced by inflammatory factors. In contrast to cyclooxygenase inhibitors that suppress arachidonic acid metabolism, antipyretic herbs possess a well-established clinical history in effectively managing fever. However, the specific mechanisms underlying their efficacy remain unclear. Following the screening for lead compounds that inhibit PGE2 from antipyretic herbs, alkynylated active molecule probes were designed and synthesized to track and identify potential targets. The target investigation revealed that three antipyretic compounds, namely cinnamaldehyde, 2,4-decadienal, and perillaldehyde, containing α,β-unsaturated aldehyde groups irreversibly targeted the microsomal PGES1-TM4 helix (mPGES1-TM4) at Ser139. This specific interaction effectually inhibited PGE2 production in the cerebral vasculature, leading to exert potent antipyretic effects. α,β-Unsaturated aldehydes targeting mPGES1-TM4 offer a new approach for antipyretic effects with significant potential for various applications.
2025, 36(4): 109914
doi: 10.1016/j.cclet.2024.109914
Abstract:
Acute lung injury (ALI) is a critical respiratory disorder with a high mortality rate and is caused by several factors. Addressing oxidative stress and inflammation is a pivotal strategy for ALI treatment. In this study, we introduced a novel nanotherapeutic approach involving a curcumin-loaded ceria nanoenzyme delivery system tailored to counteract the multifaceted aspects of ALI. This system leverages the individual and combined effects of the components to provide a comprehensive therapeutic solution. The dual-action capability of this nanosystem was manifested by mitigating mitochondrial oxidative stress in lung epithelial cells and inhibiting the transient receptor potential melanosome-associated protein 2 (TRPM2)-NOD-like receptor thermal protein domain associated protein 3 (NLRP3) signaling pathway, offering a highly effective therapeutic approach to ALI. Our findings reveal the underlying mechanisms of this innovative nanodelivery system, showcasing its potential as a versatile strategy for ALI treatment and encouraging further exploration of nanoenzyme-based therapies for ALI.
Acute lung injury (ALI) is a critical respiratory disorder with a high mortality rate and is caused by several factors. Addressing oxidative stress and inflammation is a pivotal strategy for ALI treatment. In this study, we introduced a novel nanotherapeutic approach involving a curcumin-loaded ceria nanoenzyme delivery system tailored to counteract the multifaceted aspects of ALI. This system leverages the individual and combined effects of the components to provide a comprehensive therapeutic solution. The dual-action capability of this nanosystem was manifested by mitigating mitochondrial oxidative stress in lung epithelial cells and inhibiting the transient receptor potential melanosome-associated protein 2 (TRPM2)-NOD-like receptor thermal protein domain associated protein 3 (NLRP3) signaling pathway, offering a highly effective therapeutic approach to ALI. Our findings reveal the underlying mechanisms of this innovative nanodelivery system, showcasing its potential as a versatile strategy for ALI treatment and encouraging further exploration of nanoenzyme-based therapies for ALI.
2025, 36(4): 109917
doi: 10.1016/j.cclet.2024.109917
Abstract:
Diabetes mellitus (DM) is a serious health problem in the world, and infections are common complications in diabetic patients, particularly methicillin-resistant Staphylococcus aureus (MRSA) infections, which substantially increases mortality in patients. In clinical practice, the treatment of diabetic complication-related infections involves multiple issues such as drug resistance when combining antidiabetic drugs with antibiotics. In this study, a series of derivatives were synthesized with alkyl radicals with different chain lengths substituted at the C8 and C12 positions of berberine, with compounds CY1 and CY3 with good antidiabetic and antibacterial activities screened out after identification. Then, oral liposomes (CY1-Lip and CY3-Lip) were prepared, and their particle sizes, stability, and pharmacokinetics were investigated. In acquired mouse models of diabetes, induced with an acute MRSA lung infection, we demonstrate that CY1-Lip and CY3-Lip can effectively reduce levels of fasting blood glucose (FBG), fasting insulin (FINS), and insulin resistance index among diabetic mice with pneumonia, thus exerting their multi-targets effects. Furthermore, both preparations significantly reduced lung MRSA loads and improved lung tissue lesions, reduced high infiltration of M1 macrophages in lung, and suppressed the expression levels of pro-inflammatory factors such as necrosis factor-α (TNF-α) and interleukin-6 (IL-6). This provides new insights into the clinical treatment of diabetes complicated with pulmonary infections.
Diabetes mellitus (DM) is a serious health problem in the world, and infections are common complications in diabetic patients, particularly methicillin-resistant Staphylococcus aureus (MRSA) infections, which substantially increases mortality in patients. In clinical practice, the treatment of diabetic complication-related infections involves multiple issues such as drug resistance when combining antidiabetic drugs with antibiotics. In this study, a series of derivatives were synthesized with alkyl radicals with different chain lengths substituted at the C8 and C12 positions of berberine, with compounds CY1 and CY3 with good antidiabetic and antibacterial activities screened out after identification. Then, oral liposomes (CY1-Lip and CY3-Lip) were prepared, and their particle sizes, stability, and pharmacokinetics were investigated. In acquired mouse models of diabetes, induced with an acute MRSA lung infection, we demonstrate that CY1-Lip and CY3-Lip can effectively reduce levels of fasting blood glucose (FBG), fasting insulin (FINS), and insulin resistance index among diabetic mice with pneumonia, thus exerting their multi-targets effects. Furthermore, both preparations significantly reduced lung MRSA loads and improved lung tissue lesions, reduced high infiltration of M1 macrophages in lung, and suppressed the expression levels of pro-inflammatory factors such as necrosis factor-α (TNF-α) and interleukin-6 (IL-6). This provides new insights into the clinical treatment of diabetes complicated with pulmonary infections.
2025, 36(4): 109922
doi: 10.1016/j.cclet.2024.109922
Abstract:
Photoinitiators (PIs), as the key substances for photopolymerized antibacterial film (PAF), affect the cure rate and color of PAF. Herein, two enone dyes were designed and synthesized by a facile approach. Among the candidates, BDO1 has demonstrated the ability to initiate polymerization of acrylate monomers as single-component PI with the advantages of low mobility, outstanding photobleaching, excellent cytocompatibility, and suitability for light emitting diode (LED) light sources above 365 nm. Taking BDOs as examples, a novel method based on theoretical calculations aiming to assess the potential of enone molecules as single-component PIs was proposed. Finally, under the initiation of BDO1, tannic acid was photopolymerized to a colorless and transparent antibacterial film with high antibacterial ability, which indicated that BDO1 was expected to be used in environmentally friendly PAF.
Photoinitiators (PIs), as the key substances for photopolymerized antibacterial film (PAF), affect the cure rate and color of PAF. Herein, two enone dyes were designed and synthesized by a facile approach. Among the candidates, BDO1 has demonstrated the ability to initiate polymerization of acrylate monomers as single-component PI with the advantages of low mobility, outstanding photobleaching, excellent cytocompatibility, and suitability for light emitting diode (LED) light sources above 365 nm. Taking BDOs as examples, a novel method based on theoretical calculations aiming to assess the potential of enone molecules as single-component PIs was proposed. Finally, under the initiation of BDO1, tannic acid was photopolymerized to a colorless and transparent antibacterial film with high antibacterial ability, which indicated that BDO1 was expected to be used in environmentally friendly PAF.
2025, 36(4): 109942
doi: 10.1016/j.cclet.2024.109942
Abstract:
Established evidence has unveiled two strategies for treating cancer: depleting tumor-associated macrophages (TAMs) and reprogramming M2-like TAMs into an antitumor M1 phenotype. Here, we designed novel pH-sensitive biomimetic hybrid nanovesicles (EDHPA) loaded with doxorubicin (DOX). DOX@EDHPA can specifically target TAMs by activating macrophage-derived exosomes (M1-Exos) and anisamide (AA) as cancer-specific targeting ligands. In vitro and in vivo studies demonstrated that DOX@EDHPA could efficiently be delivered to the tumor site and taken up by cells. Meanwhile, it synergistically enhanced immunogenic cell death (ICD) and induced a subsequent antigen-specific T cell immune response. The tumor inhibitory rate of the DOX@EDHPA group was 1.42 times that of the free DOX group. Further analysis showed that the excellent antitumor effects of DOX@EDHPA should ascribe to the homing effect of M1-Exos on macrophages and the repolarization to antitumor M1 TAMs, which induced the elevated secretion of pro-inflammatory factors. Therefore, the hybrid EDHPA targeting TAMs to reshape the tumor microenvironment constituted a novel immunochemotherapy strategy to inhibit tumor growth.
Established evidence has unveiled two strategies for treating cancer: depleting tumor-associated macrophages (TAMs) and reprogramming M2-like TAMs into an antitumor M1 phenotype. Here, we designed novel pH-sensitive biomimetic hybrid nanovesicles (EDHPA) loaded with doxorubicin (DOX). DOX@EDHPA can specifically target TAMs by activating macrophage-derived exosomes (M1-Exos) and anisamide (AA) as cancer-specific targeting ligands. In vitro and in vivo studies demonstrated that DOX@EDHPA could efficiently be delivered to the tumor site and taken up by cells. Meanwhile, it synergistically enhanced immunogenic cell death (ICD) and induced a subsequent antigen-specific T cell immune response. The tumor inhibitory rate of the DOX@EDHPA group was 1.42 times that of the free DOX group. Further analysis showed that the excellent antitumor effects of DOX@EDHPA should ascribe to the homing effect of M1-Exos on macrophages and the repolarization to antitumor M1 TAMs, which induced the elevated secretion of pro-inflammatory factors. Therefore, the hybrid EDHPA targeting TAMs to reshape the tumor microenvironment constituted a novel immunochemotherapy strategy to inhibit tumor growth.
2025, 36(4): 109943
doi: 10.1016/j.cclet.2024.109943
Abstract:
The occurrence, development, and metastasis of tumors often entail abnormal expression of genetic substances. Monitoring and regulating changes in intracellular nucleic acid substances hold promise for achieving accurate tumor diagnosis and effective treatment. However, the effectiveness of integrated tumor diagnosis and treatment based on functional nucleic acids still needs to be improved. In this study, we engineered a multifunctional nucleic acid delivery system grounded in a cationic covalent organic framework carrier. This system not only showcases effective gene silencing but also boasts high sensitivity in detecting miR21 levels within tumor cells, enabling real-time monitoring of tumor gene therapy efficacy. The construction of this integrated functional nucleic acid delivery platform provides new ideas for precise tumor detection and effective tumor treatment.
The occurrence, development, and metastasis of tumors often entail abnormal expression of genetic substances. Monitoring and regulating changes in intracellular nucleic acid substances hold promise for achieving accurate tumor diagnosis and effective treatment. However, the effectiveness of integrated tumor diagnosis and treatment based on functional nucleic acids still needs to be improved. In this study, we engineered a multifunctional nucleic acid delivery system grounded in a cationic covalent organic framework carrier. This system not only showcases effective gene silencing but also boasts high sensitivity in detecting miR21 levels within tumor cells, enabling real-time monitoring of tumor gene therapy efficacy. The construction of this integrated functional nucleic acid delivery platform provides new ideas for precise tumor detection and effective tumor treatment.
2025, 36(4): 109956
doi: 10.1016/j.cclet.2024.109956
Abstract:
Idiopathic pulmonary fibrosis (IPF) is a progressive lung disease with high mortality rate but effective therapeutics are still lacking. Phosphodiesterase-4 (PDE4) inhibitors were reported to be promising anti-IPF agents. Herein, series of biflavonoids isolated from Selaginella uncinate were found to be PDE4 inhibitors and the most active amentoflavone gave a half maximal inhibitory concentration (IC50) of 12 nmol/L, which was further validated by isothermal titration calorimetry with Kd of 23 nmol/L. Besides, co-crystal structure of PDE4-amentoflavone was determined and gave a different binding pattern from roflumilast with multiple H-bonds between it and key residues such as Asn321/Thr333/Gln369/Gly371. So far, this was the first reported co-crystal structure of amentoflavone with its potential binding target in despite of the extensive investigations of this common natural biflavonoid. Furthermore, amentoflavone exhibited remarkable anti-IPF effects in vivo and in vitro, suggesting it as a novel anti-fibrotic agent by targeting PDE4.
Idiopathic pulmonary fibrosis (IPF) is a progressive lung disease with high mortality rate but effective therapeutics are still lacking. Phosphodiesterase-4 (PDE4) inhibitors were reported to be promising anti-IPF agents. Herein, series of biflavonoids isolated from Selaginella uncinate were found to be PDE4 inhibitors and the most active amentoflavone gave a half maximal inhibitory concentration (IC50) of 12 nmol/L, which was further validated by isothermal titration calorimetry with Kd of 23 nmol/L. Besides, co-crystal structure of PDE4-amentoflavone was determined and gave a different binding pattern from roflumilast with multiple H-bonds between it and key residues such as Asn321/Thr333/Gln369/Gly371. So far, this was the first reported co-crystal structure of amentoflavone with its potential binding target in despite of the extensive investigations of this common natural biflavonoid. Furthermore, amentoflavone exhibited remarkable anti-IPF effects in vivo and in vitro, suggesting it as a novel anti-fibrotic agent by targeting PDE4.
2025, 36(4): 109965
doi: 10.1016/j.cclet.2024.109965
Abstract:
Recently, MP-10, a previous drug candidate with potent inhibition of phosphodiesterase 10A (PDE10A) in clinical phase II trials for schizophrenia or Alzheimer's disease, has shown significant potential in preventing and treating cardiovascular diseases. However, its poor metabolic stability and high permeability across the blood-brain barrier (BBB) make it unsuitable for preventing and treating peripheral cardiovascular diseases. Herein, the hit-to-lead optimization was performed to discover novel 3-trifluoromethyl-substituted pyrazole derivatives as potent and selective PDE10A inhibitors. The structure-activity relationships, biological characterization, molecular mechanism, and drug-like evaluation were discussed to identify compound C7 which showed potent inhibition against PDE10A (half maximal inhibitory concentration, IC50 = 11.9 nmol/L), more than 840-fold selectivity over other PDE subtypes, enhanced liver microsomes stability (T1/2 = 239 min) compared to MP-10 and low BBB permeability. Importantly, oral pretreatment with C7·3HCl at a dose of 5.0 mg/kg significantly attenuated the pathological and functional changes induced by isoprenaline (ISO)-induced pathological cardiac hypertrophy in mice, particularly suppressing increase of cardiac weight, atrial natriuretic peptide (ANP) and β-myosin heavy chain (β-MHC) hypertrophic markers along with cardiac fibrosis. These findings further support that targeting PDE10A provides an innovative therapeutic approach for preventing and treating cardiac diseases.
Recently, MP-10, a previous drug candidate with potent inhibition of phosphodiesterase 10A (PDE10A) in clinical phase II trials for schizophrenia or Alzheimer's disease, has shown significant potential in preventing and treating cardiovascular diseases. However, its poor metabolic stability and high permeability across the blood-brain barrier (BBB) make it unsuitable for preventing and treating peripheral cardiovascular diseases. Herein, the hit-to-lead optimization was performed to discover novel 3-trifluoromethyl-substituted pyrazole derivatives as potent and selective PDE10A inhibitors. The structure-activity relationships, biological characterization, molecular mechanism, and drug-like evaluation were discussed to identify compound C7 which showed potent inhibition against PDE10A (half maximal inhibitory concentration, IC50 = 11.9 nmol/L), more than 840-fold selectivity over other PDE subtypes, enhanced liver microsomes stability (T1/2 = 239 min) compared to MP-10 and low BBB permeability. Importantly, oral pretreatment with C7·3HCl at a dose of 5.0 mg/kg significantly attenuated the pathological and functional changes induced by isoprenaline (ISO)-induced pathological cardiac hypertrophy in mice, particularly suppressing increase of cardiac weight, atrial natriuretic peptide (ANP) and β-myosin heavy chain (β-MHC) hypertrophic markers along with cardiac fibrosis. These findings further support that targeting PDE10A provides an innovative therapeutic approach for preventing and treating cardiac diseases.
2025, 36(4): 109994
doi: 10.1016/j.cclet.2024.109994
Abstract:
In this work, we put forward a new and universal approach, i.e., cyanine ketone method, for fabricating meso–aryl heptamethine indocyanines, which is so simple that the treatment of the easy-to-get cyanine ketones with various aromatic lithium (ArLi), followed by acidification, could straightforwardly give rise to the products in one-pot way. Importantly, due to the strong nucleophilicity of ArLi, a series of bulky hydrophilic aromatic groups can be facilely integrated into the meso–position of heptamethine indocyanines, not only effectively inhibiting the undesired dye self-aggregation but also largely improving the water-solubility. Using one of anti-aggregation meso–aryl heptamethine indocyanines, we fabricated a dye-antibody conjugate for in vivo imaging tumor in a mouse model and achieved a high tumor-to-normal tissue ratio. The work laid a chemical foundation for constructing various meso–aryl heptamethine indocyanines, facilitating the advanced imaging and therapeutic applications in future.
In this work, we put forward a new and universal approach, i.e., cyanine ketone method, for fabricating meso–aryl heptamethine indocyanines, which is so simple that the treatment of the easy-to-get cyanine ketones with various aromatic lithium (ArLi), followed by acidification, could straightforwardly give rise to the products in one-pot way. Importantly, due to the strong nucleophilicity of ArLi, a series of bulky hydrophilic aromatic groups can be facilely integrated into the meso–position of heptamethine indocyanines, not only effectively inhibiting the undesired dye self-aggregation but also largely improving the water-solubility. Using one of anti-aggregation meso–aryl heptamethine indocyanines, we fabricated a dye-antibody conjugate for in vivo imaging tumor in a mouse model and achieved a high tumor-to-normal tissue ratio. The work laid a chemical foundation for constructing various meso–aryl heptamethine indocyanines, facilitating the advanced imaging and therapeutic applications in future.
2025, 36(4): 110002
doi: 10.1016/j.cclet.2024.110002
Abstract:
A highly sensitive zinc ion fluorescent probe NOD-NY with controlled release of nitric oxide was designed, synthesized and used for tracking intracellular zinc ions in living A549 cells. NOD-NY was prepared from naphthalimide as the fluorophore and N,N-bis(2-pyridylmethyl)amine as the zinc ion recognition receptor, the amide N atom of the naphthalimide was connected to n-butylamine. Under the irradiation of ultraviolet light, NOD-NY can quantitatively release nitric oxide and generate a highly sensitive zinc ion probe Zn-HN, accompanied by a red-shift process of maximum ultraviolet absorption from 350 nm to 450 nm. Upon addition of Zn2+ to the solutions of Zn-HN, a remarkable fluorescence enhancement was observed, which could be attributed to the photo-induced electron transfer (PET) mechanism. By replaced the n-butylamine on NOD-NY with diethylene glycolamine or triphenylphosphine structures, NOD-AY with good biocompatibility and NOD-BY that can target mitochondria were obtained respectively. In addition, the nitric oxide released by NOD-NY enriched in lysosome can diffuse into mitochondria. The released nitric oxide can stimulate metallothionein to release zinc ions, and the light-induced in situ generated zinc ion probe Zn-HN can have a highly sensitive fluorescence response to free zinc ions in living A549 cells.
A highly sensitive zinc ion fluorescent probe NOD-NY with controlled release of nitric oxide was designed, synthesized and used for tracking intracellular zinc ions in living A549 cells. NOD-NY was prepared from naphthalimide as the fluorophore and N,N-bis(2-pyridylmethyl)amine as the zinc ion recognition receptor, the amide N atom of the naphthalimide was connected to n-butylamine. Under the irradiation of ultraviolet light, NOD-NY can quantitatively release nitric oxide and generate a highly sensitive zinc ion probe Zn-HN, accompanied by a red-shift process of maximum ultraviolet absorption from 350 nm to 450 nm. Upon addition of Zn2+ to the solutions of Zn-HN, a remarkable fluorescence enhancement was observed, which could be attributed to the photo-induced electron transfer (PET) mechanism. By replaced the n-butylamine on NOD-NY with diethylene glycolamine or triphenylphosphine structures, NOD-AY with good biocompatibility and NOD-BY that can target mitochondria were obtained respectively. In addition, the nitric oxide released by NOD-NY enriched in lysosome can diffuse into mitochondria. The released nitric oxide can stimulate metallothionein to release zinc ions, and the light-induced in situ generated zinc ion probe Zn-HN can have a highly sensitive fluorescence response to free zinc ions in living A549 cells.
2025, 36(4): 110003
doi: 10.1016/j.cclet.2024.110003
Abstract:
The rapid emergence of drug-resistant bacterial strains undermines the efficacy of conventional antibiotics, necessitating the development of alternative therapies. Antimicrobial photodynamic therapy (PDT) is a promising approach, but its effectiveness is often limited by the suboptimal photocatalytic activity of photosensitizers. In this study, we introduce a novel photoresponsive carbon-based antibacterial agent, Ce6/g-C3N4, which combines the photocatalytic properties of graphite-phase carbon nitride (g-C3N4) with the photodynamic attributes of chlorin e6 (Ce6). This agent, with an average particle size of 250.7 nm, demonstrates significantly enhanced photocatalytic activity. Additionally, the strong affinity of Ce6/g-C3N4 for bacteria and efficient delivery of Ce6 result in an inhibition rate exceeding 99% against Gram-positive bacteria and excellent biofilm eradication under light irradiation. In vivo experiments reveal that Ce6/g-C3N4 effectively inhibits bacterial growth on wounds, and promotes wound healing post-light treatment, while maintaining good biocompatibility. Overall, the Ce6/g-C3N4 antibacterial agent synergizes photodynamic and photocatalytic mechanisms, offering a new avenue for the photo-mediated, multi-strategic treatment of bacterial infections and wound healing.
The rapid emergence of drug-resistant bacterial strains undermines the efficacy of conventional antibiotics, necessitating the development of alternative therapies. Antimicrobial photodynamic therapy (PDT) is a promising approach, but its effectiveness is often limited by the suboptimal photocatalytic activity of photosensitizers. In this study, we introduce a novel photoresponsive carbon-based antibacterial agent, Ce6/g-C3N4, which combines the photocatalytic properties of graphite-phase carbon nitride (g-C3N4) with the photodynamic attributes of chlorin e6 (Ce6). This agent, with an average particle size of 250.7 nm, demonstrates significantly enhanced photocatalytic activity. Additionally, the strong affinity of Ce6/g-C3N4 for bacteria and efficient delivery of Ce6 result in an inhibition rate exceeding 99% against Gram-positive bacteria and excellent biofilm eradication under light irradiation. In vivo experiments reveal that Ce6/g-C3N4 effectively inhibits bacterial growth on wounds, and promotes wound healing post-light treatment, while maintaining good biocompatibility. Overall, the Ce6/g-C3N4 antibacterial agent synergizes photodynamic and photocatalytic mechanisms, offering a new avenue for the photo-mediated, multi-strategic treatment of bacterial infections and wound healing.
2025, 36(4): 110004
doi: 10.1016/j.cclet.2024.110004
Abstract:
Molecular recognition of fullerene using various host compounds is well-known in literature. But most studies focus on host-guest complexation in solution using host compounds with a single binding cavity. Herein, we report a series of highly preorganized janusarene derivatives with homoditopic binding sites. These novel janusarenes can bind and align various fullerenes such as C60, C70, C84, and Gd@C82 in a highly efficient manner. Robust shape complementary association and assembly are observed in solution, in the bulk solid state, in the liquid crystalline state, or on surface, and the assembled structures are characterized by nuclear magnetic resonance (NMR) titration, X-ray diffraction, polarized optical microscopy, and scanning tunneling microscopy.
Molecular recognition of fullerene using various host compounds is well-known in literature. But most studies focus on host-guest complexation in solution using host compounds with a single binding cavity. Herein, we report a series of highly preorganized janusarene derivatives with homoditopic binding sites. These novel janusarenes can bind and align various fullerenes such as C60, C70, C84, and Gd@C82 in a highly efficient manner. Robust shape complementary association and assembly are observed in solution, in the bulk solid state, in the liquid crystalline state, or on surface, and the assembled structures are characterized by nuclear magnetic resonance (NMR) titration, X-ray diffraction, polarized optical microscopy, and scanning tunneling microscopy.
2025, 36(4): 110012
doi: 10.1016/j.cclet.2024.110012
Abstract:
Wound healing in diabetic patients presents significant challenges due to heightened risks of bacterial infection, elevated glucose levels, and insufficient angiogenesis. Nanozymes are widely employed for wound healing, but most current nanozyme systems exhibit only moderate activity limited by incompatible reaction microenvironments including pH and hydrogen peroxide (H2O2) concentration. Herein, a glucose-activated nanozyme hydrogel was developed using bovine serum albumin (BSA)-modified gold nanoparticles (Au NPs) attached to a two-dimensional (2D) metal-organic framework (MOF) (Cu-TCPP(Fe)@Au@BSA) by an in situ growth method. The Au NPs function as a glucose oxidase (GOx)-like enzyme, converting glucose to gluconic acid and H2O2, triggering the peroxidase (POD)-like activity of Cu-TCPP(Fe) to produce hydroxyl radicals (•OH), effectively eliminating bacteria. Additionally, the modification of BSA reduces the Au NP size, enhancing enzyme activity. Both in vitro and in vivo tests demonstrate that this nanozyme hydrogel can be activated by the microenvironment to lower blood glucose, eliminate bacterial infections, and promote epithelial formation and collagen deposition, thus accelerating diabetic wound healing effectively. The multifunctional nanozyme hydrogel dressing developed in this study presents a promising therapeutic approach to enhance diabetic wound healing.
Wound healing in diabetic patients presents significant challenges due to heightened risks of bacterial infection, elevated glucose levels, and insufficient angiogenesis. Nanozymes are widely employed for wound healing, but most current nanozyme systems exhibit only moderate activity limited by incompatible reaction microenvironments including pH and hydrogen peroxide (H2O2) concentration. Herein, a glucose-activated nanozyme hydrogel was developed using bovine serum albumin (BSA)-modified gold nanoparticles (Au NPs) attached to a two-dimensional (2D) metal-organic framework (MOF) (Cu-TCPP(Fe)@Au@BSA) by an in situ growth method. The Au NPs function as a glucose oxidase (GOx)-like enzyme, converting glucose to gluconic acid and H2O2, triggering the peroxidase (POD)-like activity of Cu-TCPP(Fe) to produce hydroxyl radicals (•OH), effectively eliminating bacteria. Additionally, the modification of BSA reduces the Au NP size, enhancing enzyme activity. Both in vitro and in vivo tests demonstrate that this nanozyme hydrogel can be activated by the microenvironment to lower blood glucose, eliminate bacterial infections, and promote epithelial formation and collagen deposition, thus accelerating diabetic wound healing effectively. The multifunctional nanozyme hydrogel dressing developed in this study presents a promising therapeutic approach to enhance diabetic wound healing.
2025, 36(4): 110027
doi: 10.1016/j.cclet.2024.110027
Abstract:
Photoheranostics have emerged as a promising tool for cancer theranostics owing to their real-time feedback on treatment and their precise diagnosis. Among them, how to improve the photothermal conversion efficiency (PCE) of phototheranostic agents (PTAs) is the key factor for phototheranostic systems. Herein, we provided an efficient method to improve PCE and constructed a biocompatible nano-material ICR-Qu@NH2-Fe3O4@PEG (QNFP) by combing near-infrared second region (NIR-Ⅱ) molecular dye ICR-Qu and amino-modified magnetic nanoparticles and then encapsulated by DSPE-mPEG2000. QNFP exhibited excellent performance for photothermal therapy with a high PCE of 95.6%. Both in vitro and in vivo experiments indicated that QNFP could inhibit the growth of tumors under laser irradiation with low toxicity and realized real-time NIR-Ⅱ fluorescent imaging of tumors. In general, we realized a simple but efficient method to improve the PCE of NIR-Ⅱ molecular dye without reduce its quantum yield, which is an ideal choice for cancer diagnosis and treatment.
Photoheranostics have emerged as a promising tool for cancer theranostics owing to their real-time feedback on treatment and their precise diagnosis. Among them, how to improve the photothermal conversion efficiency (PCE) of phototheranostic agents (PTAs) is the key factor for phototheranostic systems. Herein, we provided an efficient method to improve PCE and constructed a biocompatible nano-material ICR-Qu@NH2-Fe3O4@PEG (QNFP) by combing near-infrared second region (NIR-Ⅱ) molecular dye ICR-Qu and amino-modified magnetic nanoparticles and then encapsulated by DSPE-mPEG2000. QNFP exhibited excellent performance for photothermal therapy with a high PCE of 95.6%. Both in vitro and in vivo experiments indicated that QNFP could inhibit the growth of tumors under laser irradiation with low toxicity and realized real-time NIR-Ⅱ fluorescent imaging of tumors. In general, we realized a simple but efficient method to improve the PCE of NIR-Ⅱ molecular dye without reduce its quantum yield, which is an ideal choice for cancer diagnosis and treatment.
2025, 36(4): 110029
doi: 10.1016/j.cclet.2024.110029
Abstract:
Liquid-liquid phase separation (LLPS) of proteins and nucleic acids is a common phenomenon in cells that underlies the formation of membraneless organelles. Although the macroscopic behavior of biomolecular coacervates has been elucidated by microscopy, the detailed dynamic properties of proteins/peptides during the LLPS process remain poorly characterized. Here, site-directed spin labeling-electron paramagnetic resonance (SDSL-EPR) spectroscopy was employed to characterize the dynamic properties of a minimal model LLPS system consisting of positively charged peptides and RNA. The degree of phase separation, indicated by broadening of the EPR spectrum of the spin-labeled peptide due to slow molecular tumbling, was monitored by EPR. In addition, three distinct populations with varying molecular motion during LLPS, featuring different spectral lineshapes, were identified. These populations included a fast motion component (Ⅰ), a slower motion component (Ⅱ) associated with peptides in the dispersed phase and an immobile component (Ⅲ) observed in the dense phase. With gradual titration of the peptides to RNA, the EPR spectrum gradually shifted, reflecting changes in the populations of the components. Together, SDSL-EPR method not only provides new insights into the dynamic behavior of biomolecules during LLPS, but also offers a sensitive method for biomolecular phase separation processes at the molecular level.
Liquid-liquid phase separation (LLPS) of proteins and nucleic acids is a common phenomenon in cells that underlies the formation of membraneless organelles. Although the macroscopic behavior of biomolecular coacervates has been elucidated by microscopy, the detailed dynamic properties of proteins/peptides during the LLPS process remain poorly characterized. Here, site-directed spin labeling-electron paramagnetic resonance (SDSL-EPR) spectroscopy was employed to characterize the dynamic properties of a minimal model LLPS system consisting of positively charged peptides and RNA. The degree of phase separation, indicated by broadening of the EPR spectrum of the spin-labeled peptide due to slow molecular tumbling, was monitored by EPR. In addition, three distinct populations with varying molecular motion during LLPS, featuring different spectral lineshapes, were identified. These populations included a fast motion component (Ⅰ), a slower motion component (Ⅱ) associated with peptides in the dispersed phase and an immobile component (Ⅲ) observed in the dense phase. With gradual titration of the peptides to RNA, the EPR spectrum gradually shifted, reflecting changes in the populations of the components. Together, SDSL-EPR method not only provides new insights into the dynamic behavior of biomolecules during LLPS, but also offers a sensitive method for biomolecular phase separation processes at the molecular level.
2025, 36(4): 110032
doi: 10.1016/j.cclet.2024.110032
Abstract:
A decomposable and sono-enzyme co-triggered nanoparticle (pTCP-CR NP) with “AND gate” logic was synthesized, combining a meso‑carboxyl-porphyrin-based sonosensitizer (5,10,15,20-tetrakis(carboxyl)porphyrin, TCP) and a thiophenyl-croconium (2,5-bis[(2-(2-(2-hydroxyethoxy)ethoxy)ethyl-4-carboxylate-piperidylamino)thiophenyl]-croconium, CR) via ester groups. TCP releases carbon monoxide (CO) under ultrasound (US) irradiation, offering both sonodynamic and gas therapy. CR decomposes into stronger reactive oxygen species (ROS) compared to oxygen-based radicals. The Förster resonance energy transfer (FRET) effect between TCP and CR inhibits ROS and CO generation until triggered by tumor cell overexpressed carboxylesterase (CEs). pTCP-CR NPs “AND gate” logic ensures activation only in the presence of both CEs and US, targeting tumor cells while safety in normal tissues. The ROS and CO generation abilities, as well as the releasing of SO4•− have been systemically examined. pTCP-CR can be thoroughly decomposed into low-toxic molecules post the treatment, showing the safety with negligible phototoxic reactions. In vivo anti-cancer therapy has been evaluated using mice bearing hepatocellular carcinoma.
A decomposable and sono-enzyme co-triggered nanoparticle (pTCP-CR NP) with “AND gate” logic was synthesized, combining a meso‑carboxyl-porphyrin-based sonosensitizer (5,10,15,20-tetrakis(carboxyl)porphyrin, TCP) and a thiophenyl-croconium (2,5-bis[(2-(2-(2-hydroxyethoxy)ethoxy)ethyl-4-carboxylate-piperidylamino)thiophenyl]-croconium, CR) via ester groups. TCP releases carbon monoxide (CO) under ultrasound (US) irradiation, offering both sonodynamic and gas therapy. CR decomposes into stronger reactive oxygen species (ROS) compared to oxygen-based radicals. The Förster resonance energy transfer (FRET) effect between TCP and CR inhibits ROS and CO generation until triggered by tumor cell overexpressed carboxylesterase (CEs). pTCP-CR NPs “AND gate” logic ensures activation only in the presence of both CEs and US, targeting tumor cells while safety in normal tissues. The ROS and CO generation abilities, as well as the releasing of SO4•− have been systemically examined. pTCP-CR can be thoroughly decomposed into low-toxic molecules post the treatment, showing the safety with negligible phototoxic reactions. In vivo anti-cancer therapy has been evaluated using mice bearing hepatocellular carcinoma.
2025, 36(4): 110033
doi: 10.1016/j.cclet.2024.110033
Abstract:
Inspired by the light-dependent signal transduction in nature, we herein report a fully synthetic receptor AZO with the capacity of transmembrane signaling, working by photo-induced change of molecular conformation. Our receptor has an anchoring group, a rigid and photoresponsive transmembrane unit and a precatalyst tailgroup. After doping in lipid membranes, AZO is membrane anchored and the extended trans-isomer enables the tailgroup to bind with intravesicular Zn2+, thereby achieving enzyme activation and triggering downstream events (ester hydrolysis). However, the shortened cis-isomer pulls the tailgroup into lipids, thereby preventing the complexation and all transduction processes. Upon alternative irradiation of ultraviolet (UV) and visible light, the transduction process can be reversible switch between "ON" and "OFF", achieving light signal transduction. This study provides a new strategy for future design of artificial signal transduction receptors.
Inspired by the light-dependent signal transduction in nature, we herein report a fully synthetic receptor AZO with the capacity of transmembrane signaling, working by photo-induced change of molecular conformation. Our receptor has an anchoring group, a rigid and photoresponsive transmembrane unit and a precatalyst tailgroup. After doping in lipid membranes, AZO is membrane anchored and the extended trans-isomer enables the tailgroup to bind with intravesicular Zn2+, thereby achieving enzyme activation and triggering downstream events (ester hydrolysis). However, the shortened cis-isomer pulls the tailgroup into lipids, thereby preventing the complexation and all transduction processes. Upon alternative irradiation of ultraviolet (UV) and visible light, the transduction process can be reversible switch between "ON" and "OFF", achieving light signal transduction. This study provides a new strategy for future design of artificial signal transduction receptors.
2025, 36(4): 110051
doi: 10.1016/j.cclet.2024.110051
Abstract:
A general process for the construction of azaaryl alkanes was achieved by employing the photoredox/palladium dual catalysis under mild visible light irradiation. The palladium catalyst ligated with a diphosphamide ligand exhibited high effectiveness in facilitating the modular three-components transformation. Furthermore, the cascade transformation was not restricted to constructing tertiary carbon centers; it also encompassed the synthesis of more challenging quaternary carbon centers with sixteen representative azaarene-derived substrates as reactants. In addition, alkyl 1,4-dihydropyridines (DHP), alkyl BF3K, and alkyl carboxylic acids were identified as precursors for alkyl radicals. Mechanistic investigations revealed the involvement of two different active benzylic nucleophiles in the cascade transformation. One is azabenzylic radical, which generate the terminal product through an “inner sphere” reductive elimination process. The other is azabenzylic anions, generated through visible light induced radical anion cross-over, leading to the formation of terminal products via an “outer sphere” reaction pathway. The efficiency of current modular transformation was also demonstarted by the concise of oliceridine, a prominent USFDA drug for pain management.
A general process for the construction of azaaryl alkanes was achieved by employing the photoredox/palladium dual catalysis under mild visible light irradiation. The palladium catalyst ligated with a diphosphamide ligand exhibited high effectiveness in facilitating the modular three-components transformation. Furthermore, the cascade transformation was not restricted to constructing tertiary carbon centers; it also encompassed the synthesis of more challenging quaternary carbon centers with sixteen representative azaarene-derived substrates as reactants. In addition, alkyl 1,4-dihydropyridines (DHP), alkyl BF3K, and alkyl carboxylic acids were identified as precursors for alkyl radicals. Mechanistic investigations revealed the involvement of two different active benzylic nucleophiles in the cascade transformation. One is azabenzylic radical, which generate the terminal product through an “inner sphere” reductive elimination process. The other is azabenzylic anions, generated through visible light induced radical anion cross-over, leading to the formation of terminal products via an “outer sphere” reaction pathway. The efficiency of current modular transformation was also demonstarted by the concise of oliceridine, a prominent USFDA drug for pain management.
2025, 36(4): 110052
doi: 10.1016/j.cclet.2024.110052
Abstract:
In most Suzuki–Miyaura carbon-carbon cross-coupling reactions, the borabicyclo[3.3.1]nonane scaffold (9-BBN) only serves as an auxiliary facilitating the transmetalation step and thus is transformed into by-products. There are rare examples where the 9-BBN derivatives serve as the potentially diverse C8 building blocks in cross-coupling reactions. Herein, we report a cobalt-catalyzed migratory carbon-carbon cross-coupling reaction of the in situ formed 9-BBN ate complexes to afford diverse aryl- and alkyl-functionalized cyclooctenes. Preliminary mechanistic studies suggest the oxidation-induced cis-bicyclo[3.3.0]oct-1-ylborane is the key intermediate in this migratory cross-coupling reaction, which promotes the development of other diverse migratory cross-coupling of borate complexes.
In most Suzuki–Miyaura carbon-carbon cross-coupling reactions, the borabicyclo[3.3.1]nonane scaffold (9-BBN) only serves as an auxiliary facilitating the transmetalation step and thus is transformed into by-products. There are rare examples where the 9-BBN derivatives serve as the potentially diverse C8 building blocks in cross-coupling reactions. Herein, we report a cobalt-catalyzed migratory carbon-carbon cross-coupling reaction of the in situ formed 9-BBN ate complexes to afford diverse aryl- and alkyl-functionalized cyclooctenes. Preliminary mechanistic studies suggest the oxidation-induced cis-bicyclo[3.3.0]oct-1-ylborane is the key intermediate in this migratory cross-coupling reaction, which promotes the development of other diverse migratory cross-coupling of borate complexes.
2025, 36(4): 110056
doi: 10.1016/j.cclet.2024.110056
Abstract:
Herein, we report an iron-promoted carbonylation-rearrangement of α-aminoaryl-tethered alkylidene cyclopropanes with CO2 to generate quinolinofuran derivatives. A variety of quinolinofuran derivatives are obtained in moderate to excellent yields, and two promising luminescent material molecules have been synthesized using the developed method. The Lewis acid FeCl3 was introduced into this reaction, which effectively promoted the ring opening and rearrangement of cyclopropanes. This reaction features a broad substrate scope, satisfactory functional group tolerance, facile scalability, and easy derivatization of the products.
Herein, we report an iron-promoted carbonylation-rearrangement of α-aminoaryl-tethered alkylidene cyclopropanes with CO2 to generate quinolinofuran derivatives. A variety of quinolinofuran derivatives are obtained in moderate to excellent yields, and two promising luminescent material molecules have been synthesized using the developed method. The Lewis acid FeCl3 was introduced into this reaction, which effectively promoted the ring opening and rearrangement of cyclopropanes. This reaction features a broad substrate scope, satisfactory functional group tolerance, facile scalability, and easy derivatization of the products.
2025, 36(4): 110057
doi: 10.1016/j.cclet.2024.110057
Abstract:
The construction of triplet-to-singlet Förster resonance energy transfer (TS-FRET) systems has significantly contributed to the advancement of high-performance optoelectronic materials, particularly in the development of metal-free organic environmental afterglow materials. Despite these notable advancements, achieving highly efficient energy transfer between luminescent donor and acceptor molecules remains a formidable challenge. In this study, we present the utilization of cation-π interactions as an effective strategy to enhance TS-FRET efficiency, with the ultimate objective of further advancing fluorescence afterglow materials. Our results demonstrate that the cation-π interaction in 1D supramolecular nanorods (1D-SNRs) enhances the dipole-dipole coupling, a crucial parameter for regulating TS-FRET between the triplet state phosphorescent donor and singlet state fluorescent acceptor. As a result, we achieved an outstanding TS-FRET efficiency of up to 97%. Furthermore, the 1D-SNRs exhibit a long-lifetime afterglow property, which suggests their potential application as a cost-effective and secure medium for information encryption. Thus, our findings highlight the promising prospects of cation-π interactions in enhancing TS-FRET efficiency and advancing the field of organic photo-functional materials.
The construction of triplet-to-singlet Förster resonance energy transfer (TS-FRET) systems has significantly contributed to the advancement of high-performance optoelectronic materials, particularly in the development of metal-free organic environmental afterglow materials. Despite these notable advancements, achieving highly efficient energy transfer between luminescent donor and acceptor molecules remains a formidable challenge. In this study, we present the utilization of cation-π interactions as an effective strategy to enhance TS-FRET efficiency, with the ultimate objective of further advancing fluorescence afterglow materials. Our results demonstrate that the cation-π interaction in 1D supramolecular nanorods (1D-SNRs) enhances the dipole-dipole coupling, a crucial parameter for regulating TS-FRET between the triplet state phosphorescent donor and singlet state fluorescent acceptor. As a result, we achieved an outstanding TS-FRET efficiency of up to 97%. Furthermore, the 1D-SNRs exhibit a long-lifetime afterglow property, which suggests their potential application as a cost-effective and secure medium for information encryption. Thus, our findings highlight the promising prospects of cation-π interactions in enhancing TS-FRET efficiency and advancing the field of organic photo-functional materials.
2025, 36(4): 110075
doi: 10.1016/j.cclet.2024.110075
Abstract:
Two thioamino acids and four fluorinated amino acids were employed to substitute either partially or entirely the Ile2, Ser3, Ile6, and Ser7 residues of Leu10-teixobactin to prepare ten analogues and the bioactivity of them was investigated. The SAR studies revealed that Ile6 was tolerable for both thioamidation and fluoridation, while Ser7 was identified as the most tolerable site for thioamidation. Analogue 1a demonstrated comparable or slightly improved antibacterial activity, superior protease stability compared to Leu10-teixobactin, while not exhibiting obvious cytotoxicity against mammalian cells.
Two thioamino acids and four fluorinated amino acids were employed to substitute either partially or entirely the Ile2, Ser3, Ile6, and Ser7 residues of Leu10-teixobactin to prepare ten analogues and the bioactivity of them was investigated. The SAR studies revealed that Ile6 was tolerable for both thioamidation and fluoridation, while Ser7 was identified as the most tolerable site for thioamidation. Analogue 1a demonstrated comparable or slightly improved antibacterial activity, superior protease stability compared to Leu10-teixobactin, while not exhibiting obvious cytotoxicity against mammalian cells.
2025, 36(4): 110076
doi: 10.1016/j.cclet.2024.110076
Abstract:
A strategy for copper-catalyzed and biphosphine ligand controlled boracarboxylation of 1,3-dienes and CO2 with 3,4-selectivity was developed. The CuCl coupled with DPPF (1,1′-bis(diphenylphosphino)ferrocene) was assigned to be the best catalyst, with 84% yield and exclusive 3,4-selectivity. The ligand effect on both catalytic activity and regioselectivity of boracarboxylation was disclosed, which is rarely reported in any copper catalyzed boracarboxylation. The borocupration process is revealed to be a vital step for the biphosphine participated boracarboxylation of 1,3-dienes with CO2. The minimal substrate distortion occurring in 3,4-borocupration favors the 3,4-regioselectivity of boracarboxylation. The “pocket” confinement and suitable βn (92°–106°) of bisphosphine ligands are demonstrated to be in favour of the interaction between LCu-Bpin complex (the catalytic precursor) and 1,3-diene substrate to decrease their interaction energy ∆Eint(ζ) in 3,4-borocupration, thus promoting the 3,4-boracarboxylation.
A strategy for copper-catalyzed and biphosphine ligand controlled boracarboxylation of 1,3-dienes and CO2 with 3,4-selectivity was developed. The CuCl coupled with DPPF (1,1′-bis(diphenylphosphino)ferrocene) was assigned to be the best catalyst, with 84% yield and exclusive 3,4-selectivity. The ligand effect on both catalytic activity and regioselectivity of boracarboxylation was disclosed, which is rarely reported in any copper catalyzed boracarboxylation. The borocupration process is revealed to be a vital step for the biphosphine participated boracarboxylation of 1,3-dienes with CO2. The minimal substrate distortion occurring in 3,4-borocupration favors the 3,4-regioselectivity of boracarboxylation. The “pocket” confinement and suitable βn (92°–106°) of bisphosphine ligands are demonstrated to be in favour of the interaction between LCu-Bpin complex (the catalytic precursor) and 1,3-diene substrate to decrease their interaction energy ∆Eint(ζ) in 3,4-borocupration, thus promoting the 3,4-boracarboxylation.
2025, 36(4): 110081
doi: 10.1016/j.cclet.2024.110081
Abstract:
A cobalt pincer complex bearing both P and C-stereogenic centers has been designed and synthesized, allowing for the development of the first cobalt-catalyzed asymmetric hydrogenation of quinoxalines under relatively mild conditions. Valuable chiral 1,2,3,4-tetrahydroquinoxalines could be obtained with high yields and excellent enantioselectivities (35 examples, up to > 99% ee).
A cobalt pincer complex bearing both P and C-stereogenic centers has been designed and synthesized, allowing for the development of the first cobalt-catalyzed asymmetric hydrogenation of quinoxalines under relatively mild conditions. Valuable chiral 1,2,3,4-tetrahydroquinoxalines could be obtained with high yields and excellent enantioselectivities (35 examples, up to > 99% ee).
2025, 36(4): 110093
doi: 10.1016/j.cclet.2024.110093
Abstract:
Although inductively coupled plasma mass spectrometry (ICP-MS) retains high sensitivity and has been intensively used for the measurement of 99Tc, it usually suffers from tedious, expensive, and time-consuming sample pretreatments due to the isobaric interferences from 99Ru and 98Mo1H. Herein, capillary electrophoresis (CE) was applied as sample introduction system for the sensitive, and interference-free determination of 99TcO4- from RuO4-, and MoO42- by ICP-MS with a simple sample treatment. Compared to the conventional methods, the hyphenated CE-ICP-MS avoids the use of expensive separation resins and reduces the consumption of mineral acid, representing a simpler, more efficient and environmentally benign approach. Moreover, the proposed method exhibits higher accuracy compared with the mathematical correction method using the natural isotope ratio of 99Ru and 101Ru, and significantly reduces sample consumption and the amount of waste, thus remarkably alleviating the radioactive exposure to operators and the pressure of radioactive waste treatment. Under the optimized conditions, the detection limits of 25 µg/L and 0.06 µg/L were obtained for RuO4- and ReO4- (Tc was replaced by Re), respectively, with relative standard deviation (RSD) lower than 5%. In addition, efficient recoveries of RuO4-, ReO4-, and 99TcO4- from simulated Hanford site groundwater were achieved. The method is expected to be a promising candidate for sensitive and accurate analysis of 99Tc from contaminated environmental samples.
Although inductively coupled plasma mass spectrometry (ICP-MS) retains high sensitivity and has been intensively used for the measurement of 99Tc, it usually suffers from tedious, expensive, and time-consuming sample pretreatments due to the isobaric interferences from 99Ru and 98Mo1H. Herein, capillary electrophoresis (CE) was applied as sample introduction system for the sensitive, and interference-free determination of 99TcO4- from RuO4-, and MoO42- by ICP-MS with a simple sample treatment. Compared to the conventional methods, the hyphenated CE-ICP-MS avoids the use of expensive separation resins and reduces the consumption of mineral acid, representing a simpler, more efficient and environmentally benign approach. Moreover, the proposed method exhibits higher accuracy compared with the mathematical correction method using the natural isotope ratio of 99Ru and 101Ru, and significantly reduces sample consumption and the amount of waste, thus remarkably alleviating the radioactive exposure to operators and the pressure of radioactive waste treatment. Under the optimized conditions, the detection limits of 25 µg/L and 0.06 µg/L were obtained for RuO4- and ReO4- (Tc was replaced by Re), respectively, with relative standard deviation (RSD) lower than 5%. In addition, efficient recoveries of RuO4-, ReO4-, and 99TcO4- from simulated Hanford site groundwater were achieved. The method is expected to be a promising candidate for sensitive and accurate analysis of 99Tc from contaminated environmental samples.
2025, 36(4): 110095
doi: 10.1016/j.cclet.2024.110095
Abstract:
The hydration state of amphiphilic block copolymers during the self-assembly transition is closely related to the structure and properties of copolymers. In this study, the temperature-induced self-assembly of copolymer poly(N,N-dimethylacrylamide)-poly(diacetone acrylamide) (PDMAA30-PDAAM60)2 in aqueous solution was monitored by near-infrared spectroscopy with water as a probe. The wavelet packet transform was employed to improve the spectral resolution. The spectral information of hydrated water surrounding the hydrophilic PDMAA and hydrophobic PDAAM blocks was then extracted, revealing the significant roles of water in morphological transition of the copolymer from spherical to worm-like micelles. Specifically, water molecules interacting with N atoms and C=O groups of the hydrophilic block gradually decrease during the morphological transition, while hydrogen-bond structures NH-CO of the hydrophobic block gradually break, bringing more water molecules into contact with the hydrophobic block. This work provides a foundation for exploring the role of water molecules during the self-assembly transition of complex block copolymers.
The hydration state of amphiphilic block copolymers during the self-assembly transition is closely related to the structure and properties of copolymers. In this study, the temperature-induced self-assembly of copolymer poly(N,N-dimethylacrylamide)-poly(diacetone acrylamide) (PDMAA30-PDAAM60)2 in aqueous solution was monitored by near-infrared spectroscopy with water as a probe. The wavelet packet transform was employed to improve the spectral resolution. The spectral information of hydrated water surrounding the hydrophilic PDMAA and hydrophobic PDAAM blocks was then extracted, revealing the significant roles of water in morphological transition of the copolymer from spherical to worm-like micelles. Specifically, water molecules interacting with N atoms and C=O groups of the hydrophilic block gradually decrease during the morphological transition, while hydrogen-bond structures NH-CO of the hydrophobic block gradually break, bringing more water molecules into contact with the hydrophobic block. This work provides a foundation for exploring the role of water molecules during the self-assembly transition of complex block copolymers.
2025, 36(4): 110096
doi: 10.1016/j.cclet.2024.110096
Abstract:
Researchers have shown significant interest in modulating the peroxidase-like activity of nanozymes. Among these, bimetallic nanozymes have shown superior peroxidase-like activity over monometallic counterparts, offering enhanced performance and cost-efficiency in nanozyme designs. Herein, bimetallic nanozymes comprising nickel (Ni) and osmium (Os) incorporated into hyaluronate (HA) have been developed, resulting in HA-Nin/Os nanoclusters. Subsequently, comprehensive characterizations have been conducted. Further investigation has revealed that HA-Nin/Os efficiently catalyzed 3,3′,5,5′-tetramethylbenzidine (TMB) oxidation with hydrogen peroxide (H2O2), confirming its peroxidase-like behavior and role as a nanozyme. Impressively, HA-Ni2/Os (Ni/Os = 2:1) displays heightened substrate affinity, accelerated reaction rates, enhanced hydroxyl radical production in acidic conditions, and exhibits activity unit of 1224 U/mg, representing more than two-fold increase compared to non-Ni-supported Os nanozyme. Theoretical calculations indicate that Ni support enhances the peroxidase-like process of Os nanozyme by improving H2O2 adsorption and TMB oxidation. Crucially, the support of Ni does not significantly alter the other enzyme-like activities of Os nanozymes, thereby enabling Ni to selectively enhance their peroxidase-like activity. In terms of application, the peroxidase-like ability of HA-Ni2/Os, facilitated by HA's carboxyl groups enabling crosslinking, proves effective in a squamous carcinoma antigen immunoassay. Moreover, HA-Ni2/Os exhibit reliable stability, promising as a peroxidase substitute. This work underscores the advantages of incorporating Ni into Os, specifically enhancing peroxidase-like activity, highlighting the potential of Os bimetallic nanozymes for peroxidase-based applications.
Researchers have shown significant interest in modulating the peroxidase-like activity of nanozymes. Among these, bimetallic nanozymes have shown superior peroxidase-like activity over monometallic counterparts, offering enhanced performance and cost-efficiency in nanozyme designs. Herein, bimetallic nanozymes comprising nickel (Ni) and osmium (Os) incorporated into hyaluronate (HA) have been developed, resulting in HA-Nin/Os nanoclusters. Subsequently, comprehensive characterizations have been conducted. Further investigation has revealed that HA-Nin/Os efficiently catalyzed 3,3′,5,5′-tetramethylbenzidine (TMB) oxidation with hydrogen peroxide (H2O2), confirming its peroxidase-like behavior and role as a nanozyme. Impressively, HA-Ni2/Os (Ni/Os = 2:1) displays heightened substrate affinity, accelerated reaction rates, enhanced hydroxyl radical production in acidic conditions, and exhibits activity unit of 1224 U/mg, representing more than two-fold increase compared to non-Ni-supported Os nanozyme. Theoretical calculations indicate that Ni support enhances the peroxidase-like process of Os nanozyme by improving H2O2 adsorption and TMB oxidation. Crucially, the support of Ni does not significantly alter the other enzyme-like activities of Os nanozymes, thereby enabling Ni to selectively enhance their peroxidase-like activity. In terms of application, the peroxidase-like ability of HA-Ni2/Os, facilitated by HA's carboxyl groups enabling crosslinking, proves effective in a squamous carcinoma antigen immunoassay. Moreover, HA-Ni2/Os exhibit reliable stability, promising as a peroxidase substitute. This work underscores the advantages of incorporating Ni into Os, specifically enhancing peroxidase-like activity, highlighting the potential of Os bimetallic nanozymes for peroxidase-based applications.
2025, 36(4): 110101
doi: 10.1016/j.cclet.2024.110101
Abstract:
Herein, a simple and effective outer-surface interactions assisted supramolecular hierarchical assembly has been first exploited to uniformly distribute tungstosilicic acid (TSA) inside the porous structure of cucurbit[10]uril-based single-layer 2D supramolecular-organic-frameworks (Q[10]-SOFs) in water. Importantly, the 2D Q[10]-SOFs can further serve as light harvesting antenna, achieving fast energy transfer to the embedded redox-active TSA upon photoexcitation, resulting in efficient visible light-driven selective oxidation of benzyl alcohols into the corresponding aldehydes in high yield at room temperature. Further studies revealed that the integrated of 2D Q[10]-SOFs and TSA played a key role in the catalytic process, due to the presence of a novel stepwise electron transfer route in the single-layer hybrid 2D structures.
Herein, a simple and effective outer-surface interactions assisted supramolecular hierarchical assembly has been first exploited to uniformly distribute tungstosilicic acid (TSA) inside the porous structure of cucurbit[10]uril-based single-layer 2D supramolecular-organic-frameworks (Q[10]-SOFs) in water. Importantly, the 2D Q[10]-SOFs can further serve as light harvesting antenna, achieving fast energy transfer to the embedded redox-active TSA upon photoexcitation, resulting in efficient visible light-driven selective oxidation of benzyl alcohols into the corresponding aldehydes in high yield at room temperature. Further studies revealed that the integrated of 2D Q[10]-SOFs and TSA played a key role in the catalytic process, due to the presence of a novel stepwise electron transfer route in the single-layer hybrid 2D structures.
2025, 36(4): 110102
doi: 10.1016/j.cclet.2024.110102
Abstract:
The separation of alicyclic ketones and alicyclic alcohols is one of the challenges in the field of petrochemical industry. However, traditional separation methods suffer from excessive energy consumption, complicated operation, and unsatisfactory separation efficiency for substances with similar boiling points. Herein, we offer an innovative method for the separation of alicyclic ketones and alicyclic alcohols employing nonporous adaptive crystals (NACs) of perethylated pillar[5]arene (EtP5) and perethylated pillar[6]arene (EtP6). NACs of EtP5 cannot adsorb either alicyclic ketones or alicyclic alcohols because of the small cavity size of EtP5. By contrast, NACs of EtP6 can separate cyclopentanone from the vapor mixture of cyclopentanone/cyclopentanol (v:v = 1:1) and cyclohexanone from the vapor mixture of cyclohexanone/cyclohexanol (v:v = 1:1) with purities of 99.1% and 100%, respectively. Density functional theory calculations show that the selectivity comes from the thermodynamic stability of the newly formed crystal structure after adsorption of the preferred guest molecule. Moreover, NACs of EtP6 can be reused without losing selectivity and performance.
The separation of alicyclic ketones and alicyclic alcohols is one of the challenges in the field of petrochemical industry. However, traditional separation methods suffer from excessive energy consumption, complicated operation, and unsatisfactory separation efficiency for substances with similar boiling points. Herein, we offer an innovative method for the separation of alicyclic ketones and alicyclic alcohols employing nonporous adaptive crystals (NACs) of perethylated pillar[5]arene (EtP5) and perethylated pillar[6]arene (EtP6). NACs of EtP5 cannot adsorb either alicyclic ketones or alicyclic alcohols because of the small cavity size of EtP5. By contrast, NACs of EtP6 can separate cyclopentanone from the vapor mixture of cyclopentanone/cyclopentanol (v:v = 1:1) and cyclohexanone from the vapor mixture of cyclohexanone/cyclohexanol (v:v = 1:1) with purities of 99.1% and 100%, respectively. Density functional theory calculations show that the selectivity comes from the thermodynamic stability of the newly formed crystal structure after adsorption of the preferred guest molecule. Moreover, NACs of EtP6 can be reused without losing selectivity and performance.
2025, 36(4): 110103
doi: 10.1016/j.cclet.2024.110103
Abstract:
Pt(Ⅱ)−salophen complexes (S-1~S-4) and 9,10-diphenylanthracene (DPA) tethering pillar[5]arene derivatives (A-1 and A-2) were synthesized to act as sensitizers and annihilators for triplet-triplet annihilation upconversion (TTA-UC), respectively. It turned out that the pyridine cation served as a mask for the excited state of the sensitizer, the triplet states of S-2 and S-3 were significantly quenched by photo-induced electron transfer (PET) with phosphorescence quantum yield quenched from 24.4% for S-4 to 9.3% for S-3, and therefore, both S-2 and S-3 led to negligible UC emissions when traditional annihilator DPA was used as the annihilator. Delightfully, when supramolecular annihilator A-1 and A-2 were employed to include the pyridine cation, PET was significantly inhibited and the triplet states of the sensitizers were activated, TTA-UC emission was therefore boosted. The UC quantum yield of A-2/S-3 system was up to 130 times higher than that of DPA/S-3 system, and the UC emission was switchable by the addition of competitive guests.
Pt(Ⅱ)−salophen complexes (S-1~S-4) and 9,10-diphenylanthracene (DPA) tethering pillar[5]arene derivatives (A-1 and A-2) were synthesized to act as sensitizers and annihilators for triplet-triplet annihilation upconversion (TTA-UC), respectively. It turned out that the pyridine cation served as a mask for the excited state of the sensitizer, the triplet states of S-2 and S-3 were significantly quenched by photo-induced electron transfer (PET) with phosphorescence quantum yield quenched from 24.4% for S-4 to 9.3% for S-3, and therefore, both S-2 and S-3 led to negligible UC emissions when traditional annihilator DPA was used as the annihilator. Delightfully, when supramolecular annihilator A-1 and A-2 were employed to include the pyridine cation, PET was significantly inhibited and the triplet states of the sensitizers were activated, TTA-UC emission was therefore boosted. The UC quantum yield of A-2/S-3 system was up to 130 times higher than that of DPA/S-3 system, and the UC emission was switchable by the addition of competitive guests.
2025, 36(4): 110109
doi: 10.1016/j.cclet.2024.110109
Abstract:
Lung cancer-derived exosomes are a kind of valuable and clinically-predictable biomarkers for lung cancer, but they have the limitations in individual differences when being applied in liquid biopsy. To improve their application value and accuracy in clinical diagnosis, a dual-labelled electrochemical method is herein reported for precise assessment of lung cancer-derived exosomes. To do so, two probes are prepared for the dual labeling of exosome membrane to run DNA assembly reactions: One is modified with cholesterol and can insert into exosome membrane through hydrophobic interaction; another one is linked with programmed death ligand-1 (PD-L1) antibody and can bind to exosome surface-expressing PD-L1 via specific immunoreaction. Quantum dots-tagged signal strands are used to collect respective DNA products, and produce stripping signals corresponding to the amounts of total exosome and surface-expressing PD-L1, respectively. A wide linear relationship is established for the quantitative determination of lung cancer-derived exosomes in the range from 103 to 1010 particles/mL, whereas the ratiometric value of the two stripping signals is proven to have a better diagnostic use in screening and staging of lung cancer when being applied to clinical samples. Therefore, our method might provide a new insight into precise diagnosis of lung cancer, and offer sufficient information to reflect the biomarker level and guide the personalized treatment level even at an early stage in clinic.
Lung cancer-derived exosomes are a kind of valuable and clinically-predictable biomarkers for lung cancer, but they have the limitations in individual differences when being applied in liquid biopsy. To improve their application value and accuracy in clinical diagnosis, a dual-labelled electrochemical method is herein reported for precise assessment of lung cancer-derived exosomes. To do so, two probes are prepared for the dual labeling of exosome membrane to run DNA assembly reactions: One is modified with cholesterol and can insert into exosome membrane through hydrophobic interaction; another one is linked with programmed death ligand-1 (PD-L1) antibody and can bind to exosome surface-expressing PD-L1 via specific immunoreaction. Quantum dots-tagged signal strands are used to collect respective DNA products, and produce stripping signals corresponding to the amounts of total exosome and surface-expressing PD-L1, respectively. A wide linear relationship is established for the quantitative determination of lung cancer-derived exosomes in the range from 103 to 1010 particles/mL, whereas the ratiometric value of the two stripping signals is proven to have a better diagnostic use in screening and staging of lung cancer when being applied to clinical samples. Therefore, our method might provide a new insight into precise diagnosis of lung cancer, and offer sufficient information to reflect the biomarker level and guide the personalized treatment level even at an early stage in clinic.
2025, 36(4): 110113
doi: 10.1016/j.cclet.2024.110113
Abstract:
The design and synthesis of a novel π-conjugated fluorescent framework by external ligand-assisted C−H olefination of heterocycles with excellent regioselectivity and broad substrate scope are reported herein. These novel fluorescent materials could present full-color-tunable emissions with large Stokes shifts. Furthermore, the protocol provides an opportunity to rapidly screen novel organic single-molecule white-light materials with high fluorescence quantum yields. The robust organic and low-cost white light-emitting diodes could rapidly be fabricated using the white-light-emitting material. Experimental data and theoretical calculations indicate that in the white-light dual emission the relatively short wavelength from high-lying singlet state emission and the relatively long wavelength from low-lying singlet state emission. The anti-Kasha dual-emission systems will provide a foundation for the development and application of organic single-molecule white light materials, effectively promoting the development and innovation of luminescent materials. In addition, this method demonstrated its potential application in the synthesis of new near-infrared (NIR) fluorescence materials with large Stokes shifts based on the olefination of heterocycles.
The design and synthesis of a novel π-conjugated fluorescent framework by external ligand-assisted C−H olefination of heterocycles with excellent regioselectivity and broad substrate scope are reported herein. These novel fluorescent materials could present full-color-tunable emissions with large Stokes shifts. Furthermore, the protocol provides an opportunity to rapidly screen novel organic single-molecule white-light materials with high fluorescence quantum yields. The robust organic and low-cost white light-emitting diodes could rapidly be fabricated using the white-light-emitting material. Experimental data and theoretical calculations indicate that in the white-light dual emission the relatively short wavelength from high-lying singlet state emission and the relatively long wavelength from low-lying singlet state emission. The anti-Kasha dual-emission systems will provide a foundation for the development and application of organic single-molecule white light materials, effectively promoting the development and innovation of luminescent materials. In addition, this method demonstrated its potential application in the synthesis of new near-infrared (NIR) fluorescence materials with large Stokes shifts based on the olefination of heterocycles.
2025, 36(4): 110114
doi: 10.1016/j.cclet.2024.110114
Abstract:
An enantioselective catalytic method for the direct [4 + 1] annulation of yne–allylic acetates with pyrazolones has been realized by a copper-catalyzed remote strategy. A variety of enantioenriched spiropyrazolones are rapidly accessed in high yields with moderate to good enantiocontrol. The facile follow-up transformations highlight its potential utility in the synthesis of diverse spiropyrazolones building blocks.
An enantioselective catalytic method for the direct [4 + 1] annulation of yne–allylic acetates with pyrazolones has been realized by a copper-catalyzed remote strategy. A variety of enantioenriched spiropyrazolones are rapidly accessed in high yields with moderate to good enantiocontrol. The facile follow-up transformations highlight its potential utility in the synthesis of diverse spiropyrazolones building blocks.
2025, 36(4): 110127
doi: 10.1016/j.cclet.2024.110127
Abstract:
Utilizing small molecules as markers for specific cells or organs within biosystems is a crucial approach for studying and regulating physiological processes. However, current tagging strategies, due to the presence of exposed highly reactive groups, suffer from drawbacks such as low tagging efficiency or insufficient spatial specificity, thereby diminishing their expected effectiveness. Consequently, there is a pressing need to develop a strategy capable of in situ labeling of active groups in response to cellular or in vivo stimuli, ensuring both high tagging efficiency and spatial specificity. In this work, we devised a strategy for releasing aldehyde groups activated by hypochlorous acid (HOCl). Compounds synthesized through this strategy can release the fluorophore methylene blue (MB) and aldehyde-based compounds upon HOCl activation. Given high reactivity of the released aldehyde group, it can effectively interact with macromolecules in biological systems, facilitating tagging and enabling prolonged imaging. To validate this concept, we further incorporated a naphthalimide structure with stable light emission to create SW-110. SW-110 can specifically respond to in vitro and endogenous HOCl, when release MB, it also releases naphthalimide fluorophore with highly reactive aldehyde group for tagging within cells. This strategy provides a simple but efficient strategy for proximity tagging in situ.
Utilizing small molecules as markers for specific cells or organs within biosystems is a crucial approach for studying and regulating physiological processes. However, current tagging strategies, due to the presence of exposed highly reactive groups, suffer from drawbacks such as low tagging efficiency or insufficient spatial specificity, thereby diminishing their expected effectiveness. Consequently, there is a pressing need to develop a strategy capable of in situ labeling of active groups in response to cellular or in vivo stimuli, ensuring both high tagging efficiency and spatial specificity. In this work, we devised a strategy for releasing aldehyde groups activated by hypochlorous acid (HOCl). Compounds synthesized through this strategy can release the fluorophore methylene blue (MB) and aldehyde-based compounds upon HOCl activation. Given high reactivity of the released aldehyde group, it can effectively interact with macromolecules in biological systems, facilitating tagging and enabling prolonged imaging. To validate this concept, we further incorporated a naphthalimide structure with stable light emission to create SW-110. SW-110 can specifically respond to in vitro and endogenous HOCl, when release MB, it also releases naphthalimide fluorophore with highly reactive aldehyde group for tagging within cells. This strategy provides a simple but efficient strategy for proximity tagging in situ.
2025, 36(4): 110129
doi: 10.1016/j.cclet.2024.110129
Abstract:
Tuning the nanozyme′s activity and specificity is very crucial for developing highly sensitive sensors for various applications. Herein, selenium-doped porous N-doped carbon skeletons (Se/NC) nanozymes with highly specific peroxidase-like activity were synthesized by a MOF-pyrolysis-doping protocol. Se doping adjusted the electronic structure of NC by introducing more vacancies, defective carbon and graphitic N, and endowed the resultant Se/NC enhanced charge transfer and substrate affinity. The Se/NC exhibited specific peroxidase-mimicking activity and could catalyze 3,3′,5,5′-tetramethylbenzidine oxidation by H2O2. Density functional theory (DFT) calculations and experimental trials indicated that both Se=O and C–Se–C species were the main active sites of Se/NC. The C–Se–C bond is the main catalytic active site endowing Se/NC with the property of nanozyme, while the Se=O bond effectively enhances its affinity to H2O2 and accelerate H2O2 dissociation. The Se/NC showed an approximately 185-fold increase in peroxidase-like activity compared to NC. Based on the inhibition of the peroxidase-like activity of Se/NC by methimazole, a colorimetric sensor was developed to achieve its sensitive detection with 2 nmol/L of limit of detection. It was successfully used for detecting methimazole in real samples. Current Se doping strategy simplifies the fabrication process of high performance specific nanozyme and promises great potential for environmental analysis.
Tuning the nanozyme′s activity and specificity is very crucial for developing highly sensitive sensors for various applications. Herein, selenium-doped porous N-doped carbon skeletons (Se/NC) nanozymes with highly specific peroxidase-like activity were synthesized by a MOF-pyrolysis-doping protocol. Se doping adjusted the electronic structure of NC by introducing more vacancies, defective carbon and graphitic N, and endowed the resultant Se/NC enhanced charge transfer and substrate affinity. The Se/NC exhibited specific peroxidase-mimicking activity and could catalyze 3,3′,5,5′-tetramethylbenzidine oxidation by H2O2. Density functional theory (DFT) calculations and experimental trials indicated that both Se=O and C–Se–C species were the main active sites of Se/NC. The C–Se–C bond is the main catalytic active site endowing Se/NC with the property of nanozyme, while the Se=O bond effectively enhances its affinity to H2O2 and accelerate H2O2 dissociation. The Se/NC showed an approximately 185-fold increase in peroxidase-like activity compared to NC. Based on the inhibition of the peroxidase-like activity of Se/NC by methimazole, a colorimetric sensor was developed to achieve its sensitive detection with 2 nmol/L of limit of detection. It was successfully used for detecting methimazole in real samples. Current Se doping strategy simplifies the fabrication process of high performance specific nanozyme and promises great potential for environmental analysis.
2025, 36(4): 110131
doi: 10.1016/j.cclet.2024.110131
Abstract:
MicroRNA-133a (miRNA-133a) and cardiac troponin I (cTnI) are different-type crucial biomarkers of acute myocardial infarction (AMI), whose levels are great significance for AMI diagnosis and treatment. Herein, a novel photoelectrochemical-electrochemical (PEC-EC) dual-mode biosensing platform for dual-target assays of miRNA-133a and cTnI was developed. In which, a PEC-EC dual-mode sensing platform for miRNA-133a was constructed based on the changes of the photocurrent inhibition effect and the electrochemical signal of Fc on the Fc-hairpin DNA probe (Fc-HP)/ZnCdS-quantum dots (QDs)/ITO electrode. Furthermore, under magnetic separation and the specific interaction between cTnI and its aptamer, the N-doped porous carbon-ZnO polyhedra (NPC-ZnO)-hemin-capture DNA probe hybrid (NH-CP) was obtained and introduced to the Fc-HP/ZnCdS-QDs/ITO electrode via hybridization between NH-CP and Fc-HP. The hemin molecules encapsulated in NH-CP could effectively induce the photocurrent-polarity-switching of the Fc-HP/ZnCdS-QDs/ITO electrode and generate a new electrochemical signal originating from hemin. Thus, cTnI was assayed sensitively and selectively by the PEC-EC dual-mode biosensing platform. Here, Fc and hemin not only serve as the electrochemical indicators, but also respectively inhibit the photocurrent and switch the photocurrent polarity of ZnCdS-QDs. Furthermore, the proposed biosensing platform could be easily expanded to the detection of other multiplex-type biomarkers via the change of the sequences of the related DNA probes, implying its significant potential in clinical diagnosis and biological analysis.
MicroRNA-133a (miRNA-133a) and cardiac troponin I (cTnI) are different-type crucial biomarkers of acute myocardial infarction (AMI), whose levels are great significance for AMI diagnosis and treatment. Herein, a novel photoelectrochemical-electrochemical (PEC-EC) dual-mode biosensing platform for dual-target assays of miRNA-133a and cTnI was developed. In which, a PEC-EC dual-mode sensing platform for miRNA-133a was constructed based on the changes of the photocurrent inhibition effect and the electrochemical signal of Fc on the Fc-hairpin DNA probe (Fc-HP)/ZnCdS-quantum dots (QDs)/ITO electrode. Furthermore, under magnetic separation and the specific interaction between cTnI and its aptamer, the N-doped porous carbon-ZnO polyhedra (NPC-ZnO)-hemin-capture DNA probe hybrid (NH-CP) was obtained and introduced to the Fc-HP/ZnCdS-QDs/ITO electrode via hybridization between NH-CP and Fc-HP. The hemin molecules encapsulated in NH-CP could effectively induce the photocurrent-polarity-switching of the Fc-HP/ZnCdS-QDs/ITO electrode and generate a new electrochemical signal originating from hemin. Thus, cTnI was assayed sensitively and selectively by the PEC-EC dual-mode biosensing platform. Here, Fc and hemin not only serve as the electrochemical indicators, but also respectively inhibit the photocurrent and switch the photocurrent polarity of ZnCdS-QDs. Furthermore, the proposed biosensing platform could be easily expanded to the detection of other multiplex-type biomarkers via the change of the sequences of the related DNA probes, implying its significant potential in clinical diagnosis and biological analysis.
2025, 36(4): 110132
doi: 10.1016/j.cclet.2024.110132
Abstract:
The fabrication of bioreceptor-free method for accurate and sensitive detection of ochratoxin A (OTA) in cereal is critical, but still a significant challenge to mitigate risks to food industries and public health. In this study, a smartphone-ratiometric fluorescence sensor for the ultrasensitive detection of OTA is developed based on a porphyrinic metal-organic framework and silica nanoparticle composite (Zr-MOF/SiNPs) away from the use of antibodies and aptamers. Due to the excellent recognition ability of Zr-MOF and good storage stability of SiNPs, OTA is detected by Zr-MOF/SiNPs with a wide linear range of 0.05–1000 ng/mL and low detection limit of 0.016 ng/mL. Moreover, the red–blue ratio values of the fluorescence images are extracted through the smartphone color recognizer application with a limit of detection of 1.74 ng/mL, lower than the permissible content of OTA in cereal prescribed by World Health Organization. This sensing platform has been successfully applied in maize samples with superior repeatability and satisfactory recoveries, providing a novel way for simple and label-free analysis of OTA in cereal.
The fabrication of bioreceptor-free method for accurate and sensitive detection of ochratoxin A (OTA) in cereal is critical, but still a significant challenge to mitigate risks to food industries and public health. In this study, a smartphone-ratiometric fluorescence sensor for the ultrasensitive detection of OTA is developed based on a porphyrinic metal-organic framework and silica nanoparticle composite (Zr-MOF/SiNPs) away from the use of antibodies and aptamers. Due to the excellent recognition ability of Zr-MOF and good storage stability of SiNPs, OTA is detected by Zr-MOF/SiNPs with a wide linear range of 0.05–1000 ng/mL and low detection limit of 0.016 ng/mL. Moreover, the red–blue ratio values of the fluorescence images are extracted through the smartphone color recognizer application with a limit of detection of 1.74 ng/mL, lower than the permissible content of OTA in cereal prescribed by World Health Organization. This sensing platform has been successfully applied in maize samples with superior repeatability and satisfactory recoveries, providing a novel way for simple and label-free analysis of OTA in cereal.
2025, 36(4): 110136
doi: 10.1016/j.cclet.2024.110136
Abstract:
A novel Fe-doping three-dimensional flower-like Bi7O9I3 microspheres with plasmonic Bi and rich surface oxygen vacancies (Fe-Bi/Bi7O9I3/OVs) was prepared as catalysts, and further coupled with natural air diffusion electrode (NADE) to construct the heterogeneous visible-light-driven photoelectro-Fenton (HE-VL-PEF) process to enhance the degradation and mineralization of tetracycline (TC). Interfacial ≡Fe sites, OVs and Bi metal were simultaneously constructed via Fe doping, which effectively improved visible light absorption and the separation efficiency of photogenerated carriers to further accelerate the transformation of Fe(Ⅲ) to Fe(Ⅱ), achieving Fenton reaction recycling. HE-VL-PEF process could achieve enhanced treatment of pollutants, thanks to the synergistic effect of electro-Fenton (EF) and photo-Fenton (PF). NADE exhibited excellent H2O2 electrosynthesis without external oxygen-pumping equipment. Under the irradiation of visible light, Fe-Bi/Bi7O9I3/OVs could achieve more photoelectrons to accelerate the transformation of Fe(Ⅲ) to Fe(Ⅱ) or directly activate H2O2. DFT calculations also clearly demonstrated that except for the fast charge separation and transfer, Fe-Bi/Bi7O9I3/OVs could achieve a faster electron transport between Fe-O, facilitating Fe site acquire more electron. Consequently, the Fe-Bi/Bi7O9I3/OVs in HE-VL-PEF process presented performance superiorities including excellent pollutant removal (91.91%), low electric energy consumption of 66.34 kWh/kg total organic carbon (TOC), excellent reusability and wide pH adaptability (3–9).
A novel Fe-doping three-dimensional flower-like Bi7O9I3 microspheres with plasmonic Bi and rich surface oxygen vacancies (Fe-Bi/Bi7O9I3/OVs) was prepared as catalysts, and further coupled with natural air diffusion electrode (NADE) to construct the heterogeneous visible-light-driven photoelectro-Fenton (HE-VL-PEF) process to enhance the degradation and mineralization of tetracycline (TC). Interfacial ≡Fe sites, OVs and Bi metal were simultaneously constructed via Fe doping, which effectively improved visible light absorption and the separation efficiency of photogenerated carriers to further accelerate the transformation of Fe(Ⅲ) to Fe(Ⅱ), achieving Fenton reaction recycling. HE-VL-PEF process could achieve enhanced treatment of pollutants, thanks to the synergistic effect of electro-Fenton (EF) and photo-Fenton (PF). NADE exhibited excellent H2O2 electrosynthesis without external oxygen-pumping equipment. Under the irradiation of visible light, Fe-Bi/Bi7O9I3/OVs could achieve more photoelectrons to accelerate the transformation of Fe(Ⅲ) to Fe(Ⅱ) or directly activate H2O2. DFT calculations also clearly demonstrated that except for the fast charge separation and transfer, Fe-Bi/Bi7O9I3/OVs could achieve a faster electron transport between Fe-O, facilitating Fe site acquire more electron. Consequently, the Fe-Bi/Bi7O9I3/OVs in HE-VL-PEF process presented performance superiorities including excellent pollutant removal (91.91%), low electric energy consumption of 66.34 kWh/kg total organic carbon (TOC), excellent reusability and wide pH adaptability (3–9).
2025, 36(4): 110137
doi: 10.1016/j.cclet.2024.110137
Abstract:
Degrading volatile organic compounds at low temperatures and active sites aggregation are still challenging. In this study, a novel mesoporous zeolite silicalite-1 (S-1-meso) enveloped Pt–Ni bimetallic catalysts (noted as Pt1Ni1@S-1-meso) were synthesized via a facile in situ mesoporous template-free method. The Pt–Ni bimetallic nanoparticles were uniformly distributed and displayed a large specific surface area and enriched mesopores to facilitate the deep oxidation of toluene. The presence of the Pt–NiO interface both increased the dispersion of the catalyst and improved its catalytic performance, thereby reducing the consumption of Pt. The Mars-van Krevelen mechanism and density function theory (DFT) calculations revealed that the Pt–NiO interface effect changed the electronic structure of Pt and Ni species, reduced the activation potential for oxygen, formed reactive oxygen species, and facilitated the adsorption and activation of reactants in the direction favorable to the toluene oxidation. This study provides a guideline for minimizing the proportion of precious metals used in practical applications and a promising method for toluene elimination at low temperatures.
Degrading volatile organic compounds at low temperatures and active sites aggregation are still challenging. In this study, a novel mesoporous zeolite silicalite-1 (S-1-meso) enveloped Pt–Ni bimetallic catalysts (noted as Pt1Ni1@S-1-meso) were synthesized via a facile in situ mesoporous template-free method. The Pt–Ni bimetallic nanoparticles were uniformly distributed and displayed a large specific surface area and enriched mesopores to facilitate the deep oxidation of toluene. The presence of the Pt–NiO interface both increased the dispersion of the catalyst and improved its catalytic performance, thereby reducing the consumption of Pt. The Mars-van Krevelen mechanism and density function theory (DFT) calculations revealed that the Pt–NiO interface effect changed the electronic structure of Pt and Ni species, reduced the activation potential for oxygen, formed reactive oxygen species, and facilitated the adsorption and activation of reactants in the direction favorable to the toluene oxidation. This study provides a guideline for minimizing the proportion of precious metals used in practical applications and a promising method for toluene elimination at low temperatures.
2025, 36(4): 110139
doi: 10.1016/j.cclet.2024.110139
Abstract:
Developing BiVO4 photoanode with efficient carrier transfer and fast water oxidation kinetics is the permanent pursuit to achieve the state-of-art solar-driven photoelectrochemical (PEC) water splitting. The capacity to increase the PEC activity of BiVO4 by loading oxygen evolution co-catalysts (OECs) has been proven, however it suffers from sluggish charge carriers dynamics brought on by the complicated interface between BiVO4 and OECs as well as poor long-term durability. Herein, we connected OECs (NiFeOx) and photoanode with a Al-O bridge for bettering the PEC performance of BiVO4. The Al-O bridge served as a channel to extract hole from BiVO4 to NiFeOx, thus boosting charge carriers′ separation and preventing BiVO4 from photo-corrosion. The Al-O bridging photoanode (NiFeOx/Al2O3/BiVO4) demonstrated a high photocurrent density of 5.87 mA/cm2 at 1.23 V vs. RHE and long-term photostability in comparison to NiFeOx/BiVO4 photoanode. This study proposes a unique technique to boost charge carriers′ separation between BiVO4 and OECs for high-efficiency solar-driven PEC water splitting.
Developing BiVO4 photoanode with efficient carrier transfer and fast water oxidation kinetics is the permanent pursuit to achieve the state-of-art solar-driven photoelectrochemical (PEC) water splitting. The capacity to increase the PEC activity of BiVO4 by loading oxygen evolution co-catalysts (OECs) has been proven, however it suffers from sluggish charge carriers dynamics brought on by the complicated interface between BiVO4 and OECs as well as poor long-term durability. Herein, we connected OECs (NiFeOx) and photoanode with a Al-O bridge for bettering the PEC performance of BiVO4. The Al-O bridge served as a channel to extract hole from BiVO4 to NiFeOx, thus boosting charge carriers′ separation and preventing BiVO4 from photo-corrosion. The Al-O bridging photoanode (NiFeOx/Al2O3/BiVO4) demonstrated a high photocurrent density of 5.87 mA/cm2 at 1.23 V vs. RHE and long-term photostability in comparison to NiFeOx/BiVO4 photoanode. This study proposes a unique technique to boost charge carriers′ separation between BiVO4 and OECs for high-efficiency solar-driven PEC water splitting.
2025, 36(4): 110143
doi: 10.1016/j.cclet.2024.110143
Abstract:
Rapid diagnosis of Salmonella is crucial for the effective control of food safety incidents, especially in regions with poor hygiene conditions. Polymerase chain reaction (PCR), as a promising tool for Salmonella detection, is facing a lack of simple and fast sensing methods that are compatible with field applications in resource-limited areas. In this work, we developed a sensing approach to identify PCR-amplified Salmonella genomic DNA with the naked eye in a snapshot. Based on the ratiometric fluorescence signals from SYBR Green Ⅰ and Hydroxyl naphthol blue, positive samples stood out from negative ones with a distinct color pattern under UV exposure. The proposed sensing scheme enabled highly specific identification of Salmonella with a detection limit at the single-copy level. Also, as a supplement to the intuitive naked-eye visualization results, numerical analysis of the colored images was available with a smartphone app to extract RGB values from colored images. This work provides a simple, rapid, and user-friendly solution for PCR identification, which promises great potential in molecular diagnosis of Salmonella and other pathogens in field.
Rapid diagnosis of Salmonella is crucial for the effective control of food safety incidents, especially in regions with poor hygiene conditions. Polymerase chain reaction (PCR), as a promising tool for Salmonella detection, is facing a lack of simple and fast sensing methods that are compatible with field applications in resource-limited areas. In this work, we developed a sensing approach to identify PCR-amplified Salmonella genomic DNA with the naked eye in a snapshot. Based on the ratiometric fluorescence signals from SYBR Green Ⅰ and Hydroxyl naphthol blue, positive samples stood out from negative ones with a distinct color pattern under UV exposure. The proposed sensing scheme enabled highly specific identification of Salmonella with a detection limit at the single-copy level. Also, as a supplement to the intuitive naked-eye visualization results, numerical analysis of the colored images was available with a smartphone app to extract RGB values from colored images. This work provides a simple, rapid, and user-friendly solution for PCR identification, which promises great potential in molecular diagnosis of Salmonella and other pathogens in field.
2025, 36(4): 110148
doi: 10.1016/j.cclet.2024.110148
Abstract:
For nano-collision, regulating the interaction between nanoparticles (NPs) and electrode interfaces is crucial for the precise analysis of individual NPs. However, existing ultramicroelectrodes (UMEs) suffer from narrow electrochemical window and poor electrode interface adhesion, severely hindering the application of precise single NP analysis. Here, we propose a simple and effective interface modification strategy. By electrochemically self-assembling poly(diallyldimethylammonium chloride) (PC) on the surface of carbon nanocone electrodes (CNCEs), we successfully prepared PC-modified CNCEs (PC‑CNCEs). These electrodes not only possess sufficiently wide electrochemical window but also exhibit strong adhesion to negatively charged Ag NPs on their surfaces. Surface physical analysis and electrochemical molecule detection validated the high-density loading of PC on the modified electrodes. Furthermore, the working principle of PC‑CNCEs for single Ag NP collision detection was further verified through the techniques of nano-collision and double-potential steps. Leveraging these significant advantages, PC‑CNCEs not only achieved precise measurements of single or mixed-sized Ag NPs but also detected Ag NP solutions at concentrations as low as fmol/L levels. This advancement offers a new strategy for the rapid and precise analysis of NP colloids.
For nano-collision, regulating the interaction between nanoparticles (NPs) and electrode interfaces is crucial for the precise analysis of individual NPs. However, existing ultramicroelectrodes (UMEs) suffer from narrow electrochemical window and poor electrode interface adhesion, severely hindering the application of precise single NP analysis. Here, we propose a simple and effective interface modification strategy. By electrochemically self-assembling poly(diallyldimethylammonium chloride) (PC) on the surface of carbon nanocone electrodes (CNCEs), we successfully prepared PC-modified CNCEs (PC‑CNCEs). These electrodes not only possess sufficiently wide electrochemical window but also exhibit strong adhesion to negatively charged Ag NPs on their surfaces. Surface physical analysis and electrochemical molecule detection validated the high-density loading of PC on the modified electrodes. Furthermore, the working principle of PC‑CNCEs for single Ag NP collision detection was further verified through the techniques of nano-collision and double-potential steps. Leveraging these significant advantages, PC‑CNCEs not only achieved precise measurements of single or mixed-sized Ag NPs but also detected Ag NP solutions at concentrations as low as fmol/L levels. This advancement offers a new strategy for the rapid and precise analysis of NP colloids.
2025, 36(4): 110153
doi: 10.1016/j.cclet.2024.110153
Abstract:
Compared with natural enzymes, nanozymes have the advantages of high stability and low cost; however, selectivity and sensitivity are key issues that prevent their further development. In this study, we report a cascade nanozymatic system with significantly improved selectivity and sensitivity that combines more substrate-specific reactions and sensitive fluorescence detection. Taking detection of ascorbic acid (AA) as an example, a cascade catalytic reaction system consisting of oxidase-like N-doped carbon nanocages (NC) and peroxidase-like copper oxide (CuO) improved the reaction selectivity in transforming the substrate into the target product by more than 1200 times against the interference of uric acid. The cascade catalytic reaction system was also applicable for transfer from open reactors into a spatially confined microfluidic device, increasing the slope of the calibration curves by approximately 1000-fold with a linear detection range of 2.5 nmol/L to 100 nmol/L and a low limit of detection of 0.77 nmol/L. This work offers a new strategy that achieves significant improvements in selectivity and sensitivity.
Compared with natural enzymes, nanozymes have the advantages of high stability and low cost; however, selectivity and sensitivity are key issues that prevent their further development. In this study, we report a cascade nanozymatic system with significantly improved selectivity and sensitivity that combines more substrate-specific reactions and sensitive fluorescence detection. Taking detection of ascorbic acid (AA) as an example, a cascade catalytic reaction system consisting of oxidase-like N-doped carbon nanocages (NC) and peroxidase-like copper oxide (CuO) improved the reaction selectivity in transforming the substrate into the target product by more than 1200 times against the interference of uric acid. The cascade catalytic reaction system was also applicable for transfer from open reactors into a spatially confined microfluidic device, increasing the slope of the calibration curves by approximately 1000-fold with a linear detection range of 2.5 nmol/L to 100 nmol/L and a low limit of detection of 0.77 nmol/L. This work offers a new strategy that achieves significant improvements in selectivity and sensitivity.
2025, 36(4): 110164
doi: 10.1016/j.cclet.2024.110164
Abstract:
Selective separation of phenanthrene (PHE) from aromatic isomer mixtures poses a significant challenge in industry due to the similar physical properties of PHE and its isomer anthracene (ANT). Herein, we report the self-assembly of a water-soluble Pd2L2 cage 1 with a large hydrophobic cavity, formed from novel macrocyclic ligands (L) and cis-Pd(Ⅱ). Cage 1 can selectively encapsulate PHE instead of ANT. Based on host-guest recognition followed by extraction, we achieve a remarkable 99% purity of PHE separation from an equimolar mixture of PHE and ANT using cage 1 in aqueous solution. Importantly, the separation performance of PHE using cage 1 remains unaffected even after five extraction cycles, demonstrating its robustness. This work highlights the potential of supramolecular cages for efficient and cost-effective PHE separation from the isomer ANT in aqueous solutions using such promising host-guest strategy.
Selective separation of phenanthrene (PHE) from aromatic isomer mixtures poses a significant challenge in industry due to the similar physical properties of PHE and its isomer anthracene (ANT). Herein, we report the self-assembly of a water-soluble Pd2L2 cage 1 with a large hydrophobic cavity, formed from novel macrocyclic ligands (L) and cis-Pd(Ⅱ). Cage 1 can selectively encapsulate PHE instead of ANT. Based on host-guest recognition followed by extraction, we achieve a remarkable 99% purity of PHE separation from an equimolar mixture of PHE and ANT using cage 1 in aqueous solution. Importantly, the separation performance of PHE using cage 1 remains unaffected even after five extraction cycles, demonstrating its robustness. This work highlights the potential of supramolecular cages for efficient and cost-effective PHE separation from the isomer ANT in aqueous solutions using such promising host-guest strategy.
2025, 36(4): 110165
doi: 10.1016/j.cclet.2024.110165
Abstract:
The micro-dispersion structure of silica fillers exerts significant influences on the performance characteristics of rubber-based products. How to monitor this parameter is an important issue in the rubber industry, but there is currently no suitable technical solution for numerical monitoring that can be applied in automatic production line. The labeling of silica in rubber is a challenge that bottlenecks the development of numerical quality monitoring technology. In this work, we employed the organometallic europium to modify silica endowing the fluorescence properties for characterization. It provides more feasible solutions for visually studying the relationship between the submicroscopic structure and macroscopic properties of inorganic-filled polymers, and is the key foundation for achieving numerical monitoring of rubber filler qualities in industry.
The micro-dispersion structure of silica fillers exerts significant influences on the performance characteristics of rubber-based products. How to monitor this parameter is an important issue in the rubber industry, but there is currently no suitable technical solution for numerical monitoring that can be applied in automatic production line. The labeling of silica in rubber is a challenge that bottlenecks the development of numerical quality monitoring technology. In this work, we employed the organometallic europium to modify silica endowing the fluorescence properties for characterization. It provides more feasible solutions for visually studying the relationship between the submicroscopic structure and macroscopic properties of inorganic-filled polymers, and is the key foundation for achieving numerical monitoring of rubber filler qualities in industry.
2025, 36(4): 110177
doi: 10.1016/j.cclet.2024.110177
Abstract:
A thickness-controllable method for preparing metal-organic framework hollow nanoflowers on magnetic cores (Fe3O4@MOFs HFs) was demonstrated for the first time. The petal of magnetic core with hollow nanoflower structure served as medium for assembling UiO-66-NH2 shell with different thickness. To further improve its performance, Zr4+ was immobilized on the surface of Fe3O4@UiO-66-NH2. Compared with conventional Fe3O4@UiO-66-NH2-Zr4+ nanospheres, the Fe3O4@UiO-66-NH2-Zr4+ HFs showed increased enrichment performance for phosphopeptides. The Fe3O4@UiO-66-NH2-Zr4+ HFs served as an attractive restricted-access adsorption material exhibited good selectivity (mβ-casein:mBSA=1:1000), high sensitivity (1.0 fmol) and excellent size-exclusion effect (mβ-casein digests:mBSA=1:200). Furthermore, the Fe3O4@UiO-66-NH2-Zr4+ HFs was successfully applied to the specific capture of ultratrace phosphopeptide from complex biological samples, revealing the great potential for the identification and analysis of trace phosphopeptides in clinical analysis. This work can be easily extended to the fabrication of diverse mag-MOF HFs with multifunctional and easy to post-modify properties, and open up a new avenue for the design and construction of new MOFs material.
A thickness-controllable method for preparing metal-organic framework hollow nanoflowers on magnetic cores (Fe3O4@MOFs HFs) was demonstrated for the first time. The petal of magnetic core with hollow nanoflower structure served as medium for assembling UiO-66-NH2 shell with different thickness. To further improve its performance, Zr4+ was immobilized on the surface of Fe3O4@UiO-66-NH2. Compared with conventional Fe3O4@UiO-66-NH2-Zr4+ nanospheres, the Fe3O4@UiO-66-NH2-Zr4+ HFs showed increased enrichment performance for phosphopeptides. The Fe3O4@UiO-66-NH2-Zr4+ HFs served as an attractive restricted-access adsorption material exhibited good selectivity (mβ-casein:mBSA=1:1000), high sensitivity (1.0 fmol) and excellent size-exclusion effect (mβ-casein digests:mBSA=1:200). Furthermore, the Fe3O4@UiO-66-NH2-Zr4+ HFs was successfully applied to the specific capture of ultratrace phosphopeptide from complex biological samples, revealing the great potential for the identification and analysis of trace phosphopeptides in clinical analysis. This work can be easily extended to the fabrication of diverse mag-MOF HFs with multifunctional and easy to post-modify properties, and open up a new avenue for the design and construction of new MOFs material.
2025, 36(4): 110193
doi: 10.1016/j.cclet.2024.110193
Abstract:
Black phosphorus (BP), as a rising star of 2D nanomaterials has drawn considerable attention in cancer therapy. However, the poor stability under ambient conditions limits their practical applications. Herein, a multiple supramolecular assembly composed of adamantane-modified hyaluronic acid (HAADA), ferrocene-modified cinnamaldehyde (Fc-CA), guanidinium-functionalized β-cyclodextrin (Guano-CD), and black phosphorus (BP) nanosheets was successfully fabricated through cooperative host-guest and electrostatic interactions. Owing to the cooperative contribution of these building blocks, the obtained supramolecular assembly simultaneously possesses multiple functions including excellent stability, good biocompatibility and targeting property, and a high inhibition effect toward cancer cells. We believe that this work might provide new insights into designing a new generation of cancer theranostic protocols for potential clinical applications.
Black phosphorus (BP), as a rising star of 2D nanomaterials has drawn considerable attention in cancer therapy. However, the poor stability under ambient conditions limits their practical applications. Herein, a multiple supramolecular assembly composed of adamantane-modified hyaluronic acid (HAADA), ferrocene-modified cinnamaldehyde (Fc-CA), guanidinium-functionalized β-cyclodextrin (Guano-CD), and black phosphorus (BP) nanosheets was successfully fabricated through cooperative host-guest and electrostatic interactions. Owing to the cooperative contribution of these building blocks, the obtained supramolecular assembly simultaneously possesses multiple functions including excellent stability, good biocompatibility and targeting property, and a high inhibition effect toward cancer cells. We believe that this work might provide new insights into designing a new generation of cancer theranostic protocols for potential clinical applications.
Adsorption and visual detection of nitro explosives by pillar[n]arenes-based host–guest interactions
2025, 36(4): 110205
doi: 10.1016/j.cclet.2024.110205
Abstract:
Aromatic nitro compounds present substantial health and environmental concerns due to their toxic nature and potential explosive properties. Consequently, the development of host–guest molecular recognition systems for these compounds serves a dual-purpose: enabling the fabrication of high-performance sensors for detection and guiding the design of efficient adsorbents for environmental remediation. This study investigated the host–guest recognition behavior of perethylated pillar[n]arenes toward two aromatic nitro molecules, 1-chloro-2,4-dinitrobenzene and picric acid. Various techniques including 1H NMR, 2D NOESY NMR, and UV-vis spectroscopy were employed to explore the binding behavior between pillararenes and aromatic nitro guests in solution. Moreover, valuable single crystal structures were obtained to elucidate the distinct solid-state assembly behaviors of these guests with different pillararenes. The assembled solid-state supramolecular structures observed encompassed a 1:1 host–guest inclusion complex, an external binding complex, and an exo-wall tessellation complex. Furthermore, based on the findings from these systems, a pillararene-based test paper was developed for efficient picric acid detection, and the removal of picric acid from solution was also achieved using pillararenes powder. This research provides novel insights into the development of diverse host–guest systems toward hazardous compounds, offering potential applications in environmental protection and explosive detection domains.
Aromatic nitro compounds present substantial health and environmental concerns due to their toxic nature and potential explosive properties. Consequently, the development of host–guest molecular recognition systems for these compounds serves a dual-purpose: enabling the fabrication of high-performance sensors for detection and guiding the design of efficient adsorbents for environmental remediation. This study investigated the host–guest recognition behavior of perethylated pillar[n]arenes toward two aromatic nitro molecules, 1-chloro-2,4-dinitrobenzene and picric acid. Various techniques including 1H NMR, 2D NOESY NMR, and UV-vis spectroscopy were employed to explore the binding behavior between pillararenes and aromatic nitro guests in solution. Moreover, valuable single crystal structures were obtained to elucidate the distinct solid-state assembly behaviors of these guests with different pillararenes. The assembled solid-state supramolecular structures observed encompassed a 1:1 host–guest inclusion complex, an external binding complex, and an exo-wall tessellation complex. Furthermore, based on the findings from these systems, a pillararene-based test paper was developed for efficient picric acid detection, and the removal of picric acid from solution was also achieved using pillararenes powder. This research provides novel insights into the development of diverse host–guest systems toward hazardous compounds, offering potential applications in environmental protection and explosive detection domains.
2025, 36(4): 110212
doi: 10.1016/j.cclet.2024.110212
Abstract:
Visual assessment of tumor metastatic capacity is crucial for predicting hepatocellular carcinoma (HCC) prognosis and guiding clinical therapeutic approaches. In this study, we developed an enzyme-responsive probe based on the peptide GK10, which is selectively cleaved by matrix metalloproteinase-9 (MMP-9), a critical marker for metastasis in HCC. The GK10 peptide was conjugated with near-infrared fluorescent molecule IR783, fluorescent quencher black hole quencher 3 (BHQ3), and magnetic resonance (MR) contrast agent DOTA-Gd, forming the IR783-GK10-BHQ3-Gd probe. Upon MMP-9 cleavage of GK10, BHQ3 is released from the probe, thereby amplifying the previously quenched IR783 fluorescence signal. In vitro experiments demonstrate the probe’s impressive detection limit for MMP-9, as low as 1.84 ng/mL. Moreover, in vivo imaging results reveal that the probe can differentiate liver cancers with varying metastatic capacities. The fluorescence and MR imaging signal intensity of high metastatic HCC are approximately 1.2 times greater than that of low metastatic HCC. Thus, this engineered probe holds promise as a valuable tool for evaluating HCC metastatic capacity through fluorescence-MR dual-mode imaging.
Visual assessment of tumor metastatic capacity is crucial for predicting hepatocellular carcinoma (HCC) prognosis and guiding clinical therapeutic approaches. In this study, we developed an enzyme-responsive probe based on the peptide GK10, which is selectively cleaved by matrix metalloproteinase-9 (MMP-9), a critical marker for metastasis in HCC. The GK10 peptide was conjugated with near-infrared fluorescent molecule IR783, fluorescent quencher black hole quencher 3 (BHQ3), and magnetic resonance (MR) contrast agent DOTA-Gd, forming the IR783-GK10-BHQ3-Gd probe. Upon MMP-9 cleavage of GK10, BHQ3 is released from the probe, thereby amplifying the previously quenched IR783 fluorescence signal. In vitro experiments demonstrate the probe’s impressive detection limit for MMP-9, as low as 1.84 ng/mL. Moreover, in vivo imaging results reveal that the probe can differentiate liver cancers with varying metastatic capacities. The fluorescence and MR imaging signal intensity of high metastatic HCC are approximately 1.2 times greater than that of low metastatic HCC. Thus, this engineered probe holds promise as a valuable tool for evaluating HCC metastatic capacity through fluorescence-MR dual-mode imaging.
2025, 36(4): 110242
doi: 10.1016/j.cclet.2024.110242
Abstract:
Polyetheretherketone (PEEK) is a desirable candidate to replace conventional metal implants owing to its excellent mechanical properties. However, the intrinsic bioinertness of PEEK results in inferior or delayed osseointegration, which limits its further clinical application. To address these challenges, one leading strategy is to construct a biofunctionalized surface on PEEK that provides a coordinated osteoblast-osteoclast interactions microenvironment. Herein, alendronate (ALN), a common bone absorption inhibitor, was loaded in biomedical inorganic/organic microspheres, consisting of bioactive inorganic nano-hydroxyapatite core, and chitosan (CS) shell. Polydopamine (PDA) modification was employed to ensure the adherence of the microspheres to the PEEK surface. The delivery of ALN and Ca2+ from these microspheres simultaneously suppressed osteoclastogenesis and promoted osteogenesis, resulting in a coordinated cascade of osteoblast-osteoclast interactions crucial for the per-implant osseointegration. In vitro experiments demonstrated that the PEEK surface exhibited satisfactory biocompatibility and enhanced the proliferation and osteogenic differentiation of rat bone mesenchymal stem cells while inhibiting the osteoclast differentiation. Moreover, the in vivo rat femoral drilling model demonstrated superior osseointegration three months after implantation. By considering the bone remodeling processes, this study proposes a novel biofunctionalized PEEK surface that regulates the activities of both osteoblasts and osteoclasts to promote osseointegration.
Polyetheretherketone (PEEK) is a desirable candidate to replace conventional metal implants owing to its excellent mechanical properties. However, the intrinsic bioinertness of PEEK results in inferior or delayed osseointegration, which limits its further clinical application. To address these challenges, one leading strategy is to construct a biofunctionalized surface on PEEK that provides a coordinated osteoblast-osteoclast interactions microenvironment. Herein, alendronate (ALN), a common bone absorption inhibitor, was loaded in biomedical inorganic/organic microspheres, consisting of bioactive inorganic nano-hydroxyapatite core, and chitosan (CS) shell. Polydopamine (PDA) modification was employed to ensure the adherence of the microspheres to the PEEK surface. The delivery of ALN and Ca2+ from these microspheres simultaneously suppressed osteoclastogenesis and promoted osteogenesis, resulting in a coordinated cascade of osteoblast-osteoclast interactions crucial for the per-implant osseointegration. In vitro experiments demonstrated that the PEEK surface exhibited satisfactory biocompatibility and enhanced the proliferation and osteogenic differentiation of rat bone mesenchymal stem cells while inhibiting the osteoclast differentiation. Moreover, the in vivo rat femoral drilling model demonstrated superior osseointegration three months after implantation. By considering the bone remodeling processes, this study proposes a novel biofunctionalized PEEK surface that regulates the activities of both osteoblasts and osteoclasts to promote osseointegration.
2025, 36(4): 110380
doi: 10.1016/j.cclet.2024.110380
Abstract:
Cobalt sulfide has received widespread attention in the advanced oxidation treatment of wastewater, and its catalytic activity is influenced by crystal structure and exposed active sites. This work successfully constructed three types of cobalt sulfides, namely Co9S8, Co3S4 and CoS2, by changing the molar ratio of cobalt to sulfur. The results showed that the degradation efficiency of Co9S8, Co3S4 and CoS2 on chloroxylenol by activated peroxomonosulfate (PMS) were 100%, 88.70% and 67.73%, respectively. Combined with density functional theory (DFT), the structural properties and reaction energy barriers of different cobalt-sulfur ratios were calculated. As the ratio of cobalt to sulfur increases, the sulfur vacancies realized a fuller exposure of active sites (Co2+surf.) on the surface of the catalysts, with a highly linear relationship with the reaction rate constant (R2 = 0.945). This work explores the structure-activity relationship between cobalt sulfur ratio and degradation efficiency, which can guide new catalyst synthesis.
Cobalt sulfide has received widespread attention in the advanced oxidation treatment of wastewater, and its catalytic activity is influenced by crystal structure and exposed active sites. This work successfully constructed three types of cobalt sulfides, namely Co9S8, Co3S4 and CoS2, by changing the molar ratio of cobalt to sulfur. The results showed that the degradation efficiency of Co9S8, Co3S4 and CoS2 on chloroxylenol by activated peroxomonosulfate (PMS) were 100%, 88.70% and 67.73%, respectively. Combined with density functional theory (DFT), the structural properties and reaction energy barriers of different cobalt-sulfur ratios were calculated. As the ratio of cobalt to sulfur increases, the sulfur vacancies realized a fuller exposure of active sites (Co2+surf.) on the surface of the catalysts, with a highly linear relationship with the reaction rate constant (R2 = 0.945). This work explores the structure-activity relationship between cobalt sulfur ratio and degradation efficiency, which can guide new catalyst synthesis.
2025, 36(4): 110381
doi: 10.1016/j.cclet.2024.110381
Abstract:
Designing carbon materials with ideal stable hierarchical porous structures and flexible functional properties for efficient and sustainable Zn2+ ion storage still faces great challenges. Herein, the three-dimensional carbon superstructures with spherical nanoflower-like structures were tailor-made by the self-assembly strategy. Specifically, organic polymer units (i.e., organic motifs) were formed by tetrachloro-p-benzoquinone (TBQ) and 2, 6-diamino anthraquinone (DAQ) via a noble-metal-free catalyzed coupling reaction. Subsequently, the organic motifs assemble into spherical nanoflower-like superstructures induced by intermolecular hydrogen bonding and aromatic π-π stacking interactions. Well-designed carbon superstructures can provide a stable backbone that effectively blocks structural stacking and collapse. Meanwhile, the hierarchical porous structures in 3D carbon superstructures provide continuous charge transport pathways to greatly shorten the ion diffusion distance, and as a result, the carbon superstructures-based zinc-ion hybrid capacitors (ZIHCs) provide a capacity of 245 mAh/g at 0.5 A/g, a high energy density of 152 Wh/kg and an ultra-long life of 300, 000 cycles at 20 A/g. The excellent electrochemical performance is also attributed to the corresponding charge storage mechanism, i.e., the alternate binding of Zn2+/CF3SO3− ions. Besides, the high-level N/O motifs improve the surface properties of the carbon superstructures and reduce the ion migration barriers for more efficient charge storage. This paper provides insights into the design of advanced carbon-based cathodes and presents a fundamental understanding of their charge storage mechanisms.
Designing carbon materials with ideal stable hierarchical porous structures and flexible functional properties for efficient and sustainable Zn2+ ion storage still faces great challenges. Herein, the three-dimensional carbon superstructures with spherical nanoflower-like structures were tailor-made by the self-assembly strategy. Specifically, organic polymer units (i.e., organic motifs) were formed by tetrachloro-p-benzoquinone (TBQ) and 2, 6-diamino anthraquinone (DAQ) via a noble-metal-free catalyzed coupling reaction. Subsequently, the organic motifs assemble into spherical nanoflower-like superstructures induced by intermolecular hydrogen bonding and aromatic π-π stacking interactions. Well-designed carbon superstructures can provide a stable backbone that effectively blocks structural stacking and collapse. Meanwhile, the hierarchical porous structures in 3D carbon superstructures provide continuous charge transport pathways to greatly shorten the ion diffusion distance, and as a result, the carbon superstructures-based zinc-ion hybrid capacitors (ZIHCs) provide a capacity of 245 mAh/g at 0.5 A/g, a high energy density of 152 Wh/kg and an ultra-long life of 300, 000 cycles at 20 A/g. The excellent electrochemical performance is also attributed to the corresponding charge storage mechanism, i.e., the alternate binding of Zn2+/CF3SO3− ions. Besides, the high-level N/O motifs improve the surface properties of the carbon superstructures and reduce the ion migration barriers for more efficient charge storage. This paper provides insights into the design of advanced carbon-based cathodes and presents a fundamental understanding of their charge storage mechanisms.
2025, 36(4): 110477
doi: 10.1016/j.cclet.2024.110477
Abstract:
Lead-free hybrid double perovskites (LFHDPs) have received a lot of attention due to their environmental friendliness and promising attributes. However, studying the effect of film thickness on LFHDPs optoelectronic properties has not yet been investigated. Herein, we synthesized two new Ruddlesden–Popper LFHDPs, namely (C5H12N)4AgBiI8 (CAB-1) and (C6H14N)4AgBiI8 (CAB-2) using cyclopentylamine and cyclohexylamine as monoamine ligands. Indeed, these two Ag(Ⅰ)-Bi(Ⅲ) LFHDPs form smooth and uniform films ranging in thickness from 250 nm to 1 µm, with preferred orientations. Notably, the studies on the optical properties showed that the direct band gap value decreased from 2.17 eV to 1.91 eV for CAB-1 and from 2.05 eV to 1.86 eV for CAB-2 with increasing thickness. Accordingly, photo-current response using a xenon lamp revealed a significant difference of over 1000 nA between light and dark conditions for 1 µm-thickness films, suggesting potential for light harvesting. Other than that, thicker films of CAB-1 and CAB-2 exhibit high stability for 90 days in a relatively humid environment (RH of 55%), paving the way for promising optoelectronic applications.
Lead-free hybrid double perovskites (LFHDPs) have received a lot of attention due to their environmental friendliness and promising attributes. However, studying the effect of film thickness on LFHDPs optoelectronic properties has not yet been investigated. Herein, we synthesized two new Ruddlesden–Popper LFHDPs, namely (C5H12N)4AgBiI8 (CAB-1) and (C6H14N)4AgBiI8 (CAB-2) using cyclopentylamine and cyclohexylamine as monoamine ligands. Indeed, these two Ag(Ⅰ)-Bi(Ⅲ) LFHDPs form smooth and uniform films ranging in thickness from 250 nm to 1 µm, with preferred orientations. Notably, the studies on the optical properties showed that the direct band gap value decreased from 2.17 eV to 1.91 eV for CAB-1 and from 2.05 eV to 1.86 eV for CAB-2 with increasing thickness. Accordingly, photo-current response using a xenon lamp revealed a significant difference of over 1000 nA between light and dark conditions for 1 µm-thickness films, suggesting potential for light harvesting. Other than that, thicker films of CAB-1 and CAB-2 exhibit high stability for 90 days in a relatively humid environment (RH of 55%), paving the way for promising optoelectronic applications.
2025, 36(4): 110478
doi: 10.1016/j.cclet.2024.110478
Abstract:
Hyperforatone A (1), the 1,8-seco rearranged polycyclic polyprenylated acylphloroglucinol, possessed an unusual bicyclo[5.4.0]undecane skeleton bearing a 5/7/6/5 ring system, and two known biosynthetically related precursors (2 and 3) were isolated from Hypericum perforatum (St. John’s wort). The structure and absolute configuration were unambiguously confirmed by a combination of comprehensive spectroscopic data, computational methods including residual dipolar couplings (RDCs), and X-ray crystallography. Density functional theory (DFT) calculations revealed that the cationic cyclization reaction was key to proposed formation mechanism for hyperforatone A. Furthermore, in vitro and in vivo experiments demonstrated that compound 1 was a potential anti-neuroinflammatory agent.
Hyperforatone A (1), the 1,8-seco rearranged polycyclic polyprenylated acylphloroglucinol, possessed an unusual bicyclo[5.4.0]undecane skeleton bearing a 5/7/6/5 ring system, and two known biosynthetically related precursors (2 and 3) were isolated from Hypericum perforatum (St. John’s wort). The structure and absolute configuration were unambiguously confirmed by a combination of comprehensive spectroscopic data, computational methods including residual dipolar couplings (RDCs), and X-ray crystallography. Density functional theory (DFT) calculations revealed that the cationic cyclization reaction was key to proposed formation mechanism for hyperforatone A. Furthermore, in vitro and in vivo experiments demonstrated that compound 1 was a potential anti-neuroinflammatory agent.
2025, 36(4): 110495
doi: 10.1016/j.cclet.2024.110495
Abstract:
The exploitation of organic-inorganic hybrid perovskites (OIHPs) as active layer materials for typical sandwich-structured resistive memories has attracted widespread interest due to the property of low power consumption and fast switching. However, the inherent thermal instability of perovskites limits the application of OIHPs-based resistive memories under extreme conditions, while the influence of thermal effects on their resistance change characteristics remains unclear. Herein, a novel 2D <100>-oriented high-temperature resistant OIHP [(BIZ-H)2(PbBr4)]n (BIZ = benzimidazole) is prepared as an active layer material to fabricate FTO/[(BIZ-H)2(PbBr4)]n/Ag resistive memory with excellent thermal reproducibility and stability up to 120 ℃. The increase in temperature leads to a decrease in the PbBr6 octahedral distortion in the crystal structure, an increase in hydrogen bonding between the (BIZ-H)+ cation and the (PbBr4)n2n- layer, and a shortening of the spacing of the inorganic layers, which is found to result in the creation and predominance of thermally activated traps with increasing temperature. This work provides a new direction for the next generation of OIHPs-based resistive memories with high-temperature tolerance.
The exploitation of organic-inorganic hybrid perovskites (OIHPs) as active layer materials for typical sandwich-structured resistive memories has attracted widespread interest due to the property of low power consumption and fast switching. However, the inherent thermal instability of perovskites limits the application of OIHPs-based resistive memories under extreme conditions, while the influence of thermal effects on their resistance change characteristics remains unclear. Herein, a novel 2D <100>-oriented high-temperature resistant OIHP [(BIZ-H)2(PbBr4)]n (BIZ = benzimidazole) is prepared as an active layer material to fabricate FTO/[(BIZ-H)2(PbBr4)]n/Ag resistive memory with excellent thermal reproducibility and stability up to 120 ℃. The increase in temperature leads to a decrease in the PbBr6 octahedral distortion in the crystal structure, an increase in hydrogen bonding between the (BIZ-H)+ cation and the (PbBr4)n2n- layer, and a shortening of the spacing of the inorganic layers, which is found to result in the creation and predominance of thermally activated traps with increasing temperature. This work provides a new direction for the next generation of OIHPs-based resistive memories with high-temperature tolerance.
2025, 36(4): 110498
doi: 10.1016/j.cclet.2024.110498
Abstract:
Developing efficient electrocatalysts for oxygen evolution reaction (OER) is imperative to enhance the overall efficiency of electrolysis systems and rechargeable metal-air batteries operating in aqueous solutions. High-entropy materials, featured with their distinctive multi-component properties, have found extensive application as catalysts in electrochemical energy storage and conversion devices. However, synthesizing nanostructured high-entropy compounds under mild conditions poses a significant challenge due to the difficulty in overcoming the immiscibility of multiple metallic constituents. In this context, the current study focuses on the synthesis of an array of nano-sized high entropy sulfides tailored for OER via a facile precursor pyrolysis method at low temperature. The representative compound, FeCoNiCuMnSx, demonstrates remarkable OER performance, achieving a current density of 10 mA/cm2 at an overpotential of merely 220 mV and excellent stability with constant electrolysis at 100 mA/cm2 for over 400 h. The in-situ formed metal (oxy)hydroxide has been confirmed as the real active sites and its exceptional performance can be primarily attributed to the synergistic effects arising from its multiple components. Furthermore, the synthetic methodology presented here is versatile and can be extended to the preparation of high entropy phosphides, which also present favorable OER performance. This research not only introduces promising non-noble electrocatalysts for OER but also offers a facile approach to expand the family of nano high-entropy materials, contributing significantly to the field of electrochemical energy conversion.
Developing efficient electrocatalysts for oxygen evolution reaction (OER) is imperative to enhance the overall efficiency of electrolysis systems and rechargeable metal-air batteries operating in aqueous solutions. High-entropy materials, featured with their distinctive multi-component properties, have found extensive application as catalysts in electrochemical energy storage and conversion devices. However, synthesizing nanostructured high-entropy compounds under mild conditions poses a significant challenge due to the difficulty in overcoming the immiscibility of multiple metallic constituents. In this context, the current study focuses on the synthesis of an array of nano-sized high entropy sulfides tailored for OER via a facile precursor pyrolysis method at low temperature. The representative compound, FeCoNiCuMnSx, demonstrates remarkable OER performance, achieving a current density of 10 mA/cm2 at an overpotential of merely 220 mV and excellent stability with constant electrolysis at 100 mA/cm2 for over 400 h. The in-situ formed metal (oxy)hydroxide has been confirmed as the real active sites and its exceptional performance can be primarily attributed to the synergistic effects arising from its multiple components. Furthermore, the synthetic methodology presented here is versatile and can be extended to the preparation of high entropy phosphides, which also present favorable OER performance. This research not only introduces promising non-noble electrocatalysts for OER but also offers a facile approach to expand the family of nano high-entropy materials, contributing significantly to the field of electrochemical energy conversion.
2025, 36(4): 110511
doi: 10.1016/j.cclet.2024.110511
Abstract:
A binary-mixed electron transport layer (ETL) has been reported for constructing solution-processable near-infrared organic light-emitting diodes (NIR OLEDs). Relative to the single-component ETL, the binary-mixed ETL composed of PDINN:TPBi can enhance the carrier transport capacity, reduce device impedance, and weaken fluorescence quenching of the emitting layer. By carefully selecting an appropriate luminescent material Y5 (a nonfullerene electron acceptor in organic solar cells) and precisely fine-tuning the molecular aggregation in active layer using a mixed solvent, the morphology is optimized and luminescence performance is enhanced, resulting in efficient NIR OLEDs with an emission peak at 890 nm. The experiment showcases a Y5-based near-infrared OLED with a maximum radiance of 34.9 W sr-1 m-2 and a maximum external quantum efficiency of 0.50%, which is among the highest values reported for non-doped fluorescent NIR OLEDs with an emission peak over 850 nm.
A binary-mixed electron transport layer (ETL) has been reported for constructing solution-processable near-infrared organic light-emitting diodes (NIR OLEDs). Relative to the single-component ETL, the binary-mixed ETL composed of PDINN:TPBi can enhance the carrier transport capacity, reduce device impedance, and weaken fluorescence quenching of the emitting layer. By carefully selecting an appropriate luminescent material Y5 (a nonfullerene electron acceptor in organic solar cells) and precisely fine-tuning the molecular aggregation in active layer using a mixed solvent, the morphology is optimized and luminescence performance is enhanced, resulting in efficient NIR OLEDs with an emission peak at 890 nm. The experiment showcases a Y5-based near-infrared OLED with a maximum radiance of 34.9 W sr-1 m-2 and a maximum external quantum efficiency of 0.50%, which is among the highest values reported for non-doped fluorescent NIR OLEDs with an emission peak over 850 nm.
2025, 36(4): 110528
doi: 10.1016/j.cclet.2024.110528
Abstract:
Redox dyshomeostasis is a critical factor in the initiation of numerous diseases, making the accurate evaluation of the redox status of the cellular environment an important aspect of physiological research. However, maintaining redox homeostasis relies on a complex and dynamic physiological system involving multiple substrate-enzyme interactions, so its accurately detection remains a challenge. With this research, we developed an activable fluorescence switching platform by incorporating different conjugate acceptors to a fluorophore using ester bonds and resulting in fluorescence quenching due to donor-excited photo-induced electron transfer (d-PeT), which was confirmed through density functional theory calculations. The reaction-based probe was deployed for recognizing all major intracellular reducing sulfur species (RSS), including H2S, cysteine (Cys), homocysteine (Hcy), glutathione (GSH), and protein free thiols. The quenched fluorescence was significantly recovered by RSS, through releasing the fluorophore and diminishing the d-PeT effect. Furthermore, the fluorescent probe was used for the sensing and imaging RSS in living cells, demonstrating good cell-permeability, low cytotoxicity, and negative correlation with reactive oxygen species content, enabling the evaluating of global thiols redox state in HepG2 cellular lines during ferroptosis processes.
Redox dyshomeostasis is a critical factor in the initiation of numerous diseases, making the accurate evaluation of the redox status of the cellular environment an important aspect of physiological research. However, maintaining redox homeostasis relies on a complex and dynamic physiological system involving multiple substrate-enzyme interactions, so its accurately detection remains a challenge. With this research, we developed an activable fluorescence switching platform by incorporating different conjugate acceptors to a fluorophore using ester bonds and resulting in fluorescence quenching due to donor-excited photo-induced electron transfer (d-PeT), which was confirmed through density functional theory calculations. The reaction-based probe was deployed for recognizing all major intracellular reducing sulfur species (RSS), including H2S, cysteine (Cys), homocysteine (Hcy), glutathione (GSH), and protein free thiols. The quenched fluorescence was significantly recovered by RSS, through releasing the fluorophore and diminishing the d-PeT effect. Furthermore, the fluorescent probe was used for the sensing and imaging RSS in living cells, demonstrating good cell-permeability, low cytotoxicity, and negative correlation with reactive oxygen species content, enabling the evaluating of global thiols redox state in HepG2 cellular lines during ferroptosis processes.
2025, 36(4): 110532
doi: 10.1016/j.cclet.2024.110532
Abstract:
Unraveling the essence of electronic structure effected by d-d orbital coupling of transition metal and methanol oxidation reaction (MOR) performance can fundamentally guide high efficient catalyst design. Herein, density functional theory (DFT) calculations were performed at first to study the d–d orbital interaction of metallic PtPdCu, revealing that the incorporation of Pd and Cu atoms into Pt system can enhance d-d electron interaction via capturing antibonding orbital electrons of Pt to fill the surrounding Pd and Cu atoms. Under the theoretical guidance, PtPdCu medium entropy alloy aerogels (PtPdCu MEAAs) catalysts have been designed and systematically screened for MOR under acid, alkaline and neutral electrolyte. Furthermore, DFT calculation and in-situ fourier transform infrared spectroscopy analysis indicate that PtPdCu MEAAs follow the direct pathway via formate as the reactive intermediate to be directly oxidized to CO2. For practical direct methanol fuel cells (DMFCs), the PtPdCu MEAAs-integrated ultra-thin catalyst layer (4–5 µm thickness) as anode exhibits higher peak power density of 35 mW/cm2 than commercial Pt/C of 20 mW/cm2 (~40 µm thickness) under the similar noble metal loading and an impressive stability retention at a 50-mA/cm2 constant current for 10 h. This work clearly proves that optimizing the intermediate adsorption capacity via d-d orbital coupling is an effective strategy to design highly efficient catalysts for DMFCs.
Unraveling the essence of electronic structure effected by d-d orbital coupling of transition metal and methanol oxidation reaction (MOR) performance can fundamentally guide high efficient catalyst design. Herein, density functional theory (DFT) calculations were performed at first to study the d–d orbital interaction of metallic PtPdCu, revealing that the incorporation of Pd and Cu atoms into Pt system can enhance d-d electron interaction via capturing antibonding orbital electrons of Pt to fill the surrounding Pd and Cu atoms. Under the theoretical guidance, PtPdCu medium entropy alloy aerogels (PtPdCu MEAAs) catalysts have been designed and systematically screened for MOR under acid, alkaline and neutral electrolyte. Furthermore, DFT calculation and in-situ fourier transform infrared spectroscopy analysis indicate that PtPdCu MEAAs follow the direct pathway via formate as the reactive intermediate to be directly oxidized to CO2. For practical direct methanol fuel cells (DMFCs), the PtPdCu MEAAs-integrated ultra-thin catalyst layer (4–5 µm thickness) as anode exhibits higher peak power density of 35 mW/cm2 than commercial Pt/C of 20 mW/cm2 (~40 µm thickness) under the similar noble metal loading and an impressive stability retention at a 50-mA/cm2 constant current for 10 h. This work clearly proves that optimizing the intermediate adsorption capacity via d-d orbital coupling is an effective strategy to design highly efficient catalysts for DMFCs.
2025, 36(4): 110554
doi: 10.1016/j.cclet.2024.110554
Abstract:
Gel-based sensors have provided unprecedented opportunities for bioelectric monitoring. Until now, sensors for underwater applicants have remained a notable challenge, as most sensors work effectively in air but swell underwater leading to functional failure. Herein, we introduce an innovative amphibian-inspired high-performance ionogel, where multiple supramolecular interactions in the ionogel's network confer good stretchability, elasticity, conductivity, and the hydrophobic C-F bonds play a key role in diminishing water molecule hydration and provide outstanding environmental stability. These unique properties of ionogels make them suitable as wearable amphibious flexible sensors, and the sensors are capable of highly sensitive and stable human motion monitoring in air and underwater. Integration of the designed sensor into an artificial intelligence drowning alarm system, which recognizes the swimmer's movement status by monitoring the amplitude and frequency, especially in the drowning status for real-time alarms. This work provides novel strategies for motion recognition and hazard monitoring in amphibious environments, meeting the new generation of wearable sensors.
Gel-based sensors have provided unprecedented opportunities for bioelectric monitoring. Until now, sensors for underwater applicants have remained a notable challenge, as most sensors work effectively in air but swell underwater leading to functional failure. Herein, we introduce an innovative amphibian-inspired high-performance ionogel, where multiple supramolecular interactions in the ionogel's network confer good stretchability, elasticity, conductivity, and the hydrophobic C-F bonds play a key role in diminishing water molecule hydration and provide outstanding environmental stability. These unique properties of ionogels make them suitable as wearable amphibious flexible sensors, and the sensors are capable of highly sensitive and stable human motion monitoring in air and underwater. Integration of the designed sensor into an artificial intelligence drowning alarm system, which recognizes the swimmer's movement status by monitoring the amplitude and frequency, especially in the drowning status for real-time alarms. This work provides novel strategies for motion recognition and hazard monitoring in amphibious environments, meeting the new generation of wearable sensors.
2025, 36(4): 110555
doi: 10.1016/j.cclet.2024.110555
Abstract:
Multiple donor-acceptor (D-A) combinations represent a promising category of thermally activated delayed fluorescence (TADF) materials, offering potential for superior efficiency and stability. However, current systems are predominantly composed of limited donor groups, primarily carbazole-based derivatives. In this work, we developed a series of D-A type materials incorporating helical π-expanded carbazole (CzNaph) and 7H-dinaphtho[1,8-bc:1′,8′-ef]azepine (AzNaph), alongside traditional carbazole, ranging from mono- to tetra-substituted configurations (Dn-A). Through systematic investigation of geometric and electronic structures, the number and positioning of multiple donors are confirmed with significant manipulations on charge transfer characteristics and the S1 state via steric effects. Density functional theory (DFT) calculations reveal that varying the number of π-extended donors within the acceptor framework produces emission colors from ultraviolet to red, providing a diverse range of emitters. Furthermore, the reduced reorganization energy of S1 observed in tetra-substituted Cz and CzNaph, as well as MonoAzN, indicates lower structural relaxation, highlighting these materials' potential as stable luminescent candidates. This study underscores the importance of diverse composing units in achieving efficient and stable TADF emitters with multiple and hetero-donor configurations.
Multiple donor-acceptor (D-A) combinations represent a promising category of thermally activated delayed fluorescence (TADF) materials, offering potential for superior efficiency and stability. However, current systems are predominantly composed of limited donor groups, primarily carbazole-based derivatives. In this work, we developed a series of D-A type materials incorporating helical π-expanded carbazole (CzNaph) and 7H-dinaphtho[1,8-bc:1′,8′-ef]azepine (AzNaph), alongside traditional carbazole, ranging from mono- to tetra-substituted configurations (Dn-A). Through systematic investigation of geometric and electronic structures, the number and positioning of multiple donors are confirmed with significant manipulations on charge transfer characteristics and the S1 state via steric effects. Density functional theory (DFT) calculations reveal that varying the number of π-extended donors within the acceptor framework produces emission colors from ultraviolet to red, providing a diverse range of emitters. Furthermore, the reduced reorganization energy of S1 observed in tetra-substituted Cz and CzNaph, as well as MonoAzN, indicates lower structural relaxation, highlighting these materials' potential as stable luminescent candidates. This study underscores the importance of diverse composing units in achieving efficient and stable TADF emitters with multiple and hetero-donor configurations.
2025, 36(4): 110567
doi: 10.1016/j.cclet.2024.110567
Abstract:
In response to the increasing demand of ethylene, electrochemical ethane nonoxidative dehydrogenation (EENDH) to ethylene by protonic ceramic electrolysis cells (PCECs) is developed. However, existing anode materials exhibit poor proton conductivity and limited catalytic activity. Herein, a novel Sr1.95Fe1.4Co0.1Mo0.4Zr0.1O6-δ (SFCMZ) anode is prepared as PCECs anode for EENDH. Zr doping increases the oxygen vacancies and enhances the proton conductivity of SFCMZ. Moreover, an alloy-oxide heterostructure (CoFe@SFCMZ) is formed through in-situ exsolution of CoFe alloy nanoparticles under reduction conditions, generating abundant oxygen vacancies and improving its catalytic activity. CoFe@SFCMZ cell achieves an electrolysis current density of 0.87 A/cm2 at 700 ℃ under 1.6 V, with an ethane conversion rate of 34.22% and corresponding ethylene selectivity of 93.4%. These results demonstrate that CoFe@SFCMZ anode exhibits excellent electrocatalytic activity, suggesting promising applications for EENDH.
In response to the increasing demand of ethylene, electrochemical ethane nonoxidative dehydrogenation (EENDH) to ethylene by protonic ceramic electrolysis cells (PCECs) is developed. However, existing anode materials exhibit poor proton conductivity and limited catalytic activity. Herein, a novel Sr1.95Fe1.4Co0.1Mo0.4Zr0.1O6-δ (SFCMZ) anode is prepared as PCECs anode for EENDH. Zr doping increases the oxygen vacancies and enhances the proton conductivity of SFCMZ. Moreover, an alloy-oxide heterostructure (CoFe@SFCMZ) is formed through in-situ exsolution of CoFe alloy nanoparticles under reduction conditions, generating abundant oxygen vacancies and improving its catalytic activity. CoFe@SFCMZ cell achieves an electrolysis current density of 0.87 A/cm2 at 700 ℃ under 1.6 V, with an ethane conversion rate of 34.22% and corresponding ethylene selectivity of 93.4%. These results demonstrate that CoFe@SFCMZ anode exhibits excellent electrocatalytic activity, suggesting promising applications for EENDH.
2025, 36(4): 110601
doi: 10.1016/j.cclet.2024.110601
Abstract:
Secondary trauma, resulting in undesirable injury and bleeding during wound dressing treatment, which will cause the treatment of chronic wounds ineffective. The medical cotton gauzes often bring strong adhesion due to the exudates absorbed and clots formed. Conversely, the easily detachable wound dressings neglect the wound seepage management, rendering them ineffective in facing the complexities of chronic wounds. To address this challenge, we propose a novel draining anti-adhesion dressings (DAD) by constructing the hydrophilic microchannels array on the superhydrophobic dressing. The superhydrophobic areas facilitate stable wound fluid repellence leading to achieve the anti-adhesion (18.7% detachment energy of cotton) and the microchannel array ensures the transportation of excess exudates (>92%) by the capillary force. Notably, our dressing demonstrates a significant healing-promoting in a chronic wound model in rats. The development of such dressings holds promise for advancing wound care practices and addressing the unique challenges posed by chronic wounds, offering a valuable solution for improved clinical outcomes.
Secondary trauma, resulting in undesirable injury and bleeding during wound dressing treatment, which will cause the treatment of chronic wounds ineffective. The medical cotton gauzes often bring strong adhesion due to the exudates absorbed and clots formed. Conversely, the easily detachable wound dressings neglect the wound seepage management, rendering them ineffective in facing the complexities of chronic wounds. To address this challenge, we propose a novel draining anti-adhesion dressings (DAD) by constructing the hydrophilic microchannels array on the superhydrophobic dressing. The superhydrophobic areas facilitate stable wound fluid repellence leading to achieve the anti-adhesion (18.7% detachment energy of cotton) and the microchannel array ensures the transportation of excess exudates (>92%) by the capillary force. Notably, our dressing demonstrates a significant healing-promoting in a chronic wound model in rats. The development of such dressings holds promise for advancing wound care practices and addressing the unique challenges posed by chronic wounds, offering a valuable solution for improved clinical outcomes.
2025, 36(4): 110602
doi: 10.1016/j.cclet.2024.110602
Abstract:
The oxygen evolution reaction (OER) is the bottleneck in the overall photocatalytic splitting of water. The active sites (terminal titanium or bridging oxygen) and active species (molecular or dissociative water) of the initial step of the photocatalyzed OER on the prototypical photocatalyst TiO2, remain debatable. Herein, the photocatalytic chemistry of monolayer water on oxygen-pretreated TiO2(110) (o-TiO2(110)) and reduced TiO2(110) (r-TiO2(110)) surfaces initiated by 400 nm light illumination was investigated by time-dependent two-photon photoemission spectroscopy (TD-2PPE). The photoinduced reduction of the H2O/o-TiO2(110) interface rather than the H2O/r-TiO2(110) interface was detected by TD-2PPE. The difference in 2PPE originated from the presence of the terminal hydroxyl anions (OHt¯) on H2O/o-TiO2(110), as identified by X-ray photoelectron spectroscopy and temperature-programmed desorption. Therefore, the evolution of the electronic structure of H2O/o-TiO2(110) was attributed to the photocatalyzed oxidation of the terminal hydroxyl anions, which most likely formed gaseous •OH radicals, reducing the interface. This work suggested that the oxidation of hydroxyl anions on top of the terminal titanium ions on TiO2, which were excluded previously in solution, need to be considered in the mechanistic studies of the photocatalyzed OER.
The oxygen evolution reaction (OER) is the bottleneck in the overall photocatalytic splitting of water. The active sites (terminal titanium or bridging oxygen) and active species (molecular or dissociative water) of the initial step of the photocatalyzed OER on the prototypical photocatalyst TiO2, remain debatable. Herein, the photocatalytic chemistry of monolayer water on oxygen-pretreated TiO2(110) (o-TiO2(110)) and reduced TiO2(110) (r-TiO2(110)) surfaces initiated by 400 nm light illumination was investigated by time-dependent two-photon photoemission spectroscopy (TD-2PPE). The photoinduced reduction of the H2O/o-TiO2(110) interface rather than the H2O/r-TiO2(110) interface was detected by TD-2PPE. The difference in 2PPE originated from the presence of the terminal hydroxyl anions (OHt¯) on H2O/o-TiO2(110), as identified by X-ray photoelectron spectroscopy and temperature-programmed desorption. Therefore, the evolution of the electronic structure of H2O/o-TiO2(110) was attributed to the photocatalyzed oxidation of the terminal hydroxyl anions, which most likely formed gaseous •OH radicals, reducing the interface. This work suggested that the oxidation of hydroxyl anions on top of the terminal titanium ions on TiO2, which were excluded previously in solution, need to be considered in the mechanistic studies of the photocatalyzed OER.
2025, 36(4): 110608
doi: 10.1016/j.cclet.2024.110608
Abstract:
Maintaining high metal dispersion of supported metal catalysts to achieve superior reactivity under harsh conditions poses one of the main challenges for their practical applications. Constructing and regulating the strong metal-support interactions (SMSI) by diverse methodologies has emerged as one of the promising approaches to fabricating robust supported metal catalysts. In this study, we report an L-ascorbic acid (AA)-inducing strategy to generate SMSI on a titania-supported gold (Au) catalyst after high-temperature treatment in an inert atmosphere (600 ℃, N2). The AA-induced SMSI can efficiently stabilize Au nanoparticles (NPs) and preserve their catalytic performance. The detailed study reveals that the key to realizing this SMSI is the generation of oxygen vacancies within the TiO2 support induced by the adsorbed AA, which drives the formation of the TiOx permeable layer onto the Au NPs. The strategy could be extended to TiO2-supported Au catalysts with different crystal phases and platinum group metals, such as Pt, Pd, and Rh. This work offers a promising novel route to design stable and efficient supported noble metal catalysts by constructing SMSI using simple reducing organic adsorbent.
Maintaining high metal dispersion of supported metal catalysts to achieve superior reactivity under harsh conditions poses one of the main challenges for their practical applications. Constructing and regulating the strong metal-support interactions (SMSI) by diverse methodologies has emerged as one of the promising approaches to fabricating robust supported metal catalysts. In this study, we report an L-ascorbic acid (AA)-inducing strategy to generate SMSI on a titania-supported gold (Au) catalyst after high-temperature treatment in an inert atmosphere (600 ℃, N2). The AA-induced SMSI can efficiently stabilize Au nanoparticles (NPs) and preserve their catalytic performance. The detailed study reveals that the key to realizing this SMSI is the generation of oxygen vacancies within the TiO2 support induced by the adsorbed AA, which drives the formation of the TiOx permeable layer onto the Au NPs. The strategy could be extended to TiO2-supported Au catalysts with different crystal phases and platinum group metals, such as Pt, Pd, and Rh. This work offers a promising novel route to design stable and efficient supported noble metal catalysts by constructing SMSI using simple reducing organic adsorbent.
2025, 36(4): 110611
doi: 10.1016/j.cclet.2024.110611
Abstract:
Manipulating catalyst structures to control product selectivity while maintaining high activity presents a considerable challenge in CO2 hydrogenation. Combining density functional theory calculations and microkinetic analysis, we proposed that graphene-supported isolated Pt atoms (Pt1/graphene) and Pt2 dimers (Pt2/graphene) exhibited distinct selectivity in CO2 hydrogenation. Pt1/graphene facilitated the conversion of CO2 into formic acid, whereas Pt2/graphene favored methanol generation. The variation in product selectivity arose from the synergistic interaction of Pt2 dimers, which facilitated the migration of H atoms between two Pt atoms and promoted the transformation from *COOH intermediates to *C(OH)2 intermediates, altering the reaction pathways compared to isolated Pt atoms. Additionally, an analysis of the catalytic activities of three Pt1/graphene and three Pt2/graphene structures revealed that the turnover frequencies for formic acid generation on Pt1ⅱ/graphene and methanol generation on Pt2ⅰ/graphene were as high as 744.48 h-1 and 789.48 h-1, respectively. These values rivaled or even surpassed those previously reported in the literature under identical conditions. This study provides valuable insights into optimizing catalyst structures to achieve desired products in CO2 hydrogenation
Manipulating catalyst structures to control product selectivity while maintaining high activity presents a considerable challenge in CO2 hydrogenation. Combining density functional theory calculations and microkinetic analysis, we proposed that graphene-supported isolated Pt atoms (Pt1/graphene) and Pt2 dimers (Pt2/graphene) exhibited distinct selectivity in CO2 hydrogenation. Pt1/graphene facilitated the conversion of CO2 into formic acid, whereas Pt2/graphene favored methanol generation. The variation in product selectivity arose from the synergistic interaction of Pt2 dimers, which facilitated the migration of H atoms between two Pt atoms and promoted the transformation from *COOH intermediates to *C(OH)2 intermediates, altering the reaction pathways compared to isolated Pt atoms. Additionally, an analysis of the catalytic activities of three Pt1/graphene and three Pt2/graphene structures revealed that the turnover frequencies for formic acid generation on Pt1ⅱ/graphene and methanol generation on Pt2ⅰ/graphene were as high as 744.48 h-1 and 789.48 h-1, respectively. These values rivaled or even surpassed those previously reported in the literature under identical conditions. This study provides valuable insights into optimizing catalyst structures to achieve desired products in CO2 hydrogenation
2025, 36(4): 110789
doi: 10.1016/j.cclet.2024.110789
Abstract:
Platinum (Pt) nanoparticle catalysts remain the most popular cathode materials for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. Non-metallic alloying of Pt has become an emerging strategy to improve electrocatalytic performance, however, the electrocatalytic ORR mechanisms still need to be understood for further improvement toward practical application. Herein, a rapid microwave reduction method is employed for alloying phosphorous (P) into Pt to form a carbon supported phosphorus-alloyed Pt nanoparticle catalyst (P-Pt/C), which demonstrates the ability to replace commercial Pt/C. By a combination of density functional theory calculations and in-situ electrochemical Raman spectroscopy, the regulation role of P-alloying in the electrocatalytic mechanisms is revealed. It is found that the nearby Pt atoms can convert the ORR pathway from associative one to dissociative one, exhibiting a spontaneous dissociation of *OOH intermediate to *OH and *O species as well as a change of potential determining step to *O protonation. Furthermore, the strategy of large-scale economic synthesis of such alloying Pt-based catalyst is also established, demonstrated by a gram-level synthesis per batch. This study puts insight into the electrocatalytic ORR fundamentals of Pt-alloying with non-metals and provides a basis for the reasonable design and synthesis of efficient nonmetals-alloyed Pt catalysts.
Platinum (Pt) nanoparticle catalysts remain the most popular cathode materials for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. Non-metallic alloying of Pt has become an emerging strategy to improve electrocatalytic performance, however, the electrocatalytic ORR mechanisms still need to be understood for further improvement toward practical application. Herein, a rapid microwave reduction method is employed for alloying phosphorous (P) into Pt to form a carbon supported phosphorus-alloyed Pt nanoparticle catalyst (P-Pt/C), which demonstrates the ability to replace commercial Pt/C. By a combination of density functional theory calculations and in-situ electrochemical Raman spectroscopy, the regulation role of P-alloying in the electrocatalytic mechanisms is revealed. It is found that the nearby Pt atoms can convert the ORR pathway from associative one to dissociative one, exhibiting a spontaneous dissociation of *OOH intermediate to *OH and *O species as well as a change of potential determining step to *O protonation. Furthermore, the strategy of large-scale economic synthesis of such alloying Pt-based catalyst is also established, demonstrated by a gram-level synthesis per batch. This study puts insight into the electrocatalytic ORR fundamentals of Pt-alloying with non-metals and provides a basis for the reasonable design and synthesis of efficient nonmetals-alloyed Pt catalysts.
2025, 36(4): 109851
doi: 10.1016/j.cclet.2024.109851
Abstract:
In recent years, sodium-ion batteries (SIBs) have become one of the hot discussions and have gradually moved toward industrialization. However, there are still some shortcomings in their performance that have not been well addressed, including phase transition, structural degradation, and voltage platform. High entropy materials have recently gained significant attention from researchers due to their effects on thermodynamics, dynamics, structure, and performance. Researchers have attempted to use these materials in sodium-ion batteries to overcome their problems, making it a modification method. This paper aims to discuss the research status of high-entropy cathode materials for sodium-ion batteries and summarize their effects on sodium-ion batteries from three perspectives: Layered oxide, polyanion, and Prussian blue. The influence on material structure, the inhibition of phase transition, and the improvement of ion diffusivity are described. Finally, the advantages and disadvantages of high-entropy cathode materials for sodium-ion batteries are summarized, and their future development has prospected.
In recent years, sodium-ion batteries (SIBs) have become one of the hot discussions and have gradually moved toward industrialization. However, there are still some shortcomings in their performance that have not been well addressed, including phase transition, structural degradation, and voltage platform. High entropy materials have recently gained significant attention from researchers due to their effects on thermodynamics, dynamics, structure, and performance. Researchers have attempted to use these materials in sodium-ion batteries to overcome their problems, making it a modification method. This paper aims to discuss the research status of high-entropy cathode materials for sodium-ion batteries and summarize their effects on sodium-ion batteries from three perspectives: Layered oxide, polyanion, and Prussian blue. The influence on material structure, the inhibition of phase transition, and the improvement of ion diffusivity are described. Finally, the advantages and disadvantages of high-entropy cathode materials for sodium-ion batteries are summarized, and their future development has prospected.
2025, 36(4): 109905
doi: 10.1016/j.cclet.2024.109905
Abstract:
Chitin is an abundant aminopolysaccharide found in insect pests and phytopathogenic microorganisms but absent in higher plants and vertebrates. It is crucial for mitigating threats posed by chitin-containing organisms to human health, food safety, and agriculture. Therefore, targeting the chitin biosynthesis-associated bioprocess holds a promise for developing human-safe and eco-friendly antifungal agents or pesticides. Chitin biosynthesis requires chitin synthase and associated factors, which are involved in the modification, regulation, organization or turnover of chitin during its biosynthesis. A number of enzymes such as chitinases, hexosaminidases, chitin deacetylases are closely related and therefore are promising targets for designing novel agrochemicals that target at chitin biosynthesis. This review summarizes the advances in understanding chitin biology over the past decade by our research group and collaborates, specifically regarding essential proteins linked to chitin biosynthesis that can be exploited as promising pesticide targets. Examples of small bioactive molecules that against the activity of these targets are given.
Chitin is an abundant aminopolysaccharide found in insect pests and phytopathogenic microorganisms but absent in higher plants and vertebrates. It is crucial for mitigating threats posed by chitin-containing organisms to human health, food safety, and agriculture. Therefore, targeting the chitin biosynthesis-associated bioprocess holds a promise for developing human-safe and eco-friendly antifungal agents or pesticides. Chitin biosynthesis requires chitin synthase and associated factors, which are involved in the modification, regulation, organization or turnover of chitin during its biosynthesis. A number of enzymes such as chitinases, hexosaminidases, chitin deacetylases are closely related and therefore are promising targets for designing novel agrochemicals that target at chitin biosynthesis. This review summarizes the advances in understanding chitin biology over the past decade by our research group and collaborates, specifically regarding essential proteins linked to chitin biosynthesis that can be exploited as promising pesticide targets. Examples of small bioactive molecules that against the activity of these targets are given.
2025, 36(4): 109996
doi: 10.1016/j.cclet.2024.109996
Abstract:
Glioma is the most common malignant tumor of the brain. The postoperative recurrence rate was high, and the 2-year survival rate only increased by 20%–25%. The reason is the blood-brain barrier (BBB). BBB is a physical barrier that stabilizes the physiological environment of brain tissue and protects the central nervous system from the invasion of harmful substances. Drug delivery based on nanotechnology and nanocarriers has attracted much attention due to its biological safety, continuous drug release time, increasing solubility, biological drug activity, and enhanced BBB permeability. By modifying different substances on the surface of nanocarriers, the BBB is bypassed by receptor-mediated and cell endocytosis and exocytosis. In addition, the purpose of bypassing BBB-targeted drug delivery can also be achieved by intranasal administration and local administration. This paper reviews different target transport mechanisms, mainly in invasive and non-invasive strategies, the nanocarriers that have made progress and the nanocarrier strategy of bypassing BBB are listed.
Glioma is the most common malignant tumor of the brain. The postoperative recurrence rate was high, and the 2-year survival rate only increased by 20%–25%. The reason is the blood-brain barrier (BBB). BBB is a physical barrier that stabilizes the physiological environment of brain tissue and protects the central nervous system from the invasion of harmful substances. Drug delivery based on nanotechnology and nanocarriers has attracted much attention due to its biological safety, continuous drug release time, increasing solubility, biological drug activity, and enhanced BBB permeability. By modifying different substances on the surface of nanocarriers, the BBB is bypassed by receptor-mediated and cell endocytosis and exocytosis. In addition, the purpose of bypassing BBB-targeted drug delivery can also be achieved by intranasal administration and local administration. This paper reviews different target transport mechanisms, mainly in invasive and non-invasive strategies, the nanocarriers that have made progress and the nanocarrier strategy of bypassing BBB are listed.
2025, 36(4): 110044
doi: 10.1016/j.cclet.2024.110044
Abstract:
Plant bacterial diseases have inflicted substantial economic losses in global crop, fruit, and vegetable production. The conventional methods for managing these diseases typically rely on the application of antibiotics. However, these antibiotics often target the growth factors of the pathogenic bacteria, leading to the accumulation and emergence of drug-resistant strains, which exacerbates antibiotic resistance. Innovative methods are urgently needed to treat and prevent the toxicity caused by these pathogenic bacteria. Targeting virulence mechanisms in pathogens is a globally recognized and effective strategy for mitigating bacterial resistance. Type III secretion system (T3SS) serves as a crucial virulence determinant in Gram-negative pathogens, and its non-essentials for pathogen growth renders it an ideal target. Targeting the T3SS holds significant potential to alleviate selective pressure for resistance mutations in pathogens. Therefore, targeting T3SS in pathogenic bacteria, while preserving their growth, has emerged as a novel avenue for the development of antimicrobial drugs. In recent years, a multitude of small molecular inhibitors targeting T3SS have been identified. This article offers a comprehensive review of T3SS inhibitors in plant pathogens, while also presenting the latest research advancements in this research direction.
Plant bacterial diseases have inflicted substantial economic losses in global crop, fruit, and vegetable production. The conventional methods for managing these diseases typically rely on the application of antibiotics. However, these antibiotics often target the growth factors of the pathogenic bacteria, leading to the accumulation and emergence of drug-resistant strains, which exacerbates antibiotic resistance. Innovative methods are urgently needed to treat and prevent the toxicity caused by these pathogenic bacteria. Targeting virulence mechanisms in pathogens is a globally recognized and effective strategy for mitigating bacterial resistance. Type III secretion system (T3SS) serves as a crucial virulence determinant in Gram-negative pathogens, and its non-essentials for pathogen growth renders it an ideal target. Targeting the T3SS holds significant potential to alleviate selective pressure for resistance mutations in pathogens. Therefore, targeting T3SS in pathogenic bacteria, while preserving their growth, has emerged as a novel avenue for the development of antimicrobial drugs. In recent years, a multitude of small molecular inhibitors targeting T3SS have been identified. This article offers a comprehensive review of T3SS inhibitors in plant pathogens, while also presenting the latest research advancements in this research direction.
A short review on research progress of ZnIn2S4-based S-scheme heterojunction: Improvement strategies
2025, 36(4): 110108
doi: 10.1016/j.cclet.2024.110108
Abstract:
ZnIn2S4, a typical n-type semiconductor, has received intensive attention due to its suitable bandgap, excellent visible light absorption performance, and simple and flexible preparation methods. However, its application is curbed by photo-generated carrier recombination and photo corrosion. Although constructing S-scheme heterojunctions by combining ZnIn2S4 with other semiconductors can solve these problems, the photocatalytic activity of S-scheme heterojunctions can be further improved. Therefore, this short review summarizes modification strategies of ZnIn2S4-based S-scheme heterojunctions. This article also introduces the concept, design principles, and characterization methods of ZnIn2S4-based S-scheme heterojunction. Finally, current challenges and future research focuses related to ZnIn2S4-based S-scheme heterojunctions are discussed and summarized, including the utilization of advanced in-situ characterization techniques to further illuminate the photocatalytic mechanism, the DFT-assisted design of catalysts to increase the selectivity of products during photocatalytic CO2 reduction, and extending the photo-response of ZnIn2S4-based S-scheme heterojunction to near-infrared range, etc.
ZnIn2S4, a typical n-type semiconductor, has received intensive attention due to its suitable bandgap, excellent visible light absorption performance, and simple and flexible preparation methods. However, its application is curbed by photo-generated carrier recombination and photo corrosion. Although constructing S-scheme heterojunctions by combining ZnIn2S4 with other semiconductors can solve these problems, the photocatalytic activity of S-scheme heterojunctions can be further improved. Therefore, this short review summarizes modification strategies of ZnIn2S4-based S-scheme heterojunctions. This article also introduces the concept, design principles, and characterization methods of ZnIn2S4-based S-scheme heterojunction. Finally, current challenges and future research focuses related to ZnIn2S4-based S-scheme heterojunctions are discussed and summarized, including the utilization of advanced in-situ characterization techniques to further illuminate the photocatalytic mechanism, the DFT-assisted design of catalysts to increase the selectivity of products during photocatalytic CO2 reduction, and extending the photo-response of ZnIn2S4-based S-scheme heterojunction to near-infrared range, etc.
2025, 36(4): 110138
doi: 10.1016/j.cclet.2024.110138
Abstract:
The widespread occurrence of antibiotics in wastewater aroused serious attention. UV-based advanced oxidation processes (UV-AOPs) are powerful technologies in removing antibiotics in wastewater, which include UV/catalyst, UV/H2O2, UV/Fenton, UV/persulfate, UV/chlorine, UV/ozone, and UV/peracetic acid. In this review, we collated recent advances in application of UV-AOPs for the abatement of fluoroquinolones (FQs) as widely used class of antibiotics. Representative FQs of ciprofloxacin, norfloxacin, ofloxacin, and enrofloxacin were most extensively studied in the state-of-art studies. The evolvement of gas-state and solid-state UV light sources was presented and batch and continuous flow UV reactors were compared towards practical applications in UV-AOPs. Generally, degradation of FQs followed the pseudo-first order kinetics in UV-AOPs and strongly affected by the operating factors and components of water matrix. Participation of reactive species and transformation mechanisms of FQs were compared among different UV-AOPs. Challenges and future prospects were pointed out for providing insights into the practical application of UV-AOPs for antibiotic remediation in wastewater.
The widespread occurrence of antibiotics in wastewater aroused serious attention. UV-based advanced oxidation processes (UV-AOPs) are powerful technologies in removing antibiotics in wastewater, which include UV/catalyst, UV/H2O2, UV/Fenton, UV/persulfate, UV/chlorine, UV/ozone, and UV/peracetic acid. In this review, we collated recent advances in application of UV-AOPs for the abatement of fluoroquinolones (FQs) as widely used class of antibiotics. Representative FQs of ciprofloxacin, norfloxacin, ofloxacin, and enrofloxacin were most extensively studied in the state-of-art studies. The evolvement of gas-state and solid-state UV light sources was presented and batch and continuous flow UV reactors were compared towards practical applications in UV-AOPs. Generally, degradation of FQs followed the pseudo-first order kinetics in UV-AOPs and strongly affected by the operating factors and components of water matrix. Participation of reactive species and transformation mechanisms of FQs were compared among different UV-AOPs. Challenges and future prospects were pointed out for providing insights into the practical application of UV-AOPs for antibiotic remediation in wastewater.
2025, 36(4): 110217
doi: 10.1016/j.cclet.2024.110217
Abstract:
With the rapid development of electric vehicles, hybrid electric vehicles and smart grids, people's demand for large-scale energy storage devices is increasingly intense. As a new type of secondary battery, potassium ion battery is promising to replace the lithium-ion battery in the field of large-scale energy storage by virtue of its low price and environmental friendliness. At present, the research on the anode materials of potassium ion batteries mainly focuses on carbon materials and the design of various nanostructured metal-based materials. Problems such as poor rate performance and inferior cycle life caused by electrode structure comminution during charge and discharge have not been solved. Quantum dots/nanodots materials are a new type of nanomaterials that can effectively improve the utilization of electrode materials and reduce production costs. In addition, quantum dots/nanodots materials can enhance the electrode reaction kinetics, reduce the stress generated in cycling, and effectively alleviate the agglomeration and crushing of electrode materials. In this review, we will systematically introduce the synthesis methods, K+ storage properties and K+ storage mechanisms of carbon quantum dots and carbon-based transition metal compound quantum dots composites. This review will have significant references for potassium ion battery researchers.
With the rapid development of electric vehicles, hybrid electric vehicles and smart grids, people's demand for large-scale energy storage devices is increasingly intense. As a new type of secondary battery, potassium ion battery is promising to replace the lithium-ion battery in the field of large-scale energy storage by virtue of its low price and environmental friendliness. At present, the research on the anode materials of potassium ion batteries mainly focuses on carbon materials and the design of various nanostructured metal-based materials. Problems such as poor rate performance and inferior cycle life caused by electrode structure comminution during charge and discharge have not been solved. Quantum dots/nanodots materials are a new type of nanomaterials that can effectively improve the utilization of electrode materials and reduce production costs. In addition, quantum dots/nanodots materials can enhance the electrode reaction kinetics, reduce the stress generated in cycling, and effectively alleviate the agglomeration and crushing of electrode materials. In this review, we will systematically introduce the synthesis methods, K+ storage properties and K+ storage mechanisms of carbon quantum dots and carbon-based transition metal compound quantum dots composites. This review will have significant references for potassium ion battery researchers.
2025, 36(4): 110462
doi: 10.1016/j.cclet.2024.110462
Abstract:
Agrochemicals, especially plant growth regulators (PGRs), are extensively used to modulate endogenous phytohormone signals in small quantities, significantly influencing plant growth and development. Plant hormones typically exhibit diverse chemical structures, with common examples including indole rings, terpenoid frameworks, adenine motifs, cyclic lactones, cyclopentanones, and steroidal compounds, which are extensively employed in pesticides. This article explores the interactions and biological activities of small molecules on proteins, enzymes, and other reactive sites involved in the biosynthesis, metabolism, transport, and signal transduction pathways of various plant hormones. Additionally, it analyzes the structure-activity relationships (SARs) of pesticides incorporating these structural motifs to elucidate the relationship between active fragments, pharmacophores, and targets, highlighting the characteristics of potent small molecules and their derivatives. This comprehensive review aims to provide novel perspectives for the development and design of pesticides, offering valuable insights for researchers in the field.
Agrochemicals, especially plant growth regulators (PGRs), are extensively used to modulate endogenous phytohormone signals in small quantities, significantly influencing plant growth and development. Plant hormones typically exhibit diverse chemical structures, with common examples including indole rings, terpenoid frameworks, adenine motifs, cyclic lactones, cyclopentanones, and steroidal compounds, which are extensively employed in pesticides. This article explores the interactions and biological activities of small molecules on proteins, enzymes, and other reactive sites involved in the biosynthesis, metabolism, transport, and signal transduction pathways of various plant hormones. Additionally, it analyzes the structure-activity relationships (SARs) of pesticides incorporating these structural motifs to elucidate the relationship between active fragments, pharmacophores, and targets, highlighting the characteristics of potent small molecules and their derivatives. This comprehensive review aims to provide novel perspectives for the development and design of pesticides, offering valuable insights for researchers in the field.
2025, 36(4): 110466
doi: 10.1016/j.cclet.2024.110466
Abstract:
Carbon materials have long been a subject of study, offering diverse properties based on their hybridized structures. Except sp2-hybridized graphene and carbon nanotubes, the focus on sp1-hybridized carbon chains has garnered significant interest due to its unique predicted properties, despite limitations in research and development stemming from its high reactivity. This comprehensive review summaries recent advancements in synthetic methodologies and characterization of the sp1-hybridized carbon chains, encompassing linear carbon chains and cyclo[n]carbons. The review traces significant milestones in synthesis and offers a thorough overview of various properties on linear and cyclic carbon chains, from their initial discovery to recent development. The advancing synthetic methods have led to practical breakthroughs, transitioning theoretical concepts into tangible carbon-chain materials. However, challenges persist in achieving controlled and scalable preparation due to the high reactivity associated with sp1-hybridization. Future research prospects focus on fundamental studies, such as exploring the transition length from polyyne to carbyne and experimentally determining the properties of single carbon chains. This review underscores both the progress made and the compelling avenues for future exploration in the dynamic field of sp1-hybridized carbon chains.
Carbon materials have long been a subject of study, offering diverse properties based on their hybridized structures. Except sp2-hybridized graphene and carbon nanotubes, the focus on sp1-hybridized carbon chains has garnered significant interest due to its unique predicted properties, despite limitations in research and development stemming from its high reactivity. This comprehensive review summaries recent advancements in synthetic methodologies and characterization of the sp1-hybridized carbon chains, encompassing linear carbon chains and cyclo[n]carbons. The review traces significant milestones in synthesis and offers a thorough overview of various properties on linear and cyclic carbon chains, from their initial discovery to recent development. The advancing synthetic methods have led to practical breakthroughs, transitioning theoretical concepts into tangible carbon-chain materials. However, challenges persist in achieving controlled and scalable preparation due to the high reactivity associated with sp1-hybridization. Future research prospects focus on fundamental studies, such as exploring the transition length from polyyne to carbyne and experimentally determining the properties of single carbon chains. This review underscores both the progress made and the compelling avenues for future exploration in the dynamic field of sp1-hybridized carbon chains.
2025, 36(4): 110566
doi: 10.1016/j.cclet.2024.110566
Abstract:
Using different external stimuli to control interfacial friction, rather than just pursuing low friction, is a highly attractive research regime due to its economic and scientific importance. One option to achieve such a goal is to use external stimuli that modulate the energy dissipation pathways. In particular, electric stimuli such as surface potential has gained remarkable interest for two reasons: Electrotunable friction has the potential for real-time, in situ manipulation of friction, and external electric stimuli is relatively easy to apply and to remove for reversible change. In this review, we explore the emerging research area of electrotunable friction mainly under the boundary lubrication situation, when the contacting surfaces are separated by a molecularly thin layer, reviewing typical achievements from experiments using electrochemical atomic force microscopy and modified surface force balances, as well as molecular dynamics simulations. Additionally, we explore the theoretical and practical challenges that may need to be tackled in the future.
Using different external stimuli to control interfacial friction, rather than just pursuing low friction, is a highly attractive research regime due to its economic and scientific importance. One option to achieve such a goal is to use external stimuli that modulate the energy dissipation pathways. In particular, electric stimuli such as surface potential has gained remarkable interest for two reasons: Electrotunable friction has the potential for real-time, in situ manipulation of friction, and external electric stimuli is relatively easy to apply and to remove for reversible change. In this review, we explore the emerging research area of electrotunable friction mainly under the boundary lubrication situation, when the contacting surfaces are separated by a molecularly thin layer, reviewing typical achievements from experiments using electrochemical atomic force microscopy and modified surface force balances, as well as molecular dynamics simulations. Additionally, we explore the theoretical and practical challenges that may need to be tackled in the future.
2025, 36(4): 110512
doi: 10.1016/j.cclet.2024.110512
Abstract:
Tailoring interatomic active sites for highly selective electrocatalytic biomass conversion reaction
2025, 36(4): 110670
doi: 10.1016/j.cclet.2024.110670
Abstract:
2025, 36(4): 110787
doi: 10.1016/j.cclet.2024.110787
Abstract:
2025, 36(4): 110806
doi: 10.1016/j.cclet.2024.110806
Abstract:
