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2025 Volume 36 Issue 11
2025, 36(11): 110413
doi: 10.1016/j.cclet.2024.110413
Abstract:
Reaction crystallization method is a common cocrystal synthesis approach attributed to the advantage of avoiding individual crystallization of insoluble components, but faces the defects of soluble components precipitated due to organic solvent volatilization and the formation of unwanted solvates. Our group recently proposed a slurry method based on deep eutectic solvents (DESs) for cocrystal synthesis, which is green, safe and can avoid solvate formation. However, some reactions only produce insoluble raw materials rather than cocrystals due to insufficient activity of the soluble cocrystal co-formers in DESs. Herein, combining the dual benefits of the two methods, a novel reaction crystallization method based on DESs was proposed and employed for cocrystal synthesis of nicotinamide, carbamazepine and theophylline, which can prevent individual crystallization, unwanted solvate formation, and soluble component precipitation, providing a promising alternative for green and efficient synthesis of cocrystals.
Reaction crystallization method is a common cocrystal synthesis approach attributed to the advantage of avoiding individual crystallization of insoluble components, but faces the defects of soluble components precipitated due to organic solvent volatilization and the formation of unwanted solvates. Our group recently proposed a slurry method based on deep eutectic solvents (DESs) for cocrystal synthesis, which is green, safe and can avoid solvate formation. However, some reactions only produce insoluble raw materials rather than cocrystals due to insufficient activity of the soluble cocrystal co-formers in DESs. Herein, combining the dual benefits of the two methods, a novel reaction crystallization method based on DESs was proposed and employed for cocrystal synthesis of nicotinamide, carbamazepine and theophylline, which can prevent individual crystallization, unwanted solvate formation, and soluble component precipitation, providing a promising alternative for green and efficient synthesis of cocrystals.
2025, 36(11): 110415
doi: 10.1016/j.cclet.2024.110415
Abstract:
Heterojunction engineering is considered as one of the most effective methods to improve the hydrogen production performance of photocatalysts. In this study, a green, simple and gentle method was used to deposit tiny NiS onto CTF-ES200 under xenon lamp irradiation to form heterostructures. The experimental results show that the hydrogen production rate of the synthesized NiS/CTF-ES200 is as high as 22.98 mmol g-1 h-1, showing a higher photocatalytic hydrogen production rate compared to other NiS-loaded nonmetallic semiconductor materials, which is also much higher than that of pure CTF-ES200. The interface electric field (IEF) in this p-n heterojunction leads to an accumulation of photoelectrons on the conduction band of CTF-ES200, which makes CTF-ES200 to keep a high reductiveness for the hydrogen evolution reaction (HER), and significantly improve the separation efficiency of photoelectrons and holes. Furthermore, XPS and EXAFS data show that an efficient electron transport channel is constructed through the formation of Ni-N bond, which further accelerates the interface carrier transport efficiency. This study provides an effective idea for the preparation of highly efficient heterojunction photocatalysts.
Heterojunction engineering is considered as one of the most effective methods to improve the hydrogen production performance of photocatalysts. In this study, a green, simple and gentle method was used to deposit tiny NiS onto CTF-ES200 under xenon lamp irradiation to form heterostructures. The experimental results show that the hydrogen production rate of the synthesized NiS/CTF-ES200 is as high as 22.98 mmol g-1 h-1, showing a higher photocatalytic hydrogen production rate compared to other NiS-loaded nonmetallic semiconductor materials, which is also much higher than that of pure CTF-ES200. The interface electric field (IEF) in this p-n heterojunction leads to an accumulation of photoelectrons on the conduction band of CTF-ES200, which makes CTF-ES200 to keep a high reductiveness for the hydrogen evolution reaction (HER), and significantly improve the separation efficiency of photoelectrons and holes. Furthermore, XPS and EXAFS data show that an efficient electron transport channel is constructed through the formation of Ni-N bond, which further accelerates the interface carrier transport efficiency. This study provides an effective idea for the preparation of highly efficient heterojunction photocatalysts.
2025, 36(11): 110416
doi: 10.1016/j.cclet.2024.110416
Abstract:
Earth-abundant, layered birnessite is promising cathode for electrochemical capacitors due to the presence of confined nanofluids in interlayers for rapid ion storage. Previous work has demonstrated the capacitive co-intercalation of water and K+ ions into birnessite in aqueous electrolytes, but in-depth quantitative investigations of the interactions between confined water and an external organic electrolyte are still lacking. In this work, we reveal the intercalation pseudocapacitance of hydrated birnessite (Na0.4MnO2·0.53H2O) in sodium-based organic electrolytes via operando electrochemical quartz crystal microbalance (EQCM), and ex situ X-ray diffraction and Raman spectroscopy. The Na+ ions are completely desolvated at the Na0.4MnO2·0.53H2O-organic electrolyte interfaces and intercalate into the interlayers, while the confined water does not co-extract. The net Na+ intercalation is a pseudocapacitive behavior without phase changes, displaying a high capacitive contribution of 85.6% at 1.0 mV/s. Additionally, EQCM results indicate the contributions of cation-dominated electric double layer (EDL) adsorption to the total charge storage. By replacing different solvents and anions in sodium-based organic electrolytes, we verify that Na+ pseudocapacitive intercalation dominates the charge storage properties.
Earth-abundant, layered birnessite is promising cathode for electrochemical capacitors due to the presence of confined nanofluids in interlayers for rapid ion storage. Previous work has demonstrated the capacitive co-intercalation of water and K+ ions into birnessite in aqueous electrolytes, but in-depth quantitative investigations of the interactions between confined water and an external organic electrolyte are still lacking. In this work, we reveal the intercalation pseudocapacitance of hydrated birnessite (Na0.4MnO2·0.53H2O) in sodium-based organic electrolytes via operando electrochemical quartz crystal microbalance (EQCM), and ex situ X-ray diffraction and Raman spectroscopy. The Na+ ions are completely desolvated at the Na0.4MnO2·0.53H2O-organic electrolyte interfaces and intercalate into the interlayers, while the confined water does not co-extract. The net Na+ intercalation is a pseudocapacitive behavior without phase changes, displaying a high capacitive contribution of 85.6% at 1.0 mV/s. Additionally, EQCM results indicate the contributions of cation-dominated electric double layer (EDL) adsorption to the total charge storage. By replacing different solvents and anions in sodium-based organic electrolytes, we verify that Na+ pseudocapacitive intercalation dominates the charge storage properties.
2025, 36(11): 110421
doi: 10.1016/j.cclet.2024.110421
Abstract:
Crystal structure prediction aims to predict stable and easily experimentally synthesized materials, which accelerates the discovery of new materials. It is worth noting that the stability of materials is the basis for ensuring high performance and reliable application of materials. Among which, the thermodynamic and molecular dynamics stability is especially important. Therefore, this paper proposes a method to predict stable crystal structures using formation energy and Lennard-Jones potential as evaluation indicators. Specifically, we use graph neural network models to predict the formation energy of crystals, and employ empirical formulas to calculate the Lennard-Jones potential. Then, we apply Bayesian optimization algorithms to search for crystal structures with low formation energy and Lennard-Jones potential approaching zero, in order to ensure the thermodynamic stability and dynamics stability of materials. In addition, considering the impact of the bonding situation between atoms in the crystal on the structural stability, this article uses contact map to analyze the atomic bonding situation of each crystal to screen out more stable materials. Finally, the experimental results show that the method we proposed can not only reduce the time for crystal structure prediction, but also ensure the stability of crystal materials.
Crystal structure prediction aims to predict stable and easily experimentally synthesized materials, which accelerates the discovery of new materials. It is worth noting that the stability of materials is the basis for ensuring high performance and reliable application of materials. Among which, the thermodynamic and molecular dynamics stability is especially important. Therefore, this paper proposes a method to predict stable crystal structures using formation energy and Lennard-Jones potential as evaluation indicators. Specifically, we use graph neural network models to predict the formation energy of crystals, and employ empirical formulas to calculate the Lennard-Jones potential. Then, we apply Bayesian optimization algorithms to search for crystal structures with low formation energy and Lennard-Jones potential approaching zero, in order to ensure the thermodynamic stability and dynamics stability of materials. In addition, considering the impact of the bonding situation between atoms in the crystal on the structural stability, this article uses contact map to analyze the atomic bonding situation of each crystal to screen out more stable materials. Finally, the experimental results show that the method we proposed can not only reduce the time for crystal structure prediction, but also ensure the stability of crystal materials.
2025, 36(11): 110422
doi: 10.1016/j.cclet.2024.110422
Abstract:
Aqueous zinc ion batteries (ZIBs) feature high theoretical capacity, low cost, and high safety, but they suffer from moderate reversibility arising from electrolyte decomposition, Zn corrosion/passivation, and dendrite growth. To address this issue, an effective strategy is to construct a functional solid electrolyte interface (SEI) in situ. However, this is substantially challenging owing to the severe hydrogen evolution reaction (HER) and a lack of substances that can be decomposed to form SEI in the aqueous electrolytes. Herein, we propose the fabrication of a stable SEI in situ via a synergistic electrochemical reduction-chemical precipitation approach. By chemically capturing the hydroxide ions (OH−) from HER, fatty acid methyl ester ethoxylate (FMEE), as an aqueous electrolyte additive, undergoes ester group hydrolysis following by a combination with Zn2+ to form insoluble fatty acid-zinc, enabling intelligent growth of a SEI on the Zn anode surface. As a result, the enhanced Zn anode exhibits a prolonged cycling life of up to 2700 h at 1 mA/cm2 and 1 mAh/cm2. The Zn-V2O5 full cell with the designed electrolyte demonstrates excellent rate capability and significantly improved cycling stability. This study presents a simple and practical strategy for in-situ formation of SEI in aqueous electrolytes, advancing the development of high-performance aqueous batteries.
Aqueous zinc ion batteries (ZIBs) feature high theoretical capacity, low cost, and high safety, but they suffer from moderate reversibility arising from electrolyte decomposition, Zn corrosion/passivation, and dendrite growth. To address this issue, an effective strategy is to construct a functional solid electrolyte interface (SEI) in situ. However, this is substantially challenging owing to the severe hydrogen evolution reaction (HER) and a lack of substances that can be decomposed to form SEI in the aqueous electrolytes. Herein, we propose the fabrication of a stable SEI in situ via a synergistic electrochemical reduction-chemical precipitation approach. By chemically capturing the hydroxide ions (OH−) from HER, fatty acid methyl ester ethoxylate (FMEE), as an aqueous electrolyte additive, undergoes ester group hydrolysis following by a combination with Zn2+ to form insoluble fatty acid-zinc, enabling intelligent growth of a SEI on the Zn anode surface. As a result, the enhanced Zn anode exhibits a prolonged cycling life of up to 2700 h at 1 mA/cm2 and 1 mAh/cm2. The Zn-V2O5 full cell with the designed electrolyte demonstrates excellent rate capability and significantly improved cycling stability. This study presents a simple and practical strategy for in-situ formation of SEI in aqueous electrolytes, advancing the development of high-performance aqueous batteries.
2025, 36(11): 110471
doi: 10.1016/j.cclet.2024.110471
Abstract:
Poly(vinylidene fluoride) (PVDF) based piezoelectric materials have received tremendous scientific attention for many decades. However, the high output power density remains a significant challenge and an area of intense interest. Herein, we present a piezoelectric sensor with high output power density by incorporating liquid metal (LM) microdroplets into PVDF piezoelectric substrate. Remarkably, the LM/PVDF composite showed the β-phase content above 90% and the output power density is enhanced to 353 µW/cm2, nearly 1000 times higher than that of pure PVDF materials and significantly surpassing other PVDF-based composite materials. These exceptional performances are attributed to two key factors: The formation of a liquid-solid/electric-dielectric interface between the LM and PVDF, and the incorporation of the LM's outstanding charge transfer capability. This work might present an effective strategy for advancing the utilization of PVDF-based piezoelectric materials in compelling applications within the realm of intelligent wearable electronics.
Poly(vinylidene fluoride) (PVDF) based piezoelectric materials have received tremendous scientific attention for many decades. However, the high output power density remains a significant challenge and an area of intense interest. Herein, we present a piezoelectric sensor with high output power density by incorporating liquid metal (LM) microdroplets into PVDF piezoelectric substrate. Remarkably, the LM/PVDF composite showed the β-phase content above 90% and the output power density is enhanced to 353 µW/cm2, nearly 1000 times higher than that of pure PVDF materials and significantly surpassing other PVDF-based composite materials. These exceptional performances are attributed to two key factors: The formation of a liquid-solid/electric-dielectric interface between the LM and PVDF, and the incorporation of the LM's outstanding charge transfer capability. This work might present an effective strategy for advancing the utilization of PVDF-based piezoelectric materials in compelling applications within the realm of intelligent wearable electronics.
2025, 36(11): 110472
doi: 10.1016/j.cclet.2024.110472
Abstract:
The facet effect of metal-organic frameworks (MOF) on regulating the property of loaded co-catalysts is an important but unexplored issue in the field of photocatalysis. In this work, a series of MIL-125-NH2 polyhedrons (MIL = Materials Institute Lavoisier) with facet exposure of {001}, {001}/{111} and {111} are synthesized and used to load Pd-based co-catalysts for photocatalytic oxygen reduction reaction (ORR) toward H2O2 production. The different facets with distinct chemical environments (Ti-O clusters on {111} facets and carboxyl ligands on {001} facets) result in the selective loading of Pd0 and PdO dominated cocatalysts on {001} and {111} facets, respectively. The {001}/{111} co-exposed MIL-125-NH2 thus enables the spatially separated loading of Pd0 and PdO dual cocatalysts respectively. Pd0 efficiently traps the photoexcited electrons and PdO trends to capture the holes, collaboratively promoting the directional separation of photogenerated electron-hole pairs. As a result, the photocatalytic ORR activity is significantly enhanced with a H2O2 production rate of 128.6 mmol L-1 g-1 h-1, superior than pristine and single cocatalyst modified MIL-125-NH2 samples. Our findings provide new insight into the design of high-performance photocatalysts.
The facet effect of metal-organic frameworks (MOF) on regulating the property of loaded co-catalysts is an important but unexplored issue in the field of photocatalysis. In this work, a series of MIL-125-NH2 polyhedrons (MIL = Materials Institute Lavoisier) with facet exposure of {001}, {001}/{111} and {111} are synthesized and used to load Pd-based co-catalysts for photocatalytic oxygen reduction reaction (ORR) toward H2O2 production. The different facets with distinct chemical environments (Ti-O clusters on {111} facets and carboxyl ligands on {001} facets) result in the selective loading of Pd0 and PdO dominated cocatalysts on {001} and {111} facets, respectively. The {001}/{111} co-exposed MIL-125-NH2 thus enables the spatially separated loading of Pd0 and PdO dual cocatalysts respectively. Pd0 efficiently traps the photoexcited electrons and PdO trends to capture the holes, collaboratively promoting the directional separation of photogenerated electron-hole pairs. As a result, the photocatalytic ORR activity is significantly enhanced with a H2O2 production rate of 128.6 mmol L-1 g-1 h-1, superior than pristine and single cocatalyst modified MIL-125-NH2 samples. Our findings provide new insight into the design of high-performance photocatalysts.
2025, 36(11): 110473
doi: 10.1016/j.cclet.2024.110473
Abstract:
The efficient production of acetate through electrochemical CO2 reduction reaction (eCO2RR) with low energy consumption has consistently been a challenging yet extremely significant task. Current catalysts suffered from high energy consumption and low relative purity of acetate product. Herein, we report ultrasmall Cu2O nanoparticles with an average size of 2.5 ± 0.09 nm immobilized on a conductive copper-based metal–organic framework (Cu–THQ) (denoted as Cu2O@Cu–THQ), which attained a Faradaic efficiency of 65(3)% for acetate at a very low potential of –0.3 V vs. RHE with a current density of 10.5 mA/cm2. Importantly, as there are no other liquid phase products such as formate, methanol or ethanol, the relative purity of the obtained acetate product was as high as 100%. Taking into account the relative purity of the liquid product, current density, and energy consumption, the performance for electroreduction of CO2 to acetate of Cu2O@Cu–THQ is not only much higher than that of the commercial Cu2O nanoparticles, but also higher than those of all reported catalysts. Operando infrared spectroscopy and theoretical calculations indicated that the synergy effect between Cu–THQ and Cu2O promoted the eCO2RR to yield acetate. Specifically, the hydroxyl group on the organic ligand THQ in the Cu–THQ formed hydrogen bond interactions with the key C2 intermediates (*CH2COOH and *HOCCOH) adsorbed on Cu2O, which played a crucial role in stabilizing the key C2 intermediates and thus reduced the formation energy of the key C2 intermediates.
The efficient production of acetate through electrochemical CO2 reduction reaction (eCO2RR) with low energy consumption has consistently been a challenging yet extremely significant task. Current catalysts suffered from high energy consumption and low relative purity of acetate product. Herein, we report ultrasmall Cu2O nanoparticles with an average size of 2.5 ± 0.09 nm immobilized on a conductive copper-based metal–organic framework (Cu–THQ) (denoted as Cu2O@Cu–THQ), which attained a Faradaic efficiency of 65(3)% for acetate at a very low potential of –0.3 V vs. RHE with a current density of 10.5 mA/cm2. Importantly, as there are no other liquid phase products such as formate, methanol or ethanol, the relative purity of the obtained acetate product was as high as 100%. Taking into account the relative purity of the liquid product, current density, and energy consumption, the performance for electroreduction of CO2 to acetate of Cu2O@Cu–THQ is not only much higher than that of the commercial Cu2O nanoparticles, but also higher than those of all reported catalysts. Operando infrared spectroscopy and theoretical calculations indicated that the synergy effect between Cu–THQ and Cu2O promoted the eCO2RR to yield acetate. Specifically, the hydroxyl group on the organic ligand THQ in the Cu–THQ formed hydrogen bond interactions with the key C2 intermediates (*CH2COOH and *HOCCOH) adsorbed on Cu2O, which played a crucial role in stabilizing the key C2 intermediates and thus reduced the formation energy of the key C2 intermediates.
2025, 36(11): 110513
doi: 10.1016/j.cclet.2024.110513
Abstract:
Birefringence and second harmonic generation (SHG) are important optical properties of functional crystals. However, it is relatively rare for a compound to exhibit both enhanced properties simultaneously. In this study, we used DFT calculations to discover an ideal functional gene: protonated 3, 5-dipicolinic acid (C7H4NO4, HDPA). By combining HPDA with the traditional IO3- anion, we obtained a non-centrosymmetric and polar semiorganic iodate, namely HDPA(IO3). The organic cations and iodate anions in HDPA(IO3) are bridged via the N-H···O and O-H···O hydrogen bonds, forming the wave-shaped layers. The synergistic effect between the expanded π-conjugation of the organic cation and the stereochemically active lone pair electrons in the inorganic iodate anion results that HDPA(IO3) exhibiting a strong SHG effect, 3.6 times that of KH2PO4, and an unusually large birefringence of 0.35 at 546 nm, larger than most of SHG-active iodates. Additionally, HDPA(IO3) has a wide bandgap of 4.12 eV with a corresponding cutoff edge at 269 nm, indicating its potential as a promising short-wave ultraviolet (UV) optical crystal.
Birefringence and second harmonic generation (SHG) are important optical properties of functional crystals. However, it is relatively rare for a compound to exhibit both enhanced properties simultaneously. In this study, we used DFT calculations to discover an ideal functional gene: protonated 3, 5-dipicolinic acid (C7H4NO4, HDPA). By combining HPDA with the traditional IO3- anion, we obtained a non-centrosymmetric and polar semiorganic iodate, namely HDPA(IO3). The organic cations and iodate anions in HDPA(IO3) are bridged via the N-H···O and O-H···O hydrogen bonds, forming the wave-shaped layers. The synergistic effect between the expanded π-conjugation of the organic cation and the stereochemically active lone pair electrons in the inorganic iodate anion results that HDPA(IO3) exhibiting a strong SHG effect, 3.6 times that of KH2PO4, and an unusually large birefringence of 0.35 at 546 nm, larger than most of SHG-active iodates. Additionally, HDPA(IO3) has a wide bandgap of 4.12 eV with a corresponding cutoff edge at 269 nm, indicating its potential as a promising short-wave ultraviolet (UV) optical crystal.
2025, 36(11): 110552
doi: 10.1016/j.cclet.2024.110552
Abstract:
Exploring the synthesis of novel structures is crucial for the development of functional materials. In this context, a novel and intriguing 3d-5p heterometallic cluster-substituted polyoxotungstate material, H29Na9(H2O)21{Ca(H2O)2@Sb12O18[Ni2(OH)(A-α-SiW10O37)]3}2·40H2O (1), was constructed using Keggin-type polyoxotungstate A-α-SiW10O37, along with Ni and Sb elements. The structure features a Td-symmetric Sb12O18 ({Sb12}) cage that encapsulates an 8-coordinate Ca2+ ion at its face. Additionally, the {Sb12} cage forms an 18-nuclear 3d-5p heterometallic cluster by connecting with three di-nuclear nickel clusters through shared oxygen atoms. Electrochemical impedance spectra studies reveal that the single crystal of 1 achieves a proton conductivity of 1.11×10−1 S/cm along the [110] direction and 1.04×10−1 S/cm along the [100] direction at 85 ℃ and 98% relative humidity (RH). Furthermore, the powder form of 1 exhibits a proton conductivity of 3.00×10−2 S/cm. These findings suggest that compound 1 holds promise as a practical proton conducting material.
Exploring the synthesis of novel structures is crucial for the development of functional materials. In this context, a novel and intriguing 3d-5p heterometallic cluster-substituted polyoxotungstate material, H29Na9(H2O)21{Ca(H2O)2@Sb12O18[Ni2(OH)(A-α-SiW10O37)]3}2·40H2O (1), was constructed using Keggin-type polyoxotungstate A-α-SiW10O37, along with Ni and Sb elements. The structure features a Td-symmetric Sb12O18 ({Sb12}) cage that encapsulates an 8-coordinate Ca2+ ion at its face. Additionally, the {Sb12} cage forms an 18-nuclear 3d-5p heterometallic cluster by connecting with three di-nuclear nickel clusters through shared oxygen atoms. Electrochemical impedance spectra studies reveal that the single crystal of 1 achieves a proton conductivity of 1.11×10−1 S/cm along the [110] direction and 1.04×10−1 S/cm along the [100] direction at 85 ℃ and 98% relative humidity (RH). Furthermore, the powder form of 1 exhibits a proton conductivity of 3.00×10−2 S/cm. These findings suggest that compound 1 holds promise as a practical proton conducting material.
2025, 36(11): 110589
doi: 10.1016/j.cclet.2024.110589
Abstract:
The Li4Ti5O12 (LTO) is demonstrated to be one of the most promising anode materials for lithium-ion batteries (LIBs) to provide safe and high-power density cells but suffer from poor electrical conductivity. In this study, we present a TiN-decorated N-LTO on a vertical graphene (VG) array (TiN@N-LTO) as a potential anode material for lithium-ion batteries (LIBs). The use of atomic layer deposition (ALD) enables the formation of a thin layer of LTO on VG, with precise control over the thickness. The VG serves as highly conductive channels, facilitating the transfer of electrons. Moreover, the introduction of nitrogen heteroatoms into the LTO under an active N2 plasma atmosphere has been shown to enhance its intrinsic conductivity, which is achieved by reducing the bandgap and expanding the diffusion pathways of ions. Concurrently, a small number of metallic TiN are formed and deposited on the surface of N-LTO, thereby further improving its conductivity. COMSOL simulations and DFT calculations demonstrate that the introduced TiN acts as a "conductive bridge", improving the charge distribution of LTO electrodes and enhancing the Li+ transport rate. The TiN@N-LTO exhibits a high rate performance (169.51, 131.61 and 101.08 mAh/g at 0.2, 2 and 20 C, respectively) and remarkable cycling stability (a capacity retention of 99.6% after 5000 cycles at 10 C).
The Li4Ti5O12 (LTO) is demonstrated to be one of the most promising anode materials for lithium-ion batteries (LIBs) to provide safe and high-power density cells but suffer from poor electrical conductivity. In this study, we present a TiN-decorated N-LTO on a vertical graphene (VG) array (TiN@N-LTO) as a potential anode material for lithium-ion batteries (LIBs). The use of atomic layer deposition (ALD) enables the formation of a thin layer of LTO on VG, with precise control over the thickness. The VG serves as highly conductive channels, facilitating the transfer of electrons. Moreover, the introduction of nitrogen heteroatoms into the LTO under an active N2 plasma atmosphere has been shown to enhance its intrinsic conductivity, which is achieved by reducing the bandgap and expanding the diffusion pathways of ions. Concurrently, a small number of metallic TiN are formed and deposited on the surface of N-LTO, thereby further improving its conductivity. COMSOL simulations and DFT calculations demonstrate that the introduced TiN acts as a "conductive bridge", improving the charge distribution of LTO electrodes and enhancing the Li+ transport rate. The TiN@N-LTO exhibits a high rate performance (169.51, 131.61 and 101.08 mAh/g at 0.2, 2 and 20 C, respectively) and remarkable cycling stability (a capacity retention of 99.6% after 5000 cycles at 10 C).
2025, 36(11): 110753
doi: 10.1016/j.cclet.2024.110753
Abstract:
The escalating demand for advanced energy storage solutions has positioned lithium metal anodes at the forefront of battery technology research. However, the practical implementation of lithium metal anodes is impeded by challenges such as dendrite formation and the inherent instability of the native oxide layer. This study introduces a novel liquid-source plasma technique to create a high-quality solid electrolyte interphase (SEI) composed of LiBr and LiBO2. According to first-principal calculation, LiBO2 optimizes the electrochemical dynamics and LiBr improves Li diffusion at the interfaces, thus protecting the Li metal from severe Li dendrite growth. This well-designed artificial SEI endows the Li metal with remarkable cycling stability over 550 cycles at a current density of 1 mA/cm2, significantly superior to the bare Li anode. Meanwhile, the full cell paired with a high-voltage LiNi0.8Co0.1Mn0.1O2 cathode delivers long-term stability with capacity retention (78% after 200 cycles) at 1 C and excellent rate performance. The findings highlight the importance of interface engineering in optimizing battery performance and longevity.
The escalating demand for advanced energy storage solutions has positioned lithium metal anodes at the forefront of battery technology research. However, the practical implementation of lithium metal anodes is impeded by challenges such as dendrite formation and the inherent instability of the native oxide layer. This study introduces a novel liquid-source plasma technique to create a high-quality solid electrolyte interphase (SEI) composed of LiBr and LiBO2. According to first-principal calculation, LiBO2 optimizes the electrochemical dynamics and LiBr improves Li diffusion at the interfaces, thus protecting the Li metal from severe Li dendrite growth. This well-designed artificial SEI endows the Li metal with remarkable cycling stability over 550 cycles at a current density of 1 mA/cm2, significantly superior to the bare Li anode. Meanwhile, the full cell paired with a high-voltage LiNi0.8Co0.1Mn0.1O2 cathode delivers long-term stability with capacity retention (78% after 200 cycles) at 1 C and excellent rate performance. The findings highlight the importance of interface engineering in optimizing battery performance and longevity.
2025, 36(11): 110805
doi: 10.1016/j.cclet.2024.110805
Abstract:
Steroidal saponins are major bioactive compounds of the medicinal plant Paris polyphylla var. yunnanensis. In this work, two O-rhamnosyltransferases PpRhaGT1 and PpRhaGT2 with strict substrate specificity were characterized from this plant. These enzymes could catalyze the synthesis of paris saponins Ⅱ and Ⅶ, and realized semi-biosynthesis of a series of paris steroidal saponins in tobacco leaves. Molecular dynamics simulation revealed the substrate specificity of PpRhaGT1 was due to interactions between the 2′-O-rhamnosyl group and surrounding amino acids particularly S382 and E383.
Steroidal saponins are major bioactive compounds of the medicinal plant Paris polyphylla var. yunnanensis. In this work, two O-rhamnosyltransferases PpRhaGT1 and PpRhaGT2 with strict substrate specificity were characterized from this plant. These enzymes could catalyze the synthesis of paris saponins Ⅱ and Ⅶ, and realized semi-biosynthesis of a series of paris steroidal saponins in tobacco leaves. Molecular dynamics simulation revealed the substrate specificity of PpRhaGT1 was due to interactions between the 2′-O-rhamnosyl group and surrounding amino acids particularly S382 and E383.
2025, 36(11): 110812
doi: 10.1016/j.cclet.2024.110812
Abstract:
Human cytochrome P450 1B1 (hCYP1B1), an extrahepatic heme-dependent monooxygenase, has been validated as a key target for overcoming chemotherapy resistance and tumorigenesis. Herein, to discover novel efficacious hCYP1B1 inhibitors, a suite of 1,8-naphthalimide derivatives was designed, synthesized, and biologically evaluated, via integrating structure-based drug design (SBDD) and biochemical assays. After two rounds of structural modifications and structure-activity relationship (SAR) studies, the results suggested that introducing a benzene ring at the north part and a halogen atom at the C-4 site significantly enhanced the anti-hCYP1B1 effects of naphthalimides. Among all tested 1,8-naphthalimides, NB-10 showed the most potent anti-hCYP1B1 effect (half maximal inhibitory concentration (IC50) = 0.41 nmol/L) and excellent specificity, while this agent did not activate AhR transcription activity in living cells. Further cellular assays and in vivo tests in paclitaxel (PTX)-resistance xenograft mice showed that NB-10 could significantly potentiate the anti-cancer effects of PTX both in vitro and in vivo, while this agent also showed high safety profiles in mice. Mechanistically, NB-10 potently inhibited hCYP1B1-catalyzed 7-ethoxyresorufin O-deethylation in a competitive manner, with an estimated Ki value of 0.15 nmol/L. Docking simulations showed that NB-10 could be well-fitted in the catalytic pocket of hCYP1B1 to form a stable conformation with a high binding affinity. Collectively, several potent 4-halogenated naphthalimides were developed as novel hCYP1B1 inhibitors, while NB-10 showed high safety profiles and impressive efficacy for overcoming hCYP1B1-associated PTX resistance both in vitro and in vivo.
Human cytochrome P450 1B1 (hCYP1B1), an extrahepatic heme-dependent monooxygenase, has been validated as a key target for overcoming chemotherapy resistance and tumorigenesis. Herein, to discover novel efficacious hCYP1B1 inhibitors, a suite of 1,8-naphthalimide derivatives was designed, synthesized, and biologically evaluated, via integrating structure-based drug design (SBDD) and biochemical assays. After two rounds of structural modifications and structure-activity relationship (SAR) studies, the results suggested that introducing a benzene ring at the north part and a halogen atom at the C-4 site significantly enhanced the anti-hCYP1B1 effects of naphthalimides. Among all tested 1,8-naphthalimides, NB-10 showed the most potent anti-hCYP1B1 effect (half maximal inhibitory concentration (IC50) = 0.41 nmol/L) and excellent specificity, while this agent did not activate AhR transcription activity in living cells. Further cellular assays and in vivo tests in paclitaxel (PTX)-resistance xenograft mice showed that NB-10 could significantly potentiate the anti-cancer effects of PTX both in vitro and in vivo, while this agent also showed high safety profiles in mice. Mechanistically, NB-10 potently inhibited hCYP1B1-catalyzed 7-ethoxyresorufin O-deethylation in a competitive manner, with an estimated Ki value of 0.15 nmol/L. Docking simulations showed that NB-10 could be well-fitted in the catalytic pocket of hCYP1B1 to form a stable conformation with a high binding affinity. Collectively, several potent 4-halogenated naphthalimides were developed as novel hCYP1B1 inhibitors, while NB-10 showed high safety profiles and impressive efficacy for overcoming hCYP1B1-associated PTX resistance both in vitro and in vivo.
2025, 36(11): 110814
doi: 10.1016/j.cclet.2025.110814
Abstract:
Herein, a recrystallization approach was used to produce anhydrous sodium sulfate (ASS) microparticles, which are highly efficient and reusable for separating surfactant-stabilized water from water-in-oil emulsions. The ASS microparticles exhibit distinct morphologies and crystal structures. Remarkably, 0.1 g of ASS170 enables the separation of 10 mL of emulsion (water content: 0.1 g) with a high separation efficiency of 98.63%. A stepwise separation mechanism, including demulsification and water immobilization in the crystal lattice of ASS, is proposed. The superhydrophilicity of ASS particles enables tiny water droplets to aggregate and merge into larger droplets on their surfaces. This process facilitates the phase transition from ASS to sodium sulfate decahydrate (SSD), during which water molecules are immobilized in the expanded crystal lattice of ASS. SSD particles can be collected to regenerate ASS, retaining the high performance of the original ASS. This unique renewable feature reduces the cost of utilizing ASS and simultaneously prevents secondary pollution. Further economic evaluation reveals that it only costs 66.51 USD/m3 to purify emulsion with a water content of 10 g/L, significantly lower than previously reported materials. Coupled with a facile and environmentally friendly preparation strategy, this method shows great application potential for water-in-oil emulsion separation and oil purification.
Herein, a recrystallization approach was used to produce anhydrous sodium sulfate (ASS) microparticles, which are highly efficient and reusable for separating surfactant-stabilized water from water-in-oil emulsions. The ASS microparticles exhibit distinct morphologies and crystal structures. Remarkably, 0.1 g of ASS170 enables the separation of 10 mL of emulsion (water content: 0.1 g) with a high separation efficiency of 98.63%. A stepwise separation mechanism, including demulsification and water immobilization in the crystal lattice of ASS, is proposed. The superhydrophilicity of ASS particles enables tiny water droplets to aggregate and merge into larger droplets on their surfaces. This process facilitates the phase transition from ASS to sodium sulfate decahydrate (SSD), during which water molecules are immobilized in the expanded crystal lattice of ASS. SSD particles can be collected to regenerate ASS, retaining the high performance of the original ASS. This unique renewable feature reduces the cost of utilizing ASS and simultaneously prevents secondary pollution. Further economic evaluation reveals that it only costs 66.51 USD/m3 to purify emulsion with a water content of 10 g/L, significantly lower than previously reported materials. Coupled with a facile and environmentally friendly preparation strategy, this method shows great application potential for water-in-oil emulsion separation and oil purification.
2025, 36(11): 110815
doi: 10.1016/j.cclet.2025.110815
Abstract:
As a semiconductor material with inorganic functional properties, titanium dioxide (TiO2) demonstrates exceptional optical, electrical, and catalytic characteristics. The catalytic performance of TiO2 is notably affected by the proportion of anatase to rutile within its mixed phase, which plays a crucial role in modulating its performance. The phase transition in TiO2 enhances the effective separation of photogenerated charge carriers, thereby improving their utilization. In this study, we present an efficient and proportionally adjustable TiO2 phase transition strategy induced by near-infrared light (NIR light) utilizing TiO2 and titanium carbide (TiC) composites. Notably, the transition ratio of anatase to rutile phases can be adjusted by controlling the NIR light irradiation time in 1s intervals (within 6 s), resulting in conversion rates of 5.88%, 13.29%, 20.42%, 26.02%, 32.8% and 40.12%, respectively. This capability for tunable ratios is attributed to the photothermal effect of TiC, which converts to anatase at higher temperatures while simultaneously promoting the layer-by-layer aggregation of adjacent anatase grains, thereby facilitating the phase transition. In addition, we assessed the photocatalytic efficiency of tetracycline hydrochloride (TC–HCl, an antibiotic) and methylene blue (MB, a dye) when exposed to visible light using different ratios of obtained phase junctions. The findings revealed that after a brief 3 s exposure to laser sintering, the weight fractions of rutile and anatase TiO2 were approximately 0.2 and 0.8, respectively. This specific ratio of phase transition exhibits superior photocatalytic performance compared to alternative phase transition ratios. The creation of heterojunctions in anatase/rutile TiO2 facilitated greater oxygen adsorption and heightened the density of localized states, thus effectively boosting the production of superoxide radicals (•O2-) and hole (h+) species. The phase junction of TiO2 shows significant potential for application in wastewater treating, resulting in improved photocatalytic degradation of pollutants and highlighting its efficacy in environmental pollution control.
As a semiconductor material with inorganic functional properties, titanium dioxide (TiO2) demonstrates exceptional optical, electrical, and catalytic characteristics. The catalytic performance of TiO2 is notably affected by the proportion of anatase to rutile within its mixed phase, which plays a crucial role in modulating its performance. The phase transition in TiO2 enhances the effective separation of photogenerated charge carriers, thereby improving their utilization. In this study, we present an efficient and proportionally adjustable TiO2 phase transition strategy induced by near-infrared light (NIR light) utilizing TiO2 and titanium carbide (TiC) composites. Notably, the transition ratio of anatase to rutile phases can be adjusted by controlling the NIR light irradiation time in 1s intervals (within 6 s), resulting in conversion rates of 5.88%, 13.29%, 20.42%, 26.02%, 32.8% and 40.12%, respectively. This capability for tunable ratios is attributed to the photothermal effect of TiC, which converts to anatase at higher temperatures while simultaneously promoting the layer-by-layer aggregation of adjacent anatase grains, thereby facilitating the phase transition. In addition, we assessed the photocatalytic efficiency of tetracycline hydrochloride (TC–HCl, an antibiotic) and methylene blue (MB, a dye) when exposed to visible light using different ratios of obtained phase junctions. The findings revealed that after a brief 3 s exposure to laser sintering, the weight fractions of rutile and anatase TiO2 were approximately 0.2 and 0.8, respectively. This specific ratio of phase transition exhibits superior photocatalytic performance compared to alternative phase transition ratios. The creation of heterojunctions in anatase/rutile TiO2 facilitated greater oxygen adsorption and heightened the density of localized states, thus effectively boosting the production of superoxide radicals (•O2-) and hole (h+) species. The phase junction of TiO2 shows significant potential for application in wastewater treating, resulting in improved photocatalytic degradation of pollutants and highlighting its efficacy in environmental pollution control.
2025, 36(11): 110819
doi: 10.1016/j.cclet.2025.110819
Abstract:
Alcohols are often used as scavengers to identify the contribution of radicals for contaminant degradation in heterogeneous catalysis. The generation of alcohol radicals is often overlooked, leading to misinterpretation of degradation mechanisms and alcohol's role. Herein, a series of bismuth oxybromide (BiOBr) with varying amounts of active species was synthesized as representative catalysts to elucidate the role of alcohols in heterogeneous catalysis. Among various alcohols, isopropanol (IPA) was found to significantly enhance the photocatalytic degradation of carbamazepine (CBZ) by BiOBr. Electron paramagnetic resonance results confirmed that IPA was oxidized to alcohol radicals by BiOBr. The promotional effect of IPA was due to the generation of H2O2 through the reaction between alcohol radicals and dissolved oxygen. H2O2 subsequently led to the production of superoxide anion, the dominant radical in CBZ degradation. The promotional effect was also observed with other alcohols. The bond dissociation energy of the C–H bond adjacent to the hydroxyl group in alcohols determined the extent of promotion, while other characteristics such as the number of hydroxyl groups did not. Higher bond dissociation energy corresponded to a greater promotional effect. This study clarifies the inconsistent observations resulting from the use of various alcohols in heterogeneous catalysis and provides new insights into the overlooked role of alcohols.
Alcohols are often used as scavengers to identify the contribution of radicals for contaminant degradation in heterogeneous catalysis. The generation of alcohol radicals is often overlooked, leading to misinterpretation of degradation mechanisms and alcohol's role. Herein, a series of bismuth oxybromide (BiOBr) with varying amounts of active species was synthesized as representative catalysts to elucidate the role of alcohols in heterogeneous catalysis. Among various alcohols, isopropanol (IPA) was found to significantly enhance the photocatalytic degradation of carbamazepine (CBZ) by BiOBr. Electron paramagnetic resonance results confirmed that IPA was oxidized to alcohol radicals by BiOBr. The promotional effect of IPA was due to the generation of H2O2 through the reaction between alcohol radicals and dissolved oxygen. H2O2 subsequently led to the production of superoxide anion, the dominant radical in CBZ degradation. The promotional effect was also observed with other alcohols. The bond dissociation energy of the C–H bond adjacent to the hydroxyl group in alcohols determined the extent of promotion, while other characteristics such as the number of hydroxyl groups did not. Higher bond dissociation energy corresponded to a greater promotional effect. This study clarifies the inconsistent observations resulting from the use of various alcohols in heterogeneous catalysis and provides new insights into the overlooked role of alcohols.
2025, 36(11): 110833
doi: 10.1016/j.cclet.2025.110833
Abstract:
mRNA is a highly promising approach for disease prevention, yet its further application is currently limited by the low efficiency of delivery. Lipid nanoparticles (LNPs) are the mainstream delivery vehicles at present, and ionizable lipids, as a key component, have a particularly significant impact on delivery efficiency. To improve the efficiency of delivery, a library of ionizable lipids with tetra-branched hydrophobic tails was designed and synthesized by the Michael addition reaction. From this library, the lipid 10A was selected for the highest delivery efficiency. Further formulation screening yielded LNPs with excellent performance, which showed good efficacy in tumor prevention experiments. At the same time, the structure-activity relationship between the ionizable lipid structure and the delivery efficiency was elucidated. It was that the tetra-branched hydrophobic tails, as compared with the di-branched hydrophobic tails enhanced the stability of LNPs, provided uniformity of particle size and improved the efficiency of endocytosis and lysosomal escape, resulting in higher delivery efficiency. Meanwhile, tetra-branched lipids with hydroxyl groups in the head group performed even better. This research provides a theoretical basis and foundation for guiding the development of the next generation of ionizable lipids, and the developed 10A LNP also shows broad prospects for clinical translation.
mRNA is a highly promising approach for disease prevention, yet its further application is currently limited by the low efficiency of delivery. Lipid nanoparticles (LNPs) are the mainstream delivery vehicles at present, and ionizable lipids, as a key component, have a particularly significant impact on delivery efficiency. To improve the efficiency of delivery, a library of ionizable lipids with tetra-branched hydrophobic tails was designed and synthesized by the Michael addition reaction. From this library, the lipid 10A was selected for the highest delivery efficiency. Further formulation screening yielded LNPs with excellent performance, which showed good efficacy in tumor prevention experiments. At the same time, the structure-activity relationship between the ionizable lipid structure and the delivery efficiency was elucidated. It was that the tetra-branched hydrophobic tails, as compared with the di-branched hydrophobic tails enhanced the stability of LNPs, provided uniformity of particle size and improved the efficiency of endocytosis and lysosomal escape, resulting in higher delivery efficiency. Meanwhile, tetra-branched lipids with hydroxyl groups in the head group performed even better. This research provides a theoretical basis and foundation for guiding the development of the next generation of ionizable lipids, and the developed 10A LNP also shows broad prospects for clinical translation.
2025, 36(11): 110834
doi: 10.1016/j.cclet.2025.110834
Abstract:
Near-infrared (NIR) theranostics have received considerable attention because of their advantages in precise diagnostic imaging and efficient simultaneous treatment and have achieved tremendous advancements in the last few years. However, their progress is severely restricted by the rarity of efficient second NIR (NIR-Ⅱ) responsive phototheranostic materials, especially in the NIR-Ⅱb region. Moreover, these materials often embarrass the quenching puzzle in the aggregative state, thus greatly reducing their theranostic performance. To overcome this limitation, we developed anti-quenching donor-acceptor-donor (D-A-D)-conjugated oligomers with NIR-Ⅱb emission for high-performance NIR-Ⅱ angiography and phototheranostics. Through multi-acceptor engineering, a series of multi-acceptor conjugated oligomer SU-n (n = 1, 2, and 5) with tunable acceptor ratios were synthesized, and their efficiency in anti-quenching NIR-Ⅱ emission was demonstrated. When prepared into water-dispersed nanoparticles (NPs), SU-5 NPs exhibit bright NIR-Ⅱ emission and dual phototherapy for photothermal therapy and photodynamic therapy simultaneously upon 808 nm light excitation. With these benefits, high-resolution whole-body and local angiography in vivo of SU-5 NPs were successfully realized in the NIR-Ⅱb window. Moreover, in vivo, theranostics experiments demonstrated the efficiency of SU-5 NPs in NIR-Ⅱ imaging-guided complete tumor photoablation without any relapses with high biosafety. This work explores a practical multi-acceptor engineering strategy for developing anti-quenching theranostic materials, providing an efficient theranostic agent for efficient NIR-Ⅱb bioimaging and phototheranostics.
Near-infrared (NIR) theranostics have received considerable attention because of their advantages in precise diagnostic imaging and efficient simultaneous treatment and have achieved tremendous advancements in the last few years. However, their progress is severely restricted by the rarity of efficient second NIR (NIR-Ⅱ) responsive phototheranostic materials, especially in the NIR-Ⅱb region. Moreover, these materials often embarrass the quenching puzzle in the aggregative state, thus greatly reducing their theranostic performance. To overcome this limitation, we developed anti-quenching donor-acceptor-donor (D-A-D)-conjugated oligomers with NIR-Ⅱb emission for high-performance NIR-Ⅱ angiography and phototheranostics. Through multi-acceptor engineering, a series of multi-acceptor conjugated oligomer SU-n (n = 1, 2, and 5) with tunable acceptor ratios were synthesized, and their efficiency in anti-quenching NIR-Ⅱ emission was demonstrated. When prepared into water-dispersed nanoparticles (NPs), SU-5 NPs exhibit bright NIR-Ⅱ emission and dual phototherapy for photothermal therapy and photodynamic therapy simultaneously upon 808 nm light excitation. With these benefits, high-resolution whole-body and local angiography in vivo of SU-5 NPs were successfully realized in the NIR-Ⅱb window. Moreover, in vivo, theranostics experiments demonstrated the efficiency of SU-5 NPs in NIR-Ⅱ imaging-guided complete tumor photoablation without any relapses with high biosafety. This work explores a practical multi-acceptor engineering strategy for developing anti-quenching theranostic materials, providing an efficient theranostic agent for efficient NIR-Ⅱb bioimaging and phototheranostics.
2025, 36(11): 110835
doi: 10.1016/j.cclet.2025.110835
Abstract:
The development of highly effective photosensitizers (PSs) based on supramolecular coordination complexes (SCCs) is highly appealing in supramolecular chemistry, materials science, and biology. SCCs offer promising platforms for incorporating multiple PSs and other functional units into their well-defined structures, allowing for precise control over the number and distribution of these components. In this study, we present an efficient and straightforward method for modulating the photosensitization process of PSs derived from a family of BF2-chelated dipyrromethene (BODIPY)-containing Pt(Ⅱ) metallacycles by varying pre-designed Pt(Ⅱ) acceptors. By utilizing different Pt(Ⅱ) acceptors with varying Pt atom configurations and degrees of π-conjugated organic moieties, we observed tunable characteristics in the photosensitization process and singlet oxygen (1O2) generation efficiency of these targeted metallacycles. Furthermore, we successfully conducted the visible-light-driven oxidative coupling of various amines to imines, catalyzed by the prepared metallacycle PSs. This study offers a novel approach for fabricating efficient PSs based on SCCs, featuring tunable photosensitization efficiency and excellent photocatalytic reactivity, while providing new insights into the preparation of effective PSs.
The development of highly effective photosensitizers (PSs) based on supramolecular coordination complexes (SCCs) is highly appealing in supramolecular chemistry, materials science, and biology. SCCs offer promising platforms for incorporating multiple PSs and other functional units into their well-defined structures, allowing for precise control over the number and distribution of these components. In this study, we present an efficient and straightforward method for modulating the photosensitization process of PSs derived from a family of BF2-chelated dipyrromethene (BODIPY)-containing Pt(Ⅱ) metallacycles by varying pre-designed Pt(Ⅱ) acceptors. By utilizing different Pt(Ⅱ) acceptors with varying Pt atom configurations and degrees of π-conjugated organic moieties, we observed tunable characteristics in the photosensitization process and singlet oxygen (1O2) generation efficiency of these targeted metallacycles. Furthermore, we successfully conducted the visible-light-driven oxidative coupling of various amines to imines, catalyzed by the prepared metallacycle PSs. This study offers a novel approach for fabricating efficient PSs based on SCCs, featuring tunable photosensitization efficiency and excellent photocatalytic reactivity, while providing new insights into the preparation of effective PSs.
2025, 36(11): 110839
doi: 10.1016/j.cclet.2025.110839
Abstract:
The complex skin structure and insufficient intracellular entrapment limit the therapeutic effects of active substances, therefore appealing to a more effective transdermal drug delivery system design. Herein, a hyaluronic acid (HA) modified steareth-2-based niosomes (HA-nio) with satisfactory deformability and targeting properties was designed for ergothioneine (EGT) (EGT@HA-nio) against ultraviolet (UV)-induced skin damage. The unique composition allows EGT@HA-nio to exhibit high mechanical softness, making it deformable to pass through the stratum corneum by the intercellular space without rupture. For further intracellular delivery, HA modification enables EGT to target human dermal cells (HDFs) with increased distribution in mitochondria without the restriction of specific EGT transporter-organic cation transporter 1 (OCTN-1). Benefiting from the above properties, an adequate amount of EGT in the active form was accumulated in the desired cellular sites, alleviating UV-radiation-induced reactive oxygen species (ROS) generation, inflammatory factor release, DNA damage, and mitochondrial dysfunction. The in vivo experimental results show that EGT@HA-nio could significantly decrease collagen degradation, restore epidermal thickness and morphology to healthy levels, and effectively prevent UV-induced skin damage. With the ability to penetrate biological barriers and deliver drugs, HA-nio may promote the development of inadequate drug penetration disease treatment including skin diseases, cancers, and bacterial infections.
The complex skin structure and insufficient intracellular entrapment limit the therapeutic effects of active substances, therefore appealing to a more effective transdermal drug delivery system design. Herein, a hyaluronic acid (HA) modified steareth-2-based niosomes (HA-nio) with satisfactory deformability and targeting properties was designed for ergothioneine (EGT) (EGT@HA-nio) against ultraviolet (UV)-induced skin damage. The unique composition allows EGT@HA-nio to exhibit high mechanical softness, making it deformable to pass through the stratum corneum by the intercellular space without rupture. For further intracellular delivery, HA modification enables EGT to target human dermal cells (HDFs) with increased distribution in mitochondria without the restriction of specific EGT transporter-organic cation transporter 1 (OCTN-1). Benefiting from the above properties, an adequate amount of EGT in the active form was accumulated in the desired cellular sites, alleviating UV-radiation-induced reactive oxygen species (ROS) generation, inflammatory factor release, DNA damage, and mitochondrial dysfunction. The in vivo experimental results show that EGT@HA-nio could significantly decrease collagen degradation, restore epidermal thickness and morphology to healthy levels, and effectively prevent UV-induced skin damage. With the ability to penetrate biological barriers and deliver drugs, HA-nio may promote the development of inadequate drug penetration disease treatment including skin diseases, cancers, and bacterial infections.
2025, 36(11): 110840
doi: 10.1016/j.cclet.2025.110840
Abstract:
Formaldehyde (FA) and excessive nitrite (NO2−) are highly carcinogenic compounds that pose serious risks to human health. In this study, we designed a sensing platform 8-hydrazine-boron dipyrromethene (OPTY) for the detection of FA and nitrite in food. Upon aldimine condensation with FA, OPTY produced strong blue fluorescence. By contrast, NO2− underwent an intramolecular cyclization cascade reaction with OPTY to boast bright green fluorescence. OPTY has the advantages of high signal-to-noise ratio, good selectivity, and a low limit of detection (LOD = 26.5 nmol/L for FA, LOD = 20.8 nmol/L for NO2−). Furthermore, OPTY was fabricated into a portable sensing chip, which was combined with smartphone to form a portable sensing platform. This platform has been successfully applied for the determination of FA/NO2− in meat and seafood with high accuracy (93.49%–102.35%). Therefore, the intelligent sensing platform can realize on-site visual detection of FA/NO2− content in food, demonstrating great potential for ensuring food safety.
Formaldehyde (FA) and excessive nitrite (NO2−) are highly carcinogenic compounds that pose serious risks to human health. In this study, we designed a sensing platform 8-hydrazine-boron dipyrromethene (OPTY) for the detection of FA and nitrite in food. Upon aldimine condensation with FA, OPTY produced strong blue fluorescence. By contrast, NO2− underwent an intramolecular cyclization cascade reaction with OPTY to boast bright green fluorescence. OPTY has the advantages of high signal-to-noise ratio, good selectivity, and a low limit of detection (LOD = 26.5 nmol/L for FA, LOD = 20.8 nmol/L for NO2−). Furthermore, OPTY was fabricated into a portable sensing chip, which was combined with smartphone to form a portable sensing platform. This platform has been successfully applied for the determination of FA/NO2− in meat and seafood with high accuracy (93.49%–102.35%). Therefore, the intelligent sensing platform can realize on-site visual detection of FA/NO2− content in food, demonstrating great potential for ensuring food safety.
2025, 36(11): 110841
doi: 10.1016/j.cclet.2025.110841
Abstract:
Currently, various clinical treatment methods struggle to halt the rapid progression of common acute liver failure. To address this issue, significant advancements in stem cell derivatives and bioactive hydrogels in regenerative medicine have been utilized. A bioactive hydrogel with good tissue adhesion, CCO/HGF@EV, has been designed by incorporating cytokine hepatocyte growth factor (HGF), which plays a major role in the early regenerative phase of the liver, into stem cell-derived exosomal vesicles (EV) through electroporation. Under ultrasonic guidance, CCO/HGF@EV is administered near the liver, adhering firmly and degrading over three days to release HGF@EV. Through a series of rigorous experiments, it was confirmed that the abundant anti-inflammatory and regenerative cytokines in HGF@EV significantly reduced reactive oxygen species (ROS) during the acute phase of liver failure, alleviated hepatocyte apoptosis, decreased inflammatory damage and necrosis of liver tissue, and significantly promoted the regeneration and repair of liver parenchymal cells and vascular tissues. Additionally, the release of HGF after EV fusion with hepatocytes synergistically enhanced the regeneration of liver cells during the acute phase, thereby stabilizing liver function. This hydrogel, with its powerful therapeutic effects, forms a protective layer over the liver. It holds great potential for advancing research in tissue engineering and regenerative medicine and has significant clinical translational value.
Currently, various clinical treatment methods struggle to halt the rapid progression of common acute liver failure. To address this issue, significant advancements in stem cell derivatives and bioactive hydrogels in regenerative medicine have been utilized. A bioactive hydrogel with good tissue adhesion, CCO/HGF@EV, has been designed by incorporating cytokine hepatocyte growth factor (HGF), which plays a major role in the early regenerative phase of the liver, into stem cell-derived exosomal vesicles (EV) through electroporation. Under ultrasonic guidance, CCO/HGF@EV is administered near the liver, adhering firmly and degrading over three days to release HGF@EV. Through a series of rigorous experiments, it was confirmed that the abundant anti-inflammatory and regenerative cytokines in HGF@EV significantly reduced reactive oxygen species (ROS) during the acute phase of liver failure, alleviated hepatocyte apoptosis, decreased inflammatory damage and necrosis of liver tissue, and significantly promoted the regeneration and repair of liver parenchymal cells and vascular tissues. Additionally, the release of HGF after EV fusion with hepatocytes synergistically enhanced the regeneration of liver cells during the acute phase, thereby stabilizing liver function. This hydrogel, with its powerful therapeutic effects, forms a protective layer over the liver. It holds great potential for advancing research in tissue engineering and regenerative medicine and has significant clinical translational value.
2025, 36(11): 110844
doi: 10.1016/j.cclet.2025.110844
Abstract:
In order to realize the simple and rapid detection of antibiotic contaminants in environmental water, the para-sulfocalix[4]arene (pSC4) functionalized gold nanoparticles (AuNPs) composites (pSC4-AuNPs) were prepared by sodium borohydride reduction. Here, a rapid and sensitive electrochemical sensor for the detection of antibiotic contaminants in water was constructed. The detection mechanism and the signaling changes of the different sulfamethazine (SMZ) concentrations were further explored based on pSC4-AuNPs/SMZ modified glassy carbon electrode through aggregation of gold nanoparticles induced by host-guest recognition of SMZ and pSC4. The results suggested that this method achieved rapid and ultrasensitive detection of SMZ with a limit of detection of 0.0038 ng/mL (linear detection range of 1.0 - 1.0 × 104 ng/mL). The recoveries ranged from 91.1% to 97.0% with relative standard deviations (RSDs) of 1.5%-3.5%. The accurate detection of SMZ in recovery rate of spiking assay proved the potential practical application of the sensor. Host-guest recognition induced AuNPs aggregation results in dramatic signal enhancement for electrochemical impedimetric detection assay of SMZ. This detection method provides a new concept for developing sensitive electrochemical sensors for simple and sensitive detection of small molecules in water.
In order to realize the simple and rapid detection of antibiotic contaminants in environmental water, the para-sulfocalix[4]arene (pSC4) functionalized gold nanoparticles (AuNPs) composites (pSC4-AuNPs) were prepared by sodium borohydride reduction. Here, a rapid and sensitive electrochemical sensor for the detection of antibiotic contaminants in water was constructed. The detection mechanism and the signaling changes of the different sulfamethazine (SMZ) concentrations were further explored based on pSC4-AuNPs/SMZ modified glassy carbon electrode through aggregation of gold nanoparticles induced by host-guest recognition of SMZ and pSC4. The results suggested that this method achieved rapid and ultrasensitive detection of SMZ with a limit of detection of 0.0038 ng/mL (linear detection range of 1.0 - 1.0 × 104 ng/mL). The recoveries ranged from 91.1% to 97.0% with relative standard deviations (RSDs) of 1.5%-3.5%. The accurate detection of SMZ in recovery rate of spiking assay proved the potential practical application of the sensor. Host-guest recognition induced AuNPs aggregation results in dramatic signal enhancement for electrochemical impedimetric detection assay of SMZ. This detection method provides a new concept for developing sensitive electrochemical sensors for simple and sensitive detection of small molecules in water.
2025, 36(11): 110848
doi: 10.1016/j.cclet.2025.110848
Abstract:
Diabetic wounds are among the most challenging chronic wounds to heal, due to the presence of multiple factors, including continuous oxidative stress, impaired vascular integrity, and biofilm formation. The development of innovative treatment strategies is of paramount importance for the management of diabetic wounds. Stemmed from the pleiotropic physicochemical properties of ferrocene and spermidine, this essay reported the ferrocene-spermidine co-polymer (FcS) for the first time through facile amidation reaction. Molecular dynamics simulation revealed its self-assembly through hydrogen bonds, van der Waals forces instead of traditional nanoprecipitation. The self-assembled nanoparticles were demonstrated to exhibit great antioxidant property on cells to facilitate their migration and angiogenesis. Moreover, the integration with photocuring hydrogel, gelatin methacrylate (GelMA), to construct FcS nanoparticles loaded wound dressing (GelMA@FcS) further confirmed the potential on promoting diabetic wound enclosure through enhancement of re-epithelization and collagen deposition. Together with its great biocompatibility and biosafety, GelMA@FcS is expected to be developed into a wound dressing for clinical diabetic wounds management.
Diabetic wounds are among the most challenging chronic wounds to heal, due to the presence of multiple factors, including continuous oxidative stress, impaired vascular integrity, and biofilm formation. The development of innovative treatment strategies is of paramount importance for the management of diabetic wounds. Stemmed from the pleiotropic physicochemical properties of ferrocene and spermidine, this essay reported the ferrocene-spermidine co-polymer (FcS) for the first time through facile amidation reaction. Molecular dynamics simulation revealed its self-assembly through hydrogen bonds, van der Waals forces instead of traditional nanoprecipitation. The self-assembled nanoparticles were demonstrated to exhibit great antioxidant property on cells to facilitate their migration and angiogenesis. Moreover, the integration with photocuring hydrogel, gelatin methacrylate (GelMA), to construct FcS nanoparticles loaded wound dressing (GelMA@FcS) further confirmed the potential on promoting diabetic wound enclosure through enhancement of re-epithelization and collagen deposition. Together with its great biocompatibility and biosafety, GelMA@FcS is expected to be developed into a wound dressing for clinical diabetic wounds management.
2025, 36(11): 110850
doi: 10.1016/j.cclet.2025.110850
Abstract:
Cancer is one of the main causes of death throughout the world. Radical elimination of tumor is crucial for a successful treatment. However, during cancer treatment, it is difficult to distinguish tumor boundaries with the naked eye and to accurately exterminate it. In this work, based on the overexpression of H2S in some tumors, an activatable second near-infrared (NIR-Ⅱ) theranostic agent (NRS) for distinguishing tumor tissues from normal tissues, guiding surgical resection and ablating tumor tissues by efficient photothermal therapy is proposed. This developed probe NRS can emit fluorescence in the range of 900–1100 nm and detect tumor tissues with H2S overexpression. Under the guidance of NIR-Ⅱ fluorescence imaging, the tumor margins can be delineated clearly with high signal-to-background ratio. In addition, with the help of NIR-Ⅱ fluorescence surgery navigation, tumors tissues can be precisely resected. More importantly, the probe displays a high photothermal conversion efficiency and can efficiently induce tumor cells apoptosis under 808 nm laser irradiation. By using the desirable attributes of NRS, the tumor tissues with H2S overexpression was successfully ablated. This work provides a new tool for the future precision eradicate tumors without recurrence, which may have translational potential in biological and clinical systems.
Cancer is one of the main causes of death throughout the world. Radical elimination of tumor is crucial for a successful treatment. However, during cancer treatment, it is difficult to distinguish tumor boundaries with the naked eye and to accurately exterminate it. In this work, based on the overexpression of H2S in some tumors, an activatable second near-infrared (NIR-Ⅱ) theranostic agent (NRS) for distinguishing tumor tissues from normal tissues, guiding surgical resection and ablating tumor tissues by efficient photothermal therapy is proposed. This developed probe NRS can emit fluorescence in the range of 900–1100 nm and detect tumor tissues with H2S overexpression. Under the guidance of NIR-Ⅱ fluorescence imaging, the tumor margins can be delineated clearly with high signal-to-background ratio. In addition, with the help of NIR-Ⅱ fluorescence surgery navigation, tumors tissues can be precisely resected. More importantly, the probe displays a high photothermal conversion efficiency and can efficiently induce tumor cells apoptosis under 808 nm laser irradiation. By using the desirable attributes of NRS, the tumor tissues with H2S overexpression was successfully ablated. This work provides a new tool for the future precision eradicate tumors without recurrence, which may have translational potential in biological and clinical systems.
2025, 36(11): 110853
doi: 10.1016/j.cclet.2025.110853
Abstract:
The linker defect engineering for MOFs is a viable strategy that usually can effectively augment conductivity to further promote charge carrier separation, which is the most excellent conductivity of preserved metal clusters. However, the partially missing photosensitive linker often leads to the diminished light utilization efficiency. As we know, in the linker defect engineering, addressing the lack of photosensitivity while maintaining outstanding conductivity is still in its infancy. In this essay, the linker-defective NH2-MIL-125 was obtained by adding the glacial acetic acid regulator, subsequently, the excellent light-responsive Pt/CQDs with up-conversion effect was in-situ encapsulated into the enlarged pore space of linker-defective NH2-MIL-125. It is excited that the fabricated dual-functional composite ideally integrates photosensitivity and conductivity for photocatalytic hydrogen evolution and NO elimination. The optimal Pt/CQDs@NM-125-4 exhibited very superior photocatalytic hydrogen evolution (28.75 mmol/g), it was 11.63 times as that of the initial NH2-MIL-125 (2.47 mmol/g) and 1.4 times as that of the defective NM-125-4 (20.46 mmol/g). In addition, the excellent photocatalytic NO removal efficiency was 52.12% for Pt/CQDs@NM-125-4, whereas the original NH2-MIL-125 only reached 30% and the defective NM-125-4 achieved 44.96%. The corresponding optical and electrical characterization based on UV–vis, up-conversion photoluminescence (UCPL), and electrochemical impedance spectroscopy (EIS) etc. demonstrated the defect engineering accelerates the charge carriers transfer via enhancing conductivity, and the in-situ confined up-conversion Pt/CQDs promote the visible light response. Our work presents a feasible avenue to integrate photosensitivity and conductivity via in-situ fabricating excellent light-responsive Pt/CQDs within linker-defective NH2-MIL-125 for further significantly boosting photocatalytic performance
The linker defect engineering for MOFs is a viable strategy that usually can effectively augment conductivity to further promote charge carrier separation, which is the most excellent conductivity of preserved metal clusters. However, the partially missing photosensitive linker often leads to the diminished light utilization efficiency. As we know, in the linker defect engineering, addressing the lack of photosensitivity while maintaining outstanding conductivity is still in its infancy. In this essay, the linker-defective NH2-MIL-125 was obtained by adding the glacial acetic acid regulator, subsequently, the excellent light-responsive Pt/CQDs with up-conversion effect was in-situ encapsulated into the enlarged pore space of linker-defective NH2-MIL-125. It is excited that the fabricated dual-functional composite ideally integrates photosensitivity and conductivity for photocatalytic hydrogen evolution and NO elimination. The optimal Pt/CQDs@NM-125-4 exhibited very superior photocatalytic hydrogen evolution (28.75 mmol/g), it was 11.63 times as that of the initial NH2-MIL-125 (2.47 mmol/g) and 1.4 times as that of the defective NM-125-4 (20.46 mmol/g). In addition, the excellent photocatalytic NO removal efficiency was 52.12% for Pt/CQDs@NM-125-4, whereas the original NH2-MIL-125 only reached 30% and the defective NM-125-4 achieved 44.96%. The corresponding optical and electrical characterization based on UV–vis, up-conversion photoluminescence (UCPL), and electrochemical impedance spectroscopy (EIS) etc. demonstrated the defect engineering accelerates the charge carriers transfer via enhancing conductivity, and the in-situ confined up-conversion Pt/CQDs promote the visible light response. Our work presents a feasible avenue to integrate photosensitivity and conductivity via in-situ fabricating excellent light-responsive Pt/CQDs within linker-defective NH2-MIL-125 for further significantly boosting photocatalytic performance
2025, 36(11): 110854
doi: 10.1016/j.cclet.2025.110854
Abstract:
Synergistic therapy using multiple modalities is a highly promising therapeutic strategy. Near-infrared-Ⅱ (NIR-Ⅱ) fluorescence imaging, with its deep penetration and high fidelity, has frequently been employed in the literature to guide and assist treatment. Herein, we report the development of a NIR-Ⅱ fluorescence imaging guided multi-therapy platform PDI-DS NPs, which integrates a novel activatable phototheranostic agent PDI-DBU, a H2S donor DPS and an amphiphilic polymer DSPE-mPEG2000. In order to maximize redshift of absorption and emission of PDI derivatives, we introduced an electron donating group DBU on PDI to obtain PDI-DBU. PDI-DBU exhibits a distinct absorption band at 700–900 nm and demonstrates excellent NIR-Ⅱ fluorescence emission/imaging properties and good photothermal effects under 808 nm laser irradiation. More importantly, under 808 nm laser irradiation, PDI-DBU could be oxidized, and the photodynamic effect of the material could be subsequently activated under 530 nm laser irradiation, achieving the combination of photothermal and activatable photodynamic dual modality treatment. The H2S donor DPS, when triggered by the abundant glutathione (GSH) within the tumor microenvironment (TME), is capable of generating H2S. On one hand, H2S can inhibit tumor growth by disrupting mitochondrial function, on the other hand, it can also repress the expression of heat shock protein 90 (HSP90), thereby reversing tumor cell resistance mechanism against photothermal therapy. The utilization of PDI-DS NPs combined with DPS for efficient tumor ablation has been successfully demonstrated both in vitro and in vivo. This synergistic therapeutic platform thus offers a promising strategy in the field of NIR-Ⅱ fluorescence imaging guided tumor therapy.
Synergistic therapy using multiple modalities is a highly promising therapeutic strategy. Near-infrared-Ⅱ (NIR-Ⅱ) fluorescence imaging, with its deep penetration and high fidelity, has frequently been employed in the literature to guide and assist treatment. Herein, we report the development of a NIR-Ⅱ fluorescence imaging guided multi-therapy platform PDI-DS NPs, which integrates a novel activatable phototheranostic agent PDI-DBU, a H2S donor DPS and an amphiphilic polymer DSPE-mPEG2000. In order to maximize redshift of absorption and emission of PDI derivatives, we introduced an electron donating group DBU on PDI to obtain PDI-DBU. PDI-DBU exhibits a distinct absorption band at 700–900 nm and demonstrates excellent NIR-Ⅱ fluorescence emission/imaging properties and good photothermal effects under 808 nm laser irradiation. More importantly, under 808 nm laser irradiation, PDI-DBU could be oxidized, and the photodynamic effect of the material could be subsequently activated under 530 nm laser irradiation, achieving the combination of photothermal and activatable photodynamic dual modality treatment. The H2S donor DPS, when triggered by the abundant glutathione (GSH) within the tumor microenvironment (TME), is capable of generating H2S. On one hand, H2S can inhibit tumor growth by disrupting mitochondrial function, on the other hand, it can also repress the expression of heat shock protein 90 (HSP90), thereby reversing tumor cell resistance mechanism against photothermal therapy. The utilization of PDI-DS NPs combined with DPS for efficient tumor ablation has been successfully demonstrated both in vitro and in vivo. This synergistic therapeutic platform thus offers a promising strategy in the field of NIR-Ⅱ fluorescence imaging guided tumor therapy.
2025, 36(11): 110855
doi: 10.1016/j.cclet.2025.110855
Abstract:
Electrochromic phosphorescent materials have recently attracted much attention, however, achieving the efficient electrophosphorochromism in pure organic materials is highly challenging and has not been reported yet. Herein, a kind of pure organic host-guest system (BA@CzPA) is constructed by one-pot in-situ melt blending of (9-phenyl-9H-carbazol-2-yl)boronic acid (CzPA) and boric acid (BA). Because of the efficient intersystem crossing promoted by covalent, hydrogen bonding, and confinement effect, the proposed BA@CzPA exhibit the superior room temperature phosphorescence (RTP) efficiency, including an ultralong lifetime of up to 4.23 s and a high phosphorescent quantum yield of 10.9%. Importantly, the BA@CzPA have a unique electrophosphorochromism property, and their electrically-induced RTP emission can gradually red-shift from 440 nm to 548 nm as the current density increases, which is attributed to the transformation of host matrices of BA@CzPA from metaboric acid to B2O3 under the electrical stimuli. This finding provides us not only with a new idea to develop pure organic electrophosphorochromism materials with high RTP efficiency, but also with a powerful strategy to fabricate correlation color temperature tunable white light emitting diodes.
Electrochromic phosphorescent materials have recently attracted much attention, however, achieving the efficient electrophosphorochromism in pure organic materials is highly challenging and has not been reported yet. Herein, a kind of pure organic host-guest system (BA@CzPA) is constructed by one-pot in-situ melt blending of (9-phenyl-9H-carbazol-2-yl)boronic acid (CzPA) and boric acid (BA). Because of the efficient intersystem crossing promoted by covalent, hydrogen bonding, and confinement effect, the proposed BA@CzPA exhibit the superior room temperature phosphorescence (RTP) efficiency, including an ultralong lifetime of up to 4.23 s and a high phosphorescent quantum yield of 10.9%. Importantly, the BA@CzPA have a unique electrophosphorochromism property, and their electrically-induced RTP emission can gradually red-shift from 440 nm to 548 nm as the current density increases, which is attributed to the transformation of host matrices of BA@CzPA from metaboric acid to B2O3 under the electrical stimuli. This finding provides us not only with a new idea to develop pure organic electrophosphorochromism materials with high RTP efficiency, but also with a powerful strategy to fabricate correlation color temperature tunable white light emitting diodes.
2025, 36(11): 110856
doi: 10.1016/j.cclet.2025.110856
Abstract:
The removal of highly toxic arsenic (As) and antimony (Sb) contaminants in water by adsorption presents a great challenge worldwide. Conventional adsorbents exhibit insufficient efficacy for removing pentavalent oxyanions, As(Ⅴ) and Sb(Ⅴ), which are predominant compared with the trivalent species, As(Ⅲ) and Sb(Ⅲ), in surface waters. Here, we synthesized a novel composite adsorbent, amine-functionalized polystyrene resin loaded with nano TiO2 (AmPSd-Ti). The mm-scale spheres showed outstanding adsorption capacities for As(Ⅲ), As(Ⅴ), Sb(Ⅲ), and Sb(Ⅴ) at 73.85, 153.29, 86.80, and 123.71 mg/g, respectively. AmPSd-Ti exhibited selective adsorption for As and Sb in the presence of Cl−, NO3−, SO42−, and F−. As and Sb were adsorbed by the nano-sized TiO2 confined in the porous resin via forming inner-sphere complexes. The protonated amine groups enhanced the adsorption of As(Ⅴ) and Sb(Ⅴ) by electrostatic attraction and hydrogen bonding, which was confirmed by experimental results and molecular dynamics simulations. Fixed-bed column tests showed breakthrough curves with adsorption capacities of 1.38 mg/g (6600 BV) and 6.65 mg/g (1260 BV) upon treating real As-contaminated groundwater and Sb-contaminated industrial wastewater. Our study highlights a feasible strategy by incorporating inorganic metal oxides into organic polymers to achieve highly efficient removal of As and Sb in real-world scenarios.
The removal of highly toxic arsenic (As) and antimony (Sb) contaminants in water by adsorption presents a great challenge worldwide. Conventional adsorbents exhibit insufficient efficacy for removing pentavalent oxyanions, As(Ⅴ) and Sb(Ⅴ), which are predominant compared with the trivalent species, As(Ⅲ) and Sb(Ⅲ), in surface waters. Here, we synthesized a novel composite adsorbent, amine-functionalized polystyrene resin loaded with nano TiO2 (AmPSd-Ti). The mm-scale spheres showed outstanding adsorption capacities for As(Ⅲ), As(Ⅴ), Sb(Ⅲ), and Sb(Ⅴ) at 73.85, 153.29, 86.80, and 123.71 mg/g, respectively. AmPSd-Ti exhibited selective adsorption for As and Sb in the presence of Cl−, NO3−, SO42−, and F−. As and Sb were adsorbed by the nano-sized TiO2 confined in the porous resin via forming inner-sphere complexes. The protonated amine groups enhanced the adsorption of As(Ⅴ) and Sb(Ⅴ) by electrostatic attraction and hydrogen bonding, which was confirmed by experimental results and molecular dynamics simulations. Fixed-bed column tests showed breakthrough curves with adsorption capacities of 1.38 mg/g (6600 BV) and 6.65 mg/g (1260 BV) upon treating real As-contaminated groundwater and Sb-contaminated industrial wastewater. Our study highlights a feasible strategy by incorporating inorganic metal oxides into organic polymers to achieve highly efficient removal of As and Sb in real-world scenarios.
2025, 36(11): 110882
doi: 10.1016/j.cclet.2025.110882
Abstract:
The application of photocatalytic technology in treating various environmental pollution issues has been extensively studied. However, its further utilization has been hindered by the limited response to visible light and the serious recombination of charge carriers. In this study, the two-dimensional (2D) layered carbon-supported TiO2 particles derived from Ti3C2 Mxene were tightly attached on Bi2WO6 containing oxygen-rich vacancies, fabricating an efficient S-scheme bifunctional heterojunction. This development aimed to improve the photocatalytic performance towards antibiotics degradation and NO removal. The photochemical characterizations confirmed that the presence of oxygen vacancies broaden the visible light responsiveness of Bi2WO6. Subsequently, the formation of S-scheme heterojunction between oxygen vacancy-containing Bi2WO6 and TiO2 allowed for the maximum retention of the high oxidation and reduction capabilities of the monomer material. Simultaneously, layered carbon between Bi2WO6 and TiO2 accelerated charge transfer and carrier separation. The optimized BWO/TiO2@C exhibited superior performance, with an 84.03% degradation rate of tetracycline (TC) and a 44.2% removal rate of NO under visible light, representing 1.54 and 4.79 times the performance of the original Bi2WO6, respectively. Intermediate species generated during the photocatalytic oxidation processes of TC and NO were identified using liquid chromatograph mass spectrometry (LC-MS) and in-situ DRIFTS. By combining electron paramagnetic resonance (EPR) and density functional theory (DFT) calculations, in-depth mechanisms were elucidated. This study sheds new light on the applications of Bi2WO6 and MXene in photocatalysis, offering potential for the development of efficient dual-functional photocatalysts for addressing water and air pollution.
The application of photocatalytic technology in treating various environmental pollution issues has been extensively studied. However, its further utilization has been hindered by the limited response to visible light and the serious recombination of charge carriers. In this study, the two-dimensional (2D) layered carbon-supported TiO2 particles derived from Ti3C2 Mxene were tightly attached on Bi2WO6 containing oxygen-rich vacancies, fabricating an efficient S-scheme bifunctional heterojunction. This development aimed to improve the photocatalytic performance towards antibiotics degradation and NO removal. The photochemical characterizations confirmed that the presence of oxygen vacancies broaden the visible light responsiveness of Bi2WO6. Subsequently, the formation of S-scheme heterojunction between oxygen vacancy-containing Bi2WO6 and TiO2 allowed for the maximum retention of the high oxidation and reduction capabilities of the monomer material. Simultaneously, layered carbon between Bi2WO6 and TiO2 accelerated charge transfer and carrier separation. The optimized BWO/TiO2@C exhibited superior performance, with an 84.03% degradation rate of tetracycline (TC) and a 44.2% removal rate of NO under visible light, representing 1.54 and 4.79 times the performance of the original Bi2WO6, respectively. Intermediate species generated during the photocatalytic oxidation processes of TC and NO were identified using liquid chromatograph mass spectrometry (LC-MS) and in-situ DRIFTS. By combining electron paramagnetic resonance (EPR) and density functional theory (DFT) calculations, in-depth mechanisms were elucidated. This study sheds new light on the applications of Bi2WO6 and MXene in photocatalysis, offering potential for the development of efficient dual-functional photocatalysts for addressing water and air pollution.
2025, 36(11): 110883
doi: 10.1016/j.cclet.2025.110883
Abstract:
Ultrasensitive detection of multiple diseases markers is of great importance in improving diagnostic accuracy, precision, and efficiency. A versatile Au nanozyme Raman probe strategy was employed to develop an ultrasensitive multiplex surface-enhanced Raman scattering (SERS) immunosensor using encoded silica photonic crystal beads (SPCBs). The efficient Au nanozyme Raman probe strategy was constructed using a robust Au nanozyme with high dual enzyme-like activity and SERS activity. On the one hand, Au nanozyme tags with oxidase-like activity can catalyze the oxidation of Raman-inactive 3,3′,5,5′-tetramethylbenzidine (TMB) to Raman-active oxidized TMB (ox-TMB) in the presence of O2. On the other hand, Au nanozyme tags with peroxidase-like activity can catalyze Raman-inactive TMB to Raman-active ox-TMB in the presence of H2O2. This dual catalysis action results in many Raman-active reporter molecules (ox-TMB) enabling highly sensitive detection. Meanwhile, the Au nanozyme as an extraordinary SERS substrate further enhances the detection signals of these Raman reporter molecules. Using reflection peaks of different SPCBs to encode tumor markers, an ultrasensitive multiplex SERS immunosensor was developed for detection of carcinoembryonic antigen (CEA) and alpha-fetoprotein (AFP), which exhibited wide linear ranges of 0.001–100 ng/mL for CEA and 0.01–1000 ng/mL for AFP, accompanied by low detection limits of 0.66 pg/mL for CEA and 9.5 pg/mL for AFP, respectively. This work demonstrates a universal and promising nanozyme Raman probe strategy to develop ultrasensitive multiplex SERS immunosensors for precise clinical diagnosis of disease.
Ultrasensitive detection of multiple diseases markers is of great importance in improving diagnostic accuracy, precision, and efficiency. A versatile Au nanozyme Raman probe strategy was employed to develop an ultrasensitive multiplex surface-enhanced Raman scattering (SERS) immunosensor using encoded silica photonic crystal beads (SPCBs). The efficient Au nanozyme Raman probe strategy was constructed using a robust Au nanozyme with high dual enzyme-like activity and SERS activity. On the one hand, Au nanozyme tags with oxidase-like activity can catalyze the oxidation of Raman-inactive 3,3′,5,5′-tetramethylbenzidine (TMB) to Raman-active oxidized TMB (ox-TMB) in the presence of O2. On the other hand, Au nanozyme tags with peroxidase-like activity can catalyze Raman-inactive TMB to Raman-active ox-TMB in the presence of H2O2. This dual catalysis action results in many Raman-active reporter molecules (ox-TMB) enabling highly sensitive detection. Meanwhile, the Au nanozyme as an extraordinary SERS substrate further enhances the detection signals of these Raman reporter molecules. Using reflection peaks of different SPCBs to encode tumor markers, an ultrasensitive multiplex SERS immunosensor was developed for detection of carcinoembryonic antigen (CEA) and alpha-fetoprotein (AFP), which exhibited wide linear ranges of 0.001–100 ng/mL for CEA and 0.01–1000 ng/mL for AFP, accompanied by low detection limits of 0.66 pg/mL for CEA and 9.5 pg/mL for AFP, respectively. This work demonstrates a universal and promising nanozyme Raman probe strategy to develop ultrasensitive multiplex SERS immunosensors for precise clinical diagnosis of disease.
2025, 36(11): 110884
doi: 10.1016/j.cclet.2025.110884
Abstract:
In this study, we presented a wearable electrochemical sensor for accurate and reliable cortisol detection in sweat. The sensor was built upon a novel platform by combination of conducting polyaniline (PANI) hydrogel and hydrophilic polypeptides, endowing the sensor with superior antifouling property. PANI hydrogel's distinctive water storage characteristic and the attachment of numerous antifouling peptides (Pep) effectively prevent nonspecific adsorption in complex human sweat environment. This innovative configuration significantly enhanced the accuracy of cortisol detection in complex sweat samples. The prepared biosensor was able to achieve reliable cortisol detection in both buffer solution and artificial sweat, covering a detection concentration range from 10−10 to 10–6 g/mL, with the minimum detection limitation of 33 pg/mL. And this electrochemical biosensor demonstrated outstanding selectivity, excellent stability, and good reproducibility. Notably, the cortisol levels were measured in volunteers during both morning and evening. The observed data exhibited distinct circadian rhythm, consistenting with the results gained from commercially available enzyme-linked immunosorption (ELISA) kit. This wearable biosensor shows giant potential for monitoring cortisol levels in human sweat, enabling real-time evaluation for mental and stress state.
In this study, we presented a wearable electrochemical sensor for accurate and reliable cortisol detection in sweat. The sensor was built upon a novel platform by combination of conducting polyaniline (PANI) hydrogel and hydrophilic polypeptides, endowing the sensor with superior antifouling property. PANI hydrogel's distinctive water storage characteristic and the attachment of numerous antifouling peptides (Pep) effectively prevent nonspecific adsorption in complex human sweat environment. This innovative configuration significantly enhanced the accuracy of cortisol detection in complex sweat samples. The prepared biosensor was able to achieve reliable cortisol detection in both buffer solution and artificial sweat, covering a detection concentration range from 10−10 to 10–6 g/mL, with the minimum detection limitation of 33 pg/mL. And this electrochemical biosensor demonstrated outstanding selectivity, excellent stability, and good reproducibility. Notably, the cortisol levels were measured in volunteers during both morning and evening. The observed data exhibited distinct circadian rhythm, consistenting with the results gained from commercially available enzyme-linked immunosorption (ELISA) kit. This wearable biosensor shows giant potential for monitoring cortisol levels in human sweat, enabling real-time evaluation for mental and stress state.
2025, 36(11): 110885
doi: 10.1016/j.cclet.2025.110885
Abstract:
Carbon dot (CD) is an edge-bound, nanometer-sized carbon material possessing unique optical and electronic properties, making it promising metal-free, environmentally benign. In this study, we identified a highly hydrophilic CD complexed with Fe(Ⅲ) via carboxyl groups to form CD-COOFeⅢ, which exhibited remarkably enhanced Fenton-like reaction performance boosted by visible light irradiation. CD-COOFeⅢ enabled high activity in the visible region beyond λ > 420 nm, and maintained stable oxidation efficiency in the presence of H2O2 over at least ten cycles. The capacity of electrons transferred from photo-excited CD to reduce Fe(Ⅲ) was calculated to be 1.1 mmol/g of CD. Furthermore, the quantum yield (QY) of solar-to-Fe(Ⅱ) conversion reached an impressive 87.7%. These findings not only suggest a viable strategy for efficient conversion of solar-to-chemical using a CD-COOFeⅢ complex in visible light boosted Fenton-like oxidation reaction, but also provide insight for understanding the effect of nanosized artificial and/or natural carbon materials in iron recycling in a natural surface environment.
Carbon dot (CD) is an edge-bound, nanometer-sized carbon material possessing unique optical and electronic properties, making it promising metal-free, environmentally benign. In this study, we identified a highly hydrophilic CD complexed with Fe(Ⅲ) via carboxyl groups to form CD-COOFeⅢ, which exhibited remarkably enhanced Fenton-like reaction performance boosted by visible light irradiation. CD-COOFeⅢ enabled high activity in the visible region beyond λ > 420 nm, and maintained stable oxidation efficiency in the presence of H2O2 over at least ten cycles. The capacity of electrons transferred from photo-excited CD to reduce Fe(Ⅲ) was calculated to be 1.1 mmol/g of CD. Furthermore, the quantum yield (QY) of solar-to-Fe(Ⅱ) conversion reached an impressive 87.7%. These findings not only suggest a viable strategy for efficient conversion of solar-to-chemical using a CD-COOFeⅢ complex in visible light boosted Fenton-like oxidation reaction, but also provide insight for understanding the effect of nanosized artificial and/or natural carbon materials in iron recycling in a natural surface environment.
2025, 36(11): 110886
doi: 10.1016/j.cclet.2025.110886
Abstract:
The advanced oxidation system based on peracetic acid (PAA) has been proved to be a green and safe oxidation decontamination technology. Among them, the key challenge and complexity in current research lies in the directional induction of PAA and its utilization for selective removal of refractory pollutants. This study prepared nitrogen-doped biochar (NBC) using compound pharmaceutical residues commonly found in traditional Chinese medicine as a precursor. A system based on NBC-activated PAA was constructed for sulfamethoxazole (SMX) degradation. The introduction of nitrogen significantly enhanced the degree of graphitization in NBC. The degradation system achieved 87.89% SMX degradation efficiency within 60 min. Furthermore, the formation of the intricate NBC-PAA* complex detected by in-situ Raman was of paramount importance as it facilitates enhanced electron transfer processes within the complex, thereby promoting PAA decomposition through electron loss. The formation of a new complex between SMX and NBC-PAA* facilitated the completion of electron transfer process within the complex. In summary, this study explored a novel approach for treating and disposing of solid waste from Chinese medicine residue by successfully inducing non-free radical degradation pathway using PAA system. It offers fresh insights and ideas in the fields of water treatment and solid waste management.
The advanced oxidation system based on peracetic acid (PAA) has been proved to be a green and safe oxidation decontamination technology. Among them, the key challenge and complexity in current research lies in the directional induction of PAA and its utilization for selective removal of refractory pollutants. This study prepared nitrogen-doped biochar (NBC) using compound pharmaceutical residues commonly found in traditional Chinese medicine as a precursor. A system based on NBC-activated PAA was constructed for sulfamethoxazole (SMX) degradation. The introduction of nitrogen significantly enhanced the degree of graphitization in NBC. The degradation system achieved 87.89% SMX degradation efficiency within 60 min. Furthermore, the formation of the intricate NBC-PAA* complex detected by in-situ Raman was of paramount importance as it facilitates enhanced electron transfer processes within the complex, thereby promoting PAA decomposition through electron loss. The formation of a new complex between SMX and NBC-PAA* facilitated the completion of electron transfer process within the complex. In summary, this study explored a novel approach for treating and disposing of solid waste from Chinese medicine residue by successfully inducing non-free radical degradation pathway using PAA system. It offers fresh insights and ideas in the fields of water treatment and solid waste management.
2025, 36(11): 110910
doi: 10.1016/j.cclet.2025.110910
Abstract:
Type 2 diabetes mellitus (T2DM) is one of the most prevalent chronic metabolic disorder characterized by insulin resistance and relative insulin deficiency. PPARδ activation has been reported to have several beneficial effects in alleviating dyslipidemia and insulin resistance. GW501516, a synthetic PPARδ agonist, was developed to target hyperlipidemia and reported to alleviating insulin resistance in T2DM. Studies indicate that PPARδ activation by GW501516 can reduce adiposity, enhance β-oxidation of fatty acids, and improve insulin sensitivity in T2DM animal models. Despite its therapeutic promise, potential carcinogenic effects also have been reported. Therefore, a comprehensive non-targeted and targeted lipidomics study was carried out to evaluate the regulatory effect of GW501516 in the plasma of db/db mice. The results revealed that GW501516 is effective in reducing the accumulation of lipids in the fatty acid metabolism pathway and lipid classes including triglycerides and phosphatidylglycerols. Furthermore, activation of PPARδ by GW501516 demonstrated a beneficial effect on improving circulating cholesterol homeostasis. However, while the levels of hexosylceramides and sphingomyelin were partially reversed, ceramide levels, which are negatively associated with insulin sensitivity, were significantly elevated by GW501516. Despite these mixed outcomes, the study highlights both the promising therapeutic potential of PPARδ activation in metabolic disorders and the safety concerns regarding long-term clinical use. The findings provide valuable insights into the impact of GW501516-induced PPARδ activation on lipid metabolism in T2DM, contributing to a better understanding of its therapeutic potential and risks.
Type 2 diabetes mellitus (T2DM) is one of the most prevalent chronic metabolic disorder characterized by insulin resistance and relative insulin deficiency. PPARδ activation has been reported to have several beneficial effects in alleviating dyslipidemia and insulin resistance. GW501516, a synthetic PPARδ agonist, was developed to target hyperlipidemia and reported to alleviating insulin resistance in T2DM. Studies indicate that PPARδ activation by GW501516 can reduce adiposity, enhance β-oxidation of fatty acids, and improve insulin sensitivity in T2DM animal models. Despite its therapeutic promise, potential carcinogenic effects also have been reported. Therefore, a comprehensive non-targeted and targeted lipidomics study was carried out to evaluate the regulatory effect of GW501516 in the plasma of db/db mice. The results revealed that GW501516 is effective in reducing the accumulation of lipids in the fatty acid metabolism pathway and lipid classes including triglycerides and phosphatidylglycerols. Furthermore, activation of PPARδ by GW501516 demonstrated a beneficial effect on improving circulating cholesterol homeostasis. However, while the levels of hexosylceramides and sphingomyelin were partially reversed, ceramide levels, which are negatively associated with insulin sensitivity, were significantly elevated by GW501516. Despite these mixed outcomes, the study highlights both the promising therapeutic potential of PPARδ activation in metabolic disorders and the safety concerns regarding long-term clinical use. The findings provide valuable insights into the impact of GW501516-induced PPARδ activation on lipid metabolism in T2DM, contributing to a better understanding of its therapeutic potential and risks.
2025, 36(11): 110916
doi: 10.1016/j.cclet.2025.110916
Abstract:
Nanozymes, characterized by their stability, cost-effectiveness, and tunable catalytic activity, are promising alternatives to natural enzymes. However, specifically mimicking a single natural enzyme's activity presents a challenge. By exploiting the catalytic selectivity derived from the valence-band hybridization of noble metal nanoalloys, we introduce an alloying strategy to modulate the reaction specificity of metallic nanozymes. AgPd nanoalloy exhibits enhanced peroxidase-like activity and eliminated oxidase-like activity by adjusting the Ag content. The introduction of Ag changes the hybrid d band energy of the alloyed metal and inhibits the O2 adsorption and decomposition on Pd, while improving the peroxidase mimicry by allowing for the H2O2 activation. By exemplifying the construction of a highly sensitive and selective colorimetric glucose detection platform with its practicality validated in serum samples, this strategy pioneers a multi-noble metal nanozyme with tailored peroxidase activity based on the chemical structure engineering and would advance the development of single-catalytic function nanozymes for building exclusively specific biosensors through reducing substrate competition.
Nanozymes, characterized by their stability, cost-effectiveness, and tunable catalytic activity, are promising alternatives to natural enzymes. However, specifically mimicking a single natural enzyme's activity presents a challenge. By exploiting the catalytic selectivity derived from the valence-band hybridization of noble metal nanoalloys, we introduce an alloying strategy to modulate the reaction specificity of metallic nanozymes. AgPd nanoalloy exhibits enhanced peroxidase-like activity and eliminated oxidase-like activity by adjusting the Ag content. The introduction of Ag changes the hybrid d band energy of the alloyed metal and inhibits the O2 adsorption and decomposition on Pd, while improving the peroxidase mimicry by allowing for the H2O2 activation. By exemplifying the construction of a highly sensitive and selective colorimetric glucose detection platform with its practicality validated in serum samples, this strategy pioneers a multi-noble metal nanozyme with tailored peroxidase activity based on the chemical structure engineering and would advance the development of single-catalytic function nanozymes for building exclusively specific biosensors through reducing substrate competition.
2025, 36(11): 110935
doi: 10.1016/j.cclet.2025.110935
Abstract:
Purely organic room-temperature phosphorescence (RTP) and fluorescence dual-emission materials in aqueous solution have attracted growing attention. Herein, we report a fluorescence-phosphorescence dual emission host-guest complex by simple assembly of cucurbit[8]uril (CB[8]) and 4-(4-bromophenyl)pyridinium derivative in water. Macrocyclic confinement and unique 1:2 host-guest structure could effectively inhibit non-radiative transition of the guest and the quenching of water molecule, thus induce effective RTP emission in water (τRTP = 0.472 ms, ΦRTP = 1.37%). Specifically, based on competitive binding, this host-guest complex exhibits rapid ratiometric luminescent detection behavior to 3-nitrotyrosine, a specific biomarker of kidney injury, with a low limit of detection of 10.7 nmol/L. This work highlights the great potential of macrocyclic-confinement-derived RTP materials in biomarker detection, and will undoubtedly broaden the utilization scope of RTP.
Purely organic room-temperature phosphorescence (RTP) and fluorescence dual-emission materials in aqueous solution have attracted growing attention. Herein, we report a fluorescence-phosphorescence dual emission host-guest complex by simple assembly of cucurbit[8]uril (CB[8]) and 4-(4-bromophenyl)pyridinium derivative in water. Macrocyclic confinement and unique 1:2 host-guest structure could effectively inhibit non-radiative transition of the guest and the quenching of water molecule, thus induce effective RTP emission in water (τRTP = 0.472 ms, ΦRTP = 1.37%). Specifically, based on competitive binding, this host-guest complex exhibits rapid ratiometric luminescent detection behavior to 3-nitrotyrosine, a specific biomarker of kidney injury, with a low limit of detection of 10.7 nmol/L. This work highlights the great potential of macrocyclic-confinement-derived RTP materials in biomarker detection, and will undoubtedly broaden the utilization scope of RTP.
2025, 36(11): 110939
doi: 10.1016/j.cclet.2025.110939
Abstract:
The Scholl cyclization for creating seven-membered rings is of great importance in synthesizing negatively curved polycyclic aromatic compounds. In this study, we systematically report a methodical approach for converting [6]helicenes into negatively curved hexa[7]circulene using Scholl cyclization. The reaction revealed that the electron-donating substituents on the helicene terminal rings of helicenes facilitate the cyclization process while electron-withdrawing substituents would impede the cyclization. This was supported by theoretical calculations on the reaction process focusing on the arenium cation pathways. Through the application of this Scholl cyclization, a series of negatively curved hexa[7]circulene derivatives were synthesized, showing highly curved and twisted geometries. Notably, 2,15-substituted derivatives exhibited high conformational stability against racemization, thereby performing circularly polarized luminescence with |glum| up to 4 × 10−3.
The Scholl cyclization for creating seven-membered rings is of great importance in synthesizing negatively curved polycyclic aromatic compounds. In this study, we systematically report a methodical approach for converting [6]helicenes into negatively curved hexa[7]circulene using Scholl cyclization. The reaction revealed that the electron-donating substituents on the helicene terminal rings of helicenes facilitate the cyclization process while electron-withdrawing substituents would impede the cyclization. This was supported by theoretical calculations on the reaction process focusing on the arenium cation pathways. Through the application of this Scholl cyclization, a series of negatively curved hexa[7]circulene derivatives were synthesized, showing highly curved and twisted geometries. Notably, 2,15-substituted derivatives exhibited high conformational stability against racemization, thereby performing circularly polarized luminescence with |glum| up to 4 × 10−3.
2025, 36(11): 110945
doi: 10.1016/j.cclet.2025.110945
Abstract:
Herein, we report the first asymmetric synthesis of illihenin A, an antiviral sesquiterpenoid bearing a cage-like tricyclo[6.2.2.01,5]dodecane skeleton. Starting from an abundant feedstock (-)-α-cedrene, this 19-step synthesis approach features a novel ring-reorganization strategy that includes early stage C7-hydroxylation of the cedrane skeleton and a later-stage ring disassembly-reassembly procedure, affording the desired product with high synthetic efficiency and minimal chiral manipulation. The key transformations include the following: (ⅰ) a hydroxy group-directed SmI2-mediated reductive coupling to construct the congested tertiary 7-OH cedrane, (ⅱ) a β-fragmentation triggered by an alkoxy radical to release a spiro[4.5]decane, and (ⅲ) an intramolecular Aldol reaction, concomitant with α-epimerization, to furnish the tricyclic framework. In addition, preliminary investigation of antiviral activity against CVB3 revealed that illihenin A can significantly inhibit ROS production and apoptosis.
Herein, we report the first asymmetric synthesis of illihenin A, an antiviral sesquiterpenoid bearing a cage-like tricyclo[6.2.2.01,5]dodecane skeleton. Starting from an abundant feedstock (-)-α-cedrene, this 19-step synthesis approach features a novel ring-reorganization strategy that includes early stage C7-hydroxylation of the cedrane skeleton and a later-stage ring disassembly-reassembly procedure, affording the desired product with high synthetic efficiency and minimal chiral manipulation. The key transformations include the following: (ⅰ) a hydroxy group-directed SmI2-mediated reductive coupling to construct the congested tertiary 7-OH cedrane, (ⅱ) a β-fragmentation triggered by an alkoxy radical to release a spiro[4.5]decane, and (ⅲ) an intramolecular Aldol reaction, concomitant with α-epimerization, to furnish the tricyclic framework. In addition, preliminary investigation of antiviral activity against CVB3 revealed that illihenin A can significantly inhibit ROS production and apoptosis.
2025, 36(11): 110946
doi: 10.1016/j.cclet.2025.110946
Abstract:
New water-soluble fluorescent tetracationic imidazolium-based macrocycles are synthesized via a modular SN2 nucleophilic substitution reaction. The positive charge and acidic C–H sites of these macrocycles enable them to bind with nucleotides in water, driven by hydrogen bonds and electrostatic interactions. The binding is high affinity for suitable nucleotides. These properties position them as promising candidates for the selective sensing of nucleotides.
New water-soluble fluorescent tetracationic imidazolium-based macrocycles are synthesized via a modular SN2 nucleophilic substitution reaction. The positive charge and acidic C–H sites of these macrocycles enable them to bind with nucleotides in water, driven by hydrogen bonds and electrostatic interactions. The binding is high affinity for suitable nucleotides. These properties position them as promising candidates for the selective sensing of nucleotides.
2025, 36(11): 110968
doi: 10.1016/j.cclet.2025.110968
Abstract:
Chemical reactions, which transform one set of substances to another, drive research in chemistry and biology. Recently, computer-aided chemical reaction prediction has spurred rapidly growing interest, and various deep learning–based algorithms have been proposed. However, current efforts primarily focus on developing models that support specific applications, with less emphasis on building unified frameworks that predict chemical reactions. Here, we developed Bidirectional Chemical Intelligent Net (BiCINet), a prediction framework based on Bidirectional and Auto-Regressive Transformers (BARTs), for predicting chemical reactions in various tasks, including the bidirectional prediction of organic synthesis and enzyme-mediated chemical reactions. This versatile framework was trained using general chemical reactions and achieved top-1 forward and backward accuracies of 80.7% and 48.6%, respectively, for the public benchmark dataset USPTO_50K. By multitask transfer learning and integrating various task prompts into the model, BiCINet enables retrosynthetic planning and metabolic prediction for small molecules, as well as retrosynthetic analysis and enzyme-catalyzed product prediction for natural products. These results demonstrate the superiority of our multifunctional framework for comprehensively understanding chemical reactions.
Chemical reactions, which transform one set of substances to another, drive research in chemistry and biology. Recently, computer-aided chemical reaction prediction has spurred rapidly growing interest, and various deep learning–based algorithms have been proposed. However, current efforts primarily focus on developing models that support specific applications, with less emphasis on building unified frameworks that predict chemical reactions. Here, we developed Bidirectional Chemical Intelligent Net (BiCINet), a prediction framework based on Bidirectional and Auto-Regressive Transformers (BARTs), for predicting chemical reactions in various tasks, including the bidirectional prediction of organic synthesis and enzyme-mediated chemical reactions. This versatile framework was trained using general chemical reactions and achieved top-1 forward and backward accuracies of 80.7% and 48.6%, respectively, for the public benchmark dataset USPTO_50K. By multitask transfer learning and integrating various task prompts into the model, BiCINet enables retrosynthetic planning and metabolic prediction for small molecules, as well as retrosynthetic analysis and enzyme-catalyzed product prediction for natural products. These results demonstrate the superiority of our multifunctional framework for comprehensively understanding chemical reactions.
2025, 36(11): 110982
doi: 10.1016/j.cclet.2025.110982
Abstract:
The controlled incorporation of heptagons into helicene frameworks offers a promising approach to modulate their structural and electronic properties. This study demonstrates the synthesis of two heptagon-embedded oxa-helicenes: one with a single heptagon (5) and another with two heptagons (6), achieved through controlled oxidative cyclization of a triple oxa-helicene (4). UV–vis absorption and emission spectra revealed red-shifts and slight increases in Stokes shifts from 4 to 6, attributed to π-system extension and greater structural relaxation in the excited state. 5 and 6 exhibited fluorescence quantum yields 2–3 times higher than 4. Chiral separation and thermal stability analyses showed a significant decrease in enantiomeric stability for 5 and 6 compared to 4, due to planarization effects induced by heptagon incorporation. The chiroptical properties were also investigated, revealing reduced optical dissymmetry factors after heptagon embedding.
The controlled incorporation of heptagons into helicene frameworks offers a promising approach to modulate their structural and electronic properties. This study demonstrates the synthesis of two heptagon-embedded oxa-helicenes: one with a single heptagon (5) and another with two heptagons (6), achieved through controlled oxidative cyclization of a triple oxa-helicene (4). UV–vis absorption and emission spectra revealed red-shifts and slight increases in Stokes shifts from 4 to 6, attributed to π-system extension and greater structural relaxation in the excited state. 5 and 6 exhibited fluorescence quantum yields 2–3 times higher than 4. Chiral separation and thermal stability analyses showed a significant decrease in enantiomeric stability for 5 and 6 compared to 4, due to planarization effects induced by heptagon incorporation. The chiroptical properties were also investigated, revealing reduced optical dissymmetry factors after heptagon embedding.
2025, 36(11): 110983
doi: 10.1016/j.cclet.2025.110983
Abstract:
Alduronic acid lactones and glyconolactones are highly functionalized and versatile chiral building blocks. Herein, we describe a novel approach to these compounds via decarboxylative oxygenation of uronic acids. The transformations proceed using Selectfluor and TEMPO as oxidants, either in the presence of catalytic amounts of Ag2CO3 or in the absence of this catalyst. The methodology provides structurally diverse alduronic acid lactones and enables the preparation of rare sugar glyconolactones from easily available D-C-glycosides. Based on the 18O-labeling experiments, control experiments, and isolation of the key intermediates, a radical-polar crossover reaction mechanism is proposed. The utility of this method is demonstrated through efficient conversions of alduronic acid lactones into polyhydroxylated cyclic alkaloids and castanospermine-type architectures.
Alduronic acid lactones and glyconolactones are highly functionalized and versatile chiral building blocks. Herein, we describe a novel approach to these compounds via decarboxylative oxygenation of uronic acids. The transformations proceed using Selectfluor and TEMPO as oxidants, either in the presence of catalytic amounts of Ag2CO3 or in the absence of this catalyst. The methodology provides structurally diverse alduronic acid lactones and enables the preparation of rare sugar glyconolactones from easily available D-C-glycosides. Based on the 18O-labeling experiments, control experiments, and isolation of the key intermediates, a radical-polar crossover reaction mechanism is proposed. The utility of this method is demonstrated through efficient conversions of alduronic acid lactones into polyhydroxylated cyclic alkaloids and castanospermine-type architectures.
2025, 36(11): 111024
doi: 10.1016/j.cclet.2025.111024
Abstract:
A series of [1, 1′-binaphthalene]-2, 2′-diol-pyrene (BINOL-Py) functionalized pillar[5]arenes with different spacer lengths were synthesized and separated by chiral HPLC to obtain their enantiomers. We elucidated the synergistic effect of the planar chirality of pillar[5]arenes and axial chirality of BINOL on the circularly polarized luminescence (CPL) behaviors of hybrid chiral BINOL-Py functionalized pillar[5]arenes, achieving high glum up to 1.7 × 10–2. In addition, ascribed to the regulation of chirality information transmission through planar chirality of pillar[5]arenes, the resolved BINOL-Py functionalized pillar[5]arenes reveal unique tunable circular dichroism (CD) and CPL in different aggregation state and upon the addition of guest, providing not only a novel design strategy for developing molecular systems with chiroptical tunability but also an intriguing platform for the construction of CPL luminescent materials based on chiral macrocycles.
A series of [1, 1′-binaphthalene]-2, 2′-diol-pyrene (BINOL-Py) functionalized pillar[5]arenes with different spacer lengths were synthesized and separated by chiral HPLC to obtain their enantiomers. We elucidated the synergistic effect of the planar chirality of pillar[5]arenes and axial chirality of BINOL on the circularly polarized luminescence (CPL) behaviors of hybrid chiral BINOL-Py functionalized pillar[5]arenes, achieving high glum up to 1.7 × 10–2. In addition, ascribed to the regulation of chirality information transmission through planar chirality of pillar[5]arenes, the resolved BINOL-Py functionalized pillar[5]arenes reveal unique tunable circular dichroism (CD) and CPL in different aggregation state and upon the addition of guest, providing not only a novel design strategy for developing molecular systems with chiroptical tunability but also an intriguing platform for the construction of CPL luminescent materials based on chiral macrocycles.
2025, 36(11): 111050
doi: 10.1016/j.cclet.2025.111050
Abstract:
The carbon–carbon bond is the one of the most fundamental and abundant bonds that exist in organic molecules, and the challenge of functionalization of carbon–carbon bond has always been a critical pursuit in organic synthesis. In recent years, there have been a growing number of studies on the C–C bond activation. Nevertheless, the metal-catalyzed cleavage of the C–C(O) bond in unstrained ketones has remained relatively underexplored due to the strong affinity of carbonyl groups for metals. In this study, we report a nickel-catalyzed strategy for the reductive alkynylation of ketoimines via β-carbon elimination. This method involves the conversion of aryl ketones into aryl ketoimines, thus expanding the toolbox of aryl electrophiles. The use of a N-heterocyclic carbene (NHC) ligand is crucial for this catalytic transformation. This discovery leads to a cross electrophile coupling reaction characterized by its operational simplicity, unique chemo-selectivity and excellent functional group tolerance. In addition, the approach has been effectively applied to the late-stage alkynylation of diverse pharmaceuticals. Ultimately, a series of comprehensive experiments and theoretical studies were conducted to provide insights into the reaction pathway, which supports the proposed β-carbon elimination process.
The carbon–carbon bond is the one of the most fundamental and abundant bonds that exist in organic molecules, and the challenge of functionalization of carbon–carbon bond has always been a critical pursuit in organic synthesis. In recent years, there have been a growing number of studies on the C–C bond activation. Nevertheless, the metal-catalyzed cleavage of the C–C(O) bond in unstrained ketones has remained relatively underexplored due to the strong affinity of carbonyl groups for metals. In this study, we report a nickel-catalyzed strategy for the reductive alkynylation of ketoimines via β-carbon elimination. This method involves the conversion of aryl ketones into aryl ketoimines, thus expanding the toolbox of aryl electrophiles. The use of a N-heterocyclic carbene (NHC) ligand is crucial for this catalytic transformation. This discovery leads to a cross electrophile coupling reaction characterized by its operational simplicity, unique chemo-selectivity and excellent functional group tolerance. In addition, the approach has been effectively applied to the late-stage alkynylation of diverse pharmaceuticals. Ultimately, a series of comprehensive experiments and theoretical studies were conducted to provide insights into the reaction pathway, which supports the proposed β-carbon elimination process.
2025, 36(11): 111068
doi: 10.1016/j.cclet.2025.111068
Abstract:
Herein, anthracene-pyridinium derivative (A1) is synthesized to assemble with amphiphilic sulfonatocalix[4]arene (SC4AD) with a porous cavity through electrostatic interaction, exhibiting enhanced fluorescence emission and multipath fluorescence resonance energy transfer (FRET) with organic dyes (EY, NiR or Cy5.5). In this nanoassembly, A1/SC4AD first transfers the energy to dye EY (first acceptor), and then delivers it to NiR (second acceptor), which further transfers the energy to Cy5.5 (third acceptor), accompanying with an emission ranging from 535 nm to 570 nm, then to 638 nm, and finally to near-infrared emission at 717 nm. Compared to one-step FRET (43.0%), the three-step FRET system shows higher energy transfer efficiency (FRET Ⅰ: 84.9%, FRET Ⅱ: 81.4%, FRET Ⅲ: 66.9%). The donor/acceptor ratio is 3000 (A1): 20 (EY): 8 (NiR): 5 (Cy5.5), together with an antenna effect of 2.3. Additionally, diverse two-step cascade light-harvesting systems are successfully fabricated via tuning combination of dye acceptors. We believe that this multipath light-harvesting assembly will provide a direction for designing multiple sequential FRET and artificial light-harvesting systems.
Herein, anthracene-pyridinium derivative (A1) is synthesized to assemble with amphiphilic sulfonatocalix[4]arene (SC4AD) with a porous cavity through electrostatic interaction, exhibiting enhanced fluorescence emission and multipath fluorescence resonance energy transfer (FRET) with organic dyes (EY, NiR or Cy5.5). In this nanoassembly, A1/SC4AD first transfers the energy to dye EY (first acceptor), and then delivers it to NiR (second acceptor), which further transfers the energy to Cy5.5 (third acceptor), accompanying with an emission ranging from 535 nm to 570 nm, then to 638 nm, and finally to near-infrared emission at 717 nm. Compared to one-step FRET (43.0%), the three-step FRET system shows higher energy transfer efficiency (FRET Ⅰ: 84.9%, FRET Ⅱ: 81.4%, FRET Ⅲ: 66.9%). The donor/acceptor ratio is 3000 (A1): 20 (EY): 8 (NiR): 5 (Cy5.5), together with an antenna effect of 2.3. Additionally, diverse two-step cascade light-harvesting systems are successfully fabricated via tuning combination of dye acceptors. We believe that this multipath light-harvesting assembly will provide a direction for designing multiple sequential FRET and artificial light-harvesting systems.
2025, 36(11): 111133
doi: 10.1016/j.cclet.2025.111133
Abstract:
Porphyrin-based photodynamic therapy (PDT) has emerged as a promising approach in clinic. However, its therapeutic efficacy is remarkedly constrained due to the intrinsic hydrophobicity of porphyrins and their limited absorption in the near-infrared (NIR) region. Inspired by the unique supramolecular structures and optical properties of pigment-binding proteins during photosynthesis, we herein developed a carbon dot derived from porphyrin and amino acid mixture (TPP-AA-CDs) for efficient PDT. Having precisely tuned the optical properties of TPP-AA-CDs in the range of visible to NIR region, such a pigment-binding protein-mimicking system leveraged the hydrophilic amino acid-hybrid framework as a light-harvesting scaffold to support the hydrophobic porphyrin centre. TPP-AA-CDs exhibited enhanced light-harvesting efficiency in the presence of amino and hydroxyl residues from amino acid side chains, which facilitate the incorporation of porphyrin within the framework. Among the variants, histidine-derived carbon dots (TPP-H-CDs) performed markedly improved PDT efficiency with high biocompatibility, leading to accelerated wound healing and boosted antitumor effects under NIR light irradiation. This light-harvesting pigment-binding protein-mimicking framework that scaffolded the porphyrin, offered a promising strategy for developing the next-generation of efficient NIR-absorbing materials with potential clinical translations.
Porphyrin-based photodynamic therapy (PDT) has emerged as a promising approach in clinic. However, its therapeutic efficacy is remarkedly constrained due to the intrinsic hydrophobicity of porphyrins and their limited absorption in the near-infrared (NIR) region. Inspired by the unique supramolecular structures and optical properties of pigment-binding proteins during photosynthesis, we herein developed a carbon dot derived from porphyrin and amino acid mixture (TPP-AA-CDs) for efficient PDT. Having precisely tuned the optical properties of TPP-AA-CDs in the range of visible to NIR region, such a pigment-binding protein-mimicking system leveraged the hydrophilic amino acid-hybrid framework as a light-harvesting scaffold to support the hydrophobic porphyrin centre. TPP-AA-CDs exhibited enhanced light-harvesting efficiency in the presence of amino and hydroxyl residues from amino acid side chains, which facilitate the incorporation of porphyrin within the framework. Among the variants, histidine-derived carbon dots (TPP-H-CDs) performed markedly improved PDT efficiency with high biocompatibility, leading to accelerated wound healing and boosted antitumor effects under NIR light irradiation. This light-harvesting pigment-binding protein-mimicking framework that scaffolded the porphyrin, offered a promising strategy for developing the next-generation of efficient NIR-absorbing materials with potential clinical translations.
2025, 36(11): 111150
doi: 10.1016/j.cclet.2025.111150
Abstract:
Carboxylic acid derivatives with α-quaternary carbon center are one of the most ubiquitous moieties in synthetic and medicinal chemistry. Hence, novel and efficient synthetic methods towards carboxylic acid derivatives with α-quaternary carbon remain in high demand. However, most of the precursors of these complex compounds are not easy to prepare. Reported herein is a carbonylative five-component synthesis of amides and esters with α-quaternary carbon center enabled by palladium catalysis from abundant acrylonitrile, carbon monoxide, fluoroalkyl halides, and nucleophiles. Diverse amides and esters with α-quaternary carbon which contain difluoromethyl or perfluoroalkyl moiety were prepared in good to excellent yields, providing an efficient synthetic platform for sequential transformations.
Carboxylic acid derivatives with α-quaternary carbon center are one of the most ubiquitous moieties in synthetic and medicinal chemistry. Hence, novel and efficient synthetic methods towards carboxylic acid derivatives with α-quaternary carbon remain in high demand. However, most of the precursors of these complex compounds are not easy to prepare. Reported herein is a carbonylative five-component synthesis of amides and esters with α-quaternary carbon center enabled by palladium catalysis from abundant acrylonitrile, carbon monoxide, fluoroalkyl halides, and nucleophiles. Diverse amides and esters with α-quaternary carbon which contain difluoromethyl or perfluoroalkyl moiety were prepared in good to excellent yields, providing an efficient synthetic platform for sequential transformations.
2025, 36(11): 111190
doi: 10.1016/j.cclet.2025.111190
Abstract:
Lithium-ion batteries (LIBs) are increasingly required to operate under harsh conditions, particularly at low-temperature condition. Developing novel electrolytes is a facile and effective approach to elevate the electrochemical performances of LIBs at low temperature. Herein, a dual-salt electrolyte consisting of (lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium difluoro(oxalato)borate (LiODFB)) is proposed to regulate the solvation structure of Li+ ions and improve the reaction kinetics under low temperature. Based on the comprehensive electrochemical tests and theoretical computations, the introduction of LiODFB component not only effectively benefits the formation of cathode electrolyte interface (CEI) layer on the surface of LiFePO4 electrode, but also inhibits the chemical corrosion effect of LiTFSI-containing electrolytes on Al foil. As expected, the optimized LiLiFePO4 cells can display high reversible capacity of 117.0 mAh/g after 100 cycles at -20 ℃. This work provides both theoretical basis and experimental guidance for the rational design of low-temperature resistant electrolytes.
Lithium-ion batteries (LIBs) are increasingly required to operate under harsh conditions, particularly at low-temperature condition. Developing novel electrolytes is a facile and effective approach to elevate the electrochemical performances of LIBs at low temperature. Herein, a dual-salt electrolyte consisting of (lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium difluoro(oxalato)borate (LiODFB)) is proposed to regulate the solvation structure of Li+ ions and improve the reaction kinetics under low temperature. Based on the comprehensive electrochemical tests and theoretical computations, the introduction of LiODFB component not only effectively benefits the formation of cathode electrolyte interface (CEI) layer on the surface of LiFePO4 electrode, but also inhibits the chemical corrosion effect of LiTFSI-containing electrolytes on Al foil. As expected, the optimized LiLiFePO4 cells can display high reversible capacity of 117.0 mAh/g after 100 cycles at -20 ℃. This work provides both theoretical basis and experimental guidance for the rational design of low-temperature resistant electrolytes.
2025, 36(11): 111286
doi: 10.1016/j.cclet.2025.111286
Abstract:
The selective addition reaction of unsaturated C–C bonds has always been a classic and constant research topic. Different from well-developed hydroboration, hydrosilylation, and hydrostannylation reaction, hydrogermylation reaction remains challenging which hasn't been much reported. Herein, we developed a new metal-porous ligand polymers Pd1@POL-PPhnCym (n + m = 3) with monoatomic dispersion characteristics for highly selective and efficient hydrogermylation of unsaturated C–C bonds, including alkynes, alkenes, and allenes. X-ray photoelectron spectroscopy and theoretical calculations further proved the introduction of cyclohexyl could gently adjust the charge on monoatomic Pd center which effectively facilitate the recognition and transformation of various substrates. With the electrically fine-tuned single atom palladium catalysts, we realized the α-germanium addition for the first time, obtaining corresponding allyl germanium and alkyl germanium compounds.
The selective addition reaction of unsaturated C–C bonds has always been a classic and constant research topic. Different from well-developed hydroboration, hydrosilylation, and hydrostannylation reaction, hydrogermylation reaction remains challenging which hasn't been much reported. Herein, we developed a new metal-porous ligand polymers Pd1@POL-PPhnCym (n + m = 3) with monoatomic dispersion characteristics for highly selective and efficient hydrogermylation of unsaturated C–C bonds, including alkynes, alkenes, and allenes. X-ray photoelectron spectroscopy and theoretical calculations further proved the introduction of cyclohexyl could gently adjust the charge on monoatomic Pd center which effectively facilitate the recognition and transformation of various substrates. With the electrically fine-tuned single atom palladium catalysts, we realized the α-germanium addition for the first time, obtaining corresponding allyl germanium and alkyl germanium compounds.
2025, 36(11): 111374
doi: 10.1016/j.cclet.2025.111374
Abstract:
Thiol-ene click polymerization has become an effective synthetic tool for constructing diverse sulfur-containing polymers with advanced functions. However, the polymerization of internal alkene and thiol has been rarely used to prepare functional polymers because of large steric hindrance and relatively weak reactivity. In this work, a base-catalyzed click polymerization of thiols and internal olefins was successfully established in air. Notably, the polymerization went smoothly in halogen-containing solvent even without any catalyst via a radical step-growth polymerization. The polymerization enjoys excellent monomer applicability, which affords 16 well-defined polythioethers in high yields (up to 99%) with high molecular weights (Mw up to 19,600), good thermal stability (Td,5% up to 326 ℃), broadly regulated glass transition temperatures (-24~95 ℃), and unconventional fluorescence. Via a simple solvent regulation strategy, the vanillin-derived polythioether could be used as a turn-off fluorescence probe for Fe3+ ions in DMF/H2O and a turn-on probe for Ag+ ions in THF, with low detection limits of 9.15 × 10–7 mol/L and 4.60 × 10–7 mol/L, respectively. Additionally, the detection of Ag+ presented a transformation from a clear solution to an emulsion, expanding the application prospects through observing colorimetric and fluorescent dual signals. Thus, this work not only holds significance in establishing an efficient polymerization, but also provides a strategy to prepare sensitive fluorescent probes for multiple metal ions.
Thiol-ene click polymerization has become an effective synthetic tool for constructing diverse sulfur-containing polymers with advanced functions. However, the polymerization of internal alkene and thiol has been rarely used to prepare functional polymers because of large steric hindrance and relatively weak reactivity. In this work, a base-catalyzed click polymerization of thiols and internal olefins was successfully established in air. Notably, the polymerization went smoothly in halogen-containing solvent even without any catalyst via a radical step-growth polymerization. The polymerization enjoys excellent monomer applicability, which affords 16 well-defined polythioethers in high yields (up to 99%) with high molecular weights (Mw up to 19,600), good thermal stability (Td,5% up to 326 ℃), broadly regulated glass transition temperatures (-24~95 ℃), and unconventional fluorescence. Via a simple solvent regulation strategy, the vanillin-derived polythioether could be used as a turn-off fluorescence probe for Fe3+ ions in DMF/H2O and a turn-on probe for Ag+ ions in THF, with low detection limits of 9.15 × 10–7 mol/L and 4.60 × 10–7 mol/L, respectively. Additionally, the detection of Ag+ presented a transformation from a clear solution to an emulsion, expanding the application prospects through observing colorimetric and fluorescent dual signals. Thus, this work not only holds significance in establishing an efficient polymerization, but also provides a strategy to prepare sensitive fluorescent probes for multiple metal ions.
2025, 36(11): 111382
doi: 10.1016/j.cclet.2025.111382
Abstract:
Developing polymer materials combining high strength, toughness, multifunctionality, and environmental sustainability remains a major challenge. Herein, high-performance PVA-PCSx composite films were successfully fabricated by incorporating H3PO3-protonated chitosan (PCS) into the PVA matrix as both a bio-based multi-hydrogen-bonding crosslinking agent and a macromolecular flame retardant. Specifically, a comprehensive investigation was conducted on the hydrogen bonding interactions, microstructure, mechanical properties, antibacterial performance, and flame retardancy of the PVA-PCSx films. Strong hydrogen bonds between PCS and PVA enabled excellent compatibility and formed a unique mechanical interlocking interface architecture. This further resulted in superior transparency and synchronous reinforcement and toughening effects in the composites films. Compared with pure PVA, the PVA-PCSx films showed a 23%-51% increase in tensile strength and an 80%-108% improvement in fracture toughness. Moreover, PVA-PCSx films exhibited superior fire safety performance, achieving an LOI value of 31.3%, attaining UL-94 V-0 rating, and reducing the heat release rate by up to 73.1%. Additionally, PVA-PCSx films demonstrated 99.99% antibacterial efficacy against both Escherichia coli and Staphylococcus aureus. Collectively, this study presents a simple yet effective strategy for fabricating high-strength, high-toughness, multifunctional composites using biopolysaccharides as additives.
Developing polymer materials combining high strength, toughness, multifunctionality, and environmental sustainability remains a major challenge. Herein, high-performance PVA-PCSx composite films were successfully fabricated by incorporating H3PO3-protonated chitosan (PCS) into the PVA matrix as both a bio-based multi-hydrogen-bonding crosslinking agent and a macromolecular flame retardant. Specifically, a comprehensive investigation was conducted on the hydrogen bonding interactions, microstructure, mechanical properties, antibacterial performance, and flame retardancy of the PVA-PCSx films. Strong hydrogen bonds between PCS and PVA enabled excellent compatibility and formed a unique mechanical interlocking interface architecture. This further resulted in superior transparency and synchronous reinforcement and toughening effects in the composites films. Compared with pure PVA, the PVA-PCSx films showed a 23%-51% increase in tensile strength and an 80%-108% improvement in fracture toughness. Moreover, PVA-PCSx films exhibited superior fire safety performance, achieving an LOI value of 31.3%, attaining UL-94 V-0 rating, and reducing the heat release rate by up to 73.1%. Additionally, PVA-PCSx films demonstrated 99.99% antibacterial efficacy against both Escherichia coli and Staphylococcus aureus. Collectively, this study presents a simple yet effective strategy for fabricating high-strength, high-toughness, multifunctional composites using biopolysaccharides as additives.
2025, 36(11): 111393
doi: 10.1016/j.cclet.2025.111393
Abstract:
Designing efficient and stable electrocatalysts for the oxygen evolution reaction (OER) is of paramount importance for many energy-related technologies and devices. Herein, we propose a controlled oxidation pyrolysis strategy to develop carbonized polymer dots (CPDs)-modified Rh-doped RuO2 electrocatalyst (Rh-RuO2/CPDs). CPDs act as structure-directing agents, facilitating the formation of small-sized Rh-RuO2/CPDs nanoparticles and engineering them with abundant defective structures and stable Ru-O sites. The experimental results and theoretical simulation unravel that the modulation effect of CPDs and Rh doping can effectively regulate the electronic structure, valence state and morphology of active Ru-O sites, thereby enhancing the electron transfer at the active site interface and optimizing the chemisorption behavior of oxygen intermediates. The resultant Rh-RuO2/CPDs demonstrates overpotentials of 168 and 197 mV at 10 mA/cm2 for OER in 0.5 mol/L H2SO4 and 1.0 mol/L KOH solution, respectively, and long-term catalytic stability.
Designing efficient and stable electrocatalysts for the oxygen evolution reaction (OER) is of paramount importance for many energy-related technologies and devices. Herein, we propose a controlled oxidation pyrolysis strategy to develop carbonized polymer dots (CPDs)-modified Rh-doped RuO2 electrocatalyst (Rh-RuO2/CPDs). CPDs act as structure-directing agents, facilitating the formation of small-sized Rh-RuO2/CPDs nanoparticles and engineering them with abundant defective structures and stable Ru-O sites. The experimental results and theoretical simulation unravel that the modulation effect of CPDs and Rh doping can effectively regulate the electronic structure, valence state and morphology of active Ru-O sites, thereby enhancing the electron transfer at the active site interface and optimizing the chemisorption behavior of oxygen intermediates. The resultant Rh-RuO2/CPDs demonstrates overpotentials of 168 and 197 mV at 10 mA/cm2 for OER in 0.5 mol/L H2SO4 and 1.0 mol/L KOH solution, respectively, and long-term catalytic stability.
2025, 36(11): 111394
doi: 10.1016/j.cclet.2025.111394
Abstract:
Building heterojunctions has proven its efficiency in promoting charge separation for highly efficient photocatalysis. However, most heterojunctions often suffer from inadequate interfacial contact between the two semiconductor phases, hindering charge separation and producing suboptimal photocatalytic performance. Herein, leveraging the soft lattice feature of halide perovskite, we intentionally introduced In2O3 nanoparticles as seeds in situ during the crystallization process of CsPbBr3, constructing In2O3/CsPbBr3 heterojunction with intimate and abundant interface contact. Through in situ X-ray photoelectron spectroscopy and band structure analysis, we revealed the creation of a direct Z-type heterojunction that combines the catalytic advantages of both CsPbBr3 and In2O3 for CO2 reduction and water oxidation, respectively. The enhanced interfacial contact further enables this heterojunction to separate more photogenerated charges and prolong carrier lifetime effectively. Benefiting from the improved charge utilization, as well as the chemisorption and activation of CO2 molecules on the catalyst, the In2O3/CsPbBr3 heterojunction exhibits significantly enhanced performance in CO2 photoreduction, achieving a 3.8-fold increase in the photoelectron consumption rate as compared to that of CsPbBr3 alone. This study emphasizes the critical importance of a tight and rich heterojunction interface in achieving efficient photocatalytic reactions.
Building heterojunctions has proven its efficiency in promoting charge separation for highly efficient photocatalysis. However, most heterojunctions often suffer from inadequate interfacial contact between the two semiconductor phases, hindering charge separation and producing suboptimal photocatalytic performance. Herein, leveraging the soft lattice feature of halide perovskite, we intentionally introduced In2O3 nanoparticles as seeds in situ during the crystallization process of CsPbBr3, constructing In2O3/CsPbBr3 heterojunction with intimate and abundant interface contact. Through in situ X-ray photoelectron spectroscopy and band structure analysis, we revealed the creation of a direct Z-type heterojunction that combines the catalytic advantages of both CsPbBr3 and In2O3 for CO2 reduction and water oxidation, respectively. The enhanced interfacial contact further enables this heterojunction to separate more photogenerated charges and prolong carrier lifetime effectively. Benefiting from the improved charge utilization, as well as the chemisorption and activation of CO2 molecules on the catalyst, the In2O3/CsPbBr3 heterojunction exhibits significantly enhanced performance in CO2 photoreduction, achieving a 3.8-fold increase in the photoelectron consumption rate as compared to that of CsPbBr3 alone. This study emphasizes the critical importance of a tight and rich heterojunction interface in achieving efficient photocatalytic reactions.
2025, 36(11): 111417
doi: 10.1016/j.cclet.2025.111417
Abstract:
Metal-free electrocatalysts for the oxygen evolution reaction (OER) are gaining attention for their low cost, high conductivity, and moderate catalytic performance. While trace metal interference in as-synthesized catalysts has been ruled out, the impact of trace metal contamination during electrochemical activation remains unexplored. This study demonstrates that anodic pretreatment in alkaline electrolytes enhances the catalytic performance of carbon cloth. Specifically, carbon cloth activated in 8 mol/L NaOH achieves a current density of 10 mA/cm2 with an overpotential of only 338 mV, comparable to metal-based OER catalysts. Electrochemical and spectroscopic analyses show the deposition of FeNiOxHy oxyhydroxides (0.19 ± 0.06 µg/cm2) on specific sites of the carbon substrate during activation. These nanoparticles contribute significantly to the catalytic activity, with a synergistic effect between FeNiOxHy and the carbon substrate. The turnover frequency (TOF) for Fe correlates with the amount of C=O groups on the carbon substrate, providing evidence for an interfacial synergistic effect. This work emphasizes the importance of considering trace metal effects in metal-free catalyst evaluation and offers insights for the design of more efficient carbon-based hybrid OER catalysts.
Metal-free electrocatalysts for the oxygen evolution reaction (OER) are gaining attention for their low cost, high conductivity, and moderate catalytic performance. While trace metal interference in as-synthesized catalysts has been ruled out, the impact of trace metal contamination during electrochemical activation remains unexplored. This study demonstrates that anodic pretreatment in alkaline electrolytes enhances the catalytic performance of carbon cloth. Specifically, carbon cloth activated in 8 mol/L NaOH achieves a current density of 10 mA/cm2 with an overpotential of only 338 mV, comparable to metal-based OER catalysts. Electrochemical and spectroscopic analyses show the deposition of FeNiOxHy oxyhydroxides (0.19 ± 0.06 µg/cm2) on specific sites of the carbon substrate during activation. These nanoparticles contribute significantly to the catalytic activity, with a synergistic effect between FeNiOxHy and the carbon substrate. The turnover frequency (TOF) for Fe correlates with the amount of C=O groups on the carbon substrate, providing evidence for an interfacial synergistic effect. This work emphasizes the importance of considering trace metal effects in metal-free catalyst evaluation and offers insights for the design of more efficient carbon-based hybrid OER catalysts.
2025, 36(11): 111440
doi: 10.1016/j.cclet.2025.111440
Abstract:
Iron-nitrogen-carbon (Fe-N-C) materials with Fe-N4 structures have been considered as the most promising alternatives of scarce and precious platinum (Pt) for oxygen reduction reaction. Particularly, the high-temperature pyrolysis of a precursor mixture of N-containing amine polymers, Fe salts, and carbon supports, has become a popular method for the synthesis of high-performance Fe-N-C catalysts. The oxidative polymerization of amine monomers can usually proceed under acidic conditions, however, the acid-caused protonation of N-groups is not conducive to their coordination with Fe ions for the formation of high-density Fe-N4 sites. Here, we propose a protonation elimination strategy of soaking the polymerization products in alkaline solutions to increase Fe-N4 active sites. Theoretical calculations display that the Gibbs free energy change values of binding reactions between Fe ions and N-groups are -3.70 and -26.99 kcal/mol at pH 0 and 7, respectively, suggesting that the deprotonation can facilitate the Fe-N coordination. There is a two-fold increase in the number of Fe-N4 active sites for final Fe-N-C catalyst which exhibits significantly enhanced ORR activity and excellent Zn-air battery performance. This deprotonation effect can be applied to different amine compounds and transition-metal ions as a universal strategy for the development of preeminent non-precious metal carbon catalysts.
Iron-nitrogen-carbon (Fe-N-C) materials with Fe-N4 structures have been considered as the most promising alternatives of scarce and precious platinum (Pt) for oxygen reduction reaction. Particularly, the high-temperature pyrolysis of a precursor mixture of N-containing amine polymers, Fe salts, and carbon supports, has become a popular method for the synthesis of high-performance Fe-N-C catalysts. The oxidative polymerization of amine monomers can usually proceed under acidic conditions, however, the acid-caused protonation of N-groups is not conducive to their coordination with Fe ions for the formation of high-density Fe-N4 sites. Here, we propose a protonation elimination strategy of soaking the polymerization products in alkaline solutions to increase Fe-N4 active sites. Theoretical calculations display that the Gibbs free energy change values of binding reactions between Fe ions and N-groups are -3.70 and -26.99 kcal/mol at pH 0 and 7, respectively, suggesting that the deprotonation can facilitate the Fe-N coordination. There is a two-fold increase in the number of Fe-N4 active sites for final Fe-N-C catalyst which exhibits significantly enhanced ORR activity and excellent Zn-air battery performance. This deprotonation effect can be applied to different amine compounds and transition-metal ions as a universal strategy for the development of preeminent non-precious metal carbon catalysts.
2025, 36(11): 111441
doi: 10.1016/j.cclet.2025.111441
Abstract:
Transition metal selenides (TMS) demonstrate exceptional catalytic activity in the oxygen evolution reaction (OER), yet their performance is hindered by surface reconstruction under OER conditions, particularly at high current densities. This study reveals that embedding Co0.85Se nanoparticles into the interlayer spacing of MXene-Ti3C2 effectively suppresses surface reconstruction during OER. This configuration establishes a Schottky heterojunction with an intrinsic built-in electric field (BEF) between Co0.85Se and Ti3C2, which enhances charge redistribution and accelerates electron transport. Consequently, the Co0.85Se@Ti3C2 composite exhibits outstanding OER performance, achieving low overpotentials (230 mV at 100 mA/cm2, 376 mV at 1000 mA/cm2, 417 mV at 1500 mA/cm2) and exceptional durability (200 h at 200 mA/cm2). In-situ XRD/Raman characterization verifies that the encapsulated Co0.85Se within Ti3C2 inhibits CoOOH formation on the surface during OER. Both experimental and theoretical investigations indicate that the heterojunction's superhydrophilicity/superaerophobicity, synergized with BEF-regulated oxygen intermediate adsorption/desorption, collectively enhance catalytic efficiency of Co0.85Se@Ti3C2. This strategy of spatially confining chalcogenide catalysts to prevent structural degradation while leveraging interfacial electric fields presents a rational approach for developing durable electrocatalysts in high-current densities water electrolysis.
Transition metal selenides (TMS) demonstrate exceptional catalytic activity in the oxygen evolution reaction (OER), yet their performance is hindered by surface reconstruction under OER conditions, particularly at high current densities. This study reveals that embedding Co0.85Se nanoparticles into the interlayer spacing of MXene-Ti3C2 effectively suppresses surface reconstruction during OER. This configuration establishes a Schottky heterojunction with an intrinsic built-in electric field (BEF) between Co0.85Se and Ti3C2, which enhances charge redistribution and accelerates electron transport. Consequently, the Co0.85Se@Ti3C2 composite exhibits outstanding OER performance, achieving low overpotentials (230 mV at 100 mA/cm2, 376 mV at 1000 mA/cm2, 417 mV at 1500 mA/cm2) and exceptional durability (200 h at 200 mA/cm2). In-situ XRD/Raman characterization verifies that the encapsulated Co0.85Se within Ti3C2 inhibits CoOOH formation on the surface during OER. Both experimental and theoretical investigations indicate that the heterojunction's superhydrophilicity/superaerophobicity, synergized with BEF-regulated oxygen intermediate adsorption/desorption, collectively enhance catalytic efficiency of Co0.85Se@Ti3C2. This strategy of spatially confining chalcogenide catalysts to prevent structural degradation while leveraging interfacial electric fields presents a rational approach for developing durable electrocatalysts in high-current densities water electrolysis.
2025, 36(11): 111455
doi: 10.1016/j.cclet.2025.111455
Abstract:
Metal-based antimicrobial materials have been extensively studied and applied over decades. While these materials are notably characterized by their superior antibacterial performance and low propensity to induce drug resistance, critical limitations such as inherent cytotoxicity, poor solubility, and instability in aqueous solution remain significant challenges requiring systematic optimization. In this study, we synthesized water-soluble molecular iron-oxo clusters (MIC) with excellent biosafety and stability of aqueous solution. Our findings demonstrate that MIC exhibits marked therapeutic efficacy in cecal ligation and puncture induced sepsis models, a critical validation given sepsis' etiology as a life-threatening infection mediated systemic inflammatory syndrome. MIC combats bacteria by enhancing humoral immune responsiveness. MIC significantly improved the survival rate, reduced bacterial burden, stabilized body temperature, and modulated cytokine profiles in mice with sepsis. Further investigations revealed that MIC promotes B cells proliferation and oxidative phosphorylation, and mitigates mitochondrial damage and apoptosis in B cells, suggesting its role in modulating cellular metabolism. RNA sequencing analysis demonstrated that MIC exerts its effects by influencing key pathways involved in humoral immunity, inflammatory responses, and metabolic adaptation. These findings establish MIC as a novel therapeutic agent for regulating immune responses in sepsis, providing innovative strategies to improve recovery from this life-threatening condition.
Metal-based antimicrobial materials have been extensively studied and applied over decades. While these materials are notably characterized by their superior antibacterial performance and low propensity to induce drug resistance, critical limitations such as inherent cytotoxicity, poor solubility, and instability in aqueous solution remain significant challenges requiring systematic optimization. In this study, we synthesized water-soluble molecular iron-oxo clusters (MIC) with excellent biosafety and stability of aqueous solution. Our findings demonstrate that MIC exhibits marked therapeutic efficacy in cecal ligation and puncture induced sepsis models, a critical validation given sepsis' etiology as a life-threatening infection mediated systemic inflammatory syndrome. MIC combats bacteria by enhancing humoral immune responsiveness. MIC significantly improved the survival rate, reduced bacterial burden, stabilized body temperature, and modulated cytokine profiles in mice with sepsis. Further investigations revealed that MIC promotes B cells proliferation and oxidative phosphorylation, and mitigates mitochondrial damage and apoptosis in B cells, suggesting its role in modulating cellular metabolism. RNA sequencing analysis demonstrated that MIC exerts its effects by influencing key pathways involved in humoral immunity, inflammatory responses, and metabolic adaptation. These findings establish MIC as a novel therapeutic agent for regulating immune responses in sepsis, providing innovative strategies to improve recovery from this life-threatening condition.
2025, 36(11): 111477
doi: 10.1016/j.cclet.2025.111477
Abstract:
Chirality is pervasive and plays a crucial role in biological processes. Although amino acids possess inherent chirality, the stereochemical influence of this property on the regulation of immune cells remains insufficiently explored. To address this, the unimolecular chiral poly(amino acid)s were synthesized to evaluate their immunostimulatory effects and anti-cancer potential. Among the candidates, G0-PD-Lys50 emerged as the most effective adjuvant through in vitro screening. When complexed with antigen ovalbumin (OVA) to form chiral nanovaccines, G0-PL-Lys50-OVA and G0-PD-Lys50-OVA exhibited similar morphology, particle size, and zeta potential. Despite these comparable physicochemical properties, G0-PD-Lys50-OVA induced significantly stronger activation of dendritic cells (DCs). Specifically, it resulted in 1.38- and 1.34-fold increases in CD11c+CD80+ DCs and CD11c+SIINFEKL-H-2Kb+ DCs in lymph nodes, respectively. In the LLC-OVA cancer model, G0-PD-Lys50-OVA reduced tumor volume by 50% compared to its enantiomer. These results establish a unique approach to designing chiral nanovaccines and provide a foundational strategy for developing broadly applicable immunotherapies.
Chirality is pervasive and plays a crucial role in biological processes. Although amino acids possess inherent chirality, the stereochemical influence of this property on the regulation of immune cells remains insufficiently explored. To address this, the unimolecular chiral poly(amino acid)s were synthesized to evaluate their immunostimulatory effects and anti-cancer potential. Among the candidates, G0-PD-Lys50 emerged as the most effective adjuvant through in vitro screening. When complexed with antigen ovalbumin (OVA) to form chiral nanovaccines, G0-PL-Lys50-OVA and G0-PD-Lys50-OVA exhibited similar morphology, particle size, and zeta potential. Despite these comparable physicochemical properties, G0-PD-Lys50-OVA induced significantly stronger activation of dendritic cells (DCs). Specifically, it resulted in 1.38- and 1.34-fold increases in CD11c+CD80+ DCs and CD11c+SIINFEKL-H-2Kb+ DCs in lymph nodes, respectively. In the LLC-OVA cancer model, G0-PD-Lys50-OVA reduced tumor volume by 50% compared to its enantiomer. These results establish a unique approach to designing chiral nanovaccines and provide a foundational strategy for developing broadly applicable immunotherapies.
2025, 36(11): 111497
doi: 10.1016/j.cclet.2025.111497
Abstract:
Liver diseases, particularly acute alcoholic liver injury (AALI), drug-induced liver injury (DILI), and hepatocellular carcinoma (HCC), have become global public health issues. Glutathione (GSH), as an important antioxidant, plays a crucial role in the liver, and its changes are closely associated with liver injury and the development of liver cancer. Therefore, accurately monitoring GSH variations is critical for understanding liver injury mechanisms, early diagnosis, and treatment evaluation. However, traditional detection methods suffer from insufficient sensitivity and selectivity. To address these challenges, we developed an innovative DR-Au3+/DR-Pd2+ complex probe that can rapidly and sensitively detect GSH through near-infrared (NIR) fluorescence changes. This probe, with the optimal excitation and emission wavelengths of the probe both located in the NIR region, exhibits excellent selectivity and liver-targeting ability, overcoming the imprecision localization problems of traditional methods. In the AALI and DILI models, the optimized DR-Au3+ probe enables real-time monitoring of GSH level fluctuations, providing a powerful tool for early diagnosis of liver injury and dynamic evaluation of therapeutic efficacy. In the DILI and HCC models, the DR-Au3+ probe enables visualization and quantitative monitoring of the ferroptosis process, offering new perspectives and approaches for targeted therapy research. The DR-Au3+ probe we developed pioneers innovative strategies for establishing accurate diagnostic protocols and individualized therapeutic regimens in hepatic injury and hepatocellular carcinoma management.
Liver diseases, particularly acute alcoholic liver injury (AALI), drug-induced liver injury (DILI), and hepatocellular carcinoma (HCC), have become global public health issues. Glutathione (GSH), as an important antioxidant, plays a crucial role in the liver, and its changes are closely associated with liver injury and the development of liver cancer. Therefore, accurately monitoring GSH variations is critical for understanding liver injury mechanisms, early diagnosis, and treatment evaluation. However, traditional detection methods suffer from insufficient sensitivity and selectivity. To address these challenges, we developed an innovative DR-Au3+/DR-Pd2+ complex probe that can rapidly and sensitively detect GSH through near-infrared (NIR) fluorescence changes. This probe, with the optimal excitation and emission wavelengths of the probe both located in the NIR region, exhibits excellent selectivity and liver-targeting ability, overcoming the imprecision localization problems of traditional methods. In the AALI and DILI models, the optimized DR-Au3+ probe enables real-time monitoring of GSH level fluctuations, providing a powerful tool for early diagnosis of liver injury and dynamic evaluation of therapeutic efficacy. In the DILI and HCC models, the DR-Au3+ probe enables visualization and quantitative monitoring of the ferroptosis process, offering new perspectives and approaches for targeted therapy research. The DR-Au3+ probe we developed pioneers innovative strategies for establishing accurate diagnostic protocols and individualized therapeutic regimens in hepatic injury and hepatocellular carcinoma management.
2025, 36(11): 111591
doi: 10.1016/j.cclet.2025.111591
Abstract:
Iron carbodiimide (FeNCN) anode demonstrates significant potential for rapid sodium-ion storage owing to its high reaction activity and near-metallic conductivity. However, further development of FeNCN is hindered by inherent structural instability and ambiguous structure-kinetics correlation. In this study, FeNCN crystallites with selectively exposed (002) and {010} facets were precisely engineered and synthesized. Notably, the sodium storage kinetics and electrochemical performance of FeNCN exhibit facet-dependent variations. Polyhedral-FeNCN (P-FeNCN) dominated by {010} facets exhibited a pseudocapacitance-driven storage mechanism and delivered exceptional rate capability (372 mAh/g at 5 A/g) and long cyclability (95.8% capacity retention after 300 cycles at 0.5 A/g). In contrast, sheet-like FeNCN (S-FeNCN) with predominant (002) facet exposure displayed diffusion-limited kinetics due to sluggish ion diffusion rate. Crucially, time-resolved operando XRD analysis and DFT simulation bridge this performance gap to mechanistic origins: FeNCN as an intercalation-conversion type anode, the solid-state diffusion is the rate-determining step during charge/discharge process. Active {010} facets possess numerous broad hexagonal tunnels, coupled with a low diffusion barrier of 0.168 eV along 〈010〉 directions. This unique architectural configuration enables rapid sodium-ion transport, thereby shifting the diffusion-controlled kinetics to intercalation-pseudocapacitive behavior. This discovery establishes active facet exposure as a storage kinetic switch, offering a generalized paradigm for optimizing the rate performance and stability of sodium-ion batteries.
Iron carbodiimide (FeNCN) anode demonstrates significant potential for rapid sodium-ion storage owing to its high reaction activity and near-metallic conductivity. However, further development of FeNCN is hindered by inherent structural instability and ambiguous structure-kinetics correlation. In this study, FeNCN crystallites with selectively exposed (002) and {010} facets were precisely engineered and synthesized. Notably, the sodium storage kinetics and electrochemical performance of FeNCN exhibit facet-dependent variations. Polyhedral-FeNCN (P-FeNCN) dominated by {010} facets exhibited a pseudocapacitance-driven storage mechanism and delivered exceptional rate capability (372 mAh/g at 5 A/g) and long cyclability (95.8% capacity retention after 300 cycles at 0.5 A/g). In contrast, sheet-like FeNCN (S-FeNCN) with predominant (002) facet exposure displayed diffusion-limited kinetics due to sluggish ion diffusion rate. Crucially, time-resolved operando XRD analysis and DFT simulation bridge this performance gap to mechanistic origins: FeNCN as an intercalation-conversion type anode, the solid-state diffusion is the rate-determining step during charge/discharge process. Active {010} facets possess numerous broad hexagonal tunnels, coupled with a low diffusion barrier of 0.168 eV along 〈010〉 directions. This unique architectural configuration enables rapid sodium-ion transport, thereby shifting the diffusion-controlled kinetics to intercalation-pseudocapacitive behavior. This discovery establishes active facet exposure as a storage kinetic switch, offering a generalized paradigm for optimizing the rate performance and stability of sodium-ion batteries.
2025, 36(11): 111652
doi: 10.1016/j.cclet.2025.111652
Abstract:
The development of cost-effective and energy-efficient anode materials is essential for the advancement of industrial water electrolysis. Herein, we report a rapid, ambient-temperature method to prepare large-area nickel mesh electrodes (SFN/NM) via surface functionalization completed within 3 min, without relying on thermal treatments or noble metals. The as-prepared electrodes achieve a high current density of 100 mA/cm2 at an overpotential of just 300 mV in 6 mol/L KOH, and exhibit remarkable stability over 1600 h of continuous operation. With comparable activity to commercial Raney nickel yet significantly lower processing and material costs (reduced by 50%–70%), this approach provides a practical solution for low-energy water splitting. Beyond its industrial relevance, the strategy offers a scalable model for engineering high-performance OER electrodes, inspiring future directions in electrocatalyst design.
The development of cost-effective and energy-efficient anode materials is essential for the advancement of industrial water electrolysis. Herein, we report a rapid, ambient-temperature method to prepare large-area nickel mesh electrodes (SFN/NM) via surface functionalization completed within 3 min, without relying on thermal treatments or noble metals. The as-prepared electrodes achieve a high current density of 100 mA/cm2 at an overpotential of just 300 mV in 6 mol/L KOH, and exhibit remarkable stability over 1600 h of continuous operation. With comparable activity to commercial Raney nickel yet significantly lower processing and material costs (reduced by 50%–70%), this approach provides a practical solution for low-energy water splitting. Beyond its industrial relevance, the strategy offers a scalable model for engineering high-performance OER electrodes, inspiring future directions in electrocatalyst design.
2025, 36(11): 110470
doi: 10.1016/j.cclet.2024.110470
Abstract:
H2O2 is an excellent green oxidant with important applications in many fields. The conventional anthraquinone process for synthesizing H2O2 is usually accompanied by high economic costs and stringent process requirements. The photocatalytic production of H2O2 via heterojunction semiconductors has proven to overcome these limitations, which is a promising alternative to the conventional anthraquinone process. In this review, we provide a comprehensive summary of the semiconductor heterojunction materials that have been attempted to be used in the photocatalytic generation of H2O2 in recent years. Firstly, a brief description of the photoreaction mechanisms of different types of heterojunctions in the photocatalytic process is presented, focusing on the generation pathways and competing reactions for the photoproduction of H2O2. Then, the types of heterojunctions applied for photoproduction of H2O2 are comprehensively summarized. Among them, the four most widely used types of heterojunctions, including type-Ⅱ heterojunctions, Z-scheme systems, S-scheme systems, and Schottky heterojunctions, and their current applications in the reaction of photoproduction of H2O2 are highlighted. By comparing the differences in the internal electric fields of different types of heterojunctions, different charge transfer pathways of various types of heterojunctions in the photoproduction of H2O2 are distinguished. Furthermore, the great potential of other types of heterojunctions, such as p-n heterojunctions, in photocatalysis is further outlined. Finally, the challenges as well as opportunities for the development of novel heterostructural photocatalysts for H2O2 production are outlined. We sincerely hope this minireview can attract more attention from scientific research workers in the field of photocatalytic H2O2 generation, making them valuable for environmental remediation and industrial applications in the future.
H2O2 is an excellent green oxidant with important applications in many fields. The conventional anthraquinone process for synthesizing H2O2 is usually accompanied by high economic costs and stringent process requirements. The photocatalytic production of H2O2 via heterojunction semiconductors has proven to overcome these limitations, which is a promising alternative to the conventional anthraquinone process. In this review, we provide a comprehensive summary of the semiconductor heterojunction materials that have been attempted to be used in the photocatalytic generation of H2O2 in recent years. Firstly, a brief description of the photoreaction mechanisms of different types of heterojunctions in the photocatalytic process is presented, focusing on the generation pathways and competing reactions for the photoproduction of H2O2. Then, the types of heterojunctions applied for photoproduction of H2O2 are comprehensively summarized. Among them, the four most widely used types of heterojunctions, including type-Ⅱ heterojunctions, Z-scheme systems, S-scheme systems, and Schottky heterojunctions, and their current applications in the reaction of photoproduction of H2O2 are highlighted. By comparing the differences in the internal electric fields of different types of heterojunctions, different charge transfer pathways of various types of heterojunctions in the photoproduction of H2O2 are distinguished. Furthermore, the great potential of other types of heterojunctions, such as p-n heterojunctions, in photocatalysis is further outlined. Finally, the challenges as well as opportunities for the development of novel heterostructural photocatalysts for H2O2 production are outlined. We sincerely hope this minireview can attract more attention from scientific research workers in the field of photocatalytic H2O2 generation, making them valuable for environmental remediation and industrial applications in the future.
2025, 36(11): 110475
doi: 10.1016/j.cclet.2024.110475
Abstract:
Advanced lithium-chalcogen (S, Se, Te) batteries (LCBs) are among the most promising candidates for next generation energy storage systems because of their high energy density and theoretical capacities. However, they are still facing many challenges, such as expansion of the volume problems of chalcogen elements, the shuttle effect of intermediate products, low Coulombic efficiency and inferior cycling stability, which seriously hinder their commercial applications. The presence of a binder in the cathode causes an uneven distribution of the active substances, and also occupies a part of the electrode's volume, resulting in the unsatisfactory energy density of LCBs. In this regard, binder-free electrodes which do not need binders, conductive materials and even collectors, can be used as electrodes for flexible batteries, effectively solving the above-mentioned problems. In this review, the main methods of fabricating binder-free cathodes and their advantages and disadvantages are discussed. Furthermore, a review of representative works on binder-free cathodes for high-performance LCBs over the last decade is presented. The main binder-free electrode materials include paper cloth (PC), graphene oxide (GO), carbon nanotubes (CNTs), carbon nanofibers (CNFs), carbon cloth (CC), polymers, metallic compounds, and their composites. In addition, we discuss these works from four aspects: Advanced structures, methods of fabrication, electrochemical performance and the potential mechanism of binder-free cathode materials, providing important guidance for further researches. Finally, we propose the current challenges of binder-free LCBs and look forward to breakthroughs in this field through the use of binder-free electrodes.
Advanced lithium-chalcogen (S, Se, Te) batteries (LCBs) are among the most promising candidates for next generation energy storage systems because of their high energy density and theoretical capacities. However, they are still facing many challenges, such as expansion of the volume problems of chalcogen elements, the shuttle effect of intermediate products, low Coulombic efficiency and inferior cycling stability, which seriously hinder their commercial applications. The presence of a binder in the cathode causes an uneven distribution of the active substances, and also occupies a part of the electrode's volume, resulting in the unsatisfactory energy density of LCBs. In this regard, binder-free electrodes which do not need binders, conductive materials and even collectors, can be used as electrodes for flexible batteries, effectively solving the above-mentioned problems. In this review, the main methods of fabricating binder-free cathodes and their advantages and disadvantages are discussed. Furthermore, a review of representative works on binder-free cathodes for high-performance LCBs over the last decade is presented. The main binder-free electrode materials include paper cloth (PC), graphene oxide (GO), carbon nanotubes (CNTs), carbon nanofibers (CNFs), carbon cloth (CC), polymers, metallic compounds, and their composites. In addition, we discuss these works from four aspects: Advanced structures, methods of fabrication, electrochemical performance and the potential mechanism of binder-free cathode materials, providing important guidance for further researches. Finally, we propose the current challenges of binder-free LCBs and look forward to breakthroughs in this field through the use of binder-free electrodes.
2025, 36(11): 110837
doi: 10.1016/j.cclet.2025.110837
Abstract:
Phosphorus-based luminescent materials consist of certain phosphorus in the aromatic backbones, endowing a larger nuclear charge (Z, 15P), rich valence states for the phosphorus core, and various electron geometries. These features enable promising exploitation for luminescent materials with significant quantum efficiencies and tunable singlet and triplet populations. This mini review focuses on the break-throughs of organic and organometallic phosphorus compounds in advanced circularly polarized fluorescence (CPF) and circularly polarized room-temperature phosphorescence (CP-RTP) by unveiling the structure-function relationships, e.g., design concept, charge transfer (CT) type, chiral conformation, and excited state transition configuration, and the recent applications in optical information encryption, lighting-displaying, and organic light emitting diodes (OLEDs). By dedicated analysis of current progresses, we hope this work will throw insights into phosphorus-based CPF and CP-RTP behaviors and provide a reference for the rational design of high-performance phosphorus-based emitters.
Phosphorus-based luminescent materials consist of certain phosphorus in the aromatic backbones, endowing a larger nuclear charge (Z, 15P), rich valence states for the phosphorus core, and various electron geometries. These features enable promising exploitation for luminescent materials with significant quantum efficiencies and tunable singlet and triplet populations. This mini review focuses on the break-throughs of organic and organometallic phosphorus compounds in advanced circularly polarized fluorescence (CPF) and circularly polarized room-temperature phosphorescence (CP-RTP) by unveiling the structure-function relationships, e.g., design concept, charge transfer (CT) type, chiral conformation, and excited state transition configuration, and the recent applications in optical information encryption, lighting-displaying, and organic light emitting diodes (OLEDs). By dedicated analysis of current progresses, we hope this work will throw insights into phosphorus-based CPF and CP-RTP behaviors and provide a reference for the rational design of high-performance phosphorus-based emitters.
2025, 36(11): 110845
doi: 10.1016/j.cclet.2025.110845
Abstract:
Green extraction of bioactive components from natural sources has been a hot topic in the field of chemistry and biology. As a kind of green solvents, deep eutectic solvents (DESs) have unique advantages in the extraction of bioactive substances. In recent years, as a new subgroup of DESs, the switchable deep eutectic solvents (SDESs) can realize reversible phase switching between hydrophobic and hydrophilic by external driving forces (CO2/pH/temperature), allowing for the extraction of different polar components while avoiding the problem of difficult recovery of DESs. The application of SDESs reduces the consumption of large amounts of organic solvents during the extraction process, thereby promoting sustainability. In the meanwhile, it presents an advantage over traditional extraction methods in preserving product activity. Based on the recent researches on SDESs, this work summarized the composition, driving factors, and conversion mechanism of SDESs. The applications of SDESs in the extraction of natural products were primarily highlighted to provide a reference for future research.
Green extraction of bioactive components from natural sources has been a hot topic in the field of chemistry and biology. As a kind of green solvents, deep eutectic solvents (DESs) have unique advantages in the extraction of bioactive substances. In recent years, as a new subgroup of DESs, the switchable deep eutectic solvents (SDESs) can realize reversible phase switching between hydrophobic and hydrophilic by external driving forces (CO2/pH/temperature), allowing for the extraction of different polar components while avoiding the problem of difficult recovery of DESs. The application of SDESs reduces the consumption of large amounts of organic solvents during the extraction process, thereby promoting sustainability. In the meanwhile, it presents an advantage over traditional extraction methods in preserving product activity. Based on the recent researches on SDESs, this work summarized the composition, driving factors, and conversion mechanism of SDESs. The applications of SDESs in the extraction of natural products were primarily highlighted to provide a reference for future research.
2025, 36(11): 110846
doi: 10.1016/j.cclet.2025.110846
Abstract:
Approximately 99% of micro(nano)plastics in wastewater are retained in waste activated sludge, inhibiting anaerobic digestion, while their specific effects on functional microbes remain unclear. To break through the limitations of current knowledge, in this review, we focused on summarizing the impacts of micro(nano)plastics on the microbial communities within anaerobic digestion systems, analyzing the toxicity mechanisms and developing strategies to mitigate their inhibitory effects. Firstly, the impacts of micro(nano)plastics on methane production and functional microbes were summarized, including direct cell pitting effects, inhibition caused by toxic leachates, and the adsorption of pollutants onto micro(nano)plastics surfaces, which further interfere with microbial activity and metabolic processes. Then, the specific performances and potential mechanisms by which micro(nano)plastics affect microbes were innovatively analyzed from the aspects of community variation, cellular activity and genetic expression. Moreover, various factors of micro(nano)plastics were found to influence their effects on microbes, including hormesis-like effects at different dosages, increased toxicity with decreasing particle size, enhanced biotoxicity due to surface functional groups, and variations in toxicity based on morphology and aggregation state. Furthermore, potential mitigation strategies, including activated carbon addition, thermal hydrolysis and cationic polyacrylamide application, were firstly summarized in here to alleviate inhibition on microbe. Finally, the current challenges and future directions were fully discussed and prospected. These insights could not only elucidate the biotoxic effects of micro(nano)plastics, but also provide a new avenue for helping to develop effective remediation techniques in micro(nano)plastic pollution management.
Approximately 99% of micro(nano)plastics in wastewater are retained in waste activated sludge, inhibiting anaerobic digestion, while their specific effects on functional microbes remain unclear. To break through the limitations of current knowledge, in this review, we focused on summarizing the impacts of micro(nano)plastics on the microbial communities within anaerobic digestion systems, analyzing the toxicity mechanisms and developing strategies to mitigate their inhibitory effects. Firstly, the impacts of micro(nano)plastics on methane production and functional microbes were summarized, including direct cell pitting effects, inhibition caused by toxic leachates, and the adsorption of pollutants onto micro(nano)plastics surfaces, which further interfere with microbial activity and metabolic processes. Then, the specific performances and potential mechanisms by which micro(nano)plastics affect microbes were innovatively analyzed from the aspects of community variation, cellular activity and genetic expression. Moreover, various factors of micro(nano)plastics were found to influence their effects on microbes, including hormesis-like effects at different dosages, increased toxicity with decreasing particle size, enhanced biotoxicity due to surface functional groups, and variations in toxicity based on morphology and aggregation state. Furthermore, potential mitigation strategies, including activated carbon addition, thermal hydrolysis and cationic polyacrylamide application, were firstly summarized in here to alleviate inhibition on microbe. Finally, the current challenges and future directions were fully discussed and prospected. These insights could not only elucidate the biotoxic effects of micro(nano)plastics, but also provide a new avenue for helping to develop effective remediation techniques in micro(nano)plastic pollution management.
2025, 36(11): 110847
doi: 10.1016/j.cclet.2025.110847
Abstract:
As a key step in waste activated sludge (WAS) treatment and disposal, WAS dewatering can minimize the amount of WAS and decrease the costs of transportation, storage management, treatment, and disposal. Advanced oxidation processes (AOPs) have been widely explored in WAS dewatering due to the excellent oxidizing properties and efficient decomposition capacity since the 21st century. This review outlined the mechanisms of AOPs to improve WAS dewatering and pointed out the shortcomings of the existing mechanisms. Then, the applications of AOPs-based WAS dewatering processes for enhanced WAS dewatering were reviewed, and the intrinsic limitations of AOPs-based WAS dewatering processes in engineering applications were proposed. In addition, an overall review of AOPs-based WAS dewatering researches was also conducted through bibliometric analysis, and future research hotspots in the field of AOPs-based WAS dewatering were proposed. Finally, the positive effects of the AOPs-based WAS dewatering processes on pollutant removal and resource recovery were investigated, and an integrated plan for the harmless disposal of WAS was constructed to achieve a positive reform of the traditional WAS management plan. This review provided theoretical basis and technical reference for the development of efficient, economical, and environmental AOPs for enhanced WAS dewatering to facilitate the application of AOPs in actual WAS dewatering engineering.
As a key step in waste activated sludge (WAS) treatment and disposal, WAS dewatering can minimize the amount of WAS and decrease the costs of transportation, storage management, treatment, and disposal. Advanced oxidation processes (AOPs) have been widely explored in WAS dewatering due to the excellent oxidizing properties and efficient decomposition capacity since the 21st century. This review outlined the mechanisms of AOPs to improve WAS dewatering and pointed out the shortcomings of the existing mechanisms. Then, the applications of AOPs-based WAS dewatering processes for enhanced WAS dewatering were reviewed, and the intrinsic limitations of AOPs-based WAS dewatering processes in engineering applications were proposed. In addition, an overall review of AOPs-based WAS dewatering researches was also conducted through bibliometric analysis, and future research hotspots in the field of AOPs-based WAS dewatering were proposed. Finally, the positive effects of the AOPs-based WAS dewatering processes on pollutant removal and resource recovery were investigated, and an integrated plan for the harmless disposal of WAS was constructed to achieve a positive reform of the traditional WAS management plan. This review provided theoretical basis and technical reference for the development of efficient, economical, and environmental AOPs for enhanced WAS dewatering to facilitate the application of AOPs in actual WAS dewatering engineering.
2025, 36(11): 110849
doi: 10.1016/j.cclet.2025.110849
Abstract:
The potential of messenger RNA (mRNA) as a therapeutic tool for treating diseases has garnered considerable interest, especially in the wake of the successful creation of mRNA vaccines to counter corona virus disease 2019 (COVID-19). Nucleic acid-based drug gene therapies have emerged as exceptionally promising avenues for combating disease. Furthermore, lipid nanoparticles (LNPs) are ideal carriers for nucleic acid delivery owing to their ionic nature, which enables nucleic acids to electrostatically interact with intracellular membranes, thereby promoting efficient intracellular nucleic acid release. Unfortunately, the effectiveness of LNPs in targeting organs beyond the liver is relatively poor. Thus, enhanced extrahepatic targeting is another important property that would lead to improved in vivo delivery by LNPs. This review focuses on the fundamental characteristics and functions of LNPs developed to facilitate cellular uptake and ensure effective intracellular release of mRNAs. Promising applications, possible advantages and potential challenges associated with use of LNPs in organ specific delivery and release of mRNAs are summarized. Furthermore, the need for future research to address limitations of currently developed LNPs for clinical applications of the mRNA technology is emphasized.
The potential of messenger RNA (mRNA) as a therapeutic tool for treating diseases has garnered considerable interest, especially in the wake of the successful creation of mRNA vaccines to counter corona virus disease 2019 (COVID-19). Nucleic acid-based drug gene therapies have emerged as exceptionally promising avenues for combating disease. Furthermore, lipid nanoparticles (LNPs) are ideal carriers for nucleic acid delivery owing to their ionic nature, which enables nucleic acids to electrostatically interact with intracellular membranes, thereby promoting efficient intracellular nucleic acid release. Unfortunately, the effectiveness of LNPs in targeting organs beyond the liver is relatively poor. Thus, enhanced extrahepatic targeting is another important property that would lead to improved in vivo delivery by LNPs. This review focuses on the fundamental characteristics and functions of LNPs developed to facilitate cellular uptake and ensure effective intracellular release of mRNAs. Promising applications, possible advantages and potential challenges associated with use of LNPs in organ specific delivery and release of mRNAs are summarized. Furthermore, the need for future research to address limitations of currently developed LNPs for clinical applications of the mRNA technology is emphasized.
2025, 36(11): 110907
doi: 10.1016/j.cclet.2025.110907
Abstract:
Intratumoral bacteria have been proven to be widely exist in tumors, different tumors of different systems have different types of characteristic bacteria. Intratumoral bacteria will become a new and important biomarker in the full cycle of tumor development. This article emphasizes the key role of intratumoral bacteria in the occurrence and progress of tumors, including promoting tumor development, accelerating tumor metastasis and promoting tumor cell resistance. In addition, this article also summarizes the application of intratumoral bacteria in tumor diagnosis and prognosis. Especially, this article outlines the treatment strategies of intratumoral bacteria, including non-nanodelivery therapy strategies and nanodelivery therapy strategies, such as antibiotic, macromolecular, inflammatory factor inhibitors, near-infrared-photothermal therapy, inorganic antibacterial agents, reactive species and microbes therapy, in these strategies, nano delivery system provides a promising treatment that solves the problem of drug resistance, reducing toxicity and improving patient compliance. This article is hoped to guide future research on intratumoral bacteria on tumors.
Intratumoral bacteria have been proven to be widely exist in tumors, different tumors of different systems have different types of characteristic bacteria. Intratumoral bacteria will become a new and important biomarker in the full cycle of tumor development. This article emphasizes the key role of intratumoral bacteria in the occurrence and progress of tumors, including promoting tumor development, accelerating tumor metastasis and promoting tumor cell resistance. In addition, this article also summarizes the application of intratumoral bacteria in tumor diagnosis and prognosis. Especially, this article outlines the treatment strategies of intratumoral bacteria, including non-nanodelivery therapy strategies and nanodelivery therapy strategies, such as antibiotic, macromolecular, inflammatory factor inhibitors, near-infrared-photothermal therapy, inorganic antibacterial agents, reactive species and microbes therapy, in these strategies, nano delivery system provides a promising treatment that solves the problem of drug resistance, reducing toxicity and improving patient compliance. This article is hoped to guide future research on intratumoral bacteria on tumors.
2025, 36(11): 110909
doi: 10.1016/j.cclet.2025.110909
Abstract:
Derivatives of metal−organic frameworks (MOFs) are a promising bifunctional electrocatalysts in electrochemical advanced oxidation processes (EAOPs). These metal/carbon materials overcome the limitations of individual components by creating synergistic effects. EAOPs is primarily constrained by the generation and activation of H2O2. This article examines the regulatory strategies employed in MOFs derivatives to enhance the production of H2O2 via 2e− pathways and its activation to •OH, focusing on preparation techniques, structures, and compositions. The design of these derivatives involves methods such as metal dispersion on the surface of nanocarbons, embedding in carbon shells, and atomic dispersion of metals anchored in porous carbon. MOFs derivatives promote •OH production and enhance wastewater purification through mechanisms such as boosting the Fe(Ⅱ)/Fe(Ⅲ) cycle, facilitating direct 3e− reactions of O2, and interacting of O2•−. Moreover, the performance and durability of MOFs derivatives in wastewater treatment, particularly in influencing •OH generation within EAOPs, were investigated. This review addresses current challenges and future prospects, offering valuable insights for the development of MOFs derivatives as 3e− ORR electrocatalysts and the advancement of sustainable water treatment technologies.
Derivatives of metal−organic frameworks (MOFs) are a promising bifunctional electrocatalysts in electrochemical advanced oxidation processes (EAOPs). These metal/carbon materials overcome the limitations of individual components by creating synergistic effects. EAOPs is primarily constrained by the generation and activation of H2O2. This article examines the regulatory strategies employed in MOFs derivatives to enhance the production of H2O2 via 2e− pathways and its activation to •OH, focusing on preparation techniques, structures, and compositions. The design of these derivatives involves methods such as metal dispersion on the surface of nanocarbons, embedding in carbon shells, and atomic dispersion of metals anchored in porous carbon. MOFs derivatives promote •OH production and enhance wastewater purification through mechanisms such as boosting the Fe(Ⅱ)/Fe(Ⅲ) cycle, facilitating direct 3e− reactions of O2, and interacting of O2•−. Moreover, the performance and durability of MOFs derivatives in wastewater treatment, particularly in influencing •OH generation within EAOPs, were investigated. This review addresses current challenges and future prospects, offering valuable insights for the development of MOFs derivatives as 3e− ORR electrocatalysts and the advancement of sustainable water treatment technologies.
2025, 36(11): 111023
doi: 10.1016/j.cclet.2025.111023
Abstract:
Chiral 3-aryl alkanoic acids and their derivatives present a class of highly valued framework in natural products and pharmaceuticals. Among multifarious synthetic strategies, asymmetric intermolecular hydrocarbonylation of α-alkyl styrenes exhibit high atom-economy and straightforwardness, nonetheless facing problems in simultaneously addressing the activity, chemoselectivity, regioselectivity and stereoselectivity of the strategy, which remain unresolved to date. Herein, we disclosed an enantioselective Pd-catalyzed exclusive anti-Markovnikov hydroesterification of α-alkyl styrenes with thiols (hydrothiocarbonylation). The catalytic system, consisting of Pd source, chiral sulfoxide phosphine ligand (SOP), p-TsOH·H2O and LiCl, efficiently achieved the corresponding α-chiral 3-aryl alkanoic thioesters in excellent results (68 examples, up to 99% yield, generally 90%−98% ee). The chloride anion from lithium chloride (LiCl) acts as a coordinating ligand for palladium, promoting the activity while simultaneously enhancing stereochemical control. Moreover, the potential of the method was demonstrated by the late-stage functionalization of natural products, formal synthesis of biologically active molecules intermediates (RC-33, AM-6226) as well as intermediate analogue of R-106578.
Chiral 3-aryl alkanoic acids and their derivatives present a class of highly valued framework in natural products and pharmaceuticals. Among multifarious synthetic strategies, asymmetric intermolecular hydrocarbonylation of α-alkyl styrenes exhibit high atom-economy and straightforwardness, nonetheless facing problems in simultaneously addressing the activity, chemoselectivity, regioselectivity and stereoselectivity of the strategy, which remain unresolved to date. Herein, we disclosed an enantioselective Pd-catalyzed exclusive anti-Markovnikov hydroesterification of α-alkyl styrenes with thiols (hydrothiocarbonylation). The catalytic system, consisting of Pd source, chiral sulfoxide phosphine ligand (SOP), p-TsOH·H2O and LiCl, efficiently achieved the corresponding α-chiral 3-aryl alkanoic thioesters in excellent results (68 examples, up to 99% yield, generally 90%−98% ee). The chloride anion from lithium chloride (LiCl) acts as a coordinating ligand for palladium, promoting the activity while simultaneously enhancing stereochemical control. Moreover, the potential of the method was demonstrated by the late-stage functionalization of natural products, formal synthesis of biologically active molecules intermediates (RC-33, AM-6226) as well as intermediate analogue of R-106578.
2025, 36(11): 111216
doi: 10.1016/j.cclet.2025.111216
Abstract:
Electrochemical synthesis is a safe, mild and environmentally friendly alternative to chemical oxidants and reductants. It uses electricity to catalyze redox reactions. However, understanding the tools and techniques involved is crucial for maximizing its benefits in academic and industrial applications. Still, for a novice, electrosynthesis can be a somewhat intimidating. Therefore, we provide guidance to synthetic chemists by highlighting key concepts and offering practical tips. In this review article, we focus on the utilization of electro-auxiliaries, indirect electrosynthesis, alternating electrode electrolysis (AEE), microreactors for electrochemical processes, and paired electrochemical reactions. These strategies are illustrated with selected examples. The use of electrodes and electroanalytical methods such as cyclic voltammetry are discussed. It highlights the advantages of merging electrochemistry and photochemistry, and the challenges of specific organic solvents and electrolytes. The incorporation of electrochemistry into a continuous chemical flow system further advances green activation technologies in terms of efficiency, applicability, sustainability, and selectivity to deliver more efficient and cleaner synthetic processes. Furthermore, this manuscript also emphasizes improvements in current approaches and future directions for large-scale electrosynthesis.
Electrochemical synthesis is a safe, mild and environmentally friendly alternative to chemical oxidants and reductants. It uses electricity to catalyze redox reactions. However, understanding the tools and techniques involved is crucial for maximizing its benefits in academic and industrial applications. Still, for a novice, electrosynthesis can be a somewhat intimidating. Therefore, we provide guidance to synthetic chemists by highlighting key concepts and offering practical tips. In this review article, we focus on the utilization of electro-auxiliaries, indirect electrosynthesis, alternating electrode electrolysis (AEE), microreactors for electrochemical processes, and paired electrochemical reactions. These strategies are illustrated with selected examples. The use of electrodes and electroanalytical methods such as cyclic voltammetry are discussed. It highlights the advantages of merging electrochemistry and photochemistry, and the challenges of specific organic solvents and electrolytes. The incorporation of electrochemistry into a continuous chemical flow system further advances green activation technologies in terms of efficiency, applicability, sustainability, and selectivity to deliver more efficient and cleaner synthetic processes. Furthermore, this manuscript also emphasizes improvements in current approaches and future directions for large-scale electrosynthesis.
2025, 36(11): 111406
doi: 10.1016/j.cclet.2025.111406
Abstract:
Nanoscale drug delivery systems (nano-DDSs) have attracted intense interest in tumor chemotherapy in the last decades, to improve antitumor efficacy and minimize toxic and side effects. As a versatile supramolecular building block, cyclodextrins (CDs) have been widely used in the fabrication of the smart nano-DDSs. Besides their multifunctionality, which makes them versatile core in the star (co)polymers for micellar nanomedicines, specific host-guest inclusion complexation via their hydrophobic cavities endows them diversified functions: (ⅰ) design of amphiphilic copolymers for micellar nanomedicines, (ⅱ) supramolecular hydrogels and poly(pseudo)rotaxane nano-hydrogels as drug carriers, and (ⅲ) recipient for direct and indirect drug-loading. In the present work, the recent progress of CDs in nano-DDSs for tumor chemotherapy was reviewed, classified by the crucial roles of CD units. Based on the structure-performance relationship, the future perspective was also proposed.
Nanoscale drug delivery systems (nano-DDSs) have attracted intense interest in tumor chemotherapy in the last decades, to improve antitumor efficacy and minimize toxic and side effects. As a versatile supramolecular building block, cyclodextrins (CDs) have been widely used in the fabrication of the smart nano-DDSs. Besides their multifunctionality, which makes them versatile core in the star (co)polymers for micellar nanomedicines, specific host-guest inclusion complexation via their hydrophobic cavities endows them diversified functions: (ⅰ) design of amphiphilic copolymers for micellar nanomedicines, (ⅱ) supramolecular hydrogels and poly(pseudo)rotaxane nano-hydrogels as drug carriers, and (ⅲ) recipient for direct and indirect drug-loading. In the present work, the recent progress of CDs in nano-DDSs for tumor chemotherapy was reviewed, classified by the crucial roles of CD units. Based on the structure-performance relationship, the future perspective was also proposed.
2025, 36(11): 111485
doi: 10.1016/j.cclet.2025.111485
Abstract:
Phenanthridine is a key structural motif in numerous natural products and biologically active compounds, making it an attractive target for pharmaceuticals and advanced materials. Recently, visible-light-induced cyclization through radical process has emerged as a powerful and sustainable strategy for building such a core under mild and environmentally friendly conditions, paving the way for new applications in synthetic and medicinal chemistry. This review highlights recent progress in the photochemical synthesis of phenanthridines, mainly focusing on various radical acceptors, including 2-isocyanobiaryls, cyanides, vinyl azides and vinyl benzotriazoles.
Phenanthridine is a key structural motif in numerous natural products and biologically active compounds, making it an attractive target for pharmaceuticals and advanced materials. Recently, visible-light-induced cyclization through radical process has emerged as a powerful and sustainable strategy for building such a core under mild and environmentally friendly conditions, paving the way for new applications in synthetic and medicinal chemistry. This review highlights recent progress in the photochemical synthesis of phenanthridines, mainly focusing on various radical acceptors, including 2-isocyanobiaryls, cyanides, vinyl azides and vinyl benzotriazoles.
2025, 36(11): 111612
doi: 10.1016/j.cclet.2025.111612
Abstract:
Since the discovery of carbonized polymer dots (CPDs) two decades ago, this emerging family of carbon-based nanomaterials has rapidly risen to prominence. CPDs have found widespread applications in sensing, catalysis, energy, and biomedicine due to their flexible precursors and synthesis methods, tunable photoluminescence (PL) properties, and excellent biocompatibility. This report presents the advancements made in the realm of CPD precursors, elucidates their luminescence properties and underlying mechanisms, and explores the diverse applications of CPD-based materials. It comprehensively addresses key issues by delving into several interconnected chapters: Initially exploring the intriguing fluorescence and afterglow properties exhibited by CPDs, subsequently unraveling the complex luminescence mechanisms that underlie these phenomena, emphasizing the crucial aspect of controllable synthesis of CPDs, and ultimately culminating in the precise construction of composite materials tailored for applications in laser and electroluminescent devices. Furthermore, this report aims to provide communication and assistance for the controlled synthesis and expanded applications of CPDs.
Since the discovery of carbonized polymer dots (CPDs) two decades ago, this emerging family of carbon-based nanomaterials has rapidly risen to prominence. CPDs have found widespread applications in sensing, catalysis, energy, and biomedicine due to their flexible precursors and synthesis methods, tunable photoluminescence (PL) properties, and excellent biocompatibility. This report presents the advancements made in the realm of CPD precursors, elucidates their luminescence properties and underlying mechanisms, and explores the diverse applications of CPD-based materials. It comprehensively addresses key issues by delving into several interconnected chapters: Initially exploring the intriguing fluorescence and afterglow properties exhibited by CPDs, subsequently unraveling the complex luminescence mechanisms that underlie these phenomena, emphasizing the crucial aspect of controllable synthesis of CPDs, and ultimately culminating in the precise construction of composite materials tailored for applications in laser and electroluminescent devices. Furthermore, this report aims to provide communication and assistance for the controlled synthesis and expanded applications of CPDs.
2025, 36(11): 111583
doi: 10.1016/j.cclet.2025.111583
Abstract:
