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Chinese Chemical Letters
Chinese Chemical Letters
主管 : 中国科学技术协会
刊期 : 月刊主编 : 钱旭红
语种 : 英文主办 : 中国化学会、中国医学科学院药物研究所
ISSN : 1001-8417 CN : 11-2710/O6本刊创办于1990年7月，是由中国化学会主办，中国医学科学院药物研究所承办的核心期刊。本刊由著名化学家梁晓天院士任主编，其内容涵盖化学研究的各个领域，及时报道我国化学界各个研究领域的最新进展及世界上一些化学研究的热点问题。本刊自1993年起为SCI、CA、日本科技文献速报等收录，2000年美国化学文摘引用中国期刊频次中位列第四。展开 > - 影响因子: 8.9
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Synthesis of a new ratiometric emission Ca2+ indicator for in vivo bioimaging
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Synthesis of a water-soluble macromolecular light stabilizer containing hindered amine structures
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Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation
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Superiority of poly(L-lactic acid) microspheres as dermal fillers
2025, 36(11): 110413
doi: 10.1016/j.cclet.2024.110413
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
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
摘要:
2025, 36(5): 109726
doi: 10.1016/j.cclet.2024.109726
摘要:
Conventional hydrometallurgy recycling process for treating wasted lithium-ion batteries (LIBs) typically results in the consumption of large amounts of corrosive leachates. Recent research on reusable leachate is expected to significantly improve the economic and environmental benefits, but is usually limited to specific and unique chemical reactions which could only apply to one type of metal elements. Herein, we report the co-extraction of multiple metal elements can be extracted without adding precipitates by mixed crystal co-precipitation, which enables the reusability of the leachate. We show that an oxalic acid (OA): choline chloride (ChCl): ethylene glycol (EG) type DES leachate system can leach transition metals from wasted LiNixCoyMn1-x-yO2 (NCM) cathode materials with satisfactory efficiency (The time required for complete leaching at 120 ℃ is 1.5 h). The transition metals were then efficiently extracted (with a recovery efficiency of over 96% for all elements) by directly adding water without precipitants. Noteworthy, the leachate can be efficiently recovered by directly evaporating the added water. The successful realization of reusability of leachate for the synergistic extraction of multiple elements relies on the regulation of the mixed crystal co-precipitation coefficient, which is realized by rationally design the reaction condition (composition of leachate, temperature and time) and induces the extraction of originally soluble manganese element. Our strategy is expected to be generally applicable and highly competent for industrial applications.
Conventional hydrometallurgy recycling process for treating wasted lithium-ion batteries (LIBs) typically results in the consumption of large amounts of corrosive leachates. Recent research on reusable leachate is expected to significantly improve the economic and environmental benefits, but is usually limited to specific and unique chemical reactions which could only apply to one type of metal elements. Herein, we report the co-extraction of multiple metal elements can be extracted without adding precipitates by mixed crystal co-precipitation, which enables the reusability of the leachate. We show that an oxalic acid (OA): choline chloride (ChCl): ethylene glycol (EG) type DES leachate system can leach transition metals from wasted LiNixCoyMn1-x-yO2 (NCM) cathode materials with satisfactory efficiency (The time required for complete leaching at 120 ℃ is 1.5 h). The transition metals were then efficiently extracted (with a recovery efficiency of over 96% for all elements) by directly adding water without precipitants. Noteworthy, the leachate can be efficiently recovered by directly evaporating the added water. The successful realization of reusability of leachate for the synergistic extraction of multiple elements relies on the regulation of the mixed crystal co-precipitation coefficient, which is realized by rationally design the reaction condition (composition of leachate, temperature and time) and induces the extraction of originally soluble manganese element. Our strategy is expected to be generally applicable and highly competent for industrial applications.
2025, 36(5): 109853
doi: 10.1016/j.cclet.2024.109853
摘要:
Even the sulfur cathode in lithium-sulfur (Li-S) battery has the advantages of high theoretical energy density, wide source of raw materials, no pollution to the environment, and so on. It still suffers the sore points of easy electrode collapse due to large volume expansion during charge and discharge and low active materials utilization caused by the severe shuttle effect of lithium polysulfides (LiPSs). Therefore, in this work, ramie gum (RG) was extracted from ramie fiber degumming liquid and used as the functional binder to address the above problems and improve the Li-S battery's performance for the first time. Surprisingly, the sulfur cathode using RG binder illustrates a high initial capacity of 1152.2 mAh/g, and a reversible capacity of 644.6 mAh/g after 500 cycles at 0.5 C, far better than the sulfur cathode using polyvinylidene fluoride (PVDF) and sodium carboxymethyl cellulose (CMC) binder. More importantly, even if the active materials loading increased to as high as 4.30 mg/cm2, the area capacity is still around 3.1 mAh/cm2 after 200 cycles. Such excellent performances could be attributed to the abundant oxygen- and nitrogen-containing functional groups of RG that can effectively inhibit the shuttle effect of LiPSs, as well as the excellent viscosity and mechanical properties that can maintain electrode integrity during long-term charging/discharging. This work verifies the feasibility of RG as an eco-friendly and high-performance Li-S battery binder and provides a new idea for the utilization of agricultural biomass resources.
Even the sulfur cathode in lithium-sulfur (Li-S) battery has the advantages of high theoretical energy density, wide source of raw materials, no pollution to the environment, and so on. It still suffers the sore points of easy electrode collapse due to large volume expansion during charge and discharge and low active materials utilization caused by the severe shuttle effect of lithium polysulfides (LiPSs). Therefore, in this work, ramie gum (RG) was extracted from ramie fiber degumming liquid and used as the functional binder to address the above problems and improve the Li-S battery's performance for the first time. Surprisingly, the sulfur cathode using RG binder illustrates a high initial capacity of 1152.2 mAh/g, and a reversible capacity of 644.6 mAh/g after 500 cycles at 0.5 C, far better than the sulfur cathode using polyvinylidene fluoride (PVDF) and sodium carboxymethyl cellulose (CMC) binder. More importantly, even if the active materials loading increased to as high as 4.30 mg/cm2, the area capacity is still around 3.1 mAh/cm2 after 200 cycles. Such excellent performances could be attributed to the abundant oxygen- and nitrogen-containing functional groups of RG that can effectively inhibit the shuttle effect of LiPSs, as well as the excellent viscosity and mechanical properties that can maintain electrode integrity during long-term charging/discharging. This work verifies the feasibility of RG as an eco-friendly and high-performance Li-S battery binder and provides a new idea for the utilization of agricultural biomass resources.
2025, 36(5): 109870
doi: 10.1016/j.cclet.2024.109870
摘要:
Although lithium-ion batteries (LIBs) currently dominate a wide spectrum of energy storage applications, they face challenges such as fast cycle life decay and poor stability that hinder their further application. To address these limitations, element doping has emerged as a prevalent strategy to enhance the discharge capacity and extend the durability of Li-Ni-Co-Mn (LNCM) ternary compounds. This study utilized a machine learning-driven feature screening method to effectively pinpoint four key features crucially impacting the initial discharge capacity (IC) of Li-Ni-Co-Mn (LNCM) ternary cathode materials. These features were also proved highly predictive for the 50th cycle discharge capacity (EC). Additionally, the application of SHAP value analysis yielded an in-depth understanding of the interplay between these features and discharge performance. This insight offers valuable direction for future advancements in the development of LNCM cathode materials, effectively promoting this field toward greater efficiency and sustainability.
Although lithium-ion batteries (LIBs) currently dominate a wide spectrum of energy storage applications, they face challenges such as fast cycle life decay and poor stability that hinder their further application. To address these limitations, element doping has emerged as a prevalent strategy to enhance the discharge capacity and extend the durability of Li-Ni-Co-Mn (LNCM) ternary compounds. This study utilized a machine learning-driven feature screening method to effectively pinpoint four key features crucially impacting the initial discharge capacity (IC) of Li-Ni-Co-Mn (LNCM) ternary cathode materials. These features were also proved highly predictive for the 50th cycle discharge capacity (EC). Additionally, the application of SHAP value analysis yielded an in-depth understanding of the interplay between these features and discharge performance. This insight offers valuable direction for future advancements in the development of LNCM cathode materials, effectively promoting this field toward greater efficiency and sustainability.
2025, 36(5): 109873
doi: 10.1016/j.cclet.2024.109873
摘要:
In this work, the synthesis of uniform zeolitic imidazolate framework-coated Mo-glycerate spheres and their subsequent conversion into hierarchical architecture containing bimetallic selenides heterostructures and nitrogen-doped carbon shell are reported. Selenization temperature plays a significant role in determining the phases, morphology, and lithium-ion storage performance of the composite. Notably, the optimal electrode demonstrates an ultrahigh reversible capacity of 1298.2 mAh/g after 100 cycles at 0.2 A/g and an outstanding rate capability with the capacity still maintained 505.7 mAh/g after 300 cycles at 1.0 A/g, surpassing the calculated theoretical capacity according to individual component and most of the reported MoSe@C- or ZnSe@C-based anodes. Furthermore, ex-situ X-ray diffraction patterns reveal the combined conversion and alloying reaction mechanisms of the composite.
In this work, the synthesis of uniform zeolitic imidazolate framework-coated Mo-glycerate spheres and their subsequent conversion into hierarchical architecture containing bimetallic selenides heterostructures and nitrogen-doped carbon shell are reported. Selenization temperature plays a significant role in determining the phases, morphology, and lithium-ion storage performance of the composite. Notably, the optimal electrode demonstrates an ultrahigh reversible capacity of 1298.2 mAh/g after 100 cycles at 0.2 A/g and an outstanding rate capability with the capacity still maintained 505.7 mAh/g after 300 cycles at 1.0 A/g, surpassing the calculated theoretical capacity according to individual component and most of the reported MoSe@C- or ZnSe@C-based anodes. Furthermore, ex-situ X-ray diffraction patterns reveal the combined conversion and alloying reaction mechanisms of the composite.
2025, 36(5): 109919
doi: 10.1016/j.cclet.2024.109919
摘要:
Industrial high-current-density oxygen evolution catalyst is the key to accelerating the practical application of hydrogen energy. Herein, Co9S8/CoS heterojunctions were rationally encapsulated in S, N-codoped carbon ((Co9S8/CoS)@SNC) microleaf arrays, which are rooted on S-doped carbonized wood fibers (SCWF). Benefiting from the synergistic electronic interactions on heterointerfaces and the accelerated mass transfer by array structure, the obtained self-supporting (Co9S8/CoS)@SNC/SCWF electrode exhibits superior performance toward alkaline oxygen evolution reaction (OER) with an ultra-low overpotential of 274 mV at 1000 mA/cm2, a small Tafel slope of 48.84 mV/dec, and ultralong stability up to 100 h. Theoretical calculations show that interfacing Co9S8 with CoS can upshift the d-band center of the Co atoms and strengthen the interactions with oxygen intermediates, thereby favoring OER performance. Furthermore, the (Co9S8/CoS)@SNC/SCWF electrode shows outstanding rechargeability and stable cycle life in aqueous Zn-air batteries with a peak power density of 201.3 mW/cm2, exceeding the commercial RuO2 and Pt/C hybrid catalysts. This work presents a promising strategy for the design of high-current-density OER electrocatalysts from sustainable wood fiber resources, thus promoting their practical applications in the field of electrochemical energy storage and conversion.
Industrial high-current-density oxygen evolution catalyst is the key to accelerating the practical application of hydrogen energy. Herein, Co9S8/CoS heterojunctions were rationally encapsulated in S, N-codoped carbon ((Co9S8/CoS)@SNC) microleaf arrays, which are rooted on S-doped carbonized wood fibers (SCWF). Benefiting from the synergistic electronic interactions on heterointerfaces and the accelerated mass transfer by array structure, the obtained self-supporting (Co9S8/CoS)@SNC/SCWF electrode exhibits superior performance toward alkaline oxygen evolution reaction (OER) with an ultra-low overpotential of 274 mV at 1000 mA/cm2, a small Tafel slope of 48.84 mV/dec, and ultralong stability up to 100 h. Theoretical calculations show that interfacing Co9S8 with CoS can upshift the d-band center of the Co atoms and strengthen the interactions with oxygen intermediates, thereby favoring OER performance. Furthermore, the (Co9S8/CoS)@SNC/SCWF electrode shows outstanding rechargeability and stable cycle life in aqueous Zn-air batteries with a peak power density of 201.3 mW/cm2, exceeding the commercial RuO2 and Pt/C hybrid catalysts. This work presents a promising strategy for the design of high-current-density OER electrocatalysts from sustainable wood fiber resources, thus promoting their practical applications in the field of electrochemical energy storage and conversion.
2025, 36(5): 109920
doi: 10.1016/j.cclet.2024.109920
摘要:
Aqueous proton batteries (APBs) embody a compelling alternative in the realm of economical and reliable energy technologies by virtue of their distinctive "Grotthuss mechanism". Sustainable production and adjustable molecular structure make organic polymers a promising choice for APB electrodes. However, inadequate proton-storage redox capability currently hinders their practical implementation. To address this issue, we introduce a pioneering phenazine-conjugated polymer (PPZ), synthesized through a straightforward polymerization process, marking its debut in APB applications. The inclusion of N-heteroaromatic fused-ring in the extended π-conjugated framework not only prevents the dissolution of redox-active units but also refines the energy bandgap and electronic properties, endowing the PPZ polymer with both structural integrity and enhanced redox activity. Consequently, the PPZ polymer as an electrode material achieves a remarkable proton-storage capacity of 211.5 mAh/g, maintaining a notable capacity of 158.3 mAh/g even under a high rate of 8 A/g with a minimal capacity fade of merely 0.00226% per cycle. The rapid, stable and impressive redox behavior is further elucidated through in-situ techniques and theoretical calculations. Ultimately, we fabricate an APB device featuring satisfactory electrochemical attributes with an extraordinary longevity over 10,000 cycles, thereby affirming its auspicious potential for eminent applications.
Aqueous proton batteries (APBs) embody a compelling alternative in the realm of economical and reliable energy technologies by virtue of their distinctive "Grotthuss mechanism". Sustainable production and adjustable molecular structure make organic polymers a promising choice for APB electrodes. However, inadequate proton-storage redox capability currently hinders their practical implementation. To address this issue, we introduce a pioneering phenazine-conjugated polymer (PPZ), synthesized through a straightforward polymerization process, marking its debut in APB applications. The inclusion of N-heteroaromatic fused-ring in the extended π-conjugated framework not only prevents the dissolution of redox-active units but also refines the energy bandgap and electronic properties, endowing the PPZ polymer with both structural integrity and enhanced redox activity. Consequently, the PPZ polymer as an electrode material achieves a remarkable proton-storage capacity of 211.5 mAh/g, maintaining a notable capacity of 158.3 mAh/g even under a high rate of 8 A/g with a minimal capacity fade of merely 0.00226% per cycle. The rapid, stable and impressive redox behavior is further elucidated through in-situ techniques and theoretical calculations. Ultimately, we fabricate an APB device featuring satisfactory electrochemical attributes with an extraordinary longevity over 10,000 cycles, thereby affirming its auspicious potential for eminent applications.
2025, 36(5): 109935
doi: 10.1016/j.cclet.2024.109935
摘要:
Developing effective strategy for constructing the electrocatalysts enable tri-functional electrocatalytic activity of hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is the premise to achieve both the zinc-air battery (ZAB) and overall water splitting. Herein, we utilize density functional theory to calculate the cobalt nitride (CoxN, x = 1, 2, 4, 5.47) system, revealing that the Co5.47N maybe exhibits a tri-functional activity due to the diverse valence states and high-density d-electron state of Co site. Furthermore, the electron of Co site is further delocalized by the electronic compensation effect of vanadium nitride (VN), thus improving the intermediates absorption and electrocatalytic activity. Accordingly, the Co5.47N/VN heterojunction is designed and synthesized via an electrospinning and a subsequent pyrolysis route. As expected, it displays excellent HER, OER, and ORR activity in alkaline electrolyte, which can be applied to assemble ZAB with a high power density of 207 mW/cm2 and overall water splitting system only requires a lower voltage of 1.53 V to achieve 10 mA/cm2. The electron regulation effect of VN makes the Co valence state decrease in the reduction reaction whereas increase in the oxidization reaction as evidenced by quasi-operando XPS analyses. Importantly, two ZABs connected in series could drive overall water splitting, indicating the potential application in renewable energy technologies.
Developing effective strategy for constructing the electrocatalysts enable tri-functional electrocatalytic activity of hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is the premise to achieve both the zinc-air battery (ZAB) and overall water splitting. Herein, we utilize density functional theory to calculate the cobalt nitride (CoxN, x = 1, 2, 4, 5.47) system, revealing that the Co5.47N maybe exhibits a tri-functional activity due to the diverse valence states and high-density d-electron state of Co site. Furthermore, the electron of Co site is further delocalized by the electronic compensation effect of vanadium nitride (VN), thus improving the intermediates absorption and electrocatalytic activity. Accordingly, the Co5.47N/VN heterojunction is designed and synthesized via an electrospinning and a subsequent pyrolysis route. As expected, it displays excellent HER, OER, and ORR activity in alkaline electrolyte, which can be applied to assemble ZAB with a high power density of 207 mW/cm2 and overall water splitting system only requires a lower voltage of 1.53 V to achieve 10 mA/cm2. The electron regulation effect of VN makes the Co valence state decrease in the reduction reaction whereas increase in the oxidization reaction as evidenced by quasi-operando XPS analyses. Importantly, two ZABs connected in series could drive overall water splitting, indicating the potential application in renewable energy technologies.
2025, 36(5): 109936
doi: 10.1016/j.cclet.2024.109936
摘要:
Metal-organic frameworks (MOFs) provide great prospective in the photodegradation of pollutants. Nevertheless, the poor separation and recovery hamper their pilot- or industrial-scare applications because of their microcrystalline features. Herein, this challenge can be tackled by integrating Cu-MOFs into an alginate substrate to offer environmentally friendly, sustainable, facile separation, and high-performance MOF-based hydrogel photocatalysis platforms. The CuII-MOF 1 and CuI-MOF 2 were initially synthesized through a direct diffusion and single-crystal to single-crystal (SCSC) transformation method, respectively, and after the immobilization into alginate, more effective pollutant decontamination was achieved via the synergistic effect of the adsorption feature of hydrogel and in situ photodegradation of Cu-MOFs. Specifically, Cu-MOF-alginate composites present an improved and nearly completed Cr(VI) elimination at a short time of 15–25 min. Additionally, the congo red (CR) decolorization can be effectively enhanced in the presence of Cr(VI), and 1-alginate showed superior simultaneous decontamination efficiency of CR and Cr(VI) with 99% and 78%, respectively. Furthermore, Cu-MOF-alginate composites can maintain a high pollutant removal after over 10 continuous cycles (95% for Cr(VI) after 14 runs, and 90% for CR after 10 runs). Moreover, the Cr(VI)/CR degradation mechanism for Cu-MOF-alginate composite was investigated.
Metal-organic frameworks (MOFs) provide great prospective in the photodegradation of pollutants. Nevertheless, the poor separation and recovery hamper their pilot- or industrial-scare applications because of their microcrystalline features. Herein, this challenge can be tackled by integrating Cu-MOFs into an alginate substrate to offer environmentally friendly, sustainable, facile separation, and high-performance MOF-based hydrogel photocatalysis platforms. The CuII-MOF 1 and CuI-MOF 2 were initially synthesized through a direct diffusion and single-crystal to single-crystal (SCSC) transformation method, respectively, and after the immobilization into alginate, more effective pollutant decontamination was achieved via the synergistic effect of the adsorption feature of hydrogel and in situ photodegradation of Cu-MOFs. Specifically, Cu-MOF-alginate composites present an improved and nearly completed Cr(VI) elimination at a short time of 15–25 min. Additionally, the congo red (CR) decolorization can be effectively enhanced in the presence of Cr(VI), and 1-alginate showed superior simultaneous decontamination efficiency of CR and Cr(VI) with 99% and 78%, respectively. Furthermore, Cu-MOF-alginate composites can maintain a high pollutant removal after over 10 continuous cycles (95% for Cr(VI) after 14 runs, and 90% for CR after 10 runs). Moreover, the Cr(VI)/CR degradation mechanism for Cu-MOF-alginate composite was investigated.
2025, 36(5): 109937
doi: 10.1016/j.cclet.2024.109937
摘要:
Cu-based metal-organic frameworks (MOFs) are widely employed in CO2 reduction reactions (CO2RR). Mostly, the in-situ reconstructed derivatives such as Cu or Cu oxides during CO2RR are regarded as the catalytic active center for the formation of catalytic products. However, in many cases, the pristine MOFs still exist during the catalytic process, the key role of these pristine MOFs is often ignored in revealing the catalytic mechanism. Here, we designed two Cu(imidazole) with different coordination environments, namely CuN2 and Cu2N4 for CO2RR. The structures of the two MOFs were still remained after the catalytic reaction. We discovered that the pristine MOFs served as activation catalysts for converting CO2 into CO. Sequentially, the Cu-based derivatives, in the two cases, Cu(111) converted the CO into C2+ products. The CuN2 with more exposed Cu-N centers showed a higher FECO and a higher final FEC2+ than Cu2N4. This auto-tandem catalytic mechanism was supported by electrocatalytic performance, TPD-CO, HRTEM, SAED, XPS, in-situ XANES and XES and DFT computation. The auto-tandem catalytic mechanism provides a new route to design Cu-based MOF electrocatalysts for high product selectivity in CO2RR.
Cu-based metal-organic frameworks (MOFs) are widely employed in CO2 reduction reactions (CO2RR). Mostly, the in-situ reconstructed derivatives such as Cu or Cu oxides during CO2RR are regarded as the catalytic active center for the formation of catalytic products. However, in many cases, the pristine MOFs still exist during the catalytic process, the key role of these pristine MOFs is often ignored in revealing the catalytic mechanism. Here, we designed two Cu(imidazole) with different coordination environments, namely CuN2 and Cu2N4 for CO2RR. The structures of the two MOFs were still remained after the catalytic reaction. We discovered that the pristine MOFs served as activation catalysts for converting CO2 into CO. Sequentially, the Cu-based derivatives, in the two cases, Cu(111) converted the CO into C2+ products. The CuN2 with more exposed Cu-N centers showed a higher FECO and a higher final FEC2+ than Cu2N4. This auto-tandem catalytic mechanism was supported by electrocatalytic performance, TPD-CO, HRTEM, SAED, XPS, in-situ XANES and XES and DFT computation. The auto-tandem catalytic mechanism provides a new route to design Cu-based MOF electrocatalysts for high product selectivity in CO2RR.
2025, 36(5): 109939
doi: 10.1016/j.cclet.2024.109939
摘要:
Listeria monocytogenes (LM) is a dangerous foodborne pathogen for humans. One emerging and validated method of indirectly assessing LM in food is detecting 3-hydroxy-2-butanone (3H2B) gas. In this study, the synthesis of 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTMS) functionalized hierarchical hollow TiO2 nanospheres was achieved via precise controlling of solvothermal reaction temperature and post-grafting route. The sensors based on as-prepared materials exhibited excellent sensitivity (480 Hz@50 ppm), low detection limit (100 ppb), and outstanding selectivity. Moreover, the evaluation of LM with high sensitivity and specificity was achieved using the sensors. Such stable three-dimensional spheres, whose distinctive hierarchical and hollow nanostructure simultaneously improved both sensitivity and response/recovery speed dramatically, were spontaneously assembled by nanosheets. Meanwhile, the moderate loadings of AAPTMS significantly improved the selectivity of sensors. Then, the gas-sensing mechanism was explored by utilizing thermodynamic investigation, Gaussian 16 software, and in situ diffuse reflectance infrared transform spectroscopy, illustrating the weak chemisorption between the -NH- group and 3H2B molecules. These portable sensors are promising for real-time assessment of LM at room temperature, which will make a magnificent contribution to food safety.
Listeria monocytogenes (LM) is a dangerous foodborne pathogen for humans. One emerging and validated method of indirectly assessing LM in food is detecting 3-hydroxy-2-butanone (3H2B) gas. In this study, the synthesis of 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTMS) functionalized hierarchical hollow TiO2 nanospheres was achieved via precise controlling of solvothermal reaction temperature and post-grafting route. The sensors based on as-prepared materials exhibited excellent sensitivity (480 Hz@50 ppm), low detection limit (100 ppb), and outstanding selectivity. Moreover, the evaluation of LM with high sensitivity and specificity was achieved using the sensors. Such stable three-dimensional spheres, whose distinctive hierarchical and hollow nanostructure simultaneously improved both sensitivity and response/recovery speed dramatically, were spontaneously assembled by nanosheets. Meanwhile, the moderate loadings of AAPTMS significantly improved the selectivity of sensors. Then, the gas-sensing mechanism was explored by utilizing thermodynamic investigation, Gaussian 16 software, and in situ diffuse reflectance infrared transform spectroscopy, illustrating the weak chemisorption between the -NH- group and 3H2B molecules. These portable sensors are promising for real-time assessment of LM at room temperature, which will make a magnificent contribution to food safety.
2025, 36(5): 109940
doi: 10.1016/j.cclet.2024.109940
摘要:
Shape control of nickel sulfide (NiS2) catalysts is beneficial for boosting their catalytic performances, which is vital to their practical application as a class of advanced non-noble electro-catalysts. However, precisely controlling the formation kinetics and fabricate ultrathin NiS2 nanostructures still remains challenge. Herein, we provide an injection rate-mediated method to fabricate ultrathin NiS2 nanocages (HNCs) with hierarchical walls, high-density lattice defects and abundant grain boundaries (GBs). Through mechanism analysis, we find the injection rate determines the concentration of S2− in the steady state and thus control the growth pattern, leading to the formation of NiS2 HNCs at slow etching kinetics and NiCo PBA@NiS2 frames at fast etching kinetics, respectively. Benefiting from the ultrathin and hierarchical walls that minimize the mass transport restrictions, the high-density lattice defects and GBs that offer abundant unsaturated reaction sites, the NiS2 HNCs exhibit obviously enhanced electrocatalytic activity and stability toward OER, with overpotential of 255 mV to reach 10 mA/cm2 and a Tafel slope of 27.44 mV/dec, surpassing the performances of NiCo PBA@NiS2 frames and commercial RuO2.
Shape control of nickel sulfide (NiS2) catalysts is beneficial for boosting their catalytic performances, which is vital to their practical application as a class of advanced non-noble electro-catalysts. However, precisely controlling the formation kinetics and fabricate ultrathin NiS2 nanostructures still remains challenge. Herein, we provide an injection rate-mediated method to fabricate ultrathin NiS2 nanocages (HNCs) with hierarchical walls, high-density lattice defects and abundant grain boundaries (GBs). Through mechanism analysis, we find the injection rate determines the concentration of S2− in the steady state and thus control the growth pattern, leading to the formation of NiS2 HNCs at slow etching kinetics and NiCo PBA@NiS2 frames at fast etching kinetics, respectively. Benefiting from the ultrathin and hierarchical walls that minimize the mass transport restrictions, the high-density lattice defects and GBs that offer abundant unsaturated reaction sites, the NiS2 HNCs exhibit obviously enhanced electrocatalytic activity and stability toward OER, with overpotential of 255 mV to reach 10 mA/cm2 and a Tafel slope of 27.44 mV/dec, surpassing the performances of NiCo PBA@NiS2 frames and commercial RuO2.
2025, 36(5): 110015
doi: 10.1016/j.cclet.2024.110015
摘要:
Mn-based P2-type oxides are considered as promising cathodes for Na-ion batteries; however, they face significant challenges, including structural degradation when charged at high cutoff voltages and structural changes upon storing in a humid atmosphere. In response to these issues, we have designed an oxide with co-doping of Cu and Al which can balance both cost and structural stability. The redox reaction of Cu2+/3+ can provide certain charge compensation, and the introduction of Al can further suppress the Jahn-Teller effect of Mn, thereby achieving superior long-term cycling performance. The ex-situ XRD testing indicates that Cu/Al co-doping can effectively suppress the phase transition of P2-O2 at high voltage, thereby explaining the improvement in electrochemical performance. DFT calculations reveal a high chemical tolerance to moisture, with lower adsorption energy for H2O compared to pure Na0.67Cu0.25Mn0.75O2. A representative Na0.67Cu0.20Al0.05Mn0.75O2 cathode demonstrates impressive reversible capacities of 148.7 mAh/g at 0.2 C, along with a remarkable capacity retention of 79.1% (2 C, 500 cycles).
Mn-based P2-type oxides are considered as promising cathodes for Na-ion batteries; however, they face significant challenges, including structural degradation when charged at high cutoff voltages and structural changes upon storing in a humid atmosphere. In response to these issues, we have designed an oxide with co-doping of Cu and Al which can balance both cost and structural stability. The redox reaction of Cu2+/3+ can provide certain charge compensation, and the introduction of Al can further suppress the Jahn-Teller effect of Mn, thereby achieving superior long-term cycling performance. The ex-situ XRD testing indicates that Cu/Al co-doping can effectively suppress the phase transition of P2-O2 at high voltage, thereby explaining the improvement in electrochemical performance. DFT calculations reveal a high chemical tolerance to moisture, with lower adsorption energy for H2O compared to pure Na0.67Cu0.25Mn0.75O2. A representative Na0.67Cu0.20Al0.05Mn0.75O2 cathode demonstrates impressive reversible capacities of 148.7 mAh/g at 0.2 C, along with a remarkable capacity retention of 79.1% (2 C, 500 cycles).
2025, 36(5): 110034
doi: 10.1016/j.cclet.2024.110034
摘要:
Environmentally friendly slow-release fertilizers are highly desired in sustainable agriculture. Encapsulating fertilizers can routinely achieve controlled releasing performances but suffers from short-term effectiveness or environmental unfriendliness. In this work, a bio-derived shellac incorporated with poly-dodecyl trimethoxysilane (SL-PDTMS) capsule was developed for long-term controlled releasing urea. Due to enhanced hydrophobicity and thus water resistance, the SL-PDTMS encapsulated urea fertilizer (SPEU) demonstrated a long-term effectiveness of 60 d, compared with SL encapsulated urea fertilizer (SEU, 30 d) and pure urea fertilizer (U, 5 min). In addition, SPEU showed a broad pH tolerance from 5.0 to 9.0, covering most various soil pH conditions. In the pot experiments, promoted growth of maize seedlings was observed after applying SPEU, rendering it promising as a high-performance controlled-released fertilizer.
Environmentally friendly slow-release fertilizers are highly desired in sustainable agriculture. Encapsulating fertilizers can routinely achieve controlled releasing performances but suffers from short-term effectiveness or environmental unfriendliness. In this work, a bio-derived shellac incorporated with poly-dodecyl trimethoxysilane (SL-PDTMS) capsule was developed for long-term controlled releasing urea. Due to enhanced hydrophobicity and thus water resistance, the SL-PDTMS encapsulated urea fertilizer (SPEU) demonstrated a long-term effectiveness of 60 d, compared with SL encapsulated urea fertilizer (SEU, 30 d) and pure urea fertilizer (U, 5 min). In addition, SPEU showed a broad pH tolerance from 5.0 to 9.0, covering most various soil pH conditions. In the pot experiments, promoted growth of maize seedlings was observed after applying SPEU, rendering it promising as a high-performance controlled-released fertilizer.
2025, 36(5): 110043
doi: 10.1016/j.cclet.2024.110043
摘要:
Carbon monoxide (CO) is a crucial gaseous signaling molecule that regulates various physiological and pathological processes, and may exert an anti-inflammatory and protective role in drug-induced liver injury (DILI). Despite this, understanding the exact relationship between CO and the occurrence and development of DILI remains challenging. Hence, there is an urgent need to develop a reliable and robust tool for the rapid visual detection and assessment of CO in this context. Herein, we presented a novel near-infrared (NIR) fluorescent nanoprobe with aggregation-induced emission (AIE) properties and excited-state intramolecular proton transfer (ESIPT) characteristics for the detection and imaging of CO both in vitro and in vivo. Simultaneously, the nanoprobe enables self-assembly form nanoaggregates in aqueous media with high biocompatible, which can sense CO in situ through the conversion of yellow-to-red fluorescence facilitated aggregation-induced dual-color fluorescence. What is more, this nanoprobe shows ratiometric respond to CO, which demonstrates excellent stability, high sensitivity (with a detection limit of 12.5 nmol/L), and superior selectivity. Crucially, this nanoprobe enables the visual detection of exogenous and endogenous CO in living cells and tissues affected by DILI, offering a user-friendly tool for real-time visualization of CO in living system. Hence, it holds great promise in advancing our understanding of CO's role.
Carbon monoxide (CO) is a crucial gaseous signaling molecule that regulates various physiological and pathological processes, and may exert an anti-inflammatory and protective role in drug-induced liver injury (DILI). Despite this, understanding the exact relationship between CO and the occurrence and development of DILI remains challenging. Hence, there is an urgent need to develop a reliable and robust tool for the rapid visual detection and assessment of CO in this context. Herein, we presented a novel near-infrared (NIR) fluorescent nanoprobe with aggregation-induced emission (AIE) properties and excited-state intramolecular proton transfer (ESIPT) characteristics for the detection and imaging of CO both in vitro and in vivo. Simultaneously, the nanoprobe enables self-assembly form nanoaggregates in aqueous media with high biocompatible, which can sense CO in situ through the conversion of yellow-to-red fluorescence facilitated aggregation-induced dual-color fluorescence. What is more, this nanoprobe shows ratiometric respond to CO, which demonstrates excellent stability, high sensitivity (with a detection limit of 12.5 nmol/L), and superior selectivity. Crucially, this nanoprobe enables the visual detection of exogenous and endogenous CO in living cells and tissues affected by DILI, offering a user-friendly tool for real-time visualization of CO in living system. Hence, it holds great promise in advancing our understanding of CO's role.
2025, 36(5): 110045
doi: 10.1016/j.cclet.2024.110045
摘要:
This study presents an approach to enhanced cancer immunotherapy through the in situ synthesis of potassium permanganate (KMnO4) derived manganese dioxide (MnO2) micro/nano-adjuvants. Addressing the limitations of traditional immunotherapy due to patient variability and the complexity of the tumor microenvironment, our research establishes KMnO4 as a potent immunomodulator that enhances the efficacy of anti-programmed death-ligand 1 (αPD-L1) antibodies. The in situ synthesized MnO2 adjuvants in the tumor exhibit direct interactions with biological systems, leading to the reduction of MnO2 to Mn2+ within the tumor, and thereby improving the microenvironment for immune cell activity. Our in vitro and in vivo models demonstrate KMnO4’s capability to induce concentration-dependent cytotoxicity in tumor cells, triggering DNA damage and apoptosis. It also potentiates immunogenic cell death by upregulating calreticulin and high mobility group box 1 (HMGB1) on the cell surface. The combination of KMnO4 with αPD-L1 antibodies substantially inhibits tumor growth, promotes dendritic cell maturation, and enhances CD8+ T cell infiltration, resulting in a significant phenotypic shift in tumor-associated macrophages towards a pro-inflammatory M1 profile. Our findings advocate for further research into the long-term efficacy of KMnO4 and its application in diverse tumor models, emphasizing its potential to redefine immune checkpoint blockade therapy and offering a new vista in the fight against cancer.
This study presents an approach to enhanced cancer immunotherapy through the in situ synthesis of potassium permanganate (KMnO4) derived manganese dioxide (MnO2) micro/nano-adjuvants. Addressing the limitations of traditional immunotherapy due to patient variability and the complexity of the tumor microenvironment, our research establishes KMnO4 as a potent immunomodulator that enhances the efficacy of anti-programmed death-ligand 1 (αPD-L1) antibodies. The in situ synthesized MnO2 adjuvants in the tumor exhibit direct interactions with biological systems, leading to the reduction of MnO2 to Mn2+ within the tumor, and thereby improving the microenvironment for immune cell activity. Our in vitro and in vivo models demonstrate KMnO4’s capability to induce concentration-dependent cytotoxicity in tumor cells, triggering DNA damage and apoptosis. It also potentiates immunogenic cell death by upregulating calreticulin and high mobility group box 1 (HMGB1) on the cell surface. The combination of KMnO4 with αPD-L1 antibodies substantially inhibits tumor growth, promotes dendritic cell maturation, and enhances CD8+ T cell infiltration, resulting in a significant phenotypic shift in tumor-associated macrophages towards a pro-inflammatory M1 profile. Our findings advocate for further research into the long-term efficacy of KMnO4 and its application in diverse tumor models, emphasizing its potential to redefine immune checkpoint blockade therapy and offering a new vista in the fight against cancer.
2025, 36(5): 110053
doi: 10.1016/j.cclet.2024.110053
摘要:
Crucial for mediating inflammation and the perception of pain, the ion channel known as transient receptor potential ankyrin 1 (TRPA1) holds significant importance. It contributes to the increased production of cytokines in the inflammatory cells of cartilage affected by osteoarthritis and represents a promising target for the treatment of this condition. By leveraging the unique advantages of liposomes, a composite microsphere drug delivery system with stable structural properties and high adaptability can be developed, providing a new strategy for osteoarthritis (OA) drug therapy. The liposomes as drug reservoirs for TRPA1 inhibitors were loaded into hyaluronic acid methacrylate (HAMA) hydrogels to make hydrogel microspheres via microfluidic technology. An in vitro inflammatory chondrocyte model was established with interleukin-1β (IL-1β) to demonstrate HAMA@Lipo@HC's capabilities. A destabilization of the medial meniscus (DMM) mouse model was also created to evaluate the efficacy of intra-articular injections for treating OA. HAMA@Lipo@HC has a uniform particle-size distribution and is injectable. The drug encapsulation rate was 64.29% ± 2.58%, with a sustained release period of 28 days. Inhibition of TRPA1 via HC-030031 effectively alleviated IL-1β-induced chondrocyte inflammation and matrix degradation. In DMM model OA mice, microspheres showed good long-term sustained drug release properties, improved joint inflammation microenvironment, reduced articular cartilage damage and decreased mechanical nociceptive threshold. This research pioneers the creation of a drug delivery system tailored for delivery into the joint cavity, focusing on TRPA1 as a therapeutic target for osteoarthritis. Additionally, it offers a cutting-edge drug delivery platform aimed at addressing diseases linked to inflammation.
Crucial for mediating inflammation and the perception of pain, the ion channel known as transient receptor potential ankyrin 1 (TRPA1) holds significant importance. It contributes to the increased production of cytokines in the inflammatory cells of cartilage affected by osteoarthritis and represents a promising target for the treatment of this condition. By leveraging the unique advantages of liposomes, a composite microsphere drug delivery system with stable structural properties and high adaptability can be developed, providing a new strategy for osteoarthritis (OA) drug therapy. The liposomes as drug reservoirs for TRPA1 inhibitors were loaded into hyaluronic acid methacrylate (HAMA) hydrogels to make hydrogel microspheres via microfluidic technology. An in vitro inflammatory chondrocyte model was established with interleukin-1β (IL-1β) to demonstrate HAMA@Lipo@HC's capabilities. A destabilization of the medial meniscus (DMM) mouse model was also created to evaluate the efficacy of intra-articular injections for treating OA. HAMA@Lipo@HC has a uniform particle-size distribution and is injectable. The drug encapsulation rate was 64.29% ± 2.58%, with a sustained release period of 28 days. Inhibition of TRPA1 via HC-030031 effectively alleviated IL-1β-induced chondrocyte inflammation and matrix degradation. In DMM model OA mice, microspheres showed good long-term sustained drug release properties, improved joint inflammation microenvironment, reduced articular cartilage damage and decreased mechanical nociceptive threshold. This research pioneers the creation of a drug delivery system tailored for delivery into the joint cavity, focusing on TRPA1 as a therapeutic target for osteoarthritis. Additionally, it offers a cutting-edge drug delivery platform aimed at addressing diseases linked to inflammation.
2025, 36(5): 110067
doi: 10.1016/j.cclet.2024.110067
摘要:
Postoperative recurrence and metastasis are still the main challenges of cancer therapy. Tumor vaccines that induce potent and long-lasting immune activation have great potential for postoperative cancer therapy. However, the clinical effects of therapeutic tumor vaccines are unsatisfactory due to immune escape caused by the lack of immunogenicity after surgery and the local fibrosis barrier of the tumor which limits effector T cell infiltration. To overcome these challenges, we developed an injectable hydrogel-based tumor vaccine, RATG, which contains whole tumor cell lysates (TCL), Toll-like receptor (TLR) 7/8 agonist imiquimod (R837) and an antifibrotic drug ARV-825. TCL and R837 were loaded onto the hydrogel to achieve a powerful reservoir of antigens and adjuvants that induced potent and lasting immune activation. More importantly, ARV-825 could be slowly and sustainably released in the tumor resection cavity to downregulate α-smooth muscle actin (α-SMA) and collagen levels, disintegrate fibrosis barriers and promote T cell infiltration after immune activation to reduce immune escape. In addition, ARV-825 also directly acted on the remaining tumor cells to degrade bromodomain-containing protein 4 (BRD4) which is a critical epigenetic reader overexpressed in tumor cells, inhibiting tumor cell migration and invasion. Therefore, our injectable hydrogel created a powerful immune niche in postoperative tumor resection cavity, significantly enhancing the efficacy of tumor vaccines. Our strategy potently activates the immune system and disintegrates the fibrotic barrier of residual tumors with immune microenvironment remodeling in situ, showing anti-recurrence and anti-metastatic effects, and provides a new paradigm for postoperative treatment of tumors.
Postoperative recurrence and metastasis are still the main challenges of cancer therapy. Tumor vaccines that induce potent and long-lasting immune activation have great potential for postoperative cancer therapy. However, the clinical effects of therapeutic tumor vaccines are unsatisfactory due to immune escape caused by the lack of immunogenicity after surgery and the local fibrosis barrier of the tumor which limits effector T cell infiltration. To overcome these challenges, we developed an injectable hydrogel-based tumor vaccine, RATG, which contains whole tumor cell lysates (TCL), Toll-like receptor (TLR) 7/8 agonist imiquimod (R837) and an antifibrotic drug ARV-825. TCL and R837 were loaded onto the hydrogel to achieve a powerful reservoir of antigens and adjuvants that induced potent and lasting immune activation. More importantly, ARV-825 could be slowly and sustainably released in the tumor resection cavity to downregulate α-smooth muscle actin (α-SMA) and collagen levels, disintegrate fibrosis barriers and promote T cell infiltration after immune activation to reduce immune escape. In addition, ARV-825 also directly acted on the remaining tumor cells to degrade bromodomain-containing protein 4 (BRD4) which is a critical epigenetic reader overexpressed in tumor cells, inhibiting tumor cell migration and invasion. Therefore, our injectable hydrogel created a powerful immune niche in postoperative tumor resection cavity, significantly enhancing the efficacy of tumor vaccines. Our strategy potently activates the immune system and disintegrates the fibrotic barrier of residual tumors with immune microenvironment remodeling in situ, showing anti-recurrence and anti-metastatic effects, and provides a new paradigm for postoperative treatment of tumors.
2025, 36(5): 110069
doi: 10.1016/j.cclet.2024.110069
摘要:
Efficient electrocatalysts for oxygen reduction reaction (ORR) show significant importance for advancing the performance and affordability of proton exchange membrane fuel cells and other energy conversion devices. Herein, PtCo3 nanoalloys dispersed on a carbon black support, were prepared using ultrafast Joule heating method. By tuning the heating modes, such as high-temperature shock and heating for 2 s, two kinds of PtCo3 nanoalloys with varying crystallinities were obtained, referred to as PtCo3HTS (average size of 5.4 nm) and PtCo3HT-2 s (average size of 6.4 nm), respectively. Impressively, PtCo3HTS exhibited superior electrocatalytic ORR activity and stability (E1/2 = 0.897 V vs. RHE and 36 mV negative shift after 50, 000 cycles), outperforming PtCo3HT-2 s (E1/2 = 0.872 V and 16.2 mV negative shift), as well as the commercial Pt/C (20 wt%) catalyst (E1/2 = 0.847 V and 21.0 mV negative shift). The enhanced ORR performance of PtCo3HTS may be attributed to its low crystallinity, which results in an active local electronic structure and chemical state, as confirmed by X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) analyses. The ultrafast Joule heating method showed great potential for crystallinity engineering, offering a promising pathway to revolutionize the manufacturing of cost-effective and environmentally friendly catalysts for clean energy applications.
Efficient electrocatalysts for oxygen reduction reaction (ORR) show significant importance for advancing the performance and affordability of proton exchange membrane fuel cells and other energy conversion devices. Herein, PtCo3 nanoalloys dispersed on a carbon black support, were prepared using ultrafast Joule heating method. By tuning the heating modes, such as high-temperature shock and heating for 2 s, two kinds of PtCo3 nanoalloys with varying crystallinities were obtained, referred to as PtCo3HTS (average size of 5.4 nm) and PtCo3HT-2 s (average size of 6.4 nm), respectively. Impressively, PtCo3HTS exhibited superior electrocatalytic ORR activity and stability (E1/2 = 0.897 V vs. RHE and 36 mV negative shift after 50, 000 cycles), outperforming PtCo3HT-2 s (E1/2 = 0.872 V and 16.2 mV negative shift), as well as the commercial Pt/C (20 wt%) catalyst (E1/2 = 0.847 V and 21.0 mV negative shift). The enhanced ORR performance of PtCo3HTS may be attributed to its low crystallinity, which results in an active local electronic structure and chemical state, as confirmed by X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) analyses. The ultrafast Joule heating method showed great potential for crystallinity engineering, offering a promising pathway to revolutionize the manufacturing of cost-effective and environmentally friendly catalysts for clean energy applications.
2025, 36(5): 110073
doi: 10.1016/j.cclet.2024.110073
摘要:
Diseases associated with bacterial infection, especially those caused by gram-negative bacteria, have been posing a serious threat to human health. Photodynamic therapy based on aggregation-induced emission (AIE) photosensitizer have recently emerged and provided a promising approach for bacterial discrimination and efficient photodynamic antimicrobial applications. However, they often suffer from the shorter excitation wavelength and lower molar extinction coefficients in the visible region, severely limiting their further applications. Herein, three novel BF2-curcuminoid-based AIE photosensitizers, TBBC, TBC and TBBC-C8, have been rationally designed and successfully developed, in which OCH3- and OC8H17-substituted tetraphenylethene (TPE) groups serve as both electron donor (D) and AIE active moieties, BF2bdk group functions as electron acceptor (A), and styrene (or ethylene) group as π-bridge in this D-π-A-π-D system, respectively. As expected, these resulting BF2-curcuminoids presented solvent-dependent photophysical properties with large molar extinction coefficients in solutions and excellent AIE properties. Notably, TBBC showed an effective singlet oxygen generation efficiency thanks to the smaller singlet-triplet energy gap (ΔEST), and remarkable photostability under green light exposure at 530 nm (8.9 mW/cm2). More importantly, TBBC was demonstrated effectiveness in selective staining and photodynamic killing of Escherichia coli (E. coli) in vitro probably due to its optimal molecular size compared with TBC and TBBC-C8. Therefore, TBBC will have great potential as a novel AIE photosensitizer to apply in the discrimination and selective sterilization between Gram-positive and Gram-negative bacteria.
Diseases associated with bacterial infection, especially those caused by gram-negative bacteria, have been posing a serious threat to human health. Photodynamic therapy based on aggregation-induced emission (AIE) photosensitizer have recently emerged and provided a promising approach for bacterial discrimination and efficient photodynamic antimicrobial applications. However, they often suffer from the shorter excitation wavelength and lower molar extinction coefficients in the visible region, severely limiting their further applications. Herein, three novel BF2-curcuminoid-based AIE photosensitizers, TBBC, TBC and TBBC-C8, have been rationally designed and successfully developed, in which OCH3- and OC8H17-substituted tetraphenylethene (TPE) groups serve as both electron donor (D) and AIE active moieties, BF2bdk group functions as electron acceptor (A), and styrene (or ethylene) group as π-bridge in this D-π-A-π-D system, respectively. As expected, these resulting BF2-curcuminoids presented solvent-dependent photophysical properties with large molar extinction coefficients in solutions and excellent AIE properties. Notably, TBBC showed an effective singlet oxygen generation efficiency thanks to the smaller singlet-triplet energy gap (ΔEST), and remarkable photostability under green light exposure at 530 nm (8.9 mW/cm2). More importantly, TBBC was demonstrated effectiveness in selective staining and photodynamic killing of Escherichia coli (E. coli) in vitro probably due to its optimal molecular size compared with TBC and TBBC-C8. Therefore, TBBC will have great potential as a novel AIE photosensitizer to apply in the discrimination and selective sterilization between Gram-positive and Gram-negative bacteria.
2025, 36(5): 110082
doi: 10.1016/j.cclet.2024.110082
摘要:
Acute lung injury (ALI) is a serious clinical condition with a high mortality rate. Oxidative stress and inflammatory responses play pivotal roles in the pathogenesis of ALI. ONOO− is a key mediator that exacerbates oxidative damage and microvascular permeability in ALI. Accurate detection of ONOO− would facilitate early diagnosis and intervention in ALI. Near-infrared fluorescence (NIRF) probes offer new solutions due to their sensitivity, depth of tissue penetration, and imaging capabilities. However, the developed ONOO− fluorescent probes face problems such as interference from other reactive oxygen species and easy intracellular diffusion. To address these issues, we introduced an innovative self-immobilizing NIRF probe, DCI2F-OTf, which was capable of monitoring ONOO− in vitro and in vivo. Importantly, leveraging the high reactivity of the methylene quinone (QM) intermediate, DCI2F-OTf was able to covalently label proteins in the presence of ONOO−, enabling in situ imaging. In mice models of ALI, DCI2F-OTf enabled real-time imaging of ONOO− levels and found that ONOO− was tightly correlated with the progression of ALI. Our findings demonstrated that DCI2F-OTf was a promising chemical tool for the detection of ONOO−, which could help to gain insight into the pathogenesis of ALI and monitor treatment efficacy.
Acute lung injury (ALI) is a serious clinical condition with a high mortality rate. Oxidative stress and inflammatory responses play pivotal roles in the pathogenesis of ALI. ONOO− is a key mediator that exacerbates oxidative damage and microvascular permeability in ALI. Accurate detection of ONOO− would facilitate early diagnosis and intervention in ALI. Near-infrared fluorescence (NIRF) probes offer new solutions due to their sensitivity, depth of tissue penetration, and imaging capabilities. However, the developed ONOO− fluorescent probes face problems such as interference from other reactive oxygen species and easy intracellular diffusion. To address these issues, we introduced an innovative self-immobilizing NIRF probe, DCI2F-OTf, which was capable of monitoring ONOO− in vitro and in vivo. Importantly, leveraging the high reactivity of the methylene quinone (QM) intermediate, DCI2F-OTf was able to covalently label proteins in the presence of ONOO−, enabling in situ imaging. In mice models of ALI, DCI2F-OTf enabled real-time imaging of ONOO− levels and found that ONOO− was tightly correlated with the progression of ALI. Our findings demonstrated that DCI2F-OTf was a promising chemical tool for the detection of ONOO−, which could help to gain insight into the pathogenesis of ALI and monitor treatment efficacy.
2025, 36(5): 110084
doi: 10.1016/j.cclet.2024.110084
摘要:
Glioma is a severe malignant brain tumor marked by an exceedingly dire prognosis and elevated incidence of recurrence. The resilience of such tumors to chemotherapeutic agents, coupled with the formidable obstacle the blood-brain barrier (BBB) presents to most pharmacological interventions are major challenges in anti-glioma therapy. In an endeavor to surmount these impediments, we have synergized pH-sensitive nanoparticles carrying doxorubicin and apatinib to amplify the anti-neoplastic efficacy with cyclic arginine–glycine–aspartate acid (cRGD) modification. In this study, we found that the combination of doxorubicin (DOX) and apatinib (AP) showed a significant synergistic effect, achieved through cytotoxicity and induction of apoptosis, which might be due to the increased intracellular uptake of DOX following AP treatment. Besides, polycaprolactone-polyethylene glycol-cRGD (PCL-PEG-cRGD) drug carrier could cross the BBB by its targeting ability, and then deliver the drug to the glioma site via pH-responsive release, increasing the concentration of the drugs in the tumor. Meanwhile, DOX/AP-loaded PCL-PEG-cRGD nanoparticles effectively inhibited cell proliferation, enhanced glioma cell apoptosis, and retarded tumor growth in vivo. These results collectively identified DOX/AP-loaded PCL-PEG-cRGD nanoparticles as a promising therapeutic candidate for the treatment of glioma.
Glioma is a severe malignant brain tumor marked by an exceedingly dire prognosis and elevated incidence of recurrence. The resilience of such tumors to chemotherapeutic agents, coupled with the formidable obstacle the blood-brain barrier (BBB) presents to most pharmacological interventions are major challenges in anti-glioma therapy. In an endeavor to surmount these impediments, we have synergized pH-sensitive nanoparticles carrying doxorubicin and apatinib to amplify the anti-neoplastic efficacy with cyclic arginine–glycine–aspartate acid (cRGD) modification. In this study, we found that the combination of doxorubicin (DOX) and apatinib (AP) showed a significant synergistic effect, achieved through cytotoxicity and induction of apoptosis, which might be due to the increased intracellular uptake of DOX following AP treatment. Besides, polycaprolactone-polyethylene glycol-cRGD (PCL-PEG-cRGD) drug carrier could cross the BBB by its targeting ability, and then deliver the drug to the glioma site via pH-responsive release, increasing the concentration of the drugs in the tumor. Meanwhile, DOX/AP-loaded PCL-PEG-cRGD nanoparticles effectively inhibited cell proliferation, enhanced glioma cell apoptosis, and retarded tumor growth in vivo. These results collectively identified DOX/AP-loaded PCL-PEG-cRGD nanoparticles as a promising therapeutic candidate for the treatment of glioma.
2025, 36(5): 110097
doi: 10.1016/j.cclet.2024.110097
摘要:
Insufficient endogenous H2O2 for generation of hydroxyl radicals (•OH) has strikingly compromised anti-tumor benefits of ferroptosis. Herein, we develop a H2O2 self-supplying nanoparticle based on a pH-responsive lipopeptide C18-pHis10. Inspired by the coordinate pattern of hemoglobin binding heme, Fe2+ and tetrakis(4-carboxyphenyl)porphyrin (TCPP) were delicately encapsulated by formation of coordination compounds with His. Ascorbgyl palmitate (AscP) was also incorporated into the nanoparticles for generation of H2O2 by reduction 1O2 produced from TCPP, meanwhile prevented Fe2+ from being oxidized. The protonation of pHis in acidic endo-lysosome induced the breakage of Fe2+/His/TCPP coordinate interactions, leading to accelerated release of payloads and the following escape to cytoplasm. Upon laser irradiation, TCPP produces excessive 1O2 followed by conversion to H2O2 in the presence of AscP, which is further catalyzed to lethal •OH by Fe2+ via Fenton reaction. The self-supplying H2O2 was found to result significantly higher accumulation of lipid peroxides and more effective tumor inhibition. Overall, this work sheds new a light on H2O2 self-supplying strategy to enhance ferroptosis by taking advantage of 1O2 generated by photodynamic therapy (PDT).
Insufficient endogenous H2O2 for generation of hydroxyl radicals (•OH) has strikingly compromised anti-tumor benefits of ferroptosis. Herein, we develop a H2O2 self-supplying nanoparticle based on a pH-responsive lipopeptide C18-pHis10. Inspired by the coordinate pattern of hemoglobin binding heme, Fe2+ and tetrakis(4-carboxyphenyl)porphyrin (TCPP) were delicately encapsulated by formation of coordination compounds with His. Ascorbgyl palmitate (AscP) was also incorporated into the nanoparticles for generation of H2O2 by reduction 1O2 produced from TCPP, meanwhile prevented Fe2+ from being oxidized. The protonation of pHis in acidic endo-lysosome induced the breakage of Fe2+/His/TCPP coordinate interactions, leading to accelerated release of payloads and the following escape to cytoplasm. Upon laser irradiation, TCPP produces excessive 1O2 followed by conversion to H2O2 in the presence of AscP, which is further catalyzed to lethal •OH by Fe2+ via Fenton reaction. The self-supplying H2O2 was found to result significantly higher accumulation of lipid peroxides and more effective tumor inhibition. Overall, this work sheds new a light on H2O2 self-supplying strategy to enhance ferroptosis by taking advantage of 1O2 generated by photodynamic therapy (PDT).
2025, 36(5): 110098
doi: 10.1016/j.cclet.2024.110098
摘要:
D-D'-A type aza-borondipyrromethenes (aza-BODIPYs) were prepared by Suzuki cross-coupling reaction. Photothermal conversion efficiency of self-assemble aza-BODIPY-based nanoparticles (DA-azaBDP-NPs) with NIR-II emission (λem = 1065 nm) was 37.2% under near infrared (NIR) irradiation, and the outstanding cytotoxicity was triggered by coexistence of DA-azaBDP-NPs and the NIR irradiation, with the decrease of glioblastoma migration and the inhibition of glioblastoma proliferation. DA-azaBDP-NPs could promote glioblastoma autophagy and accelerate the process of cell death. The photothermal therapy (PTT) of DA-azaBDP-NPs can effectively induce glioblastoma death by apoptosis under the NIR irradiation, which is highly promising to be applied in vivo experiments of brain.
D-D'-A type aza-borondipyrromethenes (aza-BODIPYs) were prepared by Suzuki cross-coupling reaction. Photothermal conversion efficiency of self-assemble aza-BODIPY-based nanoparticles (DA-azaBDP-NPs) with NIR-II emission (λem = 1065 nm) was 37.2% under near infrared (NIR) irradiation, and the outstanding cytotoxicity was triggered by coexistence of DA-azaBDP-NPs and the NIR irradiation, with the decrease of glioblastoma migration and the inhibition of glioblastoma proliferation. DA-azaBDP-NPs could promote glioblastoma autophagy and accelerate the process of cell death. The photothermal therapy (PTT) of DA-azaBDP-NPs can effectively induce glioblastoma death by apoptosis under the NIR irradiation, which is highly promising to be applied in vivo experiments of brain.
2025, 36(5): 110105
doi: 10.1016/j.cclet.2024.110105
摘要:
Singlet oxygen (1O2), as the primary reactive oxygen species in photodynamic therapy, can effectively induce excessive oxidative stress to ablate tumors and kill germs in clinical treatment. However, monitoring endogenous 1O2 is greatly challenging due to its extremely short lifetime and high reactivity in biological condition. Herein, we report an ultra-high signal-to-ratio near-infrared chemiluminescent probe (DCM-Cy) for the precise detection of endogenous 1O2 during photodynamic therapy (PDT). The methoxy moiety was removed from enolether unit in DCM-Cy to suppress the potential self-photooxidation reaction, thus greatly eliminating the photoinduced background signals during PDT. Additionally, the compact cyclobutane modification of DCM-Cy resulted in a significant 6-fold increase in cell permeability compared to conventional adamantane-dioxane probes. Therefore, our "step-by-step" strategy for DCM-Cy addressed the limitations of traditional chemiluminescent (CL) probes for 1O2, enabling effectively tracking of endogenous 1O2 level changes in living cells, pathogenic bacteria and mice in PDT.
Singlet oxygen (1O2), as the primary reactive oxygen species in photodynamic therapy, can effectively induce excessive oxidative stress to ablate tumors and kill germs in clinical treatment. However, monitoring endogenous 1O2 is greatly challenging due to its extremely short lifetime and high reactivity in biological condition. Herein, we report an ultra-high signal-to-ratio near-infrared chemiluminescent probe (DCM-Cy) for the precise detection of endogenous 1O2 during photodynamic therapy (PDT). The methoxy moiety was removed from enolether unit in DCM-Cy to suppress the potential self-photooxidation reaction, thus greatly eliminating the photoinduced background signals during PDT. Additionally, the compact cyclobutane modification of DCM-Cy resulted in a significant 6-fold increase in cell permeability compared to conventional adamantane-dioxane probes. Therefore, our "step-by-step" strategy for DCM-Cy addressed the limitations of traditional chemiluminescent (CL) probes for 1O2, enabling effectively tracking of endogenous 1O2 level changes in living cells, pathogenic bacteria and mice in PDT.
2025, 36(5): 110106
doi: 10.1016/j.cclet.2024.110106
摘要:
Interstitial hypertension and extracellular matrix (ECM) barriers imposed by cancer-associated fibroblasts (CAFs) at the tumor site significantly impede the retention of intratumorally administered oncolytic viruses (OVs) as well as their efficacy in infecting and eradicating tumor cells. Herein, a stable, controllable, and easily prepared hydrogel was developed for employing a differential release strategy to deliver OVs. The oncolytic herpes simplex virus-2 (oH2) particles were loaded within sodium alginate (ALG), together with the small molecule drug PT-100 targeting CAFs. The rapid release of PT-100 functions as an anti-CAFs agent, reducing ECM, and alleviating interstitial pressure at the tumor site. Consequently, the delayed release of oH2 could more effectively invade and eradicate tumor cells while also facilitating enhanced infiltration of immune cells into the tumor microenvironment, thereby establishing an immunologically favorable milieu against tumors. This approach holds significant potential for achieving highly efficient oncolytic virus therapy with minimal toxicity, particularly in tumors rich in stromal components.
Interstitial hypertension and extracellular matrix (ECM) barriers imposed by cancer-associated fibroblasts (CAFs) at the tumor site significantly impede the retention of intratumorally administered oncolytic viruses (OVs) as well as their efficacy in infecting and eradicating tumor cells. Herein, a stable, controllable, and easily prepared hydrogel was developed for employing a differential release strategy to deliver OVs. The oncolytic herpes simplex virus-2 (oH2) particles were loaded within sodium alginate (ALG), together with the small molecule drug PT-100 targeting CAFs. The rapid release of PT-100 functions as an anti-CAFs agent, reducing ECM, and alleviating interstitial pressure at the tumor site. Consequently, the delayed release of oH2 could more effectively invade and eradicate tumor cells while also facilitating enhanced infiltration of immune cells into the tumor microenvironment, thereby establishing an immunologically favorable milieu against tumors. This approach holds significant potential for achieving highly efficient oncolytic virus therapy with minimal toxicity, particularly in tumors rich in stromal components.
2025, 36(5): 110116
doi: 10.1016/j.cclet.2024.110116
摘要:
Constructing multi-dimensional hydrogen bond (H-bond) regulated single-molecule systems with multi-emission remains a challenge. Herein, we report the design of a new excited-state intramolecular proton transfer (ESIPT) featured chromophore (HBT-DPI) that shows flexible emission tunability via the multi-dimensional regulation of intra- and intermolecular H-bonds. The feature of switchable intramolecular H-bonds is induced via incorporating several hydrogen bond acceptors and donors into one single HBT-DPI molecule, allowing the "turn on/off" of ESIPT process by forming isomers with distinct intramolecular H-bonds configurations. In response to different external H-bonding environments, the obtained four types of crystal/cocrystals vary in the contents of isomers and the molecular packing modes, which are mainly guided by the intermolecular H-bonds, exhibiting non-emissive features or emissions ranging from green to orange. Utilizing the feature of intermolecular H-bond guided molecular packing, we demonstrate the utility of this fluorescent material for visualizing hydrophobic/hydrophilic areas on large-scale heterogeneous surfaces of modified poly(1,1-difluoroethylene) (PVDF) membranes and quantitatively estimating the surface hydrophobicity, providing a new approach for hydrophobicity/hydrophilicity monitoring and measurement. Overall, this study represents a new design strategy for constructing multi-dimensional hydrogen bond regulated ESIPT-based fluorescent materials that enable multiple emissions and unique applications.
Constructing multi-dimensional hydrogen bond (H-bond) regulated single-molecule systems with multi-emission remains a challenge. Herein, we report the design of a new excited-state intramolecular proton transfer (ESIPT) featured chromophore (HBT-DPI) that shows flexible emission tunability via the multi-dimensional regulation of intra- and intermolecular H-bonds. The feature of switchable intramolecular H-bonds is induced via incorporating several hydrogen bond acceptors and donors into one single HBT-DPI molecule, allowing the "turn on/off" of ESIPT process by forming isomers with distinct intramolecular H-bonds configurations. In response to different external H-bonding environments, the obtained four types of crystal/cocrystals vary in the contents of isomers and the molecular packing modes, which are mainly guided by the intermolecular H-bonds, exhibiting non-emissive features or emissions ranging from green to orange. Utilizing the feature of intermolecular H-bond guided molecular packing, we demonstrate the utility of this fluorescent material for visualizing hydrophobic/hydrophilic areas on large-scale heterogeneous surfaces of modified poly(1,1-difluoroethylene) (PVDF) membranes and quantitatively estimating the surface hydrophobicity, providing a new approach for hydrophobicity/hydrophilicity monitoring and measurement. Overall, this study represents a new design strategy for constructing multi-dimensional hydrogen bond regulated ESIPT-based fluorescent materials that enable multiple emissions and unique applications.
2025, 36(5): 110119
doi: 10.1016/j.cclet.2024.110119
摘要:
Photodynamic therapy (PDT) has emerged as a promising approach for tumor treatment due to its non-invasiveness and high selectivity. However, the off-target activation of phototoxicity and the limited availability of tumor-specific biomarkers pose challenges for effective PDT. Here, we present the development of a novel ratiometric near-infrared-Ⅱ (NIR-Ⅱ) fluorescent organic nanoprobe, BTz-IC@IR1061, which responds specifically to hypochlorite (HClO) within tumors. This nanoprobe allows ratiometric fluorescence imaging to monitor and guide activated tumor PDT. BTz-IC@IR1061 nanoparticles were synthesized by codoping the small molecule dye BTz-IC, which generates reactive oxygen species (ROS), with the commercial dye IR1061. The presence of HClO selectively activates the fluorescence and photodynamic properties of BTz-IC while destroying IR1061, enabling controlled release of ROS for tumor therapy. We demonstrated the high selectivity of the nanoprobe for HClO, as well as its excellent photostability, photoacoustic imaging capability, and photothermal effects. Furthermore, in vivo studies revealed effective tumor targeting and remarkable tumor growth inhibition through tumor-activated PDT. Our findings highlight the potential of BTz-IC@IR1061 as a promising tool for tumor-specific PDT, providing new opportunities for precise and controlled cancer therapy.
Photodynamic therapy (PDT) has emerged as a promising approach for tumor treatment due to its non-invasiveness and high selectivity. However, the off-target activation of phototoxicity and the limited availability of tumor-specific biomarkers pose challenges for effective PDT. Here, we present the development of a novel ratiometric near-infrared-Ⅱ (NIR-Ⅱ) fluorescent organic nanoprobe, BTz-IC@IR1061, which responds specifically to hypochlorite (HClO) within tumors. This nanoprobe allows ratiometric fluorescence imaging to monitor and guide activated tumor PDT. BTz-IC@IR1061 nanoparticles were synthesized by codoping the small molecule dye BTz-IC, which generates reactive oxygen species (ROS), with the commercial dye IR1061. The presence of HClO selectively activates the fluorescence and photodynamic properties of BTz-IC while destroying IR1061, enabling controlled release of ROS for tumor therapy. We demonstrated the high selectivity of the nanoprobe for HClO, as well as its excellent photostability, photoacoustic imaging capability, and photothermal effects. Furthermore, in vivo studies revealed effective tumor targeting and remarkable tumor growth inhibition through tumor-activated PDT. Our findings highlight the potential of BTz-IC@IR1061 as a promising tool for tumor-specific PDT, providing new opportunities for precise and controlled cancer therapy.
2025, 36(5): 110128
doi: 10.1016/j.cclet.2024.110128
摘要:
The bioactive constituents found in natural products (NPs) are crucial in protein-ligand interactions and drug discovery. However, it is difficult to identify ligand molecules from complex NPs that specifically bind to target protein, which often requires time-consuming and labor-intensive processes such as isolation and enrichment. To address this issue, in this study we developed a method that combines ultra-high performance liquid chromatography-electrospray ionization-mass spectrometry (UHPLC-ESI-MS) with molecular dynamics (MD) simulation to identify and observe, rapidly and efficiently, the bioactive components in NPs that bind to specific protein target. In this method, a specific protein target was introduced online using a three-way valve to form a protein-ligand complex. The complex was then detected in real time using high-resolution MS to identify potential ligands. Based on our method, only 10 molecules from green tea (a representative natural product), including the commonly reported epigallocatechin gallate (EGCG) and epicatechin gallate (ECG), as well as the previously unreported eepicatechin (4β→8)-epigallocatechin 3-O-gallate (EC-EGCG) and eepiafzelechin 3-O-gallate-(4β→8)-epigallocatechin 3-O-gallate (EFG-EGCG), were screened out, which could form complexes with Aβ1–42 (a representative protein target), and could be potential ligands of Aβ1–42. Among of them, EC-EGCG demonstrated the highest binding free energy with Aβ1–42 (−68.54 ± 3.82 kcal/mol). On the other side, even though the caffeine had the highest signal among green tea extracts, it was not observed to form a complex with Aβ1–42. Compared to other methods such as affinity selection mass spectrometry (ASMS) and native MS, our method is easy to operate and interpret the data. Undoubtedly, it provides a new methodology for potential drug discovery in NPs, and will accelerate the research on screening ligands for specific proteins from complex NPs.
The bioactive constituents found in natural products (NPs) are crucial in protein-ligand interactions and drug discovery. However, it is difficult to identify ligand molecules from complex NPs that specifically bind to target protein, which often requires time-consuming and labor-intensive processes such as isolation and enrichment. To address this issue, in this study we developed a method that combines ultra-high performance liquid chromatography-electrospray ionization-mass spectrometry (UHPLC-ESI-MS) with molecular dynamics (MD) simulation to identify and observe, rapidly and efficiently, the bioactive components in NPs that bind to specific protein target. In this method, a specific protein target was introduced online using a three-way valve to form a protein-ligand complex. The complex was then detected in real time using high-resolution MS to identify potential ligands. Based on our method, only 10 molecules from green tea (a representative natural product), including the commonly reported epigallocatechin gallate (EGCG) and epicatechin gallate (ECG), as well as the previously unreported eepicatechin (4β→8)-epigallocatechin 3-O-gallate (EC-EGCG) and eepiafzelechin 3-O-gallate-(4β→8)-epigallocatechin 3-O-gallate (EFG-EGCG), were screened out, which could form complexes with Aβ1–42 (a representative protein target), and could be potential ligands of Aβ1–42. Among of them, EC-EGCG demonstrated the highest binding free energy with Aβ1–42 (−68.54 ± 3.82 kcal/mol). On the other side, even though the caffeine had the highest signal among green tea extracts, it was not observed to form a complex with Aβ1–42. Compared to other methods such as affinity selection mass spectrometry (ASMS) and native MS, our method is easy to operate and interpret the data. Undoubtedly, it provides a new methodology for potential drug discovery in NPs, and will accelerate the research on screening ligands for specific proteins from complex NPs.
2025, 36(5): 110130
doi: 10.1016/j.cclet.2024.110130
摘要:
The overuse of surfactants has made them well-known environmental pollutants. So far, it is still a challenge to simultaneously distinguish cationic, anionic, zwitterionic, nonionic surfactants and surfactants with similar structures based on traditional analytical techniques. We developed a high-throughput method for distinguishing various surfactants based on the adaptive emission profile as fingerprints (AEPF). The fluorescence response of the sensor was based on the interaction between surfactants and 1,3-diacetylpyrene (o-DAP) probe. The interaction affected the reversible conversion of free molecules and two aggregates in the solution, thereby changing the relative abundance and the fluorescence intensity ratio of two aggregates emitting different fluorescence. The o-DAP sensor can distinguish four types of surfactants (16 surfactants), especially surfactants of the same type with similar structures. The o-DAP sensor sensitively determined the critical micelle concentration (CMC) of 16 surfactants based on the interaction between o-DAP and surfactants. Additionally, the o-DAP sensor can detect and distinguish artificial vesicles made from different surfactants.
The overuse of surfactants has made them well-known environmental pollutants. So far, it is still a challenge to simultaneously distinguish cationic, anionic, zwitterionic, nonionic surfactants and surfactants with similar structures based on traditional analytical techniques. We developed a high-throughput method for distinguishing various surfactants based on the adaptive emission profile as fingerprints (AEPF). The fluorescence response of the sensor was based on the interaction between surfactants and 1,3-diacetylpyrene (o-DAP) probe. The interaction affected the reversible conversion of free molecules and two aggregates in the solution, thereby changing the relative abundance and the fluorescence intensity ratio of two aggregates emitting different fluorescence. The o-DAP sensor can distinguish four types of surfactants (16 surfactants), especially surfactants of the same type with similar structures. The o-DAP sensor sensitively determined the critical micelle concentration (CMC) of 16 surfactants based on the interaction between o-DAP and surfactants. Additionally, the o-DAP sensor can detect and distinguish artificial vesicles made from different surfactants.
2025, 36(5): 110133
doi: 10.1016/j.cclet.2024.110133
摘要:
Severe traumatic bone healing relies on the involvement of growth factors. However, excessive supplementation of growth factors can lead to ectopic ossification and inflammation. In this study, utilizing the neural regulatory mechanism of bone regeneration, we have developed a multifunctional three dimensions (3D) printed scaffold containing both vasoactive intestinal peptide (VIP) and nerve growth factor (NGF) as an effective new method for achieving bone defect regeneration. The scaffold is provided by a controlled biodegradable and biomechanically matched poly(lactide-ethylene glycol-trimethylene carbonate) (PLTG), providing long-term support for the bone healing cycle. Factor loading is provided by peptide fiber-reinforced biomimetic antimicrobial extracellular matrix (ECM) (B-ECM) hydrogels with different release kinetics, the hydrogel guides rapid bone growth and resists bacterial infection at the early stage of healing. Physical and chemical characterization indicates that the scaffold has good structural stability and mechanical properties, providing an ideal 3D microenvironment for bone reconstruction. In the skull defect model, compared to releasing VIP or NGF alone, this drug delivery system can simulate a natural healing cascade of controllable release factors, significantly accelerating nerve/vascular bone regeneration. In conclusion, this study provides a promising strategy for implanting materials to repair bone defects by utilizing neuroregulatory mechanisms during bone regeneration.
Severe traumatic bone healing relies on the involvement of growth factors. However, excessive supplementation of growth factors can lead to ectopic ossification and inflammation. In this study, utilizing the neural regulatory mechanism of bone regeneration, we have developed a multifunctional three dimensions (3D) printed scaffold containing both vasoactive intestinal peptide (VIP) and nerve growth factor (NGF) as an effective new method for achieving bone defect regeneration. The scaffold is provided by a controlled biodegradable and biomechanically matched poly(lactide-ethylene glycol-trimethylene carbonate) (PLTG), providing long-term support for the bone healing cycle. Factor loading is provided by peptide fiber-reinforced biomimetic antimicrobial extracellular matrix (ECM) (B-ECM) hydrogels with different release kinetics, the hydrogel guides rapid bone growth and resists bacterial infection at the early stage of healing. Physical and chemical characterization indicates that the scaffold has good structural stability and mechanical properties, providing an ideal 3D microenvironment for bone reconstruction. In the skull defect model, compared to releasing VIP or NGF alone, this drug delivery system can simulate a natural healing cascade of controllable release factors, significantly accelerating nerve/vascular bone regeneration. In conclusion, this study provides a promising strategy for implanting materials to repair bone defects by utilizing neuroregulatory mechanisms during bone regeneration.
2025, 36(5): 110135
doi: 10.1016/j.cclet.2024.110135
摘要:
Biomolecular condensates, also known as membraneless organelles, play a crucial role in cellular organization by concentrating or sequestering biomolecules. Despite their importance, synthetically mimicking these organelles using non-peptidic small organic molecules has posed a significant challenge. The present study reports the discovery of D008, a self-assembling small molecule that sequesters a unique subset of RNA-binding proteins. Analysis and screening of a comprehensive collection of approximately 1 million compounds in the Chinese National Compound Library (Shanghai) identified 44 self-assembling small molecules in aqueous solutions. Subsequent screening of the focused library, coupled with proteome analysis, led to the discovery of D008 as a small organic molecule with the ability to condensate a specific subset of RNA-binding proteins. In vitro experiments demonstrated that the D008-induced sequestration of RNA-binding proteins impeded mRNA translation. D008 may offer a unique opportunity for studying the condensations of RNA-binding proteins and for developing an unprecedented class of small molecules that control gene expression.
Biomolecular condensates, also known as membraneless organelles, play a crucial role in cellular organization by concentrating or sequestering biomolecules. Despite their importance, synthetically mimicking these organelles using non-peptidic small organic molecules has posed a significant challenge. The present study reports the discovery of D008, a self-assembling small molecule that sequesters a unique subset of RNA-binding proteins. Analysis and screening of a comprehensive collection of approximately 1 million compounds in the Chinese National Compound Library (Shanghai) identified 44 self-assembling small molecules in aqueous solutions. Subsequent screening of the focused library, coupled with proteome analysis, led to the discovery of D008 as a small organic molecule with the ability to condensate a specific subset of RNA-binding proteins. In vitro experiments demonstrated that the D008-induced sequestration of RNA-binding proteins impeded mRNA translation. D008 may offer a unique opportunity for studying the condensations of RNA-binding proteins and for developing an unprecedented class of small molecules that control gene expression.
2025, 36(5): 110140
doi: 10.1016/j.cclet.2024.110140
摘要:
Diabetic kidney disease (DKD) is recognized as a severe complication in the development of diabetes mellitus (DM), posing a significant burden for global health. Major characteristics of DKD kidneys include tubulointerstitial oxidative stress, inflammation, excessive extracellular matrix deposition, and progressing renal fibrosis. However, current treatment options are limited and cannot offer enough efficacy, thus urgently requiring novel therapeutic approaches. Tetrahedral framework nucleic acids (tFNAs) are a novel type of self-assembled DNA nanomaterial with excellent structural stability, biocompatibility, tailorable functionality, and regulatory effects on cellular behaviors. In this study, we established an in vitro high glucose (HG)-induced human renal tubular epithelial cells (HK-2 cells) pro-fibrogenic model and explored the antioxidative, anti-inflammatory, and antifibrotic capacity of tFNAs and the potential molecular mechanisms. tFNAs not only effectively alleviated oxidative stress through reactive oxygen species (ROS)-scavenging and activating the serine and threonine kinase (Akt)/nuclear factor erythroid 2-related factor 2 (Nrf2)/heme oxygenase-1 (HO-1) signaling pathway but also inhibited the production of pro-inflammatory factors such as tumor necrosis factor (TNF-α), interleukin-1β (IL-1β), and interleukin-6 (IL-6) in diabetic HK-2 cells. Additionally, tFNAs significantly downregulated the expression of Collagen I and α-smooth muscle actin (α-SMA), two representative biomarkers of pro-fibrogenic myofibroblasts in the renal tubular epithelial-mesenchymal transition (EMT). Furthermore, we found that tFNAs exerted this function by inhibiting the Wnt/β-catenin signaling pathway, preventing the occurrence of EMT and fibrosis. The findings of this study demonstrated that tFNAs are naturally endowed with great potential to prevent fibrosis progress in DKD kidneys and can be further combined with emerging pharmacotherapies, providing a secure and efficient drug delivery strategy for future DKD therapy.
Diabetic kidney disease (DKD) is recognized as a severe complication in the development of diabetes mellitus (DM), posing a significant burden for global health. Major characteristics of DKD kidneys include tubulointerstitial oxidative stress, inflammation, excessive extracellular matrix deposition, and progressing renal fibrosis. However, current treatment options are limited and cannot offer enough efficacy, thus urgently requiring novel therapeutic approaches. Tetrahedral framework nucleic acids (tFNAs) are a novel type of self-assembled DNA nanomaterial with excellent structural stability, biocompatibility, tailorable functionality, and regulatory effects on cellular behaviors. In this study, we established an in vitro high glucose (HG)-induced human renal tubular epithelial cells (HK-2 cells) pro-fibrogenic model and explored the antioxidative, anti-inflammatory, and antifibrotic capacity of tFNAs and the potential molecular mechanisms. tFNAs not only effectively alleviated oxidative stress through reactive oxygen species (ROS)-scavenging and activating the serine and threonine kinase (Akt)/nuclear factor erythroid 2-related factor 2 (Nrf2)/heme oxygenase-1 (HO-1) signaling pathway but also inhibited the production of pro-inflammatory factors such as tumor necrosis factor (TNF-α), interleukin-1β (IL-1β), and interleukin-6 (IL-6) in diabetic HK-2 cells. Additionally, tFNAs significantly downregulated the expression of Collagen I and α-smooth muscle actin (α-SMA), two representative biomarkers of pro-fibrogenic myofibroblasts in the renal tubular epithelial-mesenchymal transition (EMT). Furthermore, we found that tFNAs exerted this function by inhibiting the Wnt/β-catenin signaling pathway, preventing the occurrence of EMT and fibrosis. The findings of this study demonstrated that tFNAs are naturally endowed with great potential to prevent fibrosis progress in DKD kidneys and can be further combined with emerging pharmacotherapies, providing a secure and efficient drug delivery strategy for future DKD therapy.
2025, 36(5): 110141
doi: 10.1016/j.cclet.2024.110141
摘要:
A computer-assisted chemical investigation of an intriguing photoreaction of norditerpenoids (3‒7) has been first reported, leading to not only their biomimetic conversion, but also the generation of several new products with uncommon 4,14-dioxabicyclo[10.2.1]pentadecane scaffold (8, 9, 12‒14). In bioassay, compounds 10 and 15 exhibited significant stimulation of GLP-1 secretion. This study has given an insight for the application of computational methods on the late-stage skeleton transformation of complex natural products towards new bioactive compounds.
A computer-assisted chemical investigation of an intriguing photoreaction of norditerpenoids (3‒7) has been first reported, leading to not only their biomimetic conversion, but also the generation of several new products with uncommon 4,14-dioxabicyclo[10.2.1]pentadecane scaffold (8, 9, 12‒14). In bioassay, compounds 10 and 15 exhibited significant stimulation of GLP-1 secretion. This study has given an insight for the application of computational methods on the late-stage skeleton transformation of complex natural products towards new bioactive compounds.
2025, 36(5): 110146
doi: 10.1016/j.cclet.2024.110146
摘要:
Tumor blockade therapy inhibits tumor progression by cutting off essential supplies of nutrients, oxygen, and biomolecules from the surrounding microenvironments. Inspired by natural processes, tumor biomineralization has evolved due to its biocompatibility, self-reinforcing capability, and penetration-independent mechanism. However, the selective induction of tumor biomineralization using synthetic tools presents a significant challenge. Herein, a metabolic glycoengineering-assistant tumor biomineralization strategy was developed. Specifically, the azido group (N3) was introduced onto the cytomembrane by incubating tumor cells with glycose analog Ac4ManNAz. In addition, a bisphosphonate-containing polymer, dibenzocyclooctyne-poly(ethylene glycol)-alendronate (DBCO-PEG-ALN, DBPA) was synthesized, which attached to the tumor cell surface via "click chemistry" reaction between DBCO and N3. Subsequently, the bisphosphonate group on the cell surface chelated with positively charged ions in the microenvironments, triggering a consecutive process of biomineralization. This physical barrier significantly reduced tumor cell viability and mobility in a calcium ion concentration-dependent manner, suggesting its potential as an effective anti-tumor strategy for in vivo applications.
Tumor blockade therapy inhibits tumor progression by cutting off essential supplies of nutrients, oxygen, and biomolecules from the surrounding microenvironments. Inspired by natural processes, tumor biomineralization has evolved due to its biocompatibility, self-reinforcing capability, and penetration-independent mechanism. However, the selective induction of tumor biomineralization using synthetic tools presents a significant challenge. Herein, a metabolic glycoengineering-assistant tumor biomineralization strategy was developed. Specifically, the azido group (N3) was introduced onto the cytomembrane by incubating tumor cells with glycose analog Ac4ManNAz. In addition, a bisphosphonate-containing polymer, dibenzocyclooctyne-poly(ethylene glycol)-alendronate (DBCO-PEG-ALN, DBPA) was synthesized, which attached to the tumor cell surface via "click chemistry" reaction between DBCO and N3. Subsequently, the bisphosphonate group on the cell surface chelated with positively charged ions in the microenvironments, triggering a consecutive process of biomineralization. This physical barrier significantly reduced tumor cell viability and mobility in a calcium ion concentration-dependent manner, suggesting its potential as an effective anti-tumor strategy for in vivo applications.
2025, 36(5): 110147
doi: 10.1016/j.cclet.2024.110147
摘要:
The aggressive nature and high mortality rate of lung cancer underscore the imperative need for early diagnosis of the disease. Thus, aminopeptidase N (APN), a potential biomarker for lung cancer, should be thoroughly investigated in this context. This report describes the development of HA-apn, a novel near-infrared fluorescent probe, specifically engineered for the sensitive detection of endogenous APN. Characterized by its high selectivity, straightforward molecular architecture, and suitable optical properties, including a long-wavelength emission at 835 nm and a large Stokes shift of 285 nm, HA-apn had high efficacy in identifying overexpressed APN in tumor cells, which shows its potential in pinpointing malignancies. To further validate its applicability and effectiveness in facilitating the direct and enhanced visualization of pulmonary alterations, an in situ lung cancer mouse model was employed. Notably, HA-apn was applied for in vivo imaging of APN activity in the lung cancer mouse model receiving the probe through aerosol inhalation, and rapid and precise diagnostic results were achieved within 30 min post-administration. Overall, HA-apn can be applied as an effective, non-intrusive tool for the rapid and accurate detection of pulmonary conditions.
The aggressive nature and high mortality rate of lung cancer underscore the imperative need for early diagnosis of the disease. Thus, aminopeptidase N (APN), a potential biomarker for lung cancer, should be thoroughly investigated in this context. This report describes the development of HA-apn, a novel near-infrared fluorescent probe, specifically engineered for the sensitive detection of endogenous APN. Characterized by its high selectivity, straightforward molecular architecture, and suitable optical properties, including a long-wavelength emission at 835 nm and a large Stokes shift of 285 nm, HA-apn had high efficacy in identifying overexpressed APN in tumor cells, which shows its potential in pinpointing malignancies. To further validate its applicability and effectiveness in facilitating the direct and enhanced visualization of pulmonary alterations, an in situ lung cancer mouse model was employed. Notably, HA-apn was applied for in vivo imaging of APN activity in the lung cancer mouse model receiving the probe through aerosol inhalation, and rapid and precise diagnostic results were achieved within 30 min post-administration. Overall, HA-apn can be applied as an effective, non-intrusive tool for the rapid and accurate detection of pulmonary conditions.
2025, 36(5): 110149
doi: 10.1016/j.cclet.2024.110149
摘要:
[2+2]-Type cyclobutane derivatives comprise a large family of natural products with diverse molecular architectures. However, the structure elucidation of the cyclobutane ring, including its connection mode and stereochemistry, presents a significant challenge. Plumerubradins A–C (1–3), three novel iridoid glycoside [2+2] dimers featuring a highly functionalized cyclobutane core and multiple stereogenic centers, were isolated from the flowers of Plumeria rubra. Through biomimetic semisynthesis and chemical degradation of compounds 1–3, synthesis of phenylpropanoid-derived [2+2] dimers 7–10, combined with extensive spectroscopic analysis, single-crystal X-ray crystallography, and microcrystal electron diffraction experiments, the structures with absolute configurations of 1–3 were unequivocally elucidated. Furthermore, quantum mechanics-based 1H NMR iterative full spin analysis successfully established the correlations between the signal patterns of cyclobutane protons and the structural information of the cyclobutane ring in phenylpropanoid-derived [2+2] dimers, providing a diagnostic tool for the rapid structural elucidation of [2+2]-type cyclobutane derivatives.
[2+2]-Type cyclobutane derivatives comprise a large family of natural products with diverse molecular architectures. However, the structure elucidation of the cyclobutane ring, including its connection mode and stereochemistry, presents a significant challenge. Plumerubradins A–C (1–3), three novel iridoid glycoside [2+2] dimers featuring a highly functionalized cyclobutane core and multiple stereogenic centers, were isolated from the flowers of Plumeria rubra. Through biomimetic semisynthesis and chemical degradation of compounds 1–3, synthesis of phenylpropanoid-derived [2+2] dimers 7–10, combined with extensive spectroscopic analysis, single-crystal X-ray crystallography, and microcrystal electron diffraction experiments, the structures with absolute configurations of 1–3 were unequivocally elucidated. Furthermore, quantum mechanics-based 1H NMR iterative full spin analysis successfully established the correlations between the signal patterns of cyclobutane protons and the structural information of the cyclobutane ring in phenylpropanoid-derived [2+2] dimers, providing a diagnostic tool for the rapid structural elucidation of [2+2]-type cyclobutane derivatives.
2025, 36(5): 110166
doi: 10.1016/j.cclet.2024.110166
摘要:
Early recognition is key to improving the prognosis of ischemic stroke (IS), while available imaging methods tend to target events that have already undergone ischemia. A new method to detect early IS is urgently needed, as well as further study of its mechanisms. Viscosity and cysteine (Cys) levels of mitochondria have been associated with ferroptosis and IS. It is possible to identify IS and ferroptosis accurately and early by monitoring changes in mitochondrial Cys and viscosity simultaneously. In this work, a viscosity/Cys dual-responsive mitochondrial-targeted near-infrared (NIR) fluorescent probe (NVCP) was constructed for the precise tracking of IS using a two-dimensional design strategy. NVCP consists of a chromophore dyad containing diethylaminostyrene quinolinium rotor and chloro-sulfonylbenzoxadiazole (SBD-Cl) derivative with two easily distinguished emission bands (λem = 592 and 670 nm). NVCP performs the way of killing two birds with one stone, that is, the probe exhibits excellent selectivity and sensitivity for detecting viscosity and Cys in living cells with excellent biocompatibility and accurate mitochondrial targeting capability by dual channel imaging mode. In addition, NVCP recognized that the viscosity increases and Cys level decreases in cells when undergoing ferroptosis and oxygen-glucose deprivation (OGD) stress by confocal imaging, flow cytometry, and Western blot experiments. Treatment of ferroptosis inhibitors (ferrostatin-1 (Fer-1) and deferoxamine (DFO)) could reverse the variation tendency of viscosity and Cys. This is the first time that the relationship between ferroptosis and IS was identified through an analysis of Cys and viscosity. More importantly, the ischemic area was also instantly distinguished from normal tissues through fluorescence imaging of NVCP in vivo. The developed NIR dual-responsive probe NVCP toward viscosity and Cys could serve as a sensitive and reliable tool for tracking ferroptosis-related pathological processes during IS.
Early recognition is key to improving the prognosis of ischemic stroke (IS), while available imaging methods tend to target events that have already undergone ischemia. A new method to detect early IS is urgently needed, as well as further study of its mechanisms. Viscosity and cysteine (Cys) levels of mitochondria have been associated with ferroptosis and IS. It is possible to identify IS and ferroptosis accurately and early by monitoring changes in mitochondrial Cys and viscosity simultaneously. In this work, a viscosity/Cys dual-responsive mitochondrial-targeted near-infrared (NIR) fluorescent probe (NVCP) was constructed for the precise tracking of IS using a two-dimensional design strategy. NVCP consists of a chromophore dyad containing diethylaminostyrene quinolinium rotor and chloro-sulfonylbenzoxadiazole (SBD-Cl) derivative with two easily distinguished emission bands (λem = 592 and 670 nm). NVCP performs the way of killing two birds with one stone, that is, the probe exhibits excellent selectivity and sensitivity for detecting viscosity and Cys in living cells with excellent biocompatibility and accurate mitochondrial targeting capability by dual channel imaging mode. In addition, NVCP recognized that the viscosity increases and Cys level decreases in cells when undergoing ferroptosis and oxygen-glucose deprivation (OGD) stress by confocal imaging, flow cytometry, and Western blot experiments. Treatment of ferroptosis inhibitors (ferrostatin-1 (Fer-1) and deferoxamine (DFO)) could reverse the variation tendency of viscosity and Cys. This is the first time that the relationship between ferroptosis and IS was identified through an analysis of Cys and viscosity. More importantly, the ischemic area was also instantly distinguished from normal tissues through fluorescence imaging of NVCP in vivo. The developed NIR dual-responsive probe NVCP toward viscosity and Cys could serve as a sensitive and reliable tool for tracking ferroptosis-related pathological processes during IS.
2025, 36(5): 110168
doi: 10.1016/j.cclet.2024.110168
摘要:
Photodynamic therapy (PDT) has received much attention in recent years. However, traditional photosensitizers (PSs) applied in PDT usually suffer from aggregation-caused quenching (ACQ) effect in H2O, single and inefficient photochemical mechanism of action (MoA), poor cancer targeting ability, etc. In this work, two novel Ru(Ⅱ)-based aggregation-induced emission (AIE) agents (Ru1 and Ru2) were developed. Both complexes exhibited long triplet excited lifetimes and nearly 100% singlet oxygen quantum yields in H2O. In addition, Ru1 and Ru2 displayed potent photo-catalytic reduced nicotinamide adenine dinucleotide (NADH) oxidation activity with turnover frequency (TOF) values of about 1779 and 2000 h−1, respectively. Therefore, both Ru1 and Ru2 showed efficient PDT activity towards a series of cancer cells. Moreover, Ru2 was further loaded in bovine serum albumin (BSA) to enhance the tumor targeting ability in vivo, and the obtained Ru2@BSA could selectively accumulate in tumor tissues and effectively inhibit tumor growth on a 4T1 tumor-bearing mouse model. So far as we know, this work represents the first report about Ru(Ⅱ) AIE agents that possess high singlet oxygen quantum yields and also potent photo-catalytic NADH oxidation activity, and may provide new ideas for rational design of novel PSs with efficient PDT activity.
Photodynamic therapy (PDT) has received much attention in recent years. However, traditional photosensitizers (PSs) applied in PDT usually suffer from aggregation-caused quenching (ACQ) effect in H2O, single and inefficient photochemical mechanism of action (MoA), poor cancer targeting ability, etc. In this work, two novel Ru(Ⅱ)-based aggregation-induced emission (AIE) agents (Ru1 and Ru2) were developed. Both complexes exhibited long triplet excited lifetimes and nearly 100% singlet oxygen quantum yields in H2O. In addition, Ru1 and Ru2 displayed potent photo-catalytic reduced nicotinamide adenine dinucleotide (NADH) oxidation activity with turnover frequency (TOF) values of about 1779 and 2000 h−1, respectively. Therefore, both Ru1 and Ru2 showed efficient PDT activity towards a series of cancer cells. Moreover, Ru2 was further loaded in bovine serum albumin (BSA) to enhance the tumor targeting ability in vivo, and the obtained Ru2@BSA could selectively accumulate in tumor tissues and effectively inhibit tumor growth on a 4T1 tumor-bearing mouse model. So far as we know, this work represents the first report about Ru(Ⅱ) AIE agents that possess high singlet oxygen quantum yields and also potent photo-catalytic NADH oxidation activity, and may provide new ideas for rational design of novel PSs with efficient PDT activity.
2025, 36(5): 110178
doi: 10.1016/j.cclet.2024.110178
摘要:
Chemodynamic therapy (CDT), using Fenton agents to generate highly cytotoxic •OH from H2O2 has been demonstrated as a powerful anticancer method. However, the insufficient endogenous H2O2 in tumor cells greatly limited its therapeutic effect. Herein, we prepared a pH-responsive β-lapachone-loaded iron-polyphenol nanocomplex (LIPN) through a one-pot method. β-Lapachone in LIPN selectively enhanced H2O2 concentration in tumor cells, and ferrous ions cascadely generated abundant cytotoxic •OH. Therefore, LIPN with cascade amplification of reactive oxygen species (ROS) showed high chemodynamic cytotoxicity in tumor cells, efficiently improving the expression of damage-associated molecular patterns (DAMPs), and exerting strong immunogenic cell death (ICD). As a result, LIPN exhibited efficient tumor inhibition ability in 4T1 subcutaneous tumor model in vivo with great biocompatibility. Additionally, the infiltration of cytotoxic CD8+ T lymphocytes and inhibition of regulatory CD4+ FoxP3+ T lymphocytes in tumors demonstrated the activation of immunosuppressive tumor microenvironment by LIPN-induced ICD. Therefore, this work provided a new approach to enhance ICD of chemodynamic therapy through selective cascade amplification of ROS in cancer cells.
Chemodynamic therapy (CDT), using Fenton agents to generate highly cytotoxic •OH from H2O2 has been demonstrated as a powerful anticancer method. However, the insufficient endogenous H2O2 in tumor cells greatly limited its therapeutic effect. Herein, we prepared a pH-responsive β-lapachone-loaded iron-polyphenol nanocomplex (LIPN) through a one-pot method. β-Lapachone in LIPN selectively enhanced H2O2 concentration in tumor cells, and ferrous ions cascadely generated abundant cytotoxic •OH. Therefore, LIPN with cascade amplification of reactive oxygen species (ROS) showed high chemodynamic cytotoxicity in tumor cells, efficiently improving the expression of damage-associated molecular patterns (DAMPs), and exerting strong immunogenic cell death (ICD). As a result, LIPN exhibited efficient tumor inhibition ability in 4T1 subcutaneous tumor model in vivo with great biocompatibility. Additionally, the infiltration of cytotoxic CD8+ T lymphocytes and inhibition of regulatory CD4+ FoxP3+ T lymphocytes in tumors demonstrated the activation of immunosuppressive tumor microenvironment by LIPN-induced ICD. Therefore, this work provided a new approach to enhance ICD of chemodynamic therapy through selective cascade amplification of ROS in cancer cells.
2025, 36(5): 110179
doi: 10.1016/j.cclet.2024.110179
摘要:
The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants, with little attention to the involved selectivity which may correlate with toxicant residues. Herein, an electron localization strategy for specific O2 adsorption/activation enabled by photothermal/pyroelectric effect and in situ constructed active centers of single-atom Co and oxygen vacancy (Co-OV) on the Co/BiOCl-OV photocatalyst was developed for photocatalytic degradation of glyphosate (GLP) wastewater of high performance/selectivity. Under full-spectrum-light irradiation, a high GLP degradation rate of 99.8% with over 90% C‒P bond-breaking selectivity was achieved within 2 h, while effectively circumventing toxicant residues such as aminomethylphosphonic acid (AMPA). X-ray absorption spectroscopy and relevant characterizations expounded the tailored anchoring of Co single atoms onto the BiOCl-OV carrier and photothermal/pyroelectric effect. The oriented formation of more •O2− on Co/BiOCl-OV could be achieved with the Co-OV coupled center that had excellent O2 adsorption/activation capacity, as demonstrated by quantum calculations. The formed unique Co-OV active sites could largely decrease the C‒P bond-breaking energy barrier, thus greatly improving the selectivity toward the initial C‒P bond scission and the activity in subsequent conversion steps in the directional photocatalytic degradation of GLP. The electron localization strategy by in situ constructing the coupled active centers provides an efficient scheme and new insights for the low-toxic photodegradation of organic pollutants containing C‒X bonds.
The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants, with little attention to the involved selectivity which may correlate with toxicant residues. Herein, an electron localization strategy for specific O2 adsorption/activation enabled by photothermal/pyroelectric effect and in situ constructed active centers of single-atom Co and oxygen vacancy (Co-OV) on the Co/BiOCl-OV photocatalyst was developed for photocatalytic degradation of glyphosate (GLP) wastewater of high performance/selectivity. Under full-spectrum-light irradiation, a high GLP degradation rate of 99.8% with over 90% C‒P bond-breaking selectivity was achieved within 2 h, while effectively circumventing toxicant residues such as aminomethylphosphonic acid (AMPA). X-ray absorption spectroscopy and relevant characterizations expounded the tailored anchoring of Co single atoms onto the BiOCl-OV carrier and photothermal/pyroelectric effect. The oriented formation of more •O2− on Co/BiOCl-OV could be achieved with the Co-OV coupled center that had excellent O2 adsorption/activation capacity, as demonstrated by quantum calculations. The formed unique Co-OV active sites could largely decrease the C‒P bond-breaking energy barrier, thus greatly improving the selectivity toward the initial C‒P bond scission and the activity in subsequent conversion steps in the directional photocatalytic degradation of GLP. The electron localization strategy by in situ constructing the coupled active centers provides an efficient scheme and new insights for the low-toxic photodegradation of organic pollutants containing C‒X bonds.
2025, 36(5): 110183
doi: 10.1016/j.cclet.2024.110183
摘要:
Lipids serve as fundamental constituents of cell membranes and organelles. Recent studies have highlighted the significance of lipids as biomarkers in the diagnosis of breast cancer. Although liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) is widely employed for lipid analysis in complex samples, it suffers from limitations such as complexity and time-consuming procedures. In this study, we have developed dopamine-modified TiO2 nanoparticles (TiO2-DA) and applied the materials to assist the analysis of lipids by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The TiO2-DA can provide large specific surface area and acidic environment, well suited for lipid analysis. The method was initially validated using standard lipid molecules. Good sensitivity, reproducibility and quantification performance was observed. Then, the method was applied to the analysis of 90 serum samples from 30 patients with breast cancer, 30 patients with benign breast disease and 30 healthy controls. Five lipid molecules were identified as potential biomarkers for breast cancer. We constructed a classification model based on the MALDI-TOF MS signal of the 5 lipid molecules, and achieved high sensitivity, specificity and accuracy for the differentiation of breast cancer from benign breast disease and healthy control. We further collected another 60 serum samples from 20 healthy controls, 20 patients with benign breast disease and 20 patients with breast cancer for MALDI-TOF MS analysis to verify the accuracy of the classification model. This advancement holds great promise for the development of diagnostic models for other lipid metabolism-related diseases.
Lipids serve as fundamental constituents of cell membranes and organelles. Recent studies have highlighted the significance of lipids as biomarkers in the diagnosis of breast cancer. Although liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) is widely employed for lipid analysis in complex samples, it suffers from limitations such as complexity and time-consuming procedures. In this study, we have developed dopamine-modified TiO2 nanoparticles (TiO2-DA) and applied the materials to assist the analysis of lipids by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The TiO2-DA can provide large specific surface area and acidic environment, well suited for lipid analysis. The method was initially validated using standard lipid molecules. Good sensitivity, reproducibility and quantification performance was observed. Then, the method was applied to the analysis of 90 serum samples from 30 patients with breast cancer, 30 patients with benign breast disease and 30 healthy controls. Five lipid molecules were identified as potential biomarkers for breast cancer. We constructed a classification model based on the MALDI-TOF MS signal of the 5 lipid molecules, and achieved high sensitivity, specificity and accuracy for the differentiation of breast cancer from benign breast disease and healthy control. We further collected another 60 serum samples from 20 healthy controls, 20 patients with benign breast disease and 20 patients with breast cancer for MALDI-TOF MS analysis to verify the accuracy of the classification model. This advancement holds great promise for the development of diagnostic models for other lipid metabolism-related diseases.
2025, 36(5): 110190
doi: 10.1016/j.cclet.2024.110190
摘要:
Boron neutron capture therapy (BNCT) has emerged as a promising treatment for cancers, offering a unique approach to selectively target tumor cells while sparing healthy tissues. Despite its clinical utility, the widespread use of fructose-BPA (F-BPA) has been hampered by its limited ability to penetrate the blood-brain barrier (BBB) and potential risks for patients with certain complications such as diabetes, hyperuricemia, and gout, particularly with substantial dosages. Herein, a series of novel BPA derivatives were synthesized. After the primary screening, geniposide-BPA (G-BPA) and salidroside-BPA (S-BPA) exhibited high water solubility, low cytotoxicity and safe profiles for intravenous injection. Furthermore, both G-BPA and S-BPA had demonstrated superior efficacy in vitro against the 4T1 cell line compared with F-BPA. Notably, S-BPA displayed optimal BBB penetration capability, as evidenced by in vitro BBB models and glioblastoma models in vivo, surpassing all other BPA derivative candidates. Meanwhile, G-BPA also exhibited enhanced performance relative to the clinical drug F-BPA. In brief, G-BPA and S-BPA, as novel BPA derivatives, demonstrated notable safety profiles and remarkable boron delivery capabilities, thereby offering promising therapeutic options for BNCT in the clinic.
Boron neutron capture therapy (BNCT) has emerged as a promising treatment for cancers, offering a unique approach to selectively target tumor cells while sparing healthy tissues. Despite its clinical utility, the widespread use of fructose-BPA (F-BPA) has been hampered by its limited ability to penetrate the blood-brain barrier (BBB) and potential risks for patients with certain complications such as diabetes, hyperuricemia, and gout, particularly with substantial dosages. Herein, a series of novel BPA derivatives were synthesized. After the primary screening, geniposide-BPA (G-BPA) and salidroside-BPA (S-BPA) exhibited high water solubility, low cytotoxicity and safe profiles for intravenous injection. Furthermore, both G-BPA and S-BPA had demonstrated superior efficacy in vitro against the 4T1 cell line compared with F-BPA. Notably, S-BPA displayed optimal BBB penetration capability, as evidenced by in vitro BBB models and glioblastoma models in vivo, surpassing all other BPA derivative candidates. Meanwhile, G-BPA also exhibited enhanced performance relative to the clinical drug F-BPA. In brief, G-BPA and S-BPA, as novel BPA derivatives, demonstrated notable safety profiles and remarkable boron delivery capabilities, thereby offering promising therapeutic options for BNCT in the clinic.
2025, 36(5): 110191
doi: 10.1016/j.cclet.2024.110191
摘要:
Gallstones are a common disease worldwide, often leading to obstruction and inflammatory complications, which seriously affect the quality of life of patients. Research has shown that gallstone disease is associated with ferroptosis, lipid droplets (LDs), and abnormal levels of nitric oxide (NO). Fluorescent probes provide a sensitive and convenient method for detecting important substances in life systems and diseases. However, so far, no fluorescent probes for NO and LDs in gallstone disease have been reported. In this work, an effective ratiometric fluorescent probe LR-NH was designed for the detection of NO in LDs. With an anthracimide fluorophore and a secondary amine as a response site for NO, LR-NH exhibits high selectivity, sensitivity, and attractive ratiometric capability in detecting NO. Importantly, it can target LDs and shows excellent imaging ability for NO in cells and ferroptosis. Moreover, LR-NH can target the gallbladder and image NO in gallstone disease models, providing a unique and unprecedented tool for studying NO in LDs and gallbladder.
Gallstones are a common disease worldwide, often leading to obstruction and inflammatory complications, which seriously affect the quality of life of patients. Research has shown that gallstone disease is associated with ferroptosis, lipid droplets (LDs), and abnormal levels of nitric oxide (NO). Fluorescent probes provide a sensitive and convenient method for detecting important substances in life systems and diseases. However, so far, no fluorescent probes for NO and LDs in gallstone disease have been reported. In this work, an effective ratiometric fluorescent probe LR-NH was designed for the detection of NO in LDs. With an anthracimide fluorophore and a secondary amine as a response site for NO, LR-NH exhibits high selectivity, sensitivity, and attractive ratiometric capability in detecting NO. Importantly, it can target LDs and shows excellent imaging ability for NO in cells and ferroptosis. Moreover, LR-NH can target the gallbladder and image NO in gallstone disease models, providing a unique and unprecedented tool for studying NO in LDs and gallbladder.
2025, 36(5): 110192
doi: 10.1016/j.cclet.2024.110192
摘要:
Photocatalytic overall water splitting is a promising method for producing clean hydrogen energy, but faces challenges such as low light utilization efficiency and high charge carrier recombination rates. This study demonstrates that dielectric Mie resonance in TiO2 hollow nanoshells can enhance electric field intensity and increase light absorption through resonant energy transfer, compared to crushed TiO2 nanoparticles. The Mie resonance effect was confirmed through fluorescence spectra, photo-response current measurements, photocatalytic water splitting experiments, and Mie calculation. The incident electric-field amplitude was doubled in hollow nanoshells, allowing for increased light trapping. Additionally, the spatially separated Pt and RuO2 cocatalysts on the inner and outer surfaces facilitated the separation of photoinduced electrons and holes. Pt@TiO2@RuO2 hollow nanoshells exhibited superior photocatalytic water splitting performance, with a stable H2 generation rate of 50.1 µmol g−1 h−1 and O2 evolution rate of 25.1 µmol g−1 h−1, outperforming other nanostructures such as TiO2, Pt@TiO2, and TiO2@RuO2 hollow nanoshells. This study suggests that dielectric Mie resonance and spatially-separated cocatalysts offer a new approach to simultaneously enhance light absorption and charge carrier transfer in photocatalysis.
Photocatalytic overall water splitting is a promising method for producing clean hydrogen energy, but faces challenges such as low light utilization efficiency and high charge carrier recombination rates. This study demonstrates that dielectric Mie resonance in TiO2 hollow nanoshells can enhance electric field intensity and increase light absorption through resonant energy transfer, compared to crushed TiO2 nanoparticles. The Mie resonance effect was confirmed through fluorescence spectra, photo-response current measurements, photocatalytic water splitting experiments, and Mie calculation. The incident electric-field amplitude was doubled in hollow nanoshells, allowing for increased light trapping. Additionally, the spatially separated Pt and RuO2 cocatalysts on the inner and outer surfaces facilitated the separation of photoinduced electrons and holes. Pt@TiO2@RuO2 hollow nanoshells exhibited superior photocatalytic water splitting performance, with a stable H2 generation rate of 50.1 µmol g−1 h−1 and O2 evolution rate of 25.1 µmol g−1 h−1, outperforming other nanostructures such as TiO2, Pt@TiO2, and TiO2@RuO2 hollow nanoshells. This study suggests that dielectric Mie resonance and spatially-separated cocatalysts offer a new approach to simultaneously enhance light absorption and charge carrier transfer in photocatalysis.
2025, 36(5): 110195
doi: 10.1016/j.cclet.2024.110195
摘要:
Traditional Pt/C electrode materials are prone to corrosion and detachment during H2S detection, leading to a decrease in fuel cell-type sensor performance. Here, a high-performance H2S sensor based on Pt loaded Ti3C2 electrode material with -O/-OH terminal groups was designed and prepared. Experimental tests showed that the Pt/Ti3C2 sensor has good sensitivity (0.162 µA/ppm) and a very low detection limit to H2S (10 ppb). After 90 days of stability testing, the response of the Pt/Ti3C2 sensor shows a smaller decrease of 2% compared to that of the Pt/C sensor (22.9%). Meanwhile, the sensor also has high selectivity and repeatability. The density functional theory (DFT) calculation combined with the experiment results revealed that the improved H2S sensing mechanism is attributed to the fact that the strong interaction between Pt and Ti3C2 via the Pt-O-Ti bonding can reduce the formation energy of Pt and Ti3C2, ultimately prolonging the sensor’s service life. Furthermore, the catalytic property of Pt can decrease the adsorption energy and dissociation barrier of H2S on Pt/Ti3C2 surface, greatly enhance the ability to generate protons and effectively transfer charges, realizing good sensitivity and high selectivity of the sensor. The sensor works at room temperature, making it very promising in the field of H2S detection in future.
Traditional Pt/C electrode materials are prone to corrosion and detachment during H2S detection, leading to a decrease in fuel cell-type sensor performance. Here, a high-performance H2S sensor based on Pt loaded Ti3C2 electrode material with -O/-OH terminal groups was designed and prepared. Experimental tests showed that the Pt/Ti3C2 sensor has good sensitivity (0.162 µA/ppm) and a very low detection limit to H2S (10 ppb). After 90 days of stability testing, the response of the Pt/Ti3C2 sensor shows a smaller decrease of 2% compared to that of the Pt/C sensor (22.9%). Meanwhile, the sensor also has high selectivity and repeatability. The density functional theory (DFT) calculation combined with the experiment results revealed that the improved H2S sensing mechanism is attributed to the fact that the strong interaction between Pt and Ti3C2 via the Pt-O-Ti bonding can reduce the formation energy of Pt and Ti3C2, ultimately prolonging the sensor’s service life. Furthermore, the catalytic property of Pt can decrease the adsorption energy and dissociation barrier of H2S on Pt/Ti3C2 surface, greatly enhance the ability to generate protons and effectively transfer charges, realizing good sensitivity and high selectivity of the sensor. The sensor works at room temperature, making it very promising in the field of H2S detection in future.
2025, 36(5): 110196
doi: 10.1016/j.cclet.2024.110196
摘要:
The addition of cold flow improvers (CFIs) is considered as the optimum strategy to improve the cold flow properties (CFPs) of diesel fuels, but this strategy is always limited by the required large dosage. To obtain low-dosage and high-efficiency CFIs for diesel, 1,2,3,6-tetrahydrophthalic anhydride (THPA) was introduced as a third and polar monomer to enhance the depressive effects of alkyl methacrylate-trans anethole copolymers (C14MC-TA). The terpolymers of alkyl methacrylate-trans anethole-1,2,3,6-tetrahydrophthalic anhydride (C14MC-TA-THPA) were synthesized and compared with the binary copolymers of C14MC-TA and alkyl methacrylate-1,2,3,6-tetrahydrophthalic anhydride (C14MC-THPA). Results showed that C14MC -THPA achieved the best depressive effects on the cold filter plugging point (CFPP) and solid point (SP) by 11 ℃ and 16 ℃ at a dosage of 1250 mg/L and monomer ratio of 6:1, while 1500 mg/L C14MC-TA (1:1) reached the optimal depressive effects on the CFPP and SP by 12 ℃ and 18 ℃. THPA introduction significantly improved the depressive effects of C14MC-TA. Lower dosages of C14MC-TA-THPA in diesel exerted better improvement effects on the CFPP and SP than that of C14MC-TA and C14MC-THPA. When the monomer ratio and dosage were 6:0.6:0.4 and 1000 mg/L, the improvement effect of C14MC-TA-THPA on diesel reached the optimum level, and the CFPP and SP were reduced by 13 ℃ and 19 ℃, respectively. A 3D nonlinear surface diagram fitted by a mathematical model was also used for the first time to better understand the relationships of monomer ratios, dosages, and depressive effects of CFIs in diesel. Surface analysis results showed that C14MC-TA-THPA achieved the optimum depressive effects at a monomer ratio of 6:0.66:0.34 and dosage of 1000 mg/L, and the CFPP and SP decreased by 14 ℃ and 19 ℃, respectively. The predicted results were consistent with the actual ones. Additionally, the improvement mechanism of these copolymers in diesel was also explored.
The addition of cold flow improvers (CFIs) is considered as the optimum strategy to improve the cold flow properties (CFPs) of diesel fuels, but this strategy is always limited by the required large dosage. To obtain low-dosage and high-efficiency CFIs for diesel, 1,2,3,6-tetrahydrophthalic anhydride (THPA) was introduced as a third and polar monomer to enhance the depressive effects of alkyl methacrylate-trans anethole copolymers (C14MC-TA). The terpolymers of alkyl methacrylate-trans anethole-1,2,3,6-tetrahydrophthalic anhydride (C14MC-TA-THPA) were synthesized and compared with the binary copolymers of C14MC-TA and alkyl methacrylate-1,2,3,6-tetrahydrophthalic anhydride (C14MC-THPA). Results showed that C14MC -THPA achieved the best depressive effects on the cold filter plugging point (CFPP) and solid point (SP) by 11 ℃ and 16 ℃ at a dosage of 1250 mg/L and monomer ratio of 6:1, while 1500 mg/L C14MC-TA (1:1) reached the optimal depressive effects on the CFPP and SP by 12 ℃ and 18 ℃. THPA introduction significantly improved the depressive effects of C14MC-TA. Lower dosages of C14MC-TA-THPA in diesel exerted better improvement effects on the CFPP and SP than that of C14MC-TA and C14MC-THPA. When the monomer ratio and dosage were 6:0.6:0.4 and 1000 mg/L, the improvement effect of C14MC-TA-THPA on diesel reached the optimum level, and the CFPP and SP were reduced by 13 ℃ and 19 ℃, respectively. A 3D nonlinear surface diagram fitted by a mathematical model was also used for the first time to better understand the relationships of monomer ratios, dosages, and depressive effects of CFIs in diesel. Surface analysis results showed that C14MC-TA-THPA achieved the optimum depressive effects at a monomer ratio of 6:0.66:0.34 and dosage of 1000 mg/L, and the CFPP and SP decreased by 14 ℃ and 19 ℃, respectively. The predicted results were consistent with the actual ones. Additionally, the improvement mechanism of these copolymers in diesel was also explored.
2025, 36(5): 110200
doi: 10.1016/j.cclet.2024.110200
摘要:
Simultaneous degradation and detoxification during pharmaceutical and personal care product removal are important for water treatment. In this study, sodium niobate nanocubes decorated with graphitic carbon nitride (NbNC/g-C3N4) were fabricated to achieve the efficient photocatalytic degradation and detoxification of ciprofloxacin (CIP) under simulated solar light. NaNbO3 nanocubes were in-situ transformed from Na2Nb2O6·H2O via thermal dehydration at the interface of g-C3N4. The optimized NbNC/g-C3N4–1 was a type-Ⅰ heterojunction, which showed a high conduction band (CB) level of −1.68 eV, leading to the efficient transfer of photogenerated electrons to O2 to produce primary reactive species, •O2−. Density functional theory (DFT) calculations of the density of states indicated that C 2p and Nb 3d contributed to the CB, and 0.37 e– transferred from NaNbO3 to g-C3N4 in NbNC/g-C3N4 based on the Mulliken population analysis of the built-in electric field intensity. NbNC/g-C3N4–1 had 3.3- and 2.3-fold of CIP degradation rate constants (k1 = 0.173 min−1) compared with those of pristine g-C3N4 and NaNbO3, respectively. In addition, N24, N19, and C5 in CIP with a high Fukui index were reactive sites for electrophilic attack by •O2−, resulting in the defluorination and ring-opening of the piperazine moiety of the dominant degradation pathways. Intermediate/product identification, integrated with computational toxicity evaluation, further indicated a substantial detoxification effect during CIP degradation in the photocatalysis system.
Simultaneous degradation and detoxification during pharmaceutical and personal care product removal are important for water treatment. In this study, sodium niobate nanocubes decorated with graphitic carbon nitride (NbNC/g-C3N4) were fabricated to achieve the efficient photocatalytic degradation and detoxification of ciprofloxacin (CIP) under simulated solar light. NaNbO3 nanocubes were in-situ transformed from Na2Nb2O6·H2O via thermal dehydration at the interface of g-C3N4. The optimized NbNC/g-C3N4–1 was a type-Ⅰ heterojunction, which showed a high conduction band (CB) level of −1.68 eV, leading to the efficient transfer of photogenerated electrons to O2 to produce primary reactive species, •O2−. Density functional theory (DFT) calculations of the density of states indicated that C 2p and Nb 3d contributed to the CB, and 0.37 e– transferred from NaNbO3 to g-C3N4 in NbNC/g-C3N4 based on the Mulliken population analysis of the built-in electric field intensity. NbNC/g-C3N4–1 had 3.3- and 2.3-fold of CIP degradation rate constants (k1 = 0.173 min−1) compared with those of pristine g-C3N4 and NaNbO3, respectively. In addition, N24, N19, and C5 in CIP with a high Fukui index were reactive sites for electrophilic attack by •O2−, resulting in the defluorination and ring-opening of the piperazine moiety of the dominant degradation pathways. Intermediate/product identification, integrated with computational toxicity evaluation, further indicated a substantial detoxification effect during CIP degradation in the photocatalysis system.
2025, 36(5): 110201
doi: 10.1016/j.cclet.2024.110201
摘要:
Rational tuning of crystallographic surface and metal doping were effective to enhance the catalytic performance of metal organic frameworks, but limited work has been explored for achieving modulation of crystal facets and metal doping in a single system. MIL-68(In) was promising for photocatalytic applications due to its low toxicity and excellent photoresponsivity. However, its catalytic activity was constrained by severe carrier recombination and a lack of active sites. Herein, increased (001) facet ratio and active sites exposure were simultaneously realized by cobalt doping in MIL-68(In) through a one-pot solvothermal strategy. Optimized MIL-68(In/Co)-2.5 exhibited remarkable catalytic performance in comparison with pristine MIL-68(In) and other MIL-68(In/Co). The reaction kinetic constant and degradation efficiency of MIL-68(In/Co) were approximately twice and 17% higher than the pristine MIL-68(In) in 36 min reaction, respectively. Density functional theory calculations revealed that Co dopant could modulate the orientation of MIL-68(In) facets, facilitate the exchange of electrons and reduce the adsorption energy of peroxymonosulfate (PMS). This work provides a novel pathway for improvement of In-based MOFs in PMS/vis system, it also promotes the profound comprehension of the correlation between crystal facet regulation and catalytic activation in the PMS/vis system.
Rational tuning of crystallographic surface and metal doping were effective to enhance the catalytic performance of metal organic frameworks, but limited work has been explored for achieving modulation of crystal facets and metal doping in a single system. MIL-68(In) was promising for photocatalytic applications due to its low toxicity and excellent photoresponsivity. However, its catalytic activity was constrained by severe carrier recombination and a lack of active sites. Herein, increased (001) facet ratio and active sites exposure were simultaneously realized by cobalt doping in MIL-68(In) through a one-pot solvothermal strategy. Optimized MIL-68(In/Co)-2.5 exhibited remarkable catalytic performance in comparison with pristine MIL-68(In) and other MIL-68(In/Co). The reaction kinetic constant and degradation efficiency of MIL-68(In/Co) were approximately twice and 17% higher than the pristine MIL-68(In) in 36 min reaction, respectively. Density functional theory calculations revealed that Co dopant could modulate the orientation of MIL-68(In) facets, facilitate the exchange of electrons and reduce the adsorption energy of peroxymonosulfate (PMS). This work provides a novel pathway for improvement of In-based MOFs in PMS/vis system, it also promotes the profound comprehension of the correlation between crystal facet regulation and catalytic activation in the PMS/vis system.
2025, 36(5): 110202
doi: 10.1016/j.cclet.2024.110202
摘要:
As antibiotic pollutants cannot be incompletely removed by conventional wastewater treatment plants, ultraviolet (UV) based advanced oxidation processes (AOPs) such as UV/persulfate (UV/PS) and UV/chlorine are increasingly concerned for the effective removal of antibiotics from wastewaters. However, the specific mechanisms involving degradation kinetics and transformation mechanisms are not well elucidated. Here we report a detailed examination of SO4•−/Cl•-mediated degradation kinetics, products, and toxicities of sulfathiazole (ST), sarafloxacin (SAR), and lomefloxacin (LOM) in the two processes. Both SO4•−/Cl•-mediated transformation kinetics were found to be dependent on pH (P < 0.05), which was attributed to the disparate reactivities of their individual dissociated forms. Based on competition kinetic experiments and matrix calculations, the cationic forms (H2ST+, H2SAR+, and H2LOM+) were more highly reactive towards SO4•− in most cases, while the neutral forms (e.g., HSAR0 and HLOM0) reacted the fastest with Cl• for the most of the antibiotics tested. Based on the identification of 31 key intermediates using tandem mass spectrometry, these reactions generated different products, of which the majority still retained the core chemical structure of the parent compounds. The corresponding diverse transformation pathways were proposed, involving S−N breaking, hydroxylation, defluorination, and chlorination reactions. Furthermore, the toxicity changes of their reaction solutions as well as the toxicity of each intermediate were evaluated by the vibrio fischeri and ECOSAR model, respectively. Many primary by-products were proven to be more toxic than the parent chemicals, raising the wider issue of extended potency for these compounds with regards to their ecotoxicity. These results have implications for assessing the degradative fate and risk of these chemicals during the AOPs.
As antibiotic pollutants cannot be incompletely removed by conventional wastewater treatment plants, ultraviolet (UV) based advanced oxidation processes (AOPs) such as UV/persulfate (UV/PS) and UV/chlorine are increasingly concerned for the effective removal of antibiotics from wastewaters. However, the specific mechanisms involving degradation kinetics and transformation mechanisms are not well elucidated. Here we report a detailed examination of SO4•−/Cl•-mediated degradation kinetics, products, and toxicities of sulfathiazole (ST), sarafloxacin (SAR), and lomefloxacin (LOM) in the two processes. Both SO4•−/Cl•-mediated transformation kinetics were found to be dependent on pH (P < 0.05), which was attributed to the disparate reactivities of their individual dissociated forms. Based on competition kinetic experiments and matrix calculations, the cationic forms (H2ST+, H2SAR+, and H2LOM+) were more highly reactive towards SO4•− in most cases, while the neutral forms (e.g., HSAR0 and HLOM0) reacted the fastest with Cl• for the most of the antibiotics tested. Based on the identification of 31 key intermediates using tandem mass spectrometry, these reactions generated different products, of which the majority still retained the core chemical structure of the parent compounds. The corresponding diverse transformation pathways were proposed, involving S−N breaking, hydroxylation, defluorination, and chlorination reactions. Furthermore, the toxicity changes of their reaction solutions as well as the toxicity of each intermediate were evaluated by the vibrio fischeri and ECOSAR model, respectively. Many primary by-products were proven to be more toxic than the parent chemicals, raising the wider issue of extended potency for these compounds with regards to their ecotoxicity. These results have implications for assessing the degradative fate and risk of these chemicals during the AOPs.
2025, 36(5): 110203
doi: 10.1016/j.cclet.2024.110203
摘要:
Recent advances in drug development and bioactive molecules that covalently target lysine residues have shown substantial progress. Both reversible and irreversible covalent inhibitors are developed for targeting lysine residues. The identification of protein targets and binding sites of these lysine-targeting molecules in the whole proteome is crucial to understand their proteome-wide selectivity. For covalent inhibitors, the pull down-based methods including activity-based protein profiling (ABPP) are commonly used to profile their target proteins. For covalent reversible inhibitors, it is not easy to pull down the potential protein targets as the captured proteins may get off beads because of the reversible manner. Here, we report a pair of isotope-labelled click-free probes to competitively identify the protein targets of lysine-targeting covalent reversible small molecules. This pair of isotopic probes consists of a lysine-reactive warhead, a desthiobiotin moiety and isotopicable linker. This integrated probe could eliminate the background proteins induced by the click chemistry during the pull-down process. To demonstrate the feasibility of our newly-developed probes for the protein target identification, we selected the natural product Gossypol in that we proved for the first time that it could modify the lysine residue in a covalent reversible manner. Finally, we confirmed that this pair of integrated probes can be used in a competitive manner to precisely identify the protein target as well as binding sites of Gossypol. Interestingly, pretreatment of Gossypol could stop the antibody from recognizing Gossypol-binding proteins. Together, our isotope-labeled click-free probes could be used for whole-proteome profiling of lysine-targeting covalent reversible small molecules.
Recent advances in drug development and bioactive molecules that covalently target lysine residues have shown substantial progress. Both reversible and irreversible covalent inhibitors are developed for targeting lysine residues. The identification of protein targets and binding sites of these lysine-targeting molecules in the whole proteome is crucial to understand their proteome-wide selectivity. For covalent inhibitors, the pull down-based methods including activity-based protein profiling (ABPP) are commonly used to profile their target proteins. For covalent reversible inhibitors, it is not easy to pull down the potential protein targets as the captured proteins may get off beads because of the reversible manner. Here, we report a pair of isotope-labelled click-free probes to competitively identify the protein targets of lysine-targeting covalent reversible small molecules. This pair of isotopic probes consists of a lysine-reactive warhead, a desthiobiotin moiety and isotopicable linker. This integrated probe could eliminate the background proteins induced by the click chemistry during the pull-down process. To demonstrate the feasibility of our newly-developed probes for the protein target identification, we selected the natural product Gossypol in that we proved for the first time that it could modify the lysine residue in a covalent reversible manner. Finally, we confirmed that this pair of integrated probes can be used in a competitive manner to precisely identify the protein target as well as binding sites of Gossypol. Interestingly, pretreatment of Gossypol could stop the antibody from recognizing Gossypol-binding proteins. Together, our isotope-labeled click-free probes could be used for whole-proteome profiling of lysine-targeting covalent reversible small molecules.
2025, 36(5): 110206
doi: 10.1016/j.cclet.2024.110206
摘要:
The selective conversion of CO2 and NH3 into valuable nitriles presents significant potential for CO2 utilization. In this study, we exploited the synergistic interplay between silicon and fluoride to augment the nickel-catalyzed reductive cyanation of aryl pseudohalides containing silyl groups, utilizing CO2 and NH3 as the CN source. Our methodology exhibited exceptional compatibility with diverse functional groups, such as alcohols, ketones, ethers, esters, nitriles, olefins, pyridines, and quinolines, among others, as demonstrated by the successful synthesis of 58 different nitriles. Notably, we achieved high yields in the preparation of bifunctionalized molecules, including intermediates for perampanel, derived from o-silylaryl triflates, which are well-known as aryne precursors. Remarkably, no degradation of substrates or formation of aryne intermediates were observed. Mechanistic studies imply that the formation of penta-coordinated silyl isocyanate intermediates is crucial for the key C–C coupling step and the presence of vicinal silyl group in the substrate is beneficial to further make this step kinetically favorable.
The selective conversion of CO2 and NH3 into valuable nitriles presents significant potential for CO2 utilization. In this study, we exploited the synergistic interplay between silicon and fluoride to augment the nickel-catalyzed reductive cyanation of aryl pseudohalides containing silyl groups, utilizing CO2 and NH3 as the CN source. Our methodology exhibited exceptional compatibility with diverse functional groups, such as alcohols, ketones, ethers, esters, nitriles, olefins, pyridines, and quinolines, among others, as demonstrated by the successful synthesis of 58 different nitriles. Notably, we achieved high yields in the preparation of bifunctionalized molecules, including intermediates for perampanel, derived from o-silylaryl triflates, which are well-known as aryne precursors. Remarkably, no degradation of substrates or formation of aryne intermediates were observed. Mechanistic studies imply that the formation of penta-coordinated silyl isocyanate intermediates is crucial for the key C–C coupling step and the presence of vicinal silyl group in the substrate is beneficial to further make this step kinetically favorable.
2025, 36(5): 110207
doi: 10.1016/j.cclet.2024.110207
摘要:
The development of general and practical strategies toward the construction of medium-sized rings is still challenging in organic synthesis, especially for the multiple stereocenters control of substituted groups on the ring owing to the long distance between groups. Thus, stereoselective synthesis of multi-substituted ten-membered rings is attractive. Herein, a rapid assembly of various highly substituted ten-membered nitrogen heterocycles between two 1,3-dipoles through a tandem [3 + 3] cycloaddition/aza-Claisen rearrangement of N-vinyl-α,β-unsaturated nitrones and aza-oxyallyl or oxyallyl cations are disclosed. Products containing two or multiple stereocenters could be obtained in up to 96% yield with high regioselectivity and diastereoselectivity. Selective N-O bond cleavages of ten-membered nitrogen heterocycles lead to various novel 5,6,6-perifused benzofurans, bicyclo[4.4.0] or bicyclo[5.3.0] skeletons containing three or multiple continuous stereocenters in good yields and high diastereoselectivity. Biological tests show that the obtained ten-membered N-heterocycles and bicyclo[4.4.0] skeletons inhibited nitric oxide generation in LPS-stimulated RAW264.7 cells and might serve as good anti-inflammatory agents.
The development of general and practical strategies toward the construction of medium-sized rings is still challenging in organic synthesis, especially for the multiple stereocenters control of substituted groups on the ring owing to the long distance between groups. Thus, stereoselective synthesis of multi-substituted ten-membered rings is attractive. Herein, a rapid assembly of various highly substituted ten-membered nitrogen heterocycles between two 1,3-dipoles through a tandem [3 + 3] cycloaddition/aza-Claisen rearrangement of N-vinyl-α,β-unsaturated nitrones and aza-oxyallyl or oxyallyl cations are disclosed. Products containing two or multiple stereocenters could be obtained in up to 96% yield with high regioselectivity and diastereoselectivity. Selective N-O bond cleavages of ten-membered nitrogen heterocycles lead to various novel 5,6,6-perifused benzofurans, bicyclo[4.4.0] or bicyclo[5.3.0] skeletons containing three or multiple continuous stereocenters in good yields and high diastereoselectivity. Biological tests show that the obtained ten-membered N-heterocycles and bicyclo[4.4.0] skeletons inhibited nitric oxide generation in LPS-stimulated RAW264.7 cells and might serve as good anti-inflammatory agents.
2025, 36(5): 110209
doi: 10.1016/j.cclet.2024.110209
摘要:
Algal copper uptake (i.e., Cu bioavailability) in the euphotic zone plays a vital role in algal photosynthesis and respiration, affecting the primary productivity and the source and sink of atmospheric carbon. Algal Cu uptake is controlled by natural dissolved organic Cu (DOCu) speciation (i.e., complexed with the dissolved organic matter) that conventionally could be tested by model prediction or molecular-level characterizations in the lab, while DOCu uptake are hardly directly assessed. Thus, the new chemistry-biology insight into the mechanisms of the Cu uptake process in algae is urgent. The DOCu speciation transformation (organic DOCu to free Cu(Ⅱ) ions), enzymatic reduction-induced valence change (reduction of free Cu(Ⅱ) to Cu(Ⅰ) ions), and algal Cu uptake at the algae-water interface are imitated. Herein, an intelligent system with DOCu colorimetric sensor is developed for real-time monitoring of newly generated Cu(Ⅰ) ions. Deep learning with whole sample image-based characterization and powerful feature extraction capabilities facilitates colorimetric measurement. In this context, the Cu bioavailability with 7 kinds of organic ligands (e.g., amino acids, organic acids, carbohydrates) can be predicted by the mimetic intelligent biosensor within 15.0 min, i.e., the DOCu uptake and speciation is successfully predicted and streamlined by the biomimetic approach.
Algal copper uptake (i.e., Cu bioavailability) in the euphotic zone plays a vital role in algal photosynthesis and respiration, affecting the primary productivity and the source and sink of atmospheric carbon. Algal Cu uptake is controlled by natural dissolved organic Cu (DOCu) speciation (i.e., complexed with the dissolved organic matter) that conventionally could be tested by model prediction or molecular-level characterizations in the lab, while DOCu uptake are hardly directly assessed. Thus, the new chemistry-biology insight into the mechanisms of the Cu uptake process in algae is urgent. The DOCu speciation transformation (organic DOCu to free Cu(Ⅱ) ions), enzymatic reduction-induced valence change (reduction of free Cu(Ⅱ) to Cu(Ⅰ) ions), and algal Cu uptake at the algae-water interface are imitated. Herein, an intelligent system with DOCu colorimetric sensor is developed for real-time monitoring of newly generated Cu(Ⅰ) ions. Deep learning with whole sample image-based characterization and powerful feature extraction capabilities facilitates colorimetric measurement. In this context, the Cu bioavailability with 7 kinds of organic ligands (e.g., amino acids, organic acids, carbohydrates) can be predicted by the mimetic intelligent biosensor within 15.0 min, i.e., the DOCu uptake and speciation is successfully predicted and streamlined by the biomimetic approach.
2025, 36(5): 110213
doi: 10.1016/j.cclet.2024.110213
摘要:
Bridged bicyclic cores have been recognized as valuable bioisosteres of benzene ring, which are of great value in medicinal chemistry. However, the development of fluorinated bicyclic skeletons, which encompass two privileged elements widely acknowledged for fine tuning the working effect of target molecules, are far less common. Herein, we present a general and practical synthesis of gem–difluorobicyclo[2.1.1]hexanes (diF-BCHs) from readily available difluorinated hexa-1,5-dienes through energy transfer photocatalysis. By taking advantage of an efficient Cope rearrangement, the preparation of both constitutional isomers of diF-BCHs is readily achieved under identical conditions. The operational simplicity, mild conditions and wide scope further highlight the potential application of this protocol. Moreover, computational studies indicated a positive effect of fluorine atoms in lowering either the triplet or FMO energies of the hexa-1,5-diene substrates, thus promoting the present photoinduced [2 + 2] cycloaddition.
Bridged bicyclic cores have been recognized as valuable bioisosteres of benzene ring, which are of great value in medicinal chemistry. However, the development of fluorinated bicyclic skeletons, which encompass two privileged elements widely acknowledged for fine tuning the working effect of target molecules, are far less common. Herein, we present a general and practical synthesis of gem–difluorobicyclo[2.1.1]hexanes (diF-BCHs) from readily available difluorinated hexa-1,5-dienes through energy transfer photocatalysis. By taking advantage of an efficient Cope rearrangement, the preparation of both constitutional isomers of diF-BCHs is readily achieved under identical conditions. The operational simplicity, mild conditions and wide scope further highlight the potential application of this protocol. Moreover, computational studies indicated a positive effect of fluorine atoms in lowering either the triplet or FMO energies of the hexa-1,5-diene substrates, thus promoting the present photoinduced [2 + 2] cycloaddition.
2025, 36(5): 110227
doi: 10.1016/j.cclet.2024.110227
摘要:
Combining cytotoxic drugs with tumor microenvironment (TME) modulator agents is an effective strategy to enhance anti-tumor effects. In this study, two natural anti-tumor active ingredients celastrol (CEL) and glycyrrhetinic acid (GA) were combined for tumor treatment. In order to ensure the precise co-delivery and controllable synchronous release of combined drugs to tumors, it is necessary to construct a suitable nano-drug delivery platform. Based on this, we coupled hyaluronic acid (HA) with CEL by amide reaction to obtain an amphiphilic polymer prodrug HA-SS-CEL, and GA was spontaneously loaded into polymer micelles by self-assembly to obtain G/HSSC-M. G/HSSC-M has ideal size distribution, redox-responsive synchronous drug release, enhanced tumor cell internalization and in vivo tumor targeting. Compared with free drugs, the construction of multifunctional polymer micelles makes G/HSSC-M show better anticancer effect at the same concentration, and can significantly inhibit the proliferation and migration of HepG2 and 4T1 cells. In the in vivo experiments, G/HSSC-M achieved a tumor inhibition rate as high as 75.12% in H22 tumor-bearing mice. The mechanism included regulation of M1/M2 macrophage polarization, inhibition of Janus kinase 1/signal transducer and activator of transcription 3 (JAK1/STAT3) signaling pathway, and remodeling of tumor blood vessels. Therefore, the development of prodrug micelles co-loaded with CEL and GA provides a promising drug co-delivery strategy for combined cancer therapy.
Combining cytotoxic drugs with tumor microenvironment (TME) modulator agents is an effective strategy to enhance anti-tumor effects. In this study, two natural anti-tumor active ingredients celastrol (CEL) and glycyrrhetinic acid (GA) were combined for tumor treatment. In order to ensure the precise co-delivery and controllable synchronous release of combined drugs to tumors, it is necessary to construct a suitable nano-drug delivery platform. Based on this, we coupled hyaluronic acid (HA) with CEL by amide reaction to obtain an amphiphilic polymer prodrug HA-SS-CEL, and GA was spontaneously loaded into polymer micelles by self-assembly to obtain G/HSSC-M. G/HSSC-M has ideal size distribution, redox-responsive synchronous drug release, enhanced tumor cell internalization and in vivo tumor targeting. Compared with free drugs, the construction of multifunctional polymer micelles makes G/HSSC-M show better anticancer effect at the same concentration, and can significantly inhibit the proliferation and migration of HepG2 and 4T1 cells. In the in vivo experiments, G/HSSC-M achieved a tumor inhibition rate as high as 75.12% in H22 tumor-bearing mice. The mechanism included regulation of M1/M2 macrophage polarization, inhibition of Janus kinase 1/signal transducer and activator of transcription 3 (JAK1/STAT3) signaling pathway, and remodeling of tumor blood vessels. Therefore, the development of prodrug micelles co-loaded with CEL and GA provides a promising drug co-delivery strategy for combined cancer therapy.
2025, 36(5): 110230
doi: 10.1016/j.cclet.2024.110230
摘要:
Self-assembled prodrug nanomedicine has emerged as an advanced platform for antitumor therapy, mainly comprise drug modules, response modules and modification modules. However, existing studies usually compare the differences between single types of modification modules, neglecting the impact of steric-hindrance effect caused by chemical structure. Herein, single-tailed modification module with low-steric-hindrance effect and two-tailed modification module with high-steric-hindrance effect were selected to construct paclitaxel prodrugs (P-LAC18 and P-BAC18), and the in-depth insights of the steric-hindrance effect on prodrug nanoassemblies were explored. Notably, the size stability of the two-tailed prodrugs was enhanced due to improved intermolecular interactions and steric hindrance. Single-tailed prodrug nanoassemblies were more susceptible to attack by redox agents, showing faster drug release and stronger antitumor efficacy, but with poorer safety. In contrast, two-tailed prodrug nanoassemblies exhibited significant advantages in terms of pharmacokinetics, tumor accumulation and safety due to the good size stability, thus ensuring equivalent antitumor efficacy at tolerance dose. These findings highlighted the critical role of steric-hindrance effect of the modification module in regulating the structure-activity relationship of prodrug nanoassemblies and proposed new perspectives into the precise design of self-assembled prodrugs for high-performance cancer therapeutics.
Self-assembled prodrug nanomedicine has emerged as an advanced platform for antitumor therapy, mainly comprise drug modules, response modules and modification modules. However, existing studies usually compare the differences between single types of modification modules, neglecting the impact of steric-hindrance effect caused by chemical structure. Herein, single-tailed modification module with low-steric-hindrance effect and two-tailed modification module with high-steric-hindrance effect were selected to construct paclitaxel prodrugs (P-LAC18 and P-BAC18), and the in-depth insights of the steric-hindrance effect on prodrug nanoassemblies were explored. Notably, the size stability of the two-tailed prodrugs was enhanced due to improved intermolecular interactions and steric hindrance. Single-tailed prodrug nanoassemblies were more susceptible to attack by redox agents, showing faster drug release and stronger antitumor efficacy, but with poorer safety. In contrast, two-tailed prodrug nanoassemblies exhibited significant advantages in terms of pharmacokinetics, tumor accumulation and safety due to the good size stability, thus ensuring equivalent antitumor efficacy at tolerance dose. These findings highlighted the critical role of steric-hindrance effect of the modification module in regulating the structure-activity relationship of prodrug nanoassemblies and proposed new perspectives into the precise design of self-assembled prodrugs for high-performance cancer therapeutics.
2025, 36(5): 110231
doi: 10.1016/j.cclet.2024.110231
摘要:
The chemo-, regio-, and enantio-controlled synthesis of P-chiral phosphines in a general and efficient manner remains a significant synthetic challenge. In this study, a Pd-catalyzed hydrofunctionalization is developed for the highly selective synthesis of P-stereogenic alkenylphosphinates and alkenylphosphine oxides via conjugate addition of enynes. Notably, this methodology is suitable for both phosphine oxide and phosphinate nucleophiles, providing a versatile approach for the construction of diverse P-chiral organophosphosphorus compound.
The chemo-, regio-, and enantio-controlled synthesis of P-chiral phosphines in a general and efficient manner remains a significant synthetic challenge. In this study, a Pd-catalyzed hydrofunctionalization is developed for the highly selective synthesis of P-stereogenic alkenylphosphinates and alkenylphosphine oxides via conjugate addition of enynes. Notably, this methodology is suitable for both phosphine oxide and phosphinate nucleophiles, providing a versatile approach for the construction of diverse P-chiral organophosphosphorus compound.
2025, 36(5): 110237
doi: 10.1016/j.cclet.2024.110237
摘要:
Traditional electrospray ionization tandem mass spectrometry (ESI-MSn) has been a powerful tool in diverse research areas, however, it faces great limitations in the study of protein-small molecule interactions. In this article, the state-of-the-art temperature-controlled electrospray ionization tandem mass spectrometry (TC-ESI-MSn) is applied to investigate interactions between ubiquitin and two flavonol molecules, respectively. The combination of collision-induced dissociation (CID) and MS solution-melting experiments facilitates the understanding of flavonol-protein interactions in a new dimension across varying temperature ranges. While structural changes of proteins disturbed by small molecules are unseen in ESI-MSn, TC-ESI-MSn allows a simultaneous assessment of the stability of the complex in both gas and liquid phases under various temperature conditions, meanwhile investigating the impact on the protein’s structure and tracking changes in thermodynamic data, and the characteristics of structural intermediates.
Traditional electrospray ionization tandem mass spectrometry (ESI-MSn) has been a powerful tool in diverse research areas, however, it faces great limitations in the study of protein-small molecule interactions. In this article, the state-of-the-art temperature-controlled electrospray ionization tandem mass spectrometry (TC-ESI-MSn) is applied to investigate interactions between ubiquitin and two flavonol molecules, respectively. The combination of collision-induced dissociation (CID) and MS solution-melting experiments facilitates the understanding of flavonol-protein interactions in a new dimension across varying temperature ranges. While structural changes of proteins disturbed by small molecules are unseen in ESI-MSn, TC-ESI-MSn allows a simultaneous assessment of the stability of the complex in both gas and liquid phases under various temperature conditions, meanwhile investigating the impact on the protein’s structure and tracking changes in thermodynamic data, and the characteristics of structural intermediates.
2025, 36(5): 110238
doi: 10.1016/j.cclet.2024.110238
摘要:
Neutrophil extracellular traps (NETs) formation (NETosis), is a crucial immune system mechanism mediated by neutrophils, measuring the capacity to induce NETosis is proposed as a clinical biomarker indicating the severity of COVID-19 and long COVID. Azvudine (FNC), has shown efficacy in treating SARS-CoV-2 infection and potential for alleviating inflammation. However, the molecular mechanism underlying its anti-inflammatory effects has not been extensively investigated. Therefore, a series of experiments were conducted on SARS-CoV-2 infected rhesus macaques (RMs) to investigate the anti-inflammatory effects of FNC. The experiments involved HE staining, mass spectrometry-based proteomics, validation experiments conducted in vivo using RMs tissues and in vitro differentiation of HL-60 cells. Additionally, interaction investigations were carried out utilizing LiP-MS, CETSA, Co-IP along with molecular docking. The results demonstrated that FNC treatment effectively alleviated neutrophil infiltration and attenuated inflammatory injury following infection. In addition to exhibiting antiviral effects, FNC treatment exhibited a reduction in inflammation-associated proteins and pathways such as myeloperoxidase (MPO) and the formation of NETs, respectively. Validation experiments confirmed the impact of FNC on regulating NETs formation, interaction experiments suggested that MPO may serves as a therapeutic target. The multifaceted properties of FNC, including its antiviral and anti-inflammatory characteristics, highlight the therapeutic potential in diseases associated with NETosis, particularly those involving concurrent SARS-CoV-2 infection, providing insights for drug development targeting MPO and NETosis-associated diseases.
Neutrophil extracellular traps (NETs) formation (NETosis), is a crucial immune system mechanism mediated by neutrophils, measuring the capacity to induce NETosis is proposed as a clinical biomarker indicating the severity of COVID-19 and long COVID. Azvudine (FNC), has shown efficacy in treating SARS-CoV-2 infection and potential for alleviating inflammation. However, the molecular mechanism underlying its anti-inflammatory effects has not been extensively investigated. Therefore, a series of experiments were conducted on SARS-CoV-2 infected rhesus macaques (RMs) to investigate the anti-inflammatory effects of FNC. The experiments involved HE staining, mass spectrometry-based proteomics, validation experiments conducted in vivo using RMs tissues and in vitro differentiation of HL-60 cells. Additionally, interaction investigations were carried out utilizing LiP-MS, CETSA, Co-IP along with molecular docking. The results demonstrated that FNC treatment effectively alleviated neutrophil infiltration and attenuated inflammatory injury following infection. In addition to exhibiting antiviral effects, FNC treatment exhibited a reduction in inflammation-associated proteins and pathways such as myeloperoxidase (MPO) and the formation of NETs, respectively. Validation experiments confirmed the impact of FNC on regulating NETs formation, interaction experiments suggested that MPO may serves as a therapeutic target. The multifaceted properties of FNC, including its antiviral and anti-inflammatory characteristics, highlight the therapeutic potential in diseases associated with NETosis, particularly those involving concurrent SARS-CoV-2 infection, providing insights for drug development targeting MPO and NETosis-associated diseases.
2025, 36(5): 110239
doi: 10.1016/j.cclet.2024.110239
摘要:
Here we present a highly efficient protocol utilizing nickel-hydride hydrogen atom transfer catalysis for the regio- and enantioselective hydrofluorination of internal alkenes. This method efficiently assembles a wide array of enantioenriched β-fluoro amides with excellent regio- and enantioselectivity from internal unactivated alkenes. Mechanistic investigations suggest that this transformation proceeds via a NiH-hydrogen atom transfer to alkene, followed by a stereoselective fluorine atom transfer process. The weak coordination effect of the tethered amide group is identified as a crucial factor governing the observed regio- and enantioselectivity.
Here we present a highly efficient protocol utilizing nickel-hydride hydrogen atom transfer catalysis for the regio- and enantioselective hydrofluorination of internal alkenes. This method efficiently assembles a wide array of enantioenriched β-fluoro amides with excellent regio- and enantioselectivity from internal unactivated alkenes. Mechanistic investigations suggest that this transformation proceeds via a NiH-hydrogen atom transfer to alkene, followed by a stereoselective fluorine atom transfer process. The weak coordination effect of the tethered amide group is identified as a crucial factor governing the observed regio- and enantioselectivity.
2025, 36(5): 110240
doi: 10.1016/j.cclet.2024.110240
摘要:
Nanoplastics exhibit greater environmental biotoxicity than microplastics and can be ingested by humans through major routes such as tap water, bottled water and other drinking water. Nanoplastics present a challenge for air flotation due to their minute particle size, negative surface potential, and similar density to water. This study employed dodecyltrimethylammonium chloride (DTAC) as a modifier to improve conventional air flotation, which significantly enhanced the removal of polystyrene nanoplastics (PSNPs). Conventional air flotation removed only 3.09% of PSNPs, while air flotation modified by dodecyltrimethylammonium chloride (DTAC-modified air flotation) increased the removal of PSNPs to 98.05%. The analysis of the DTAC-modified air flotation mechanism was conducted using a combination of instruments, including a zeta potential analyzer, contact angle meter, laser particle size meter, high definition camera, scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and Fourier transform infrared spectrometer (FTIR). The results indicated that the incorporation of DTAC reversed the electrostatic repulsion between bubbles and PSNPs to electrostatic attraction, significantly enhancing the hydrophobic force in the system. This, in turn, improved the collision adhesion effect between bubbles and PSNPs. The experimental results indicated that even when the flotation time was reduced to 7 min, the DTAC-modified air flotation still achieved a high removal rate of 96.26%. Furthermore, changes in aeration, pH, and ionic strength did not significantly affect the performance of the modified air flotation for the removal of PSNPs. The removal rate of PSNPs in all three water bodies exceeded 95%. The DTAC-modified air flotation has excellent resistance to interference from complex conditions and shows great potential for practical application.
Nanoplastics exhibit greater environmental biotoxicity than microplastics and can be ingested by humans through major routes such as tap water, bottled water and other drinking water. Nanoplastics present a challenge for air flotation due to their minute particle size, negative surface potential, and similar density to water. This study employed dodecyltrimethylammonium chloride (DTAC) as a modifier to improve conventional air flotation, which significantly enhanced the removal of polystyrene nanoplastics (PSNPs). Conventional air flotation removed only 3.09% of PSNPs, while air flotation modified by dodecyltrimethylammonium chloride (DTAC-modified air flotation) increased the removal of PSNPs to 98.05%. The analysis of the DTAC-modified air flotation mechanism was conducted using a combination of instruments, including a zeta potential analyzer, contact angle meter, laser particle size meter, high definition camera, scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and Fourier transform infrared spectrometer (FTIR). The results indicated that the incorporation of DTAC reversed the electrostatic repulsion between bubbles and PSNPs to electrostatic attraction, significantly enhancing the hydrophobic force in the system. This, in turn, improved the collision adhesion effect between bubbles and PSNPs. The experimental results indicated that even when the flotation time was reduced to 7 min, the DTAC-modified air flotation still achieved a high removal rate of 96.26%. Furthermore, changes in aeration, pH, and ionic strength did not significantly affect the performance of the modified air flotation for the removal of PSNPs. The removal rate of PSNPs in all three water bodies exceeded 95%. The DTAC-modified air flotation has excellent resistance to interference from complex conditions and shows great potential for practical application.
2025, 36(5): 110241
doi: 10.1016/j.cclet.2024.110241
摘要:
Hyperglycemia resulting from diabetes mellitus (DM) exacerbates osteoporosis and fractures, damaging bone regeneration due to impaired healing capacity. Stem cell therapy offers the potential for bone repair, accelerating the healing of bone defects by introducing stem cells with osteogenic differentiation ability. Dental follicle stem cells (DFSCs) are a newly emerging type of dental stem cells that not only have the potential for multipotent differentiation but also hold easy accessibility and can stand long-term storage. However, DM-associated oxidative stress and inflammation elevate the risk of DFSCs dysfunction and apoptosis, diminishing stem cell therapy efficacy. Recent nanomaterial advances, particularly in DNA nanostructures like tetrahedral framework nucleic acids (tFNAs), have been promising candidates for modulating cellular behaviors. Accumulating experiments have shown that tFNAs' cell proliferation and migration-promoting ability and induce osteogenic differentiation of stem cells. Meanwhile, tFNAs can scavenge reactive oxygen species (ROS) and downregulate the secretion of inflammatory factors by inhibiting various inflammation-related signaling pathways. Here, we applied tFNAs to modify DFSCs and observed enhanced osteogenic differentiation alongside ROS scavenging and anti-inflammatory effects mediated by suppressing the ROS/mitogen-activated protein kinases (MAPKs)/nuclear factor kappa-B (NF-κB) signaling pathway. This intervention reduced stem cell apoptosis, bolstering stem cell therapy efficacy in DM. Our study establishes a simple yet potent tFNAs-DFSCs system, offering potential as a bone repair agent for future DM treatment.
Hyperglycemia resulting from diabetes mellitus (DM) exacerbates osteoporosis and fractures, damaging bone regeneration due to impaired healing capacity. Stem cell therapy offers the potential for bone repair, accelerating the healing of bone defects by introducing stem cells with osteogenic differentiation ability. Dental follicle stem cells (DFSCs) are a newly emerging type of dental stem cells that not only have the potential for multipotent differentiation but also hold easy accessibility and can stand long-term storage. However, DM-associated oxidative stress and inflammation elevate the risk of DFSCs dysfunction and apoptosis, diminishing stem cell therapy efficacy. Recent nanomaterial advances, particularly in DNA nanostructures like tetrahedral framework nucleic acids (tFNAs), have been promising candidates for modulating cellular behaviors. Accumulating experiments have shown that tFNAs' cell proliferation and migration-promoting ability and induce osteogenic differentiation of stem cells. Meanwhile, tFNAs can scavenge reactive oxygen species (ROS) and downregulate the secretion of inflammatory factors by inhibiting various inflammation-related signaling pathways. Here, we applied tFNAs to modify DFSCs and observed enhanced osteogenic differentiation alongside ROS scavenging and anti-inflammatory effects mediated by suppressing the ROS/mitogen-activated protein kinases (MAPKs)/nuclear factor kappa-B (NF-κB) signaling pathway. This intervention reduced stem cell apoptosis, bolstering stem cell therapy efficacy in DM. Our study establishes a simple yet potent tFNAs-DFSCs system, offering potential as a bone repair agent for future DM treatment.
2025, 36(5): 110243
doi: 10.1016/j.cclet.2024.110243
摘要:
The asymmetric addition of aromatic organometallic compounds to the carbonyl group (C-3) of isatins, catalyzed by transition metals, has emerged as a remarkably efficient method for the synthesis of chiral 3-hydroxyoxindoles. Here, an exceptionally enantioselective approach was developed for the first time to achieve a catalytic NHK reaction of isatins with aromatic halides (both aryl and heteroaryl). Utilizing chiral cobalt complexes as catalysts, and the presence of a diboron reagent B2nep2 as both a reducing agent and determinant in enantiocontrol, has resulted in the triumphantly achieved synthesis of enantioenriched products. Compared to reported strategies, this approach exhibits remarkable compatibility with substrates bearing sensitive functional groups, such as halides and borate esters, while also eliminating the need for organometallic reagents as required in previous strategies. Through experimental investigations, the presence of aryl-cobalt species during the addition process was confirmed, rather than in-situ generation of an arylboron reagent. Furthermore, the successful attainment of the R absolute configuration through aryl addition was demonstrated.
The asymmetric addition of aromatic organometallic compounds to the carbonyl group (C-3) of isatins, catalyzed by transition metals, has emerged as a remarkably efficient method for the synthesis of chiral 3-hydroxyoxindoles. Here, an exceptionally enantioselective approach was developed for the first time to achieve a catalytic NHK reaction of isatins with aromatic halides (both aryl and heteroaryl). Utilizing chiral cobalt complexes as catalysts, and the presence of a diboron reagent B2nep2 as both a reducing agent and determinant in enantiocontrol, has resulted in the triumphantly achieved synthesis of enantioenriched products. Compared to reported strategies, this approach exhibits remarkable compatibility with substrates bearing sensitive functional groups, such as halides and borate esters, while also eliminating the need for organometallic reagents as required in previous strategies. Through experimental investigations, the presence of aryl-cobalt species during the addition process was confirmed, rather than in-situ generation of an arylboron reagent. Furthermore, the successful attainment of the R absolute configuration through aryl addition was demonstrated.
2025, 36(5): 110244
doi: 10.1016/j.cclet.2024.110244
摘要:
Humic acid (HA), as a represent of natural organic matter widely existing in water body, dose harm to water quality and human health; however, it was commonly treated as an environmental background substance while not targeted contaminant in advanced oxidation processes (AOPs). Herein, we investigated the removal of HA in the alkali-activated biochar (KBC)/peroxymonosulfate (PMS) system. The modification of the original biochar (BC) resulted in an increased adsorption capacity and catalytic activity due to the introduction of more micropores, mesopores, and oxygen-containing functional groups, particularly carbonyl groups. Mechanistic insights indicated that HA is primarily chemically adsorbed on the KBC surface, while singlet oxygen (1O2) produced by the PMS decomposition served as the major reactive species for the degradation of HA. An underlying synergistic adsorption and oxidation mechanism involving a local high concentration reaction region around the KBC interface was then proposed. This work not only provides a cost-effective solution for the elimination of HA but also advances our understanding of the nonradical oxidation at the biochar interface.
Humic acid (HA), as a represent of natural organic matter widely existing in water body, dose harm to water quality and human health; however, it was commonly treated as an environmental background substance while not targeted contaminant in advanced oxidation processes (AOPs). Herein, we investigated the removal of HA in the alkali-activated biochar (KBC)/peroxymonosulfate (PMS) system. The modification of the original biochar (BC) resulted in an increased adsorption capacity and catalytic activity due to the introduction of more micropores, mesopores, and oxygen-containing functional groups, particularly carbonyl groups. Mechanistic insights indicated that HA is primarily chemically adsorbed on the KBC surface, while singlet oxygen (1O2) produced by the PMS decomposition served as the major reactive species for the degradation of HA. An underlying synergistic adsorption and oxidation mechanism involving a local high concentration reaction region around the KBC interface was then proposed. This work not only provides a cost-effective solution for the elimination of HA but also advances our understanding of the nonradical oxidation at the biochar interface.
2025, 36(5): 110249
doi: 10.1016/j.cclet.2024.110249
摘要:
Nanobelts are a rapidly developing family of macrocycles with appealing features. However, their host-guest chemistry is currently limited to the recognition of fullerenes via π–π interactions. Herein, we report two heteroatom-bridged [8]cyclophenoxathiin nanobelts ([8]CP-Me and [8]CP) encapsulate corannulene (Cora) to form bowl-in-bowl supramolecular structures stabilized mainly through CH–π interactions in solid-state. The convex surface of corannulene is oriented towards the cavity due to geometry complementarity. The complex Cora⊂[8]CP exhibits a unique 2:2 capsule-like structure in crystal packing, in which corannulene adopts a concave-to-concave assembling fashion. This work enriches the molecular recognition of nanobelts and demonstrates that CH–π interactions can act as the main driving force for nanobelts host-guest complexes.
Nanobelts are a rapidly developing family of macrocycles with appealing features. However, their host-guest chemistry is currently limited to the recognition of fullerenes via π–π interactions. Herein, we report two heteroatom-bridged [8]cyclophenoxathiin nanobelts ([8]CP-Me and [8]CP) encapsulate corannulene (Cora) to form bowl-in-bowl supramolecular structures stabilized mainly through CH–π interactions in solid-state. The convex surface of corannulene is oriented towards the cavity due to geometry complementarity. The complex Cora⊂[8]CP exhibits a unique 2:2 capsule-like structure in crystal packing, in which corannulene adopts a concave-to-concave assembling fashion. This work enriches the molecular recognition of nanobelts and demonstrates that CH–π interactions can act as the main driving force for nanobelts host-guest complexes.
2025, 36(5): 110253
doi: 10.1016/j.cclet.2024.110253
摘要:
The radical difunctionalization of alkenes with sulfonyl bifunctional represents a powerful and straightforward approach to access functionalized alkane derivatives. However, both the mechanistic activation mode and the substrate scopes of this type of radical difunctionalizations are still limited. We demonstrate herein a modular photoredox strategy for the difunctionalization of alkenes, employing arylsulfonyl acetate as the bifunctional reagent. This approach involves a radical addition/Smiles rearrangement cascade process, offering a robust alternative for the synthesis of valuable γ,γ-diaryl and γ-aryl esters. A complementary oxidative bifunctional reagents activation mode is identified to govern the radical cascade reactions, facilitating the simultaneous incorporation of aryl and carboxylate-bearing alkyl groups into the alkenes with excellent diastereoselectivity. Noteworthy features of this method include mild reaction conditions, organophotocatalysis, high atom- and step-economy, excellent functional group compatibility and great structural diversity.
The radical difunctionalization of alkenes with sulfonyl bifunctional represents a powerful and straightforward approach to access functionalized alkane derivatives. However, both the mechanistic activation mode and the substrate scopes of this type of radical difunctionalizations are still limited. We demonstrate herein a modular photoredox strategy for the difunctionalization of alkenes, employing arylsulfonyl acetate as the bifunctional reagent. This approach involves a radical addition/Smiles rearrangement cascade process, offering a robust alternative for the synthesis of valuable γ,γ-diaryl and γ-aryl esters. A complementary oxidative bifunctional reagents activation mode is identified to govern the radical cascade reactions, facilitating the simultaneous incorporation of aryl and carboxylate-bearing alkyl groups into the alkenes with excellent diastereoselectivity. Noteworthy features of this method include mild reaction conditions, organophotocatalysis, high atom- and step-economy, excellent functional group compatibility and great structural diversity.
2025, 36(5): 110258
doi: 10.1016/j.cclet.2024.110258
摘要:
The continuous mutation and rapid spread of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) have led to the ineffectiveness of many antiviral drugs targeting the original strain. To keep pace with the virus' evolutionary speed, there is a crucial need for the development of rapid, cost-effective, and efficient inhibitor screening methods. In this study, we created a novel approach based on fluorescence resonance energy transfer (FRET) technology for in vitro detection of inhibitors targeting the interaction between the SARS-CoV-2 spike protein RBD (s-RBD) and the virus receptor angiotensin-converting enzyme 2 (ACE2). Utilizing crystallographic insights into the s-RBD/ACE2 interaction, we modified ACE2 by fusing SNAP tag to its N-terminus (resulting in SA740) and Halo tag to s-RBD’s C-terminus (producing R525H and R541H), thereby ensuring the proximity (< 10 nm) of labeled FRET dyes. We found that relative to the R541H fusion protein, R525H exhibited higher FRET efficiency, which attributed to the shortened distance between FRET dyes due to the truncation of s-RBD. Utilizing the sensitive FRET effect between SA740 and R525H, we evaluated its efficacy in detecting inhibitors of SARS-CoV-2 entry in solution and live cells. Ultimately, this FRET-based detection method was demonstrated high sensitivity, rapidity, and simplicity in solution and held promise for high-throughput screening of SARS-CoV-2 inhibitors.
The continuous mutation and rapid spread of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) have led to the ineffectiveness of many antiviral drugs targeting the original strain. To keep pace with the virus' evolutionary speed, there is a crucial need for the development of rapid, cost-effective, and efficient inhibitor screening methods. In this study, we created a novel approach based on fluorescence resonance energy transfer (FRET) technology for in vitro detection of inhibitors targeting the interaction between the SARS-CoV-2 spike protein RBD (s-RBD) and the virus receptor angiotensin-converting enzyme 2 (ACE2). Utilizing crystallographic insights into the s-RBD/ACE2 interaction, we modified ACE2 by fusing SNAP tag to its N-terminus (resulting in SA740) and Halo tag to s-RBD’s C-terminus (producing R525H and R541H), thereby ensuring the proximity (< 10 nm) of labeled FRET dyes. We found that relative to the R541H fusion protein, R525H exhibited higher FRET efficiency, which attributed to the shortened distance between FRET dyes due to the truncation of s-RBD. Utilizing the sensitive FRET effect between SA740 and R525H, we evaluated its efficacy in detecting inhibitors of SARS-CoV-2 entry in solution and live cells. Ultimately, this FRET-based detection method was demonstrated high sensitivity, rapidity, and simplicity in solution and held promise for high-throughput screening of SARS-CoV-2 inhibitors.
2025, 36(5): 110260
doi: 10.1016/j.cclet.2024.110260
摘要:
Perovskite oxides have been widely applied as an effective catalyst in heterogeneous catalysis. However, the rational design of active catalysts has been restricted by the lack of understanding of the electronic structure. The correlations between surface properties and bulk electronic structure have been ignored. Herein, a simple handler of LaFeO3 with diluted HNO3 was employed to tune the electronic structure and catalytic properties. Experimental analysis and theoretical calculations elucidate that acid etching could raise the Fe valence and enhance Fe–O covalency in the octahedral structure, thereby lessening charge transfer energy. Enhanced Fe–O covalency could lower oxygen vacancy formation energy and enhance oxygen mobility. In-situ DRIFTS results indicated the inherent adsorption capability of Toluene and CO molecules has been greatly improved owing to higher Fe–O covalency. As compared, the catalysts after acid etching exhibited higher catalytic activity, and the T90 had a great reduction of 45 and 58 ℃ for toluene and CO oxidation, respectively. A deeper understanding of electronic structure in perovskite oxides may inspire the design of high-performance catalysts.
Perovskite oxides have been widely applied as an effective catalyst in heterogeneous catalysis. However, the rational design of active catalysts has been restricted by the lack of understanding of the electronic structure. The correlations between surface properties and bulk electronic structure have been ignored. Herein, a simple handler of LaFeO3 with diluted HNO3 was employed to tune the electronic structure and catalytic properties. Experimental analysis and theoretical calculations elucidate that acid etching could raise the Fe valence and enhance Fe–O covalency in the octahedral structure, thereby lessening charge transfer energy. Enhanced Fe–O covalency could lower oxygen vacancy formation energy and enhance oxygen mobility. In-situ DRIFTS results indicated the inherent adsorption capability of Toluene and CO molecules has been greatly improved owing to higher Fe–O covalency. As compared, the catalysts after acid etching exhibited higher catalytic activity, and the T90 had a great reduction of 45 and 58 ℃ for toluene and CO oxidation, respectively. A deeper understanding of electronic structure in perovskite oxides may inspire the design of high-performance catalysts.
2025, 36(5): 110282
doi: 10.1016/j.cclet.2024.110282
摘要:
As a renovator in the field of gene editing, CRISPR-Cas9 has demonstrated immense potential for advancing next-generation gene therapy owing to its simplicity and precision. However, this potential faces significant challenges primarily stemming from the difficulty in efficiently delivering large-sized genome editing system (including Cas9 protein and sgRNA) into targeted cells and spatiotemporally controlling their activity in vitro and in vivo. Therefore, the development of CRISPR/Cas9 nanovectors that integrate high loading capacity, efficient encapsulation and spatiotemporally-controlled release is highly desirable. Herein, we have engineered a near-infrared (NIR) light-activated upconversion-DNA nanocapsule for the remote control of CRISPR-Cas9 genome editing. The light-responsive upconversion-DNA nanocapsules consist of macroporous silica (mSiO2) coated upconversion nanoparticles (UCNPs) and photocleavable o-nitrobenzyl-phosphate-modified DNA shells. The UCNPs act as a "nanotransducers" to convert NIR light (980 nm) into local ultraviolet light, thereby facilitating the cleavage of photosensitive DNA nanocapsules and enabling on-demand release of CRISPR-Cas9 encapsuled in the macroporous silica. Furthermore, by formulating a sgRNA targeted to a tumor gene (polo-like kinase-1, PLK-1), the CRISPR-Cas9 loaded UCNP-DNA nanocapsules (crUCNP-DNA nanocapsules) have effectively suppressed the proliferation of tumor cells through NIR light-activated gene editing both in vitro and in vivo. Overall, this UCNP-DNA nanocapsule holds tremendous potential for CRISPR-Cas9 delivery and remote-controlled gene editing in deep tissues, as well as the treatment of diverse diseases.
As a renovator in the field of gene editing, CRISPR-Cas9 has demonstrated immense potential for advancing next-generation gene therapy owing to its simplicity and precision. However, this potential faces significant challenges primarily stemming from the difficulty in efficiently delivering large-sized genome editing system (including Cas9 protein and sgRNA) into targeted cells and spatiotemporally controlling their activity in vitro and in vivo. Therefore, the development of CRISPR/Cas9 nanovectors that integrate high loading capacity, efficient encapsulation and spatiotemporally-controlled release is highly desirable. Herein, we have engineered a near-infrared (NIR) light-activated upconversion-DNA nanocapsule for the remote control of CRISPR-Cas9 genome editing. The light-responsive upconversion-DNA nanocapsules consist of macroporous silica (mSiO2) coated upconversion nanoparticles (UCNPs) and photocleavable o-nitrobenzyl-phosphate-modified DNA shells. The UCNPs act as a "nanotransducers" to convert NIR light (980 nm) into local ultraviolet light, thereby facilitating the cleavage of photosensitive DNA nanocapsules and enabling on-demand release of CRISPR-Cas9 encapsuled in the macroporous silica. Furthermore, by formulating a sgRNA targeted to a tumor gene (polo-like kinase-1, PLK-1), the CRISPR-Cas9 loaded UCNP-DNA nanocapsules (crUCNP-DNA nanocapsules) have effectively suppressed the proliferation of tumor cells through NIR light-activated gene editing both in vitro and in vivo. Overall, this UCNP-DNA nanocapsule holds tremendous potential for CRISPR-Cas9 delivery and remote-controlled gene editing in deep tissues, as well as the treatment of diverse diseases.
2025, 36(5): 110291
doi: 10.1016/j.cclet.2024.110291
摘要:
Metal hydrides serve as crucial intermediates in many chemical processes, facilitating the utilization of hydrogen resources. Traditionally, three-centre metal hydrides have been viewed as less reactive due to their multi-stabilization effects. However, recent discoveries show the "three-centre four-electron" (3c-4e) bridging hydride bond exhibits significant activity in boryl transition metal systems. This research employs computational techniques to explore the factors that influence the formation of the 3c-4e bridging hydride, focusing on boryl 3d non-noble transition metals ranging from chromium (Cr) to nickel (Ni). By analyzing bond distances and bond orders, the study sheds light on the electronic and structural characteristics of the B-H-M bridging hydride. It reveals a clear link between the metal centre's redox properties and the emergence of bridging hydrides. Specifically, metal centres like Cr and Co, which have lower oxidation states and electronegativity, are more inclined to form active 3c-4e bridging hydrides. These insights, derived from computational analyses, offer valuable guidelines for the development of active 3c-4e bridging metal hydrides, thereby contributing to the advancement of new hydrogen transformation catalysts.
Metal hydrides serve as crucial intermediates in many chemical processes, facilitating the utilization of hydrogen resources. Traditionally, three-centre metal hydrides have been viewed as less reactive due to their multi-stabilization effects. However, recent discoveries show the "three-centre four-electron" (3c-4e) bridging hydride bond exhibits significant activity in boryl transition metal systems. This research employs computational techniques to explore the factors that influence the formation of the 3c-4e bridging hydride, focusing on boryl 3d non-noble transition metals ranging from chromium (Cr) to nickel (Ni). By analyzing bond distances and bond orders, the study sheds light on the electronic and structural characteristics of the B-H-M bridging hydride. It reveals a clear link between the metal centre's redox properties and the emergence of bridging hydrides. Specifically, metal centres like Cr and Co, which have lower oxidation states and electronegativity, are more inclined to form active 3c-4e bridging hydrides. These insights, derived from computational analyses, offer valuable guidelines for the development of active 3c-4e bridging metal hydrides, thereby contributing to the advancement of new hydrogen transformation catalysts.
2025, 36(5): 110293
doi: 10.1016/j.cclet.2024.110293
摘要:
Singlet oxygen (1O2), as an electrophilic oxidant, is essential for the selective water decontamination of pollutants from water. Herein, we showcase a high-performing electrocatalytic filtration system composed of carbon nanotubes functionalized with CoFe alloy nanoparticles (CoFeCNT) to selectively facilitate the electrochemical activation of O2 to 1O2. Benefiting from the prominently featured bimetal active sites of CoFeCNT, nearly complete production of 1O2 is achieved by the electrocatalytic activation of O2. Additionally, the proposed system exhibits a consistent pollutant removal efficiency > 90% in a flow-through reactor over 48 h of continuous operation without a noticeable decline in performance, highlighting the dependable stability of the system for practical applications. The flow-through configuration demonstrates a striking 8-fold enhancement in tetracycline oxidation compared to a conventional batch reactor. This work provides a molecular level understanding of the oxygen reduction reaction, showing promising potential for the selective removal of emerging organic contaminants from water.
Singlet oxygen (1O2), as an electrophilic oxidant, is essential for the selective water decontamination of pollutants from water. Herein, we showcase a high-performing electrocatalytic filtration system composed of carbon nanotubes functionalized with CoFe alloy nanoparticles (CoFeCNT) to selectively facilitate the electrochemical activation of O2 to 1O2. Benefiting from the prominently featured bimetal active sites of CoFeCNT, nearly complete production of 1O2 is achieved by the electrocatalytic activation of O2. Additionally, the proposed system exhibits a consistent pollutant removal efficiency > 90% in a flow-through reactor over 48 h of continuous operation without a noticeable decline in performance, highlighting the dependable stability of the system for practical applications. The flow-through configuration demonstrates a striking 8-fold enhancement in tetracycline oxidation compared to a conventional batch reactor. This work provides a molecular level understanding of the oxygen reduction reaction, showing promising potential for the selective removal of emerging organic contaminants from water.
2025, 36(5): 110295
doi: 10.1016/j.cclet.2024.110295
摘要:
Developing a high-efficiency catalyst with both superior low-temperature activity and good N2 selectivity is still challenging for the NH3 selective catalytic reduction (SCR) of NOx from mobile sources. Herein, we demonstrate the improved low-temperature activity and N2 selectivity by regulating the redox and acidic properties of MnCe oxides supported on etched ZSM-5 supports. The etched ZSM-5 enables the highly dispersed state of MnCeOx species and strong interaction between Mn and Ce species, which promotes the reduction of CeO2, facilitates electron transfer from Mn to Ce, and generates more Mn4+ and Ce3+ species. The strong redox capacity contributes to forming the reactive nitrate species and -NH2 species from oxidative dehydrogenation of NH3. Moreover, the adsorbed NH3 and -NH2 species are the reactive intermediates that promote the formation of N2. This work demonstrates an effective strategy to enhance the low-temperature activity and N2 selectivity of SCR catalysts, contributing to the NOx control for the low-temperature exhaust gas during the cold-start of diesel vehicles.
Developing a high-efficiency catalyst with both superior low-temperature activity and good N2 selectivity is still challenging for the NH3 selective catalytic reduction (SCR) of NOx from mobile sources. Herein, we demonstrate the improved low-temperature activity and N2 selectivity by regulating the redox and acidic properties of MnCe oxides supported on etched ZSM-5 supports. The etched ZSM-5 enables the highly dispersed state of MnCeOx species and strong interaction between Mn and Ce species, which promotes the reduction of CeO2, facilitates electron transfer from Mn to Ce, and generates more Mn4+ and Ce3+ species. The strong redox capacity contributes to forming the reactive nitrate species and -NH2 species from oxidative dehydrogenation of NH3. Moreover, the adsorbed NH3 and -NH2 species are the reactive intermediates that promote the formation of N2. This work demonstrates an effective strategy to enhance the low-temperature activity and N2 selectivity of SCR catalysts, contributing to the NOx control for the low-temperature exhaust gas during the cold-start of diesel vehicles.
2025, 36(5): 110306
doi: 10.1016/j.cclet.2024.110306
摘要:
The intrinsic clustering behavior and kinetically sluggish conversion process of lithium polysulfides seriously limit the electrochemical reversibility of sulfur redox reactions in lithium-sulfur (Li-S) batteries. Here, we introduce molybdenum pentachloride (MoCl5) into the electrolyte which could coordinate with lithium polysulfides and inhibit their intrinsic clustering behavior, subsequently serving as an improved mediator with the bi-functional catalytic effect for Li2S deposition and activation. Moreover, the coordination bonding and accelerated conversion reaction can also greatly suppress the dissolution and shuttling of polysulfides. Consequently, such polysulfide complexes enable the Li-S coin cell to exhibit good long-term cycling stability with a capacity decay of 0.078% per cycle after 400 cycles at 2 C, and excellent rate performance with a discharge capacity of 589 mAh/g at 4 C. An area capacity of 3.94 mAh/cm2 is also achieved with a high sulfur loading of 4.5 mg/cm2 at 0.2 C. Even at -20 ℃, the modified cell maintains standard discharge plateaus with low overpotential, delivering a high capacity of 741 mAh/g at 0.2 C after 80 cycles. The low-cost and convenient MoCl5 additive opens a new avenue for the effective regulation of polysulfides and significant enhancement in sulfur redox conversion.
The intrinsic clustering behavior and kinetically sluggish conversion process of lithium polysulfides seriously limit the electrochemical reversibility of sulfur redox reactions in lithium-sulfur (Li-S) batteries. Here, we introduce molybdenum pentachloride (MoCl5) into the electrolyte which could coordinate with lithium polysulfides and inhibit their intrinsic clustering behavior, subsequently serving as an improved mediator with the bi-functional catalytic effect for Li2S deposition and activation. Moreover, the coordination bonding and accelerated conversion reaction can also greatly suppress the dissolution and shuttling of polysulfides. Consequently, such polysulfide complexes enable the Li-S coin cell to exhibit good long-term cycling stability with a capacity decay of 0.078% per cycle after 400 cycles at 2 C, and excellent rate performance with a discharge capacity of 589 mAh/g at 4 C. An area capacity of 3.94 mAh/cm2 is also achieved with a high sulfur loading of 4.5 mg/cm2 at 0.2 C. Even at -20 ℃, the modified cell maintains standard discharge plateaus with low overpotential, delivering a high capacity of 741 mAh/g at 0.2 C after 80 cycles. The low-cost and convenient MoCl5 additive opens a new avenue for the effective regulation of polysulfides and significant enhancement in sulfur redox conversion.
2025, 36(5): 110310
doi: 10.1016/j.cclet.2024.110310
摘要:
An electronic circular dichroism (ECD)-based chiroptical sensing method has been developed for β- and γ-chiral primary amines via a C–H activation reaction. With the addition of Pd(OAc)2, the flexible remote chiral primary amine fragment in the bidentate ligand intermediate was fixed to form a cyclopalladium complex, producing an intense ECD response. The correlation between the sign of Cotton effects and the absolute configuration of substrates was proposed, together with theoretical verification using time-dependent density functional theory (TDDFT). Chiroptical sensing of an important drug raw material was performed to provide rapid and accurate information on the absolute optical purity. This work introduces an alternative perspective of C–H activation reaction as well as a feasible chiroptical sensing method of remote chiral amines.
An electronic circular dichroism (ECD)-based chiroptical sensing method has been developed for β- and γ-chiral primary amines via a C–H activation reaction. With the addition of Pd(OAc)2, the flexible remote chiral primary amine fragment in the bidentate ligand intermediate was fixed to form a cyclopalladium complex, producing an intense ECD response. The correlation between the sign of Cotton effects and the absolute configuration of substrates was proposed, together with theoretical verification using time-dependent density functional theory (TDDFT). Chiroptical sensing of an important drug raw material was performed to provide rapid and accurate information on the absolute optical purity. This work introduces an alternative perspective of C–H activation reaction as well as a feasible chiroptical sensing method of remote chiral amines.
2025, 36(5): 110311
doi: 10.1016/j.cclet.2024.110311
摘要:
Achieving artificial simulations of multi-step energy transfer processes and conversions in nature remains a challenge. In this study, we present a three-step sequential energy transfer process, which was constructed through host-guest interactions between a piperazine derivative (PPE-BPI) with aggregation-induced emission (AIE) and cucurbit[7]uril (CB[7]) in water to serve as ideal energy donors. To achieve multi-step sequential energy transfer, we employ three distinct fluorescent dyes Eosin B (EsB), Sulforhodamine 101 (SR101), and Cyanine 5 (Cy5) as energy acceptors. The PPE-PBI-2CB[7]+EsB+SR101+Cy5 system demonstrates a highly efficient three-step sequential energy transfer mechanism, starting with PPE-PBI-2CB[7] and transferring energy successively to EsB, SR101, and finally to Cy5, with remarkable energy transfer efficiencies. More interestingly, with the progressive transfer of energy in the multi-step energy transfer system, the generation efficiency of superoxide anion radical (O2•–) increased gradually, which can be used as photocatalysts for selectively photooxidation of N-phenyltetrahydroisoquinoline in an aqueous medium with a high yield of 86% after irradiation for 18 h. This study offers a valuable investigation into the simulation of multi-step energy transfer processes and transformations in the natural world, paving the way for further research in the field.
Achieving artificial simulations of multi-step energy transfer processes and conversions in nature remains a challenge. In this study, we present a three-step sequential energy transfer process, which was constructed through host-guest interactions between a piperazine derivative (PPE-BPI) with aggregation-induced emission (AIE) and cucurbit[7]uril (CB[7]) in water to serve as ideal energy donors. To achieve multi-step sequential energy transfer, we employ three distinct fluorescent dyes Eosin B (EsB), Sulforhodamine 101 (SR101), and Cyanine 5 (Cy5) as energy acceptors. The PPE-PBI-2CB[7]+EsB+SR101+Cy5 system demonstrates a highly efficient three-step sequential energy transfer mechanism, starting with PPE-PBI-2CB[7] and transferring energy successively to EsB, SR101, and finally to Cy5, with remarkable energy transfer efficiencies. More interestingly, with the progressive transfer of energy in the multi-step energy transfer system, the generation efficiency of superoxide anion radical (O2•–) increased gradually, which can be used as photocatalysts for selectively photooxidation of N-phenyltetrahydroisoquinoline in an aqueous medium with a high yield of 86% after irradiation for 18 h. This study offers a valuable investigation into the simulation of multi-step energy transfer processes and transformations in the natural world, paving the way for further research in the field.
2025, 36(5): 110312
doi: 10.1016/j.cclet.2024.110312
摘要:
A sp2 carbon-conjugated covalent organic framework (BDATN) was modified through γ-ray radiation reduction and subsequent acidification with hydrochloric acid to yield a novel functional COF (named rBDATN-HCl) for Cr(VI) removal. The morphology and structure of rBDATN-HCl were analyzed and identified by SEM, FTIR, XRD and solid-state 13C NMR. It is found that the active functional groups, such as hydroxyl and amide, were introduced into BDATN after radiation reduction and acidification. The prepared rBDATN-HCl demonstrates a photocatalytic reduction removal rate of Cr(VI) above 99% after 60 min of illumination with a solid-liquid ratio of 0.5 mg/mL, showing outstanding performance, which is attributed to the increase of dispersibility and adsorption sites of rBDATN-HCl. In comparison to the cBDATN-HCl synthesized with chemical reduction, rBDATN-HCl exhibits a better photoreduction performance for Cr(VI), demonstrating the advantages of radiation preparation of rBDATN-HCl. It is expected that more functionalized sp2 carbon-conjugated COFs could be obtained by this radiation-induced reduction strategy.
A sp2 carbon-conjugated covalent organic framework (BDATN) was modified through γ-ray radiation reduction and subsequent acidification with hydrochloric acid to yield a novel functional COF (named rBDATN-HCl) for Cr(VI) removal. The morphology and structure of rBDATN-HCl were analyzed and identified by SEM, FTIR, XRD and solid-state 13C NMR. It is found that the active functional groups, such as hydroxyl and amide, were introduced into BDATN after radiation reduction and acidification. The prepared rBDATN-HCl demonstrates a photocatalytic reduction removal rate of Cr(VI) above 99% after 60 min of illumination with a solid-liquid ratio of 0.5 mg/mL, showing outstanding performance, which is attributed to the increase of dispersibility and adsorption sites of rBDATN-HCl. In comparison to the cBDATN-HCl synthesized with chemical reduction, rBDATN-HCl exhibits a better photoreduction performance for Cr(VI), demonstrating the advantages of radiation preparation of rBDATN-HCl. It is expected that more functionalized sp2 carbon-conjugated COFs could be obtained by this radiation-induced reduction strategy.
2025, 36(5): 110334
doi: 10.1016/j.cclet.2024.110334
摘要:
An unprecedented 2,3-arylacylation reaction of allenes with aryl iodides and aldehydes was developed by resorting to Pd/NHC synergetic catalysis. It is the first time that allene was introduced into transition metal and NHC synergetic catalysis, which demonstrated a versatile three-component reaction pattern, thus enabling two C-C bonds forged regioselectively in the reaction. The important reaction intermediates were successfully captured and characterized by HRMS analysis, and the migrative insertion of allene to the Ph-Pd species was identified as the reaction rate-limiting step by kinetic experiments.
An unprecedented 2,3-arylacylation reaction of allenes with aryl iodides and aldehydes was developed by resorting to Pd/NHC synergetic catalysis. It is the first time that allene was introduced into transition metal and NHC synergetic catalysis, which demonstrated a versatile three-component reaction pattern, thus enabling two C-C bonds forged regioselectively in the reaction. The important reaction intermediates were successfully captured and characterized by HRMS analysis, and the migrative insertion of allene to the Ph-Pd species was identified as the reaction rate-limiting step by kinetic experiments.
2025, 36(5): 110432
doi: 10.1016/j.cclet.2024.110432
摘要:
Chirality, ubiquitous in living matter, plays vital roles in a series of physiological processes. The clarification of the multiple functions of chirality in bioapplications may provide innovative methodologies for engineering anti-tumor agents. Nevertheless, the related research has been rarely explored. In this study, the chiral supramolecular l/d-cysteine (Cys)-Zn2+-indocyanine green (ICG) nanoparticles were constructed through the coordination interaction between l/d-Cys and Zn2+, followed by the encapsulation of ICG. Experimental findings revealed that the d-Cys-Zn2+-ICG exhibited 17.31 times higher binding affinity toward phospholipid-composed liposomes compared to l-Cys-Zn2+-ICG. Furthermore, driven by chirality-specific interaction, a 2.07 folds greater cellular internalization of d-Cys-Zn2+-ICG than l-Cys-Zn2+-ICG was demonstrated. Additionally, the triple-level chirality-dependent photothermal, photodynamic and Zn2+ releasing anti-tumor effects of l/d Cys-Zn2+-ICG in vitro were verified. As a result, the d-formed nanoparticles achieved 1.93 times higher anti-tumor efficiency than the l-formed ones. The triple-level chirality-mediated anti-tumor effect highlighted in this study underscores the enormous potential of chirality in biomedicine and holds substantial significance in improving cancer therapeutic efficacy.
Chirality, ubiquitous in living matter, plays vital roles in a series of physiological processes. The clarification of the multiple functions of chirality in bioapplications may provide innovative methodologies for engineering anti-tumor agents. Nevertheless, the related research has been rarely explored. In this study, the chiral supramolecular l/d-cysteine (Cys)-Zn2+-indocyanine green (ICG) nanoparticles were constructed through the coordination interaction between l/d-Cys and Zn2+, followed by the encapsulation of ICG. Experimental findings revealed that the d-Cys-Zn2+-ICG exhibited 17.31 times higher binding affinity toward phospholipid-composed liposomes compared to l-Cys-Zn2+-ICG. Furthermore, driven by chirality-specific interaction, a 2.07 folds greater cellular internalization of d-Cys-Zn2+-ICG than l-Cys-Zn2+-ICG was demonstrated. Additionally, the triple-level chirality-dependent photothermal, photodynamic and Zn2+ releasing anti-tumor effects of l/d Cys-Zn2+-ICG in vitro were verified. As a result, the d-formed nanoparticles achieved 1.93 times higher anti-tumor efficiency than the l-formed ones. The triple-level chirality-mediated anti-tumor effect highlighted in this study underscores the enormous potential of chirality in biomedicine and holds substantial significance in improving cancer therapeutic efficacy.
2025, 36(5): 110437
doi: 10.1016/j.cclet.2024.110437
摘要:
Ferroptosis in combination with immune therapy emerges as a promising approach for cancer therapy. Herein, dual-responsive metal-polyphenol coordinated nanomedicines were developed for pH/glutathione (GSH)-responsive synergistic ferroptosis and immunotherapy. Our innovative strategy involves the development of a manganese-polyphenol coordinated nanostructure, leveraging the biocompatibility of bovine serum albumin (BSA) as a template to encapsulate the anticancer drug sorafenib. The tumor microenvironment (pH/GSH) prompts the disassembly of MnO2 and epigallocatechin gallate (EGCG), thereby releases the anticancer payload. Concurrently, MnO2 acts to deplete intracellular GSH, which in turn suppresses glutathione peroxidase activity, leading to an accumulation of lipid peroxides with cell ferroptosis. Additionally, the release of Mn2+ ions bolster the cyclic guanosine monophosphlic acid (GMP)-adenosine monophosphlic acid (AMP) synthase-stimulator of interferon gene (cGAS-STING) pathway, which, in conjunction with the immunogenic cell death (ICD) effect induced by tumor cell apoptosis, significantly promotes dendritic cell (DC) maturation and enhances the presentation of tumor antigens. This successively ignites a robust innate and adaptive immune response. Both in vitro and in vivo experiments have demonstrated that the concurrent administration of ferroptosis-inducing and immune-stimulating therapies can significantly inhibit tumor growth.
Ferroptosis in combination with immune therapy emerges as a promising approach for cancer therapy. Herein, dual-responsive metal-polyphenol coordinated nanomedicines were developed for pH/glutathione (GSH)-responsive synergistic ferroptosis and immunotherapy. Our innovative strategy involves the development of a manganese-polyphenol coordinated nanostructure, leveraging the biocompatibility of bovine serum albumin (BSA) as a template to encapsulate the anticancer drug sorafenib. The tumor microenvironment (pH/GSH) prompts the disassembly of MnO2 and epigallocatechin gallate (EGCG), thereby releases the anticancer payload. Concurrently, MnO2 acts to deplete intracellular GSH, which in turn suppresses glutathione peroxidase activity, leading to an accumulation of lipid peroxides with cell ferroptosis. Additionally, the release of Mn2+ ions bolster the cyclic guanosine monophosphlic acid (GMP)-adenosine monophosphlic acid (AMP) synthase-stimulator of interferon gene (cGAS-STING) pathway, which, in conjunction with the immunogenic cell death (ICD) effect induced by tumor cell apoptosis, significantly promotes dendritic cell (DC) maturation and enhances the presentation of tumor antigens. This successively ignites a robust innate and adaptive immune response. Both in vitro and in vivo experiments have demonstrated that the concurrent administration of ferroptosis-inducing and immune-stimulating therapies can significantly inhibit tumor growth.
2025, 36(5): 110508
doi: 10.1016/j.cclet.2024.110508
摘要:
Candida albicans is one of the most common pathogens causing invasive fungal infections, with a mortality rate of up to 20%–50%. Amphotericin B (AmB), a biopharmaceutics classification system (BCS) IV drug, significantly inhibits Candida albicans. AmB is primarily administered via oral and intravenous infusion, but severe infusion adverse effects, nephrotoxicity, and potential hepatotoxicity limit its clinical application. Deep eutectic solvents (DESs), with excellent solubilization ability and skin permeability, are attractive for transdermal delivery. Herein, we used DESs to deliver AmB for antifungal therapy transdermally. We first prepared and characterized DESs with different stoichiometric ratios of choline (Ch) and geranate (Ge). DESs increased the solubility of AmB by a thousand-fold. In vitro and in vivo, skin permeation studies indicated that DES1:2 (Ch and Ge in 1:2 ratio) had the most outstanding penetration and delivered fluorescence dye to the dermis layer. Then, DES1:2-AmB was prepared and in vitro antifungal tests demonstrated that DES1:2-AmB had superior antifungal effects compared to AmB and DES1:2. Furthermore, DES1:2-AmB was skin-irritating and biocompatible. In conclusion, DES-AmB provides a new and effective therapeutic solution for fungal infections.
Candida albicans is one of the most common pathogens causing invasive fungal infections, with a mortality rate of up to 20%–50%. Amphotericin B (AmB), a biopharmaceutics classification system (BCS) IV drug, significantly inhibits Candida albicans. AmB is primarily administered via oral and intravenous infusion, but severe infusion adverse effects, nephrotoxicity, and potential hepatotoxicity limit its clinical application. Deep eutectic solvents (DESs), with excellent solubilization ability and skin permeability, are attractive for transdermal delivery. Herein, we used DESs to deliver AmB for antifungal therapy transdermally. We first prepared and characterized DESs with different stoichiometric ratios of choline (Ch) and geranate (Ge). DESs increased the solubility of AmB by a thousand-fold. In vitro and in vivo, skin permeation studies indicated that DES1:2 (Ch and Ge in 1:2 ratio) had the most outstanding penetration and delivered fluorescence dye to the dermis layer. Then, DES1:2-AmB was prepared and in vitro antifungal tests demonstrated that DES1:2-AmB had superior antifungal effects compared to AmB and DES1:2. Furthermore, DES1:2-AmB was skin-irritating and biocompatible. In conclusion, DES-AmB provides a new and effective therapeutic solution for fungal infections.
2025, 36(5): 110561
doi: 10.1016/j.cclet.2024.110561
摘要:
Nanochannel technology based on ionic current rectification has emerged as a powerful tool for the detection of biomolecules owing to unique advantages. Nevertheless, existing nanochannel sensors mainly focus on the detection of targets in solution or inside the cells, moreover, they only have a single function, greatly limiting their application. Herein, we fabricated SuperDNA self-assembled conical nanochannel, which was clamped in the middle of self-made device for two functions: Online detecting living cells released TNF-α and studying intercellular communication. Polyethylene terephthalate (PET) membrane incubated tumor associated macrophages and tumor cells was rolled up and inserted into the left and right chamber of the device, respectively. Through monitoring the ion current change in the nanochannel, tumor associated macrophages released TNF-α could be in situ and noninvasive detected with a detection limit of 0.23 pg/mL. Furthermore, the secreted TNF-α induced epithelial-mesenchymal transformation of tumor cells in the right chamber was also studied. The presented strategy displayed outstanding performance and multi-function, providing a promising platform for in situ non-destructive detection of cell secretions and related intercellular communication analysis.
Nanochannel technology based on ionic current rectification has emerged as a powerful tool for the detection of biomolecules owing to unique advantages. Nevertheless, existing nanochannel sensors mainly focus on the detection of targets in solution or inside the cells, moreover, they only have a single function, greatly limiting their application. Herein, we fabricated SuperDNA self-assembled conical nanochannel, which was clamped in the middle of self-made device for two functions: Online detecting living cells released TNF-α and studying intercellular communication. Polyethylene terephthalate (PET) membrane incubated tumor associated macrophages and tumor cells was rolled up and inserted into the left and right chamber of the device, respectively. Through monitoring the ion current change in the nanochannel, tumor associated macrophages released TNF-α could be in situ and noninvasive detected with a detection limit of 0.23 pg/mL. Furthermore, the secreted TNF-α induced epithelial-mesenchymal transformation of tumor cells in the right chamber was also studied. The presented strategy displayed outstanding performance and multi-function, providing a promising platform for in situ non-destructive detection of cell secretions and related intercellular communication analysis.
2025, 36(5): 110629
doi: 10.1016/j.cclet.2024.110629
摘要:
Room-temperature phosphorescence (RTP) materials exhibiting long emission lifetimes have gained increasing attention owing to their potential applications in encryption, anti-counterfeiting, and sensing. However, most polymers exhibit a short RTP lifetime (<1 s) because of their unstable triplet excitons. Herein, a new strategy of polymer chain stabilized phosphorescence (PCSP), which yields a new kind of RTP polymers with an ultralong lifetime and a sensitive oxygen response, has been reported. The rigid polymer chains of poly(methyl mathacrylate) (PMMA) immobilize the emitter molecules through multiple interactions between them, giving rise to efficient RTP. Meanwhile, the loosely-packed amorphous polymer chains allow oxygen to diffuse inside, endowing the doped polymers with oxygen sensitivity. Flexible and transparent polymer films exhibited an impressive ultralong RTP lifetime of 2.57 s at room temperature in vacuum, which was among the best performance of PMMA. Intriguingly, their RTP was rapidly quenched in the presence of oxygen. Furthermore, RTP microparticles with a diameter of 1.63 µm were synthesized using in situ dispersion polymerization technique. Finally, oxygen sensors for quick, visual, and quantitative oxygen detection were developed based on the RTP microparticles through phosphorescence lifetime and image analysis. With distinctive advantages such as an ultralong lifetime, oxygen sensitivity, ease of fabrication, and cost-effectiveness, PCSP opens a new avenue to sensitive materials for oxygen detection.
Room-temperature phosphorescence (RTP) materials exhibiting long emission lifetimes have gained increasing attention owing to their potential applications in encryption, anti-counterfeiting, and sensing. However, most polymers exhibit a short RTP lifetime (<1 s) because of their unstable triplet excitons. Herein, a new strategy of polymer chain stabilized phosphorescence (PCSP), which yields a new kind of RTP polymers with an ultralong lifetime and a sensitive oxygen response, has been reported. The rigid polymer chains of poly(methyl mathacrylate) (PMMA) immobilize the emitter molecules through multiple interactions between them, giving rise to efficient RTP. Meanwhile, the loosely-packed amorphous polymer chains allow oxygen to diffuse inside, endowing the doped polymers with oxygen sensitivity. Flexible and transparent polymer films exhibited an impressive ultralong RTP lifetime of 2.57 s at room temperature in vacuum, which was among the best performance of PMMA. Intriguingly, their RTP was rapidly quenched in the presence of oxygen. Furthermore, RTP microparticles with a diameter of 1.63 µm were synthesized using in situ dispersion polymerization technique. Finally, oxygen sensors for quick, visual, and quantitative oxygen detection were developed based on the RTP microparticles through phosphorescence lifetime and image analysis. With distinctive advantages such as an ultralong lifetime, oxygen sensitivity, ease of fabrication, and cost-effectiveness, PCSP opens a new avenue to sensitive materials for oxygen detection.
2025, 36(5): 110663
doi: 10.1016/j.cclet.2024.110663
摘要:
Transition metal cobalt exhibits strong activation capabilities for alkanes, however, the instability of Co sites leads to sintering and coke deposition, resulting in rapid deactivation. Hierarchical zeolites, with their diverse pore structures and high surface areas, are used to effectively anchor metals and enhance coke tolerance. Herein, a post-treatment method using an alkaline solution was employed to synthesize meso-microporous zeolite supports, which were subsequently loaded with Co species for propane dehydrogenation catalyst. The results indicate that the application of NaOH, an inorganic base, produces supports with a larger mesopore volume and more abundant hydroxyl nests compared to TPAOH, an organic base. UV–vis, Raman, and XPS analyses reveal that Co in the 0.5Co/SN-1–0.05 catalyst is mainly in the form of tetrahedral Co2+, which effectively activates CH bonds. In contrast, the 0.5Co/S-1 catalyst contains mainly Co3O4 species. Co2+ supported on hierarchical zeolites shows better propane conversion (58.6%) and propylene selectivity (>96%) compared to pure silica zeolites. Coke characterization indicates that hierarchical zeolites accumulate more coke, but it is mostly in the form of easily removable disordered carbon. The mesopores in the microporous zeolite support help disperse the active Co metal and facilitate coke removal during dehydrogenation, effectively preventing deactivation from sintering and coke coverage.
Transition metal cobalt exhibits strong activation capabilities for alkanes, however, the instability of Co sites leads to sintering and coke deposition, resulting in rapid deactivation. Hierarchical zeolites, with their diverse pore structures and high surface areas, are used to effectively anchor metals and enhance coke tolerance. Herein, a post-treatment method using an alkaline solution was employed to synthesize meso-microporous zeolite supports, which were subsequently loaded with Co species for propane dehydrogenation catalyst. The results indicate that the application of NaOH, an inorganic base, produces supports with a larger mesopore volume and more abundant hydroxyl nests compared to TPAOH, an organic base. UV–vis, Raman, and XPS analyses reveal that Co in the 0.5Co/SN-1–0.05 catalyst is mainly in the form of tetrahedral Co2+, which effectively activates CH bonds. In contrast, the 0.5Co/S-1 catalyst contains mainly Co3O4 species. Co2+ supported on hierarchical zeolites shows better propane conversion (58.6%) and propylene selectivity (>96%) compared to pure silica zeolites. Coke characterization indicates that hierarchical zeolites accumulate more coke, but it is mostly in the form of easily removable disordered carbon. The mesopores in the microporous zeolite support help disperse the active Co metal and facilitate coke removal during dehydrogenation, effectively preventing deactivation from sintering and coke coverage.
2025, 36(5): 110672
doi: 10.1016/j.cclet.2024.110672
摘要:
On-demand droplet manipulation plays a critical role in microfluidics, bio/chemical detection and micro-reactions. Acoustic droplet manipulation has emerged as a promising technique due to its non-contact nature, biocompatibility and precision, circumventing the complexities associated with other methods requiring surface or droplet pretreatment. Despite their promise, existing methods for acoustic droplet manipulation often involve complex hardware setups and difficulty for controlling individual droplet amidst multiple ones. Here we fabricate simple yet effective acoustic tweezers for in-surface and out-of-surface droplet manipulation. It is found that droplets can be transported on the superhydrophobic surfaces when the acoustic radiation force surpasses the friction force. Using a two-axis acoustic tweezer, droplets can be maneuvered along arbitrarily programmed paths on the surfaces. By introducing multiple labyrinthine structures on the superhydrophobic surface, individual droplet manipulation is realized by constraining the unselected droplets in the labyrinthine structures. In addition, a three-axis acoustic tweezer is developed for manipulating droplets in three-dimensional space. Potential applications of the acoustic tweezers for micro-reaction, bio-assay and chemical analysis are also demonstrated.
On-demand droplet manipulation plays a critical role in microfluidics, bio/chemical detection and micro-reactions. Acoustic droplet manipulation has emerged as a promising technique due to its non-contact nature, biocompatibility and precision, circumventing the complexities associated with other methods requiring surface or droplet pretreatment. Despite their promise, existing methods for acoustic droplet manipulation often involve complex hardware setups and difficulty for controlling individual droplet amidst multiple ones. Here we fabricate simple yet effective acoustic tweezers for in-surface and out-of-surface droplet manipulation. It is found that droplets can be transported on the superhydrophobic surfaces when the acoustic radiation force surpasses the friction force. Using a two-axis acoustic tweezer, droplets can be maneuvered along arbitrarily programmed paths on the surfaces. By introducing multiple labyrinthine structures on the superhydrophobic surface, individual droplet manipulation is realized by constraining the unselected droplets in the labyrinthine structures. In addition, a three-axis acoustic tweezer is developed for manipulating droplets in three-dimensional space. Potential applications of the acoustic tweezers for micro-reaction, bio-assay and chemical analysis are also demonstrated.
2025, 36(5): 110699
doi: 10.1016/j.cclet.2024.110699
摘要:
Generally, gaining fundamental insights into chain processes during the combustion of flame-retardant polymers relies on the qualitative and quantitative characterization of key chain carriers. However, polymer combustion processes based on conventional solid-fuel combustion strategies, due to the high coupling of pyrolysis, combustion, soot formation and oxidation, exhibit relatively high complexity and poor flame stability, and lead to a huge obstacle to the use of optical diagnostics. Herein, a spatial-confinement combustion strategy, which can produce a special staged flame with multi-jets secondary wave, is devised to provide a highly decoupled combustion environment. Glowing soot particles are therefore decoupled from main chemiluminescence region and confined to the flame tip to provide a well-controlled, optical-thin test environment for combustion diagnostic. Based on this strategy, a multi-nozzle-separation (MNS) burner is designed and fabricated, and the combustion processes associated with four model compounds, PVC, PS, PP/TBBA blends and PP/RP blends are investigated by spontaneous spectral diagnosis, and the chemiluminescence fingerprint of key diatomic/triatomic intermediates (such as OH, CH, C2, ClO, Br2, and PHO) are clearly observed. This encouraging result means that the strategy of spatial-confinement combustion we proposed shows promising prospect in many subjects associated with combustion chain regulation, such as efficient design of flame retardants.
Generally, gaining fundamental insights into chain processes during the combustion of flame-retardant polymers relies on the qualitative and quantitative characterization of key chain carriers. However, polymer combustion processes based on conventional solid-fuel combustion strategies, due to the high coupling of pyrolysis, combustion, soot formation and oxidation, exhibit relatively high complexity and poor flame stability, and lead to a huge obstacle to the use of optical diagnostics. Herein, a spatial-confinement combustion strategy, which can produce a special staged flame with multi-jets secondary wave, is devised to provide a highly decoupled combustion environment. Glowing soot particles are therefore decoupled from main chemiluminescence region and confined to the flame tip to provide a well-controlled, optical-thin test environment for combustion diagnostic. Based on this strategy, a multi-nozzle-separation (MNS) burner is designed and fabricated, and the combustion processes associated with four model compounds, PVC, PS, PP/TBBA blends and PP/RP blends are investigated by spontaneous spectral diagnosis, and the chemiluminescence fingerprint of key diatomic/triatomic intermediates (such as OH, CH, C2, ClO, Br2, and PHO) are clearly observed. This encouraging result means that the strategy of spatial-confinement combustion we proposed shows promising prospect in many subjects associated with combustion chain regulation, such as efficient design of flame retardants.
2025, 36(5): 110700
doi: 10.1016/j.cclet.2024.110700
摘要:
Heterocyclic compounds play an important role in organic hole transport materials (HTMs) for perovskite solar cells (PSCs). Herein, a series of linear D-π-D HTMs (OCBz, S-CBz, SO2-CBz) with different dibenzo-heterocycles core (dibenzofuran, dibenzothiophene, dibenzothiophene sulfone) were designed and synthesized, and their applications in PSCs were investigated. The intrinsic properties (CV, UV–vis, hole mobility and conductivity) were systematically investigated, demonstrating that all three materials are suitable HTMs for planar n-i-p type PSCs. Benefiting from the excellent hole mobility and conductivity, good film forming ability, and outstanding charge extraction and transport capability of S-CBz, FAPbI3-based PSCs using S-CBz as HTM achieved a PCE of 25.0%, which is superior to that of Spiro-OMeTAD-based PSCs fabricated under the same conditions (23.9%). Furthermore, due to the interaction between S and Pb2+, S-CBz-based PSC devices exhibited improved stability. This work demonstrates that dibenzothiophene-based architectures are promising candidates for high-performance HTMs in perovskite solar cell architectures.
Heterocyclic compounds play an important role in organic hole transport materials (HTMs) for perovskite solar cells (PSCs). Herein, a series of linear D-π-D HTMs (OCBz, S-CBz, SO2-CBz) with different dibenzo-heterocycles core (dibenzofuran, dibenzothiophene, dibenzothiophene sulfone) were designed and synthesized, and their applications in PSCs were investigated. The intrinsic properties (CV, UV–vis, hole mobility and conductivity) were systematically investigated, demonstrating that all three materials are suitable HTMs for planar n-i-p type PSCs. Benefiting from the excellent hole mobility and conductivity, good film forming ability, and outstanding charge extraction and transport capability of S-CBz, FAPbI3-based PSCs using S-CBz as HTM achieved a PCE of 25.0%, which is superior to that of Spiro-OMeTAD-based PSCs fabricated under the same conditions (23.9%). Furthermore, due to the interaction between S and Pb2+, S-CBz-based PSC devices exhibited improved stability. This work demonstrates that dibenzothiophene-based architectures are promising candidates for high-performance HTMs in perovskite solar cell architectures.
2025, 36(5): 110719
doi: 10.1016/j.cclet.2024.110719
摘要:
Crystalized CeO2 structures were typically considered potential photocatalysts due to their great capacity to alter the active sites’ size and ability to absorb light. However, the controllable fabrication of well-defined hierarchical structures of CeO2 with high reactive facets is significant and challenging. Herein, a series of CeO2 supports including hierarchical flower-like (F-CeO2), ball-like (B-CeO2), cube-like (CCeO2), and rod-like CeO2(R-CeO2) supports were prepared by hydrothermal method (B-CeO2, R-CeO2 and CCeO2) or ice-bath method (F-CeO2) respectively. V atoms were selected as the active atoms and loaded on these supports. Their structure-activity relationship in photo-assisted thermal propane dehydrogenation (PTPDH) was investigated systematically. The samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N2 adsorption-desorption isotherms, and Fourier transform infrared spectrum. Results show that R-CeO2 support exhibits the biggest surface area thus achieving the best dispersion of VOx species. UV–vis spectrum and photoluminescence spectrum indicate that V/F-CeO2 has the best light adsorption property and V/R-CeO2 has the best carrier migration capacity. The activity tests demonstrate that the V/R-CeO2 has the largest net growth rate and the V/F-CeO2 has the biggest relative growth ratio. Furthermore, the non-thermal effect was confirmed by the kinetic method, which lowers the propane reaction orders, selectively promoting the first C–H bond activation. The light radiation TPSR experiment confirmed this point. DFT calculations show a good linear relationship between the energy barrier and the exchanged electron number. It inspires the design of high-reactive facets for boosting the intrinsic activity of the C–H bond in photo-assisted thermal chemical processes.
Crystalized CeO2 structures were typically considered potential photocatalysts due to their great capacity to alter the active sites’ size and ability to absorb light. However, the controllable fabrication of well-defined hierarchical structures of CeO2 with high reactive facets is significant and challenging. Herein, a series of CeO2 supports including hierarchical flower-like (F-CeO2), ball-like (B-CeO2), cube-like (CCeO2), and rod-like CeO2(R-CeO2) supports were prepared by hydrothermal method (B-CeO2, R-CeO2 and CCeO2) or ice-bath method (F-CeO2) respectively. V atoms were selected as the active atoms and loaded on these supports. Their structure-activity relationship in photo-assisted thermal propane dehydrogenation (PTPDH) was investigated systematically. The samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N2 adsorption-desorption isotherms, and Fourier transform infrared spectrum. Results show that R-CeO2 support exhibits the biggest surface area thus achieving the best dispersion of VOx species. UV–vis spectrum and photoluminescence spectrum indicate that V/F-CeO2 has the best light adsorption property and V/R-CeO2 has the best carrier migration capacity. The activity tests demonstrate that the V/R-CeO2 has the largest net growth rate and the V/F-CeO2 has the biggest relative growth ratio. Furthermore, the non-thermal effect was confirmed by the kinetic method, which lowers the propane reaction orders, selectively promoting the first C–H bond activation. The light radiation TPSR experiment confirmed this point. DFT calculations show a good linear relationship between the energy barrier and the exchanged electron number. It inspires the design of high-reactive facets for boosting the intrinsic activity of the C–H bond in photo-assisted thermal chemical processes.
2025, 36(5): 110724
doi: 10.1016/j.cclet.2024.110724
摘要:
To get large dissymmetric factor (glum) of organic circularly polarized luminescence (CPL) materials is still a great challenge. Although helical chirality and planar chirality are usual efficient access to enhancement of CPL, they are not combined together to boost CPL. Here, a new tetraphenylethylene (TPE) tetracycle acid helicate bearing both helical chirality and planar chirality was designed and synthesized. Uniquely, synergy of the helical chirality and planar chirality was used to boost CPL signals both in solution and in helical self-assemblies. In the presence of octadecylamine, the TPE helicate could form helical nanofibers that emitted strong CPL signals with an absolute glum value up to 0.237. Exceptionally, followed by addition of para-phenylenediamine, the glum value was successively increased to 0.387 due to formation of bigger helical nanofibers. Compared with that of TPE helicate itself, the CPL signal of the self-assemblies was not only magnified by 104-fold but also inversed, which was very rare result for CPL-active materials. Surprisingly, the interaction of TPE helicate with xylylenediamine even gave a gel, which was transformed into suspension by shaking. Unexpectedly, the suspension showed 40-fold stronger CPL signals than the gel with signal direction inversion each other. Using synergy of the helical chirality and planar chirality to significantly boost CPL intensity provides a new strategy in preparation of organic CPL materials having very large glum value.
To get large dissymmetric factor (glum) of organic circularly polarized luminescence (CPL) materials is still a great challenge. Although helical chirality and planar chirality are usual efficient access to enhancement of CPL, they are not combined together to boost CPL. Here, a new tetraphenylethylene (TPE) tetracycle acid helicate bearing both helical chirality and planar chirality was designed and synthesized. Uniquely, synergy of the helical chirality and planar chirality was used to boost CPL signals both in solution and in helical self-assemblies. In the presence of octadecylamine, the TPE helicate could form helical nanofibers that emitted strong CPL signals with an absolute glum value up to 0.237. Exceptionally, followed by addition of para-phenylenediamine, the glum value was successively increased to 0.387 due to formation of bigger helical nanofibers. Compared with that of TPE helicate itself, the CPL signal of the self-assemblies was not only magnified by 104-fold but also inversed, which was very rare result for CPL-active materials. Surprisingly, the interaction of TPE helicate with xylylenediamine even gave a gel, which was transformed into suspension by shaking. Unexpectedly, the suspension showed 40-fold stronger CPL signals than the gel with signal direction inversion each other. Using synergy of the helical chirality and planar chirality to significantly boost CPL intensity provides a new strategy in preparation of organic CPL materials having very large glum value.
2025, 36(5): 110760
doi: 10.1016/j.cclet.2024.110760
摘要:
Triphenylamine (TPA) is the most promising donor fragment for the construction of long-wavelength thermally activated delayed fluorescence (TADF) emitters owing to its suitable dihedral angle that could enhance radiative decay to compete with the serious non-radiative decay. However, the moderate electron-donating capacity of TPA seriously limits the selection of acceptor for constructing long-wavelength TADF emitters with narrow bandgaps. To address this issue, in this work, the peripheral benzene of TPA was replaced with 1,4-benzodioxane and anisole to obtain two new electron-donating units N-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-N-phenyl-2,3-dihydrobenzo[b][1,4]dioxin-6-amine (TPADBO, −5.02 eV) and 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline (TPAMO, −5.00 eV), which possess much shallower highest occupied molecule orbital (HOMO) energy levels than the prototype TPA (−5.33 eV). Based on TPA and the modified TPA donor fragments, three TADF emitters were designed and synthesized, namely Py-TPA, Py-TPADBO and Py-TPAMO, with the same acceptor fragment 12-(2,6-diisopropylphenyl)pyrido[2′,3′:5,6]pyrazino[2,3-f][1,10]phenanthroline (Py). Among them, Py-TPAMO exhibits the highest photoluminescence quantum yield of 78.4% and the smallest singlet-triplet energy gap, which is because the introduction of anisole does not cause significant molecule deformation for the excited Py-TPAMO. And Py-TPAMO-based OLEDs successfully realize a maximum external quantum efficiency of 25.5% with the emission peak at 605 nm. This work provides a series of candidate of donor fragments for the development of efficient long-wavelength TADF emitters.
Triphenylamine (TPA) is the most promising donor fragment for the construction of long-wavelength thermally activated delayed fluorescence (TADF) emitters owing to its suitable dihedral angle that could enhance radiative decay to compete with the serious non-radiative decay. However, the moderate electron-donating capacity of TPA seriously limits the selection of acceptor for constructing long-wavelength TADF emitters with narrow bandgaps. To address this issue, in this work, the peripheral benzene of TPA was replaced with 1,4-benzodioxane and anisole to obtain two new electron-donating units N-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-N-phenyl-2,3-dihydrobenzo[b][1,4]dioxin-6-amine (TPADBO, −5.02 eV) and 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline (TPAMO, −5.00 eV), which possess much shallower highest occupied molecule orbital (HOMO) energy levels than the prototype TPA (−5.33 eV). Based on TPA and the modified TPA donor fragments, three TADF emitters were designed and synthesized, namely Py-TPA, Py-TPADBO and Py-TPAMO, with the same acceptor fragment 12-(2,6-diisopropylphenyl)pyrido[2′,3′:5,6]pyrazino[2,3-f][1,10]phenanthroline (Py). Among them, Py-TPAMO exhibits the highest photoluminescence quantum yield of 78.4% and the smallest singlet-triplet energy gap, which is because the introduction of anisole does not cause significant molecule deformation for the excited Py-TPAMO. And Py-TPAMO-based OLEDs successfully realize a maximum external quantum efficiency of 25.5% with the emission peak at 605 nm. This work provides a series of candidate of donor fragments for the development of efficient long-wavelength TADF emitters.
2025, 36(5): 110762
doi: 10.1016/j.cclet.2024.110762
摘要:
A series of “half-sandwich” bis(imino)pyridyl iron complexes with a substituted 8-(p-X-phenyl)naphthylamine (X = OMe, Me, CF3) was designed and synthesized by combining weak π-π interaction with steric and electronic tunings. The weak noncovalent π-π interaction as well as the steric and electronic effects of bis(imino)pyridyl iron complexes were identified by experimental analyses and calculations. The roles of weak π-π interaction, steric bulk, and electronic tuning on the ethylene polymerization performance of bis(imino)pyridyl iron catalysts were studied in detail. The combination of π-π interaction with steric and electronic tunings can access to thermally stable bis(imino)pyridyl iron at 130 ℃.
A series of “half-sandwich” bis(imino)pyridyl iron complexes with a substituted 8-(p-X-phenyl)naphthylamine (X = OMe, Me, CF3) was designed and synthesized by combining weak π-π interaction with steric and electronic tunings. The weak noncovalent π-π interaction as well as the steric and electronic effects of bis(imino)pyridyl iron complexes were identified by experimental analyses and calculations. The roles of weak π-π interaction, steric bulk, and electronic tuning on the ethylene polymerization performance of bis(imino)pyridyl iron catalysts were studied in detail. The combination of π-π interaction with steric and electronic tunings can access to thermally stable bis(imino)pyridyl iron at 130 ℃.
2025, 36(5): 110765
doi: 10.1016/j.cclet.2024.110765
摘要:
Metal ions trigger Fenton/Fenton-like reactions, generating highly toxic hydroxyl radicals (•OH) for chemodynamic therapy (CDT), which is crucial in inducing lethal oxidative DNA damage and subsequent cell apoptosis. However, tumor cells can counteract this damage through repair pathways, particularly MutT homolog 1 (MTH1) protein attenuation of oxidative DNA damage. Suppression of MTH1 can enhance CDT efficacy, therefore, orderly integrating Fenton/Fenton-like agents with an MTH1 inhibitor is expected to significantly augment CDT effectiveness. Carrier-free CuTH@CD, self-assembled through the supramolecular orchestration of γ-cyclodextrin (γ-CD) with Cu2+ and the MTH1 inhibitor TH588, effectively overcoming tumor resistance by greatly amplifying oxidative damage capability. Without additional carriers and mediated by multiple supramolecular regulatory effects, CuTH@CD enables high drug loading content, stability, and uniform size distribution. Upon internalization by tumor cells, CuTH@CD invalidates repair pathways through Cu2+-mediated glutathione (GSH) depletion and TH588-mediated MTH1 inhibition. Meanwhile, both generated Cu+ ions and existing ones within the nanoassembly initiate a Fenton-like reaction, leading to the accumulation of •OH. This strategy enhances CDT efficiency with minimal side effects, improving oxidative damage potency and advancing self-delivery nanoplatforms for developing effective chemodynamic tumor therapies.
Metal ions trigger Fenton/Fenton-like reactions, generating highly toxic hydroxyl radicals (•OH) for chemodynamic therapy (CDT), which is crucial in inducing lethal oxidative DNA damage and subsequent cell apoptosis. However, tumor cells can counteract this damage through repair pathways, particularly MutT homolog 1 (MTH1) protein attenuation of oxidative DNA damage. Suppression of MTH1 can enhance CDT efficacy, therefore, orderly integrating Fenton/Fenton-like agents with an MTH1 inhibitor is expected to significantly augment CDT effectiveness. Carrier-free CuTH@CD, self-assembled through the supramolecular orchestration of γ-cyclodextrin (γ-CD) with Cu2+ and the MTH1 inhibitor TH588, effectively overcoming tumor resistance by greatly amplifying oxidative damage capability. Without additional carriers and mediated by multiple supramolecular regulatory effects, CuTH@CD enables high drug loading content, stability, and uniform size distribution. Upon internalization by tumor cells, CuTH@CD invalidates repair pathways through Cu2+-mediated glutathione (GSH) depletion and TH588-mediated MTH1 inhibition. Meanwhile, both generated Cu+ ions and existing ones within the nanoassembly initiate a Fenton-like reaction, leading to the accumulation of •OH. This strategy enhances CDT efficiency with minimal side effects, improving oxidative damage potency and advancing self-delivery nanoplatforms for developing effective chemodynamic tumor therapies.
2025, 36(5): 109871
doi: 10.1016/j.cclet.2024.109871
摘要:
Green synthesis of drugs is of paramount importance for current public health and a prerequisite to new drugs exploiting. Nowadays, novel strategies of disease diagnosis and therapies are in blooming development as remarkable advances have been achieved which are all highly depended on drug development. Under the current requirements to high production capacity and novel synthesis methods of drugs, green synthesis based on strategies with different ways of empowering, advanced catalysts and unique reaction equipment are attracting huge attention and of great challenging. Higher quality products and environmentally friendly synthesis conditions are becoming more and more important for manufacturing process which has new requirements for catalyst materials and synthesis processes. Polyoxometalates (POMs) are class of transition metals-oxygen clusters with precise molecular structures and superior physicochemical properties which have made longstanding and important applications upon research community of functional materials, catalysis and medicine. In this review, the recent advances of polyoxometalates based strategies for green synthesis of drugs are summarized including POMs based catalysts, alternative reaction equipment based novel synthesis protocols. The significance of POMs to pharmaceutical and industrial field is highlighted and the related perspective for future development are well discussed.
Green synthesis of drugs is of paramount importance for current public health and a prerequisite to new drugs exploiting. Nowadays, novel strategies of disease diagnosis and therapies are in blooming development as remarkable advances have been achieved which are all highly depended on drug development. Under the current requirements to high production capacity and novel synthesis methods of drugs, green synthesis based on strategies with different ways of empowering, advanced catalysts and unique reaction equipment are attracting huge attention and of great challenging. Higher quality products and environmentally friendly synthesis conditions are becoming more and more important for manufacturing process which has new requirements for catalyst materials and synthesis processes. Polyoxometalates (POMs) are class of transition metals-oxygen clusters with precise molecular structures and superior physicochemical properties which have made longstanding and important applications upon research community of functional materials, catalysis and medicine. In this review, the recent advances of polyoxometalates based strategies for green synthesis of drugs are summarized including POMs based catalysts, alternative reaction equipment based novel synthesis protocols. The significance of POMs to pharmaceutical and industrial field is highlighted and the related perspective for future development are well discussed.
2025, 36(5): 109898
doi: 10.1016/j.cclet.2024.109898
摘要:
Two-dimensional (2D) transition metal sulfides (TMDs) are emerging and highly well received 2D materials, which are considered as an ideal 2D platform for studying various electronic properties and potential applications due to their chemical diversity. Converting 2D TMDs into one-dimensional (1D) TMDs nanotubes can not only retain some advantages of 2D nanosheets but also providing a unique direction to explore the novel properties of TMDs materials in the 1D limit. However, the controllable preparation of high-quality nanotubes remains a major challenge. It is very necessary to review the advanced development of one-dimensional transition metal dichalcogenide nanotubes from preparation to application. Here, we first summarize a series of bottom-up synthesis methods of 1D TMDs, such as template growth and metal catalyzed method. Then, top-down synthesis methods are summarized, which included self-curing and stacking of TMDs nanosheets. In addition, we discuss some key applications that utilize the properties of 1D-TMDs nanotubes in the areas of catalyst preparation, energy storage, and electronic devices. Last but not least, we prospect the preparation methods of high-quality 1D-TMDs nanotubes, which will lay a foundation for the synthesis of high-performance optoelectronic devices, catalysts, and energy storage components
Two-dimensional (2D) transition metal sulfides (TMDs) are emerging and highly well received 2D materials, which are considered as an ideal 2D platform for studying various electronic properties and potential applications due to their chemical diversity. Converting 2D TMDs into one-dimensional (1D) TMDs nanotubes can not only retain some advantages of 2D nanosheets but also providing a unique direction to explore the novel properties of TMDs materials in the 1D limit. However, the controllable preparation of high-quality nanotubes remains a major challenge. It is very necessary to review the advanced development of one-dimensional transition metal dichalcogenide nanotubes from preparation to application. Here, we first summarize a series of bottom-up synthesis methods of 1D TMDs, such as template growth and metal catalyzed method. Then, top-down synthesis methods are summarized, which included self-curing and stacking of TMDs nanosheets. In addition, we discuss some key applications that utilize the properties of 1D-TMDs nanotubes in the areas of catalyst preparation, energy storage, and electronic devices. Last but not least, we prospect the preparation methods of high-quality 1D-TMDs nanotubes, which will lay a foundation for the synthesis of high-performance optoelectronic devices, catalysts, and energy storage components
Iridium-based catalysts for oxygen evolution reaction in proton exchange membrane water electrolysis
2025, 36(5): 109906
doi: 10.1016/j.cclet.2024.109906
摘要:
Proton exchange membrane water electrolysis (PEMWE) is a favorable technology for producing high-purity hydrogen under high current density using intermittent renewable energy. The performance of PEMWE is largely determined by the oxygen evolution reaction (OER), a sluggish four-electron reaction with a high reaction barrier. Nowadays, iridium (Ir)-based catalysts are the catalysts of choice for OER due to their excellent activity and durability in acidic solution. However, its high price and unsatisfactory electrochemical performance severely restrict the PEMWE’s practical application. In this review, we initiate by introducing the current OER reaction mechanisms, namely adsorbate evolution mechanism and lattice oxygen mechanism, with degradation mechanisms discussed. Optimized strategies in the preparation of advanced Ir-based catalysts are further introduced, with merits and potential problems also discussed. The parameters that determine the performance of PEMWE are then introduced, with unsolved issues and related outlooks summarized in the end.
Proton exchange membrane water electrolysis (PEMWE) is a favorable technology for producing high-purity hydrogen under high current density using intermittent renewable energy. The performance of PEMWE is largely determined by the oxygen evolution reaction (OER), a sluggish four-electron reaction with a high reaction barrier. Nowadays, iridium (Ir)-based catalysts are the catalysts of choice for OER due to their excellent activity and durability in acidic solution. However, its high price and unsatisfactory electrochemical performance severely restrict the PEMWE’s practical application. In this review, we initiate by introducing the current OER reaction mechanisms, namely adsorbate evolution mechanism and lattice oxygen mechanism, with degradation mechanisms discussed. Optimized strategies in the preparation of advanced Ir-based catalysts are further introduced, with merits and potential problems also discussed. The parameters that determine the performance of PEMWE are then introduced, with unsolved issues and related outlooks summarized in the end.
2025, 36(5): 109938
doi: 10.1016/j.cclet.2024.109938
摘要:
Solid-state electrolytes (SSEs), as the core component within the next generation of key energy storage technologies - solid-state lithium batteries (SSLBs) - are significantly leading the development of future energy storage systems. Among the numerous types of SSEs, inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12 (LLZO) crystallized with the cubic Ia3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity, wide electrochemical voltage window, high shear modulus, and excellent chemical stability with electrodes. However, no SSEs possess all the properties necessary for SSLBs, thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement. Hence, this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration, Li vacancy concentration, Li carrier concentration and mobility, Li occupancy at available sites, lattice constant, triangle bottleneck size, oxygen vacancy defects, and Li-O bonding interactions. Furthermore, the general illustration of structures and fundamental features being crucial to chemical stability is examined, including Li concentration, Li-site occupation behavior, and Li-O bonding interactions. Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures, revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions. We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors, thus assisting in promoting the rapid development of alternative green and sustainable technologies.
Solid-state electrolytes (SSEs), as the core component within the next generation of key energy storage technologies - solid-state lithium batteries (SSLBs) - are significantly leading the development of future energy storage systems. Among the numerous types of SSEs, inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12 (LLZO) crystallized with the cubic Ia3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity, wide electrochemical voltage window, high shear modulus, and excellent chemical stability with electrodes. However, no SSEs possess all the properties necessary for SSLBs, thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement. Hence, this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration, Li vacancy concentration, Li carrier concentration and mobility, Li occupancy at available sites, lattice constant, triangle bottleneck size, oxygen vacancy defects, and Li-O bonding interactions. Furthermore, the general illustration of structures and fundamental features being crucial to chemical stability is examined, including Li concentration, Li-site occupation behavior, and Li-O bonding interactions. Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures, revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions. We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors, thus assisting in promoting the rapid development of alternative green and sustainable technologies.
2025, 36(5): 110059
doi: 10.1016/j.cclet.2024.110059
摘要:
Lateral flow immunoassay (LFIA), a rapid detection technique noted for simplicity and economy, has showcased indispensable applicability in diverse domains such as disease screening, food safety, and environmental monitoring. Nevertheless, challenges still exist in detecting ultra-low concentration analytes due to the inherent sensitivity limitations of LFIA. Recently, significant advances have been achieved by integrating enzyme activity probes and transforming LFIA into a highly sensitive tool for rapidly detecting trace analyte concentrations. Specifically, modifying natural enzymes or engineered nanozymes allows them to function as immune probes, directly catalyzing the production of signal molecules or indirectly initiating enzyme activity. Therefore, the signal intensity and detection sensitivity of LFIA are markedly elevated. The present review undertakes a comprehensive examination of pertinent research literature, offering a systematic analysis of recently proposed enzyme-based signal amplification strategies. By way of comparative assessment, the merits and demerits of current approaches are delineated, along with the identification of research avenues that still need to be explored. It is anticipated that this critical overview will garner considerable attention within the biomedical and materials science communities, providing valuable direction and insight toward the advancement of high-performance LFIA technologies.
Lateral flow immunoassay (LFIA), a rapid detection technique noted for simplicity and economy, has showcased indispensable applicability in diverse domains such as disease screening, food safety, and environmental monitoring. Nevertheless, challenges still exist in detecting ultra-low concentration analytes due to the inherent sensitivity limitations of LFIA. Recently, significant advances have been achieved by integrating enzyme activity probes and transforming LFIA into a highly sensitive tool for rapidly detecting trace analyte concentrations. Specifically, modifying natural enzymes or engineered nanozymes allows them to function as immune probes, directly catalyzing the production of signal molecules or indirectly initiating enzyme activity. Therefore, the signal intensity and detection sensitivity of LFIA are markedly elevated. The present review undertakes a comprehensive examination of pertinent research literature, offering a systematic analysis of recently proposed enzyme-based signal amplification strategies. By way of comparative assessment, the merits and demerits of current approaches are delineated, along with the identification of research avenues that still need to be explored. It is anticipated that this critical overview will garner considerable attention within the biomedical and materials science communities, providing valuable direction and insight toward the advancement of high-performance LFIA technologies.
2025, 36(5): 110072
doi: 10.1016/j.cclet.2024.110072
摘要:
Designing advanced hydrogels with controlled mechanical properties, drug delivery manner and multifunctional properties will be beneficial for biomedical applications. However, the further development of hydrogel is limited due to its poor mechanical property and structural diversity. Hydrogels combined with polymeric micelles to obtain micelle-hydrogel composites have been designed for synergistic enhancement of each original properties. Incorporation polymeric micelles into hydrogel networks can not only enhance the mechanical property of hydrogel, but also expand the functionality of hydrogel. Recent advances in polymeric micelle-hydrogel composites are herein reviewed with a focus on three typical micelle incorporation methods. In this review, we will also highlight some emerging biomedical applications in developing micelle-hydrogel composite with multiple functionalities. In addition, further development and application prospects of the micelle-hydrogels composites have also been addressed.
Designing advanced hydrogels with controlled mechanical properties, drug delivery manner and multifunctional properties will be beneficial for biomedical applications. However, the further development of hydrogel is limited due to its poor mechanical property and structural diversity. Hydrogels combined with polymeric micelles to obtain micelle-hydrogel composites have been designed for synergistic enhancement of each original properties. Incorporation polymeric micelles into hydrogel networks can not only enhance the mechanical property of hydrogel, but also expand the functionality of hydrogel. Recent advances in polymeric micelle-hydrogel composites are herein reviewed with a focus on three typical micelle incorporation methods. In this review, we will also highlight some emerging biomedical applications in developing micelle-hydrogel composite with multiple functionalities. In addition, further development and application prospects of the micelle-hydrogels composites have also been addressed.
2025, 36(5): 110126
doi: 10.1016/j.cclet.2024.110126
摘要:
Chemical modification of native peptides and proteins is a versatile strategy to facilitate late-stage diversification for functional studies. Among the proteogenic amino acids, lysine is extensively involved in post-translational modifications and the binding of ligands to target proteins, making its selective modification attractive. However, lysine’s high natural abundance and solvent accessibility, as well as its relatively low reactivity to cysteine, necessitate addressing chemoselectivity and regioselectivity for the Lys modification of native proteins. Although Lys chemoselective modification methods have been well developed, achieving site-selective modification of a specific Lys residue remains a great challenge. In this review, we discussed the challenges of Lys selective modification, presented recent examples of Lys chemoselective modification, and summarized the currently known methods and strategies for Lys site-selective modification. We also included an outlook on potential solutions for Lys site-selective labeling and its potential applications in chemical biology and drug development.
Chemical modification of native peptides and proteins is a versatile strategy to facilitate late-stage diversification for functional studies. Among the proteogenic amino acids, lysine is extensively involved in post-translational modifications and the binding of ligands to target proteins, making its selective modification attractive. However, lysine’s high natural abundance and solvent accessibility, as well as its relatively low reactivity to cysteine, necessitate addressing chemoselectivity and regioselectivity for the Lys modification of native proteins. Although Lys chemoselective modification methods have been well developed, achieving site-selective modification of a specific Lys residue remains a great challenge. In this review, we discussed the challenges of Lys selective modification, presented recent examples of Lys chemoselective modification, and summarized the currently known methods and strategies for Lys site-selective modification. We also included an outlook on potential solutions for Lys site-selective labeling and its potential applications in chemical biology and drug development.
2025, 36(5): 110226
doi: 10.1016/j.cclet.2024.110226
摘要:
The heritage preservation is of great intractability to the conservators as each kind of heritage material has unique and diverse requirements on temperature, humidity and air cleanliness. It is promising for metal-organic frameworks (MOFs), the multifunctional environment remediation materials, to be applied in heritage environmental protection. The advantages of MOFs lie in their multifunction like adsorption, photocatalysis, sterilization, as well as the controllable structure and properties that could be flexibly adjusted as demands, helping the heritage against various environmental threats. Thereby, the applications and the corresponding mechanisms of MOFs in cultural heritage preservation were reviewed in this work, including harmful gas adsorption, surface waterproofing, particulate matters (PM) removal, anti-bacterial and humidity control of environment. Finally, the selection principles and precautions of MOFs in heritage preservation were discussed, aiming to provide a forward-looking direction for the selection and application of MOFs.
The heritage preservation is of great intractability to the conservators as each kind of heritage material has unique and diverse requirements on temperature, humidity and air cleanliness. It is promising for metal-organic frameworks (MOFs), the multifunctional environment remediation materials, to be applied in heritage environmental protection. The advantages of MOFs lie in their multifunction like adsorption, photocatalysis, sterilization, as well as the controllable structure and properties that could be flexibly adjusted as demands, helping the heritage against various environmental threats. Thereby, the applications and the corresponding mechanisms of MOFs in cultural heritage preservation were reviewed in this work, including harmful gas adsorption, surface waterproofing, particulate matters (PM) removal, anti-bacterial and humidity control of environment. Finally, the selection principles and precautions of MOFs in heritage preservation were discussed, aiming to provide a forward-looking direction for the selection and application of MOFs.
2025, 36(5): 110277
doi: 10.1016/j.cclet.2024.110277
摘要:
As a versatile and environmentally benign oxidant, hydrogen peroxide (H2O2) is highly desired in sanitation, disinfection, environmental remediation, and the chemical industry. Compared with the conventional anthraquinone process, the electrosynthesis of H2O2 through the two-electron oxygen reduction reaction (2e− ORR) is an efficient, competitive, and promising avenue. Electrocatalysts and devices are two core factors in 2e− ORR, but the design principles of catalysts for different pH conditions and the development trends of relevant synthesis devices remain unclear. To this end, this review adopts a multiscale perspective to summarize recent advancements in the design principles, catalytic mechanisms, and application prospects of 2e− ORR catalysts, with a particular focus on the influence of pH conditions, aiming at providing guidance for the selective design of advanced 2e− ORR catalysts for highly-efficient H2O2 production. Moreover, in response to diverse on-site application demands, we elaborate on the evolution of H2O2 electrosynthesis devices, from rotating ring-disk electrodes and H-type cells to diverse flow-type cells. We elaborate on their characteristics and shortcomings, which can be beneficial for their further upgrades and customized applications. These insights may inspire the rational design of innovative catalysts and devices with high performance and wide serviceability for large-scale implementations.
As a versatile and environmentally benign oxidant, hydrogen peroxide (H2O2) is highly desired in sanitation, disinfection, environmental remediation, and the chemical industry. Compared with the conventional anthraquinone process, the electrosynthesis of H2O2 through the two-electron oxygen reduction reaction (2e− ORR) is an efficient, competitive, and promising avenue. Electrocatalysts and devices are two core factors in 2e− ORR, but the design principles of catalysts for different pH conditions and the development trends of relevant synthesis devices remain unclear. To this end, this review adopts a multiscale perspective to summarize recent advancements in the design principles, catalytic mechanisms, and application prospects of 2e− ORR catalysts, with a particular focus on the influence of pH conditions, aiming at providing guidance for the selective design of advanced 2e− ORR catalysts for highly-efficient H2O2 production. Moreover, in response to diverse on-site application demands, we elaborate on the evolution of H2O2 electrosynthesis devices, from rotating ring-disk electrodes and H-type cells to diverse flow-type cells. We elaborate on their characteristics and shortcomings, which can be beneficial for their further upgrades and customized applications. These insights may inspire the rational design of innovative catalysts and devices with high performance and wide serviceability for large-scale implementations.
2025, 36(5): 110284
doi: 10.1016/j.cclet.2024.110284
摘要:
Developing efficient, non-toxic, and low-cost emitters is a key issue in promoting the applications of electrochemiluminescence (ECL). Among varied ECL emitters, polymeric emitters are attracting dramatically increasing interest due to tunable structure, large surface area, brilliant transfer capability, and sustainable raw materials. In this review, we present a general overview of recent advances in developing polymeric luminophores, including their structural and synthetic methodologies. Methods rooted in straightforward unique structural modulation have been comprehensively summarized, aiming at enhancing the efficiency of ECL along with the underlying kinetic mechanisms. Moreover, as several conjugated polymers were just discovered in recent years, promising prospects and perspectives have also been deliberated. The insight of this review may provide a new avenue for helping develop advanced conjugated polymer ECL emitters and decode ECL applications.
Developing efficient, non-toxic, and low-cost emitters is a key issue in promoting the applications of electrochemiluminescence (ECL). Among varied ECL emitters, polymeric emitters are attracting dramatically increasing interest due to tunable structure, large surface area, brilliant transfer capability, and sustainable raw materials. In this review, we present a general overview of recent advances in developing polymeric luminophores, including their structural and synthetic methodologies. Methods rooted in straightforward unique structural modulation have been comprehensively summarized, aiming at enhancing the efficiency of ECL along with the underlying kinetic mechanisms. Moreover, as several conjugated polymers were just discovered in recent years, promising prospects and perspectives have also been deliberated. The insight of this review may provide a new avenue for helping develop advanced conjugated polymer ECL emitters and decode ECL applications.
2025, 36(5): 110423
doi: 10.1016/j.cclet.2024.110423
摘要:
As a novel two-dimensional (2D) material, MXenes are anticipated to have a significant impact on future aqueous energy storage and conversion technologies owing to their unique intrinsic laminar structure and exceptional physicochemical properties. Nevertheless, the fabrication and utilization of functional MXene-based devices face formidable challenges due to their susceptibility to oxidative degradation in aqueous solutions. This review begins with an outline of various preparation techniques for MXenes and their implications for structure and surface chemistry. Subsequently, the controversial oxidation mechanisms are discussed, followed by a summary of currently employed oxidation characterization techniques. Additionally, the factors influencing MXene oxidation are then introduced, encompassing chemical composition (types of M, X elements, layer numbers, terminations, and defects) as well as environment (atmosphere, temperature, light, potential, solution pH, free water and O2 content). The review then shifts its focus to strategies aiming to prevent or delay MXene oxidation, thereby expanding the applicability of MXenes in complex environments. Finally, the challenges and prospects within this rapidly-growing research field are presented to promote further advancements of MXenes in aqueous storage systems.
As a novel two-dimensional (2D) material, MXenes are anticipated to have a significant impact on future aqueous energy storage and conversion technologies owing to their unique intrinsic laminar structure and exceptional physicochemical properties. Nevertheless, the fabrication and utilization of functional MXene-based devices face formidable challenges due to their susceptibility to oxidative degradation in aqueous solutions. This review begins with an outline of various preparation techniques for MXenes and their implications for structure and surface chemistry. Subsequently, the controversial oxidation mechanisms are discussed, followed by a summary of currently employed oxidation characterization techniques. Additionally, the factors influencing MXene oxidation are then introduced, encompassing chemical composition (types of M, X elements, layer numbers, terminations, and defects) as well as environment (atmosphere, temperature, light, potential, solution pH, free water and O2 content). The review then shifts its focus to strategies aiming to prevent or delay MXene oxidation, thereby expanding the applicability of MXenes in complex environments. Finally, the challenges and prospects within this rapidly-growing research field are presented to promote further advancements of MXenes in aqueous storage systems.
2025, 36(5): 110503
doi: 10.1016/j.cclet.2024.110503
摘要:
Homogeneous C–H and C–X borylation via transition-metal-catalysis have undergone rapid development in the past decades and become one of the most practical methods for the synthesis of organoboron compounds. However, the catalysts employed in homogeneous catalysis are generally expensive, sensitive, and difficult to separate from the reaction mixture and reuse. With the rapid development of heterogeneous catalysis, heterogeneous C–H and C–X borylation have emerged as highly efficient and sustainable approaches towards the synthesis of organoboron compounds. This review aims to highlight the recent advances in the synthesis of organoboron compounds employing heterogeneous C–H and C–X borylation strategies. We endeavor to shed light on new perspectives and inspire further research and applications in this emerging area.
Homogeneous C–H and C–X borylation via transition-metal-catalysis have undergone rapid development in the past decades and become one of the most practical methods for the synthesis of organoboron compounds. However, the catalysts employed in homogeneous catalysis are generally expensive, sensitive, and difficult to separate from the reaction mixture and reuse. With the rapid development of heterogeneous catalysis, heterogeneous C–H and C–X borylation have emerged as highly efficient and sustainable approaches towards the synthesis of organoboron compounds. This review aims to highlight the recent advances in the synthesis of organoboron compounds employing heterogeneous C–H and C–X borylation strategies. We endeavor to shed light on new perspectives and inspire further research and applications in this emerging area.
2025, 36(5): 110521
doi: 10.1016/j.cclet.2024.110521
摘要:
The enantioselective separation of racemate, particularly those containing C(sp3)-H bonds knowns for their high bond dissociation energies and significant polarity, presents a significant challenge in pharmaceutical synthesis. Recent advances have witnessed the fusion of photocatalysis with hydrogen atom transfer (HAT) methodologies, marking a notable trend in synthesis of chiral molecules. This technique uses the excitation of a catalyst to activate substrates, enabling the selective isomerization of chiral centers containing C(sp3) configurations. This process distinctively facilitates the direct activation of the C(sp3)-H bond in targeted reagents. This review systematically discusses the photocatalytic isomerization of various chiral molecule featuring C(sp3)-H centers, capable of undergoing deracemization through two primary HAT mechanisms: direct and indirect pathways. From the perspective of synthetic organic chemistry, this field has progressed towards the development of isomerization strategies for molecules that incorporate an activating group at the α-position adjacent to the C(sp3) chiral center. Moreover, it covers methodologies applicable to molecules characterized by specific C-C and C-S bond configurations. The integration of photocatalysis with HAT technology thus provides valuable strategies for the synthesis of enantiopure compounds with enhanced selectivity and efficiency.
The enantioselective separation of racemate, particularly those containing C(sp3)-H bonds knowns for their high bond dissociation energies and significant polarity, presents a significant challenge in pharmaceutical synthesis. Recent advances have witnessed the fusion of photocatalysis with hydrogen atom transfer (HAT) methodologies, marking a notable trend in synthesis of chiral molecules. This technique uses the excitation of a catalyst to activate substrates, enabling the selective isomerization of chiral centers containing C(sp3) configurations. This process distinctively facilitates the direct activation of the C(sp3)-H bond in targeted reagents. This review systematically discusses the photocatalytic isomerization of various chiral molecule featuring C(sp3)-H centers, capable of undergoing deracemization through two primary HAT mechanisms: direct and indirect pathways. From the perspective of synthetic organic chemistry, this field has progressed towards the development of isomerization strategies for molecules that incorporate an activating group at the α-position adjacent to the C(sp3) chiral center. Moreover, it covers methodologies applicable to molecules characterized by specific C-C and C-S bond configurations. The integration of photocatalysis with HAT technology thus provides valuable strategies for the synthesis of enantiopure compounds with enhanced selectivity and efficiency.
2025, 36(5): 110529
doi: 10.1016/j.cclet.2024.110529
摘要:
Utilizing transporter-mediated drug delivery to achieve effective oral absorption emerges as a promising strategy. Researchers have been concentrated on discovering solutions to the issues of low solubility and poor permeability of insoluble drugs, whereas, current reports have revealed that drug transporter proteins are abundantly expressed in the mucosa of intestinal epithelial cells, and that their mediated drug absorption effectively improved the bioavailability of orally administered drugs. There are two main categories based on the transporter mechanism, which include the family of ATP-binding cassette (ABC) transporters with efflux effects that reduce drug bioavailability and the family of solute carriers (SLC) transporters with uptake effects that promote drug absorption, respectively. Thus, we review studies of intestinal transporter-mediated delivery of drugs to enhance oral absorption, including the types of intestinal transporters, distribution characteristics, and strategies for enhancing oral absorption using transporter-mediated drug delivery systems are summarized, with the aim of providing important theoretical references for the development of intestinal-targeted delivery system.
Utilizing transporter-mediated drug delivery to achieve effective oral absorption emerges as a promising strategy. Researchers have been concentrated on discovering solutions to the issues of low solubility and poor permeability of insoluble drugs, whereas, current reports have revealed that drug transporter proteins are abundantly expressed in the mucosa of intestinal epithelial cells, and that their mediated drug absorption effectively improved the bioavailability of orally administered drugs. There are two main categories based on the transporter mechanism, which include the family of ATP-binding cassette (ABC) transporters with efflux effects that reduce drug bioavailability and the family of solute carriers (SLC) transporters with uptake effects that promote drug absorption, respectively. Thus, we review studies of intestinal transporter-mediated delivery of drugs to enhance oral absorption, including the types of intestinal transporters, distribution characteristics, and strategies for enhancing oral absorption using transporter-mediated drug delivery systems are summarized, with the aim of providing important theoretical references for the development of intestinal-targeted delivery system.
2025, 36(5): 110618
doi: 10.1016/j.cclet.2024.110618
摘要:
Carbon dots (CDs) are an emerging class of zero-dimensional carbon nano optical materials that are as promising candidates for various applications. Through the exploration of scientific researchers, the optical band gap of CDs has been continuously regulated and red-shifted from the initial blue-violet light to longer wavelengths. In recent years, CDs with near-infrared (NIR) absorption/emission have been gradually reported. Because NIR light has deeper penetration and lower scattering and is invisible to the human eye, it has great application prospects in the fields of biological imaging and treatment, information encryption, optical communications, etc. Although there are a few reviews on deep red to NIR CDs, they only focus on the single biomedical direction. There is still a lack of comprehensive reviews focusing on NIR (≥700 nm) absorption and luminescent CDs and their multifunctional applications. Based on our research group’s findings on NIR CDs, this review summarizes recent advancements in their preparation strategies and applications, points out the current shortcomings and challenges, and anticipates future development trajectories.
Carbon dots (CDs) are an emerging class of zero-dimensional carbon nano optical materials that are as promising candidates for various applications. Through the exploration of scientific researchers, the optical band gap of CDs has been continuously regulated and red-shifted from the initial blue-violet light to longer wavelengths. In recent years, CDs with near-infrared (NIR) absorption/emission have been gradually reported. Because NIR light has deeper penetration and lower scattering and is invisible to the human eye, it has great application prospects in the fields of biological imaging and treatment, information encryption, optical communications, etc. Although there are a few reviews on deep red to NIR CDs, they only focus on the single biomedical direction. There is still a lack of comprehensive reviews focusing on NIR (≥700 nm) absorption and luminescent CDs and their multifunctional applications. Based on our research group’s findings on NIR CDs, this review summarizes recent advancements in their preparation strategies and applications, points out the current shortcomings and challenges, and anticipates future development trajectories.
2025, 36(5): 110628
doi: 10.1016/j.cclet.2024.110628
摘要:
Polycyclic compounds are widely found in natural products and drug molecules with important biological activities, which attracted the attention of many chemists. Phosphine-catalyzed nucleophilic addition is one of the most powerful tools for the construction of various cyclic compounds with the advantages of atom economy, mild reaction conditions and simplicity of operation. Allenolates, Morita−Baylis−Hillman (MBH) alcohols and their derivatives (MBHADs), electron-deficient olefins and alkynes are very efficient substrates in phosphine mediated annulations, which formed many phosphonium species such as β-phosphonium enolates, β-phosphonium dienolates and vinyl phosphonium ylides as intermediates. This review describes the reactivities of these phosphonium zwitterions and summarizes the synthesis of polycycle compounds through phosphine-mediated intramolecular and intermolecular sequential annulations. Thus, a systematic summary of the research process based on the phosphine-mediated sequential annulations of allenolates, MBH alcohols and MBHADs, electron-deficient olefins and alkynes are presented in Chapters 2–6, respectively.
Polycyclic compounds are widely found in natural products and drug molecules with important biological activities, which attracted the attention of many chemists. Phosphine-catalyzed nucleophilic addition is one of the most powerful tools for the construction of various cyclic compounds with the advantages of atom economy, mild reaction conditions and simplicity of operation. Allenolates, Morita−Baylis−Hillman (MBH) alcohols and their derivatives (MBHADs), electron-deficient olefins and alkynes are very efficient substrates in phosphine mediated annulations, which formed many phosphonium species such as β-phosphonium enolates, β-phosphonium dienolates and vinyl phosphonium ylides as intermediates. This review describes the reactivities of these phosphonium zwitterions and summarizes the synthesis of polycycle compounds through phosphine-mediated intramolecular and intermolecular sequential annulations. Thus, a systematic summary of the research process based on the phosphine-mediated sequential annulations of allenolates, MBH alcohols and MBHADs, electron-deficient olefins and alkynes are presented in Chapters 2–6, respectively.
2025, 36(5): 110764
doi: 10.1016/j.cclet.2024.110764
摘要:
2025, 36(5): 110869
doi: 10.1016/j.cclet.2025.110869
摘要:
2025, 36(5): 110936
doi: 10.1016/j.cclet.2025.110936
摘要:
