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2024 Volume 35 Issue 7
2024, 35(7): 108845
doi: 10.1016/j.cclet.2023.108845
Abstract:
Two-dimensional (2D) mesoporous pseudocapacitive polymer/graphene heterostructures combine the advanced merits of 2D materials and mesoporous materials, possessing unique nanosheet structure, large specific surface area (SSA), abundant oxygen/nitrogen-containing groups, desirable electrical conductivity and admirable electrochemical redox activity, and hold great potential for constructing high-performance planar micro-supercapacitors (MSCs). Herein, we demonstrate the interfacial assembly of 2D mesoporous polydopamine/graphene (mPDG) heterostructures with well-defined mesopore structure (12 nm) and adjustable thickness (7.5–14.1 nm) for planar high-energy pseudocapacitive MSCs. Attributed to medium thickness, exposed mesopore of 12 nm and large SSA of 108 m2/g, the mPDG with 10.8 nm thickness reveals prominent mass capacitance of 419 F/g and impressive cycling stability with ~96% capacitance retention after 5000 cycles. Furthermore, the symmetric mPDG-based MSCs with "water-in-salt" gel electrolyte present wide voltage window of 1.6 V, superior volumetric energy density of 11.5 mWh/cm3, outstanding flexibility and self-integration ability. Therefore, this work offers a new platform of controllably synthesizing 2D mesoporous heterostructures for high-performance MSCs.
Two-dimensional (2D) mesoporous pseudocapacitive polymer/graphene heterostructures combine the advanced merits of 2D materials and mesoporous materials, possessing unique nanosheet structure, large specific surface area (SSA), abundant oxygen/nitrogen-containing groups, desirable electrical conductivity and admirable electrochemical redox activity, and hold great potential for constructing high-performance planar micro-supercapacitors (MSCs). Herein, we demonstrate the interfacial assembly of 2D mesoporous polydopamine/graphene (mPDG) heterostructures with well-defined mesopore structure (12 nm) and adjustable thickness (7.5–14.1 nm) for planar high-energy pseudocapacitive MSCs. Attributed to medium thickness, exposed mesopore of 12 nm and large SSA of 108 m2/g, the mPDG with 10.8 nm thickness reveals prominent mass capacitance of 419 F/g and impressive cycling stability with ~96% capacitance retention after 5000 cycles. Furthermore, the symmetric mPDG-based MSCs with "water-in-salt" gel electrolyte present wide voltage window of 1.6 V, superior volumetric energy density of 11.5 mWh/cm3, outstanding flexibility and self-integration ability. Therefore, this work offers a new platform of controllably synthesizing 2D mesoporous heterostructures for high-performance MSCs.
2024, 35(7): 108865
doi: 10.1016/j.cclet.2023.108865
Abstract:
In recent years, rechargeable zinc-ion batteries (ZIBs) are considered to be a promising alternative to lithium-ion batteries owing to their high safety and theoretical capacity with low cost. Nevertheless, the in-depth development of rechargeable zinc-ion batteries is restricted by a sequence of issues, such as the dissolution and structure collapse of cathode materials, the formation of by-products, severe anode corrosion, passivation, and the growth of zinc dendrites. The covalent organic frameworks (COFs) can solve the above problems to a certain extent owing to their ideal characteristics, such as rigid structure, insolubility, high porosity, and abundant active sites. COFs, as advanced materials for ZIBs, have attracted researchers' attention. In this review, we systematically summarized the synthesis methods of COFs and discussed the application of several advanced characterization technologies in COFs, which would provide a reference for the in-depth research of COFs. In addition, we elucidated the use of COFs as cathode materials and anode protective layers in rechargeable ZIBs. Finally, we discussed the challenges and solutions in the development of COF materials, which would provide constructive insights into the future direction of COFs.
In recent years, rechargeable zinc-ion batteries (ZIBs) are considered to be a promising alternative to lithium-ion batteries owing to their high safety and theoretical capacity with low cost. Nevertheless, the in-depth development of rechargeable zinc-ion batteries is restricted by a sequence of issues, such as the dissolution and structure collapse of cathode materials, the formation of by-products, severe anode corrosion, passivation, and the growth of zinc dendrites. The covalent organic frameworks (COFs) can solve the above problems to a certain extent owing to their ideal characteristics, such as rigid structure, insolubility, high porosity, and abundant active sites. COFs, as advanced materials for ZIBs, have attracted researchers' attention. In this review, we systematically summarized the synthesis methods of COFs and discussed the application of several advanced characterization technologies in COFs, which would provide a reference for the in-depth research of COFs. In addition, we elucidated the use of COFs as cathode materials and anode protective layers in rechargeable ZIBs. Finally, we discussed the challenges and solutions in the development of COF materials, which would provide constructive insights into the future direction of COFs.
2024, 35(7): 108871
doi: 10.1016/j.cclet.2023.108871
Abstract:
Relaxor ferroic dielectrics have garnered increasing attention in the past decade as promising materials for energy storage. Among them, relaxor antiferroelectrics (AFEs) and relaxor ferroelectrics (FEs) have shown great promise in term of high energy storage density and efficiency, respectively. In this study, a unique phase transition from relaxor AFE to relaxor FE was achieved for the first time by introducing strong-ferroelectricity BaTiO3 into NaNbO3-BiFeO3 system, leading to an evolution from AFE R hierarchical nanodomains to FE polar nanoregions. A novel medium state, consisting of relaxor AFE and relaxor FE, was identified in the crossover of 0.88NaNbO3–0.07BiFeO3–0.05BaTiO3 ceramic, exhibiting a distinctive core-shell grain structure due to the composition segregation. By harnessing the advantages of high energy storage density from relaxor AFE and large efficiency from relaxor FE, the ceramic showcased excellent overall energy storage properties. It achieved a substantial recoverable energy storage density Wrec ~ 13.1 J/cm3 and an ultrahigh efficiency η ~ 88.9%. These remarkable values shattered the trade-off relationship typically observed in most dielectric capacitors between Wrec and η. The findings of this study provide valuable insights for the design of ceramic capacitors with enhanced performance, specifically targeting the development of next generation pulse power devices.
Relaxor ferroic dielectrics have garnered increasing attention in the past decade as promising materials for energy storage. Among them, relaxor antiferroelectrics (AFEs) and relaxor ferroelectrics (FEs) have shown great promise in term of high energy storage density and efficiency, respectively. In this study, a unique phase transition from relaxor AFE to relaxor FE was achieved for the first time by introducing strong-ferroelectricity BaTiO3 into NaNbO3-BiFeO3 system, leading to an evolution from AFE R hierarchical nanodomains to FE polar nanoregions. A novel medium state, consisting of relaxor AFE and relaxor FE, was identified in the crossover of 0.88NaNbO3–0.07BiFeO3–0.05BaTiO3 ceramic, exhibiting a distinctive core-shell grain structure due to the composition segregation. By harnessing the advantages of high energy storage density from relaxor AFE and large efficiency from relaxor FE, the ceramic showcased excellent overall energy storage properties. It achieved a substantial recoverable energy storage density Wrec ~ 13.1 J/cm3 and an ultrahigh efficiency η ~ 88.9%. These remarkable values shattered the trade-off relationship typically observed in most dielectric capacitors between Wrec and η. The findings of this study provide valuable insights for the design of ceramic capacitors with enhanced performance, specifically targeting the development of next generation pulse power devices.
2024, 35(7): 108887
doi: 10.1016/j.cclet.2023.108887
Abstract:
All solid-state lithium metal batteries (ASSLMBs) based on polymer solid electrolyte and lithium metal anode have attracted much attention due to their high energy density and intrinsic safety. However, the low ionic conductivity at room temperature and poor mechanical properties of the solid polymer electrolyte result in increased polarization and poor cycling stability of the Li metal batteries. In order to improve the ionic conductivity at room temperature while maintaining mechanical strength, we combine the conductivity of short chain polyethylene oxide (PEO) and strength of styrene-maleic anhydride copolymer (SMA) to obtain a grafted block copolymer with nanophase separation structure, which has room temperature ionic conductivity up to 1.14 × 10−4 S/cm and tensile strength up to 1.4 MPa. Li||Li symmetric cell can work stably for more than 1500 h under the condition of 0.1 mA/cm2. Li||LiFePO4 full cells can deliver a high capacity of 151.4 mAh/g at 25 ℃ and 0.2 C/0.2 C charge/discharge conditions, showing 85.6% capacity retention after 400 cycles. Importantly, the all solid state Li||LiFePO4 pouch cell shows excellent safety performance under different abuse conditions. These results demonstrate that the nanophase separated, grafted alternate copolymer electrolyte has huge potential for application in Li metal batteries.
All solid-state lithium metal batteries (ASSLMBs) based on polymer solid electrolyte and lithium metal anode have attracted much attention due to their high energy density and intrinsic safety. However, the low ionic conductivity at room temperature and poor mechanical properties of the solid polymer electrolyte result in increased polarization and poor cycling stability of the Li metal batteries. In order to improve the ionic conductivity at room temperature while maintaining mechanical strength, we combine the conductivity of short chain polyethylene oxide (PEO) and strength of styrene-maleic anhydride copolymer (SMA) to obtain a grafted block copolymer with nanophase separation structure, which has room temperature ionic conductivity up to 1.14 × 10−4 S/cm and tensile strength up to 1.4 MPa. Li||Li symmetric cell can work stably for more than 1500 h under the condition of 0.1 mA/cm2. Li||LiFePO4 full cells can deliver a high capacity of 151.4 mAh/g at 25 ℃ and 0.2 C/0.2 C charge/discharge conditions, showing 85.6% capacity retention after 400 cycles. Importantly, the all solid state Li||LiFePO4 pouch cell shows excellent safety performance under different abuse conditions. These results demonstrate that the nanophase separated, grafted alternate copolymer electrolyte has huge potential for application in Li metal batteries.
2024, 35(7): 108898
doi: 10.1016/j.cclet.2023.108898
Abstract:
Benzene series as highly toxic gases have inevitably entered human life and produce great threat to human health and ecological environment, and thus it is distinctly meaningful to monitor benzene series with quickly, real-time and efficient technique. Herein, novel sulfur-doped mesoporous WO3 materials were synthesized via classical in-situ solvent evaporation induced co-assembly strategy combined with doping engineering, which possessed highly crystallized frameworks, high specific surface area (40.9–63.8 m2/g) and uniform pore size (~18 nm). Benefitting from abundant oxygen vacancy and defects via S-doping, the tailored mesoporous S/mWO3 exhibited excellent benzene sensing performance, including high sensitivity (50 ppm vs. 48), low detection limit (ca. 500 ppb), outstanding selectivity and favorable stability. In addition, the reduction of band gap resulted from S-doping promotes the carrier migration in the sensing materials and the reaction at the gas–solid sensing interfaces. It provides brand-new approach to design sensitive materials with multiple reaction sites.
Benzene series as highly toxic gases have inevitably entered human life and produce great threat to human health and ecological environment, and thus it is distinctly meaningful to monitor benzene series with quickly, real-time and efficient technique. Herein, novel sulfur-doped mesoporous WO3 materials were synthesized via classical in-situ solvent evaporation induced co-assembly strategy combined with doping engineering, which possessed highly crystallized frameworks, high specific surface area (40.9–63.8 m2/g) and uniform pore size (~18 nm). Benefitting from abundant oxygen vacancy and defects via S-doping, the tailored mesoporous S/mWO3 exhibited excellent benzene sensing performance, including high sensitivity (50 ppm vs. 48), low detection limit (ca. 500 ppb), outstanding selectivity and favorable stability. In addition, the reduction of band gap resulted from S-doping promotes the carrier migration in the sensing materials and the reaction at the gas–solid sensing interfaces. It provides brand-new approach to design sensitive materials with multiple reaction sites.
2024, 35(7): 108907
doi: 10.1016/j.cclet.2023.108907
Abstract:
Gaining an understanding of the growth mechanism from single atoms to clusters and bulk materials continues to present a challenge. Thus, it is important to explore the evolving trends of clusters in the structure and properties during the size evolution. In this work, we report the synthesis and characterization of two medium-sized chain-like polyarsenic anions. [As21]3– represents a trimeric example of polyarsenic anion assembled through oxidative coupling of As73– anions. The anion As184– included in [As18Mo2(CO)8]4– is regarded as formed by two realgar-type As8 subunits connected by a dinuclear As-As dumbbell. The As18 cluster was previously predicted by theory, and this is the first time successfully synthesized using wet chemistry method. Besides, small-sized polyarsenides As22– and As102– were found in compound [K(18-crown-6)]3[As10]0.5[As4{Mo(CO)3}2]0.5·2en. Among these, the former exhibits coordination with metal atoms. Single-crystal X-ray diffraction combined with quantum chemical calculations revealed the formation of double bonded As22– stabilized by metal carbonyl groups. This work demonstrates a novel synthetic approach for the preparation of new polyarsenides and highlights their intriguing bonding characteristics, laying the foundation for the synthesis of such compounds and paving the way for their potential applications.
Gaining an understanding of the growth mechanism from single atoms to clusters and bulk materials continues to present a challenge. Thus, it is important to explore the evolving trends of clusters in the structure and properties during the size evolution. In this work, we report the synthesis and characterization of two medium-sized chain-like polyarsenic anions. [As21]3– represents a trimeric example of polyarsenic anion assembled through oxidative coupling of As73– anions. The anion As184– included in [As18Mo2(CO)8]4– is regarded as formed by two realgar-type As8 subunits connected by a dinuclear As-As dumbbell. The As18 cluster was previously predicted by theory, and this is the first time successfully synthesized using wet chemistry method. Besides, small-sized polyarsenides As22– and As102– were found in compound [K(18-crown-6)]3[As10]0.5[As4{Mo(CO)3}2]0.5·2en. Among these, the former exhibits coordination with metal atoms. Single-crystal X-ray diffraction combined with quantum chemical calculations revealed the formation of double bonded As22– stabilized by metal carbonyl groups. This work demonstrates a novel synthetic approach for the preparation of new polyarsenides and highlights their intriguing bonding characteristics, laying the foundation for the synthesis of such compounds and paving the way for their potential applications.
2024, 35(7): 108921
doi: 10.1016/j.cclet.2023.108921
Abstract:
Na+ batteries (SIBs) have been emerging as the most promising candidate for the next generation of secondary batteries. However, the development of high-performance and cost-effective anode materials is urgently needed for the large-scale applications of SIBs. In this study, carbon dots confined bimetallic sulfide (NiCo2S4) architecture (NiCo2S4@CDs) was proposed and synthesized from assembling nanosheets into cross-stacked superstructure and the subsequent confinement of carbon dots. This novel decussated structure assembly from nanosheets is greatly beneficial to the structure stability of electrode material during the successive charge/discharge processes. Besides, the CDs based carbon conductive network can enhance the electrical conductivity for facilitating the easy transport of electron/Na+. Benefitting from these advantages, NiCo2S4@CDs exhibits high-rate performance and an ultralong cycling life in SIBs. Specifically, the specific capacity of NiCo2S4@CDs can reach the discharge specific capacity as high as 568.9 mAh/g at 0.5 A/g, which can also maintain 302.7 mAh/g after 750 cycles at 5.0 A/g. Additionally, ex-situ characterization techniques such as ex-situ XRD and ex-situ XPS were employed to further explore the sodium storage mechanism of the NiCo2S4@CDs anode.
Na+ batteries (SIBs) have been emerging as the most promising candidate for the next generation of secondary batteries. However, the development of high-performance and cost-effective anode materials is urgently needed for the large-scale applications of SIBs. In this study, carbon dots confined bimetallic sulfide (NiCo2S4) architecture (NiCo2S4@CDs) was proposed and synthesized from assembling nanosheets into cross-stacked superstructure and the subsequent confinement of carbon dots. This novel decussated structure assembly from nanosheets is greatly beneficial to the structure stability of electrode material during the successive charge/discharge processes. Besides, the CDs based carbon conductive network can enhance the electrical conductivity for facilitating the easy transport of electron/Na+. Benefitting from these advantages, NiCo2S4@CDs exhibits high-rate performance and an ultralong cycling life in SIBs. Specifically, the specific capacity of NiCo2S4@CDs can reach the discharge specific capacity as high as 568.9 mAh/g at 0.5 A/g, which can also maintain 302.7 mAh/g after 750 cycles at 5.0 A/g. Additionally, ex-situ characterization techniques such as ex-situ XRD and ex-situ XPS were employed to further explore the sodium storage mechanism of the NiCo2S4@CDs anode.
2024, 35(7): 108922
doi: 10.1016/j.cclet.2023.108922
Abstract:
Three-dimentional (3D) transition metal selenides with sufficient channels could produce significant superiority on enhancing reaction kinetics for sodium-ion batteries. However, the thorough exploration of 3D architecture with a facile strategy is still challenging. Here we report that a polycrystalline Cu2-xSe film was epitaxial grown on (220) facets-exposed Cu by direct selenization of a nanoporous Cu skeleton, which is obtained by dealloying rolled CuMn@Cu alloy foil. Density functional theory calculation result shows strong adsorption energy for Se atoms on Cu (220) planes during selenization reaction, rendering a low energy consumption. By virtue of this core-shell 3D nanoporous architecture to offer abundant active sites and endow fast electron/ion transportation, the nanoporous Cu2-xSe@Cu-0.15 composite electrode exhibits remarkable sodium-ion storage properties with high reversible capacity of 950.6 µAh/cm2 at 50 µA/cm2, suprior rate capability of 457.6 µAh/cm2 at 500 µA/cm2, as well as an ultra-long stability at a high current density. Mechanism investigation reveals that the electrochemical reaction is a typical conversion-type reaction with different intermediates. This novel electrode synthetic strategy provides useful instructions to design the high-performance anode material for sodium-ion batteries.
Three-dimentional (3D) transition metal selenides with sufficient channels could produce significant superiority on enhancing reaction kinetics for sodium-ion batteries. However, the thorough exploration of 3D architecture with a facile strategy is still challenging. Here we report that a polycrystalline Cu2-xSe film was epitaxial grown on (220) facets-exposed Cu by direct selenization of a nanoporous Cu skeleton, which is obtained by dealloying rolled CuMn@Cu alloy foil. Density functional theory calculation result shows strong adsorption energy for Se atoms on Cu (220) planes during selenization reaction, rendering a low energy consumption. By virtue of this core-shell 3D nanoporous architecture to offer abundant active sites and endow fast electron/ion transportation, the nanoporous Cu2-xSe@Cu-0.15 composite electrode exhibits remarkable sodium-ion storage properties with high reversible capacity of 950.6 µAh/cm2 at 50 µA/cm2, suprior rate capability of 457.6 µAh/cm2 at 500 µA/cm2, as well as an ultra-long stability at a high current density. Mechanism investigation reveals that the electrochemical reaction is a typical conversion-type reaction with different intermediates. This novel electrode synthetic strategy provides useful instructions to design the high-performance anode material for sodium-ion batteries.
2024, 35(7): 108924
doi: 10.1016/j.cclet.2023.108924
Abstract:
The preparation of Pd-based catalysts with rich electrons and a high atom dispersion rate is of great significance for improving the reactivity of cross-coupling reactions, which is a powerful tool for pharmaceutical and fine chemical synthesis. Here, we report a PdNi single-atom alloy (SAA) catalyst in which isolated Pd single atoms are anchored onto the surface of Ni nanoparticles (NPs) applied for Suzuki coupling reactions and Heck coupling reactions. The 0.1% PdNi SAA exhibits extraordinary catalytic activity (reaction rate: 17,032.25 mmol h−1 gPd−1) toward the Suzuki cross-coupling reaction between 4-bromoanisole and phenylboronic acid at 80℃ for 1 h. The excellent activity is supposed to attribute to the 100 percent utilization rate of Pd atoms and the highly stable surface zero-valance Pd atoms, which provides abundant sites and electrons for the adsorption and fracture of the C-X (X = Cl, Br, I) bond. Moreover, our work demonstrates the excellent application prospect of SAAs for cross-coupling reactions.
The preparation of Pd-based catalysts with rich electrons and a high atom dispersion rate is of great significance for improving the reactivity of cross-coupling reactions, which is a powerful tool for pharmaceutical and fine chemical synthesis. Here, we report a PdNi single-atom alloy (SAA) catalyst in which isolated Pd single atoms are anchored onto the surface of Ni nanoparticles (NPs) applied for Suzuki coupling reactions and Heck coupling reactions. The 0.1% PdNi SAA exhibits extraordinary catalytic activity (reaction rate: 17,032.25 mmol h−1 gPd−1) toward the Suzuki cross-coupling reaction between 4-bromoanisole and phenylboronic acid at 80℃ for 1 h. The excellent activity is supposed to attribute to the 100 percent utilization rate of Pd atoms and the highly stable surface zero-valance Pd atoms, which provides abundant sites and electrons for the adsorption and fracture of the C-X (X = Cl, Br, I) bond. Moreover, our work demonstrates the excellent application prospect of SAAs for cross-coupling reactions.
2024, 35(7): 108926
doi: 10.1016/j.cclet.2023.108926
Abstract:
Recently electrochemical synthesis of H2O2 through oxygen reduction reaction (ORR) via 2e− pathway is considered as a green and on-site route. However, it still remains a big challenge for fabricating novel metal-free catalysts under acidic solutions, since it suffers from high overpotential due to the intrinsically week *OOH adsorption. Herein, a co-doped carbon nanosheet (O/NC) catalyst toward regulating O and N content was synthesized for improving the selectivity and activity of H2O2 electrosynthesis process. The O/NC exhibits outstanding 2e− ORR performance with low onset potential of 0.4 V (vs. RHE) and a selectivity of 92.4% in 0.1 mol/L HClO4 solutions. The in situ electrochemical impedance spectroscopy (EIS) tests reveals that the N incorporation contributes to the fast ORR kinetics. The density functional theory (DFT) calculations demonstrate that the binding strength of *OOH was optimized by the co-doping of oxygen and nitrogen at certain content, and the O/NCCOOH site exhibits a lower theoretical overpotential for H2O2 formation than OCCOOH site. Furthermore, the promoted kinetics for typical organic dye degradation in simultaneous electron-Fenton process on O/NC catalyst was demonstrated particularly for broadening its environmental application.
Recently electrochemical synthesis of H2O2 through oxygen reduction reaction (ORR) via 2e− pathway is considered as a green and on-site route. However, it still remains a big challenge for fabricating novel metal-free catalysts under acidic solutions, since it suffers from high overpotential due to the intrinsically week *OOH adsorption. Herein, a co-doped carbon nanosheet (O/NC) catalyst toward regulating O and N content was synthesized for improving the selectivity and activity of H2O2 electrosynthesis process. The O/NC exhibits outstanding 2e− ORR performance with low onset potential of 0.4 V (vs. RHE) and a selectivity of 92.4% in 0.1 mol/L HClO4 solutions. The in situ electrochemical impedance spectroscopy (EIS) tests reveals that the N incorporation contributes to the fast ORR kinetics. The density functional theory (DFT) calculations demonstrate that the binding strength of *OOH was optimized by the co-doping of oxygen and nitrogen at certain content, and the O/NCCOOH site exhibits a lower theoretical overpotential for H2O2 formation than OCCOOH site. Furthermore, the promoted kinetics for typical organic dye degradation in simultaneous electron-Fenton process on O/NC catalyst was demonstrated particularly for broadening its environmental application.
2024, 35(7): 108930
doi: 10.1016/j.cclet.2023.108930
Abstract:
Rationally designed novel cost-effective hydrogen evolution reaction (HER) electrocatalysts with controlled surface composition and advanced structural superiority is extremely critical to optimize the HER performance. Polyoxometalates (POMs) with structural diversity and adjustable element compositions represent a promising precursor for rational design and preparation of HER electrocatalysts. Herein, a series of transition metal-doped MoS2 materials with different surface engineered structures (Fe, Cr, V doping and S vacancies) (M-MoS2/CC, M = Fe, Cr and V) were fabricated by a simple hydrothermal-vulcanization strategy using Keplerate polyoxomolybdate nanoball ({Mo72Fe30}, {Mo72Cr30}, {Mo72V30}, {Mo132}) as precursors. The enlarged interlayer spacing as well as the integration of homogeneous transition metal doping and abundant sulfur vacancies endows prepared M-MoS2/CC with superior HER electrocatalytic performance and excellent long-term working stability in both acidic and alkaline media. The optimized Fe-MoS2/CC afford current densities of 10 and 50 mA/cm2 at overpotentials of 188/272 mV and 194/394 mV in 0.5 mol/L H2SO4 and 1.0 mol/L KOH aqueous solution, respectively, outperforming most of reported typical transition metal sulfide-based catalysts. This work represents an important breakthrough for POMs-mediated highly efficient transition metal sulfide-based HER electrocatalysts with wide range pH activity and may provide new options for the rational design of promising HER electrocatalysts and beyond.
Rationally designed novel cost-effective hydrogen evolution reaction (HER) electrocatalysts with controlled surface composition and advanced structural superiority is extremely critical to optimize the HER performance. Polyoxometalates (POMs) with structural diversity and adjustable element compositions represent a promising precursor for rational design and preparation of HER electrocatalysts. Herein, a series of transition metal-doped MoS2 materials with different surface engineered structures (Fe, Cr, V doping and S vacancies) (M-MoS2/CC, M = Fe, Cr and V) were fabricated by a simple hydrothermal-vulcanization strategy using Keplerate polyoxomolybdate nanoball ({Mo72Fe30}, {Mo72Cr30}, {Mo72V30}, {Mo132}) as precursors. The enlarged interlayer spacing as well as the integration of homogeneous transition metal doping and abundant sulfur vacancies endows prepared M-MoS2/CC with superior HER electrocatalytic performance and excellent long-term working stability in both acidic and alkaline media. The optimized Fe-MoS2/CC afford current densities of 10 and 50 mA/cm2 at overpotentials of 188/272 mV and 194/394 mV in 0.5 mol/L H2SO4 and 1.0 mol/L KOH aqueous solution, respectively, outperforming most of reported typical transition metal sulfide-based catalysts. This work represents an important breakthrough for POMs-mediated highly efficient transition metal sulfide-based HER electrocatalysts with wide range pH activity and may provide new options for the rational design of promising HER electrocatalysts and beyond.
2024, 35(7): 108933
doi: 10.1016/j.cclet.2023.108933
Abstract:
The severe interfacial charge recombination as well as the stability issues brought by the Li-TFSI still hinder the commercialization of high-performance perovskite solar cells (PSCs). Here, a polyoxometalates (POMs)-based complex, POM@ ionic liquid (IL), is synthesized and applied as an effective additive that simultaneously enhances the performance and stability of PSCs. The interactions between POM@IL complex and Li-TFSI inhibit the aggregation of Li-TFSI. The synergistic oxidation of POM@IL complex and Li-TFSI towards 2, 2′, 7, 7′-tetrakis[N, N-di(4-methoxyphenyl)amino]-9, 9'-spirobifluorene (Spiro-OMeTAD) effectively enhances the electrical properties of hole transport layer film and the photovoltaic performances of PSCs. The champion device modified with the POM@IL complex yields an excellent power conversion efficiency (PCE) of 22.73%. Moreover, the incorporation of POM@IL improves the humidity stability of PSCs. After storing under high humidity conditions (25 ℃, 60% RH) for 1200 h, the POM@IL modified device retained a remarkable 81.2% of its initial PCE. This work provides new insight into constructing POMs-based materials for high-performance photovoltaic devices.
The severe interfacial charge recombination as well as the stability issues brought by the Li-TFSI still hinder the commercialization of high-performance perovskite solar cells (PSCs). Here, a polyoxometalates (POMs)-based complex, POM@ ionic liquid (IL), is synthesized and applied as an effective additive that simultaneously enhances the performance and stability of PSCs. The interactions between POM@IL complex and Li-TFSI inhibit the aggregation of Li-TFSI. The synergistic oxidation of POM@IL complex and Li-TFSI towards 2, 2′, 7, 7′-tetrakis[N, N-di(4-methoxyphenyl)amino]-9, 9'-spirobifluorene (Spiro-OMeTAD) effectively enhances the electrical properties of hole transport layer film and the photovoltaic performances of PSCs. The champion device modified with the POM@IL complex yields an excellent power conversion efficiency (PCE) of 22.73%. Moreover, the incorporation of POM@IL improves the humidity stability of PSCs. After storing under high humidity conditions (25 ℃, 60% RH) for 1200 h, the POM@IL modified device retained a remarkable 81.2% of its initial PCE. This work provides new insight into constructing POMs-based materials for high-performance photovoltaic devices.
2024, 35(7): 108950
doi: 10.1016/j.cclet.2023.108950
Abstract:
Four new cyclohexapeptides, pyridapeptides F–I (1–4), were isolated from the fermentation broth of marine sponge-derived Streptomyces sp. OUCMDZ-4539. The pyridapeptides F–H (1–3) are composed of β-hydroxyleucine, alanine, O-methylthreonine, hexahydropyridazine-3-carboxylic acid, 5-hydroxytetrahydropyridazine-3-carboxylic acid, and (2S,3R,4E,6E)-2-amino-3–hydroxy-4,6-dienoic acid residues. Pyridapeptide Ⅰ (4) contains (2S,3R,4E,6E)-2-amino-3–hydroxy-8-methylnona-4,6-dienoic acid residue and a very rare glycose residue, aculose. Their structures were determined based on spectroscopic analysis and chemical methods. Pyridapeptides G–I (2–4) have the 2,3,6-trideoxyhexose units glycosylated at the γ-OH-TPDA residue, displayed significant antiproliferative activity against four (PC9, MKN45, HepG2, K562) or two (PC9, MKN45) human cancer cell lines.
Four new cyclohexapeptides, pyridapeptides F–I (1–4), were isolated from the fermentation broth of marine sponge-derived Streptomyces sp. OUCMDZ-4539. The pyridapeptides F–H (1–3) are composed of β-hydroxyleucine, alanine, O-methylthreonine, hexahydropyridazine-3-carboxylic acid, 5-hydroxytetrahydropyridazine-3-carboxylic acid, and (2S,3R,4E,6E)-2-amino-3–hydroxy-4,6-dienoic acid residues. Pyridapeptide Ⅰ (4) contains (2S,3R,4E,6E)-2-amino-3–hydroxy-8-methylnona-4,6-dienoic acid residue and a very rare glycose residue, aculose. Their structures were determined based on spectroscopic analysis and chemical methods. Pyridapeptides G–I (2–4) have the 2,3,6-trideoxyhexose units glycosylated at the γ-OH-TPDA residue, displayed significant antiproliferative activity against four (PC9, MKN45, HepG2, K562) or two (PC9, MKN45) human cancer cell lines.
2024, 35(7): 108955
doi: 10.1016/j.cclet.2023.108955
Abstract:
The rapid development of high-power and pulsed-power techniques inspires extensive investigates on high-performance ceramic-based capacitors. However, the low recoverable energy density (Wrec) hampers their wider applications. Herein, the non-stoichiometric Bi0.5Na0.5TiO3-based ceramics were designed and studied. The proper introduction of oxygen vacancies facilitated activating defect dipole, giving rise to reduced remanent polarization. Consequently, the optimal composition exhibited an exceptional high Wrec of 8.3 J/cm3, a high efficiency of 85%, and excellent anti-fatigue and thermal reliability. This work provides an efficient approach to explore ceramic capacitors with high capacitive energy storage performances.
The rapid development of high-power and pulsed-power techniques inspires extensive investigates on high-performance ceramic-based capacitors. However, the low recoverable energy density (Wrec) hampers their wider applications. Herein, the non-stoichiometric Bi0.5Na0.5TiO3-based ceramics were designed and studied. The proper introduction of oxygen vacancies facilitated activating defect dipole, giving rise to reduced remanent polarization. Consequently, the optimal composition exhibited an exceptional high Wrec of 8.3 J/cm3, a high efficiency of 85%, and excellent anti-fatigue and thermal reliability. This work provides an efficient approach to explore ceramic capacitors with high capacitive energy storage performances.
2024, 35(7): 108957
doi: 10.1016/j.cclet.2023.108957
Abstract:
Zero thermal expansion materials are important for the practical applications due to their shape stability as changing temperature. The reported concept of average atomic volume is an available method to hunt new zero thermal expansion materials. Here, according to this concept, a tetragonal tungstate Cs2W3O10 with zero expansion has been found. There is no structure phase transition as increasing temperature from 150 K to 573 K. The coefficient of thermal expansion of axes and volume are αa = 0.0074 × 10−6 K−1, αc = 1.63 × 10−6 K−1, and αV = 1.60 × 10−6 K−1, respectively, in the temperature range of 150 ~ 573 K. The temperature- and pressure-dependent Raman spectra reveal that the vibrations of WO6 octahedra libration modes with positive total anharmonicity and W-O-W bending mode with negative Grüneisen parameter are possibly the origin of zero thermal expansion in Cs2W3O10.
Zero thermal expansion materials are important for the practical applications due to their shape stability as changing temperature. The reported concept of average atomic volume is an available method to hunt new zero thermal expansion materials. Here, according to this concept, a tetragonal tungstate Cs2W3O10 with zero expansion has been found. There is no structure phase transition as increasing temperature from 150 K to 573 K. The coefficient of thermal expansion of axes and volume are αa = 0.0074 × 10−6 K−1, αc = 1.63 × 10−6 K−1, and αV = 1.60 × 10−6 K−1, respectively, in the temperature range of 150 ~ 573 K. The temperature- and pressure-dependent Raman spectra reveal that the vibrations of WO6 octahedra libration modes with positive total anharmonicity and W-O-W bending mode with negative Grüneisen parameter are possibly the origin of zero thermal expansion in Cs2W3O10.
2024, 35(7): 108968
doi: 10.1016/j.cclet.2023.108968
Abstract:
Fungal alkylresorcinols are a class of polyketides, which are commonly synthesized by the hybridization of highly reducing polyketide synthase (hrPKS) with non-reducing polyketide synthase (nrPKS). In this study, we identified and demonstrated a new assembly model for synthesizing alkylresorcinol (scirpilin A, 1), which was accomplished by collaboration of a hrPKS (FscA) and a type Ⅲ PKS (FscB). Furthermore, three post-tailoring enzymes (FscC, FscD, and FscE) act iteratively on 1 skeleton, including successive 14e− oxidation of inert carbons, di-halogenation, and di-methylation, to form highly oxidized and multi-substituted alkylresorcinols. Our work presents an unusual synthesis manner of alkylresorcinols, sheds light on the collaborative mechanism between hrPKS and type Ⅲ PKS and provides three valuable enzymatic catalysts for the tailoring of alkylresorcinol family natural products in future.
Fungal alkylresorcinols are a class of polyketides, which are commonly synthesized by the hybridization of highly reducing polyketide synthase (hrPKS) with non-reducing polyketide synthase (nrPKS). In this study, we identified and demonstrated a new assembly model for synthesizing alkylresorcinol (scirpilin A, 1), which was accomplished by collaboration of a hrPKS (FscA) and a type Ⅲ PKS (FscB). Furthermore, three post-tailoring enzymes (FscC, FscD, and FscE) act iteratively on 1 skeleton, including successive 14e− oxidation of inert carbons, di-halogenation, and di-methylation, to form highly oxidized and multi-substituted alkylresorcinols. Our work presents an unusual synthesis manner of alkylresorcinols, sheds light on the collaborative mechanism between hrPKS and type Ⅲ PKS and provides three valuable enzymatic catalysts for the tailoring of alkylresorcinol family natural products in future.
2024, 35(7): 108972
doi: 10.1016/j.cclet.2023.108972
Abstract:
Dynamic assembly on time scale is common in biological systems but rare for artificial materials, especially for smart luminescent materials. Programming molecular assembly in a spatio-temporal manner and resulting in white-light-including multicolor fluorescence with time-dynamic features remains challenging. Herein, controlling molecular assembly on time scale is achieved by integrating a pH-responsive motif to a transient alkaline solution which is fabricated by activators (NaOH) and deactivators (esters), leading to automatic assembly on time scale and time-dependent multicolor fluorescence changing from blue to white and yellow. The kinetics of the assembly process is dependent on the ester hydrolysis process, which can be controlled by varying ester concentrations, temperature, initial pH, stirring rate and ester structures. This dynamic fluorescent system can be further developed for intelligent fluorescent materials such as fluorescent ink, three-dimension (3D) codes and even four-dimension (4D) codes, exhibiting a promising potential for information encryption.
Dynamic assembly on time scale is common in biological systems but rare for artificial materials, especially for smart luminescent materials. Programming molecular assembly in a spatio-temporal manner and resulting in white-light-including multicolor fluorescence with time-dynamic features remains challenging. Herein, controlling molecular assembly on time scale is achieved by integrating a pH-responsive motif to a transient alkaline solution which is fabricated by activators (NaOH) and deactivators (esters), leading to automatic assembly on time scale and time-dependent multicolor fluorescence changing from blue to white and yellow. The kinetics of the assembly process is dependent on the ester hydrolysis process, which can be controlled by varying ester concentrations, temperature, initial pH, stirring rate and ester structures. This dynamic fluorescent system can be further developed for intelligent fluorescent materials such as fluorescent ink, three-dimension (3D) codes and even four-dimension (4D) codes, exhibiting a promising potential for information encryption.
2024, 35(7): 109001
doi: 10.1016/j.cclet.2023.109001
Abstract:
Lithium-sulfur (Li-S) batteries with high theoretical capacity and energy density need to solve problems such as the high decomposition energy barrier of Li2S and large volume change of sulfur in the charging process caused by the shuttle effect before practical application. Herein, a green synthesis method is used to prepare polyacrylic acid (PAA) superabsorbent material, and then the pyrolyzed PAA (P/PAA) material is obtained as the positive electrode of Li-S battery. Density functional calculation reveals that the oxygen self-doping pyrolyzed polyacrylic acid (P/PAA) delivered stronger binding energy toward Li2S species in carbonyl C=O than that of graphite powder (GP) which are −1.58 eV and −1.02 eV, respectively. Coupled with the distribution of relaxation time analysis and the in-situ electrochemical impedance approach, it is further demonstrated that the designed P/PAA as sulfur host plays a physical/chemical adsorption dual function in maintaining the stability and rate performance of batteries. With an initial discharge capacity of 1258 mAh/g at 0.1 C and a minimal capacity decline of 0.05% per cycle even after 800 cycles at 0.5 C, the produced cathode demonstrated outstanding electrochemical performance. The average Coulombic efficiency is nearly 100%. The P/PAA electrodes may typically retain 96% of their capacity while declining on average only 0.033% per cycle after 130 cycles at 3 C. This effort provides a new method for the future development of heteroatomic self-doping superabsorbent with promising adsorption properties for polysulfides as cathode materials of Li-S batteries.
Lithium-sulfur (Li-S) batteries with high theoretical capacity and energy density need to solve problems such as the high decomposition energy barrier of Li2S and large volume change of sulfur in the charging process caused by the shuttle effect before practical application. Herein, a green synthesis method is used to prepare polyacrylic acid (PAA) superabsorbent material, and then the pyrolyzed PAA (P/PAA) material is obtained as the positive electrode of Li-S battery. Density functional calculation reveals that the oxygen self-doping pyrolyzed polyacrylic acid (P/PAA) delivered stronger binding energy toward Li2S species in carbonyl C=O than that of graphite powder (GP) which are −1.58 eV and −1.02 eV, respectively. Coupled with the distribution of relaxation time analysis and the in-situ electrochemical impedance approach, it is further demonstrated that the designed P/PAA as sulfur host plays a physical/chemical adsorption dual function in maintaining the stability and rate performance of batteries. With an initial discharge capacity of 1258 mAh/g at 0.1 C and a minimal capacity decline of 0.05% per cycle even after 800 cycles at 0.5 C, the produced cathode demonstrated outstanding electrochemical performance. The average Coulombic efficiency is nearly 100%. The P/PAA electrodes may typically retain 96% of their capacity while declining on average only 0.033% per cycle after 130 cycles at 3 C. This effort provides a new method for the future development of heteroatomic self-doping superabsorbent with promising adsorption properties for polysulfides as cathode materials of Li-S batteries.
2024, 35(7): 109005
doi: 10.1016/j.cclet.2023.109005
Abstract:
Indole is a biologically active compound formed by the fusion of benzene and pyrrole, and it is widely found in natural products and drugs. Due to the unique structure and properties of indole, its derivatives often exhibit distinctive physiological activities, which has led to widespread attention in the field of pesticide development. Analyzing the design strategies and structure-activity relationships (SARs) of compounds is a crucial step in developing novel pesticides. This review mainly summarizes indole compounds with plant growth regulating, antiviral, fungicidal, herbicidal, and insecticidal activities, with the aim of providing new insights into the discovery and mechanism of action of novel indole-based pesticides.
Indole is a biologically active compound formed by the fusion of benzene and pyrrole, and it is widely found in natural products and drugs. Due to the unique structure and properties of indole, its derivatives often exhibit distinctive physiological activities, which has led to widespread attention in the field of pesticide development. Analyzing the design strategies and structure-activity relationships (SARs) of compounds is a crucial step in developing novel pesticides. This review mainly summarizes indole compounds with plant growth regulating, antiviral, fungicidal, herbicidal, and insecticidal activities, with the aim of providing new insights into the discovery and mechanism of action of novel indole-based pesticides.
2024, 35(7): 109007
doi: 10.1016/j.cclet.2023.109007
Abstract:
Due to the advantages of renewable, low pollution and wide distribution of biomass resources, it is selected as the electrode material for supercapacitors. For carbon-based electrode materials, specific surface area and pore structure have a great influence. Exploring and summarizing the influence of activation on pore structure will greatly broaden this field. Based on the activation mechanism of activator, this paper summarizes the latest progress of biomass activation applied to supercapacitors, including traditional physical and chemical activation methods and non-traditional methods such as biological activation method, self-activation method, template assisted activation method and green activator activation. Finally, the challenges, strategies and prospects for the future development of biomass-derived carbon material activation are pointed out. In summary, this review will help researchers choose appropriate strategies to design biomass-derived carbon electrode materials for supercapacitors, thereby promoting the application of biomass materials.
Due to the advantages of renewable, low pollution and wide distribution of biomass resources, it is selected as the electrode material for supercapacitors. For carbon-based electrode materials, specific surface area and pore structure have a great influence. Exploring and summarizing the influence of activation on pore structure will greatly broaden this field. Based on the activation mechanism of activator, this paper summarizes the latest progress of biomass activation applied to supercapacitors, including traditional physical and chemical activation methods and non-traditional methods such as biological activation method, self-activation method, template assisted activation method and green activator activation. Finally, the challenges, strategies and prospects for the future development of biomass-derived carbon material activation are pointed out. In summary, this review will help researchers choose appropriate strategies to design biomass-derived carbon electrode materials for supercapacitors, thereby promoting the application of biomass materials.
2024, 35(7): 109011
doi: 10.1016/j.cclet.2023.109011
Abstract:
Qubit, as the basic unit of quantum operations, has at least two quantum states for superposition. Diamond itself has no superimposable quantum states, but after injecting N atoms, the resulted nitrogen-vacancy centers form excellent-performance qubits. For the same purpose, we can also obtain qubits by modifying the matrix without effective quantum states. HKUST-1 ({Cu3(BTC)2(H2O)3}, BTC = 1,3,5-benzene-tricarboxylate) with S = 0 ground state is electron paramagnetic resonance (EPR) silent, so it is not a qubit candidate. However, the spontaneously hydrolyzed HKUST-1 produces dilute uncoupled CuⅡ ions with S = 1/2. In this paper, we utilized the hydrolysis products of HKUST-1 to obtain qubits and assembled a core-shell structural HKUST-1@ZIF-8 by ZIF-8 ({Zn(mim)2}, mim = 2-methylimidazole) coated over HKUST-1 for controlling the hydrolysis. The experimental results clearly show that the qubits come from hydrolyzed CuⅡ ions. Furthermore, the dilute uncoupled CuⅡ ions in this assembly can effectively reduce the decoherence of qubits. The EPR studies show that the T2 of this compound is 1067 ns at 10 K.
Qubit, as the basic unit of quantum operations, has at least two quantum states for superposition. Diamond itself has no superimposable quantum states, but after injecting N atoms, the resulted nitrogen-vacancy centers form excellent-performance qubits. For the same purpose, we can also obtain qubits by modifying the matrix without effective quantum states. HKUST-1 ({Cu3(BTC)2(H2O)3}, BTC = 1,3,5-benzene-tricarboxylate) with S = 0 ground state is electron paramagnetic resonance (EPR) silent, so it is not a qubit candidate. However, the spontaneously hydrolyzed HKUST-1 produces dilute uncoupled CuⅡ ions with S = 1/2. In this paper, we utilized the hydrolysis products of HKUST-1 to obtain qubits and assembled a core-shell structural HKUST-1@ZIF-8 by ZIF-8 ({Zn(mim)2}, mim = 2-methylimidazole) coated over HKUST-1 for controlling the hydrolysis. The experimental results clearly show that the qubits come from hydrolyzed CuⅡ ions. Furthermore, the dilute uncoupled CuⅡ ions in this assembly can effectively reduce the decoherence of qubits. The EPR studies show that the T2 of this compound is 1067 ns at 10 K.
Phomaketals A and B, pentacyclic meroterpenoids from a eupC overexpressed mutant strain of Phoma sp.
2024, 35(7): 109019
doi: 10.1016/j.cclet.2023.109019
Abstract:
Phomaketals A (1) and B (2), two tropolonic meroterpenoids with the unprecedented pentacyclic skeletons, were isolated from the solid-substrate fermentation cultures of a eupC overexpressed mutant strain of the fungus Phoma sp., together with a biogenetically related secondary metabolite pughiinin B (3), and the known one noreupenifeldin B (4). The structures of 1–3 were elucidated primarily by nuclear magnetic resonance (NMR) experiments. The absolute configurations of 1 and 2 were assigned by electronic circular dichroism calculations and the calculated NMR with DP4+ analysis, while that of 3 was established by single-crystal X-ray diffraction analysis using Cu Kα radiation. Biogenetically, phomaketals A (1) and B (2) could be derived from the hypothetical tropolonic sesquiterpene intermediates neosetophomone B (6) and 9-R-neosetophomone B (6′), respectively, via different reactions cascades. Compound 1 showed antiproliferative effect only against the SUPB15 cells, with an 50% inhibitory concentration (IC50) value of 4.85 µmol/L, while the co-isolated known meroterpenoid 4 displayed potent effects against three tumor cell lines, SUPB15, EL4, and H9, showing IC50 values of 0.36–27.08 µmol/L.
Phomaketals A (1) and B (2), two tropolonic meroterpenoids with the unprecedented pentacyclic skeletons, were isolated from the solid-substrate fermentation cultures of a eupC overexpressed mutant strain of the fungus Phoma sp., together with a biogenetically related secondary metabolite pughiinin B (3), and the known one noreupenifeldin B (4). The structures of 1–3 were elucidated primarily by nuclear magnetic resonance (NMR) experiments. The absolute configurations of 1 and 2 were assigned by electronic circular dichroism calculations and the calculated NMR with DP4+ analysis, while that of 3 was established by single-crystal X-ray diffraction analysis using Cu Kα radiation. Biogenetically, phomaketals A (1) and B (2) could be derived from the hypothetical tropolonic sesquiterpene intermediates neosetophomone B (6) and 9-R-neosetophomone B (6′), respectively, via different reactions cascades. Compound 1 showed antiproliferative effect only against the SUPB15 cells, with an 50% inhibitory concentration (IC50) value of 4.85 µmol/L, while the co-isolated known meroterpenoid 4 displayed potent effects against three tumor cell lines, SUPB15, EL4, and H9, showing IC50 values of 0.36–27.08 µmol/L.
2024, 35(7): 109021
doi: 10.1016/j.cclet.2023.109021
Abstract:
Mercury ion (Hg2+), as one of the most toxic heavy metal ions, accumulates easily in the environment, which can generate potential hazards to the ecosystem and human health. To effectively detect and remove Hg2+, we fabricated four types of carbon dots (CDs) using carboxymethyl nanocellulose as a carbon source doped with different elements using a hydrothermal method. All the CDs exhibited a strong fluorescence emission, excitation-dependent emission and possessed good water dispersibility. Moreover, the four fluorescent CDs were used for Hg2+ recognition in aqueous solution, where the CDs-N exhibited better sensitivity and selectivity for Hg2+ detection, with a low limit of detection of 8.29 × 10−6 mol/L. It was determined that the fluorescence quenching could be ascribed to a photoinduced charge-transfer processes between Hg2+ and the CDs. In addition, the CDs-N were used as a smart invisible ink for anti-counterfeiting, information encryption and decryption. Furthermore, the CDs-N were immersed into a cellulose (CMC)-based hydrogel network to prepare fluorescent hydrogels capable of simultaneously detecting and adsorbing Hg2+. We anticipate that this research will open possibilities for a green method to synthesize fluorescent CDs for metal ion detection and fluorescent ink production.
Mercury ion (Hg2+), as one of the most toxic heavy metal ions, accumulates easily in the environment, which can generate potential hazards to the ecosystem and human health. To effectively detect and remove Hg2+, we fabricated four types of carbon dots (CDs) using carboxymethyl nanocellulose as a carbon source doped with different elements using a hydrothermal method. All the CDs exhibited a strong fluorescence emission, excitation-dependent emission and possessed good water dispersibility. Moreover, the four fluorescent CDs were used for Hg2+ recognition in aqueous solution, where the CDs-N exhibited better sensitivity and selectivity for Hg2+ detection, with a low limit of detection of 8.29 × 10−6 mol/L. It was determined that the fluorescence quenching could be ascribed to a photoinduced charge-transfer processes between Hg2+ and the CDs. In addition, the CDs-N were used as a smart invisible ink for anti-counterfeiting, information encryption and decryption. Furthermore, the CDs-N were immersed into a cellulose (CMC)-based hydrogel network to prepare fluorescent hydrogels capable of simultaneously detecting and adsorbing Hg2+. We anticipate that this research will open possibilities for a green method to synthesize fluorescent CDs for metal ion detection and fluorescent ink production.
2024, 35(7): 109029
doi: 10.1016/j.cclet.2023.109029
Abstract:
Anti-inflammatory drugs targeting inflammatory bowel disease (IBD) have attracted considerable attention but still face low therapeutic outcomes and frequent side effects. Astaxanthin (ATX), a natural ketone, possesses potent antioxidant and anti-inflammatory properties. However, it faces problems such as poor water solubility, photothermal instability, and low bioavailability. Here, we employed a supramolecular encapsulation strategy to create a nanoscale oral delivery system for ATX (referred to as FC-ATX NPs) by coupling fucoidan (FUC) with chitosan oligosaccharides (COS). The obtained FC-ATX NPs exhibited a particular "bean pod" structure with uniform size, good encapsulation efficiency, excellent physical and chemical stability, pH-triggered intestinal targeted slow-release properties, and potent antioxidant capacity. In vitro cell culture experiments showed that FC-ATX NPs promoted cellular uptake and scavenged excessive intracellular reactive oxygen species (ROS). In mouse models of colitis, FC-ATX NPs enhanced the drug absorption of intestinal epithelial cells and effectively accumulated at the site of inflammation. This work provides an efficient approach to enhance the bioavailability of ATX and has excellent application potential as an oral targeted delivery system for colitis therapy.
Anti-inflammatory drugs targeting inflammatory bowel disease (IBD) have attracted considerable attention but still face low therapeutic outcomes and frequent side effects. Astaxanthin (ATX), a natural ketone, possesses potent antioxidant and anti-inflammatory properties. However, it faces problems such as poor water solubility, photothermal instability, and low bioavailability. Here, we employed a supramolecular encapsulation strategy to create a nanoscale oral delivery system for ATX (referred to as FC-ATX NPs) by coupling fucoidan (FUC) with chitosan oligosaccharides (COS). The obtained FC-ATX NPs exhibited a particular "bean pod" structure with uniform size, good encapsulation efficiency, excellent physical and chemical stability, pH-triggered intestinal targeted slow-release properties, and potent antioxidant capacity. In vitro cell culture experiments showed that FC-ATX NPs promoted cellular uptake and scavenged excessive intracellular reactive oxygen species (ROS). In mouse models of colitis, FC-ATX NPs enhanced the drug absorption of intestinal epithelial cells and effectively accumulated at the site of inflammation. This work provides an efficient approach to enhance the bioavailability of ATX and has excellent application potential as an oral targeted delivery system for colitis therapy.
2024, 35(7): 109034
doi: 10.1016/j.cclet.2023.109034
Abstract:
Covalent bioactive compounds are successfully used in clinic and attracted intense research efforts in the fundamental study as well as drug development. The advantageous effects of covalent compounds compared with non-covalent ones are highly dependent on electrophilic warheads. Hence, electrophilic warheads with tunable reactivity and selectivity are highly demanded in fields of medicinal chemistry and chemical biology. Herein, we report a novel electrophilic warhead, chloromethyl group activated by thiol-substituted 1,2,4-triazole. Interestingly, a pair of regioisomers could be simultaneously occurred in the step of alkylation during the synthesis of this unique motif. This is a rare example that the alkylation could simultaneously generate these two separable regioisomers of 1,2,4-triazole at the nitrogen or sulfur atom. The covalent-working mechanism of this new warhead is confirmed by various chemoproteomics experiments including target identification and binding site mapping. Importantly, the reactivity and selectivity of this new electrophilic warhead could be efficiently tuned by virtue of stereo effect. Interestingly, one pair of regioisomers (19S and 19X) induced distinct modes of cell death. Isomer 19S could induce apoptosis of colon cancer cells while 19X could induce both apoptosis and ferroptosis. Together, this study provides pairs of novel electrophilic warheads that could be useful not only in supporting the design of covalent compounds for drug discovery but also in providing chemical probes for the fundamental biological study.
Covalent bioactive compounds are successfully used in clinic and attracted intense research efforts in the fundamental study as well as drug development. The advantageous effects of covalent compounds compared with non-covalent ones are highly dependent on electrophilic warheads. Hence, electrophilic warheads with tunable reactivity and selectivity are highly demanded in fields of medicinal chemistry and chemical biology. Herein, we report a novel electrophilic warhead, chloromethyl group activated by thiol-substituted 1,2,4-triazole. Interestingly, a pair of regioisomers could be simultaneously occurred in the step of alkylation during the synthesis of this unique motif. This is a rare example that the alkylation could simultaneously generate these two separable regioisomers of 1,2,4-triazole at the nitrogen or sulfur atom. The covalent-working mechanism of this new warhead is confirmed by various chemoproteomics experiments including target identification and binding site mapping. Importantly, the reactivity and selectivity of this new electrophilic warhead could be efficiently tuned by virtue of stereo effect. Interestingly, one pair of regioisomers (19S and 19X) induced distinct modes of cell death. Isomer 19S could induce apoptosis of colon cancer cells while 19X could induce both apoptosis and ferroptosis. Together, this study provides pairs of novel electrophilic warheads that could be useful not only in supporting the design of covalent compounds for drug discovery but also in providing chemical probes for the fundamental biological study.
2024, 35(7): 109049
doi: 10.1016/j.cclet.2023.109049
Abstract:
The steep reduction in costs and systematic optimization of renewable electricity has ignited an intensifying interest in harnessing electroreduction of carbon dioxide (CO2RR) for the generation of chemicals and fuels. The focus of research over the past few decades has been on the optimization of the electrode and the electrolyte environment. Notably, cation species in the latter have recently been found to dramatically alter the selectivity of CO2RR and even their catalytic activity by multiple orders of magnitude. As a result, the selection of cations is a critical factor in designing catalytic interfaces with high selectivity and efficiency for targeted products. Informed decision-making regarding cation selection relies on a comprehensive understanding of prevailing electrolyte effect models that have been used to elucidate observed experimental trends. In this perspective, we review the hypotheses that explain how electrolyte cations influence CO2RR by mechanisms such as through tuning of the interfacial electric field, buffering of the local pH, stabilization of the key intermediates and regulation of the interfacial water. Our endeavor is to elucidate the molecular mechanisms underpinning cation effects, thus fostering the evolution of more holistic and universally applicable predictive models. In this regard, we highlight the current challenges in this area of research, while also identifying potential avenues for future investigations.
The steep reduction in costs and systematic optimization of renewable electricity has ignited an intensifying interest in harnessing electroreduction of carbon dioxide (CO2RR) for the generation of chemicals and fuels. The focus of research over the past few decades has been on the optimization of the electrode and the electrolyte environment. Notably, cation species in the latter have recently been found to dramatically alter the selectivity of CO2RR and even their catalytic activity by multiple orders of magnitude. As a result, the selection of cations is a critical factor in designing catalytic interfaces with high selectivity and efficiency for targeted products. Informed decision-making regarding cation selection relies on a comprehensive understanding of prevailing electrolyte effect models that have been used to elucidate observed experimental trends. In this perspective, we review the hypotheses that explain how electrolyte cations influence CO2RR by mechanisms such as through tuning of the interfacial electric field, buffering of the local pH, stabilization of the key intermediates and regulation of the interfacial water. Our endeavor is to elucidate the molecular mechanisms underpinning cation effects, thus fostering the evolution of more holistic and universally applicable predictive models. In this regard, we highlight the current challenges in this area of research, while also identifying potential avenues for future investigations.
2024, 35(7): 109050
doi: 10.1016/j.cclet.2023.109050
Abstract:
Electrochemical CO reduction (ECOR) as a potential strategy for producing valuable chemicals and fuels has captured substantial attention. However, the currently available electrocatalysts suffer from poor selectivity and low Faradaic efficiency, limiting their industrial application. Herein, we systematically investigate the potential of homonuclear bimetallic electrocatalysts, TM2@C9N4 (TM = Fe, Co, Ni, and Cu), for the ECOR through extensive density functional theory calculations. Our findings suggest that all four proposed monolayers exhibit exceptional stability, making them highly suitable for experimental synthesis and practical applications. Interestingly, these transition-metal dual atoms anchored on C9N4 monolayers show great potential in facilitating the production of high-value C2 products, such as C2H5OH and C2H4, due to the significantly low limiting potentials (-0.06~-0.46 V) and small kinetic energy barriers (0.54–1.08 eV) for the CO coupling process. Moreover, with the exception of Ni2@C9N4, these bimetallic catalysts demonstrate the impressive suppression of the competitive hydrogen evolution reaction (HER), leading to a high selectivity for C2 products in ECOR. Our predictions would accelerate the development of high-performance C9N4-based dual-atom catalysts for the ECOR.
Electrochemical CO reduction (ECOR) as a potential strategy for producing valuable chemicals and fuels has captured substantial attention. However, the currently available electrocatalysts suffer from poor selectivity and low Faradaic efficiency, limiting their industrial application. Herein, we systematically investigate the potential of homonuclear bimetallic electrocatalysts, TM2@C9N4 (TM = Fe, Co, Ni, and Cu), for the ECOR through extensive density functional theory calculations. Our findings suggest that all four proposed monolayers exhibit exceptional stability, making them highly suitable for experimental synthesis and practical applications. Interestingly, these transition-metal dual atoms anchored on C9N4 monolayers show great potential in facilitating the production of high-value C2 products, such as C2H5OH and C2H4, due to the significantly low limiting potentials (-0.06~-0.46 V) and small kinetic energy barriers (0.54–1.08 eV) for the CO coupling process. Moreover, with the exception of Ni2@C9N4, these bimetallic catalysts demonstrate the impressive suppression of the competitive hydrogen evolution reaction (HER), leading to a high selectivity for C2 products in ECOR. Our predictions would accelerate the development of high-performance C9N4-based dual-atom catalysts for the ECOR.
2024, 35(7): 109059
doi: 10.1016/j.cclet.2023.109059
Abstract:
Constructing composited electrode material is considered to be an efficient strategy to improve their electrochemical performance. It can accelerate the charge transfer speed of ions and enhance the conductivity of electrode. Meanwhile, the formation of the hybrid structure can largely avoid the aggregation of two dimensional materials and increase the electrochemical active area of the electrode. In this work, we synthesize NiMoSSe electrode materials on nickel foam by a facile hydrothermal avenue. The prepared composite shows a specific capacitance of 1035 C/g at 1 A/g due to the synergistic effect between MoS2 and MoSe2 phases. In addition, the devices are assembled with NiMoSSe samples, which offers an energy density of 82.71 Wh/kg at a power density of 2700 W/kg.
Constructing composited electrode material is considered to be an efficient strategy to improve their electrochemical performance. It can accelerate the charge transfer speed of ions and enhance the conductivity of electrode. Meanwhile, the formation of the hybrid structure can largely avoid the aggregation of two dimensional materials and increase the electrochemical active area of the electrode. In this work, we synthesize NiMoSSe electrode materials on nickel foam by a facile hydrothermal avenue. The prepared composite shows a specific capacitance of 1035 C/g at 1 A/g due to the synergistic effect between MoS2 and MoSe2 phases. In addition, the devices are assembled with NiMoSSe samples, which offers an energy density of 82.71 Wh/kg at a power density of 2700 W/kg.
2024, 35(7): 109060
doi: 10.1016/j.cclet.2023.109060
Abstract:
With the increasing emergence of bacterial infections, especially multidrug-resistant (MDR) bacteria, poses an urgent threat. This study demonstrated a novel multifunctional nanotheranostics platform developed by the strategic integration of both in-situ bio-assembly imaging and target bacteria inactivation. Through the introduction of copper ions into bacteria, the Cu2+ could spontaneously bio-self-assembled into a multifunctional copper nanoclusters (NCs) which efficiently enhanced epigallocatechin gallate (EGCG) uptake into bacteria. While visualizing the bacteria, the developed theranostic nanoplatform exhibited highly efficient disinfection activities with negligible side effects as reflected by higher cell viability and insignificant hemolytic effects. Furthermore, the exosomal formulation of EGCG integrated with Cu2+ showed an increased intracellular antibacterial activity, which could eliminate most of the methicillin-resistant Staphylococcus aureus (MRSA) phagocytosed by macrophages, guide macrophages toward M2-like phenotype polarization and alleviate inflammation, without exhibiting obvious cytotoxicity on host RAW264.7. The regimen could be viewed as an effective strategy for the sterilization of intractable bacterial infections.
With the increasing emergence of bacterial infections, especially multidrug-resistant (MDR) bacteria, poses an urgent threat. This study demonstrated a novel multifunctional nanotheranostics platform developed by the strategic integration of both in-situ bio-assembly imaging and target bacteria inactivation. Through the introduction of copper ions into bacteria, the Cu2+ could spontaneously bio-self-assembled into a multifunctional copper nanoclusters (NCs) which efficiently enhanced epigallocatechin gallate (EGCG) uptake into bacteria. While visualizing the bacteria, the developed theranostic nanoplatform exhibited highly efficient disinfection activities with negligible side effects as reflected by higher cell viability and insignificant hemolytic effects. Furthermore, the exosomal formulation of EGCG integrated with Cu2+ showed an increased intracellular antibacterial activity, which could eliminate most of the methicillin-resistant Staphylococcus aureus (MRSA) phagocytosed by macrophages, guide macrophages toward M2-like phenotype polarization and alleviate inflammation, without exhibiting obvious cytotoxicity on host RAW264.7. The regimen could be viewed as an effective strategy for the sterilization of intractable bacterial infections.
2024, 35(7): 109101
doi: 10.1016/j.cclet.2023.109101
Abstract:
This research aims to develop a non-invasive strategy for small interfering RNA (siRNA) nasal delivery based on ionic liquids (ILs) and cationic lipid (2,3-dioleoyloxy-propyl)-trimethylammonium-chloride (DOTAP). Other than the classical role of penetration enhancer, ILs also acted as superior solvents to simultaneously load siRNA and DOTAP, forming siRNA-DOTAP-ILs (siRNA-DILs) formulations. During nasal mucosa penetration, DOTAP and ILs components self-assembled into cationic lipid nanocomplexes to load siRNA for enhanced in situ transfection. The siRNA-DILs demonstrated resistance against RNase, significant mucosa penetration, prolonged nasal retention, and satisfying gene-silencing efficacy at lower dosage. Meanwhile, DILs were also able to deliver KCa3.1-targeted siRNA effectively for the treatment of allergic rhinitis in rat model by nasal route. Thus, DILs have great potentials to deliver biological macromolecules across nasal mucosa by in situ dynamic self-assembly.
This research aims to develop a non-invasive strategy for small interfering RNA (siRNA) nasal delivery based on ionic liquids (ILs) and cationic lipid (2,3-dioleoyloxy-propyl)-trimethylammonium-chloride (DOTAP). Other than the classical role of penetration enhancer, ILs also acted as superior solvents to simultaneously load siRNA and DOTAP, forming siRNA-DOTAP-ILs (siRNA-DILs) formulations. During nasal mucosa penetration, DOTAP and ILs components self-assembled into cationic lipid nanocomplexes to load siRNA for enhanced in situ transfection. The siRNA-DILs demonstrated resistance against RNase, significant mucosa penetration, prolonged nasal retention, and satisfying gene-silencing efficacy at lower dosage. Meanwhile, DILs were also able to deliver KCa3.1-targeted siRNA effectively for the treatment of allergic rhinitis in rat model by nasal route. Thus, DILs have great potentials to deliver biological macromolecules across nasal mucosa by in situ dynamic self-assembly.
2024, 35(7): 109104
doi: 10.1016/j.cclet.2023.109104
Abstract:
Strand displacement reaction enables the construction of enzyme-free DNA reaction networks, thus has been widely applied to DNA circuit and nanotechnology. It has the characteristics of high efficiency, universality and regulatability. However, the existing regulation tools cannot enable effective control of the reaction sequence, which undoubtedly limits the construction of complex nucleic acid circuits. Herein, we developed a regulation tool, toehold lock, and achieved strict control of reaction sequence without loss of the main reaction signal output. Furthermore, we applied the tool to scenarios such as seesaw circuits, AND/OR logic gates, and entropy-driven circuits, and respectively demonstrated its significant superiority compared to the original method. We believe that the proposed toehold lock has greatly optimized the efficiency of DNA strand displacement-based networks, and we anticipate that the tool will be widely used in multiple fields.
Strand displacement reaction enables the construction of enzyme-free DNA reaction networks, thus has been widely applied to DNA circuit and nanotechnology. It has the characteristics of high efficiency, universality and regulatability. However, the existing regulation tools cannot enable effective control of the reaction sequence, which undoubtedly limits the construction of complex nucleic acid circuits. Herein, we developed a regulation tool, toehold lock, and achieved strict control of reaction sequence without loss of the main reaction signal output. Furthermore, we applied the tool to scenarios such as seesaw circuits, AND/OR logic gates, and entropy-driven circuits, and respectively demonstrated its significant superiority compared to the original method. We believe that the proposed toehold lock has greatly optimized the efficiency of DNA strand displacement-based networks, and we anticipate that the tool will be widely used in multiple fields.
2024, 35(7): 109110
doi: 10.1016/j.cclet.2023.109110
Abstract:
Size is one of the most important characteristics of nanoparticles to influence their biodistribution and antitumoral efficacy. Particles with large sizes have difficulty in deep tumor penetration, while small particles are easily removed from tumor tissues due to the high tumor interstitial fluid pressure. To address these issues, an intelligent core-crosslinked polyion complex micelle (cPCM) with a reversibly size-switchable feature was engineered in this study. The micelles are consisting of methoxy poly(ethylene glycol)-poly(D,L-lactide) copolymer (mPEG-PLA), mPEG-PLA-(HE)6CC, and mPEG-PLA-(RG)6CC at an optimal mass ratio of 6:1:1 with an antiangiogenic compound, dabigatran etexilate (DE), encapsulated. The net charge inside the micelles is switchable when exposed to different pH conditions, thereby leading to revisable size-change of micelles. DE-loaded micelles (DE@cPCM) can swell and release drugs at the tumor sites with a mildly acidic pH, while they shrink and protect the cargo from leaking into the blood circulation with a neutral pH. Results indicated that DE@cPCM can inhibit tumor angiogenesis in vitro and in vivo, thereby efficiently restraining tumor growth in a 4T1-bearing mouse model. Collectively, the size-switchable cPCM is a promising nanoplatform for targeting delivery of anticarcinogens into the matrix of tumor tissues.
Size is one of the most important characteristics of nanoparticles to influence their biodistribution and antitumoral efficacy. Particles with large sizes have difficulty in deep tumor penetration, while small particles are easily removed from tumor tissues due to the high tumor interstitial fluid pressure. To address these issues, an intelligent core-crosslinked polyion complex micelle (cPCM) with a reversibly size-switchable feature was engineered in this study. The micelles are consisting of methoxy poly(ethylene glycol)-poly(D,L-lactide) copolymer (mPEG-PLA), mPEG-PLA-(HE)6CC, and mPEG-PLA-(RG)6CC at an optimal mass ratio of 6:1:1 with an antiangiogenic compound, dabigatran etexilate (DE), encapsulated. The net charge inside the micelles is switchable when exposed to different pH conditions, thereby leading to revisable size-change of micelles. DE-loaded micelles (DE@cPCM) can swell and release drugs at the tumor sites with a mildly acidic pH, while they shrink and protect the cargo from leaking into the blood circulation with a neutral pH. Results indicated that DE@cPCM can inhibit tumor angiogenesis in vitro and in vivo, thereby efficiently restraining tumor growth in a 4T1-bearing mouse model. Collectively, the size-switchable cPCM is a promising nanoplatform for targeting delivery of anticarcinogens into the matrix of tumor tissues.
2024, 35(7): 109129
doi: 10.1016/j.cclet.2023.109129
Abstract:
Oral administration is the most acceptable route of drug delivery at this stage due to its convenience, safety, and non-invasiveness. However, drugs given orally are exposed to a complex gastrointestinal environment, causing a tremendous challenge for their successful absorption into the circulation. Over the past decades, researchers have developed various novel pharmaceutical technologies to improve oral absorption, among which the vesicular drug delivery system (like liposomes, niosomes and transfersomes) has received extensive attention. Encouragingly, there have been several investigations confirming the improved effect of vesicular drug delivery systems on oral drug absorption. Nevertheless, the clinical translation of oral vesicular drug delivery systems has been less impressive than implied by the positive results, and few vesicular formulations for oral use have been marketed yet. Against this background, this article provides an overview of the current applications and challenges associated with the vesicular delivery systems available for oral drug delivery, specifically liposomes, niosomes, transfersomes, chitosomes and bilosomes. The composition, formation mechanism, drug delivery advantages and application cases of these carriers in oral drug delivery are summarized. The possible mechanisms by which vesicular carriers enhance oral drug absorption are analyzed in terms of the in vivo process of oral drugs. Further, the challenges that oral vesicular carriers now face, such as safety, undefined in vivo fate, and scale-up production, are summarized, while possible strategies to deal with them are indicated. By reviewing the aforementioned, it can facilitate a more comprehensive knowledge of vesicular systems that can be used for oral drug delivery, providing a theoretical basis and reference for the design of oral formulations.
Oral administration is the most acceptable route of drug delivery at this stage due to its convenience, safety, and non-invasiveness. However, drugs given orally are exposed to a complex gastrointestinal environment, causing a tremendous challenge for their successful absorption into the circulation. Over the past decades, researchers have developed various novel pharmaceutical technologies to improve oral absorption, among which the vesicular drug delivery system (like liposomes, niosomes and transfersomes) has received extensive attention. Encouragingly, there have been several investigations confirming the improved effect of vesicular drug delivery systems on oral drug absorption. Nevertheless, the clinical translation of oral vesicular drug delivery systems has been less impressive than implied by the positive results, and few vesicular formulations for oral use have been marketed yet. Against this background, this article provides an overview of the current applications and challenges associated with the vesicular delivery systems available for oral drug delivery, specifically liposomes, niosomes, transfersomes, chitosomes and bilosomes. The composition, formation mechanism, drug delivery advantages and application cases of these carriers in oral drug delivery are summarized. The possible mechanisms by which vesicular carriers enhance oral drug absorption are analyzed in terms of the in vivo process of oral drugs. Further, the challenges that oral vesicular carriers now face, such as safety, undefined in vivo fate, and scale-up production, are summarized, while possible strategies to deal with them are indicated. By reviewing the aforementioned, it can facilitate a more comprehensive knowledge of vesicular systems that can be used for oral drug delivery, providing a theoretical basis and reference for the design of oral formulations.
2024, 35(7): 109133
doi: 10.1016/j.cclet.2023.109133
Abstract:
To overcome the conflict between the long-wavelength excitation and high singlet oxygen quantum yield of photosensitizers, we conjugated a two-photon fluorophore, tetrahydroquinoxaline coumarin (TQ), and an efficient photodynamic therapeutic agent, benzo[a]phenothiazinium (NBS-NH2), through a hexamethylene linker to build a two-photon photosensitizer, TQ-NBS. In TQ-NBS, TQ served as an energy donor and NBS-NH2 acted as an energy acceptor; and TQ-NBS was a Förster resonance energy transfer (FRET) cassette with a 92.8% efficiency. The large two-photon absorption cross-section of TQ allowed photosensitizer TQ-NBS to work in a 900 nm two-photon excitation (TPE) mode, which greatly benefited the deep tissue penetration in PDT treatment. Meanwhile, the excellent phototoxicity and near-infrared fluorescence of NBS-NH2 was kept in TQ-NBS under a TPE mode via a FRET process. Photosensitizer TQ-NBS exhibited a high phototoxic efficacy in living cells and tumor-bearing mice.
To overcome the conflict between the long-wavelength excitation and high singlet oxygen quantum yield of photosensitizers, we conjugated a two-photon fluorophore, tetrahydroquinoxaline coumarin (TQ), and an efficient photodynamic therapeutic agent, benzo[a]phenothiazinium (NBS-NH2), through a hexamethylene linker to build a two-photon photosensitizer, TQ-NBS. In TQ-NBS, TQ served as an energy donor and NBS-NH2 acted as an energy acceptor; and TQ-NBS was a Förster resonance energy transfer (FRET) cassette with a 92.8% efficiency. The large two-photon absorption cross-section of TQ allowed photosensitizer TQ-NBS to work in a 900 nm two-photon excitation (TPE) mode, which greatly benefited the deep tissue penetration in PDT treatment. Meanwhile, the excellent phototoxicity and near-infrared fluorescence of NBS-NH2 was kept in TQ-NBS under a TPE mode via a FRET process. Photosensitizer TQ-NBS exhibited a high phototoxic efficacy in living cells and tumor-bearing mice.
2024, 35(7): 109134
doi: 10.1016/j.cclet.2023.109134
Abstract:
Anticancer platinum prodrugs that can be controllably activated are highly desired for personalized precision medicine and patient compliance in cancer therapy. However, the clinical application of platinum(Ⅳ) prodrugs (Pt(Ⅳ)) is restricted by tissue penetration of external irradiation. Here, we report a novel Pt(Ⅳ) activation strategy based on endogenous luminescence of tumor microenvironment responsiveness, which completely circumvents the limitation of external irradiation. The designed Pt(Ⅳ)Lu, a mixture of trans, trans, trans-[Pt(N3)2(OH)2(py)2] and luminol (Lu), has controllable activation property: it remains inert in reductant environment and normal tissues, but under tumor microenvironment, Lu will be oxidized to produce blue luminescence, which rapidly reduce Pt(Ⅳ) to Pt(Ⅱ) without the need of any external activator. Pt(Ⅳ)Lu shows excellent responsive antitumor ability both in vitro and in vivo. Compared to cisplatin, the median lethal dose in BALB/c mice increased by an order of magnitude. Our results suggest that Pt(Ⅳ)Lu exhibits highly controllable activation property, superior antitumor activity, and good biosafety, which may provide a novel strategy for the design of platinum prodrugs.
Anticancer platinum prodrugs that can be controllably activated are highly desired for personalized precision medicine and patient compliance in cancer therapy. However, the clinical application of platinum(Ⅳ) prodrugs (Pt(Ⅳ)) is restricted by tissue penetration of external irradiation. Here, we report a novel Pt(Ⅳ) activation strategy based on endogenous luminescence of tumor microenvironment responsiveness, which completely circumvents the limitation of external irradiation. The designed Pt(Ⅳ)Lu, a mixture of trans, trans, trans-[Pt(N3)2(OH)2(py)2] and luminol (Lu), has controllable activation property: it remains inert in reductant environment and normal tissues, but under tumor microenvironment, Lu will be oxidized to produce blue luminescence, which rapidly reduce Pt(Ⅳ) to Pt(Ⅱ) without the need of any external activator. Pt(Ⅳ)Lu shows excellent responsive antitumor ability both in vitro and in vivo. Compared to cisplatin, the median lethal dose in BALB/c mice increased by an order of magnitude. Our results suggest that Pt(Ⅳ)Lu exhibits highly controllable activation property, superior antitumor activity, and good biosafety, which may provide a novel strategy for the design of platinum prodrugs.
2024, 35(7): 109136
doi: 10.1016/j.cclet.2023.109136
Abstract:
Due to their superior fluorescence, phosphorescence, and catalytic capabilities, carbon dots (CDs), an emerging class of fluorescent carbon nanomaterials, have a wide range of potential applications. The properties of CDs have recently been controlled extensively by heteroatom doping. Boron atoms have been effectively doped into the structure of CDs due to their similar size to carbon atoms and excellent electron-absorbing ability to further improve the performance of CDs. In this review, we summarize the research progress of boron-doped CDs in recent years from the aspects of doping strategies, effects of boron doping on different performances of CDs and applications. Starting from the two aspects of single boron doping and boron and other atom co-doping, from different precursor materials to different synthesis methods, the doping strategies of boron-doped CDs are reviewed in detail. Then, the effects of boron doping on the fluorescence, phosphorescence and catalytic performance of CDs and applications of boron-doped CDs in optical sensors, information encryption and anti-counterfeiting are discussed. Finally, we further provide a prospect towards the future development of boron-doped CDs.
Due to their superior fluorescence, phosphorescence, and catalytic capabilities, carbon dots (CDs), an emerging class of fluorescent carbon nanomaterials, have a wide range of potential applications. The properties of CDs have recently been controlled extensively by heteroatom doping. Boron atoms have been effectively doped into the structure of CDs due to their similar size to carbon atoms and excellent electron-absorbing ability to further improve the performance of CDs. In this review, we summarize the research progress of boron-doped CDs in recent years from the aspects of doping strategies, effects of boron doping on different performances of CDs and applications. Starting from the two aspects of single boron doping and boron and other atom co-doping, from different precursor materials to different synthesis methods, the doping strategies of boron-doped CDs are reviewed in detail. Then, the effects of boron doping on the fluorescence, phosphorescence and catalytic performance of CDs and applications of boron-doped CDs in optical sensors, information encryption and anti-counterfeiting are discussed. Finally, we further provide a prospect towards the future development of boron-doped CDs.
2024, 35(7): 109139
doi: 10.1016/j.cclet.2023.109139
Abstract:
Diatomic-site catalysts (DASCs) have emerged as a kind of promising heterogeneous candidate catalysts for electrochemical CO2 reduction (ECR), which is considered to retain the advantage of single-atom catalysts (SACs) but also introduce opportunities to exceed the limit of single-atom catalysts. In the past few years, tremendous progress has been achieved in this field. Herein, the recent progress in ECR on DASCs has been summarized. It will start with the classification of DASCs. Then the challenges in the precise fabrication and characterization of DASCs have been emphasized. By introducing the advanced ECR performance on DASCs, superior to that on SACs, the synergistic effects of the dual metal atoms are highlighted, as this origin of the advanced ECR performance on DASCs is comprehensively summarized. Finally, the major challenges and perspectives of DASCs have been proposed to shed light on the development of DASCs for ECR application.
Diatomic-site catalysts (DASCs) have emerged as a kind of promising heterogeneous candidate catalysts for electrochemical CO2 reduction (ECR), which is considered to retain the advantage of single-atom catalysts (SACs) but also introduce opportunities to exceed the limit of single-atom catalysts. In the past few years, tremendous progress has been achieved in this field. Herein, the recent progress in ECR on DASCs has been summarized. It will start with the classification of DASCs. Then the challenges in the precise fabrication and characterization of DASCs have been emphasized. By introducing the advanced ECR performance on DASCs, superior to that on SACs, the synergistic effects of the dual metal atoms are highlighted, as this origin of the advanced ECR performance on DASCs is comprehensively summarized. Finally, the major challenges and perspectives of DASCs have been proposed to shed light on the development of DASCs for ECR application.
2024, 35(7): 109150
doi: 10.1016/j.cclet.2023.109150
Abstract:
Insufficient intratumoral retention of nanomedicines remains the major challenge for broad implementation in clinical sets. Herein, we proposed a legumain-triggered aggregable gold nanoparticle (GNP) delivery platform (GNPs-A&C). GNPs-A&C could form intratumoral or intracellular aggregates in response to the overexpressed legumain. The aggregates with size increase not only could reduce back-flow from interstitial space to peripheral bloodstream but also could restrict the cellular exocytosis, leading to enhanced intratumoral retention. In vitro studies demonstrated that GNPs-A&C possessed an excellent legumain responsiveness and the increased size was closely relevant with legumain expression. In vivo studies demonstrated GNPs-A&C possessed slower clearance rate and much higher intratumoral retention within legumain-overexpressed tumor compared to non-aggregable NPs, regardless of intravenous or intratumoral injection. More importantly, this delivery platform significantly improved the chemotherapeutic effect of doxorubicin (DOX) towards subcutaneous xenograft C6 tumor. The effectiveness of this stimulus-responsive aggregable delivery system provides a thinking for designing more intelligent size-tunable nanomedicine that can substantially improve intratumoral retention.
Insufficient intratumoral retention of nanomedicines remains the major challenge for broad implementation in clinical sets. Herein, we proposed a legumain-triggered aggregable gold nanoparticle (GNP) delivery platform (GNPs-A&C). GNPs-A&C could form intratumoral or intracellular aggregates in response to the overexpressed legumain. The aggregates with size increase not only could reduce back-flow from interstitial space to peripheral bloodstream but also could restrict the cellular exocytosis, leading to enhanced intratumoral retention. In vitro studies demonstrated that GNPs-A&C possessed an excellent legumain responsiveness and the increased size was closely relevant with legumain expression. In vivo studies demonstrated GNPs-A&C possessed slower clearance rate and much higher intratumoral retention within legumain-overexpressed tumor compared to non-aggregable NPs, regardless of intravenous or intratumoral injection. More importantly, this delivery platform significantly improved the chemotherapeutic effect of doxorubicin (DOX) towards subcutaneous xenograft C6 tumor. The effectiveness of this stimulus-responsive aggregable delivery system provides a thinking for designing more intelligent size-tunable nanomedicine that can substantially improve intratumoral retention.
2024, 35(7): 109158
doi: 10.1016/j.cclet.2023.109158
Abstract:
The preparation of hydrogel adsorbents with admirable performance for efficient selective remove Pb(Ⅱ) in complex wastewater still remains a great challenge. Herein, a novel bifunctional modified polymer hydrogel PAM-PAMPS was prepared by crosslinking acrylamide (AM) and 2-acrylamido-2-methylpropanesulfonic acid (AMPS). Compared with PEG, PAA and PAMPS, PAM-PAMPS exhibited both the maximum adsorption capacity of Pb(Ⅱ) (541.90 mg/g) and satisfactory selectivity for Pb(Ⅱ) in multiple heavy metal ions coexistence solutions. Various characterizations indicated that SO3H and NH2 as active sites on PAM-PAMPS occur the synergistic effects of ion-exchange and coordination with Pb(Ⅱ) during the adsorption process, respectively. The adsorption energy Ead(PAM-PAMPS) obtained from density functional theory (DFT) calculations was lower than the other three hydrogels, manifesting that PAM-PAMPS formed the most stable complex with Pb(Ⅱ), which further demonstrated that Pb(Ⅱ) preferred to combine with PAM-PAMPS to selective capture of Pb(Ⅱ). The practice utilization of PAM-PAMPS was assessed by wastewater of electroplate containing Pb(Ⅱ). Meanwhile, the removal ratio of PAM-PAMPS was maintained at about 89% after 4 adsorption-desorption cycles. This study establishes a new and effective idea for the design and fabrication of bifunctionalized modified polymer hydrogels.
The preparation of hydrogel adsorbents with admirable performance for efficient selective remove Pb(Ⅱ) in complex wastewater still remains a great challenge. Herein, a novel bifunctional modified polymer hydrogel PAM-PAMPS was prepared by crosslinking acrylamide (AM) and 2-acrylamido-2-methylpropanesulfonic acid (AMPS). Compared with PEG, PAA and PAMPS, PAM-PAMPS exhibited both the maximum adsorption capacity of Pb(Ⅱ) (541.90 mg/g) and satisfactory selectivity for Pb(Ⅱ) in multiple heavy metal ions coexistence solutions. Various characterizations indicated that SO3H and NH2 as active sites on PAM-PAMPS occur the synergistic effects of ion-exchange and coordination with Pb(Ⅱ) during the adsorption process, respectively. The adsorption energy Ead(PAM-PAMPS) obtained from density functional theory (DFT) calculations was lower than the other three hydrogels, manifesting that PAM-PAMPS formed the most stable complex with Pb(Ⅱ), which further demonstrated that Pb(Ⅱ) preferred to combine with PAM-PAMPS to selective capture of Pb(Ⅱ). The practice utilization of PAM-PAMPS was assessed by wastewater of electroplate containing Pb(Ⅱ). Meanwhile, the removal ratio of PAM-PAMPS was maintained at about 89% after 4 adsorption-desorption cycles. This study establishes a new and effective idea for the design and fabrication of bifunctionalized modified polymer hydrogels.
2024, 35(7): 109165
doi: 10.1016/j.cclet.2023.109165
Abstract:
Tumor microenvironment (TME)-activatable probes have been proven to effectively increase signal-to-background ratios (SBRs) and improve the success rate of complete tumor resection. However, many fluorescence probes have to be loaded into a nanocarrier for tumor targeted delivery, which consequently encounters poor drug loading, heterogeneous composition and non-encapsulated drug aggregates occurred during nanoformulation fabrications. Herein, a nitroreductase (NTR)-activated "OFF-ON" near-infrared fluorescence nanoprobe, named NanoBodipy, was synthesized by the spontaneous self-assembling of NTR-responsive dye-polyethylene glycol (PEG) amphiphilic polymer in water. The NTR-responsive dye acted as the hydrophobic segment in the amphiphilic polymer, yielding a homogeneous composition and a high loading of 12.2 wt% (according to calculation) in the synthesized NanoBodipy. The synthesized NanoBodipy can efficiently accumulate in tumors via the enhanced permeability and retention (EPR) effect, enabling non-invasive tumor-targeted fluorescence imaging and guiding complete tumor resection. Once the synthesized NanoBodipy entered the tumor cells, they dissociated and were activated by overexpressed NTR. With the real-time fluorescence guide of NanoBodipy, complete tumor resection surgery was performed successfully.
Tumor microenvironment (TME)-activatable probes have been proven to effectively increase signal-to-background ratios (SBRs) and improve the success rate of complete tumor resection. However, many fluorescence probes have to be loaded into a nanocarrier for tumor targeted delivery, which consequently encounters poor drug loading, heterogeneous composition and non-encapsulated drug aggregates occurred during nanoformulation fabrications. Herein, a nitroreductase (NTR)-activated "OFF-ON" near-infrared fluorescence nanoprobe, named NanoBodipy, was synthesized by the spontaneous self-assembling of NTR-responsive dye-polyethylene glycol (PEG) amphiphilic polymer in water. The NTR-responsive dye acted as the hydrophobic segment in the amphiphilic polymer, yielding a homogeneous composition and a high loading of 12.2 wt% (according to calculation) in the synthesized NanoBodipy. The synthesized NanoBodipy can efficiently accumulate in tumors via the enhanced permeability and retention (EPR) effect, enabling non-invasive tumor-targeted fluorescence imaging and guiding complete tumor resection. Once the synthesized NanoBodipy entered the tumor cells, they dissociated and were activated by overexpressed NTR. With the real-time fluorescence guide of NanoBodipy, complete tumor resection surgery was performed successfully.
2024, 35(7): 109167
doi: 10.1016/j.cclet.2023.109167
Abstract:
Chemical sensor arrays can obtain more comprehensive analyte information through high-dimensional data. It is of great significance in the analysis of multi-component complex samples. This review summarizes the development and status of chemical sensor arrays. We focused on the design of chemical sensor arrays based on various sensing materials. In addition, several pattern recognition methods in chemometrics are introduced. And applications of chemical sensor arrays in food monitoring, medical diagnosis, and environmental monitoring are illustrated. Based on the analysis of the limitations of current sensor array technology, the direction of the array is also predicted. This review aims to help the broad readership understand the research state of chemical sensor arrays and their development prospects.
Chemical sensor arrays can obtain more comprehensive analyte information through high-dimensional data. It is of great significance in the analysis of multi-component complex samples. This review summarizes the development and status of chemical sensor arrays. We focused on the design of chemical sensor arrays based on various sensing materials. In addition, several pattern recognition methods in chemometrics are introduced. And applications of chemical sensor arrays in food monitoring, medical diagnosis, and environmental monitoring are illustrated. Based on the analysis of the limitations of current sensor array technology, the direction of the array is also predicted. This review aims to help the broad readership understand the research state of chemical sensor arrays and their development prospects.
2024, 35(7): 109169
doi: 10.1016/j.cclet.2023.109169
Abstract:
Biomacromolecules are attractive in biomedical applications as therapeutic agents and potential drug carriers due to their natural active components, good biocompatibility, and high targeting. However, their large relative molecular weight, complex structure, susceptibility to degradation, and poor stability limit their usefulness. Nanotechnology can address these issues by improving the therapeutic value, bioavailability, permeability, and absorption of biomacromolecules while regulating their retention time in the body. Especially, compelling evidence has been reported that supercritical fluid (SCF) technology has emerged as an alternative that maintains the integrity of biomacromolecules and reduces environmental contamination. In this review, we highlight a set of unique nanosizing strategies based on SCF technology for biomacromolecular nanomedicine, and extensively discuss their characteristics and mechanisms. In particular, the protein-based, nucleic acid-based, and polysaccharide-based nanomedicine preparations via SCF technology and their biomedical applications are summarized, and the potential for industrial production of biomacromolecular drugs is also considered. We further provide perspectives on the opportunities and challenges in this excellent field of biomacromolecular drugs nanotechnology.
Biomacromolecules are attractive in biomedical applications as therapeutic agents and potential drug carriers due to their natural active components, good biocompatibility, and high targeting. However, their large relative molecular weight, complex structure, susceptibility to degradation, and poor stability limit their usefulness. Nanotechnology can address these issues by improving the therapeutic value, bioavailability, permeability, and absorption of biomacromolecules while regulating their retention time in the body. Especially, compelling evidence has been reported that supercritical fluid (SCF) technology has emerged as an alternative that maintains the integrity of biomacromolecules and reduces environmental contamination. In this review, we highlight a set of unique nanosizing strategies based on SCF technology for biomacromolecular nanomedicine, and extensively discuss their characteristics and mechanisms. In particular, the protein-based, nucleic acid-based, and polysaccharide-based nanomedicine preparations via SCF technology and their biomedical applications are summarized, and the potential for industrial production of biomacromolecular drugs is also considered. We further provide perspectives on the opportunities and challenges in this excellent field of biomacromolecular drugs nanotechnology.
2024, 35(7): 109171
doi: 10.1016/j.cclet.2023.109171
Abstract:
Photothermal therapy (PTT) and photodynamic therapy (PDT) have received tremendous attention owing to their great potential for tumor treatment. However, two main issues hamper the antitumor performance of PDT: overexpression of glutathione (GSH) in tumors, which consumes PDT-induced reactive oxygen species (ROS), and hypoxia within the tumor microenvironment. The drawbacks of PTT include uneven temperature distribution and the upregulation of the heat-shock proteins in tumors, both of which result in ineffective treatment. To address these issues, a MnO2 doped nano-delivery system (HTIM-PMs) was synthesized by one-step self-assembly of disulfide bond bridged copolymers for indocyanine green (ICG) and MnO2 loading. The surface of polymeric micelles was layered with hyaluronan (HA) and transactivator (TAT) peptides to improve active targeting and increase cell penetration. After internalization, HTIM-PMs showed responsiveness to the tumor microenvironment (acid pH, high glutathione, high H2O2). Breaking the disulfide bond reduced the intratumoral GSH level and simultaneously released the MnO2 and ICG. The released MnO2 further reduced the GSH level and promoted O2 generation, thus enhancing the PDT effect. The PTT-mediated hyperthermia accelerated blood flow, which is beneficial for O2 distribution, and promotes ROS diffusion. These PTT-mediated adjuvant effects further overcame the limitations of PDT and the robust PDT effect in turn compensated for the deficiency of PTT. This promising platform exhibited a significant improvement in the PTT-PDT cancer treatment strategy compared to previously reported nanostructures.
Photothermal therapy (PTT) and photodynamic therapy (PDT) have received tremendous attention owing to their great potential for tumor treatment. However, two main issues hamper the antitumor performance of PDT: overexpression of glutathione (GSH) in tumors, which consumes PDT-induced reactive oxygen species (ROS), and hypoxia within the tumor microenvironment. The drawbacks of PTT include uneven temperature distribution and the upregulation of the heat-shock proteins in tumors, both of which result in ineffective treatment. To address these issues, a MnO2 doped nano-delivery system (HTIM-PMs) was synthesized by one-step self-assembly of disulfide bond bridged copolymers for indocyanine green (ICG) and MnO2 loading. The surface of polymeric micelles was layered with hyaluronan (HA) and transactivator (TAT) peptides to improve active targeting and increase cell penetration. After internalization, HTIM-PMs showed responsiveness to the tumor microenvironment (acid pH, high glutathione, high H2O2). Breaking the disulfide bond reduced the intratumoral GSH level and simultaneously released the MnO2 and ICG. The released MnO2 further reduced the GSH level and promoted O2 generation, thus enhancing the PDT effect. The PTT-mediated hyperthermia accelerated blood flow, which is beneficial for O2 distribution, and promotes ROS diffusion. These PTT-mediated adjuvant effects further overcame the limitations of PDT and the robust PDT effect in turn compensated for the deficiency of PTT. This promising platform exhibited a significant improvement in the PTT-PDT cancer treatment strategy compared to previously reported nanostructures.
2024, 35(7): 109172
doi: 10.1016/j.cclet.2023.109172
Abstract:
The efficient and environmentally friendly recycling technology of waste residue that including abundant heavy metal produced during the recovery of lithium batteries has become a research hotspot. Herein, a novelty process of acid leaching-selective electrodeposition-deep impurity removal-regeneration was proposed to recovery of the CuS slag, which has been efficient transferred to high purity cathode copper and commercially available ternary precursors. Copper cathode with a purity of 99.67% was prepared under electrochemical reaction conditions at −0.55 V for 2 h. A novel impurity remover-Mn powder, which was used to remove the residual impurities and as a feedstock for the ternary precursor. Finally, NCM523 was regenerated by co-precipitation. The process is superior to the traditional process in economy, energy consumption, CO2 emissions, product purity and process duration. This study provides a new approach for solid waste recovery and precious metal enrichment.
The efficient and environmentally friendly recycling technology of waste residue that including abundant heavy metal produced during the recovery of lithium batteries has become a research hotspot. Herein, a novelty process of acid leaching-selective electrodeposition-deep impurity removal-regeneration was proposed to recovery of the CuS slag, which has been efficient transferred to high purity cathode copper and commercially available ternary precursors. Copper cathode with a purity of 99.67% was prepared under electrochemical reaction conditions at −0.55 V for 2 h. A novel impurity remover-Mn powder, which was used to remove the residual impurities and as a feedstock for the ternary precursor. Finally, NCM523 was regenerated by co-precipitation. The process is superior to the traditional process in economy, energy consumption, CO2 emissions, product purity and process duration. This study provides a new approach for solid waste recovery and precious metal enrichment.
2024, 35(7): 109185
doi: 10.1016/j.cclet.2023.109185
Abstract:
To surmount the obstacles of traditional Fenton method and synchronously utilize Cu2+ and polyphenol in water, an improved Fenton-like reaction applying calcium peroxide (CaO2) as H2O2 source and regulating by the complex of Cu2+-tartaric acid (TA, a representative of polyphenol) was constructed. A typical antibiotic, metronidazole (MTZ) could be effectively eliminated by the Cu2+/TA/CaO2 system, and the optimized parameters were as follows: 0.1 mmol/L Cu2+, 2 mmol/L TA, 2 mmol/L CaO2, and initial pH 5. UV spectrum confirmed the formation of Cu2+-TA complex, which promoted the Cu2+/Cu+ circulation through decreasing the Cu2+/Cu+ couple redox potential, which further enhanced the H2O2 decomposition and the formation of reactive species. Hydroxyl radical was dominant for MTZ degradation, followed by oxygen and superoxide radical. The degradation intermediates of MTZ were detected and their evolution way was speculated. Furthermore, the ternary process showed a wide pH tolerance (3–8) for removing MTZ and broad applicability for eliminating other dyes and antibiotics. This work provided a reference for Cu-based Fenton-like strategy for organic wastewater settlement.
To surmount the obstacles of traditional Fenton method and synchronously utilize Cu2+ and polyphenol in water, an improved Fenton-like reaction applying calcium peroxide (CaO2) as H2O2 source and regulating by the complex of Cu2+-tartaric acid (TA, a representative of polyphenol) was constructed. A typical antibiotic, metronidazole (MTZ) could be effectively eliminated by the Cu2+/TA/CaO2 system, and the optimized parameters were as follows: 0.1 mmol/L Cu2+, 2 mmol/L TA, 2 mmol/L CaO2, and initial pH 5. UV spectrum confirmed the formation of Cu2+-TA complex, which promoted the Cu2+/Cu+ circulation through decreasing the Cu2+/Cu+ couple redox potential, which further enhanced the H2O2 decomposition and the formation of reactive species. Hydroxyl radical was dominant for MTZ degradation, followed by oxygen and superoxide radical. The degradation intermediates of MTZ were detected and their evolution way was speculated. Furthermore, the ternary process showed a wide pH tolerance (3–8) for removing MTZ and broad applicability for eliminating other dyes and antibiotics. This work provided a reference for Cu-based Fenton-like strategy for organic wastewater settlement.
2024, 35(7): 109193
doi: 10.1016/j.cclet.2023.109193
Abstract:
TiO2-based films are one of the most attractive photocatalysts owing to their highly cost-effective properties. Nevertheless, most TiO2-based photocatalytic films for dye degradation are in the form of robust films (without flexibility), TiO2 coatings on carbon matrix (with leakage risk), or surface-covered TiO2 hybrids (not favorite to contact with external molecules). Therefore, the development of durable and highly efficient TiO2 photocatalytic films for dye degradation is still needed. Here, we fabricated soft photocatalytic hybrid membranes (TANFs) from TiO2 nanotubes (TiNT) and aramid nanofiber (ANF) by a facile vacuum filtration process. The similar morphology and dimension of TiNT and ANF enable them intricately intertwine with each other in the membrane network. Under an appropriate mixing ratio, the TANF exhibited significantly improved optical and mechanical properties. When used for dye degradation, the membrane showed excellent photocatalytic performance and could keep stable activity and integrated state for repeated usage.
TiO2-based films are one of the most attractive photocatalysts owing to their highly cost-effective properties. Nevertheless, most TiO2-based photocatalytic films for dye degradation are in the form of robust films (without flexibility), TiO2 coatings on carbon matrix (with leakage risk), or surface-covered TiO2 hybrids (not favorite to contact with external molecules). Therefore, the development of durable and highly efficient TiO2 photocatalytic films for dye degradation is still needed. Here, we fabricated soft photocatalytic hybrid membranes (TANFs) from TiO2 nanotubes (TiNT) and aramid nanofiber (ANF) by a facile vacuum filtration process. The similar morphology and dimension of TiNT and ANF enable them intricately intertwine with each other in the membrane network. Under an appropriate mixing ratio, the TANF exhibited significantly improved optical and mechanical properties. When used for dye degradation, the membrane showed excellent photocatalytic performance and could keep stable activity and integrated state for repeated usage.
2024, 35(7): 109195
doi: 10.1016/j.cclet.2023.109195
Abstract:
Sulfidation of zero-valent iron (ZVI) has attracted broad attention in recent years for improving the sequestration of contaminants from water. However, sulfidated ZVI (S-ZVI) is mostly synthesized in the aqueous phase, which usually causes the formation of a thick iron oxide layer on the ZVI surface and hinders the efficient electron transfer to the contaminants. In this study, an alcohothermal strategy was employed for S-ZVI synthesis by the one-step reaction of iron powder with elemental sulfur. It is found that ferrous sulfide (FeS) with high purity and fine crystallization was formed on the ZVI surface, which is extremely favorable for electron transfer. Cr(Ⅵ) removal experiments confirm that the rate constant of S-ZVI synthesized by the alcohothermal method was 267.1- and 5.4-fold higher than those of un-sulfidated ZVI and aqueous-phase synthesized S-ZVI, respectively. Systematic characterizations proved that Cr(Ⅵ) was reduced and co-precipitated on S-ZVI in the form of a Fe(Ⅲ)/Cr(Ⅲ)/Cr(Ⅵ) composite, suggesting its environmental benignancy.
Sulfidation of zero-valent iron (ZVI) has attracted broad attention in recent years for improving the sequestration of contaminants from water. However, sulfidated ZVI (S-ZVI) is mostly synthesized in the aqueous phase, which usually causes the formation of a thick iron oxide layer on the ZVI surface and hinders the efficient electron transfer to the contaminants. In this study, an alcohothermal strategy was employed for S-ZVI synthesis by the one-step reaction of iron powder with elemental sulfur. It is found that ferrous sulfide (FeS) with high purity and fine crystallization was formed on the ZVI surface, which is extremely favorable for electron transfer. Cr(Ⅵ) removal experiments confirm that the rate constant of S-ZVI synthesized by the alcohothermal method was 267.1- and 5.4-fold higher than those of un-sulfidated ZVI and aqueous-phase synthesized S-ZVI, respectively. Systematic characterizations proved that Cr(Ⅵ) was reduced and co-precipitated on S-ZVI in the form of a Fe(Ⅲ)/Cr(Ⅲ)/Cr(Ⅵ) composite, suggesting its environmental benignancy.
2024, 35(7): 109215
doi: 10.1016/j.cclet.2023.109215
Abstract:
Metal-organic frameworks (MOFs) combined with specific ligands are highly adaptable smart materials that can respond to external and physiological stimuli. In this study, we introduced a pyridinyl zwitterionic ligand with light/pH dual response into magnetic MOF composite (Fe3O4@ZW-MOF) for enrichment of phosphorylated peptides for the first time. The introduction of the developed ligand gives MOF material dual response properties. Light stimulation affects the generation/disappearance of free radicals of the pyridine derivative, resulting in a change in the charge gradient of the zwitterion, and zwitterion can also regulate the pH of the solution by adding acid or base. Therefore, the reversible capture and release of phosphorylated peptides can be easily achieved by adjusting light and pH. The established phosphorylated peptide enrichment platform exhibits high sensitivity (detection limit of 1 fmol), high selectivity (β-casein: BSA, 1:1000), and good reusability (7 cycles). In addition, the method was applied to the enrichment of phosphorylated peptides in complex systems (non-fat milk and human serum), demonstrating the feasibility of this method for phosphoproteom analysis. In conclusion, the synthesized Fe3O4@ZW-MOF is a promising MOF material, which provides the possibility to advance the application of responsive MOFs materials in proteomics.
Metal-organic frameworks (MOFs) combined with specific ligands are highly adaptable smart materials that can respond to external and physiological stimuli. In this study, we introduced a pyridinyl zwitterionic ligand with light/pH dual response into magnetic MOF composite (Fe3O4@ZW-MOF) for enrichment of phosphorylated peptides for the first time. The introduction of the developed ligand gives MOF material dual response properties. Light stimulation affects the generation/disappearance of free radicals of the pyridine derivative, resulting in a change in the charge gradient of the zwitterion, and zwitterion can also regulate the pH of the solution by adding acid or base. Therefore, the reversible capture and release of phosphorylated peptides can be easily achieved by adjusting light and pH. The established phosphorylated peptide enrichment platform exhibits high sensitivity (detection limit of 1 fmol), high selectivity (β-casein: BSA, 1:1000), and good reusability (7 cycles). In addition, the method was applied to the enrichment of phosphorylated peptides in complex systems (non-fat milk and human serum), demonstrating the feasibility of this method for phosphoproteom analysis. In conclusion, the synthesized Fe3O4@ZW-MOF is a promising MOF material, which provides the possibility to advance the application of responsive MOFs materials in proteomics.
2024, 35(7): 109218
doi: 10.1016/j.cclet.2023.109218
Abstract:
Aqueous perfluorooctanoic acid (PFOA) elimination has raised significant concerns due to its persistence and bioaccumulation. Although β-PbO2 plate anodes have shown efficient mineralization of PFOA, it remains unclear whether PFOA can be effectively degraded using β-PbO2 reactive electrochemical membrane (REM). Herein, we assessed the performance of Ti/SnO2-Sb/La-PbO2 REM for PFOA removal and proposed a possible degradation mechanism. At a current density of 10 mA/cm2 and a membrane flux of 8500 (liters per square meter per hour, LMH), the degradation efficiency of 10 mg/L PFOA was merely 8.8%, whereas the degradation efficiency of 0.1 mg/L PFOA increased to 96.6%. Although the porous structure of the β-PbO2 REM provided numerous electroactive sites for PFOA, the generated oxygen bubbles in the pores could block the pore channels and adsorb PFOA molecules. These hindered the protonation process and significantly impeded the degradation of high-concentration PFOA. Quenching experiments indicated that •OH played dominant role in PFOA degradation. The electrical energy per order to remove 0.1 mg/L PFOA was merely 0.74 Wh/L, which was almost an order of magnitude lower than that of other anode materials. This study presents fresh opportunities for the electrochemical degradation of low-concentration PFOA using β-PbO2 REM.
Aqueous perfluorooctanoic acid (PFOA) elimination has raised significant concerns due to its persistence and bioaccumulation. Although β-PbO2 plate anodes have shown efficient mineralization of PFOA, it remains unclear whether PFOA can be effectively degraded using β-PbO2 reactive electrochemical membrane (REM). Herein, we assessed the performance of Ti/SnO2-Sb/La-PbO2 REM for PFOA removal and proposed a possible degradation mechanism. At a current density of 10 mA/cm2 and a membrane flux of 8500 (liters per square meter per hour, LMH), the degradation efficiency of 10 mg/L PFOA was merely 8.8%, whereas the degradation efficiency of 0.1 mg/L PFOA increased to 96.6%. Although the porous structure of the β-PbO2 REM provided numerous electroactive sites for PFOA, the generated oxygen bubbles in the pores could block the pore channels and adsorb PFOA molecules. These hindered the protonation process and significantly impeded the degradation of high-concentration PFOA. Quenching experiments indicated that •OH played dominant role in PFOA degradation. The electrical energy per order to remove 0.1 mg/L PFOA was merely 0.74 Wh/L, which was almost an order of magnitude lower than that of other anode materials. This study presents fresh opportunities for the electrochemical degradation of low-concentration PFOA using β-PbO2 REM.
2024, 35(7): 109219
doi: 10.1016/j.cclet.2023.109219
Abstract:
Developing low-loading single-atom catalysts with superior catalytic activity and selectivity in formaldehyde (HCHO) oxidation at room temperature remains challenging. Herein, ZrO2 nanoparticles coupled low-loading Ir single atoms in N-doped carbon (Ir1-N-C/ZrO2) was prepared. The optimal Ir1-N-C/ZrO2 with 0.25 wt% Ir loading delivers the high HCHO removal and conversion efficiency (> 95%) at 20 ℃, which is higher than that over Ir1-N-C with the same Ir loading. The specific rate can reach 1285.6 mmol gIr−1 h−1, surpassing the Ir based catalysts reported to date. Density functional theory calculation results and electron spin resonance spectra indicate that the introduction of ZrO2 nanoparticles modulate the electronic structure of the Ir single atoms, promoting O2 activation to •O2–. Moreover, the Ir-C-Zr channel is favorable for the dissociation of •O2– to active oxygen atom (*O), and further accelerates the transformation of HCHO and intermediates (dioxymethylene and formates) to CO2 and H2O. This work provides a facile strategy to design low-loading single-atom catalysts with high catalytic activity toward HCHO oxidation.
Developing low-loading single-atom catalysts with superior catalytic activity and selectivity in formaldehyde (HCHO) oxidation at room temperature remains challenging. Herein, ZrO2 nanoparticles coupled low-loading Ir single atoms in N-doped carbon (Ir1-N-C/ZrO2) was prepared. The optimal Ir1-N-C/ZrO2 with 0.25 wt% Ir loading delivers the high HCHO removal and conversion efficiency (> 95%) at 20 ℃, which is higher than that over Ir1-N-C with the same Ir loading. The specific rate can reach 1285.6 mmol gIr−1 h−1, surpassing the Ir based catalysts reported to date. Density functional theory calculation results and electron spin resonance spectra indicate that the introduction of ZrO2 nanoparticles modulate the electronic structure of the Ir single atoms, promoting O2 activation to •O2–. Moreover, the Ir-C-Zr channel is favorable for the dissociation of •O2– to active oxygen atom (*O), and further accelerates the transformation of HCHO and intermediates (dioxymethylene and formates) to CO2 and H2O. This work provides a facile strategy to design low-loading single-atom catalysts with high catalytic activity toward HCHO oxidation.
2024, 35(7): 109220
doi: 10.1016/j.cclet.2023.109220
Abstract:
In recent years, the application of smartphone in various fields has received great attention, and it has become a promising tool in virus detection, data processing and data exchange. During the rapid spread of COVID-19 around the world, many traditional detection methods have been combined with smartphone to assist in the analysis and detection of the novel coronavirus (SARS-CoV-2), including electrochemistry, fluorescence and colorimetry. With the gradual development of artificial intelligence (AI), the combination of AI and smartphone to analyze SARS-CoV-2 was also the focus of research. Based on the summary of the traditional methods combined with smartphone to detect SARS-CoV-2 virus, in addition to AI-based data processing, AI algorithms are also employed for SARS-CoV-2 detection itself. This review discussed both strategies and focused on the application of the former. The combination of AI algorithm and smartphone to detect SARS-CoV-2 has high accuracy, which is more conducive to meeting the needs of portable detection. In addition, the classification of SARS-CoV-2 virus samples in biological fluids such as blood and saliva was also discussed. Finally, this paper briefly discussed the limitations of using smartphone analysis to detect SARS-CoV-2, as well as the prospect and future development of virus detection. In conclusion, the detection methods based on smartphone and AI algorithms show great potential in the detection of SARS-CoV-2 and can be a valuable complement to traditional analysis methods.
In recent years, the application of smartphone in various fields has received great attention, and it has become a promising tool in virus detection, data processing and data exchange. During the rapid spread of COVID-19 around the world, many traditional detection methods have been combined with smartphone to assist in the analysis and detection of the novel coronavirus (SARS-CoV-2), including electrochemistry, fluorescence and colorimetry. With the gradual development of artificial intelligence (AI), the combination of AI and smartphone to analyze SARS-CoV-2 was also the focus of research. Based on the summary of the traditional methods combined with smartphone to detect SARS-CoV-2 virus, in addition to AI-based data processing, AI algorithms are also employed for SARS-CoV-2 detection itself. This review discussed both strategies and focused on the application of the former. The combination of AI algorithm and smartphone to detect SARS-CoV-2 has high accuracy, which is more conducive to meeting the needs of portable detection. In addition, the classification of SARS-CoV-2 virus samples in biological fluids such as blood and saliva was also discussed. Finally, this paper briefly discussed the limitations of using smartphone analysis to detect SARS-CoV-2, as well as the prospect and future development of virus detection. In conclusion, the detection methods based on smartphone and AI algorithms show great potential in the detection of SARS-CoV-2 and can be a valuable complement to traditional analysis methods.
2024, 35(7): 109221
doi: 10.1016/j.cclet.2023.109221
Abstract:
Cobalt-based phosphides show excellent hydrogen evolution reaction (HER) performance, however, improving the intrinsic activity and stability of it in alkaline electrolyte still remains a challenge. Herein, CoRuOH/Co2P/CF with heterojunction structure was developed by means of molten salt and rapid hydrolysis (30 s). The OH− from rapid surface hydrolysis of Co2P as a hydrogen adsorption site can facilitate the formation of thin CoRuOH layer as a water dissociation site, which may bring out better synergistic effect for alkaline HER. Moreover, the covering of CoRuOH can improve the stability of Co2P for HER. When drives at 100 mA/cm2, it only requires overpotential of 81 mV in 1.0 mol/L KOH (25 ℃). Even at higher current density (1000 mA/cm2), CoRuOH/Co2P/CF can also operate stability for at least 100 h. When coupling with NiFe-LDH/IF in a two-electrode system, the voltage of NiFe-LDH/IF(+) || CoRuOH/Co2P/CF(−) at 1000 mA/cm2 is merely 1.77 V with 100 h, demonstrating great potential for water splitting. The implementation of this work provides a new strategy and reference for the further improvement of transition metal phosphides as HER electrocatalysts.
Cobalt-based phosphides show excellent hydrogen evolution reaction (HER) performance, however, improving the intrinsic activity and stability of it in alkaline electrolyte still remains a challenge. Herein, CoRuOH/Co2P/CF with heterojunction structure was developed by means of molten salt and rapid hydrolysis (30 s). The OH− from rapid surface hydrolysis of Co2P as a hydrogen adsorption site can facilitate the formation of thin CoRuOH layer as a water dissociation site, which may bring out better synergistic effect for alkaline HER. Moreover, the covering of CoRuOH can improve the stability of Co2P for HER. When drives at 100 mA/cm2, it only requires overpotential of 81 mV in 1.0 mol/L KOH (25 ℃). Even at higher current density (1000 mA/cm2), CoRuOH/Co2P/CF can also operate stability for at least 100 h. When coupling with NiFe-LDH/IF in a two-electrode system, the voltage of NiFe-LDH/IF(+) || CoRuOH/Co2P/CF(−) at 1000 mA/cm2 is merely 1.77 V with 100 h, demonstrating great potential for water splitting. The implementation of this work provides a new strategy and reference for the further improvement of transition metal phosphides as HER electrocatalysts.
2024, 35(7): 109232
doi: 10.1016/j.cclet.2023.109232
Abstract:
Dynamic DNA nanotechnology plays a significant role in nanomedicine and information science due to its high programmability based on Watson-Crick base pairing and nanoscale dimensions. Intelligent DNA machines and networks have been widely used in various fields, including molecular imaging, biosensors, drug delivery, information processing, and logic operations. Encoders serve as crucial components for information compilation and transfer, allowing the conversion of information from diverse application scenarios into a format recognized and applied by DNA circuits. However, there are only a few encoder designs with DNA outputs. Moreover, the molecular priority encoder is hardly designed. In this study, we introduce allosteric DNAzyme-based encoders for information transfer. The design of the allosteric domain and the recognition arm allows the input and output to be independent of each other and freely programmable. The pre-packaged mode design achieves uniformity of baseline dynamics and dynamics controllability. We also integrated non-nucleic acid molecules into the encoder through the aptamer design of the allosteric domain. Furthermore, we developed the 2-n encoder and the Endo Ⅳ-assisted priority encoder inspired by immunoglobulin's molecular structure and effector patterns. To our knowledge, the proposed encoder is the first enzyme-free DNA encoder with DNA output, and the priority encoder is the first molecular priority encoder in the DNA reaction network. Our encoders avoid complex operations on a single molecule, and their simple structure facilitates their application in complex DNA circuits and biological scenarios.
Dynamic DNA nanotechnology plays a significant role in nanomedicine and information science due to its high programmability based on Watson-Crick base pairing and nanoscale dimensions. Intelligent DNA machines and networks have been widely used in various fields, including molecular imaging, biosensors, drug delivery, information processing, and logic operations. Encoders serve as crucial components for information compilation and transfer, allowing the conversion of information from diverse application scenarios into a format recognized and applied by DNA circuits. However, there are only a few encoder designs with DNA outputs. Moreover, the molecular priority encoder is hardly designed. In this study, we introduce allosteric DNAzyme-based encoders for information transfer. The design of the allosteric domain and the recognition arm allows the input and output to be independent of each other and freely programmable. The pre-packaged mode design achieves uniformity of baseline dynamics and dynamics controllability. We also integrated non-nucleic acid molecules into the encoder through the aptamer design of the allosteric domain. Furthermore, we developed the 2-n encoder and the Endo Ⅳ-assisted priority encoder inspired by immunoglobulin's molecular structure and effector patterns. To our knowledge, the proposed encoder is the first enzyme-free DNA encoder with DNA output, and the priority encoder is the first molecular priority encoder in the DNA reaction network. Our encoders avoid complex operations on a single molecule, and their simple structure facilitates their application in complex DNA circuits and biological scenarios.
2024, 35(7): 109236
doi: 10.1016/j.cclet.2023.109236
Abstract:
Pyrite-type sulfides (PTS) exhibit promising intrinsic activities for oxygen reduction and evolution reactions (ORR/OER). However, their poor electrical conductivities may limit the charge transfer rate to inevitably lower activity. Here, yolk-shell structured cobalt-pyrite nanospheres (CoS2 YSS) are prepared and modified with amino groups as nucleation sites for coupling highly-conductive needle-like nitrogen-doped carbon via a facile solvothermal method (CoS2 YSS@NC). The as-marked CoS2 YSS@NC-0.5 shows a gap between yolk and shell, and an obvious exterior layer of grafted NC, which can provide an integrated structure, an interior place, and three exposed surfaces on CoS2. CoS2 YSS@NC-0.5 reveals higher ORR activity (half-wave potential of 0.88 V) and methanol resistance than commercial Pt/C. Due to in-situ formation of highly-active CoOOH, CoS2 YSS@NC-0.5 shows a better overpotential (244 mV at 10 mA/cm2) and Tafel slope (135 mV/dec) than RuO2. Zinc-air battery with CoS2 YSS@NC-0.5 air-cathode exhibits good open circuit potential (1.44 V), specific capacity (772.5 mAh/g) and cycling stability. Needle-like NC layer coated on the yolk-shell structure of CoS2 effectively lowers the charge transfer resistance to obtain extraordinary ORR/OER activities. It indicates that the integration of highly-conductive carbon onto pyrite-type sulfides is an effective strategy to acquire durable bifunctional ORR/OER catalysts.
Pyrite-type sulfides (PTS) exhibit promising intrinsic activities for oxygen reduction and evolution reactions (ORR/OER). However, their poor electrical conductivities may limit the charge transfer rate to inevitably lower activity. Here, yolk-shell structured cobalt-pyrite nanospheres (CoS2 YSS) are prepared and modified with amino groups as nucleation sites for coupling highly-conductive needle-like nitrogen-doped carbon via a facile solvothermal method (CoS2 YSS@NC). The as-marked CoS2 YSS@NC-0.5 shows a gap between yolk and shell, and an obvious exterior layer of grafted NC, which can provide an integrated structure, an interior place, and three exposed surfaces on CoS2. CoS2 YSS@NC-0.5 reveals higher ORR activity (half-wave potential of 0.88 V) and methanol resistance than commercial Pt/C. Due to in-situ formation of highly-active CoOOH, CoS2 YSS@NC-0.5 shows a better overpotential (244 mV at 10 mA/cm2) and Tafel slope (135 mV/dec) than RuO2. Zinc-air battery with CoS2 YSS@NC-0.5 air-cathode exhibits good open circuit potential (1.44 V), specific capacity (772.5 mAh/g) and cycling stability. Needle-like NC layer coated on the yolk-shell structure of CoS2 effectively lowers the charge transfer resistance to obtain extraordinary ORR/OER activities. It indicates that the integration of highly-conductive carbon onto pyrite-type sulfides is an effective strategy to acquire durable bifunctional ORR/OER catalysts.
2024, 35(7): 109238
doi: 10.1016/j.cclet.2023.109238
Abstract:
Herein, we unveil the intelligent detection of multiple catechol isomers in complex environments utilizing both laser-induced graphene (LIG) and artificial neural network (ANN). The large scale-up manufacturing of LIG-based sensors (LIGS) with three-electrode configuration on polyimide (PI) is achieved by direct laser-writing and screen-printing technologies. Our LIGS shows excellent electrochemical performance toward catechol isomers, i.e., hydroquinone (1, 4-dihydroxybenzene, HQ), catechol (1, 2-dihydroxybenzene, CT), and resorcinol (1, 3-dihydroxybenzene, RC), with a low limit of detection (LOD) (CC, 0.079 µmol/L; HQ, 0.093 µmol/L; RC, 1.18 µmol/L). Moreover, the ANN model is developed for machine-intelligent to predict concentrations of catechol isomers under an interfering environment via a single LIGS. Using six unique parameters extracted from the differential pulse voltammetry (DPV) response, the machine learning-based regression provides a coefficient of correlation with 0.998 and is able to correctly predict the total and individual concentrations in complex river samples. Hence, this work provides a guide for the preparation and application of LIGS via facile and cost-efficient mass production and the development of an intelligent sensing platform based on the ANN model.
Herein, we unveil the intelligent detection of multiple catechol isomers in complex environments utilizing both laser-induced graphene (LIG) and artificial neural network (ANN). The large scale-up manufacturing of LIG-based sensors (LIGS) with three-electrode configuration on polyimide (PI) is achieved by direct laser-writing and screen-printing technologies. Our LIGS shows excellent electrochemical performance toward catechol isomers, i.e., hydroquinone (1, 4-dihydroxybenzene, HQ), catechol (1, 2-dihydroxybenzene, CT), and resorcinol (1, 3-dihydroxybenzene, RC), with a low limit of detection (LOD) (CC, 0.079 µmol/L; HQ, 0.093 µmol/L; RC, 1.18 µmol/L). Moreover, the ANN model is developed for machine-intelligent to predict concentrations of catechol isomers under an interfering environment via a single LIGS. Using six unique parameters extracted from the differential pulse voltammetry (DPV) response, the machine learning-based regression provides a coefficient of correlation with 0.998 and is able to correctly predict the total and individual concentrations in complex river samples. Hence, this work provides a guide for the preparation and application of LIGS via facile and cost-efficient mass production and the development of an intelligent sensing platform based on the ANN model.
2024, 35(7): 109245
doi: 10.1016/j.cclet.2023.109245
Abstract:
The utilization of an efficient photocatalyst is crucial for the photocatalytic degradation of antibiotics in water through visible light, which is an imperative requirement for the remediation of water environments. In this study, a novel Cu-CeO2/BiOBr Z-type heterojunction was synthesized by calcination and hydrothermal methods, and the degradation rate of sulfathiazole (STZ) antibiotic solution was studied using simulated illumination (300 W xenon lamp). The results indicated that 3% Cu-CeO2/BiOBr achieved a degradation rate of 92.3% within 90 min when treating 20 mg/L STZ solution, demonstrating its potential for practical water treatment applications. Characterization using various chemical instruments revealed that 3% Cu-CeO2/BiOBr exhibited the lowest electron-hole recombination rate and electron transfer resistance. Furthermore, the utilization of ESR data and quenching experiments has substantiated the involvement of hydroxyl radicals (•OH) and superoxide radicals (•O2−) as the primary active species. Consequently, a plausible degradation mechanism has been inferred. These findings offer a prospective approach for the development of heterojunction materials with appropriate band matching.
The utilization of an efficient photocatalyst is crucial for the photocatalytic degradation of antibiotics in water through visible light, which is an imperative requirement for the remediation of water environments. In this study, a novel Cu-CeO2/BiOBr Z-type heterojunction was synthesized by calcination and hydrothermal methods, and the degradation rate of sulfathiazole (STZ) antibiotic solution was studied using simulated illumination (300 W xenon lamp). The results indicated that 3% Cu-CeO2/BiOBr achieved a degradation rate of 92.3% within 90 min when treating 20 mg/L STZ solution, demonstrating its potential for practical water treatment applications. Characterization using various chemical instruments revealed that 3% Cu-CeO2/BiOBr exhibited the lowest electron-hole recombination rate and electron transfer resistance. Furthermore, the utilization of ESR data and quenching experiments has substantiated the involvement of hydroxyl radicals (•OH) and superoxide radicals (•O2−) as the primary active species. Consequently, a plausible degradation mechanism has been inferred. These findings offer a prospective approach for the development of heterojunction materials with appropriate band matching.
2024, 35(7): 109247
doi: 10.1016/j.cclet.2023.109247
Abstract:
Described here is a divergent, biosynthetically inspired synthesis of cochlearol B and ganocin A. Key steps of the synthesis include the chromene unit construction through a biomimetic acid-catalyzed [4 + 2] ring cyclization. A photochemical [2 + 2] cycloaddition was featured to construct the cyclobutane core of cochlearol B. Different skeletal rearrangements of cochlearol B afforded ganocin A, that one of them was Lewis acid mediated epoxide rearrangement and another was DDQ induced cyclobutane formed tetrahydrofuran ring. The described syntheses not only achieved these natural products in an efficient manner, but also provided insight into the biosynthetic relationship between the two different skeletons.
Described here is a divergent, biosynthetically inspired synthesis of cochlearol B and ganocin A. Key steps of the synthesis include the chromene unit construction through a biomimetic acid-catalyzed [4 + 2] ring cyclization. A photochemical [2 + 2] cycloaddition was featured to construct the cyclobutane core of cochlearol B. Different skeletal rearrangements of cochlearol B afforded ganocin A, that one of them was Lewis acid mediated epoxide rearrangement and another was DDQ induced cyclobutane formed tetrahydrofuran ring. The described syntheses not only achieved these natural products in an efficient manner, but also provided insight into the biosynthetic relationship between the two different skeletons.
2024, 35(7): 109256
doi: 10.1016/j.cclet.2023.109256
Abstract:
Here, we designed asymmetric (mDS) and symmetrical (dDS) chiral V-shaped molecules by linking one or two dansyl groups to trans-1,2-cyclohexane diamine and investigated the solvent-regulated structural transformation and inversed circularly polarized luminescence (CPL) in the self-assemblies. Upon increasing water volume fraction (fw) in the mixed solvent of water/acetonitrile, asymmetric mDS selfassembled into hollow nanospheres and microtubes, while solid nanospheres and solid microplates were corresponding to symmetric dDS. During this transformation process, the emission of mDS and dDS was changed from yellow-green to blue and cyan color, which was ascribed to twisted intramolecular charge transfer (TICT) and locally excited (LE) fluorescence of V-shaped DS molecules. The conformation of N,N-dimethyl groups with respect to naphthalene ring also led to the transformation of structures. These tubular and platelike structures had stronger and reversed CPL signals in comparison with spheroidal structures. The chiral information of DS assembly could be effective transferred to achiral Nile red via co-assembly strategy, which endowed Nile red exhibiting inversed induced CPL signal regulated by water fraction. This work provides a method for achieving a variety of self-assembled structures with adjustable chiroptical properties.
Here, we designed asymmetric (mDS) and symmetrical (dDS) chiral V-shaped molecules by linking one or two dansyl groups to trans-1,2-cyclohexane diamine and investigated the solvent-regulated structural transformation and inversed circularly polarized luminescence (CPL) in the self-assemblies. Upon increasing water volume fraction (fw) in the mixed solvent of water/acetonitrile, asymmetric mDS selfassembled into hollow nanospheres and microtubes, while solid nanospheres and solid microplates were corresponding to symmetric dDS. During this transformation process, the emission of mDS and dDS was changed from yellow-green to blue and cyan color, which was ascribed to twisted intramolecular charge transfer (TICT) and locally excited (LE) fluorescence of V-shaped DS molecules. The conformation of N,N-dimethyl groups with respect to naphthalene ring also led to the transformation of structures. These tubular and platelike structures had stronger and reversed CPL signals in comparison with spheroidal structures. The chiral information of DS assembly could be effective transferred to achiral Nile red via co-assembly strategy, which endowed Nile red exhibiting inversed induced CPL signal regulated by water fraction. This work provides a method for achieving a variety of self-assembled structures with adjustable chiroptical properties.
2024, 35(7): 109280
doi: 10.1016/j.cclet.2023.109280
Abstract:
A highly efficient and concise bromocyclization has been successfully achieved, in which tryptamine/tryptophol derivates can be transformed to valuable HPI/TFI scaffolds with economic and green manners. Moreover, a controllable cascade transformation of bromocyclization and aromatic bromination has also been smoothly achieved to form dibrominated HPIs and TFIs. Production could be successfully scaled up under both the batch process and a continuous flow fashion. The most remarkable peculiarity of our process over all previous methods is that the generated water is the major waste. Notably, successful application of this new protocol has been demonstrated by the pharmaceutical and natural products syntheses.
A highly efficient and concise bromocyclization has been successfully achieved, in which tryptamine/tryptophol derivates can be transformed to valuable HPI/TFI scaffolds with economic and green manners. Moreover, a controllable cascade transformation of bromocyclization and aromatic bromination has also been smoothly achieved to form dibrominated HPIs and TFIs. Production could be successfully scaled up under both the batch process and a continuous flow fashion. The most remarkable peculiarity of our process over all previous methods is that the generated water is the major waste. Notably, successful application of this new protocol has been demonstrated by the pharmaceutical and natural products syntheses.
2024, 35(7): 109281
doi: 10.1016/j.cclet.2023.109281
Abstract:
Improving the highly selective and sensitive binding of chemosensor to target guest is always very challenging. In order to solve this issue, herein, the enrichment effect was introduced into the design of chemosensor molecule. A novel bi-fused-macrocyclic host molecule BPN1 was synthesized by bridging a pillar[5]arene and a naphthalene diimide (NDI) group through hydrogen-bond-rich chain. In the BPN1, the naphthalimide side ring is outside the cavity of the pillar[5]arene. In addition, Cr(Ⅵ) greatly threat human health and the environment due to its severe toxicity, and it is very important to develop effective chemosensor for sensitive and selective detection of Cr2O72− or its ion pairs. In this paper, the novel bi-fused-macrocyclic host molecule BPN1 can recognize Cr2O72− with high selectivity and sensitivity. The mechanism of BPN1 recognition of Cr2O72− was studied through experiments and density functional theory (DFT), the results show that BPN1 could supply enrichment effect to bind Cr2O72− through multiple weak interactions such as hydrogen bonds and anion-π, and achieve highly sensitive and selective detection of Cr2O72−. It is a significant and feasible strategy for improve high selectivity and sensitivity of host to specific objects by using the enrichment effect of fused bi-macrocyclic.
Improving the highly selective and sensitive binding of chemosensor to target guest is always very challenging. In order to solve this issue, herein, the enrichment effect was introduced into the design of chemosensor molecule. A novel bi-fused-macrocyclic host molecule BPN1 was synthesized by bridging a pillar[5]arene and a naphthalene diimide (NDI) group through hydrogen-bond-rich chain. In the BPN1, the naphthalimide side ring is outside the cavity of the pillar[5]arene. In addition, Cr(Ⅵ) greatly threat human health and the environment due to its severe toxicity, and it is very important to develop effective chemosensor for sensitive and selective detection of Cr2O72− or its ion pairs. In this paper, the novel bi-fused-macrocyclic host molecule BPN1 can recognize Cr2O72− with high selectivity and sensitivity. The mechanism of BPN1 recognition of Cr2O72− was studied through experiments and density functional theory (DFT), the results show that BPN1 could supply enrichment effect to bind Cr2O72− through multiple weak interactions such as hydrogen bonds and anion-π, and achieve highly sensitive and selective detection of Cr2O72−. It is a significant and feasible strategy for improve high selectivity and sensitivity of host to specific objects by using the enrichment effect of fused bi-macrocyclic.
2024, 35(7): 109283
doi: 10.1016/j.cclet.2023.109283
Abstract:
Transition-metal-catalyzed cross-electrophile coupling has emerged as a reliable method for constructing carbon–carbon bonds. Herein, we report a general method, cobalt-catalyzed reductive alkynylation, to construct C(sp)-C(sp3) and C(sp)-C(sp2) bonds. This presented reaction has a broad substrate scope, enabling the efficient cross-electrophile coupling between alkynyl bromides with alkyl halides and aryl or alkenyl (pseudo)halides. This presented reaction is conducted under mild conditions, tolerating many functional groups, thus suitable for the modification and synthesis of biologically active molecules.
Transition-metal-catalyzed cross-electrophile coupling has emerged as a reliable method for constructing carbon–carbon bonds. Herein, we report a general method, cobalt-catalyzed reductive alkynylation, to construct C(sp)-C(sp3) and C(sp)-C(sp2) bonds. This presented reaction has a broad substrate scope, enabling the efficient cross-electrophile coupling between alkynyl bromides with alkyl halides and aryl or alkenyl (pseudo)halides. This presented reaction is conducted under mild conditions, tolerating many functional groups, thus suitable for the modification and synthesis of biologically active molecules.
2024, 35(7): 109284
doi: 10.1016/j.cclet.2023.109284
Abstract:
Anode free lithium metal batteries (AF-LMBs) have conspicuous advantages both in energy density and the compatibility of battery manufacturing process. However, the limited cycle life of AF-LMBs is a crucial factor hindering its practical application. Fluorinated or nitride artificial inorganic solid electrolyte interphase (SEI) has been found as an effective method to prolong the lifespan of AF-LMBs. Herein, by investigating the impact of nano-sized inorganic gradient layers (LiF or Li3N) on initial Li deposition behavior, we notice that the Li+ diffusion barrier and the deposition morphology are highly depended on the thickness of inorganic layers. Thicker protective layers cause larger overpotential as well as more aggregated Li+ distribution. This study reveals that the ideal SEI should be synthesized thin and uniformly enough and uncontrollable artificial SEI can cause damage to the lifespan of AF-LMBs.
Anode free lithium metal batteries (AF-LMBs) have conspicuous advantages both in energy density and the compatibility of battery manufacturing process. However, the limited cycle life of AF-LMBs is a crucial factor hindering its practical application. Fluorinated or nitride artificial inorganic solid electrolyte interphase (SEI) has been found as an effective method to prolong the lifespan of AF-LMBs. Herein, by investigating the impact of nano-sized inorganic gradient layers (LiF or Li3N) on initial Li deposition behavior, we notice that the Li+ diffusion barrier and the deposition morphology are highly depended on the thickness of inorganic layers. Thicker protective layers cause larger overpotential as well as more aggregated Li+ distribution. This study reveals that the ideal SEI should be synthesized thin and uniformly enough and uncontrollable artificial SEI can cause damage to the lifespan of AF-LMBs.
2024, 35(7): 109292
doi: 10.1016/j.cclet.2023.109292
Abstract:
A nonsymmetrical PNN pincer ligand [6-(Bu2PNH)C5H4N-2-(3-Mes)C3H2N2] and its corresponding cobalt-N2 complex were synthesized and characterized. By the stoichiometric reaction of the PNN ligand lithium salt with CoCl2, the complex 3, (PNN)CoCl, was obtained. Then, reduction of 3 with NaBHEt3 under a dinitrogen atmosphere yielded complex 5, (PNN)Co(Ⅰ)(η1-N2). Single-crystal X-ray analysis, IR spectrum, and DFT calculations revealed that the dinitrogen in 5 was only weakly reduced by the cobalt center. The reactions of 5 with carbon monoxide and 2, 6-dimethylphenyl isocyanide gave carbonyl and isocyanide complexes 6 and 7 with the release of N2, respectively. Furthermore, these cobalt complexes, especially complex 5, demonstrated the capacity to convert dinitrogen to N(TMS)3 with moderate efficiency.
A nonsymmetrical PNN pincer ligand [6-(Bu2PNH)C5H4N-2-(3-Mes)C3H2N2] and its corresponding cobalt-N2 complex were synthesized and characterized. By the stoichiometric reaction of the PNN ligand lithium salt with CoCl2, the complex 3, (PNN)CoCl, was obtained. Then, reduction of 3 with NaBHEt3 under a dinitrogen atmosphere yielded complex 5, (PNN)Co(Ⅰ)(η1-N2). Single-crystal X-ray analysis, IR spectrum, and DFT calculations revealed that the dinitrogen in 5 was only weakly reduced by the cobalt center. The reactions of 5 with carbon monoxide and 2, 6-dimethylphenyl isocyanide gave carbonyl and isocyanide complexes 6 and 7 with the release of N2, respectively. Furthermore, these cobalt complexes, especially complex 5, demonstrated the capacity to convert dinitrogen to N(TMS)3 with moderate efficiency.
2024, 35(7): 109294
doi: 10.1016/j.cclet.2023.109294
Abstract:
A copper(Ⅰ)-catalyzed diastereodivergent addition of phosphinothioates (HP(S)ROR') to α, β-unsaturated thioamides is disclosed, which constructs vicinal P-chiral and C-chiral centers in generally high diastereo- and enantioselectivities. In this reaction, the kinetic resolution of HP(S)ROR' occurs, which affords (R)-HP(S)PhOMe in high enantioselectivity in the addition with (R, R)-Ph-BPE as the ligand. It is found through control experiment that dual "soft-soft" interaction, indicated by both 1H and 31P NMR experiments, is indispensable in the present reaction. The first "soft-soft" interaction between copper(Ⅰ) catalyst and HP(S)ROR' enables facile deprotonation to generate nucleophilic [Cu]-SPROR' species. The second one between the [Cu]-SPROR' species and α, β-unsaturated thioamides facilitated the nucleophilic addition. Finally, both Michael adducts and (R)-HP(S)PhOMe are easily converted to synthetically useful compounds.
A copper(Ⅰ)-catalyzed diastereodivergent addition of phosphinothioates (HP(S)ROR') to α, β-unsaturated thioamides is disclosed, which constructs vicinal P-chiral and C-chiral centers in generally high diastereo- and enantioselectivities. In this reaction, the kinetic resolution of HP(S)ROR' occurs, which affords (R)-HP(S)PhOMe in high enantioselectivity in the addition with (R, R)-Ph-BPE as the ligand. It is found through control experiment that dual "soft-soft" interaction, indicated by both 1H and 31P NMR experiments, is indispensable in the present reaction. The first "soft-soft" interaction between copper(Ⅰ) catalyst and HP(S)ROR' enables facile deprotonation to generate nucleophilic [Cu]-SPROR' species. The second one between the [Cu]-SPROR' species and α, β-unsaturated thioamides facilitated the nucleophilic addition. Finally, both Michael adducts and (R)-HP(S)PhOMe are easily converted to synthetically useful compounds.
2024, 35(7): 109322
doi: 10.1016/j.cclet.2023.109322
Abstract:
The conjugate addition of in-situ generated (aza-)quinone methides (QMs) and indole imine methides (IIMs) emerged as a powerful protocol to access densely functionalized benzenes and indoles. Hydroxybenzyl alcohols, aminobenzhydryl alcohols, and varied indolylmethanols served as most effective precursors for the in-situ generation of such reactive species under acid conditions. The relevant propargylic alcohol has proven to be an elegant precursor to generate the propargylic-QMs and -IIMs via the acid promoted dehydration process, thus enabling diverse challenging remote activation to proceed conjugate 1,6- and 1,8-additions. Moreover, the heteroarene has proven to be workable to transfer the LUMO of the p-QMs and 2-IIMs, thus inducing the remote nucleophilic dearomative additions. The conjugate additions of (aza-)p-QMs and varied IIMs has made significant contribution in the field of remote activation chemistry in past decade. This review summarizes the latest advances of the remote conjugate additions of the in-situ generated QMs and IIMs.
The conjugate addition of in-situ generated (aza-)quinone methides (QMs) and indole imine methides (IIMs) emerged as a powerful protocol to access densely functionalized benzenes and indoles. Hydroxybenzyl alcohols, aminobenzhydryl alcohols, and varied indolylmethanols served as most effective precursors for the in-situ generation of such reactive species under acid conditions. The relevant propargylic alcohol has proven to be an elegant precursor to generate the propargylic-QMs and -IIMs via the acid promoted dehydration process, thus enabling diverse challenging remote activation to proceed conjugate 1,6- and 1,8-additions. Moreover, the heteroarene has proven to be workable to transfer the LUMO of the p-QMs and 2-IIMs, thus inducing the remote nucleophilic dearomative additions. The conjugate additions of (aza-)p-QMs and varied IIMs has made significant contribution in the field of remote activation chemistry in past decade. This review summarizes the latest advances of the remote conjugate additions of the in-situ generated QMs and IIMs.
2024, 35(7): 109323
doi: 10.1016/j.cclet.2023.109323
Abstract:
Herein, we report the NHC-Ru catalyst system that realizes the chemo-selective transformation of ketones with methanol. By simply changing the base, a broad range of structurally diverse ketones, could be selectively and efficiently converted to the corresponding β-methylated secondary alcohols or secondary alcohols. Remarkably, this catalytic system was very effective for the synthesis of bio-related molecules and deuterated alcohols, as well as the three-component coupling between methyl ketones, primary alcohols, and methanol. The reaction mechanism was further revealed by experiment and DFT mechanistic investigations.
Herein, we report the NHC-Ru catalyst system that realizes the chemo-selective transformation of ketones with methanol. By simply changing the base, a broad range of structurally diverse ketones, could be selectively and efficiently converted to the corresponding β-methylated secondary alcohols or secondary alcohols. Remarkably, this catalytic system was very effective for the synthesis of bio-related molecules and deuterated alcohols, as well as the three-component coupling between methyl ketones, primary alcohols, and methanol. The reaction mechanism was further revealed by experiment and DFT mechanistic investigations.
2024, 35(7): 109328
doi: 10.1016/j.cclet.2023.109328
Abstract:
Chemodynamic therapy (CDT) combined with dual phototherapy (photothermal therapy (PTT) and photodynamic therapy (PDT)) is an efficient way to synergistically improve anti-tumor efficacy. However, the combination of multiple modes often makes the composition of the system more complex, which is not conducive to clinical application. In this study, a dual phototherapy ligand carboxyl-modified Aza-BODIPY (BOD-COOH) and metal active center Cu2+ were used to construct multiple-modes metal-photosensitizer nanoparticles (BOD-Cu NPs) via one-step coordination self-assembly for combination therapy of CDT/PDT/PTT. In order to improve delivery efficiency, the targeted hydrophilic molecule pyridine-modified glucose derivative (G-Py) was synthesized and coated onto the BOD-Cu NPs to form a glycosylated nano metal-photosensitizer BOD-Cu@G by electrostatic interaction. The Cu2+ in BOD-Cu@G could not only be used as a coordination node for metal-driven self-assembly but also consume intracellular glutathione (GSH), and then catalyze Fenton-like reaction to generate hydroxyl radical (·OH) for CDT. In vitro and in vivo studies revealed that BOD-Cu@G could achieve excellent anti-tumor efficiency by CDT-enhanced dual phototherapy.
Chemodynamic therapy (CDT) combined with dual phototherapy (photothermal therapy (PTT) and photodynamic therapy (PDT)) is an efficient way to synergistically improve anti-tumor efficacy. However, the combination of multiple modes often makes the composition of the system more complex, which is not conducive to clinical application. In this study, a dual phototherapy ligand carboxyl-modified Aza-BODIPY (BOD-COOH) and metal active center Cu2+ were used to construct multiple-modes metal-photosensitizer nanoparticles (BOD-Cu NPs) via one-step coordination self-assembly for combination therapy of CDT/PDT/PTT. In order to improve delivery efficiency, the targeted hydrophilic molecule pyridine-modified glucose derivative (G-Py) was synthesized and coated onto the BOD-Cu NPs to form a glycosylated nano metal-photosensitizer BOD-Cu@G by electrostatic interaction. The Cu2+ in BOD-Cu@G could not only be used as a coordination node for metal-driven self-assembly but also consume intracellular glutathione (GSH), and then catalyze Fenton-like reaction to generate hydroxyl radical (·OH) for CDT. In vitro and in vivo studies revealed that BOD-Cu@G could achieve excellent anti-tumor efficiency by CDT-enhanced dual phototherapy.
2024, 35(7): 109333
doi: 10.1016/j.cclet.2023.109333
Abstract:
Herein, we report the migratory hydroarylation of unactivated alkenes with aryl iodides using native and weakly coordinating amide directors under mild conditions. Synergistic coordination of the monodentate directing group and the ligand enable the highly regioselective migratory hydroarylation via a chain walking process to form the thermodynamically stable five-membered nickelacyle intermediate. The protocol provides a variety of valuable α-aryl-substituted alkylamine products, and exhibited good functional group tolerance. The modification of bioactive compounds such as fenofibrate and indomethacin further highlights the synthetic value of this protocol.
Herein, we report the migratory hydroarylation of unactivated alkenes with aryl iodides using native and weakly coordinating amide directors under mild conditions. Synergistic coordination of the monodentate directing group and the ligand enable the highly regioselective migratory hydroarylation via a chain walking process to form the thermodynamically stable five-membered nickelacyle intermediate. The protocol provides a variety of valuable α-aryl-substituted alkylamine products, and exhibited good functional group tolerance. The modification of bioactive compounds such as fenofibrate and indomethacin further highlights the synthetic value of this protocol.
2024, 35(7): 109346
doi: 10.1016/j.cclet.2023.109346
Abstract:
The kinetic of low-temperature carrier and lattice of lead-halide perovskite is yet to be fully understood. In this work, we investigate the steady-state photoluminescences (PLs) of CsPbI3 at the environmental temperature (Te) ranging from 20 K to 300 K, and observed anomalous behaviors at cryogenic temperatures: The carrier temperature (Tc) of pure CsPbI3 exhibits a negative correlation with Te, accompanied by an expansion in Urbach tails of absorption spectra (Abs.) and excessive red-shifts at peak energy of PLs. These phenomena are also observed in those samples containing a certain amount of Cs4PbI6, but to a lesser extent and occurs at lower temperatures. It is attributed to the intensified hot phonon bottleneck effect (HPB) in CsPbI3 at cryogenic Te, which hinders the energy transfer from hot carriers, via longitudinal optics (LO) phonons to longitudinal acoustic (LA) phonons, to the ambient. For samples under continuous-wave laser excitation, in specific, the barrier induced by the enhanced HPB at low Te prevents the effective thermalization among carriers, LO and LA phonons, which, therefore, form thermally isolated ensembles with different temperatures. At cryogenic Te range, the elevated temperatures of carrier and LO phonon expand the high-energy side of PLs and the low-energy tail of Abs., respectively. For those samples in which the CsPbI3 is mixed with Cs4PbI6, the interfacial LO-LO interaction across them provides a bypass for heat dissipation, mitigating the heat accumulation in LO-phonons of CsPbI3. The results suggest that a strong HPB effect may break the thermal equilibrium among different branches of phonons in the lattice under certain extreme conditions.
The kinetic of low-temperature carrier and lattice of lead-halide perovskite is yet to be fully understood. In this work, we investigate the steady-state photoluminescences (PLs) of CsPbI3 at the environmental temperature (Te) ranging from 20 K to 300 K, and observed anomalous behaviors at cryogenic temperatures: The carrier temperature (Tc) of pure CsPbI3 exhibits a negative correlation with Te, accompanied by an expansion in Urbach tails of absorption spectra (Abs.) and excessive red-shifts at peak energy of PLs. These phenomena are also observed in those samples containing a certain amount of Cs4PbI6, but to a lesser extent and occurs at lower temperatures. It is attributed to the intensified hot phonon bottleneck effect (HPB) in CsPbI3 at cryogenic Te, which hinders the energy transfer from hot carriers, via longitudinal optics (LO) phonons to longitudinal acoustic (LA) phonons, to the ambient. For samples under continuous-wave laser excitation, in specific, the barrier induced by the enhanced HPB at low Te prevents the effective thermalization among carriers, LO and LA phonons, which, therefore, form thermally isolated ensembles with different temperatures. At cryogenic Te range, the elevated temperatures of carrier and LO phonon expand the high-energy side of PLs and the low-energy tail of Abs., respectively. For those samples in which the CsPbI3 is mixed with Cs4PbI6, the interfacial LO-LO interaction across them provides a bypass for heat dissipation, mitigating the heat accumulation in LO-phonons of CsPbI3. The results suggest that a strong HPB effect may break the thermal equilibrium among different branches of phonons in the lattice under certain extreme conditions.
2024, 35(7): 109348
doi: 10.1016/j.cclet.2023.109348
Abstract:
The stable coordinated metallo-complexes based on 2,2′:6′,2″-terpyridine (tpy) and its derivatives have been widely researched for various wide-ranging applications in photoelectronics, catalysis, sensor, photoluminescence, and so on. However, the most reported studies ignored the comprehensive comparison between structures modified by different positions and photoluminescence. Herein, we design a series of metallo-complexes which were assembled with tpy substituted triphenylamine (TPA) at different positions and metal ions and explored their photophysical properties. In the solution state, MLE2 based on the 5,5″-positions modification showed the highest PLQYs and PL intensity. With the increase of solvent polarity, MLB2 exhibit the largest redshift. In the solid state, from MLA2 to MLE2, the emission colours are gradually red-shifted from yellow to red. The findings in this work may pave a new way to design functional metallo-complexes, not just for PL properties.
The stable coordinated metallo-complexes based on 2,2′:6′,2″-terpyridine (tpy) and its derivatives have been widely researched for various wide-ranging applications in photoelectronics, catalysis, sensor, photoluminescence, and so on. However, the most reported studies ignored the comprehensive comparison between structures modified by different positions and photoluminescence. Herein, we design a series of metallo-complexes which were assembled with tpy substituted triphenylamine (TPA) at different positions and metal ions and explored their photophysical properties. In the solution state, MLE2 based on the 5,5″-positions modification showed the highest PLQYs and PL intensity. With the increase of solvent polarity, MLB2 exhibit the largest redshift. In the solid state, from MLA2 to MLE2, the emission colours are gradually red-shifted from yellow to red. The findings in this work may pave a new way to design functional metallo-complexes, not just for PL properties.
2024, 35(7): 109349
doi: 10.1016/j.cclet.2023.109349
Abstract:
COVID-19 is a major event with worldwide influences. Since the beginning of the epidemic, pharmaceutical chemists have paid attention to the therapeutic effect of a variety of small molecule medicines on COVID-19 infection. A series of organic molecules are designed and found to be effective in the treatment of COVID-19 infection. In fact, no matter how effective they are, with the development of the COVID-19 epidemic, various small molecule medicines are gradually recognized by people. This is equivalent to a good science popularization of pharmaceutical chemistry. This review aims to introduce the molecules for COVID-19 treatment on the basis of their chemical structures, synthetic methods as well as their effects.
COVID-19 is a major event with worldwide influences. Since the beginning of the epidemic, pharmaceutical chemists have paid attention to the therapeutic effect of a variety of small molecule medicines on COVID-19 infection. A series of organic molecules are designed and found to be effective in the treatment of COVID-19 infection. In fact, no matter how effective they are, with the development of the COVID-19 epidemic, various small molecule medicines are gradually recognized by people. This is equivalent to a good science popularization of pharmaceutical chemistry. This review aims to introduce the molecules for COVID-19 treatment on the basis of their chemical structures, synthetic methods as well as their effects.
2024, 35(7): 109359
doi: 10.1016/j.cclet.2023.109359
Abstract:
Effective adjustment and control of the oxidation state of plutonium (Pu) and neptunium (Np) is an indispensable component of Np/Pu separation in spent nuclear fuel reprocessing. Some hydrazine derivatives including methylhydrazine (CH3N2H3) effectively achieves the reduction of Np(Ⅵ) to Np(Ⅴ) without reducing Pu(Ⅳ). Herein, we explored the reduction mechanisms of Pu(Ⅳ) and Np(Ⅵ) by CH3N2H3 in HNO3 solution using scalar-relativistic density functional theory. We elucidated the difference in the reduction mechanism between Np(Ⅵ) and Pu(Ⅳ) ions by CH3N2H3. The energy barrier for the reduction of [NpⅥO2(H2O)5]2+ and [NpⅥO2(NO3)(H2O)3]+ by CH3N2H3 is largely different due to the coordination of nitrate ion. Moreover, the energy barrier of the reduction of [NpⅥO2(H2O)5]2+ is apparently lower than that of [PuⅣ(NO3)2(H2O)7]2+, which is in line with the experimental observations. The results of Mayer bond order and localized molecular orbitals clarify the structural evolution of the reaction pathways. Analysis of the spin density demonstrates that the first Np(Ⅵ) and Pu(Ⅳ) reduction belongs to the outer-sphere electron transfer and the second Np(Ⅵ) and Pu(Ⅳ) reduction is the hydrogen transfer. This study explains theoretically why CH3N2H3 reduces Np(Ⅵ) but not Pu(Ⅳ), and helps to design promising reductants for the Np/Pu separation in spent nuclear fuel reprocessing.
Effective adjustment and control of the oxidation state of plutonium (Pu) and neptunium (Np) is an indispensable component of Np/Pu separation in spent nuclear fuel reprocessing. Some hydrazine derivatives including methylhydrazine (CH3N2H3) effectively achieves the reduction of Np(Ⅵ) to Np(Ⅴ) without reducing Pu(Ⅳ). Herein, we explored the reduction mechanisms of Pu(Ⅳ) and Np(Ⅵ) by CH3N2H3 in HNO3 solution using scalar-relativistic density functional theory. We elucidated the difference in the reduction mechanism between Np(Ⅵ) and Pu(Ⅳ) ions by CH3N2H3. The energy barrier for the reduction of [NpⅥO2(H2O)5]2+ and [NpⅥO2(NO3)(H2O)3]+ by CH3N2H3 is largely different due to the coordination of nitrate ion. Moreover, the energy barrier of the reduction of [NpⅥO2(H2O)5]2+ is apparently lower than that of [PuⅣ(NO3)2(H2O)7]2+, which is in line with the experimental observations. The results of Mayer bond order and localized molecular orbitals clarify the structural evolution of the reaction pathways. Analysis of the spin density demonstrates that the first Np(Ⅵ) and Pu(Ⅳ) reduction belongs to the outer-sphere electron transfer and the second Np(Ⅵ) and Pu(Ⅳ) reduction is the hydrogen transfer. This study explains theoretically why CH3N2H3 reduces Np(Ⅵ) but not Pu(Ⅳ), and helps to design promising reductants for the Np/Pu separation in spent nuclear fuel reprocessing.
2024, 35(7): 109364
doi: 10.1016/j.cclet.2023.109364
Abstract:
Herein, we report the first visible-light photoredox-catalyzed carboxylation of aryl epoxides with CO2 to synthesize hydroxy acid derivatives. A variety of valuable β-, γ-, δ-, ε-hydroxy acid derivatives are obtained in moderate to high yields under mild conditions. This protocol shows noteworthy functional-group compatibility, high chemo- and regioselectivities under transition-metal-free conditions with an inexpensive organo-dye as photosensitizer. Mechanistic studies indicate that the benzylic carbanion is generated as an intermediate via the sequential single electron transfer (SSET) process.
Herein, we report the first visible-light photoredox-catalyzed carboxylation of aryl epoxides with CO2 to synthesize hydroxy acid derivatives. A variety of valuable β-, γ-, δ-, ε-hydroxy acid derivatives are obtained in moderate to high yields under mild conditions. This protocol shows noteworthy functional-group compatibility, high chemo- and regioselectivities under transition-metal-free conditions with an inexpensive organo-dye as photosensitizer. Mechanistic studies indicate that the benzylic carbanion is generated as an intermediate via the sequential single electron transfer (SSET) process.
2024, 35(7): 109385
doi: 10.1016/j.cclet.2023.109385
Abstract:
Herein, the degradation of florfenicol (FLO) over zero-valent iron (ZVI) enhanced by SiC was systematically investigated. It was found that 5 g/L of ZVI/SiC (1:3) at pH 3.0 could completely degrade 20 mg/L of FLO within 1 h, with a Kobs value of 0.0873 min−1, 12.5 times greater than that of pure ZVI (0.0069 min−1). Vibrating sample magnetometer (VSM) characterizations revealed that the use of SiC supporter reduces the magnetic intensity of ZVI, which mitigates iron particle agglomeration, increases Brunauer-Emmett-Teller (BET) surface area, and enhances FLO degradation efficiency. Furthermore, ZVI/SiC exhibits a much lower hydrogen evolution potential (HEP) and significantly higher corrosion currents compared to pure ZVI. FLO was proposed to undergo degradation via reductive dechlorination, involving a hydrogenolysis mechanism that entails the cleavage of the σ bond. This study provides new insights into the reduction hydrogenation mechanism of ZVI.
Herein, the degradation of florfenicol (FLO) over zero-valent iron (ZVI) enhanced by SiC was systematically investigated. It was found that 5 g/L of ZVI/SiC (1:3) at pH 3.0 could completely degrade 20 mg/L of FLO within 1 h, with a Kobs value of 0.0873 min−1, 12.5 times greater than that of pure ZVI (0.0069 min−1). Vibrating sample magnetometer (VSM) characterizations revealed that the use of SiC supporter reduces the magnetic intensity of ZVI, which mitigates iron particle agglomeration, increases Brunauer-Emmett-Teller (BET) surface area, and enhances FLO degradation efficiency. Furthermore, ZVI/SiC exhibits a much lower hydrogen evolution potential (HEP) and significantly higher corrosion currents compared to pure ZVI. FLO was proposed to undergo degradation via reductive dechlorination, involving a hydrogenolysis mechanism that entails the cleavage of the σ bond. This study provides new insights into the reduction hydrogenation mechanism of ZVI.
2024, 35(7): 109394
doi: 10.1016/j.cclet.2023.109394
Abstract:
Utilizing CO2 for the production of bulky and valuable chemicals presents an attractive solution to address environmental and fossil energy crises. Among the various approaches, direct carboxylation of alcohols with CO2 stands out as an eco-friendly process capable of efficiently producing carboxylic acids in a sustainable manner. However, the high dissociation energy of the C-O bond poses a significant challenge in this process. Over the past few decades, several strategies have been developed to activate alcohols and establish efficient catalytic systems for carboxylation with CO2. Nevertheless, the sporadic nature of reported approaches makes it difficult to determine the most effective one. This perspective aims to provide an overview of the current state-of-the-art catalytic protocols for carboxylating alcohols with CO2, encompassing esterification, halogenation, and photocatalysis, while considering their respective advantages and limitations. We aim to discern the most promising avenues for future development in this field. The insights presented in this perspective will contribute to the advancement of efficient and sustainable carboxylation methods using CO2, leading to the production of valuable chemicals in future.
Utilizing CO2 for the production of bulky and valuable chemicals presents an attractive solution to address environmental and fossil energy crises. Among the various approaches, direct carboxylation of alcohols with CO2 stands out as an eco-friendly process capable of efficiently producing carboxylic acids in a sustainable manner. However, the high dissociation energy of the C-O bond poses a significant challenge in this process. Over the past few decades, several strategies have been developed to activate alcohols and establish efficient catalytic systems for carboxylation with CO2. Nevertheless, the sporadic nature of reported approaches makes it difficult to determine the most effective one. This perspective aims to provide an overview of the current state-of-the-art catalytic protocols for carboxylating alcohols with CO2, encompassing esterification, halogenation, and photocatalysis, while considering their respective advantages and limitations. We aim to discern the most promising avenues for future development in this field. The insights presented in this perspective will contribute to the advancement of efficient and sustainable carboxylation methods using CO2, leading to the production of valuable chemicals in future.
2024, 35(7): 109534
doi: 10.1016/j.cclet.2024.109534
Abstract:
The external stimulus response strategy has been evolved rapidly in the field of olefin polymerization. In this work, we modularly synthesized three types of double stimulus responsive α-diimine palladium catalysts, combining redox regulation and other regulation together, such as light, Lewis acid and alkali cations. The catalytic activities and the molecular weight of polyethylene products can be regulated for 4 times in ethylene polymerization. These palladium complexes were also used for the copolymerization reaction of ethylene and polar monomers, such as methyl 10-undecylenate and methyl acrylate, effectively regulating the catalytic activities, the molecular weight and polar monomer incorporation of the prepared copolymers. The research on these dual-regulated palladium complexes makes full use of prepared catalysts and provides new inspirations for regulating olefin polymerization.
The external stimulus response strategy has been evolved rapidly in the field of olefin polymerization. In this work, we modularly synthesized three types of double stimulus responsive α-diimine palladium catalysts, combining redox regulation and other regulation together, such as light, Lewis acid and alkali cations. The catalytic activities and the molecular weight of polyethylene products can be regulated for 4 times in ethylene polymerization. These palladium complexes were also used for the copolymerization reaction of ethylene and polar monomers, such as methyl 10-undecylenate and methyl acrylate, effectively regulating the catalytic activities, the molecular weight and polar monomer incorporation of the prepared copolymers. The research on these dual-regulated palladium complexes makes full use of prepared catalysts and provides new inspirations for regulating olefin polymerization.
2024, 35(7): 109535
doi: 10.1016/j.cclet.2024.109535
Abstract:
2024, 35(7): 109543
doi: 10.1016/j.cclet.2024.109543
Abstract:
Lithium-sulfur batteries (LSBs) boasting remarkable energy density have garnered significant attention within academic and industrial spheres. Nevertheless, the progression of LSBs remains constrained by the languid redox kinetics intrinsic to sulfur and the pronounced shuttle effect induced by lithium polysulfides (LiPSs), which seriously affecting the energy density, cycling life and rate capacity. The conceptualization and implementation of catalytic materials stand acknowledged as a propitious stratagem for orchestrating kinetic modulation, particularly in excavating the conversion of LiPSs and has evolved into a focal point for disposing. Among them, chalcogenide catalytic materials (CCMs) have shown satisfactory catalytic effects ascribe to the unique physicochemical properties, and have been extensively developed in recent years. Considering the lack of systematic summary regarding the development of CCMs and corresponding performance optimization strategies, herein, we initiate a comprehensive review regarding the recent progress of CCMs for effective collaborative immobilization and accelerated transformation kinetics of LiPSs. Following that, the modulation strategies to improve the catalytic activity of CCMs are summarized, including structural engineering (morphology engineering, surface/interface engineering, crystal engineering) and electronic engineering (doping and vacancy, etc.). Finally, the application prospect of CCMs in LSBs is clarified, and some enlightenment is provided for the reasonable design of CCMs serving practical LSBs.
Lithium-sulfur batteries (LSBs) boasting remarkable energy density have garnered significant attention within academic and industrial spheres. Nevertheless, the progression of LSBs remains constrained by the languid redox kinetics intrinsic to sulfur and the pronounced shuttle effect induced by lithium polysulfides (LiPSs), which seriously affecting the energy density, cycling life and rate capacity. The conceptualization and implementation of catalytic materials stand acknowledged as a propitious stratagem for orchestrating kinetic modulation, particularly in excavating the conversion of LiPSs and has evolved into a focal point for disposing. Among them, chalcogenide catalytic materials (CCMs) have shown satisfactory catalytic effects ascribe to the unique physicochemical properties, and have been extensively developed in recent years. Considering the lack of systematic summary regarding the development of CCMs and corresponding performance optimization strategies, herein, we initiate a comprehensive review regarding the recent progress of CCMs for effective collaborative immobilization and accelerated transformation kinetics of LiPSs. Following that, the modulation strategies to improve the catalytic activity of CCMs are summarized, including structural engineering (morphology engineering, surface/interface engineering, crystal engineering) and electronic engineering (doping and vacancy, etc.). Finally, the application prospect of CCMs in LSBs is clarified, and some enlightenment is provided for the reasonable design of CCMs serving practical LSBs.
2024, 35(7): 109549
doi: 10.1016/j.cclet.2024.109549
Abstract:
The development of large-scale cell cultivation and non-invasive cell harvesting is highly desired in various fields, including biological regeneration and pharmaceutical research. When using traditional microcarriers for cell culture, trypsinization is often necessary during cell collection, leading to partial cells damage. In this work, we developed a thermoresponsive glass microcarrier modified with poly(γ-propargyl-ʟ-glutamate) (PPLG) and poly(N-isopropylacrylamide) (PNIPAM). We utilized these microcarriers for three-dimensional cell culture and enzyme-free cell harvesting, and the results indicated that the prepared microcarriers exhibited excellent non-invasive cell culture performance.
The development of large-scale cell cultivation and non-invasive cell harvesting is highly desired in various fields, including biological regeneration and pharmaceutical research. When using traditional microcarriers for cell culture, trypsinization is often necessary during cell collection, leading to partial cells damage. In this work, we developed a thermoresponsive glass microcarrier modified with poly(γ-propargyl-ʟ-glutamate) (PPLG) and poly(N-isopropylacrylamide) (PNIPAM). We utilized these microcarriers for three-dimensional cell culture and enzyme-free cell harvesting, and the results indicated that the prepared microcarriers exhibited excellent non-invasive cell culture performance.
2024, 35(7): 109573
doi: 10.1016/j.cclet.2024.109573
Abstract:
Developing efficient and long wavelength sensitive unimolecular photoinitiators (PIs) is still facing a great challenge. In this work, a series of thioxanthone-based N-hydroxyphthalimide esters (TX-NHPIEs) were synthesized by installing NHPIEs along the TX backbone and characterized. The investigated TX-NHPIEs have a 60 nm redshift and demonstrate sterling initiating efficiency for free radical photopolymerization (FRP) under LED@450 nm light irradiation compared with the commercialized isopropylthioxanthone (ITX). Real-time 1Hnuclear magnetic resonance (1H NMR), electron spin resonance (ESR), decarboxylation and gas chromatograph-mass spectrometer (GC–MS) experiments and density functional theory (DFT) reveal that TX-NHPIEs can generate one alkyl radical and one N-centered iminyl radical, which can initiate FRP directly and indirectly, respectively. In other words, TX-NHPIEs absorb one photon and can generate two active radicals, which break through the limitations of common PIs. TX-NHPIE-Cpe demonstrates the highest initiating efficiency, and its application in coatings and 3D printing was also studied, indicating TX-NHPIEs have broad potential applications in photopolymerization processes.
Developing efficient and long wavelength sensitive unimolecular photoinitiators (PIs) is still facing a great challenge. In this work, a series of thioxanthone-based N-hydroxyphthalimide esters (TX-NHPIEs) were synthesized by installing NHPIEs along the TX backbone and characterized. The investigated TX-NHPIEs have a 60 nm redshift and demonstrate sterling initiating efficiency for free radical photopolymerization (FRP) under LED@450 nm light irradiation compared with the commercialized isopropylthioxanthone (ITX). Real-time 1Hnuclear magnetic resonance (1H NMR), electron spin resonance (ESR), decarboxylation and gas chromatograph-mass spectrometer (GC–MS) experiments and density functional theory (DFT) reveal that TX-NHPIEs can generate one alkyl radical and one N-centered iminyl radical, which can initiate FRP directly and indirectly, respectively. In other words, TX-NHPIEs absorb one photon and can generate two active radicals, which break through the limitations of common PIs. TX-NHPIE-Cpe demonstrates the highest initiating efficiency, and its application in coatings and 3D printing was also studied, indicating TX-NHPIEs have broad potential applications in photopolymerization processes.
2024, 35(7): 109580
doi: 10.1016/j.cclet.2024.109580
Abstract:
The photocatalytic conversion of biomass into high-value chemicals, coupled with simultaneous hydrogen (H2) evolution, leveraging the electrons and holes generated by solar energy, holds great promise for addressing energy demands. In this study, we constructed a dual functional photocatalytic system formed by NiS loaded on Ni doped two-dimensional (2D) CdS nanosheet (NiS/Ni-CdSNS) heterostructure for visible-light-driven H2 evolution and ethanol oxidation to acetaldehyde. Remarkably, the 2D NiS/Ni-CdSNS exhibited significant activity and selectivity in both photocatalytic H2 evolution and ethanol oxidation, achieving yields of 7.98 mmol g−1 h−1 for H2 and 7.33 mmol g−1 h−1 for acetaldehyde. The heterogeneous interface of the composite facilitated efficient charge separation, while NiS provided abundant sites for proton reduction, thereby promoting the overall dual-functional photocatalytic activity. Density functional theory calculations further reveal that both Ni doping and NiS loading can reduce the reaction energy barrier of ethanol oxidation of free radicals, and NiS/Ni-CdSNS composite materials exhibit stronger ethanol C-H activation ability to generate key intermediate •CH(OH)CH3 on the surface. This work serves as a valuable guide for the rational design of efficient dual functional photocatalytic systems that combine H2 evolution with the selective conversion of organic compounds into high-value chemicals.
The photocatalytic conversion of biomass into high-value chemicals, coupled with simultaneous hydrogen (H2) evolution, leveraging the electrons and holes generated by solar energy, holds great promise for addressing energy demands. In this study, we constructed a dual functional photocatalytic system formed by NiS loaded on Ni doped two-dimensional (2D) CdS nanosheet (NiS/Ni-CdSNS) heterostructure for visible-light-driven H2 evolution and ethanol oxidation to acetaldehyde. Remarkably, the 2D NiS/Ni-CdSNS exhibited significant activity and selectivity in both photocatalytic H2 evolution and ethanol oxidation, achieving yields of 7.98 mmol g−1 h−1 for H2 and 7.33 mmol g−1 h−1 for acetaldehyde. The heterogeneous interface of the composite facilitated efficient charge separation, while NiS provided abundant sites for proton reduction, thereby promoting the overall dual-functional photocatalytic activity. Density functional theory calculations further reveal that both Ni doping and NiS loading can reduce the reaction energy barrier of ethanol oxidation of free radicals, and NiS/Ni-CdSNS composite materials exhibit stronger ethanol C-H activation ability to generate key intermediate •CH(OH)CH3 on the surface. This work serves as a valuable guide for the rational design of efficient dual functional photocatalytic systems that combine H2 evolution with the selective conversion of organic compounds into high-value chemicals.
2024, 35(7): 109593
doi: 10.1016/j.cclet.2024.109593
Abstract:
Formic acid (FA), which is obtainable through CO2 hydrogenation with green hydrogen or biomass conversion, has been used as a prospective liquid organic hydrogen carrier (LOHC) because of the abundant advantages of renewability, wide availability, stability, and high volumetric capacity (53 g H2/L). The development of highly efficient catalytic systems to achieve enhanced catalytic activity is attractive but still challenging. Herein, ultrafine and highly dispersed PdAu nanoclusters (NCs) anchored on amino-modified reduced graphene oxide (ArGO) were successfully synthesized via a facile impregnation-reduction method and applied as a catalyst toward formic acid dehydrogenation (FAD). Benefiting from the promoting effect of amino groups, the strain and ligand effect in the alloy, and the Mott–Schottky effect between PdAu NCs and ArGO, the resultant PdAu/ArGO affords an ultrahigh activity under visible light irradiation with an exceptional turnover frequency value of 10, 699.5 h−1 at 298 K without any additives, more than 2.6 times improvement than that under dark, which is the highest among all reported catalysts under the same conditions. This study provides a green and convenient strategy for developing more efficient and sustainable FAD catalysts and promotes the effective utilization of FA as a prospective renewable LOHC.
Formic acid (FA), which is obtainable through CO2 hydrogenation with green hydrogen or biomass conversion, has been used as a prospective liquid organic hydrogen carrier (LOHC) because of the abundant advantages of renewability, wide availability, stability, and high volumetric capacity (53 g H2/L). The development of highly efficient catalytic systems to achieve enhanced catalytic activity is attractive but still challenging. Herein, ultrafine and highly dispersed PdAu nanoclusters (NCs) anchored on amino-modified reduced graphene oxide (ArGO) were successfully synthesized via a facile impregnation-reduction method and applied as a catalyst toward formic acid dehydrogenation (FAD). Benefiting from the promoting effect of amino groups, the strain and ligand effect in the alloy, and the Mott–Schottky effect between PdAu NCs and ArGO, the resultant PdAu/ArGO affords an ultrahigh activity under visible light irradiation with an exceptional turnover frequency value of 10, 699.5 h−1 at 298 K without any additives, more than 2.6 times improvement than that under dark, which is the highest among all reported catalysts under the same conditions. This study provides a green and convenient strategy for developing more efficient and sustainable FAD catalysts and promotes the effective utilization of FA as a prospective renewable LOHC.
2024, 35(7): 109623
doi: 10.1016/j.cclet.2024.109623
Abstract:
Disgusting deposits (e.g., scale and crude oil) in daily life and industrial production are always serious problems, posing great threats to the safety and economic development. However, most of developed coatings can only conquer one part of these deposits such as superhydrophobic coatings possess anti-scaling capacity but would adhere crude oil. To integrate scale resistance with oil repellence, we herein report a robust superamphiphobic (SAB) coating simultaneously reducing pollution of scale and oil for extended period of time (two weeks with over 98% reduction). Compared with single role of superhydrophobic and amphiphilic surfaces, the SAB coating can not only inhibit interfacial nucleation of scale but also reduce the adhesion of formed scale and polluted oil. The durability of the SAB coating is evaluated via mechanical tests (sandpaper abrasion, tape stripping and sand falling) and chemical corrosion (corrosive liquid immersing), revealed by sustainable high contact angles and low contact angle hysteresis of water and oil. The universality of this strategy can be further confirmed by adding different particles like kaolin, Al2O3, and SiO2, resisting multiple types of scale (i.e., CaSO4, BaSO4 and MgCO3) and oil (i.e., glycerol, glycol, and mineral oil). Therefore, this study provides an ideal avenue for resisting scale and oil, which may be used for conquering the complexity of application environments (e.g., oil production and transportation).
Disgusting deposits (e.g., scale and crude oil) in daily life and industrial production are always serious problems, posing great threats to the safety and economic development. However, most of developed coatings can only conquer one part of these deposits such as superhydrophobic coatings possess anti-scaling capacity but would adhere crude oil. To integrate scale resistance with oil repellence, we herein report a robust superamphiphobic (SAB) coating simultaneously reducing pollution of scale and oil for extended period of time (two weeks with over 98% reduction). Compared with single role of superhydrophobic and amphiphilic surfaces, the SAB coating can not only inhibit interfacial nucleation of scale but also reduce the adhesion of formed scale and polluted oil. The durability of the SAB coating is evaluated via mechanical tests (sandpaper abrasion, tape stripping and sand falling) and chemical corrosion (corrosive liquid immersing), revealed by sustainable high contact angles and low contact angle hysteresis of water and oil. The universality of this strategy can be further confirmed by adding different particles like kaolin, Al2O3, and SiO2, resisting multiple types of scale (i.e., CaSO4, BaSO4 and MgCO3) and oil (i.e., glycerol, glycol, and mineral oil). Therefore, this study provides an ideal avenue for resisting scale and oil, which may be used for conquering the complexity of application environments (e.g., oil production and transportation).
2024, 35(7): 109742
doi: 10.1016/j.cclet.2024.109742
Abstract:
Fe-based Fenton agents can generate highly reactive and toxic hydroxyl radicals (·OH) in the tumor microenvironment (TME) for chemodynamic therapy (CDT) with high specificity. However, the low pH environment and insufficient endogenous hydrogen peroxide (H2O2) of the highly efficient Fenton reaction limits its practical application in clinic. Here, a Cu(Ⅱ)-doped mesoporous silica nanoagent (Cu-MSN) with excellent dispersity was successfully developed. After loaded with doxorubicin (DOX) and ascorbate (AA), Cu-MSN@DA was coated with active targeting ligand folic acid (FA), dimethyl maleic an-hydride (DMMA) and carboxymethyl chitosan (CMC) to obtain an active transporting nanoagent (FCDC@Cu-MSN@DA) with tunable charge-reversal property, which is more adaptable to the pH value of TME than Fe-based Fenton agents, and can self-supply exogenous H2O2 by ascorbate to produce more toxic ·OH to trigger the apoptosis of cancer cells. Meanwhile, the high level of glutathione (GSH) in TME can reduce Cu(Ⅱ) to Cu(Ⅰ) by Fenton-like reaction, increasing the generation rate of ·OH and relieving tumor antioxidant ability. The supply of exogenous H2O2 significantly enhanced the synergistic effect of CDT by oxidative damage. Together with DOX-induced cell apoptosis, this novel nanoagent FCDC@Cu-MSN@DA can achieve maximum therapeutic efficacy, creating a new model of safe and effective tumor treatment with high specificity.
Fe-based Fenton agents can generate highly reactive and toxic hydroxyl radicals (·OH) in the tumor microenvironment (TME) for chemodynamic therapy (CDT) with high specificity. However, the low pH environment and insufficient endogenous hydrogen peroxide (H2O2) of the highly efficient Fenton reaction limits its practical application in clinic. Here, a Cu(Ⅱ)-doped mesoporous silica nanoagent (Cu-MSN) with excellent dispersity was successfully developed. After loaded with doxorubicin (DOX) and ascorbate (AA), Cu-MSN@DA was coated with active targeting ligand folic acid (FA), dimethyl maleic an-hydride (DMMA) and carboxymethyl chitosan (CMC) to obtain an active transporting nanoagent (FCDC@Cu-MSN@DA) with tunable charge-reversal property, which is more adaptable to the pH value of TME than Fe-based Fenton agents, and can self-supply exogenous H2O2 by ascorbate to produce more toxic ·OH to trigger the apoptosis of cancer cells. Meanwhile, the high level of glutathione (GSH) in TME can reduce Cu(Ⅱ) to Cu(Ⅰ) by Fenton-like reaction, increasing the generation rate of ·OH and relieving tumor antioxidant ability. The supply of exogenous H2O2 significantly enhanced the synergistic effect of CDT by oxidative damage. Together with DOX-induced cell apoptosis, this novel nanoagent FCDC@Cu-MSN@DA can achieve maximum therapeutic efficacy, creating a new model of safe and effective tumor treatment with high specificity.
2024, 35(7): 109802
doi: 10.1016/j.cclet.2024.109802
Abstract:
A solid electrolyte interphase (SEI) with a robust mechanical property and a high ionic conductivity is imperative for high-performance zinc metal batteries. However, it is difficult to form such a SEI directly from an electrolyte. In this work, a molecular crowding effect is based on the introduction of Zn(OTF)2 and Zn(ClO4)2 to 2 mol/L ZnSO4 electrolytes. Simulations and experiments indicate that the Zn(OTF)2 and Zn(ClO4)2 not only create a molecularly crowded electrolyte environment to promote the interaction of Zn2+and OTF−, but also participate in the reduction to construct a robust and high ionic-conductive SEI, thus promoting metal zinc deposition to the (002) crystal surface. With this molecular crowding electrolyte, a high current density of 1 mA/cm2 can be obtained by assembling symmetric batteries with Zn as the anode for over 1000 h. And in a temperature environment of −10 ℃, a current density of 1 mA/cm2 can be obtained by assembling symmetric batteries with Zn for over 200 h. Zn//Bi2S3/VS4@C cells achieve a CE rate of up to 99.81% over 1000 cycles. Hence, the utilization of a molecular crowding electrolyte is deemed a highly effective approach to fabricating a sophisticated SEI for a zinc anode.
A solid electrolyte interphase (SEI) with a robust mechanical property and a high ionic conductivity is imperative for high-performance zinc metal batteries. However, it is difficult to form such a SEI directly from an electrolyte. In this work, a molecular crowding effect is based on the introduction of Zn(OTF)2 and Zn(ClO4)2 to 2 mol/L ZnSO4 electrolytes. Simulations and experiments indicate that the Zn(OTF)2 and Zn(ClO4)2 not only create a molecularly crowded electrolyte environment to promote the interaction of Zn2+and OTF−, but also participate in the reduction to construct a robust and high ionic-conductive SEI, thus promoting metal zinc deposition to the (002) crystal surface. With this molecular crowding electrolyte, a high current density of 1 mA/cm2 can be obtained by assembling symmetric batteries with Zn as the anode for over 1000 h. And in a temperature environment of −10 ℃, a current density of 1 mA/cm2 can be obtained by assembling symmetric batteries with Zn for over 200 h. Zn//Bi2S3/VS4@C cells achieve a CE rate of up to 99.81% over 1000 cycles. Hence, the utilization of a molecular crowding electrolyte is deemed a highly effective approach to fabricating a sophisticated SEI for a zinc anode.
