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2024 Volume 35 Issue 6
Versatile oxidized variants derived from TMDs by various oxidation strategies and their applications
2024, 35(6): 108705
doi: 10.1016/j.cclet.2023.108705
Abstract:
The physicochemical properties of transition metal dichalcogenides (TMDs) are highly related to their structures and usually stable in air. However, under certain conditions they could be transformed into different structures due to oxidation. Considering this, various materials with fascinating structures have been explored by oxidation strategies, which possess novel properties and great potential in various applications such as solar batteries, hydrogen evolution reaction (HER) catalysts, and field effect transistors (FET). In this review, we systematically summarize the atomic structures of TMD oxidized variants and the corresponding fabrication approaches. Utilizing various characterization methods, the chemical components of TMD oxidized variants are illustrated. Furthermore, we expound the promising applications of the oxidized variants. This review is expected to provide a new insight for preparing precise materials at the atomic level through corresponding oxidation strategies.
The physicochemical properties of transition metal dichalcogenides (TMDs) are highly related to their structures and usually stable in air. However, under certain conditions they could be transformed into different structures due to oxidation. Considering this, various materials with fascinating structures have been explored by oxidation strategies, which possess novel properties and great potential in various applications such as solar batteries, hydrogen evolution reaction (HER) catalysts, and field effect transistors (FET). In this review, we systematically summarize the atomic structures of TMD oxidized variants and the corresponding fabrication approaches. Utilizing various characterization methods, the chemical components of TMD oxidized variants are illustrated. Furthermore, we expound the promising applications of the oxidized variants. This review is expected to provide a new insight for preparing precise materials at the atomic level through corresponding oxidation strategies.
2024, 35(6): 108812
doi: 10.1016/j.cclet.2023.108812
Abstract:
Lithium (Li) metal anodes (LMAs) have garnered significant attention as a potential solution for developing high-energy density batteries, given their theoretical specific capacity and redox potential. However, safety concerns and internal cycling stability issues originated from uncontrollable Li dendrite growth have impeded the practical application of LMAs. Probing the interface between Li metal and electrolyte is a crucial process that offers valuable insights into the characteristics and regularity of primary circular reactions. To illustrate the intrinsic characteristic of Li metal batteries (LMBs) in spatial and temporal, it is imperative to employ electron microscopes to characterize the structural components distribution of Li with atomic resolution. This paper summarizes the progress in the characterization and analysis of the interfaces in LMBs with electron microscopes based on the principles of electron-matter interactions. Finally, future trends and the potential of electron microscopes are also discussed to advance our understanding of LMBs.
Lithium (Li) metal anodes (LMAs) have garnered significant attention as a potential solution for developing high-energy density batteries, given their theoretical specific capacity and redox potential. However, safety concerns and internal cycling stability issues originated from uncontrollable Li dendrite growth have impeded the practical application of LMAs. Probing the interface between Li metal and electrolyte is a crucial process that offers valuable insights into the characteristics and regularity of primary circular reactions. To illustrate the intrinsic characteristic of Li metal batteries (LMBs) in spatial and temporal, it is imperative to employ electron microscopes to characterize the structural components distribution of Li with atomic resolution. This paper summarizes the progress in the characterization and analysis of the interfaces in LMBs with electron microscopes based on the principles of electron-matter interactions. Finally, future trends and the potential of electron microscopes are also discussed to advance our understanding of LMBs.
2024, 35(6): 108931
doi: 10.1016/j.cclet.2023.108931
Abstract:
NH3-SCR was one of the most promising deNOx technologies and it has been widely applied in industrial NOx reduction. However, with the further development of energy transformation in power generation sector, the development of NH3-SCR catalysts is facing some new challenges. It is becoming an urgent problem to solve low catalytic activity and stability of NH3-SCR catalysts at the working condition of ultra-low temperature (≤ 200 ℃) and high concentrations of H2O + SO2 due to the gradual deployment of new energy power plants. Furthermore, the traditional coal-fired power plants would need flexible operation with the increasing share of renewable energy generation. The NH3-SCR catalysts which were applied in coal-fired power industry would be requested to work in a wide temperature window from 200 ℃ to 500 ℃ in the near future. Therefore, in this review, we summarized the progress of NH3-SCR catalysts in solving these different industrial problems in recent years. And the research directions which were deserved to be focused on the development of NH3-SCR catalysts for the energy transition of power generation sector are proposed.
NH3-SCR was one of the most promising deNOx technologies and it has been widely applied in industrial NOx reduction. However, with the further development of energy transformation in power generation sector, the development of NH3-SCR catalysts is facing some new challenges. It is becoming an urgent problem to solve low catalytic activity and stability of NH3-SCR catalysts at the working condition of ultra-low temperature (≤ 200 ℃) and high concentrations of H2O + SO2 due to the gradual deployment of new energy power plants. Furthermore, the traditional coal-fired power plants would need flexible operation with the increasing share of renewable energy generation. The NH3-SCR catalysts which were applied in coal-fired power industry would be requested to work in a wide temperature window from 200 ℃ to 500 ℃ in the near future. Therefore, in this review, we summarized the progress of NH3-SCR catalysts in solving these different industrial problems in recent years. And the research directions which were deserved to be focused on the development of NH3-SCR catalysts for the energy transition of power generation sector are proposed.
2024, 35(6): 108934
doi: 10.1016/j.cclet.2023.108934
Abstract:
Triphenylamine (TPA)-based aggregation-induced emission luminogens (TPA-AIEgens), a type of photoactive material utilizing the typical TPA moiety, has recently attracted increasing attention for the diagnostics and treatment of tumors due to their remarkable chemo-physical performance in optoelectronic research. TPA-AIEgens are distinguished from other photoactive agents by their strong fluorescence, good sensitivity, high signal-to-noise ratio, resistance to photobleaching, and lack of high concentration or aggregation-caused fluoresce quenching effects. In this review, we summarize the current advancements and the biomedical progress of TPA-AIEgens in tumor theranostics. First, the design principles of TPA-AIEgens photoactive agents as well as the advanced targeting strategies for nuclei, cell membranes, cell organelle and tumors were introduced, respectively. Next, the applications of TPA-AIEgens in tumor diagnosis and therapeutic techniques were reviewed. Last, the challenges and prospects of TPA-AIEgens for cancer therapy were performed. The given landscape of the TPA-AIEgens hereby is meaningful for the further design and utilization of the novel photoactive material, which could be beneficial for the development of clinic applications.
Triphenylamine (TPA)-based aggregation-induced emission luminogens (TPA-AIEgens), a type of photoactive material utilizing the typical TPA moiety, has recently attracted increasing attention for the diagnostics and treatment of tumors due to their remarkable chemo-physical performance in optoelectronic research. TPA-AIEgens are distinguished from other photoactive agents by their strong fluorescence, good sensitivity, high signal-to-noise ratio, resistance to photobleaching, and lack of high concentration or aggregation-caused fluoresce quenching effects. In this review, we summarize the current advancements and the biomedical progress of TPA-AIEgens in tumor theranostics. First, the design principles of TPA-AIEgens photoactive agents as well as the advanced targeting strategies for nuclei, cell membranes, cell organelle and tumors were introduced, respectively. Next, the applications of TPA-AIEgens in tumor diagnosis and therapeutic techniques were reviewed. Last, the challenges and prospects of TPA-AIEgens for cancer therapy were performed. The given landscape of the TPA-AIEgens hereby is meaningful for the further design and utilization of the novel photoactive material, which could be beneficial for the development of clinic applications.
2024, 35(6): 109073
doi: 10.1016/j.cclet.2023.109073
Abstract:
With the deep integration of electrochemical research with energy, environment, catalysis, and other fields, more and more new electrochemical catalytic reactions have entered our research field. Alloy catalysts have recently emerged as a new type of nanomaterial due to the rapid development of kinetic controlled synthesis technology. These materials offer several advantages over monometallic catalysts, including larger element combinations, complex geometries, bifunctional sites, and reduced use of precious metals. This paper provides a review of alloy electrocatalysts that are designed and prepared specifically for electrocatalytic applications. The use of alloy materials in electrocatalyst design is also discussed, highlighting their widespread application in this field. First, various synthesis methods and synthesis mechanisms are systematically summarized. Following that, by correlating the properties of materials with the structure, relevant strategies toward advanced alloy electrocatalysts including composition regulation, size, morphology, surface engineering, defect engineering, interface engineering and strain engineering are classified. In addition, the important electrocatalytic applications and mechanisms of alloy electrocatalysts are described and summarized. Finally, the current challenges and prospects regarding the development of alloy nanomaterials are proposed. This review serves as a springboard from a fundamental understanding of alloy structural dynamics to design and various applications of electrocatalysts, particularly in energy and environmental sustainability.
With the deep integration of electrochemical research with energy, environment, catalysis, and other fields, more and more new electrochemical catalytic reactions have entered our research field. Alloy catalysts have recently emerged as a new type of nanomaterial due to the rapid development of kinetic controlled synthesis technology. These materials offer several advantages over monometallic catalysts, including larger element combinations, complex geometries, bifunctional sites, and reduced use of precious metals. This paper provides a review of alloy electrocatalysts that are designed and prepared specifically for electrocatalytic applications. The use of alloy materials in electrocatalyst design is also discussed, highlighting their widespread application in this field. First, various synthesis methods and synthesis mechanisms are systematically summarized. Following that, by correlating the properties of materials with the structure, relevant strategies toward advanced alloy electrocatalysts including composition regulation, size, morphology, surface engineering, defect engineering, interface engineering and strain engineering are classified. In addition, the important electrocatalytic applications and mechanisms of alloy electrocatalysts are described and summarized. Finally, the current challenges and prospects regarding the development of alloy nanomaterials are proposed. This review serves as a springboard from a fundamental understanding of alloy structural dynamics to design and various applications of electrocatalysts, particularly in energy and environmental sustainability.
2024, 35(6): 109078
doi: 10.1016/j.cclet.2023.109078
Abstract:
In recent years, the emerging two−dimensional material−MXenes has attracted widespread attention in the field of photocatalysis due to its high conductivity, suitable Fermi level, tunable elemental composition, and excellent photoelectric properties. The zero−dimensional quantum dots (MQDs) derived from 2D MXenes not only inherit the characteristics of MXenes but also exhibit better performance due to the quantum size effect. Based on the above excellent physical and chemical properties, MQDs are often used as co−catalysts of photocatalysts, and show excellent co−catalytic properties. At the same time, compared with other cocatalysts (precious metals, metal oxides, metal sulfides), it has the advantages of low cost and high conductivity. Therefore, understanding the status of MQDs in the field of photocatalysis is crucial for their further development. In this review, we summarized the synthesis and modification methods of MQDs in recent years, as well as their photocatalytic applications in H2 production, CO2 reduction, N2 fixation, pollutant degradation, and other aspects. In addition, the challenges and prospects faced by MQDs are also proposed, providing theoretical guidance for the further development of MQD−based photocatalysts.
In recent years, the emerging two−dimensional material−MXenes has attracted widespread attention in the field of photocatalysis due to its high conductivity, suitable Fermi level, tunable elemental composition, and excellent photoelectric properties. The zero−dimensional quantum dots (MQDs) derived from 2D MXenes not only inherit the characteristics of MXenes but also exhibit better performance due to the quantum size effect. Based on the above excellent physical and chemical properties, MQDs are often used as co−catalysts of photocatalysts, and show excellent co−catalytic properties. At the same time, compared with other cocatalysts (precious metals, metal oxides, metal sulfides), it has the advantages of low cost and high conductivity. Therefore, understanding the status of MQDs in the field of photocatalysis is crucial for their further development. In this review, we summarized the synthesis and modification methods of MQDs in recent years, as well as their photocatalytic applications in H2 production, CO2 reduction, N2 fixation, pollutant degradation, and other aspects. In addition, the challenges and prospects faced by MQDs are also proposed, providing theoretical guidance for the further development of MQD−based photocatalysts.
2024, 35(6): 109112
doi: 10.1016/j.cclet.2023.109112
Abstract:
Electrocatalytic CO2 reduction at mild conditions is a promising strategy to transform greenhouse gases into fuels or value-added chemicals to solve the increasingly serious environmental and energy problems. The most crucial factor in determining the CO2 reduction performance is to develop efficient electrocatalysts with high selectivity and stability. Among the various electrocatalysts, indium-based catalysts have attracted extensive attention due to their non-toxicity, low cost, and high formic acid/formate selectivity. In this work, we comprehensively review the recent development and research progress of indium-based electrocatalysts for CO2RR. The reaction mechanism, reaction pathways, structure–activity relationship, and strategies to enhance the activity of CO2RR on indium-based catalysts have also been briefly presented and discussed. Finally, the existing challenges and future developments for indium-based high-performance catalysts for CO2RR are proposed.
Electrocatalytic CO2 reduction at mild conditions is a promising strategy to transform greenhouse gases into fuels or value-added chemicals to solve the increasingly serious environmental and energy problems. The most crucial factor in determining the CO2 reduction performance is to develop efficient electrocatalysts with high selectivity and stability. Among the various electrocatalysts, indium-based catalysts have attracted extensive attention due to their non-toxicity, low cost, and high formic acid/formate selectivity. In this work, we comprehensively review the recent development and research progress of indium-based electrocatalysts for CO2RR. The reaction mechanism, reaction pathways, structure–activity relationship, and strategies to enhance the activity of CO2RR on indium-based catalysts have also been briefly presented and discussed. Finally, the existing challenges and future developments for indium-based high-performance catalysts for CO2RR are proposed.
2024, 35(6): 109140
doi: 10.1016/j.cclet.2023.109140
Abstract:
In some industrial wastewater, heavy metals combine with organic complexing agents to form heavy metal complexes (HMCs). These HMCs can be difficult to decompose and remove through conventional techniques due to their higher stability than free heavy metal ions. In recent years, persulfate based advanced oxidation processes (PS-based AOPs) have been recognized as a viable technique for HMCs degradation. Nevertheless, a comprehensive and in-depth understanding of the relevant HMCs decomplexation mechanisms in PS-based AOPs is still lacking. This review delineates the current progress of HMCs decomplexation in PS-based AOPs. We discuss the distinctions between the two widely used oxidant types in PS-based AOPs techniques. Moreover, we summarize and highlight the decomplexation mechanisms based on electron and energy transfer, and degradation pathways of HMCs. We also emphasize the effects of environmental water constituents, namely pH, inorganic ions, and natural organic matter (NOM), on HMCs decomplexation. Ultimately, we identify the existing challenges and perspectives that will steer the direction of advancing PS-based AOPs to remove HMCs.
In some industrial wastewater, heavy metals combine with organic complexing agents to form heavy metal complexes (HMCs). These HMCs can be difficult to decompose and remove through conventional techniques due to their higher stability than free heavy metal ions. In recent years, persulfate based advanced oxidation processes (PS-based AOPs) have been recognized as a viable technique for HMCs degradation. Nevertheless, a comprehensive and in-depth understanding of the relevant HMCs decomplexation mechanisms in PS-based AOPs is still lacking. This review delineates the current progress of HMCs decomplexation in PS-based AOPs. We discuss the distinctions between the two widely used oxidant types in PS-based AOPs techniques. Moreover, we summarize and highlight the decomplexation mechanisms based on electron and energy transfer, and degradation pathways of HMCs. We also emphasize the effects of environmental water constituents, namely pH, inorganic ions, and natural organic matter (NOM), on HMCs decomplexation. Ultimately, we identify the existing challenges and perspectives that will steer the direction of advancing PS-based AOPs to remove HMCs.
2024, 35(6): 109228
doi: 10.1016/j.cclet.2023.109228
Abstract:
Detection and observation of reactive intermediates is an essential step in investigation of reaction pathways. However, most reactive intermediates are unstable and present at low concentrations; their short lifetimes make them difficult to detect and characterize. Supramolecular containers offer opportunities for the stabilization and characterization of those labile species, through isolation from the media and protection inside the cavity of the host. In this review, we summarize the examples of labile reaction intermediates that are stabilized and characterized with the help of supramolecular containers. The container compounds include carcerands, deep cavitands and amide naphthotubes. We focus on unstable guest species – cyclobutadiene, benzocyclopropenone, o-benzyne, 1,2,4,6-cycloheptatetraene, anti-Bredt's olefin, fluorophenoxycarbene, O-acylisoamide, and hemiaminal – that act as intermediates in certain organic reactions
Detection and observation of reactive intermediates is an essential step in investigation of reaction pathways. However, most reactive intermediates are unstable and present at low concentrations; their short lifetimes make them difficult to detect and characterize. Supramolecular containers offer opportunities for the stabilization and characterization of those labile species, through isolation from the media and protection inside the cavity of the host. In this review, we summarize the examples of labile reaction intermediates that are stabilized and characterized with the help of supramolecular containers. The container compounds include carcerands, deep cavitands and amide naphthotubes. We focus on unstable guest species – cyclobutadiene, benzocyclopropenone, o-benzyne, 1,2,4,6-cycloheptatetraene, anti-Bredt's olefin, fluorophenoxycarbene, O-acylisoamide, and hemiaminal – that act as intermediates in certain organic reactions
2024, 35(6): 109229
doi: 10.1016/j.cclet.2023.109229
Abstract:
The seven-membered ring motifs are found in bioactive pharmaceuticals and a wide range of natural products, including alkaloids and terpenoids, which hold significant importance in synthetic chemistry and has garnered considerable attention from both academia and industry. Despite the challenges faced in the past decade, the total synthesis of natural products incorporating the non-aromatic cycloheptane skeletons remains a compelling pursuit. Recently, numerous elegant strategies for constructing the seven-membered ring system have been successfully developed. This review focuses on the recent advancements in this field from 2017 to April 2023, highlighting key transformations utilized to construct the non-aromatic cycloheptane core structures and serves as a valuable guide for synthetic chemists engaged in the total synthesis of natural products containing seven-membered ring motifs.
The seven-membered ring motifs are found in bioactive pharmaceuticals and a wide range of natural products, including alkaloids and terpenoids, which hold significant importance in synthetic chemistry and has garnered considerable attention from both academia and industry. Despite the challenges faced in the past decade, the total synthesis of natural products incorporating the non-aromatic cycloheptane skeletons remains a compelling pursuit. Recently, numerous elegant strategies for constructing the seven-membered ring system have been successfully developed. This review focuses on the recent advancements in this field from 2017 to April 2023, highlighting key transformations utilized to construct the non-aromatic cycloheptane core structures and serves as a valuable guide for synthetic chemists engaged in the total synthesis of natural products containing seven-membered ring motifs.
2024, 35(6): 109257
doi: 10.1016/j.cclet.2023.109257
Abstract:
The hydrosilylation of unsaturated carbon-carbon bonds is one of the most critical reactions in silicone industrial production. The homogeneous Speier's catalyst, Karstedt's catalyst, and other noble metal-based catalysts are widely used. However, simplifying the separation of the homogeneous catalyst from reaction products and reducing the high cost of precious metals is still challenging. This review describes the recent development of heterogeneous catalysts for alkene, alkyne, and allene hydrosilylations, which can effectively solve problems in homogeneous hydrosilylation.
The hydrosilylation of unsaturated carbon-carbon bonds is one of the most critical reactions in silicone industrial production. The homogeneous Speier's catalyst, Karstedt's catalyst, and other noble metal-based catalysts are widely used. However, simplifying the separation of the homogeneous catalyst from reaction products and reducing the high cost of precious metals is still challenging. This review describes the recent development of heterogeneous catalysts for alkene, alkyne, and allene hydrosilylations, which can effectively solve problems in homogeneous hydrosilylation.
2024, 35(6): 109282
doi: 10.1016/j.cclet.2023.109282
Abstract:
The over-exploitation of fossil fuel energy has brought about serious environmental problems. It would be of great significance to construct efficient energy conversion and storage system to maximize utilize renewable energy, which contributes to reducing environmental hazards. For the past few years, in terms of electrocatalysis and energy storage, carbon fiber materials show great advantages due to its outstanding electrical conductivity, good flexibility and mechanical property. As a simple and low-cost technique, electrospinning can be employed to prepare various nanofibers. It is noted that the functional fiber materials with different special structure and composition can be obtained for energy conversion and storage by combining electrospinning with other post-processing. In this paper, the structural design, controllable synthesis and multifunctional applications of electrospinning-derived functional carbon-based materials (EFCMs) is reviewed. Firstly, we briefly introduce the history, basic principle and typical equipment of electrospinning. Then we discuss the strategies for preparing EFCMs with different structures and composition in detail. In addition, we show recently the application of advanced EFCMs in energy conversion and storage, such as nitrogen species reduction reaction, CO2 reduction reaction, oxygen reduction reaction, water-splitting, supercapacitors and ion batteries. In the end, we propose some perspectives on the future development direction of EFCMs.
The over-exploitation of fossil fuel energy has brought about serious environmental problems. It would be of great significance to construct efficient energy conversion and storage system to maximize utilize renewable energy, which contributes to reducing environmental hazards. For the past few years, in terms of electrocatalysis and energy storage, carbon fiber materials show great advantages due to its outstanding electrical conductivity, good flexibility and mechanical property. As a simple and low-cost technique, electrospinning can be employed to prepare various nanofibers. It is noted that the functional fiber materials with different special structure and composition can be obtained for energy conversion and storage by combining electrospinning with other post-processing. In this paper, the structural design, controllable synthesis and multifunctional applications of electrospinning-derived functional carbon-based materials (EFCMs) is reviewed. Firstly, we briefly introduce the history, basic principle and typical equipment of electrospinning. Then we discuss the strategies for preparing EFCMs with different structures and composition in detail. In addition, we show recently the application of advanced EFCMs in energy conversion and storage, such as nitrogen species reduction reaction, CO2 reduction reaction, oxygen reduction reaction, water-splitting, supercapacitors and ion batteries. In the end, we propose some perspectives on the future development direction of EFCMs.
2024, 35(6): 109378
doi: 10.1016/j.cclet.2023.109378
Abstract:
The microstructure of the active layer in organic photovoltaics (OPVs), such as the size of phase separation, purity of the phases, and molecular packing within each phase, plays a crucial role in influencing the behavior of excitons and charge carriers within the active layer. It is also a key determinant of the photovoltaic performance of the device. During the optimization of OPV devices, the use of additives has been demonstrated to be an effective strategy in microstructure control, leading to enhanced performance. Therefore, the quest for stable and efficient novel additives, along with an exploration and summarization of the mechanisms underlying additive-induced microstructure control, is essential for a better understanding of the developmental trends of high-performance additives. In this review, we categorize additives based on their chemical structures and discuss their effects on the microstructure of the active layer from both thermodynamic and kinetic perspectives. Furthermore, we elaborate on the working mechanisms and their impact on the photovoltaic performance of the devices. This review provides an overview of recent advances in additives for OPVs, offering potential guidance for the future development of additives and further optimization of the active layer in photovoltaic devices.
The microstructure of the active layer in organic photovoltaics (OPVs), such as the size of phase separation, purity of the phases, and molecular packing within each phase, plays a crucial role in influencing the behavior of excitons and charge carriers within the active layer. It is also a key determinant of the photovoltaic performance of the device. During the optimization of OPV devices, the use of additives has been demonstrated to be an effective strategy in microstructure control, leading to enhanced performance. Therefore, the quest for stable and efficient novel additives, along with an exploration and summarization of the mechanisms underlying additive-induced microstructure control, is essential for a better understanding of the developmental trends of high-performance additives. In this review, we categorize additives based on their chemical structures and discuss their effects on the microstructure of the active layer from both thermodynamic and kinetic perspectives. Furthermore, we elaborate on the working mechanisms and their impact on the photovoltaic performance of the devices. This review provides an overview of recent advances in additives for OPVs, offering potential guidance for the future development of additives and further optimization of the active layer in photovoltaic devices.
2024, 35(6): 108707
doi: 10.1016/j.cclet.2023.108707
Abstract:
Molecular dielectric switches constitute a type of intelligent materials that are highly coveted for their distinctive advantages of switchable dielectric responses, lightweight, and mechanical flexibility. Two-dimensional (2D) hybrid perovskites have demonstrated excellent promise for assembling dielectric switches, in which the dynamic motions of organic moieties afford driving force to trigger switchable dielectric phase transition. Here, we successfully assembled a new lead-free hybrid double perovskite, (CHA)4CuBiBr8 (1, CHA = cyclohexylammonium), adopting a typical 2D structural motif, which shows dielectric anisotropy and bistable behaviors during the reversible phase transition near Tc = 378 K (the Curie temperature). That is, its dielectric constants could be switched and tuned between high-dielectric and low-dielectric states. Structure analyses reveal that the ordered-disordered transformation of the organic CHA+ moiety and distortion of inorganic framework account for its phase transition. This result will stimulate further exploration of molecular dielectric switches in this 2D environmentally friendly family.
Molecular dielectric switches constitute a type of intelligent materials that are highly coveted for their distinctive advantages of switchable dielectric responses, lightweight, and mechanical flexibility. Two-dimensional (2D) hybrid perovskites have demonstrated excellent promise for assembling dielectric switches, in which the dynamic motions of organic moieties afford driving force to trigger switchable dielectric phase transition. Here, we successfully assembled a new lead-free hybrid double perovskite, (CHA)4CuBiBr8 (1, CHA = cyclohexylammonium), adopting a typical 2D structural motif, which shows dielectric anisotropy and bistable behaviors during the reversible phase transition near Tc = 378 K (the Curie temperature). That is, its dielectric constants could be switched and tuned between high-dielectric and low-dielectric states. Structure analyses reveal that the ordered-disordered transformation of the organic CHA+ moiety and distortion of inorganic framework account for its phase transition. This result will stimulate further exploration of molecular dielectric switches in this 2D environmentally friendly family.
2024, 35(6): 108708
doi: 10.1016/j.cclet.2023.108708
Abstract:
Lead-halide perovskites exhibit outstanding performance in X-ray detection due to their intrinsic features such as high charge carrier mobility, large atomic number, and long carrier lifetime, but the toxicity of lead is regarded as the major factor hindering their development. Here, we introduce organic molecule (R)-(-)-2-methylpiperazine (R-MPz) into the bismuth-based structure to synthesize lead-free (R)-(H2MPz)BiI5 (R-MBI). The high-quality centimeter-sized single crystals have been obtained, which show a low dark current and superior environmental stability. Particularly, the single-crystal device of R-MBI exhibits a high μτ product up to 1.88 × 10−4 cm2/V and a low trap density of 1.21 × 1010 cm−3. Further, the detector displays excellent detection sensitivity of 263.58 µC Gyair−1 cm−2 and a favorable low detection limit of 4.35 µGyair/s, both of which meet the requirement for medical diagnostics. These findings shed light on the exploration of innovative bismuth-based hybrid perovskites for high-performance X-ray detection.
Lead-halide perovskites exhibit outstanding performance in X-ray detection due to their intrinsic features such as high charge carrier mobility, large atomic number, and long carrier lifetime, but the toxicity of lead is regarded as the major factor hindering their development. Here, we introduce organic molecule (R)-(-)-2-methylpiperazine (R-MPz) into the bismuth-based structure to synthesize lead-free (R)-(H2MPz)BiI5 (R-MBI). The high-quality centimeter-sized single crystals have been obtained, which show a low dark current and superior environmental stability. Particularly, the single-crystal device of R-MBI exhibits a high μτ product up to 1.88 × 10−4 cm2/V and a low trap density of 1.21 × 1010 cm−3. Further, the detector displays excellent detection sensitivity of 263.58 µC Gyair−1 cm−2 and a favorable low detection limit of 4.35 µGyair/s, both of which meet the requirement for medical diagnostics. These findings shed light on the exploration of innovative bismuth-based hybrid perovskites for high-performance X-ray detection.
2024, 35(6): 108715
doi: 10.1016/j.cclet.2023.108715
Abstract:
Nowadays, lithium-ion batteries (LIBs) play a crucial role in modern society in the aspect of portable electronic devices and large-scale smart grids. However, the current performance of lithium-ion batteries has been unable to meet the growing expectations of society and scientific community. Herein, we have synthetically investigated availability of 2D Ni-TABQ monolayer as anode based on DFT for LIBs applications. Our findings have demonstrated that 2D Ni-TABQ monolayer is a semiconductor with a small band gap of 0.2 eV, which suggest that the electronic property of 2D Ni-TABQ monolayer would take place an evident shift from semiconductor property to metallic property after Li adsorption. Furthermore, we checked the stability of 2D Ni-TABQ monolayer and investigated the viability of exfoliation from bulk multilayer Ni-TABQ to form 2D Ni-TABQ monolayer in the light of exfoliation energy and binding energy. We continuously studied electrochemical properties of 2D Ni-TABQ monolayer with respect of theoretical specific capacity, Li-ion diffusion barriers and open-circuit voltage. During the charging process, 2D Ni-TABQ monolayer can achieve a high specific capacity of 722 mAh/g with an open-circuit voltage range from 1.12 V to 0.22 V. These aforementioned results make the 2D Ni-TABQ monolayer a promising anode for LIBs.
Nowadays, lithium-ion batteries (LIBs) play a crucial role in modern society in the aspect of portable electronic devices and large-scale smart grids. However, the current performance of lithium-ion batteries has been unable to meet the growing expectations of society and scientific community. Herein, we have synthetically investigated availability of 2D Ni-TABQ monolayer as anode based on DFT for LIBs applications. Our findings have demonstrated that 2D Ni-TABQ monolayer is a semiconductor with a small band gap of 0.2 eV, which suggest that the electronic property of 2D Ni-TABQ monolayer would take place an evident shift from semiconductor property to metallic property after Li adsorption. Furthermore, we checked the stability of 2D Ni-TABQ monolayer and investigated the viability of exfoliation from bulk multilayer Ni-TABQ to form 2D Ni-TABQ monolayer in the light of exfoliation energy and binding energy. We continuously studied electrochemical properties of 2D Ni-TABQ monolayer with respect of theoretical specific capacity, Li-ion diffusion barriers and open-circuit voltage. During the charging process, 2D Ni-TABQ monolayer can achieve a high specific capacity of 722 mAh/g with an open-circuit voltage range from 1.12 V to 0.22 V. These aforementioned results make the 2D Ni-TABQ monolayer a promising anode for LIBs.
2024, 35(6): 108717
doi: 10.1016/j.cclet.2023.108717
Abstract:
FeS2 shows significant potential as cathode material for all-solid-state lithium batteries (ASSLBs) due to its high theoretical specific capacity, low cost, and environmental friendliness. However, the poor ion/electron conductivity and large volume variation effect of FeS2 inhibit its practical applications. Here, the influence of particle size of FeS2 on the corresponding sulfide-based solid-state batteries is carefully investigated by tuning FeS2 size. Moreover, low operating temperature is chosen to mitigate the large volume changes during cycling in the battery. S-FeS2 with smaller particle sizes delivers superior electrochemical performances than that of the larger L-FeS2 in Li5.5PS4.5Cl1.5-based ASSLBs under different operating temperatures. S-FeS2 shows stable discharge capacities during 50 cycles with a current density of 0.1 mA/cm2 under -20 ℃. When the current density rises to 1.0 mA/cm2, it delivers an initial discharge capacity of 146.9 mAh/g and maintains 63% of the capacity after 100 cycles. This work contributes to constructing ASSLBs enables excellent electrochemical performances under extreme operating temperatures.
FeS2 shows significant potential as cathode material for all-solid-state lithium batteries (ASSLBs) due to its high theoretical specific capacity, low cost, and environmental friendliness. However, the poor ion/electron conductivity and large volume variation effect of FeS2 inhibit its practical applications. Here, the influence of particle size of FeS2 on the corresponding sulfide-based solid-state batteries is carefully investigated by tuning FeS2 size. Moreover, low operating temperature is chosen to mitigate the large volume changes during cycling in the battery. S-FeS2 with smaller particle sizes delivers superior electrochemical performances than that of the larger L-FeS2 in Li5.5PS4.5Cl1.5-based ASSLBs under different operating temperatures. S-FeS2 shows stable discharge capacities during 50 cycles with a current density of 0.1 mA/cm2 under -20 ℃. When the current density rises to 1.0 mA/cm2, it delivers an initial discharge capacity of 146.9 mAh/g and maintains 63% of the capacity after 100 cycles. This work contributes to constructing ASSLBs enables excellent electrochemical performances under extreme operating temperatures.
2024, 35(6): 108776
doi: 10.1016/j.cclet.2023.108776
Abstract:
All-solid-state lithium batteries (ASSLBs) based on sulfide electrolytes promise next-generation energy storage with high energy density and safety. However, the sulfide electrolytes suffer from phase instability and sluggish interfacial charge transport when pairing with layered oxide cathodes at high voltages. Herein, a simple and efficient strategy is proposed using two-dimensional Ti3C2T MXene as starting material to in-situ construct a 15 nm Li2TiO3 layer on a typical oxide cathode, LiCoO2. The in-situ transformation of Ti3C2T into Li2TiO3 layer occurs at a low temperature of 500 ℃, avoiding the phase deterioration of LiCoO2. The thin Li2TiO3 layer is Li+ conducting and electrochemically stable, thereby preventing the interfacial decomposition of sulfide electrolytes induced by LiCoO2 at high voltages and facilitating Li+ transport at the interface. Moreover, Li2TiO3 can stabilize the layer structure of LiCoO2 at high voltages. Consequently, the sulfide-based ASSLB using LiCoO2@Li2TiO3 cathode can operate stably at a high voltage of up to 4.5 V (vs. Li+/Li), delivering an outstanding initial specific discharge capacity of 138.8 mAh/g with a high capacity retention of 86.2% after 100 cycles at 0.2 C. The in-situ transformation strategy may also apply to other MXenes, offering a general approach for constructing other advanced lithiated coatings for oxide cathodes.
All-solid-state lithium batteries (ASSLBs) based on sulfide electrolytes promise next-generation energy storage with high energy density and safety. However, the sulfide electrolytes suffer from phase instability and sluggish interfacial charge transport when pairing with layered oxide cathodes at high voltages. Herein, a simple and efficient strategy is proposed using two-dimensional Ti3C2T MXene as starting material to in-situ construct a 15 nm Li2TiO3 layer on a typical oxide cathode, LiCoO2. The in-situ transformation of Ti3C2T into Li2TiO3 layer occurs at a low temperature of 500 ℃, avoiding the phase deterioration of LiCoO2. The thin Li2TiO3 layer is Li+ conducting and electrochemically stable, thereby preventing the interfacial decomposition of sulfide electrolytes induced by LiCoO2 at high voltages and facilitating Li+ transport at the interface. Moreover, Li2TiO3 can stabilize the layer structure of LiCoO2 at high voltages. Consequently, the sulfide-based ASSLB using LiCoO2@Li2TiO3 cathode can operate stably at a high voltage of up to 4.5 V (vs. Li+/Li), delivering an outstanding initial specific discharge capacity of 138.8 mAh/g with a high capacity retention of 86.2% after 100 cycles at 0.2 C. The in-situ transformation strategy may also apply to other MXenes, offering a general approach for constructing other advanced lithiated coatings for oxide cathodes.
2024, 35(6): 108779
doi: 10.1016/j.cclet.2023.108779
Abstract:
Exhaled ammonia (NH3) can be used as a crucial biomarker of kidney and liver diseases. However, the high humidity in the detection conditions remains a challenge for accurate detection by gas sensors. Herein, a copper-based metal-organic framework (CH3-Cu-BTC) with methyl (CH3-) functionalization of trimesic acid was synthesized for NH3 colorimetric sensing. The CH3-Cu-BTC exhibited a strong response for 5 ppm NH3 with high selectivity under high relative humidity (75% RH). Density functional theory (DFT) simulations indicated that the NH3 molecules interacted more strongly with CH3-Cu-BTC than H2O molecules did, and the corresponding color switching was attributed to the lone-pair electron in NH3 changing the coordination environment of Cu2+ ions, leading to an obviously visible color switching response from ruby green to blue. Based on the tailor-made pore chemistry, the precise detection of trace amounts of NH3 in exhaled air was realized through functionalized MOF materials. The strategy used in this study not only offers a new pathway for the rapid detection of low concentration NH3 under humid conditions, but also shows a method for early respiration diagnosis of kidney and liver diseases.
Exhaled ammonia (NH3) can be used as a crucial biomarker of kidney and liver diseases. However, the high humidity in the detection conditions remains a challenge for accurate detection by gas sensors. Herein, a copper-based metal-organic framework (CH3-Cu-BTC) with methyl (CH3-) functionalization of trimesic acid was synthesized for NH3 colorimetric sensing. The CH3-Cu-BTC exhibited a strong response for 5 ppm NH3 with high selectivity under high relative humidity (75% RH). Density functional theory (DFT) simulations indicated that the NH3 molecules interacted more strongly with CH3-Cu-BTC than H2O molecules did, and the corresponding color switching was attributed to the lone-pair electron in NH3 changing the coordination environment of Cu2+ ions, leading to an obviously visible color switching response from ruby green to blue. Based on the tailor-made pore chemistry, the precise detection of trace amounts of NH3 in exhaled air was realized through functionalized MOF materials. The strategy used in this study not only offers a new pathway for the rapid detection of low concentration NH3 under humid conditions, but also shows a method for early respiration diagnosis of kidney and liver diseases.
2024, 35(6): 108782
doi: 10.1016/j.cclet.2023.108782
Abstract:
Hydrogen evolution electrocatalysts derived from metal-organic crystalline frameworks can inherit the merits of ordered and adjustable structures with high surface area. In this paper, organic-octamolybdate crystalline superstructures (OOCS) with a fixed stoichiometric ratio of Mo8(L)2 and high Mo content (> 40 wt%) were synthesized using flexible ligands with controllable lengths (named as OOCS-1–3). Then, molybdenum carbides coated with carbon layers as electrocatalysts (Mo2C@C-1–3) can be obtained directly from a one-step high-temperature carbonization process using OOCS-1–3 as precursors. As a typical example, Mo2C@C-3 exhibits satisfactory hydrogen evolution activity with a low overpotential of 151 mV (1.0 mol/L KOH) at 10 mA/cm2 and stability for 24 h. The electrocatalytic activity is mainly from the synergistic interactions between the carbon layers and molybdenum carbide species. Furthermore, compared with the initial content of C, N, Mo in OOCS and Mo2C@C, the catalytic activity increases with the N amount. This work makes organic-octamolybdate crystalline superstructures used as general precursors to product high Mo content electrocatalysts applied in energy storage and conversion fields.
Hydrogen evolution electrocatalysts derived from metal-organic crystalline frameworks can inherit the merits of ordered and adjustable structures with high surface area. In this paper, organic-octamolybdate crystalline superstructures (OOCS) with a fixed stoichiometric ratio of Mo8(L)2 and high Mo content (> 40 wt%) were synthesized using flexible ligands with controllable lengths (named as OOCS-1–3). Then, molybdenum carbides coated with carbon layers as electrocatalysts (Mo2C@C-1–3) can be obtained directly from a one-step high-temperature carbonization process using OOCS-1–3 as precursors. As a typical example, Mo2C@C-3 exhibits satisfactory hydrogen evolution activity with a low overpotential of 151 mV (1.0 mol/L KOH) at 10 mA/cm2 and stability for 24 h. The electrocatalytic activity is mainly from the synergistic interactions between the carbon layers and molybdenum carbide species. Furthermore, compared with the initial content of C, N, Mo in OOCS and Mo2C@C, the catalytic activity increases with the N amount. This work makes organic-octamolybdate crystalline superstructures used as general precursors to product high Mo content electrocatalysts applied in energy storage and conversion fields.
2024, 35(6): 108785
doi: 10.1016/j.cclet.2023.108785
Abstract:
Covalent organic frameworks (COFs) exhibiting reversible redox behaviors have been identified as promising candidates for constructing electrode materials in lithium-ion batteries (LIBs). However, their extensive application has been limited due to finite redox sites and poor structural stability. In this study, we design and synthesize a novel polyimide covalent organic framework (PI-COF) using the traditional solvothermal method and successfully apply it as an anode material for LIBs. The large conjugated structure of PI-COF accelerates charge transfer, while its large surface area provides more active sites, making PI-COF an attractive anode material for LIBs. Furthermore, the PI-COF anode material demonstrates high reversible specific capacity and excellent long-term cycling stability due to its COF characteristics. Specifically, the PI-COF electrodes deliver a specific capacity of 800 mAh/g at a current density of 200 mA/g after 200 cycles, while a specific capacity of 450 mAh/g at a current density of 1000 mA/g is sustained after 800 cycles. The outstanding lithium storage capacity, particularly the satisfactory long-term cycling stability, establishes PI-COF as a promising material for LIBs.
Covalent organic frameworks (COFs) exhibiting reversible redox behaviors have been identified as promising candidates for constructing electrode materials in lithium-ion batteries (LIBs). However, their extensive application has been limited due to finite redox sites and poor structural stability. In this study, we design and synthesize a novel polyimide covalent organic framework (PI-COF) using the traditional solvothermal method and successfully apply it as an anode material for LIBs. The large conjugated structure of PI-COF accelerates charge transfer, while its large surface area provides more active sites, making PI-COF an attractive anode material for LIBs. Furthermore, the PI-COF anode material demonstrates high reversible specific capacity and excellent long-term cycling stability due to its COF characteristics. Specifically, the PI-COF electrodes deliver a specific capacity of 800 mAh/g at a current density of 200 mA/g after 200 cycles, while a specific capacity of 450 mAh/g at a current density of 1000 mA/g is sustained after 800 cycles. The outstanding lithium storage capacity, particularly the satisfactory long-term cycling stability, establishes PI-COF as a promising material for LIBs.
2024, 35(6): 108797
doi: 10.1016/j.cclet.2023.108797
Abstract:
Polyethylene oxide (PEO)-based solid-state polymer electrolytes (SPEs) are limited by their poor cyclic stability and inferior ionic conductivity for applicating in high-safety, long-cycling and high-energy-density lithium metal batteries. Herein, porous boron nitride nanofibers (BNNFs) are filled into PEO-based SPE, which significantly suppresses Li dendrites growth and enhances the electrochemical performance of Li metal battery. BNNFs with high porosity have more active sites to connect with PEO, which can effectively reduce the crystallinity of the PEO matrix and enhance its ionic conductivity. Moreover, owing to the hardness and good stability of BNNFs, BNNFs/PEO/LiTFSI electrolyte exhibits a wider electrochemical window, better mechanical property and higher thermal stability compared with PEO/LiTFSI electrolyte. Consequently, the Li symmetric cell composed of 1% BNNFs/PEO/LiTFSI performs good cyclic stability (>1800 h), and the Li||1% BNNFs/PEO/LiTFSI||LFP full battery shows obviously improved performances in charge-discharge polarization voltage, discharge specific capacity, rate performance and cyclic stability than the Li||PEO/LiTFSI||LFP battery.
Polyethylene oxide (PEO)-based solid-state polymer electrolytes (SPEs) are limited by their poor cyclic stability and inferior ionic conductivity for applicating in high-safety, long-cycling and high-energy-density lithium metal batteries. Herein, porous boron nitride nanofibers (BNNFs) are filled into PEO-based SPE, which significantly suppresses Li dendrites growth and enhances the electrochemical performance of Li metal battery. BNNFs with high porosity have more active sites to connect with PEO, which can effectively reduce the crystallinity of the PEO matrix and enhance its ionic conductivity. Moreover, owing to the hardness and good stability of BNNFs, BNNFs/PEO/LiTFSI electrolyte exhibits a wider electrochemical window, better mechanical property and higher thermal stability compared with PEO/LiTFSI electrolyte. Consequently, the Li symmetric cell composed of 1% BNNFs/PEO/LiTFSI performs good cyclic stability (>1800 h), and the Li||1% BNNFs/PEO/LiTFSI||LFP full battery shows obviously improved performances in charge-discharge polarization voltage, discharge specific capacity, rate performance and cyclic stability than the Li||PEO/LiTFSI||LFP battery.
2024, 35(6): 108798
doi: 10.1016/j.cclet.2023.108798
Abstract:
Hybrid metal-organic framework (MOF) derivatives play a significant role in the novel catalyst development in energy conversion reactions. Here, we demonstrated the low-temperature fully fluorinated zeolitic imidazole framework (ZIF) coupled with a three-dimensional open framework Prussian blue analog (PBA) with combined advantages for electrocatalytic oxygen evolution reaction (OER) in water splitting reaction. The spectroscopic analysis and the electrochemical studies revealed the combined advantages of efficient electronic effect and active site synergism. Because of good conductivity improvement by N-doped carbon derived from ZIF and the high electrochemical surface area and active site exposure from PBA derivatives, good catalytic performance was obtained on the optimal catalyst of CoNi ZIF/CoFe-PBA-F-300, which required a low overpotential of 250 mV to reach 10 mA/cm2 loaded on the glassy carbon electrode, with Tafel slope of 47.4 mV/dec, and very high dynamic and steady stability. In addition, the multi-component with the mixed structure from highly polar metal fluorides promoted the easy formation of the active phase as revealed by the post-sample analysis. The current results showed a novel composite catalyst materials development from the hybrid MOF derivatives, which would be promising in the electrolysis of water oxidation reactions and energy-relevant catalysis reactions.
Hybrid metal-organic framework (MOF) derivatives play a significant role in the novel catalyst development in energy conversion reactions. Here, we demonstrated the low-temperature fully fluorinated zeolitic imidazole framework (ZIF) coupled with a three-dimensional open framework Prussian blue analog (PBA) with combined advantages for electrocatalytic oxygen evolution reaction (OER) in water splitting reaction. The spectroscopic analysis and the electrochemical studies revealed the combined advantages of efficient electronic effect and active site synergism. Because of good conductivity improvement by N-doped carbon derived from ZIF and the high electrochemical surface area and active site exposure from PBA derivatives, good catalytic performance was obtained on the optimal catalyst of CoNi ZIF/CoFe-PBA-F-300, which required a low overpotential of 250 mV to reach 10 mA/cm2 loaded on the glassy carbon electrode, with Tafel slope of 47.4 mV/dec, and very high dynamic and steady stability. In addition, the multi-component with the mixed structure from highly polar metal fluorides promoted the easy formation of the active phase as revealed by the post-sample analysis. The current results showed a novel composite catalyst materials development from the hybrid MOF derivatives, which would be promising in the electrolysis of water oxidation reactions and energy-relevant catalysis reactions.
Improved performance of LiMn0.8Fe0.2PO4 by addition of fluoroethylene carbonate electrolyte additive
2024, 35(6): 108799
doi: 10.1016/j.cclet.2023.108799
Abstract:
The addition of electrolyte additives is an effective strategy for tuning the property of the electrolyte to engineer the electrode/electrolyte interface, and there exist obvious discrepancies regarding the effect of fluoroethylene carbonate (FEC) as an electrolyte additive on the performance of cathodes. Herein FEC is introduced into the electrolyte of the LiMn0.8Fe0.2PO4/Li cell and its effect on the properties of the LiMn0.8Fe0.2PO4 is investigated. It is found that the addition of FEC in the electrolyte has a positive effect on the performance of the LiMn0.8Fe0.2PO4 cathode, which can be attributed to the reduced products generated by the interfacial side-reactions on the LiMn0.8Fe0.2PO4 cathode surface and the decreased metal dissolution in the FEC-containing electrolyte, thanks to the higher oxidation resistance of FEC and the easier and stronger binding of FEC and PF6−.
The addition of electrolyte additives is an effective strategy for tuning the property of the electrolyte to engineer the electrode/electrolyte interface, and there exist obvious discrepancies regarding the effect of fluoroethylene carbonate (FEC) as an electrolyte additive on the performance of cathodes. Herein FEC is introduced into the electrolyte of the LiMn0.8Fe0.2PO4/Li cell and its effect on the properties of the LiMn0.8Fe0.2PO4 is investigated. It is found that the addition of FEC in the electrolyte has a positive effect on the performance of the LiMn0.8Fe0.2PO4 cathode, which can be attributed to the reduced products generated by the interfacial side-reactions on the LiMn0.8Fe0.2PO4 cathode surface and the decreased metal dissolution in the FEC-containing electrolyte, thanks to the higher oxidation resistance of FEC and the easier and stronger binding of FEC and PF6−.
2024, 35(6): 108809
doi: 10.1016/j.cclet.2023.108809
Abstract:
Molecular ferroelectrics have attracted much attention because of their excellent piezoelectricity, mechanical workability, and second harmonic effect. Here, we successfully prepared two molecular ferroelectrics 1,5–3.2.2-HdabcniX (X = ClO4−, 1; ReO4−, 2) by reactions of a quasi-spherical amine 1,5-diazabicycle[3.2.2]nonane (1.5–3.2.2-dabcn) with HX aqueous solution. Compounds 1 and 2 undergo high-temperature phase transitions at 381 K (1) and 396 K (2). Before and after the phase transition, they crystallize in the polar point group mm2, and the centrosymmetric point groups mmm and 4/mmm, respectively. According to Aizu rules, these two compounds experience mmmFmm2 and 4/mmmFmm2 type ferroelectric phase transitions, respectively. The ferroelectricity of both compounds is well expressed in their polycrystalline film at room temperature with low coercive voltages of 13 V for 1 and 25 V for 2. Using piezoelectric force microscopy (PFM), the 180° anti-parallel ferroelectric domains and the reversible polarization switching can be clearly observed in 1 and 2. This high-temperature molecular ferroelectric material has great application potential in flexible materials, biomechanics, intelligent wearables and other fields.
Molecular ferroelectrics have attracted much attention because of their excellent piezoelectricity, mechanical workability, and second harmonic effect. Here, we successfully prepared two molecular ferroelectrics 1,5–3.2.2-HdabcniX (X = ClO4−, 1; ReO4−, 2) by reactions of a quasi-spherical amine 1,5-diazabicycle[3.2.2]nonane (1.5–3.2.2-dabcn) with HX aqueous solution. Compounds 1 and 2 undergo high-temperature phase transitions at 381 K (1) and 396 K (2). Before and after the phase transition, they crystallize in the polar point group mm2, and the centrosymmetric point groups mmm and 4/mmm, respectively. According to Aizu rules, these two compounds experience mmmFmm2 and 4/mmmFmm2 type ferroelectric phase transitions, respectively. The ferroelectricity of both compounds is well expressed in their polycrystalline film at room temperature with low coercive voltages of 13 V for 1 and 25 V for 2. Using piezoelectric force microscopy (PFM), the 180° anti-parallel ferroelectric domains and the reversible polarization switching can be clearly observed in 1 and 2. This high-temperature molecular ferroelectric material has great application potential in flexible materials, biomechanics, intelligent wearables and other fields.
2024, 35(6): 108814
doi: 10.1016/j.cclet.2023.108814
Abstract:
Side reactions and dendrite growth triggered by the unstable interface and inhomogeneous deposition have become the biggest obstacle to the commercialization for lithium metal batteries. In this study, a highly-chlorinated organic-inorganic hybrid interfacial protective layer is developed by rationally tuning the interfacial passivation and robustness to achieve the convenient and efficient Li metal anode. The polyvinyl chloride (PVC) can effectively resist water and oxygen, which is confirmed by density functional theory. The organic-dominant solid electrolyte interphases (SEI) with lithium chloride are investigated by the X-ray photoelectron spectroscopy (XPS) with little mineralization of oxide, such as Li2O and Li2CO3. With such artificial SEI, a uniform and dense lithium deposition morphology are formed and an ultra-long stable cycle of over 500 h are achieved even at an ultra-high current density of 10 mA/cm2. Moreover, the simple and convenient protected anode also exhibits excellent battery stability when paired with the LiNi0.8Co0.1Mn0.1O2 (NCM811) and LiFePO4 (LFP) cathode, showing great potential for the commercial application of lithium metal batteries.
Side reactions and dendrite growth triggered by the unstable interface and inhomogeneous deposition have become the biggest obstacle to the commercialization for lithium metal batteries. In this study, a highly-chlorinated organic-inorganic hybrid interfacial protective layer is developed by rationally tuning the interfacial passivation and robustness to achieve the convenient and efficient Li metal anode. The polyvinyl chloride (PVC) can effectively resist water and oxygen, which is confirmed by density functional theory. The organic-dominant solid electrolyte interphases (SEI) with lithium chloride are investigated by the X-ray photoelectron spectroscopy (XPS) with little mineralization of oxide, such as Li2O and Li2CO3. With such artificial SEI, a uniform and dense lithium deposition morphology are formed and an ultra-long stable cycle of over 500 h are achieved even at an ultra-high current density of 10 mA/cm2. Moreover, the simple and convenient protected anode also exhibits excellent battery stability when paired with the LiNi0.8Co0.1Mn0.1O2 (NCM811) and LiFePO4 (LFP) cathode, showing great potential for the commercial application of lithium metal batteries.
2024, 35(6): 108827
doi: 10.1016/j.cclet.2023.108827
Abstract:
Inspired by our previous studies to discover novel human immunodeficiency virus-1 (HIV-1) non-nucleoside reverse transcriptase inhibitors (NNRTIs) by targeting the tolerant region II of the NNRTIs binding pocket (NNIBP), a series of novel benzo[4,5]thieno[2,3-d]pyrimidine derivatives were designed through structure-based drug design as novel potent HIV-1 NNRTIs. The results showed that compound 16b was the most active inhibitor, exhibiting 50% effective concentration (EC50) values from 0.021 µmol/L to 0.298 µmol/L against wild-type (WT) and a panel of NNRTIs-resistant HIV-1 strains. Moreover, 16b was demonstrated with a significantly low 50% cytotoxicity concentration (CC50) value (> 200 µmol/L) and high selectivity index (SI) values. In addition, 16b yielded moderate reverse transcriptase (RT) enzyme inhibition with a 50% inhibition concentration (IC50) value of 0.183 µmol/L, which demonstrated that it acted as HIV-1 NNRTIs. The binding mode of 16b with RT was also illustrated via molecular docking. Overall, this work provided a novel lead compound for developing potent HIV-1 NNRTIs.
Inspired by our previous studies to discover novel human immunodeficiency virus-1 (HIV-1) non-nucleoside reverse transcriptase inhibitors (NNRTIs) by targeting the tolerant region II of the NNRTIs binding pocket (NNIBP), a series of novel benzo[4,5]thieno[2,3-d]pyrimidine derivatives were designed through structure-based drug design as novel potent HIV-1 NNRTIs. The results showed that compound 16b was the most active inhibitor, exhibiting 50% effective concentration (EC50) values from 0.021 µmol/L to 0.298 µmol/L against wild-type (WT) and a panel of NNRTIs-resistant HIV-1 strains. Moreover, 16b was demonstrated with a significantly low 50% cytotoxicity concentration (CC50) value (> 200 µmol/L) and high selectivity index (SI) values. In addition, 16b yielded moderate reverse transcriptase (RT) enzyme inhibition with a 50% inhibition concentration (IC50) value of 0.183 µmol/L, which demonstrated that it acted as HIV-1 NNRTIs. The binding mode of 16b with RT was also illustrated via molecular docking. Overall, this work provided a novel lead compound for developing potent HIV-1 NNRTIs.
2024, 35(6): 108862
doi: 10.1016/j.cclet.2023.108862
Abstract:
Integrating ring-fused modification with π-conjugated extension is an effective approach for designing, synthesizing, and application for novel borondipyrromethene (BODIPY) structures. In this work, based on phenyl[b]-fused BODIPY, we made reasonable modification of the methyl group at 1-site to generate dye NBDP. NBDP possessed near-infrared region (NIR) absorption and emission properties, and the intramolecular charge transfer (ICT) resulted in low fluorescence. Whereas, heat energy is evidently released in the presence of light, which can be exploited for intracellular photothermal therapy via the cell apoptosis process, reducing the inflammatory side-effects induced by necrosis. This research provides a crucial foundation for the novel molecule via BODIPY multi-directional alteration and its potential application in anti-tumor phototherapy.
Integrating ring-fused modification with π-conjugated extension is an effective approach for designing, synthesizing, and application for novel borondipyrromethene (BODIPY) structures. In this work, based on phenyl[b]-fused BODIPY, we made reasonable modification of the methyl group at 1-site to generate dye NBDP. NBDP possessed near-infrared region (NIR) absorption and emission properties, and the intramolecular charge transfer (ICT) resulted in low fluorescence. Whereas, heat energy is evidently released in the presence of light, which can be exploited for intracellular photothermal therapy via the cell apoptosis process, reducing the inflammatory side-effects induced by necrosis. This research provides a crucial foundation for the novel molecule via BODIPY multi-directional alteration and its potential application in anti-tumor phototherapy.
2024, 35(6): 108881
doi: 10.1016/j.cclet.2023.108881
Abstract:
The first phloroglucinol-triterpenoid hybrids, myrtphlotritins A–E (1–5), were rapidly recognized and isolated from two species of Myrtaceae by employing the building blocks-based molecular network (BBMN) strategy. Compounds 1–5 featured new carbon skeletons in which phloroglucinol derivatives were coupled with lupane- and dammarane-type triterpenoids through different linkage patterns. Their structures and absolute configurations were elucidated by comprehensive analysis of spectroscopic data and quantum chemical calculations. Biosynthetic pathways for compounds 1–5 were proposed on the basis of the coexisting precursors. Guided by the biogenetic pathways, the biomimetic synthesis of compound 1 was also achieved. Additionally, compounds 2, 3, and 5 exhibited potent antiviral activities against herpes simplex virus type-1 (HSV-1) infection, and compounds 2 and 5 displayed significant anti-inflammatory activities on RAW264.7 cells.
The first phloroglucinol-triterpenoid hybrids, myrtphlotritins A–E (1–5), were rapidly recognized and isolated from two species of Myrtaceae by employing the building blocks-based molecular network (BBMN) strategy. Compounds 1–5 featured new carbon skeletons in which phloroglucinol derivatives were coupled with lupane- and dammarane-type triterpenoids through different linkage patterns. Their structures and absolute configurations were elucidated by comprehensive analysis of spectroscopic data and quantum chemical calculations. Biosynthetic pathways for compounds 1–5 were proposed on the basis of the coexisting precursors. Guided by the biogenetic pathways, the biomimetic synthesis of compound 1 was also achieved. Additionally, compounds 2, 3, and 5 exhibited potent antiviral activities against herpes simplex virus type-1 (HSV-1) infection, and compounds 2 and 5 displayed significant anti-inflammatory activities on RAW264.7 cells.
2024, 35(6): 108889
doi: 10.1016/j.cclet.2023.108889
Abstract:
Surface modification of microporous bone scaffolds using nanoparticles has been broadly studied in bone tissue engineering. Aiming at improving vascularized bone regeneration (VBR), zeolitic imidazolate framework-8 (ZIF-8) was encapsulated with dimethyloxallyl glycine (DMOG) and the drug-carrying nanoparticles (D@Z) could be uniformly coated onto the surface of the bone scaffold. The osteogenic and angiogenic actions of D@Z are closely correlated with the amount of slowly released DMOG, and in general, exhibited a favorable association. Then, the D7.5@Z group, which showed the greatest capacity to induce in vitro osteogenesis–angiogenesis coupling, was utilized for surface modification of the bone scaffold. Biological processes including phosphate-containing compound metabolic process, cell differentiation, cell proliferation and cell motility might contribute to enhanced ability to induce VBR by the coated scaffold and signaling pathways such as Rap1, Ras, phosphatidylinositol 3-kinase/protein kinase B (PI3K-AKT) and vascular endothelial growth factor (VEGF) signaling pathways participated in these processes. Finally, as depicted by in vitro real time-polymerase chain reaction (RT-PCR), Western blot (WB) and in vivo cranial bone defect model, the microporous scaffold coated with nano-D7.5@Z greatly promoted VBR. To conclude, nano-D@Z has significant promise for practical application in modification of microporous bone scaffolds to enhance VBR, and DMOG loading quantity has a beneficial influence on D@Z to improve osteogenesis–angiogenesis coupling.
Surface modification of microporous bone scaffolds using nanoparticles has been broadly studied in bone tissue engineering. Aiming at improving vascularized bone regeneration (VBR), zeolitic imidazolate framework-8 (ZIF-8) was encapsulated with dimethyloxallyl glycine (DMOG) and the drug-carrying nanoparticles (D@Z) could be uniformly coated onto the surface of the bone scaffold. The osteogenic and angiogenic actions of D@Z are closely correlated with the amount of slowly released DMOG, and in general, exhibited a favorable association. Then, the D7.5@Z group, which showed the greatest capacity to induce in vitro osteogenesis–angiogenesis coupling, was utilized for surface modification of the bone scaffold. Biological processes including phosphate-containing compound metabolic process, cell differentiation, cell proliferation and cell motility might contribute to enhanced ability to induce VBR by the coated scaffold and signaling pathways such as Rap1, Ras, phosphatidylinositol 3-kinase/protein kinase B (PI3K-AKT) and vascular endothelial growth factor (VEGF) signaling pathways participated in these processes. Finally, as depicted by in vitro real time-polymerase chain reaction (RT-PCR), Western blot (WB) and in vivo cranial bone defect model, the microporous scaffold coated with nano-D7.5@Z greatly promoted VBR. To conclude, nano-D@Z has significant promise for practical application in modification of microporous bone scaffolds to enhance VBR, and DMOG loading quantity has a beneficial influence on D@Z to improve osteogenesis–angiogenesis coupling.
2024, 35(6): 108912
doi: 10.1016/j.cclet.2023.108912
Abstract:
Abnormal accumulation and metabolism of lipid droplets can lead to a variety of diseases. Polarity, a key parameter of the microenvironment, is closely associated with many diseases and dysfunctions in the body. It is important to elucidate the relationship between the physiological activity of lipid droplets (LDs) and the polarity of the microenvironment. In this work, based on push-pull mechanism, a fluorescent probe (E)-3-(5-(4-(diphenylamino)phenyl)thiophen-2-yl)-1-(2-hydroxyphenyl)prop-2-en-1-one (PPTH) with aggregation-induced emission (AIE) properties for the detection of polarity changes in cells was synthesized. PPTH not only visualize intracellular polarity fluctuation of iron death and inflammation but also distinguish between normal and fatty liver tissue.
Abnormal accumulation and metabolism of lipid droplets can lead to a variety of diseases. Polarity, a key parameter of the microenvironment, is closely associated with many diseases and dysfunctions in the body. It is important to elucidate the relationship between the physiological activity of lipid droplets (LDs) and the polarity of the microenvironment. In this work, based on push-pull mechanism, a fluorescent probe (E)-3-(5-(4-(diphenylamino)phenyl)thiophen-2-yl)-1-(2-hydroxyphenyl)prop-2-en-1-one (PPTH) with aggregation-induced emission (AIE) properties for the detection of polarity changes in cells was synthesized. PPTH not only visualize intracellular polarity fluctuation of iron death and inflammation but also distinguish between normal and fatty liver tissue.
2024, 35(6): 108913
doi: 10.1016/j.cclet.2023.108913
Abstract:
Hepatic ischemia-reperfusion injury (HIRI) is the cause of postoperative hepatic dysfunction and failure, and even death. As an important biological effector molecule, hydrogen sulfide (H2S) of mitochondria as a gasotransmitter that is usually used to protect against acute HIRI injury. However, the exact relationship between HIRI and mitochondrial H2S remains tangled due to the lack of an effective analytical method. Herein, we have fabricated a mitochondria-targeted H2S-activatable fluorogenic probe (Mito-GW) to explore the stability of mitochondrial H2S and track the changes of mitochondrial H2S during the HIRI. By virtue of pyridinium electropositivity and its amphiphilicity, Mito-GW could accumulate in mitochondria. It goes through an analyte-prompted immolation when reacts with H2S, resulting in the releasing of the fluorophore (GW). Therefore, the extent of Mito-GW conversion to GW can be used to evaluate the changes of mitochondrial H2S level in living cells and tissues. As proof-of-principle, we have used Mito-GW to demonstrate the mitochondria H2S-levels increase and then decrease during HIRI in vitro and in vivo. Our research highlights the tremendous potential of Mito-GW as a mitochondrial H2S fluorogenic probe in elucidating the pathogenesis of HIRI, providing a powerful tool for promoting future research on hepatology.
Hepatic ischemia-reperfusion injury (HIRI) is the cause of postoperative hepatic dysfunction and failure, and even death. As an important biological effector molecule, hydrogen sulfide (H2S) of mitochondria as a gasotransmitter that is usually used to protect against acute HIRI injury. However, the exact relationship between HIRI and mitochondrial H2S remains tangled due to the lack of an effective analytical method. Herein, we have fabricated a mitochondria-targeted H2S-activatable fluorogenic probe (Mito-GW) to explore the stability of mitochondrial H2S and track the changes of mitochondrial H2S during the HIRI. By virtue of pyridinium electropositivity and its amphiphilicity, Mito-GW could accumulate in mitochondria. It goes through an analyte-prompted immolation when reacts with H2S, resulting in the releasing of the fluorophore (GW). Therefore, the extent of Mito-GW conversion to GW can be used to evaluate the changes of mitochondrial H2S level in living cells and tissues. As proof-of-principle, we have used Mito-GW to demonstrate the mitochondria H2S-levels increase and then decrease during HIRI in vitro and in vivo. Our research highlights the tremendous potential of Mito-GW as a mitochondrial H2S fluorogenic probe in elucidating the pathogenesis of HIRI, providing a powerful tool for promoting future research on hepatology.
2024, 35(6): 108925
doi: 10.1016/j.cclet.2023.108925
Abstract:
A new aggregation-induced emission (AIE)-based fluorescence sensor, TPEPy-SS-C14, for simultaneous recognition of adenosine triphosphate (ATP) and hydrogen sulfide (H2S) has been reported via the aggregation-disaggregation mechanism. The probe self-assembles nano-structure aggregations in aqueous solution. It shows fluorescence turn-on response toward ATP for the complexation-enhanced aggregation, but leads to fluorescence quenching of H2S for cleavage the aggregations.
A new aggregation-induced emission (AIE)-based fluorescence sensor, TPEPy-SS-C14, for simultaneous recognition of adenosine triphosphate (ATP) and hydrogen sulfide (H2S) has been reported via the aggregation-disaggregation mechanism. The probe self-assembles nano-structure aggregations in aqueous solution. It shows fluorescence turn-on response toward ATP for the complexation-enhanced aggregation, but leads to fluorescence quenching of H2S for cleavage the aggregations.
2024, 35(6): 108927
doi: 10.1016/j.cclet.2023.108927
Abstract:
Three novel matrine-type alkaloids (1–3) and two unprecedented aloperine-type alkaloids (4 and 5) were isolated from the root of Sophora tonkinensis and the seeds of Sophora alopecuroides respectively. Notably, compound 1 possessed an unprecedented 6/5/6 tricyclic skeleton, while compounds 2 and 3 characterized by rare 6/6/5/6 tetracyclic system and 6/6/6/6/6 pentacyclic system respectively. Moreover, compound 4 possessed an unprecedented 6/7/6/6 tetracyclic core, and compound 5 characterized by rare 6/6/6/6 tetracyclic skeleton. Their structures were elucidated by comprehensive spectroscopic data analysis and electronic circular dichroism (ECD) calculations. Biological tests indicated that compound 5 displayed significant anti-tobacco mosaic virus (TMV) activity compared with the positive control ningnanmycin.
Three novel matrine-type alkaloids (1–3) and two unprecedented aloperine-type alkaloids (4 and 5) were isolated from the root of Sophora tonkinensis and the seeds of Sophora alopecuroides respectively. Notably, compound 1 possessed an unprecedented 6/5/6 tricyclic skeleton, while compounds 2 and 3 characterized by rare 6/6/5/6 tetracyclic system and 6/6/6/6/6 pentacyclic system respectively. Moreover, compound 4 possessed an unprecedented 6/7/6/6 tetracyclic core, and compound 5 characterized by rare 6/6/6/6 tetracyclic skeleton. Their structures were elucidated by comprehensive spectroscopic data analysis and electronic circular dichroism (ECD) calculations. Biological tests indicated that compound 5 displayed significant anti-tobacco mosaic virus (TMV) activity compared with the positive control ningnanmycin.
2024, 35(6): 108928
doi: 10.1016/j.cclet.2023.108928
Abstract:
Immunosuppressive microenvironments present critical problems in clinical chemotherapy. To regulate the tumor immune microenvironment for enhancing antitumor effect, a combination of immune checkpoint inhibitors (ICIs) with chemotherapeutics has been applied clinically. In this study, miriplatin (MiPt), the lipidic derivative of 5-fluorouracil (Fu-OA), as well as the programmed death ligand 1 (PD-L1) target siRNA (siPD-L1) were integrated into Lip-Pt/Fu@siPD-L1 nanoparticles (NPs) for chemo-immunotherapy. In vitro results showed that Lip-Pt/Fu@siPD-L1 NPs could exhibit effective siRNA gene silencing and promote the phagocytosis of tumor cells by macrophages. Furthermore, in vivo results revealed that Lip-Pt/Fu@siPD-L1 NPs showed significantly higher anti-tumor efficiency than that of the physical mixing of MiPt, 5-fluorouracil, and Lip@siPD-L1 NPs (delivery of siPD-L1 by liposomes). The best anti-tumor efficiency of Lip-Pt/Fu@siPD-L1 NPs resulted from the synergistic immunotherapeutic effects of MiPt and siPD-L1 based on the inhibition of CD47 expression and the downregulation of PD-L1 in tumor cells, which elicited a robust anti-tumor immune response through the activation of macrophage phagocytosis and immune checkpoint inhibition. The Lip-Pt/Fu@siPD-L1 NPs provide a potential strategy for tumor chemo-immunotherapy.
Immunosuppressive microenvironments present critical problems in clinical chemotherapy. To regulate the tumor immune microenvironment for enhancing antitumor effect, a combination of immune checkpoint inhibitors (ICIs) with chemotherapeutics has been applied clinically. In this study, miriplatin (MiPt), the lipidic derivative of 5-fluorouracil (Fu-OA), as well as the programmed death ligand 1 (PD-L1) target siRNA (siPD-L1) were integrated into Lip-Pt/Fu@siPD-L1 nanoparticles (NPs) for chemo-immunotherapy. In vitro results showed that Lip-Pt/Fu@siPD-L1 NPs could exhibit effective siRNA gene silencing and promote the phagocytosis of tumor cells by macrophages. Furthermore, in vivo results revealed that Lip-Pt/Fu@siPD-L1 NPs showed significantly higher anti-tumor efficiency than that of the physical mixing of MiPt, 5-fluorouracil, and Lip@siPD-L1 NPs (delivery of siPD-L1 by liposomes). The best anti-tumor efficiency of Lip-Pt/Fu@siPD-L1 NPs resulted from the synergistic immunotherapeutic effects of MiPt and siPD-L1 based on the inhibition of CD47 expression and the downregulation of PD-L1 in tumor cells, which elicited a robust anti-tumor immune response through the activation of macrophage phagocytosis and immune checkpoint inhibition. The Lip-Pt/Fu@siPD-L1 NPs provide a potential strategy for tumor chemo-immunotherapy.
2024, 35(6): 108929
doi: 10.1016/j.cclet.2023.108929
Abstract:
Artemisinin (ART) resistance has been an emerging clinical problem, severely compromising antimalarial efficacy and threatening the global malaria elimination campaign. Albeit intensive studies about the molecular mechanism for ART resistance are under way, no effective therapeutic targets for reversing resistance have been applied. Here, we explore glutathione (GSH) as a therapeutic target to develop a thermo-responsive nanoplatform to specifically co-deliver ART and GSH synthesis inhibitor (L-buthionine sulfoximine, BSO) in a sustained manner, effectively reversing ART resistance in vivo. By combining with BSO, ART exerts increased antimalarial activity with reduced half-maximal inhibitory concentration (IC50) by 7.43-fold in ART-resistant strains. This work reveals that the GSH in ART-resistant parasites can be a promising therapeutic target for reversing ART resistance, paving the way for developing drug candidates and intelligent nanomedicines in malaria therapy.
Artemisinin (ART) resistance has been an emerging clinical problem, severely compromising antimalarial efficacy and threatening the global malaria elimination campaign. Albeit intensive studies about the molecular mechanism for ART resistance are under way, no effective therapeutic targets for reversing resistance have been applied. Here, we explore glutathione (GSH) as a therapeutic target to develop a thermo-responsive nanoplatform to specifically co-deliver ART and GSH synthesis inhibitor (L-buthionine sulfoximine, BSO) in a sustained manner, effectively reversing ART resistance in vivo. By combining with BSO, ART exerts increased antimalarial activity with reduced half-maximal inhibitory concentration (IC50) by 7.43-fold in ART-resistant strains. This work reveals that the GSH in ART-resistant parasites can be a promising therapeutic target for reversing ART resistance, paving the way for developing drug candidates and intelligent nanomedicines in malaria therapy.
2024, 35(6): 108936
doi: 10.1016/j.cclet.2023.108936
Abstract:
The biosecurity hazards caused by pathogenic fungus have been widely concerned. Given the long-term coexistence of eukaryotic pathogens and quorum sensing bacteria in different habitats in environments, we hypothesized that they have social interactions via signal molecules. In this work, we firstly discovered the well-known bacterial signal molecules play an adverse role in the cell morphology and metabolism in a model pathogen Trichosporon asahii. N-Tetradecanoyl-L-homoserine lactone (C14-HSL) was discovered to increase pathogen hazards of T. asahii, which limited mycelium by 52%, but enhanced cell aggregation by 93%. Higher fluorescence intensity of tryptophan (59%) and aromatic protein (2-fold) contents after the treatment of C14-HSL, indicating that aromatic proteins helped aggregate Trichosporon and showed hydrophobicity. Transcriptome analysis revealed that C14-HSL upregulated the shikimate pathway (above 1-fold) located in downstream of tricarboxylic acid cycle, which contributed to the synthesis of more aromatic proteins and the formation of larger flocs. The limited mycelial growth of T. asahii attributed to the up-regulated expressions of cell cycle process. The fungal transboundary response to bacterial C14-HSL was controlled by signal transduction pathways. This study provides new insights into the co-evolution of bacterial and pathogenic fungi in microecosystems.
The biosecurity hazards caused by pathogenic fungus have been widely concerned. Given the long-term coexistence of eukaryotic pathogens and quorum sensing bacteria in different habitats in environments, we hypothesized that they have social interactions via signal molecules. In this work, we firstly discovered the well-known bacterial signal molecules play an adverse role in the cell morphology and metabolism in a model pathogen Trichosporon asahii. N-Tetradecanoyl-L-homoserine lactone (C14-HSL) was discovered to increase pathogen hazards of T. asahii, which limited mycelium by 52%, but enhanced cell aggregation by 93%. Higher fluorescence intensity of tryptophan (59%) and aromatic protein (2-fold) contents after the treatment of C14-HSL, indicating that aromatic proteins helped aggregate Trichosporon and showed hydrophobicity. Transcriptome analysis revealed that C14-HSL upregulated the shikimate pathway (above 1-fold) located in downstream of tricarboxylic acid cycle, which contributed to the synthesis of more aromatic proteins and the formation of larger flocs. The limited mycelial growth of T. asahii attributed to the up-regulated expressions of cell cycle process. The fungal transboundary response to bacterial C14-HSL was controlled by signal transduction pathways. This study provides new insights into the co-evolution of bacterial and pathogenic fungi in microecosystems.
2024, 35(6): 108942
doi: 10.1016/j.cclet.2023.108942
Abstract:
The efficient conversion of CO2 into hydrocarbon fuels (CH4) with high selectivity is considered as a great challenge in photocatalysis owing to the multiple-electron transfer pathway and competitive H2 generation. Herein, we developed carbon dots (CDs)-modulated S-scheme heterojunction of CDs/NiAl-LDH@In2O3 (C-DH@IN) through a facile in-situ hydrothermal method. Thanks to the multi-shell nanotube structure, the C-DH@IN shows an enhanced CH4 evolution rate of 10.67 µmol h−1 g−1 and higher selectivity of CH4 (85.70%) compared with In2O3 and NiAl-LDH@In2O3 binary catalyst in the pure water without sacrificial agent. Electron spin resonance (ESR) and in situ Fourier transform infrared spectra verify that the constructed S-scheme heterojunction can possess the strong redox capability and the HCOO− and CH3O− as critical intermediates play an important role in selective CO2 reduction to generate CH4. Furthermore, CDs with superior photoabsorption can boost the electron transfer and absorb H+, thus improving the integration of H+ and CO2 molecule. Therefore, this work emphasizes a facile strategy to achieve efficient CO2-to-CH4 conversion based on construction of CDs-based heterojunction catalysts.
The efficient conversion of CO2 into hydrocarbon fuels (CH4) with high selectivity is considered as a great challenge in photocatalysis owing to the multiple-electron transfer pathway and competitive H2 generation. Herein, we developed carbon dots (CDs)-modulated S-scheme heterojunction of CDs/NiAl-LDH@In2O3 (C-DH@IN) through a facile in-situ hydrothermal method. Thanks to the multi-shell nanotube structure, the C-DH@IN shows an enhanced CH4 evolution rate of 10.67 µmol h−1 g−1 and higher selectivity of CH4 (85.70%) compared with In2O3 and NiAl-LDH@In2O3 binary catalyst in the pure water without sacrificial agent. Electron spin resonance (ESR) and in situ Fourier transform infrared spectra verify that the constructed S-scheme heterojunction can possess the strong redox capability and the HCOO− and CH3O− as critical intermediates play an important role in selective CO2 reduction to generate CH4. Furthermore, CDs with superior photoabsorption can boost the electron transfer and absorb H+, thus improving the integration of H+ and CO2 molecule. Therefore, this work emphasizes a facile strategy to achieve efficient CO2-to-CH4 conversion based on construction of CDs-based heterojunction catalysts.
2024, 35(6): 108943
doi: 10.1016/j.cclet.2023.108943
Abstract:
Corrosion of reinforcement induced by chloride invasion is extensively considered as the dominating deterioration mechanism of reinforced concrete (RC) structures, leading to serious safety hazards and tremendous economic losses. However, it still lacks well dispersive and cost-efficient nanomaterials to improve the anti-chloride-corrosion ability of RC structures. Herein, specific carbon dots (CDs) with high dispersity and low cost are deliberately designed, successfully prepared by hydrothermal processing, and then firstly applied to immensely enhance chloride binding performance of cement, thereby contributing to suppressing the corrosion of reinforcement. Specifically, the tailored CDs are composed of the carbon core with highly crystalline sp2 C structures and oxygen-containing groups connecting on the carbon core; The typical equilibrium test confirms that with respect to that of the blank cement paste, the chloride binding capacity of cement paste involving 0.2 wt% (by weight of cement) CDs is increased by 109% after 14-day exposure to 3 mol/L NaCl solution; according to comprehensive analyses of phase compositions, the chloride binding mechanism of CDs-modified cement is rationally attributed to the fact that the incorporation of CDs advances the formation of calcium silicate hydrate (C–S–H) gels and Friedel's salt (Fs), thus enormously enhancing the physically adsorbed and chemically bound chloride ions of cement pastes. This work not only firstly provides a novel high-dispersity and low-cost nanomaterial toward the durability enhancement of RC structures, but also broadens the application of CDs in the field of engineering, conducing to stimulating their industrialization development.
Corrosion of reinforcement induced by chloride invasion is extensively considered as the dominating deterioration mechanism of reinforced concrete (RC) structures, leading to serious safety hazards and tremendous economic losses. However, it still lacks well dispersive and cost-efficient nanomaterials to improve the anti-chloride-corrosion ability of RC structures. Herein, specific carbon dots (CDs) with high dispersity and low cost are deliberately designed, successfully prepared by hydrothermal processing, and then firstly applied to immensely enhance chloride binding performance of cement, thereby contributing to suppressing the corrosion of reinforcement. Specifically, the tailored CDs are composed of the carbon core with highly crystalline sp2 C structures and oxygen-containing groups connecting on the carbon core; The typical equilibrium test confirms that with respect to that of the blank cement paste, the chloride binding capacity of cement paste involving 0.2 wt% (by weight of cement) CDs is increased by 109% after 14-day exposure to 3 mol/L NaCl solution; according to comprehensive analyses of phase compositions, the chloride binding mechanism of CDs-modified cement is rationally attributed to the fact that the incorporation of CDs advances the formation of calcium silicate hydrate (C–S–H) gels and Friedel's salt (Fs), thus enormously enhancing the physically adsorbed and chemically bound chloride ions of cement pastes. This work not only firstly provides a novel high-dispersity and low-cost nanomaterial toward the durability enhancement of RC structures, but also broadens the application of CDs in the field of engineering, conducing to stimulating their industrialization development.
2024, 35(6): 108945
doi: 10.1016/j.cclet.2023.108945
Abstract:
Elevated level of hypochlorous acid (HClO) is closely associated with cancer development. Identifying HClO level in cancer cells would provide important evidence in either early-stage cancer diagnostics or monitoring of its treatment efficiency. In this work, a new pyronine-based fluorescent probe for rapid and sensitive detection of HClO was developed by condensing meso–formyl pyronine (PyCHO) with 2-hydrazinopyridine to form meso–pyridylhydrazone-functionalized pyronine PyHP, PyHP is nonfluorescent due to the excited-state C=N isomerization nonradiative decay, whereas the HClO-triggered formation of meso–triazolopyridyl pyronine PyTP abolishes the C=N isomerization and thus greatly enhances the fluorescence. With the probe, the cancer cells/tumor were distinguished with high-contrast from normal ones by laser confocal fluorescence imaging, and the tumor-to-normal (T/N) ratios obtained exceed the clinically acceptable threshold of 2.0. Moreover, its capability of in vivo imaging tumor was also demonstrated. These results indicate the potential of PyHP as an effective tool in the early clinical diagnosis of cancers.
Elevated level of hypochlorous acid (HClO) is closely associated with cancer development. Identifying HClO level in cancer cells would provide important evidence in either early-stage cancer diagnostics or monitoring of its treatment efficiency. In this work, a new pyronine-based fluorescent probe for rapid and sensitive detection of HClO was developed by condensing meso–formyl pyronine (PyCHO) with 2-hydrazinopyridine to form meso–pyridylhydrazone-functionalized pyronine PyHP, PyHP is nonfluorescent due to the excited-state C=N isomerization nonradiative decay, whereas the HClO-triggered formation of meso–triazolopyridyl pyronine PyTP abolishes the C=N isomerization and thus greatly enhances the fluorescence. With the probe, the cancer cells/tumor were distinguished with high-contrast from normal ones by laser confocal fluorescence imaging, and the tumor-to-normal (T/N) ratios obtained exceed the clinically acceptable threshold of 2.0. Moreover, its capability of in vivo imaging tumor was also demonstrated. These results indicate the potential of PyHP as an effective tool in the early clinical diagnosis of cancers.
2024, 35(6): 108947
doi: 10.1016/j.cclet.2023.108947
Abstract:
Carbon dots (CDs) with precise targeting function show great potential in the field of drug delivery therapeutics. In this study, the functionalized nucleus-targeting orange-emissive CDs with nuclear localization sequence (NLS) were loaded with adriamycin (DOX) to obtain a nucleus-targeting orange-emissive CDs drug delivery system (CDs-NLS-DOX), which delivered DOX to tumor cell nuclei to enhance its anti-tumor activity. The drug carrier orange-emissive CDs showed excitation-independent behavior, stable and enhanced imaging capability and good biocompatibility in vitro and in vivo. Meanwhile, the CDs-NLS could target the nuclei efficiently, and the CDs-NLS-DOX complexes had a high drug loading rate (59.4%) after loading DOX, exhibiting pH-dependent DOX release behavior through breaking acylhydrazone bond in a weak acidic environment. In addition, the CDs-NLS-DOX complexes exhibited an enhanced killing activity against human hepatoma cells (HepG2). The in vivo therapeutic effects on HepG2 nude mice transplanted tumors indicated the CDs-NLS-DOX had a stronger ability to inhibit tumor growth compared to free DOX. In short, CDs-NLS-DOX is expected to be a precise and efficient nucleus-targeting nano-drug delivery system for tumor treatment.
Carbon dots (CDs) with precise targeting function show great potential in the field of drug delivery therapeutics. In this study, the functionalized nucleus-targeting orange-emissive CDs with nuclear localization sequence (NLS) were loaded with adriamycin (DOX) to obtain a nucleus-targeting orange-emissive CDs drug delivery system (CDs-NLS-DOX), which delivered DOX to tumor cell nuclei to enhance its anti-tumor activity. The drug carrier orange-emissive CDs showed excitation-independent behavior, stable and enhanced imaging capability and good biocompatibility in vitro and in vivo. Meanwhile, the CDs-NLS could target the nuclei efficiently, and the CDs-NLS-DOX complexes had a high drug loading rate (59.4%) after loading DOX, exhibiting pH-dependent DOX release behavior through breaking acylhydrazone bond in a weak acidic environment. In addition, the CDs-NLS-DOX complexes exhibited an enhanced killing activity against human hepatoma cells (HepG2). The in vivo therapeutic effects on HepG2 nude mice transplanted tumors indicated the CDs-NLS-DOX had a stronger ability to inhibit tumor growth compared to free DOX. In short, CDs-NLS-DOX is expected to be a precise and efficient nucleus-targeting nano-drug delivery system for tumor treatment.
2024, 35(6): 108967
doi: 10.1016/j.cclet.2023.108967
Abstract:
Local delivery of nanoparticles holds promise for colorectal cancer (CRC) therapy. However, the presence of the mucus layer on the epithelium poses a significant challenge to drug delivery, thereby adversely affecting treatment efficiency. It is crucial to develop efficient drug delivery carriers that can effectively overcome mucus barriers to treat colorectal cancer. Herein, we utilized poly(1,4-butadiene)-b-poly(ethylene oxide) polymers to prepare four distinct geometries of polymeric micelles, namely linear micelles (LMs), worm-like micelles (WLMs), large spherical micelles (LSMs), and small spherical micelles (SSMs) to investigate the influence of shape effects on overcoming colonic mucosal barrier. We found that the carriers exhibited diverse shapes while maintaining comparable physicochemical properties. Of these, WLMs had an aspect ratio similar to segmented filamentous bacteria, which exhibited superior mucus penetration ability, leading to prolonged drug release kinetics and faster entry into epithelial cells compared to LSMs. Furthermore, rectally administrated 10-hydroxycamptothecin-loaded WLMs traversed the colorectal mucus in orthotopic CRC nude mice model, penetrated and accumulated within tumor tissue, and effectively aggregated within cancer cells, thereby inducing significantly robust antitumor outcomes in vivo. These findings underscore the significance of shape design in overcoming colonic mucosal absorption barriers, offering a novel approach for the development of drug delivery carriers tailored for effective tumor therapy.
Local delivery of nanoparticles holds promise for colorectal cancer (CRC) therapy. However, the presence of the mucus layer on the epithelium poses a significant challenge to drug delivery, thereby adversely affecting treatment efficiency. It is crucial to develop efficient drug delivery carriers that can effectively overcome mucus barriers to treat colorectal cancer. Herein, we utilized poly(1,4-butadiene)-b-poly(ethylene oxide) polymers to prepare four distinct geometries of polymeric micelles, namely linear micelles (LMs), worm-like micelles (WLMs), large spherical micelles (LSMs), and small spherical micelles (SSMs) to investigate the influence of shape effects on overcoming colonic mucosal barrier. We found that the carriers exhibited diverse shapes while maintaining comparable physicochemical properties. Of these, WLMs had an aspect ratio similar to segmented filamentous bacteria, which exhibited superior mucus penetration ability, leading to prolonged drug release kinetics and faster entry into epithelial cells compared to LSMs. Furthermore, rectally administrated 10-hydroxycamptothecin-loaded WLMs traversed the colorectal mucus in orthotopic CRC nude mice model, penetrated and accumulated within tumor tissue, and effectively aggregated within cancer cells, thereby inducing significantly robust antitumor outcomes in vivo. These findings underscore the significance of shape design in overcoming colonic mucosal absorption barriers, offering a novel approach for the development of drug delivery carriers tailored for effective tumor therapy.
2024, 35(6): 108969
doi: 10.1016/j.cclet.2023.108969
Abstract:
As a type of new carbon-based nanomaterials, carbon dots (CDs) possess exceptional optical properties, making them highly desirable for use in fluorescent sensors. However, the CDs with deep-red (DR) or near-infrared (NIR) emission have rarely been reported. In this work, we prepared deep-red emissive fluorine-doped carbon quantum dots (F-CDs) by introducing a precursor simultaneously containing fluorine and amidogen. The synergistic effect of nitrogen doping and D-π-A pattern production contributed to the maximum emission of F-CDs at 636 nm with an absolute quantum yield of 36.00% ± 0.68%. Moreover, we designed an F-CDs-based fluorescence assay to determine the content of hypochlorite (ClO−), with a limit of detection (LOD) as low as 15.4 nmol/L, indicating the high sensitivity of F-CDs to ClO−. In real samples, the F-CDs-based fluorescent sensor exhibited excellent sensitivity and selectivity in the detection of ClO−, with an error below 2%, suggesting their great potential in daily life. In cancer cell imaging, the F-CDs not only demonstrated high sensitivity to ClO− but also exhibited excellent mitochondria targeting, as evidenced by the high Pearson's correlation coefficient (PCC) of 0.93 in colocalization analysis. The work presented here suggests the great potential of replacing commercial dyes with F-CDs for highly specific mitochondria labeling and cell imaging.
As a type of new carbon-based nanomaterials, carbon dots (CDs) possess exceptional optical properties, making them highly desirable for use in fluorescent sensors. However, the CDs with deep-red (DR) or near-infrared (NIR) emission have rarely been reported. In this work, we prepared deep-red emissive fluorine-doped carbon quantum dots (F-CDs) by introducing a precursor simultaneously containing fluorine and amidogen. The synergistic effect of nitrogen doping and D-π-A pattern production contributed to the maximum emission of F-CDs at 636 nm with an absolute quantum yield of 36.00% ± 0.68%. Moreover, we designed an F-CDs-based fluorescence assay to determine the content of hypochlorite (ClO−), with a limit of detection (LOD) as low as 15.4 nmol/L, indicating the high sensitivity of F-CDs to ClO−. In real samples, the F-CDs-based fluorescent sensor exhibited excellent sensitivity and selectivity in the detection of ClO−, with an error below 2%, suggesting their great potential in daily life. In cancer cell imaging, the F-CDs not only demonstrated high sensitivity to ClO− but also exhibited excellent mitochondria targeting, as evidenced by the high Pearson's correlation coefficient (PCC) of 0.93 in colocalization analysis. The work presented here suggests the great potential of replacing commercial dyes with F-CDs for highly specific mitochondria labeling and cell imaging.
2024, 35(6): 108970
doi: 10.1016/j.cclet.2023.108970
Abstract:
The combination of horseradish peroxidase (HRP) and a fluorescence substrate has been attracting great interests in developing sensitive biochemical analysis and immunoassays. 10-Acetyl-3,7-dihydroxyphenoxazine (ADHP or Amplex red) is the most sensitive fluorogenic substrate known for HRP in current market, however, it suffers from some drawbacks, such as non-specific reactivity to carboxylesterase and limited fluorescence stability. In the present study, a novel HRP substrate 10-cyclopropylcarbonyl-dichloro-dihydroxyphenoxazine (AR-2), has been prepared, which exhibited improved sensitivity than ADHP in sensing HRP. Moreover, the fluorescence of AR-2/HRP demonstrated improved tolerance to physiological relevant pH fluctuation as compared to ADHP/HRP. Successful detection of uric acid/urate oxidase reaction indicated excellent application prospect of AR-2/HRP for monitoring H2O2-generating biochemical reactions. More interestingly, an enzyme-linked immunosorbent assay (ELISA) using AR-2 as the fluorescence reporter has been successfully used in detecting IgG against severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) from human serum samples. Overall, AR-2 exhibits improved performances over the commercial ADHP, which will be an ideal alternative to ADHP in HRP-based fluorescence biochemical analysis and immunoassays.
The combination of horseradish peroxidase (HRP) and a fluorescence substrate has been attracting great interests in developing sensitive biochemical analysis and immunoassays. 10-Acetyl-3,7-dihydroxyphenoxazine (ADHP or Amplex red) is the most sensitive fluorogenic substrate known for HRP in current market, however, it suffers from some drawbacks, such as non-specific reactivity to carboxylesterase and limited fluorescence stability. In the present study, a novel HRP substrate 10-cyclopropylcarbonyl-dichloro-dihydroxyphenoxazine (AR-2), has been prepared, which exhibited improved sensitivity than ADHP in sensing HRP. Moreover, the fluorescence of AR-2/HRP demonstrated improved tolerance to physiological relevant pH fluctuation as compared to ADHP/HRP. Successful detection of uric acid/urate oxidase reaction indicated excellent application prospect of AR-2/HRP for monitoring H2O2-generating biochemical reactions. More interestingly, an enzyme-linked immunosorbent assay (ELISA) using AR-2 as the fluorescence reporter has been successfully used in detecting IgG against severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) from human serum samples. Overall, AR-2 exhibits improved performances over the commercial ADHP, which will be an ideal alternative to ADHP in HRP-based fluorescence biochemical analysis and immunoassays.
2024, 35(6): 108974
doi: 10.1016/j.cclet.2023.108974
Abstract:
Introducing heavy halogen atoms into organic small molecules is a practical strategy for efficient singlet oxygen (1O2) generation. Generally, bromine or iodine atoms are introduced on the aza-boron-dipyrromethene (aza-BODIPY) core, rather than on the periphery aryl rings for efficient 1O2 generation. Herein, an aza-BODIPY dye NBDPBr with unexpected bromination on the periphery aryl rings was synthesized for photoacoustic (PA) imaging-guided synergistic photothermal therapy (PTT) and photodynamic therapy (PDT) in tumor cells. Owing to unexcepted bromination at the periphery aryl rings, NBDPBr demonstrated an outstanding singlet oxygen quantum yield of 66% which was superior to similar brominated photosensitizers previously reported. After encapsulation with amphiphilic polymer F-127, hydrophilic NBDPBr nanoparticles (NPs) were fabricated and exhibited an excellent photothermal conversion efficiency (η) of 43.0% under 660 nm photoirradiation. In vivo PA imaging results demonstrated that NBDPBr NPs could specifically accumulate at tumor sites and realized the maximum tumor retention at 7 h post-injection. All the in vitro and in vivo results indicated the significant potence of NBDPBr with unexpected bis-bromination for PA imaging-guided synergetic PDT/PTT.
Introducing heavy halogen atoms into organic small molecules is a practical strategy for efficient singlet oxygen (1O2) generation. Generally, bromine or iodine atoms are introduced on the aza-boron-dipyrromethene (aza-BODIPY) core, rather than on the periphery aryl rings for efficient 1O2 generation. Herein, an aza-BODIPY dye NBDPBr with unexpected bromination on the periphery aryl rings was synthesized for photoacoustic (PA) imaging-guided synergistic photothermal therapy (PTT) and photodynamic therapy (PDT) in tumor cells. Owing to unexcepted bromination at the periphery aryl rings, NBDPBr demonstrated an outstanding singlet oxygen quantum yield of 66% which was superior to similar brominated photosensitizers previously reported. After encapsulation with amphiphilic polymer F-127, hydrophilic NBDPBr nanoparticles (NPs) were fabricated and exhibited an excellent photothermal conversion efficiency (η) of 43.0% under 660 nm photoirradiation. In vivo PA imaging results demonstrated that NBDPBr NPs could specifically accumulate at tumor sites and realized the maximum tumor retention at 7 h post-injection. All the in vitro and in vivo results indicated the significant potence of NBDPBr with unexpected bis-bromination for PA imaging-guided synergetic PDT/PTT.
2024, 35(6): 109028
doi: 10.1016/j.cclet.2023.109028
Abstract:
C-Oligosaccharides are rare in nature and possess diverse bioactivities. However, their chemical synthesis faces many challenges. In this work, enzymatic introduction of C-linked sugar chains to target aglycones was successfully achieved by multi-enzymatic cascade reactions. A C-glycosyltransferase from Aloe barbadensis was employed to introduce the first C-linked glucose and then a cyclomaltodextrin glucanotransferase from Bacillus licheniformis was used to extend the sugar chain. A total of twenty C-oligosaccharides with 2–6 sugars were synthesized from scale-up reactions and exhibited good water solubility and sodium-dependent glucose transporter 2 (SGLT2) inhibitory activity. Furthermore, a glucoamylase was used to control the length of the sugar chain and the C-maltosides were efficiently synthesized. These findings not only expanded the structural diversity of C-oligosaccharides, but also provided a strategy for the modification of C-glycoside drugs to improve the druggability.
C-Oligosaccharides are rare in nature and possess diverse bioactivities. However, their chemical synthesis faces many challenges. In this work, enzymatic introduction of C-linked sugar chains to target aglycones was successfully achieved by multi-enzymatic cascade reactions. A C-glycosyltransferase from Aloe barbadensis was employed to introduce the first C-linked glucose and then a cyclomaltodextrin glucanotransferase from Bacillus licheniformis was used to extend the sugar chain. A total of twenty C-oligosaccharides with 2–6 sugars were synthesized from scale-up reactions and exhibited good water solubility and sodium-dependent glucose transporter 2 (SGLT2) inhibitory activity. Furthermore, a glucoamylase was used to control the length of the sugar chain and the C-maltosides were efficiently synthesized. These findings not only expanded the structural diversity of C-oligosaccharides, but also provided a strategy for the modification of C-glycoside drugs to improve the druggability.
2024, 35(6): 109038
doi: 10.1016/j.cclet.2023.109038
Abstract:
Heterogeneous reaction of mineral aerosols and atmospheric polluting gases play an important role in atmospheric chemistry. In this study, the reactions of NO2 with or without SO2 mixture gas on the surface of α-Fe2O3 particles under dry conditions were studied. The effects of sodium dodecyl sulfate (SDS) and the heterogeneous reaction under both dark and UV irradiation conditions were investigated. The infrared spectrum analyzed by the two-dimensional correlation spectroscopy (2D-COS) was used to obtain the products formation sequences. The results showed that UV irradiation can promote the production of nitrate. The 2D-COS analysis indicated SDS changed the sequence order of nitrate and nitrite species during reactions. In oxidation conditions, the final product of heterogeneous reaction of NO2 and α-Fe2O3 was monodentate nitrate. Only the heterogenous reaction of NO2 and α-Fe2O3 containing SDS (FOS) without UV light, the final product was bidentate nitrate. SDS was the catalysis agent supply and photoresist to the system. With surface active compounds, the environmental lifetime of heterogeneous reactions between trace gases and aerosols extends. Surfactants, ultraviolet light, and the types of gases involved in the reaction all have complex effects on the aerosol aging process. This study provided a reference for subsequent heterogeneous reaction studies and the formation of aerosols.
Heterogeneous reaction of mineral aerosols and atmospheric polluting gases play an important role in atmospheric chemistry. In this study, the reactions of NO2 with or without SO2 mixture gas on the surface of α-Fe2O3 particles under dry conditions were studied. The effects of sodium dodecyl sulfate (SDS) and the heterogeneous reaction under both dark and UV irradiation conditions were investigated. The infrared spectrum analyzed by the two-dimensional correlation spectroscopy (2D-COS) was used to obtain the products formation sequences. The results showed that UV irradiation can promote the production of nitrate. The 2D-COS analysis indicated SDS changed the sequence order of nitrate and nitrite species during reactions. In oxidation conditions, the final product of heterogeneous reaction of NO2 and α-Fe2O3 was monodentate nitrate. Only the heterogenous reaction of NO2 and α-Fe2O3 containing SDS (FOS) without UV light, the final product was bidentate nitrate. SDS was the catalysis agent supply and photoresist to the system. With surface active compounds, the environmental lifetime of heterogeneous reactions between trace gases and aerosols extends. Surfactants, ultraviolet light, and the types of gases involved in the reaction all have complex effects on the aerosol aging process. This study provided a reference for subsequent heterogeneous reaction studies and the formation of aerosols.
2024, 35(6): 109056
doi: 10.1016/j.cclet.2023.109056
Abstract:
Exploring the therapeutic effect of single atom catalysts beyond reactive oxygen species (ROS) modulation would boost the prosperity of nanomedicine in cancer treatment. Autophagy as a vital therapy target offers new options for the control of renal cell carcinoma (RCC) progression. Herein, Fe single atom-decorated graphene oxide (Fe1-GO) nanosheet is developed to be a feasible autophagy inducer in RCC treatment. With the well-dispersed O−Fe1−O active sites, Fe1-GO kills ACHN cells effectively but maintains acceptable cytotoxicity to the normal podocyte and HK2 ones. In-depth analyses ascribe the inhibition of ACHN cells to the upregulated autophagy instead of the commonly known catalytic ROS generation. The in vivo therapeutic effect of Fe1-GO nanomedicine is also validated by the RCC-bearing BALB/c mice model, realizing an 89% reduction of tumor weight and good biosafety. This work provides new insights into the design of autophagy regulators as well as potential therapeutic strategies for RCC treatment.
Exploring the therapeutic effect of single atom catalysts beyond reactive oxygen species (ROS) modulation would boost the prosperity of nanomedicine in cancer treatment. Autophagy as a vital therapy target offers new options for the control of renal cell carcinoma (RCC) progression. Herein, Fe single atom-decorated graphene oxide (Fe1-GO) nanosheet is developed to be a feasible autophagy inducer in RCC treatment. With the well-dispersed O−Fe1−O active sites, Fe1-GO kills ACHN cells effectively but maintains acceptable cytotoxicity to the normal podocyte and HK2 ones. In-depth analyses ascribe the inhibition of ACHN cells to the upregulated autophagy instead of the commonly known catalytic ROS generation. The in vivo therapeutic effect of Fe1-GO nanomedicine is also validated by the RCC-bearing BALB/c mice model, realizing an 89% reduction of tumor weight and good biosafety. This work provides new insights into the design of autophagy regulators as well as potential therapeutic strategies for RCC treatment.
2024, 35(6): 109081
doi: 10.1016/j.cclet.2023.109081
Abstract:
The exploration of advanced materials through rational structure/phase design is the key to develop high-performance lithium-ion capacitors (LICs). However, high complexity of material preparation and difficulty in quantity production largely hinder the further development. Herein, Cu5FeS4-x/C (CFS@C) heterojunction with rich sulfur vacancies has successfully achieved from natural bornite, presenting low cost-effective and bulk-production prospect. Density functional theory (DFT) calculations indicate that rich vacancies in bulk phase can decrease band gap of bornite and thus improve its intrinsic electron conductivity, as well as the heterojunction spontaneously evokes a built-in electric field between its interfacial region, largely reducing the migration barrier from 1.27 eV to 0.75 eV. Benefited from these merits, the CFS@C electrodes deliver outperformed lithium storage performance, e.g., high reversible capacity (822.4 mAh/g at 0.1 A/g), excellent cycling stability (up to 820 cycles at 2 A/g and 540 cycles at 5 A/g with respective capacity retention of over or nearly 100%). With CFS@C as anode and porous carbon nanosheets (PCS) as cathode, the assembled CFS@C//PCS LIC full cells exhibit high energy/power density characteristics of 139.2 Wh/kg at 2500 W/kg. This work is expected to offer significant insights into structure modifications/devising toward natural minerals for advanced energy-storage systems.
The exploration of advanced materials through rational structure/phase design is the key to develop high-performance lithium-ion capacitors (LICs). However, high complexity of material preparation and difficulty in quantity production largely hinder the further development. Herein, Cu5FeS4-x/C (CFS@C) heterojunction with rich sulfur vacancies has successfully achieved from natural bornite, presenting low cost-effective and bulk-production prospect. Density functional theory (DFT) calculations indicate that rich vacancies in bulk phase can decrease band gap of bornite and thus improve its intrinsic electron conductivity, as well as the heterojunction spontaneously evokes a built-in electric field between its interfacial region, largely reducing the migration barrier from 1.27 eV to 0.75 eV. Benefited from these merits, the CFS@C electrodes deliver outperformed lithium storage performance, e.g., high reversible capacity (822.4 mAh/g at 0.1 A/g), excellent cycling stability (up to 820 cycles at 2 A/g and 540 cycles at 5 A/g with respective capacity retention of over or nearly 100%). With CFS@C as anode and porous carbon nanosheets (PCS) as cathode, the assembled CFS@C//PCS LIC full cells exhibit high energy/power density characteristics of 139.2 Wh/kg at 2500 W/kg. This work is expected to offer significant insights into structure modifications/devising toward natural minerals for advanced energy-storage systems.
2024, 35(6): 109090
doi: 10.1016/j.cclet.2023.109090
Abstract:
Membrane-based separation is a promising technology to eliminate water impurities from the oil phase. However, it remains a great challenge to separate water from highly emulsified viscous oil owing to the high stability of the water droplets in oil. Herein we report a surface wettability engineering on an alumina ceramic membrane to achieve an efficient separation of a water-in-oil (W/O) emulsion. Silanes with different carbon chain lengths and fluorinated status were introduced to endow the alumina membrane with different surface wettabilities. While all the modified membranes exhibited excellent separation of the W/O without Span 80 (surfactant), the one with amphiphobic wettability and lowest surface energy failed to separate the Span 80 stabilized W/O. The presence of Span 80 reduced the interfacial tension of water droplets, making them easier to deform and penetrate the modified membrane with the lowest surface energy. It reveals that engineering proper surface wettability is the key to separating the oil and water phases. Besides, the modified membranes maintained decent separation performance and stability under long-term run separation of the emulsified W/O.
Membrane-based separation is a promising technology to eliminate water impurities from the oil phase. However, it remains a great challenge to separate water from highly emulsified viscous oil owing to the high stability of the water droplets in oil. Herein we report a surface wettability engineering on an alumina ceramic membrane to achieve an efficient separation of a water-in-oil (W/O) emulsion. Silanes with different carbon chain lengths and fluorinated status were introduced to endow the alumina membrane with different surface wettabilities. While all the modified membranes exhibited excellent separation of the W/O without Span 80 (surfactant), the one with amphiphobic wettability and lowest surface energy failed to separate the Span 80 stabilized W/O. The presence of Span 80 reduced the interfacial tension of water droplets, making them easier to deform and penetrate the modified membrane with the lowest surface energy. It reveals that engineering proper surface wettability is the key to separating the oil and water phases. Besides, the modified membranes maintained decent separation performance and stability under long-term run separation of the emulsified W/O.
2024, 35(6): 109095
doi: 10.1016/j.cclet.2023.109095
Abstract:
Low-molecular-weight (LMW) compounds are ubiquitous in living organisms and play essential roles in biological processes. The direct analysis of LMW compounds in biological tissues by matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI) could provide a more comprehensive understanding of their essential functions. Here, we evaluated 4-nitrocatechol (4-NC) as a novel positive-ion matrix for enhancing in situ detection and imaging of LMW compounds from the rat liver, brain, and germinating Chinese-yew seed by MALDI-MS. Our results showed that the 4-NC possessed remarkable features, including strong ultraviolet absorption, uniform matrix crystal, excellent chemical stability, and fewer matrix-related background peaks. The use of 4-NC led to the successful detection of 232, 218, and 193 LMW compounds from the three abovementioned tissue sections, respectively. Also, the use of 4-NC improved the imaging quality of LMW compounds in tissue sections through MALDI-MSI and has the potential as a matrix for MALDI tissue imaging of LMW compounds.
Low-molecular-weight (LMW) compounds are ubiquitous in living organisms and play essential roles in biological processes. The direct analysis of LMW compounds in biological tissues by matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI) could provide a more comprehensive understanding of their essential functions. Here, we evaluated 4-nitrocatechol (4-NC) as a novel positive-ion matrix for enhancing in situ detection and imaging of LMW compounds from the rat liver, brain, and germinating Chinese-yew seed by MALDI-MS. Our results showed that the 4-NC possessed remarkable features, including strong ultraviolet absorption, uniform matrix crystal, excellent chemical stability, and fewer matrix-related background peaks. The use of 4-NC led to the successful detection of 232, 218, and 193 LMW compounds from the three abovementioned tissue sections, respectively. Also, the use of 4-NC improved the imaging quality of LMW compounds in tissue sections through MALDI-MSI and has the potential as a matrix for MALDI tissue imaging of LMW compounds.
2024, 35(6): 109113
doi: 10.1016/j.cclet.2023.109113
Abstract:
Electrochemical sensing provides a powerful technological means for the therapeutic drug monitoring of drug-resistant tuberculosis but requires a functionalized electrode to capture the analytes and catalyze their redox reactions. Herein, we construct a nickel–tannic acid supramolecular network (Ni–TA) on the surface of electrospun-derived C–CeO2 nanofiber for the sensitive and simultaneous detection of isoniazid (INZ) and hydrazine (HYD). Mechanistic investigations demonstrate that Ni–TA is electronegative and hydrophilic, thus facilitating an efficient mass and electron transfer. Ni–TA/C–CeO2 has higher adsorption rate constants (0.091 g mg–1 h–1 for INZ, and 0.062 g mg–1 h–1 for HYD) than native C–CeO2 (0.075 g mg–1 h–1 for INZ, and 0.047 g mg–1 h–1 for HYD). Moreover, Ni–TA/C–CeO2 (56 Ω) has lower charge transfer resistances than C–CeO2 (417 Ω). Ni–TA/C–CeO2 performs low detection limits and wide linearity ranges for INZ (0.012 µmol/L and 0.1–400 µmol/L, respectively) and HYD (0.008 µmol/L and 0.015–1420 µmol/L, respectively), coupled with high selectivity, cycle stability and reproducibility. This research demonstrated the promising applications of Ni–TA/C–CeO2 by analyzing human-collected plasma and urine samples.
Electrochemical sensing provides a powerful technological means for the therapeutic drug monitoring of drug-resistant tuberculosis but requires a functionalized electrode to capture the analytes and catalyze their redox reactions. Herein, we construct a nickel–tannic acid supramolecular network (Ni–TA) on the surface of electrospun-derived C–CeO2 nanofiber for the sensitive and simultaneous detection of isoniazid (INZ) and hydrazine (HYD). Mechanistic investigations demonstrate that Ni–TA is electronegative and hydrophilic, thus facilitating an efficient mass and electron transfer. Ni–TA/C–CeO2 has higher adsorption rate constants (0.091 g mg–1 h–1 for INZ, and 0.062 g mg–1 h–1 for HYD) than native C–CeO2 (0.075 g mg–1 h–1 for INZ, and 0.047 g mg–1 h–1 for HYD). Moreover, Ni–TA/C–CeO2 (56 Ω) has lower charge transfer resistances than C–CeO2 (417 Ω). Ni–TA/C–CeO2 performs low detection limits and wide linearity ranges for INZ (0.012 µmol/L and 0.1–400 µmol/L, respectively) and HYD (0.008 µmol/L and 0.015–1420 µmol/L, respectively), coupled with high selectivity, cycle stability and reproducibility. This research demonstrated the promising applications of Ni–TA/C–CeO2 by analyzing human-collected plasma and urine samples.
2024, 35(6): 109114
doi: 10.1016/j.cclet.2023.109114
Abstract:
Long-term excessive intake of nitrite (NO2−) poses a great threat to human health, needing a simple and fast method to detect NO2− in food. Herein, via a simple and feasible strategy, Mn/Yb/Er triple-doped CeO2 nanozyme (Mn/Yb/Er/CeO2) was synthesized for highly sensitive ratiometric detection of nitrite. By doping Mn, Yb, Er into CeO2 lattice structure, Mn/Yb/Er/CeO2 nanozyme showed enhanced oxidase-like activity, obtaining a higher density of oxygen vacancy and a higher ratio of Ce3+ to Ce4+ than that of CeO2. The 3,3′,5,5′-tetramethylbenzidine (TMB) can be effectively oxidized by Mn/Yb/Er/CeO2 to produce the oxidized TMB (oxTMB), showing a significant absorption signal at 652 nm. Additionally, nitrite can react with oxTMB to produce yellow diazotized oxTMB, which is accompanied by an elevated absorption signal at 445 nm and a decreased absorption signal at 652 nm. Thus, based on the oxidase-mimetic activity of Mn/Yb/Er/CeO2 and the diazotization reaction between NO2− and oxTMB, a ratiometric colorimetric assay was established for NO2− detection in food. Furthermore, by integrating Mn/Yb/Er/CeO2 with a smartphone, a colorimetric smartphone-sensing platform was successfully fabricated for visualization and quantitative detection of NO2−. Notably, this two-detection mode showed excellent sensitivity, selectivity, reliability and practicability in monitoring the NO2− in real samples, impling its great potential for food safety.
Long-term excessive intake of nitrite (NO2−) poses a great threat to human health, needing a simple and fast method to detect NO2− in food. Herein, via a simple and feasible strategy, Mn/Yb/Er triple-doped CeO2 nanozyme (Mn/Yb/Er/CeO2) was synthesized for highly sensitive ratiometric detection of nitrite. By doping Mn, Yb, Er into CeO2 lattice structure, Mn/Yb/Er/CeO2 nanozyme showed enhanced oxidase-like activity, obtaining a higher density of oxygen vacancy and a higher ratio of Ce3+ to Ce4+ than that of CeO2. The 3,3′,5,5′-tetramethylbenzidine (TMB) can be effectively oxidized by Mn/Yb/Er/CeO2 to produce the oxidized TMB (oxTMB), showing a significant absorption signal at 652 nm. Additionally, nitrite can react with oxTMB to produce yellow diazotized oxTMB, which is accompanied by an elevated absorption signal at 445 nm and a decreased absorption signal at 652 nm. Thus, based on the oxidase-mimetic activity of Mn/Yb/Er/CeO2 and the diazotization reaction between NO2− and oxTMB, a ratiometric colorimetric assay was established for NO2− detection in food. Furthermore, by integrating Mn/Yb/Er/CeO2 with a smartphone, a colorimetric smartphone-sensing platform was successfully fabricated for visualization and quantitative detection of NO2−. Notably, this two-detection mode showed excellent sensitivity, selectivity, reliability and practicability in monitoring the NO2− in real samples, impling its great potential for food safety.
2024, 35(6): 109116
doi: 10.1016/j.cclet.2023.109116
Abstract:
Single atom catalysts (SACs) have been in the forefront of catalysts research because of their high efficiency and low cost and provide new ideas for development of renewable energy conversion and storage technologies. However, the relationship between the intrinsic properties of materials such as lattice thermal conductivity and catalysis remains to be explored. In this work, the lattice thermal conductivity of BN and graphene was calculated by ShengBTE. In addition, the adsorption properties of 3d-TM (TM = V, Cr, Mn, Fe, Co, Ni) on BN and graphene were investigated using first-principles methods, and it was found that Ni atom can form relatively stable SACs compared to other TMs. The molecular dynamics (MD) simulation and migration barrier of Ni loaded on BN and graphene were calculated. Our study found that graphene has higher thermal conductivity and is easier to form SACs than BN, but the SACs formed on BN surface have higher thermodynamic stability.
Single atom catalysts (SACs) have been in the forefront of catalysts research because of their high efficiency and low cost and provide new ideas for development of renewable energy conversion and storage technologies. However, the relationship between the intrinsic properties of materials such as lattice thermal conductivity and catalysis remains to be explored. In this work, the lattice thermal conductivity of BN and graphene was calculated by ShengBTE. In addition, the adsorption properties of 3d-TM (TM = V, Cr, Mn, Fe, Co, Ni) on BN and graphene were investigated using first-principles methods, and it was found that Ni atom can form relatively stable SACs compared to other TMs. The molecular dynamics (MD) simulation and migration barrier of Ni loaded on BN and graphene were calculated. Our study found that graphene has higher thermal conductivity and is easier to form SACs than BN, but the SACs formed on BN surface have higher thermodynamic stability.
2024, 35(6): 109128
doi: 10.1016/j.cclet.2023.109128
Abstract:
Glycosyl radicals, produced under mild photoredox conditions, show unique utility in the preparation of C-linked glycoconjugates. We herein report the construction of C-glycosidic bonds on α,β-dehydroalanine (DHA) of peptides with easily available glycosyl bromides as glycosyl radical precursors under highly anomeric control, leading to C-glycosylation modifications of peptides. This method not only has outstanding functional group compatibility, but also is feasible in near-physiological conditions (pH ~ 7 and temperature T ≤ 37 ℃ in aqueous media).
Glycosyl radicals, produced under mild photoredox conditions, show unique utility in the preparation of C-linked glycoconjugates. We herein report the construction of C-glycosidic bonds on α,β-dehydroalanine (DHA) of peptides with easily available glycosyl bromides as glycosyl radical precursors under highly anomeric control, leading to C-glycosylation modifications of peptides. This method not only has outstanding functional group compatibility, but also is feasible in near-physiological conditions (pH ~ 7 and temperature T ≤ 37 ℃ in aqueous media).
2024, 35(6): 109130
doi: 10.1016/j.cclet.2023.109130
Abstract:
Cr(Ⅵ), one of the most hazardous metal pollutants, poses significant threats to the environment and human health. Herein, a novel MoS2 composite (MoS2/PVP/PAM) modified by polyvinylpyrrolidone (PVP) and polyacrylamide (PAM) was synthesized to enhance the removal of Cr(Ⅵ). Characterization analysis including SEM, XRD, FTIR, and XPS indicated that PVP and PAM could increase the interlayer spacing and the dispersibility of MoS2, and introduce pyrrolic N and amino functional groups. The batch experiments showed that MoS2/PVP/PAM represented excellent Cr(Ⅵ) removal performance over a wide pH range, and exhibited a significantly higher maximum Cr(Ⅵ) adsorption capacity (274.73mg/g, at pH 3.0, and 298K) than pure MoS2. The adsorption of Cr(Ⅵ) followed Langmuir and pseudo-second-order kinetic model, which was a homogeneous monolayer chemisorption process. MoS2/PVP/PAM showed stable removal of Cr(Ⅵ) in the presence of humic acid (HA), interfering cations and anions at different concentrations. Moreover, it had excellent selectivity for Cr(Ⅵ) (Kd value of 1.69× 107mL/g) when coexisting with a variety of competing ions. Multiple characterization revealed that Cr(Ⅵ) was reduced to low toxicity Cr(Ⅲ) by Mo4+ and S2−, and then chelated on the surface of the adsorbent by pyrrolic N. This research expanded the design concept for MoS2 composites by demonstrating the potential of MoS2/PVP/PAM as a promising material for selective elimination of Cr(Ⅵ) in water.
Cr(Ⅵ), one of the most hazardous metal pollutants, poses significant threats to the environment and human health. Herein, a novel MoS2 composite (MoS2/PVP/PAM) modified by polyvinylpyrrolidone (PVP) and polyacrylamide (PAM) was synthesized to enhance the removal of Cr(Ⅵ). Characterization analysis including SEM, XRD, FTIR, and XPS indicated that PVP and PAM could increase the interlayer spacing and the dispersibility of MoS2, and introduce pyrrolic N and amino functional groups. The batch experiments showed that MoS2/PVP/PAM represented excellent Cr(Ⅵ) removal performance over a wide pH range, and exhibited a significantly higher maximum Cr(Ⅵ) adsorption capacity (274.73mg/g, at pH 3.0, and 298K) than pure MoS2. The adsorption of Cr(Ⅵ) followed Langmuir and pseudo-second-order kinetic model, which was a homogeneous monolayer chemisorption process. MoS2/PVP/PAM showed stable removal of Cr(Ⅵ) in the presence of humic acid (HA), interfering cations and anions at different concentrations. Moreover, it had excellent selectivity for Cr(Ⅵ) (Kd value of 1.69× 107mL/g) when coexisting with a variety of competing ions. Multiple characterization revealed that Cr(Ⅵ) was reduced to low toxicity Cr(Ⅲ) by Mo4+ and S2−, and then chelated on the surface of the adsorbent by pyrrolic N. This research expanded the design concept for MoS2 composites by demonstrating the potential of MoS2/PVP/PAM as a promising material for selective elimination of Cr(Ⅵ) in water.
2024, 35(6): 109131
doi: 10.1016/j.cclet.2023.109131
Abstract:
To mitigate the water pollution problem by photocatalytic degradation of typical antibiotics of tetracycline (TC), we prepared defective Bi2Sn2O7 (BSO) quantum dots (QDs) with a full spectral response due to Bi metal deposition, using a one-pot hydrothermal method, labeled as Bi@BSO-OV. The optimized Bi@BSO-OV showed 73.4% removal of TC in 1 h under irradiation with a 50 W LED lamp in the wavelength band in the visible-near-infrared (vis-NIR) light, a rate that is substantially greater than that of pure BSO (14.7%). The synergistic interaction of Bi metal and oxygen vacancies (OVs) is crucial to boosting photocatalytic performance. The near-infrared region of the photo-response is extended by the surface plasmon resonance (SPR) effect of Bi metal, enhancing the photocatalytic performance and dramatically raising the efficiency of solar energy utilization. In addition to inducing defect levels in BSO, the OVs also activate the surface adsorbed O2 to promote the production of •O2− and 1O2. DFT calculations reveal that Bi metal and OVs can mutually tune the charge transfer pathways. On the one hand, Bi metal can act as both a charge transfer bridge and an electron donor to assist charge separation. On the other hand, OVs-induced defect levels allow electrons that leap to the conduction band (CB) to first leap from the valence band (VB) to the defect levels, notably improving interfacial charge separation and transfer. The concept of design executed in this study for altering the catalyst by introducing both OVs and Bi metal can provide a rational design idea and potential insight for improving the photocatalytic activity for environmental applications.
To mitigate the water pollution problem by photocatalytic degradation of typical antibiotics of tetracycline (TC), we prepared defective Bi2Sn2O7 (BSO) quantum dots (QDs) with a full spectral response due to Bi metal deposition, using a one-pot hydrothermal method, labeled as Bi@BSO-OV. The optimized Bi@BSO-OV showed 73.4% removal of TC in 1 h under irradiation with a 50 W LED lamp in the wavelength band in the visible-near-infrared (vis-NIR) light, a rate that is substantially greater than that of pure BSO (14.7%). The synergistic interaction of Bi metal and oxygen vacancies (OVs) is crucial to boosting photocatalytic performance. The near-infrared region of the photo-response is extended by the surface plasmon resonance (SPR) effect of Bi metal, enhancing the photocatalytic performance and dramatically raising the efficiency of solar energy utilization. In addition to inducing defect levels in BSO, the OVs also activate the surface adsorbed O2 to promote the production of •O2− and 1O2. DFT calculations reveal that Bi metal and OVs can mutually tune the charge transfer pathways. On the one hand, Bi metal can act as both a charge transfer bridge and an electron donor to assist charge separation. On the other hand, OVs-induced defect levels allow electrons that leap to the conduction band (CB) to first leap from the valence band (VB) to the defect levels, notably improving interfacial charge separation and transfer. The concept of design executed in this study for altering the catalyst by introducing both OVs and Bi metal can provide a rational design idea and potential insight for improving the photocatalytic activity for environmental applications.
2024, 35(6): 109132
doi: 10.1016/j.cclet.2023.109132
Abstract:
Development of hydrothermally stable, low-temperature catalysts for controlling nitrogen oxides emissions from mobile sources remains an urgent challenge. We have prepared a metal oxide-zeolite composite catalyst by depositing Mn active species on a mixture support of CeO2/Al2O3 and ZSM-5. This composite catalyst is hydrothermally stable and shows improved low-temperature SCR activity and significantly reduced N2O formation than the corresponding metal oxide catalyst. Comparing with a Cu-CHA catalyst, the composite catalyst has a faster response to NH3 injection and less NH3 slip. Our characterization results reveal that such an oxide-zeolite composite catalyst contains more acidic sites and Mn3+ species as a result of oxide-zeolite interaction, and this interaction leads to the generation of more NH4+ species bound to the Brønsted acid sites and more reactive NOx species absorbed on the Mn sites. Herein, we report our mechanistic understanding of the oxide-zeolite composite catalyst and its molecular pathway for improving the low-temperature activity and N2 selectivity for NH3-SCR reaction. Practically, this work may provide an alternative methodology for low-temperature NOx control from diesel vehicles.
Development of hydrothermally stable, low-temperature catalysts for controlling nitrogen oxides emissions from mobile sources remains an urgent challenge. We have prepared a metal oxide-zeolite composite catalyst by depositing Mn active species on a mixture support of CeO2/Al2O3 and ZSM-5. This composite catalyst is hydrothermally stable and shows improved low-temperature SCR activity and significantly reduced N2O formation than the corresponding metal oxide catalyst. Comparing with a Cu-CHA catalyst, the composite catalyst has a faster response to NH3 injection and less NH3 slip. Our characterization results reveal that such an oxide-zeolite composite catalyst contains more acidic sites and Mn3+ species as a result of oxide-zeolite interaction, and this interaction leads to the generation of more NH4+ species bound to the Brønsted acid sites and more reactive NOx species absorbed on the Mn sites. Herein, we report our mechanistic understanding of the oxide-zeolite composite catalyst and its molecular pathway for improving the low-temperature activity and N2 selectivity for NH3-SCR reaction. Practically, this work may provide an alternative methodology for low-temperature NOx control from diesel vehicles.
2024, 35(6): 109137
doi: 10.1016/j.cclet.2023.109137
Abstract:
Fluorescence Anisotropy (FA) is an effective biochemical detection method based on molecular rotations. Graphene oxide (GO) has been extensively used as an FA amplifier. However, the enhancement of FA by GO alone is limited and the strong scattering of GO will easily make the measurement of FA inaccurate. In order to address these problems, an octopus-like DNA nanostructure (ODN) was designed and coupled with GO to enhance the FA together in this work. By mimicking the multi-clawed structure of the octopus, the ODN can be adsorbed on GO tightly, which not only could improve the sensitivity because of the double FA enhancement abilities of GO and ODN, but also could improve the specificity due to the decrease of the nonspecific interaction in complex samples. Furthermore, ODN could maintain a certain distance between the fluorophore and GO to reduce the fluorescence quenching efficiency of GO, which could improve the accuracy. This method has been applied for the detection of hepatitis B virus DNA (HBV-DNA) in a range of 1–50nmol/L and the limit of detection (LOD) was 330pmol/L. In addition, the proposed method has been successfully utilized to detect HBV-DNA in human serum, indicating that this method has a great practical application prospect.
Fluorescence Anisotropy (FA) is an effective biochemical detection method based on molecular rotations. Graphene oxide (GO) has been extensively used as an FA amplifier. However, the enhancement of FA by GO alone is limited and the strong scattering of GO will easily make the measurement of FA inaccurate. In order to address these problems, an octopus-like DNA nanostructure (ODN) was designed and coupled with GO to enhance the FA together in this work. By mimicking the multi-clawed structure of the octopus, the ODN can be adsorbed on GO tightly, which not only could improve the sensitivity because of the double FA enhancement abilities of GO and ODN, but also could improve the specificity due to the decrease of the nonspecific interaction in complex samples. Furthermore, ODN could maintain a certain distance between the fluorophore and GO to reduce the fluorescence quenching efficiency of GO, which could improve the accuracy. This method has been applied for the detection of hepatitis B virus DNA (HBV-DNA) in a range of 1–50nmol/L and the limit of detection (LOD) was 330pmol/L. In addition, the proposed method has been successfully utilized to detect HBV-DNA in human serum, indicating that this method has a great practical application prospect.
2024, 35(6): 109138
doi: 10.1016/j.cclet.2023.109138
Abstract:
Dicarboxylic acids have a wide range of applications in the polymer industry to construct valuable materials. Photocatalysis has recently emerged as an efficient and sustainable strategy to generate dicarboxylic acids. However, photocatalytic dicarboxylation with CO2 is mainly limited to unsaturated bonds, and the dicarboxylation of C–C single bonds still remains a challenge. Herein, we report a photocatalytic dicarboxylation of C–C single bonds in strained rings with CO2 units via consecutive photo-induced electron transfer (ConPET). It is also the first photocatalytic reductive ring-opening reaction of cyclobutanes. Notably, this transition-metal-free protocol exhibits good functional group tolerance, broad substrate scope, facile scalability, and easy product derivatizations. Moreover, diacids can easily be derivatized to main-chain liquid crystalline polyesters.
Dicarboxylic acids have a wide range of applications in the polymer industry to construct valuable materials. Photocatalysis has recently emerged as an efficient and sustainable strategy to generate dicarboxylic acids. However, photocatalytic dicarboxylation with CO2 is mainly limited to unsaturated bonds, and the dicarboxylation of C–C single bonds still remains a challenge. Herein, we report a photocatalytic dicarboxylation of C–C single bonds in strained rings with CO2 units via consecutive photo-induced electron transfer (ConPET). It is also the first photocatalytic reductive ring-opening reaction of cyclobutanes. Notably, this transition-metal-free protocol exhibits good functional group tolerance, broad substrate scope, facile scalability, and easy product derivatizations. Moreover, diacids can easily be derivatized to main-chain liquid crystalline polyesters.
2024, 35(6): 109154
doi: 10.1016/j.cclet.2023.109154
Abstract:
Artificial macrocycle with high binding selectivity in water is often challenging but urgently needed in various research and application areas. Herein, we report a new water-soluble biomimetic tetralactam macrocycle and realize the ultra-high selectivity to nucleosides over corresponding monophosphate nucleotides by rational modification. The introduction of charged groups at the periphery of endo-functionalized cavity makes the selectivity (guanosine to guanosine 5′-monophosphate) increase remarkably from 100 to 1119. Based on the ultra-high selectivity of biomimetic tetralactam macrocycle, the sensitive CD73 enzyme activity assay was then achieved through product-selective fluorescence indicator displacement assay. Furthermore, the capability of the proposed method for inhibitor screening was successfully displayed.
Artificial macrocycle with high binding selectivity in water is often challenging but urgently needed in various research and application areas. Herein, we report a new water-soluble biomimetic tetralactam macrocycle and realize the ultra-high selectivity to nucleosides over corresponding monophosphate nucleotides by rational modification. The introduction of charged groups at the periphery of endo-functionalized cavity makes the selectivity (guanosine to guanosine 5′-monophosphate) increase remarkably from 100 to 1119. Based on the ultra-high selectivity of biomimetic tetralactam macrocycle, the sensitive CD73 enzyme activity assay was then achieved through product-selective fluorescence indicator displacement assay. Furthermore, the capability of the proposed method for inhibitor screening was successfully displayed.
2024, 35(6): 109157
doi: 10.1016/j.cclet.2023.109157
Abstract:
A novel asymmetric [4 + 2] cycloaddition of 2-methylidenetrimethylene carbonate with pyrrolidone-derived enones has been achieved to produce the functionalized tetrahydropyran-fused spirocyclic scaffolds via palladium-catalysis. An array of enantioenriched spiro-pyrrolidine-2,3-diones bearing adjacent quaternary and tertiary stereocenters are obtained in high yields with excellent enantioselectivities (up to 96% yield and 99% ee). The further transformation of the product has been accomplished for the construction of medical interesting β2,2-amino acids and β-lactams. Preliminary mechanistic research was well conducted.
A novel asymmetric [4 + 2] cycloaddition of 2-methylidenetrimethylene carbonate with pyrrolidone-derived enones has been achieved to produce the functionalized tetrahydropyran-fused spirocyclic scaffolds via palladium-catalysis. An array of enantioenriched spiro-pyrrolidine-2,3-diones bearing adjacent quaternary and tertiary stereocenters are obtained in high yields with excellent enantioselectivities (up to 96% yield and 99% ee). The further transformation of the product has been accomplished for the construction of medical interesting β2,2-amino acids and β-lactams. Preliminary mechanistic research was well conducted.
2024, 35(6): 109162
doi: 10.1016/j.cclet.2023.109162
Abstract:
Herein, a novel molecular tweezer based on 2,2′-bipyridine-bridged porphyrin subunits was constructed for efficient fullerenes recognition. The syn conformation of the molecule, which was obtained by Zn(Ⅱ) coordination, gives rise to a proper cavity to interact with fullerene guests to form a stable 1:1 complex in toluene solution. It exhibits distinct binding selectivity towards C60 over C70. Moreover, the fullerene recognition capacity can be adequately suppressed by importing H2PO4− to competitively capture Zn(Ⅱ) along with syn-anti conformational conversion. Subsequently, the molecular tweezer regenerated to bind the fullerene by introducing the Ca2+ into the system. Significantly, the association-disassociation process can be switched reversibly and repeatedly.
Herein, a novel molecular tweezer based on 2,2′-bipyridine-bridged porphyrin subunits was constructed for efficient fullerenes recognition. The syn conformation of the molecule, which was obtained by Zn(Ⅱ) coordination, gives rise to a proper cavity to interact with fullerene guests to form a stable 1:1 complex in toluene solution. It exhibits distinct binding selectivity towards C60 over C70. Moreover, the fullerene recognition capacity can be adequately suppressed by importing H2PO4− to competitively capture Zn(Ⅱ) along with syn-anti conformational conversion. Subsequently, the molecular tweezer regenerated to bind the fullerene by introducing the Ca2+ into the system. Significantly, the association-disassociation process can be switched reversibly and repeatedly.
2024, 35(6): 109183
doi: 10.1016/j.cclet.2023.109183
Abstract:
Macrocycle confinement induced guest near-infrared (NIR) luminescence was research hotspot currently. Here in, we reported a cucurbit[7]uril (CB[7]) confined 3,7-bis((E)-2-(pyridin-4-yl)vinyl)-10-H-phenothiazine bridged bis(4-(4-bromophenyl)pyridine) (G), which not only boosted its NIR luminescence but also realized detection of HClO/ClO− in living cells and lysosome imaging. Fluorescence spectroscopy experiments were performed to calculate the detection ability of probe G to HClO/ClO− up to 147 nmol/L. As compared with G, supramolecular probe G⊂CB[7] formed after encapsulated by CB[7], the detection ability towards HClO/ClO− was improved to 24 nmol/L which was ascribe to the macrocycle CB[7] confinement increasing the fluorescence intensity to 103 folds. Accompanying the excitation wavelength changing, the fluorescence red-shifted to 820 nm when excited by 570 nm light, which was used to NIR lysosome imaging. Meanwhile, the supramolecular assembly G⊂CB[7] was also successfully used to highly sense to exogenous HClO/ClO− in RAW 264.7 cells and live animal.
Macrocycle confinement induced guest near-infrared (NIR) luminescence was research hotspot currently. Here in, we reported a cucurbit[7]uril (CB[7]) confined 3,7-bis((E)-2-(pyridin-4-yl)vinyl)-10-H-phenothiazine bridged bis(4-(4-bromophenyl)pyridine) (G), which not only boosted its NIR luminescence but also realized detection of HClO/ClO− in living cells and lysosome imaging. Fluorescence spectroscopy experiments were performed to calculate the detection ability of probe G to HClO/ClO− up to 147 nmol/L. As compared with G, supramolecular probe G⊂CB[7] formed after encapsulated by CB[7], the detection ability towards HClO/ClO− was improved to 24 nmol/L which was ascribe to the macrocycle CB[7] confinement increasing the fluorescence intensity to 103 folds. Accompanying the excitation wavelength changing, the fluorescence red-shifted to 820 nm when excited by 570 nm light, which was used to NIR lysosome imaging. Meanwhile, the supramolecular assembly G⊂CB[7] was also successfully used to highly sense to exogenous HClO/ClO− in RAW 264.7 cells and live animal.
2024, 35(6): 109198
doi: 10.1016/j.cclet.2023.109198
Abstract:
Lateral flow immunoassay (LFIA) has become popular in laboratories, at-home testing, and medical diagnostics due to its minimal cost and user-friendliness. Nevertheless, conventional test strips based on colloidal gold can only obtain qualitative or semi-quantitative results with low sensitivity. In this work, Au-Fe3O4 dumbbell-like nanoparticles were synthesized and used as the LFIA labelling marker for highly sensitive colorimetric-photothermal dual-mode detection of SARS-CoV-2 spike(S) protein. The unique dumbbell structure of Au-Fe3O4 NPs makes it possible to combine the best features of both Au NPs and Fe3O4 NPs. The increased surface area of these NPs enhances their LSPR effect and photothermal effect, which achieves signal amplification to increase sensitivity. The Au-Fe3O4 NPs modified with S protein antibody could identify S protein in samples, which were recognized and accumulated on T-line by another antibody, generating color band for qualitative colorimetric detection. The T-line was irradiated by laser to obtain temperature change for quantitative detection of photothermal. In optimized conditions, the detection limit was 1.22 pg/mL, three orders of magnitude more sensitive than colorimetric detection. Finally, the approach was performed on SARS-CoV-2 pseudovirus samples and outperformed traditional colloidal gold strips. This LFIA platform exhibits significant promise for practical implementation, as it can satisfy the need for low-cost, high-sensitivity, and home-based quantitative detection for respiratory infectious diseases.
Lateral flow immunoassay (LFIA) has become popular in laboratories, at-home testing, and medical diagnostics due to its minimal cost and user-friendliness. Nevertheless, conventional test strips based on colloidal gold can only obtain qualitative or semi-quantitative results with low sensitivity. In this work, Au-Fe3O4 dumbbell-like nanoparticles were synthesized and used as the LFIA labelling marker for highly sensitive colorimetric-photothermal dual-mode detection of SARS-CoV-2 spike(S) protein. The unique dumbbell structure of Au-Fe3O4 NPs makes it possible to combine the best features of both Au NPs and Fe3O4 NPs. The increased surface area of these NPs enhances their LSPR effect and photothermal effect, which achieves signal amplification to increase sensitivity. The Au-Fe3O4 NPs modified with S protein antibody could identify S protein in samples, which were recognized and accumulated on T-line by another antibody, generating color band for qualitative colorimetric detection. The T-line was irradiated by laser to obtain temperature change for quantitative detection of photothermal. In optimized conditions, the detection limit was 1.22 pg/mL, three orders of magnitude more sensitive than colorimetric detection. Finally, the approach was performed on SARS-CoV-2 pseudovirus samples and outperformed traditional colloidal gold strips. This LFIA platform exhibits significant promise for practical implementation, as it can satisfy the need for low-cost, high-sensitivity, and home-based quantitative detection for respiratory infectious diseases.
2024, 35(6): 109200
doi: 10.1016/j.cclet.2023.109200
Abstract:
The practical application of high-energy-density lithium-sulfur (Li-S) batteries have been highly praised for energy storage devices, while are largely hindered by the "shuttling effect". Herein, core-shell carbon spheres composed of interlinked porous core and lamellar shell were designed to restrain the polysulfide shuttling. The microporous structure with pore size of around 1 nm effectively trap lithium polysulfides. Furthermore, the interconnected porous core shortens the ion transfer distance and the lamellar carbon shell endows the carbon spheres with fast electron conduction, finally facilitating polysulfide conversion kinetics. Therefore, the Li-S batteries with the carbon spheres as the interlayer show high discharge specific capacity of 1002 mAh/g at 2 C with 574 mAh/g remaining after 600 cycles, and high areal capacity of 5.48 mAh/cm2 with sulfur loading of 4.67 mg/cm2 at 0.1 C. The corresponding pouch cells also exhibit stable cycling stability with an initial discharge specific capacity of 1082 mAh/g at 0.1 C.
The practical application of high-energy-density lithium-sulfur (Li-S) batteries have been highly praised for energy storage devices, while are largely hindered by the "shuttling effect". Herein, core-shell carbon spheres composed of interlinked porous core and lamellar shell were designed to restrain the polysulfide shuttling. The microporous structure with pore size of around 1 nm effectively trap lithium polysulfides. Furthermore, the interconnected porous core shortens the ion transfer distance and the lamellar carbon shell endows the carbon spheres with fast electron conduction, finally facilitating polysulfide conversion kinetics. Therefore, the Li-S batteries with the carbon spheres as the interlayer show high discharge specific capacity of 1002 mAh/g at 2 C with 574 mAh/g remaining after 600 cycles, and high areal capacity of 5.48 mAh/cm2 with sulfur loading of 4.67 mg/cm2 at 0.1 C. The corresponding pouch cells also exhibit stable cycling stability with an initial discharge specific capacity of 1082 mAh/g at 0.1 C.
2024, 35(6): 109212
doi: 10.1016/j.cclet.2023.109212
Abstract:
Ynones are important skeletons in bioactive molecules and valuable building blocks for organic synthesis, thus great efforts have been devoted to their preparation. While, introducing prochiral substrates to construct ynones bearing a chiral framework is unrealized to date. Herein, we reported the first example of Pd/SOP-catalyzed asymmetric carbonylative alkynylation via a non-classical carbonylative Sonogashira-type approach (acyl-Pd(Ⅱ) species generated from nucleophiles). By using cyclic diaryliodonium salts as prochiral substrates, various axial chiral ynones with good functional group tolerance (39 examples), satisfied yields (71%-96%) and excellent enantioselectivities (generally 94%-99% ee) were produced. Synthesis of bioactive compounds, scale-up experiment and useful transformations were also conducted to demonstrate the utility of this process.
Ynones are important skeletons in bioactive molecules and valuable building blocks for organic synthesis, thus great efforts have been devoted to their preparation. While, introducing prochiral substrates to construct ynones bearing a chiral framework is unrealized to date. Herein, we reported the first example of Pd/SOP-catalyzed asymmetric carbonylative alkynylation via a non-classical carbonylative Sonogashira-type approach (acyl-Pd(Ⅱ) species generated from nucleophiles). By using cyclic diaryliodonium salts as prochiral substrates, various axial chiral ynones with good functional group tolerance (39 examples), satisfied yields (71%-96%) and excellent enantioselectivities (generally 94%-99% ee) were produced. Synthesis of bioactive compounds, scale-up experiment and useful transformations were also conducted to demonstrate the utility of this process.
2024, 35(6): 109214
doi: 10.1016/j.cclet.2023.109214
Abstract:
The classification of π-/σ-aromaticity depends on the electrons with the dominating contributions. Traditionally, π- and σ-aromaticity are used to describe the unsaturated and saturated systems, respectively. Thus, it is rarely reported that π-aromaticity is dominated in a saturated system. Here we demonstrate that π-aromaticity could be dominating in several fully saturated four-membered rings (4MRs), supported by various aromaticity indices including ΔBL, NICS, EDDB, MCI, and AdNDP. The origin of such π-aromaticity in saturated rings could be attributed to an introduction of two additional electrons into the π-type LUMO of the parent neutral species. Our findings represent a novel approach to achieve π-aromaticity into a fully saturated system which has traditionally been dominated by σ-aromaticity.
The classification of π-/σ-aromaticity depends on the electrons with the dominating contributions. Traditionally, π- and σ-aromaticity are used to describe the unsaturated and saturated systems, respectively. Thus, it is rarely reported that π-aromaticity is dominated in a saturated system. Here we demonstrate that π-aromaticity could be dominating in several fully saturated four-membered rings (4MRs), supported by various aromaticity indices including ΔBL, NICS, EDDB, MCI, and AdNDP. The origin of such π-aromaticity in saturated rings could be attributed to an introduction of two additional electrons into the π-type LUMO of the parent neutral species. Our findings represent a novel approach to achieve π-aromaticity into a fully saturated system which has traditionally been dominated by σ-aromaticity.
2024, 35(6): 109216
doi: 10.1016/j.cclet.2023.109216
Abstract:
An amphiphilic derivative with a large Stokes shift by introducing flexible hydrophilic long chains into a rigid ethylene-pyrene compound have been successfully synthesized. The alkylated compound exhibited a notable change in charge distribution, facilitating cation-π interactions. Through the process of amphiphilic self-assembly, the formation of highly ordered aggregates enabled effective photo-dimerization under 449 nm LED irradiation. Notably, this photo-responsive technology not only exhibited advanced multi-color emission effects, including white light emission but also exhibited environmentally friendly behavior in the aqueous phase.
An amphiphilic derivative with a large Stokes shift by introducing flexible hydrophilic long chains into a rigid ethylene-pyrene compound have been successfully synthesized. The alkylated compound exhibited a notable change in charge distribution, facilitating cation-π interactions. Through the process of amphiphilic self-assembly, the formation of highly ordered aggregates enabled effective photo-dimerization under 449 nm LED irradiation. Notably, this photo-responsive technology not only exhibited advanced multi-color emission effects, including white light emission but also exhibited environmentally friendly behavior in the aqueous phase.
2024, 35(6): 109217
doi: 10.1016/j.cclet.2023.109217
Abstract:
Single-chain nanoparticles represent an emerging class of nanomaterials designed to mimic protein's folding paradigm. Intrachain covalent crosslinking toward the formation of single-chain nanoparticles encounters complex energy landscapes, leading to the potential occurrence of misfolding issues. While non-covalent crosslinking can circumvent this issue, the resulting single-chain nanoparticles exhibit lower structural stability compared to their covalently crosslinked counterparts. In this study, we present a novel approach for the synthesis of single-chain nanoparticles, achieved through the combination of non-covalent and covalent intramolecular crosslinking. Cyanostilbenes grafted onto the linear polymer form intrachain non-covalent stacks aided by hydrogen bonds, leading to the formation of non-covalently crosslinked single-chain nanoparticles. These nanoparticles undergo conversion to covalently crosslinked nanostructures through subsequent photo-irradiation using [2 + 2] photocycloaddition, a process facilitated by the supramolecular confinement effect. Consequently, the resulting single-chain nanoparticles demonstrate both intrachain folding efficiency and substantial stability, offering significant potential for advancing applications across diverse fields.
Single-chain nanoparticles represent an emerging class of nanomaterials designed to mimic protein's folding paradigm. Intrachain covalent crosslinking toward the formation of single-chain nanoparticles encounters complex energy landscapes, leading to the potential occurrence of misfolding issues. While non-covalent crosslinking can circumvent this issue, the resulting single-chain nanoparticles exhibit lower structural stability compared to their covalently crosslinked counterparts. In this study, we present a novel approach for the synthesis of single-chain nanoparticles, achieved through the combination of non-covalent and covalent intramolecular crosslinking. Cyanostilbenes grafted onto the linear polymer form intrachain non-covalent stacks aided by hydrogen bonds, leading to the formation of non-covalently crosslinked single-chain nanoparticles. These nanoparticles undergo conversion to covalently crosslinked nanostructures through subsequent photo-irradiation using [2 + 2] photocycloaddition, a process facilitated by the supramolecular confinement effect. Consequently, the resulting single-chain nanoparticles demonstrate both intrachain folding efficiency and substantial stability, offering significant potential for advancing applications across diverse fields.
2024, 35(6): 109239
doi: 10.1016/j.cclet.2023.109239
Abstract:
Selenium is an essential trace element for humans and animals. As the active center of selenoproteins, the addition of selenium is beneficial to enhance the antioxidant ability. However, the high cost limits the application of organic Se in agriculture animal production. Selenized glucose (SeGlu) is a newly invented organoselenium material with good stability, low toxicity and low cost. This assay found that SeGlu was able to increase selenium deposition in liver of newborn broilers, and enhance the antioxidant capacity of liver by elevating the activities of antioxidant enzymes such as total superoxide dismutase and glutathione peroxidase. This paper as the first example clarifying the mechanism of SeGlu to enhance the antioxidant ability of chicks, shows that SeGlu can be used as an organic selenium enrichment additive for early nutrition of poultry. As a cross-discipline study involving chemistry, biology and agriculture animal science, the work may be beneficial for studies in related fields and prompt the development of the selenium science.
Selenium is an essential trace element for humans and animals. As the active center of selenoproteins, the addition of selenium is beneficial to enhance the antioxidant ability. However, the high cost limits the application of organic Se in agriculture animal production. Selenized glucose (SeGlu) is a newly invented organoselenium material with good stability, low toxicity and low cost. This assay found that SeGlu was able to increase selenium deposition in liver of newborn broilers, and enhance the antioxidant capacity of liver by elevating the activities of antioxidant enzymes such as total superoxide dismutase and glutathione peroxidase. This paper as the first example clarifying the mechanism of SeGlu to enhance the antioxidant ability of chicks, shows that SeGlu can be used as an organic selenium enrichment additive for early nutrition of poultry. As a cross-discipline study involving chemistry, biology and agriculture animal science, the work may be beneficial for studies in related fields and prompt the development of the selenium science.
2024, 35(6): 109244
doi: 10.1016/j.cclet.2023.109244
Abstract:
Tryptophan (Trp) carries a unique heteroaromatic indole side chain and plays a critical role in peptide or protein modification. Herein, we have reported a metal-free photoinduced N-H alkylation strategy using N-aryl glycines for specific modification of tryptophan-containing peptides. The robustness of our approach is demonstrated by its wide substrate scope, excellent isolated yields, as well as almost unobservable side effects. Using this highly efficiently metal-free condition, alkylated Trp-containing peptides can be smoothly assembled. This study provides a reliable and practical tool for the chemo-selective modification of various tryptophan containing oligopeptides.
Tryptophan (Trp) carries a unique heteroaromatic indole side chain and plays a critical role in peptide or protein modification. Herein, we have reported a metal-free photoinduced N-H alkylation strategy using N-aryl glycines for specific modification of tryptophan-containing peptides. The robustness of our approach is demonstrated by its wide substrate scope, excellent isolated yields, as well as almost unobservable side effects. Using this highly efficiently metal-free condition, alkylated Trp-containing peptides can be smoothly assembled. This study provides a reliable and practical tool for the chemo-selective modification of various tryptophan containing oligopeptides.
2024, 35(6): 109246
doi: 10.1016/j.cclet.2023.109246
Abstract:
The H-bond promoted electrochemical [2 + 2 + 1] annulation of benzo[d]isothiazole 1,1-dioxides, N-arylglycines and paraformaldehyde for the synthesis of various benzo[d]imidazo[1,5-b]isothiazole 5,5-dioxide derivatives under redox mediator, catalyst and electrolyte-free conditions was developed.
The H-bond promoted electrochemical [2 + 2 + 1] annulation of benzo[d]isothiazole 1,1-dioxides, N-arylglycines and paraformaldehyde for the synthesis of various benzo[d]imidazo[1,5-b]isothiazole 5,5-dioxide derivatives under redox mediator, catalyst and electrolyte-free conditions was developed.
2024, 35(6): 109250
doi: 10.1016/j.cclet.2023.109250
Abstract:
We report the unprecedent Pd(I) catalyzed ring-opening arylation of cyclopropyl-α-aminoamides. This protocol allows facile access to biologically important α-ketoamide-containing oligopeptides and even more challenging peptide-natural product conjugates. Site selectivity was achieved by introduction of special unnatural amino acids, which also meets the requisite of bioorthogonal chemistry. Mechanism investigations reveals a distinct domino radical ring-opening process through Pd(I) catalysis.
We report the unprecedent Pd(I) catalyzed ring-opening arylation of cyclopropyl-α-aminoamides. This protocol allows facile access to biologically important α-ketoamide-containing oligopeptides and even more challenging peptide-natural product conjugates. Site selectivity was achieved by introduction of special unnatural amino acids, which also meets the requisite of bioorthogonal chemistry. Mechanism investigations reveals a distinct domino radical ring-opening process through Pd(I) catalysis.
2024, 35(6): 109263
doi: 10.1016/j.cclet.2023.109263
Abstract:
A photoinduced copper-catalyzed alkoxyl triggered C−C bond cleavage/aminocarbonylation cascade is presented. Through adjusting the structure of alkoxyl radical precursors, functionalized lactones and keto-amides were synthesized with good yields and excellent functional group tolerance under redox-neutral conditions. Notably, this protocol enables the integration of lactone fragments with many amine drugs and drug fragments.
A photoinduced copper-catalyzed alkoxyl triggered C−C bond cleavage/aminocarbonylation cascade is presented. Through adjusting the structure of alkoxyl radical precursors, functionalized lactones and keto-amides were synthesized with good yields and excellent functional group tolerance under redox-neutral conditions. Notably, this protocol enables the integration of lactone fragments with many amine drugs and drug fragments.
2024, 35(6): 109266
doi: 10.1016/j.cclet.2023.109266
Abstract:
Closed pores formed in hard carbons play an essential role in sodium storage at plateau region. However, the effect of different structural features on the diffusion of sodium ions into closed pores remains unclear. Herein, a precursor reconstruction strategy is conducted to regulate carbon microstructures including interlayer spacing, defect concentration, and closed pore volume by changing the ratio of aromatic and polysaccharide components. Aromatic structure parts tend to develop disordered carbons with fewer defects, larger interlayer spacing, and smaller closed pore volume, while polysaccharide components prefer to form disordered carbons with more defects, smaller interlayer spacing, and larger closed pore volume. Through the correlation analysis of microstructure features and the sodium storage capacity below 0.1 V. It finds that the intercalation capacity is proportional to the ratio of pseudo-graphitic domains, whereas the pore filling capacity appeared at lower potential gradually decreases with the increasing defect concentration due to homo-ionic repulsion effect, without linear correlation with short-range microcrystalline and closed pore volume. The optimized sample with suitable interlayer spacing and defect concentration exhibits a high plateau capacity of 241.7 mAh/g. This work provides insights into the exploitation of closed pore sodium storage performance.
Closed pores formed in hard carbons play an essential role in sodium storage at plateau region. However, the effect of different structural features on the diffusion of sodium ions into closed pores remains unclear. Herein, a precursor reconstruction strategy is conducted to regulate carbon microstructures including interlayer spacing, defect concentration, and closed pore volume by changing the ratio of aromatic and polysaccharide components. Aromatic structure parts tend to develop disordered carbons with fewer defects, larger interlayer spacing, and smaller closed pore volume, while polysaccharide components prefer to form disordered carbons with more defects, smaller interlayer spacing, and larger closed pore volume. Through the correlation analysis of microstructure features and the sodium storage capacity below 0.1 V. It finds that the intercalation capacity is proportional to the ratio of pseudo-graphitic domains, whereas the pore filling capacity appeared at lower potential gradually decreases with the increasing defect concentration due to homo-ionic repulsion effect, without linear correlation with short-range microcrystalline and closed pore volume. The optimized sample with suitable interlayer spacing and defect concentration exhibits a high plateau capacity of 241.7 mAh/g. This work provides insights into the exploitation of closed pore sodium storage performance.
2024, 35(6): 109271
doi: 10.1016/j.cclet.2023.109271
Abstract:
Traditional photo-electcatalyst structures of small noble metal nanoparticles assembling into large-scale photoactive semiconductors still suffer from agglomeration of noble metal nanoparticles, insufficient charge transfer, undesirable photoresponse ability that restricted the photo-electrocatalytic performance. To this end, a novel design strategy is proposed in this work, namely integrating small-scale photoactive materials (doped graphene quantum dots, S,N-GQDs) with large-sized noble metal (PdP) nanoflowers to form novel photo-electrocatalysts for high-efficient alcohol oxidation reaction. As expected, superior electrocatalytic performance of PdP/S,N-GQDs for ethylene glycol oxidation is acquired, thanks to the nanoflower structure with larger specific surface area and abundant active sites. Furthermore, nonmetal P are demonstrated, especially optimizing the adsorption strength, enhancing the interfacial contact, reducing metal agglomeration, ensuring uniform and efficient doping of S,N-GQDs, and ultimately significantly boost the catalytic activity of photo-electrocatalysts.
Traditional photo-electcatalyst structures of small noble metal nanoparticles assembling into large-scale photoactive semiconductors still suffer from agglomeration of noble metal nanoparticles, insufficient charge transfer, undesirable photoresponse ability that restricted the photo-electrocatalytic performance. To this end, a novel design strategy is proposed in this work, namely integrating small-scale photoactive materials (doped graphene quantum dots, S,N-GQDs) with large-sized noble metal (PdP) nanoflowers to form novel photo-electrocatalysts for high-efficient alcohol oxidation reaction. As expected, superior electrocatalytic performance of PdP/S,N-GQDs for ethylene glycol oxidation is acquired, thanks to the nanoflower structure with larger specific surface area and abundant active sites. Furthermore, nonmetal P are demonstrated, especially optimizing the adsorption strength, enhancing the interfacial contact, reducing metal agglomeration, ensuring uniform and efficient doping of S,N-GQDs, and ultimately significantly boost the catalytic activity of photo-electrocatalysts.
2024, 35(6): 109298
doi: 10.1016/j.cclet.2023.109298
Abstract:
A variety of research reports on novel supramolecular topologies have been published over the last years. However, it is still a great challenge to tap into the inner functional properties of these complexes. Herein, two tetranuclear metallamacrocycles 1 and 2 and four octonuclear [2]catenanes 3–6 were constructed successfully via a coordination-driven self-assembly strategy, by conscious design and use of the tetramethyl bidentate pyridine ligand L1, and the appropriate selection of six binuclear half-sandwich rhodium building units with different longitudinal dimensions. The complexes have been fully characterized by single crystal X-ray diffraction analysis and NMR spectroscopy. Furthermore, near-infrared photothermal studies of the obtained [2]catenanes reveal different photothermal response in solid and solution states, which may be attributed to a strong fluorescence quenching effect of the half-sandwich organometallic fragment and different conjugated effect of Cp*Rh based building blocks in the interlocking structures. The photothermal conversion efficiencies of [2]catenanes 4–6 fall in the range 30.5%–16.5% respectively. This contribution aims to play a key role in the experimental development of Cp*-based photothermal materials.
A variety of research reports on novel supramolecular topologies have been published over the last years. However, it is still a great challenge to tap into the inner functional properties of these complexes. Herein, two tetranuclear metallamacrocycles 1 and 2 and four octonuclear [2]catenanes 3–6 were constructed successfully via a coordination-driven self-assembly strategy, by conscious design and use of the tetramethyl bidentate pyridine ligand L1, and the appropriate selection of six binuclear half-sandwich rhodium building units with different longitudinal dimensions. The complexes have been fully characterized by single crystal X-ray diffraction analysis and NMR spectroscopy. Furthermore, near-infrared photothermal studies of the obtained [2]catenanes reveal different photothermal response in solid and solution states, which may be attributed to a strong fluorescence quenching effect of the half-sandwich organometallic fragment and different conjugated effect of Cp*Rh based building blocks in the interlocking structures. The photothermal conversion efficiencies of [2]catenanes 4–6 fall in the range 30.5%–16.5% respectively. This contribution aims to play a key role in the experimental development of Cp*-based photothermal materials.
2024, 35(6): 109401
doi: 10.1016/j.cclet.2023.109401
Abstract:
Inkjet printing has emerged as a potential solution processing method for large-area patterned films. During inkjet printing, a single droplet without satellite droplet is required for high-quality film. Herein, we propose a strategy for obtaining a single droplet by adjusting the reduced concentration (c/c*, where c* is the critical overlap concentration) in the range of 1.0–1.5. Droplet formation can be categorized into three distinct regimes: (1) c/c* < 1.0, satellite droplet; (2) c/c* = 1.0–1.5, single droplet; (3) c/c* > 2.0, no droplet. Furthermore, an inertial-capillary balance led to the 2/3-power scaling of the minimum radius with time for the solutions of c/c* < 1.0. However, for the solutions of c/c* = 1.0–1.5, the ligament radius decreased exponentially with time. Moreover, the Weissenberg number was higher than the critical value of 0.5, indicating that the polymer chains underwent coil-stretch transition. The viscoelastic-capillary balance dominated instead of the inertial-capillary balance. The resulting viscoelastic resistance reduced the length of the ligament and increased the velocity difference between the satellite and main droplets. Consequently, a single droplet was formed. In addition, the law can be successfully generalized to various molecular weights, molecular structures and solvents.
Inkjet printing has emerged as a potential solution processing method for large-area patterned films. During inkjet printing, a single droplet without satellite droplet is required for high-quality film. Herein, we propose a strategy for obtaining a single droplet by adjusting the reduced concentration (c/c*, where c* is the critical overlap concentration) in the range of 1.0–1.5. Droplet formation can be categorized into three distinct regimes: (1) c/c* < 1.0, satellite droplet; (2) c/c* = 1.0–1.5, single droplet; (3) c/c* > 2.0, no droplet. Furthermore, an inertial-capillary balance led to the 2/3-power scaling of the minimum radius with time for the solutions of c/c* < 1.0. However, for the solutions of c/c* = 1.0–1.5, the ligament radius decreased exponentially with time. Moreover, the Weissenberg number was higher than the critical value of 0.5, indicating that the polymer chains underwent coil-stretch transition. The viscoelastic-capillary balance dominated instead of the inertial-capillary balance. The resulting viscoelastic resistance reduced the length of the ligament and increased the velocity difference between the satellite and main droplets. Consequently, a single droplet was formed. In addition, the law can be successfully generalized to various molecular weights, molecular structures and solvents.
2024, 35(6): 109421
doi: 10.1016/j.cclet.2023.109421
Abstract:
Inspired by biological ion channels, numerous artificial asymmetric ion channels have been synthesized to facilitate the fabrication of ionic circuits. Nevertheless, the creation of biomimetic asymmetric ion channels necessitates expensive scientific apparatus and intricate material processing procedures, which constrains its advancement within the realm of ionic devices. In this study, we have devised dynamic asymmetric ion channels with mechanical responsiveness by combining polymers of varying elastic modulus along the longitudinal axis of carbon nanotube fiber (CNTF). The ion rectification can be modulated via the disparate response of CNTF-based ion channels to mechanical stress. We have effectively employed these asymmetric ion channels with mechanical sensitivity in the design of a logic gate device, achieving logic operations such as “AND” and “OR”. The conception of these dynamic asymmetric ion channels with mechanical sensitivity offers a straightforward, cost-effective, and versatile approach for generating ion channels, highlighting their potential application in intricate, highly integrated ionic circuits.
Inspired by biological ion channels, numerous artificial asymmetric ion channels have been synthesized to facilitate the fabrication of ionic circuits. Nevertheless, the creation of biomimetic asymmetric ion channels necessitates expensive scientific apparatus and intricate material processing procedures, which constrains its advancement within the realm of ionic devices. In this study, we have devised dynamic asymmetric ion channels with mechanical responsiveness by combining polymers of varying elastic modulus along the longitudinal axis of carbon nanotube fiber (CNTF). The ion rectification can be modulated via the disparate response of CNTF-based ion channels to mechanical stress. We have effectively employed these asymmetric ion channels with mechanical sensitivity in the design of a logic gate device, achieving logic operations such as “AND” and “OR”. The conception of these dynamic asymmetric ion channels with mechanical sensitivity offers a straightforward, cost-effective, and versatile approach for generating ion channels, highlighting their potential application in intricate, highly integrated ionic circuits.
2024, 35(6): 109508
doi: 10.1016/j.cclet.2024.109508
Abstract:
Carbon materials have been used as the support for catalysts in the field of acetylene hydrochlorination, the influence of inevitable oxygen-containing moieties on the reaction is often ignored and the mechanism of the oxygen-doping structure remains ambiguous. Herein, we explored the effect of the oxygen-containing group (C–O–C) in the support on the activity of single-atom dispersed Cu catalysts. By immersing the Cu single-atom catalyst in an alkaline solution, the epoxy species on the carbon support was cleaved to obtain a pure ether species while the Cu site was modified to a more electron-deficient state. The turnover frequency value of Cu/O-FLP catalyst with epoxy groups was 1.6-fold higher than that of alkaline treated catalyst. Our result indicated that the epoxy groups could assist adjacent single-atom Cu sites to synergistically promote the adsorption and cleavage of the reactant hydrogen chloride toward form C–OH and Cu–Cl bonds, and reduce the reaction energy barrier. The presence of electron deficient Cu sites and ether species could induce competitive adsorption of the acetylene and hydrogen chloride, thereby reducing the activity of the catalyst. This study highlights the influence of surface oxygen species and the tunability of the support, providing the foundation for the fabrication of higher-activity Cu catalysts for acetylene hydrochlorination.
Carbon materials have been used as the support for catalysts in the field of acetylene hydrochlorination, the influence of inevitable oxygen-containing moieties on the reaction is often ignored and the mechanism of the oxygen-doping structure remains ambiguous. Herein, we explored the effect of the oxygen-containing group (C–O–C) in the support on the activity of single-atom dispersed Cu catalysts. By immersing the Cu single-atom catalyst in an alkaline solution, the epoxy species on the carbon support was cleaved to obtain a pure ether species while the Cu site was modified to a more electron-deficient state. The turnover frequency value of Cu/O-FLP catalyst with epoxy groups was 1.6-fold higher than that of alkaline treated catalyst. Our result indicated that the epoxy groups could assist adjacent single-atom Cu sites to synergistically promote the adsorption and cleavage of the reactant hydrogen chloride toward form C–OH and Cu–Cl bonds, and reduce the reaction energy barrier. The presence of electron deficient Cu sites and ether species could induce competitive adsorption of the acetylene and hydrogen chloride, thereby reducing the activity of the catalyst. This study highlights the influence of surface oxygen species and the tunability of the support, providing the foundation for the fabrication of higher-activity Cu catalysts for acetylene hydrochlorination.
2024, 35(6): 109516
doi: 10.1016/j.cclet.2024.109516
Abstract:
To promote the practices of perovskite photovoltaics, it requires to develop efficient perovskite solar cells (PVSCs) standing long-time operation under the adverse environments. Herein, we demonstrate that the tailor-made conjugated polymers as conductive adhesives stabilized the originally redox-reactive heterointerface between perovskite and metal oxide, facilitating the access of efficient and stable inverted PVSCs. It was revealed that bithiophene and phenyl alternating conjugated polymers with partial glycol chains atop of the metal oxide layer has resulted in effective organic-inorganic hybrid hole transporting bilayers, which allow maintaining efficient hole extraction and transport, meanwhile preventing halide migration to directly contact with the nickel oxide (NiOx) layer. As a result, the corresponding inverted PVSCs with the organic-inorganic hole transporting bilayers have achieved an excellent power conversion efficiency of 23.22%, outperforming 20.65% of bare NiOx-based devices. Moreover, the encapsulated PVSCs with organic-inorganic bilayers exhibited the excellent photostability with 91% of the initial efficiency after 1000-h one-sun equivalent illumination in ambient conditions. Overall, this work provides new insights into stabilizing the vulnerable heterointerface for perovskite solar cells.
To promote the practices of perovskite photovoltaics, it requires to develop efficient perovskite solar cells (PVSCs) standing long-time operation under the adverse environments. Herein, we demonstrate that the tailor-made conjugated polymers as conductive adhesives stabilized the originally redox-reactive heterointerface between perovskite and metal oxide, facilitating the access of efficient and stable inverted PVSCs. It was revealed that bithiophene and phenyl alternating conjugated polymers with partial glycol chains atop of the metal oxide layer has resulted in effective organic-inorganic hybrid hole transporting bilayers, which allow maintaining efficient hole extraction and transport, meanwhile preventing halide migration to directly contact with the nickel oxide (NiOx) layer. As a result, the corresponding inverted PVSCs with the organic-inorganic hole transporting bilayers have achieved an excellent power conversion efficiency of 23.22%, outperforming 20.65% of bare NiOx-based devices. Moreover, the encapsulated PVSCs with organic-inorganic bilayers exhibited the excellent photostability with 91% of the initial efficiency after 1000-h one-sun equivalent illumination in ambient conditions. Overall, this work provides new insights into stabilizing the vulnerable heterointerface for perovskite solar cells.
2024, 35(6): 109680
doi: 10.1016/j.cclet.2024.109680
Abstract:
Due to the heterogeneity of tumors, single phototherapy cannot completely ablate tumors and inhibit tumor metastasis. To overcome these, we formulated targeted and multifunctional polymersomes ABC@ICG-IMQ-LHRH (AIRL) that encapsulated Toll-like receptor (TLR) 7/8 agonist imiquimod (IMQ) and photosensitizer indocyanine green (ICG) in the hydrophobic layer as well as bubble-generator NH4HCO3 in the hydrophilic cavity to inhibit the growth of primary and distant tumors, and prevent tumor metastasis through synergistic photoimmunotherapy. The AIRL polymersomes exhibited uniform and stable size, and high drug encapsulation efficiency, acid/reduction/laser responsiveness, excellent photothermal conversion efficiency, effective reactive oxygen species generation, high tumor accumulation. AIRL could be effectively internalized by dendritic cells (DCs), achieve lysosome escape and enhance DCs maturation. The synergistic photoimmunotherapy via AIRL polymersomes remarkably promoted the differentiation and activation of T cells, elevated strong systemic immune response to eradicate primary tumors and inhibit the growth of distant tumors. Simultaneously, the endurable immunological memory prevented tumor metastasis, which provided a promising nanoplatform for the combination therapy of cancer.
Due to the heterogeneity of tumors, single phototherapy cannot completely ablate tumors and inhibit tumor metastasis. To overcome these, we formulated targeted and multifunctional polymersomes ABC@ICG-IMQ-LHRH (AIRL) that encapsulated Toll-like receptor (TLR) 7/8 agonist imiquimod (IMQ) and photosensitizer indocyanine green (ICG) in the hydrophobic layer as well as bubble-generator NH4HCO3 in the hydrophilic cavity to inhibit the growth of primary and distant tumors, and prevent tumor metastasis through synergistic photoimmunotherapy. The AIRL polymersomes exhibited uniform and stable size, and high drug encapsulation efficiency, acid/reduction/laser responsiveness, excellent photothermal conversion efficiency, effective reactive oxygen species generation, high tumor accumulation. AIRL could be effectively internalized by dendritic cells (DCs), achieve lysosome escape and enhance DCs maturation. The synergistic photoimmunotherapy via AIRL polymersomes remarkably promoted the differentiation and activation of T cells, elevated strong systemic immune response to eradicate primary tumors and inhibit the growth of distant tumors. Simultaneously, the endurable immunological memory prevented tumor metastasis, which provided a promising nanoplatform for the combination therapy of cancer.
2024, 35(6): 109736
doi: 10.1016/j.cclet.2024.109736
Abstract:
Ulcerative colitis (UC) is a chronic inflammatory bowel disease characterized by persistent inflammation of the colon and disrupted intestinal function. Ramulus mori (Sangzhi) alkaloids (SZ-A), derived from twigs of mulberry, were approved by the National Medical Products Administration in 2020 for treating type 2 diabetes mellitus. Accumulated evidence has confirmed that SZ-A also alleviates non-alcoholic fatty liver disease and ameliorates inflammation, indicating its potential to address inflammation in UC. However, the treatment of UC faces challenges due to low drug delivery efficiency and short retention time. To overcome these challenges, an injectable and adherent in-situ thermo-sensitive hydrogel containing SZ-A was developed for rectal drug delivery, utilizing the thermo-sensitive polymers Poloxamer 407 and 188. The thermo-sensitive hydrogel system was designed with a moderate gelation temperature of 32 ± 0.5 ℃, a short gelation time of 64 s, a pH range of 7–10, high moisturizing capability exceeding 90%, and moderate mechanical strength of 4–5 s. In a rat model with UC, the in situ thermo-sensitive hydrogel significantly extended the retention time at the colonic site and enabled sustained release after rectal administration. Symptoms of UC were markedly reduced following rectal administration of SZ-A thermo-sensitive hydrogel. Furthermore, the release of inflammatory factors, such as interleukin-1β (IL-1β), IL-6, IL-18, tumor necrosis factor-α (TNF-α), and transforming growth factor-β1 (TGF-β1), significantly decreased in the SZ-A thermo-sensitive hydrogel group. The integrity of the colonic mucosal barrier was significantly enhanced following the application of SZ-A thermo-sensitive hydrogel. In conclusion, rectal administration of SZ-A in situ thermo-sensitive hydrogel effectively alleviated UC symptoms, inhibited the secretion of inflammatory factors, and promoted the repair of the colonic mucosal barrier. This approach holds promise as a potential treatment for UC.
Ulcerative colitis (UC) is a chronic inflammatory bowel disease characterized by persistent inflammation of the colon and disrupted intestinal function. Ramulus mori (Sangzhi) alkaloids (SZ-A), derived from twigs of mulberry, were approved by the National Medical Products Administration in 2020 for treating type 2 diabetes mellitus. Accumulated evidence has confirmed that SZ-A also alleviates non-alcoholic fatty liver disease and ameliorates inflammation, indicating its potential to address inflammation in UC. However, the treatment of UC faces challenges due to low drug delivery efficiency and short retention time. To overcome these challenges, an injectable and adherent in-situ thermo-sensitive hydrogel containing SZ-A was developed for rectal drug delivery, utilizing the thermo-sensitive polymers Poloxamer 407 and 188. The thermo-sensitive hydrogel system was designed with a moderate gelation temperature of 32 ± 0.5 ℃, a short gelation time of 64 s, a pH range of 7–10, high moisturizing capability exceeding 90%, and moderate mechanical strength of 4–5 s. In a rat model with UC, the in situ thermo-sensitive hydrogel significantly extended the retention time at the colonic site and enabled sustained release after rectal administration. Symptoms of UC were markedly reduced following rectal administration of SZ-A thermo-sensitive hydrogel. Furthermore, the release of inflammatory factors, such as interleukin-1β (IL-1β), IL-6, IL-18, tumor necrosis factor-α (TNF-α), and transforming growth factor-β1 (TGF-β1), significantly decreased in the SZ-A thermo-sensitive hydrogel group. The integrity of the colonic mucosal barrier was significantly enhanced following the application of SZ-A thermo-sensitive hydrogel. In conclusion, rectal administration of SZ-A in situ thermo-sensitive hydrogel effectively alleviated UC symptoms, inhibited the secretion of inflammatory factors, and promoted the repair of the colonic mucosal barrier. This approach holds promise as a potential treatment for UC.
2024, 35(6): 109320
doi: 10.1016/j.cclet.2023.109320
Abstract:
