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Chinese Chemical Letters
Chinese Chemical Letters
主管 : 中国科学技术协会
刊期 : 月刊主编 : 钱旭红
语种 : 英文主办 : 中国化学会、中国医学科学院药物研究所
ISSN : 1001-8417 CN : 11-2710/O6本刊创办于1990年7月，是由中国化学会主办，中国医学科学院药物研究所承办的核心期刊。本刊由著名化学家梁晓天院士任主编，其内容涵盖化学研究的各个领域，及时报道我国化学界各个研究领域的最新进展及世界上一些化学研究的热点问题。本刊自1993年起为SCI、CA、日本科技文献速报等收录，2000年美国化学文摘引用中国期刊频次中位列第四。展开 > - 影响因子: 6.779
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Synthesis of a new ratiometric emission Ca2+ indicator for in vivo bioimaging
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Synthesis of a water-soluble macromolecular light stabilizer containing hindered amine structures
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Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation
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Superiority of poly(L-lactic acid) microspheres as dermal fillers
2024, 35(12): 109507
doi: 10.1016/j.cclet.2024.109507
摘要:
Multi-stimuli responsive materials controlled and coupled by two or more channels have a broad range of applications in the field of switches, memories, and molecular machines. The exploration of the material is currently focused on the pure organic system, which limits the development of such materials greatly. In this work, we present a new chiral organic-inorganic hybrid salt, (R-3-hydroxypyrrolidinium)2[Fe(CN)5(NO)] (1), which exhibits rare multi-stimuli responsive behaviors in thermal, mechanical and optical channels. In detail, 1 undergoes a C2-P21221 phase transition deriving from the thermal motion of organic cations with the increase of temperature, but the reverse transition can only be induced by mechanical pressure. Moreover, polycrystalline hybrid salt showed photo-responsive performance, i.e., the ground-state N-bound nitrosyl ligand adopts two configurations in excited states caused by light in 532 nm irradiation, accompanying with a photo-induced structural transformation of the anionic framework. Namely, the thermal motion characteristics of organic cations, the photoresponse characteristics of anionic inorganic skeleton and the pressure characteristics from hydrogen bonds are simultaneously integrated in 1. This unprecedented coupling mechanism of multi-stimuli responses makes 1 a potential candidate for future multichannel data storage applications.
Multi-stimuli responsive materials controlled and coupled by two or more channels have a broad range of applications in the field of switches, memories, and molecular machines. The exploration of the material is currently focused on the pure organic system, which limits the development of such materials greatly. In this work, we present a new chiral organic-inorganic hybrid salt, (R-3-hydroxypyrrolidinium)2[Fe(CN)5(NO)] (1), which exhibits rare multi-stimuli responsive behaviors in thermal, mechanical and optical channels. In detail, 1 undergoes a C2-P21221 phase transition deriving from the thermal motion of organic cations with the increase of temperature, but the reverse transition can only be induced by mechanical pressure. Moreover, polycrystalline hybrid salt showed photo-responsive performance, i.e., the ground-state N-bound nitrosyl ligand adopts two configurations in excited states caused by light in 532 nm irradiation, accompanying with a photo-induced structural transformation of the anionic framework. Namely, the thermal motion characteristics of organic cations, the photoresponse characteristics of anionic inorganic skeleton and the pressure characteristics from hydrogen bonds are simultaneously integrated in 1. This unprecedented coupling mechanism of multi-stimuli responses makes 1 a potential candidate for future multichannel data storage applications.
2024, 35(12): 109522
doi: 10.1016/j.cclet.2024.109522
摘要:
Most photodynamic therapies (PDT) rely on reactive oxygen species (ROS) produced by type Ⅱ mechanisms. However, since the production of type Ⅰ ROS is not limited by oxygen content, making it more favorable for antimicrobial phototherapy in complex microenvironments. Herein, we report a substituent cationization design strategy that not only improves the hydrophilicity of the prepared phthalocyanine molecule, but also promotes the electron transfer process in the photosensitizer, resulting in the strong type Ⅰ photodynamic effect of the phthalocyanine self-assembled photosensitizer to efficiently generate O2•- under both normal and hypoxic conditions. This in combination with its excellent bacteria recognition capability derived from the cationic part on its surface and intrinsic photothermal therapy effect of the phthalocyanine macrocycle endows the phthalocyanine self-assembled photosensitizer with excellent phototherapeutic antimicrobial properties in preclinical models, effectively promoting the wound healing process. This work provides a promising strategy for designing efficient multi-mode photosensitizers.
Most photodynamic therapies (PDT) rely on reactive oxygen species (ROS) produced by type Ⅱ mechanisms. However, since the production of type Ⅰ ROS is not limited by oxygen content, making it more favorable for antimicrobial phototherapy in complex microenvironments. Herein, we report a substituent cationization design strategy that not only improves the hydrophilicity of the prepared phthalocyanine molecule, but also promotes the electron transfer process in the photosensitizer, resulting in the strong type Ⅰ photodynamic effect of the phthalocyanine self-assembled photosensitizer to efficiently generate O2•- under both normal and hypoxic conditions. This in combination with its excellent bacteria recognition capability derived from the cationic part on its surface and intrinsic photothermal therapy effect of the phthalocyanine macrocycle endows the phthalocyanine self-assembled photosensitizer with excellent phototherapeutic antimicrobial properties in preclinical models, effectively promoting the wound healing process. This work provides a promising strategy for designing efficient multi-mode photosensitizers.
Subsurface carbon modification of Ni-Ga for improved selectivity in acetylene hydrogenation reaction
2024, 35(12): 109525
doi: 10.1016/j.cclet.2024.109525
摘要:
Control of subsurface interstitial atoms in transition metals is an effective approach to modulate selectivity in hydrogenation reactions. In this study, nickel was alloyed with gallium to form Ni3Ga, thereby regulating the octahedral interstitial sites. Subsequently, carbon atoms were introduced into the Ni3Ga (forming Ni3GaC0.5) via thermal treatment in an acetylene atmosphere, leading to a significant enhancement in selectivity for acetylene hydrogenation reaction. The X-ray diffraction and transmission electron microscopy results demonstrate an increase in the lattice parameter due to the incorporation of carbon atoms and the uniform distribution of carbon in Ni3GaC0.5 nanoparticles. The obtained Ni3GaC0.5/oCNT catalyst exhibits significantly improved selectivity in acetylene hydrogenation reaction, with approximately 82% ethylene selectivity at 98% conversion. Furthermore, it maintains good selectivity at various hydrogen-to-alkyne ratios and displays good stability during long-term operation. The introduction of carbon suppresses the formation of the subsurface hydrogen structure under reaction conditions. Additionally, the charge transfer between carbon and nickel results in the electron deficiency of nickel, effectively inhibiting the over-hydrogenation pathway and enhancing the selectivity. These results provide insights for the design of non-precious metal catalysts in selective hydrogenation reactions.
Control of subsurface interstitial atoms in transition metals is an effective approach to modulate selectivity in hydrogenation reactions. In this study, nickel was alloyed with gallium to form Ni3Ga, thereby regulating the octahedral interstitial sites. Subsequently, carbon atoms were introduced into the Ni3Ga (forming Ni3GaC0.5) via thermal treatment in an acetylene atmosphere, leading to a significant enhancement in selectivity for acetylene hydrogenation reaction. The X-ray diffraction and transmission electron microscopy results demonstrate an increase in the lattice parameter due to the incorporation of carbon atoms and the uniform distribution of carbon in Ni3GaC0.5 nanoparticles. The obtained Ni3GaC0.5/oCNT catalyst exhibits significantly improved selectivity in acetylene hydrogenation reaction, with approximately 82% ethylene selectivity at 98% conversion. Furthermore, it maintains good selectivity at various hydrogen-to-alkyne ratios and displays good stability during long-term operation. The introduction of carbon suppresses the formation of the subsurface hydrogen structure under reaction conditions. Additionally, the charge transfer between carbon and nickel results in the electron deficiency of nickel, effectively inhibiting the over-hydrogenation pathway and enhancing the selectivity. These results provide insights for the design of non-precious metal catalysts in selective hydrogenation reactions.
2024, 35(12): 109529
doi: 10.1016/j.cclet.2024.109529
摘要:
The design of pnictide nonlinear optical crystals is quite different from chalcogenide and oxide those, in which a new paradigm need be developed to regulate the band gap, one of key optical parameters. In this work, two non-centrosymmetric halidepnictides, [Cd2P]2[CdBr4] (CPB) and [Cd2As]2[CdBr4] (CAB) were reported. The complete octet binding electrons of pnictogens were constructed by four Cd-P polar covalent bonds under the anchoring effect of halogens, creating an extremely flat valence band maximum with band dispersion of only 0.17 eV. As expected, the balance of the covalency and ionicity in CPB and CAB was successfully realized, leading to a wide band gap of 2.58 eV and 1.88 eV. Remarkably, CPB not only has a widest band gap among Cd-containing pnictides, but also exhibits a SHG effect of 1.2 × AgGaS2, moderate birefringence (0.088@visible light and calcd. 0.043@2050 nm) and a wide IR transmission range. This is the first time that the octet binding electrons construction strategy was utilized to design non-diamond like NLO pnictides with excellent performances.
The design of pnictide nonlinear optical crystals is quite different from chalcogenide and oxide those, in which a new paradigm need be developed to regulate the band gap, one of key optical parameters. In this work, two non-centrosymmetric halidepnictides, [Cd2P]2[CdBr4] (CPB) and [Cd2As]2[CdBr4] (CAB) were reported. The complete octet binding electrons of pnictogens were constructed by four Cd-P polar covalent bonds under the anchoring effect of halogens, creating an extremely flat valence band maximum with band dispersion of only 0.17 eV. As expected, the balance of the covalency and ionicity in CPB and CAB was successfully realized, leading to a wide band gap of 2.58 eV and 1.88 eV. Remarkably, CPB not only has a widest band gap among Cd-containing pnictides, but also exhibits a SHG effect of 1.2 × AgGaS2, moderate birefringence (0.088@visible light and calcd. 0.043@2050 nm) and a wide IR transmission range. This is the first time that the octet binding electrons construction strategy was utilized to design non-diamond like NLO pnictides with excellent performances.
2024, 35(12): 109536
doi: 10.1016/j.cclet.2024.109536
摘要:
The prototype material, Li1.23Ru0.41Ni0.36O2, is proposed to gain the deep and comprehensive understanding of chemical and structural changes of the novel layered/rocksalt intergrown cathodes. Synchrotron-based X-ray absorption spectra and resonant inelastic X-ray scattering reveal that both cationic and anionic redox evolves in the charge compensation process of the intergrown material, while synchrotron-based extended X-ray fine structure spectra and in situ X-ray diffraction measurements demonstrates that the intergrown material undergoes minimal local- and long-range structural variations at deep de/lithiation. This work highlights the great potential of the intergrown structure to inspire the design of advanced cathode materials for lithium-ion batteries.
The prototype material, Li1.23Ru0.41Ni0.36O2, is proposed to gain the deep and comprehensive understanding of chemical and structural changes of the novel layered/rocksalt intergrown cathodes. Synchrotron-based X-ray absorption spectra and resonant inelastic X-ray scattering reveal that both cationic and anionic redox evolves in the charge compensation process of the intergrown material, while synchrotron-based extended X-ray fine structure spectra and in situ X-ray diffraction measurements demonstrates that the intergrown material undergoes minimal local- and long-range structural variations at deep de/lithiation. This work highlights the great potential of the intergrown structure to inspire the design of advanced cathode materials for lithium-ion batteries.
2024, 35(12): 109542
doi: 10.1016/j.cclet.2024.109542
摘要:
The usage of flexible ligands in constructing MOF materials (FL-MOFs) has been widely studied due to its numerous advantages, including the structural diversity, polynuclear MOFs, transmitting magnetic exchanges, enantioselective separation, asymmetric catalysis, etc. However, the field still faces challenges in deeply understanding the effect of ligand configuration on the properties of these materials. Here, we employ a flexible aggregation-induced emission ligand (4,4′-((1E, 1′E)-anthracene-9,10-diylbis(ethene-2,1-diyl))dibenzoic acid) with great mechanical stability to construct FL-MOFs to lock the ligand configuration to explore the pressure-induced evolution of the ligand with coordination restriction, involving changes in fluorescence and intermolecular interaction. In-situ high-pressure fluorescence, Raman, and FT-IR experiments have revealed that the intermolecular interaction of AIE-Mn-MOF with configuration restriction increased more rapidly than that of free AIE-L. This discovery offers valuable insights for synthesizing MOF materials with exceptional mechanical stability and significantly advances our understanding of the impact of coordination restriction in FL-MOFs on their response to external stimuli.
The usage of flexible ligands in constructing MOF materials (FL-MOFs) has been widely studied due to its numerous advantages, including the structural diversity, polynuclear MOFs, transmitting magnetic exchanges, enantioselective separation, asymmetric catalysis, etc. However, the field still faces challenges in deeply understanding the effect of ligand configuration on the properties of these materials. Here, we employ a flexible aggregation-induced emission ligand (4,4′-((1E, 1′E)-anthracene-9,10-diylbis(ethene-2,1-diyl))dibenzoic acid) with great mechanical stability to construct FL-MOFs to lock the ligand configuration to explore the pressure-induced evolution of the ligand with coordination restriction, involving changes in fluorescence and intermolecular interaction. In-situ high-pressure fluorescence, Raman, and FT-IR experiments have revealed that the intermolecular interaction of AIE-Mn-MOF with configuration restriction increased more rapidly than that of free AIE-L. This discovery offers valuable insights for synthesizing MOF materials with exceptional mechanical stability and significantly advances our understanding of the impact of coordination restriction in FL-MOFs on their response to external stimuli.
2024, 35(12): 109545
doi: 10.1016/j.cclet.2024.109545
摘要:
BA2(MA)n-1PbnI3n+1 series low-dimensional (2D) perovskites have been widely investigated for their remarkable environmental stability, but still suffer the poor light absorption and disordered phase distribution, hindering their practical applications. In this work, we combine the introduction of FA and the addition of PbCl2 to optimize the film quality, strengthen the light absorption, regulate internal phase distribution, and promote carrier transport inside 2D perovskite films. The incorporation of FA promotes sufficient light absorption and improve the film crystallinity. Furthermore, the addition of PbCl2 eliminates the low n phase (n = 1) and suppresses the forming of the low n phase of n = 2, enhancing the film conductivity and diminishing carrier recombination. The synergistic of A-site cation engineering and phase manipulation achieves a high efficiency of 16.48%. Importantly, the synergistic prepared perovskite film does not show any changes after 60 days in the air with an average humidity of 57% ± 3%, and the corresponding solar cell maintains 85% of the original efficiency after more than 800 h, demonstrating remarkable environmental stability. The results indicate that the synergistic of A-site cation engineering and phase manipulation is promising for producing superior efficiency, along with satisfying humidity stability.
BA2(MA)n-1PbnI3n+1 series low-dimensional (2D) perovskites have been widely investigated for their remarkable environmental stability, but still suffer the poor light absorption and disordered phase distribution, hindering their practical applications. In this work, we combine the introduction of FA and the addition of PbCl2 to optimize the film quality, strengthen the light absorption, regulate internal phase distribution, and promote carrier transport inside 2D perovskite films. The incorporation of FA promotes sufficient light absorption and improve the film crystallinity. Furthermore, the addition of PbCl2 eliminates the low n phase (n = 1) and suppresses the forming of the low n phase of n = 2, enhancing the film conductivity and diminishing carrier recombination. The synergistic of A-site cation engineering and phase manipulation achieves a high efficiency of 16.48%. Importantly, the synergistic prepared perovskite film does not show any changes after 60 days in the air with an average humidity of 57% ± 3%, and the corresponding solar cell maintains 85% of the original efficiency after more than 800 h, demonstrating remarkable environmental stability. The results indicate that the synergistic of A-site cation engineering and phase manipulation is promising for producing superior efficiency, along with satisfying humidity stability.
2024, 35(12): 109552
doi: 10.1016/j.cclet.2024.109552
摘要:
Graphene-like materials and metal-organic framework (MOF) materials hold significant promise for advanced energy systems. However, the accumulation of two-dimensional (2D) material and the low conductivity of MOF have seriously affected their practical application. The universal method for synthesizing homogeneous nitrogen-doped graphene-like carbon/metal-organic framework (N-GLC/MOF) composites, including N-GLC/MOF-74, N-GLC/ZIF-8, N-GLC/Cu-BTC, and N-GLC/FeCo-PBA was presented. Thanks to the synergistic effect of the two components, the N-GLC/MOF-74 composite exhibits a specific capacitance of 470.18 F/g at 1 A/g and maintains a coulombic efficiency of 95.04% at 5 A/g over 5500 cycles. Our work lays a solid foundation for the design and synthesis of N-GLC-based composites. We anticipate that this research will furnish valuable insights for the advancement of N-GLC/MOF composites, with a primary focus on enhancing supercapacitor performance.
Graphene-like materials and metal-organic framework (MOF) materials hold significant promise for advanced energy systems. However, the accumulation of two-dimensional (2D) material and the low conductivity of MOF have seriously affected their practical application. The universal method for synthesizing homogeneous nitrogen-doped graphene-like carbon/metal-organic framework (N-GLC/MOF) composites, including N-GLC/MOF-74, N-GLC/ZIF-8, N-GLC/Cu-BTC, and N-GLC/FeCo-PBA was presented. Thanks to the synergistic effect of the two components, the N-GLC/MOF-74 composite exhibits a specific capacitance of 470.18 F/g at 1 A/g and maintains a coulombic efficiency of 95.04% at 5 A/g over 5500 cycles. Our work lays a solid foundation for the design and synthesis of N-GLC-based composites. We anticipate that this research will furnish valuable insights for the advancement of N-GLC/MOF composites, with a primary focus on enhancing supercapacitor performance.
2024, 35(12): 109553
doi: 10.1016/j.cclet.2024.109553
摘要:
The increasing demand for energy density pushes LiCoO2 (LCO) to work at higher voltage (≥4.5 V), which brings a series of problems including detrimental phase transition and structural instability. Various elemental doping has been proven an effective strategy to improve its structure stability. However, the understanding of elemental doping homogeneity effect is not enough, whether in terms of the controllability of doping homogeneity or its complex consequences. In this work, LCO powders with different Al doping homogeneity were synthesized and tested under high voltage (≥4.5 V) in both half and full cell at room and high temperature, respectively. The results show that the Al homogeneously doped LCO showed better cycling stability and rate performance compared to the inhomogeneous LCO sample. Particularly, the discharge capacity of Al homogeneously doped LCO after 500 cycles under 4.5 V in full cells could reach 160.1 mAh/g at 1.0 C with 94.1% capacity retention. Postmortem characterization demonstrates that a better doping homogeneity favors the stability of both the bulk and interface as well as the kinetic conditions. This study provided new insights about LCO performance fading, which sheds new light on the development of high-voltage LCO products
The increasing demand for energy density pushes LiCoO2 (LCO) to work at higher voltage (≥4.5 V), which brings a series of problems including detrimental phase transition and structural instability. Various elemental doping has been proven an effective strategy to improve its structure stability. However, the understanding of elemental doping homogeneity effect is not enough, whether in terms of the controllability of doping homogeneity or its complex consequences. In this work, LCO powders with different Al doping homogeneity were synthesized and tested under high voltage (≥4.5 V) in both half and full cell at room and high temperature, respectively. The results show that the Al homogeneously doped LCO showed better cycling stability and rate performance compared to the inhomogeneous LCO sample. Particularly, the discharge capacity of Al homogeneously doped LCO after 500 cycles under 4.5 V in full cells could reach 160.1 mAh/g at 1.0 C with 94.1% capacity retention. Postmortem characterization demonstrates that a better doping homogeneity favors the stability of both the bulk and interface as well as the kinetic conditions. This study provided new insights about LCO performance fading, which sheds new light on the development of high-voltage LCO products
2024, 35(12): 109595
doi: 10.1016/j.cclet.2024.109595
摘要:
Highly active cathode catalysts for efficient formation/decomposition of Li2O2 are essential for the performance improvement of lithium-oxygen batteries (LOBs). In this study, a grain-refining Co0.85Se catalyst with a lattice spacing of 2.69 Å of (101) plane closely matching with the (100) plane (2.72 Å) of Li2O2 was applied for high-performance LOBs. Highly (101) plane exposed Co0.85Se@CNT was synthesized by a simple one-pot hydrothermal method. The Co0.85Se with the lattice matching effect not only led to the efficient conversion and polarized growth of Li2O2, but also prevented the formation of byproducts. Density functional theory (DFT) calculations reveal that Co0.85Se (101) plane has the intrinsic catalytic ability to generate/decompose Li2O2 during ORR/OER process, due to its homogeneous electron distribution, suitable adsorption energy, and promoted Li2O2 growth kinetics. As a consequence, the (101) plane highly exposed Co0.85Se@CNT-80 electrode exhibited remarkable cycle stability over 2400 h at 100 mA/g and 290 cycles at 500 mA/g, which is about 2 times longer than other electrodes.
Highly active cathode catalysts for efficient formation/decomposition of Li2O2 are essential for the performance improvement of lithium-oxygen batteries (LOBs). In this study, a grain-refining Co0.85Se catalyst with a lattice spacing of 2.69 Å of (101) plane closely matching with the (100) plane (2.72 Å) of Li2O2 was applied for high-performance LOBs. Highly (101) plane exposed Co0.85Se@CNT was synthesized by a simple one-pot hydrothermal method. The Co0.85Se with the lattice matching effect not only led to the efficient conversion and polarized growth of Li2O2, but also prevented the formation of byproducts. Density functional theory (DFT) calculations reveal that Co0.85Se (101) plane has the intrinsic catalytic ability to generate/decompose Li2O2 during ORR/OER process, due to its homogeneous electron distribution, suitable adsorption energy, and promoted Li2O2 growth kinetics. As a consequence, the (101) plane highly exposed Co0.85Se@CNT-80 electrode exhibited remarkable cycle stability over 2400 h at 100 mA/g and 290 cycles at 500 mA/g, which is about 2 times longer than other electrodes.
2024, 35(12): 109617
doi: 10.1016/j.cclet.2024.109617
摘要:
A copper-catalyzed three-component reaction involving cyclic carbonates, elemental sulfur, and H-phosphonates is presented. It proceeds with excellent yields and provides an attractive approach for the construction of valuable trisubstituted allenyl phosphorothioates using a one-step strategy. Moreover, this method can be easily adapted to large-scale preparation.
A copper-catalyzed three-component reaction involving cyclic carbonates, elemental sulfur, and H-phosphonates is presented. It proceeds with excellent yields and provides an attractive approach for the construction of valuable trisubstituted allenyl phosphorothioates using a one-step strategy. Moreover, this method can be easily adapted to large-scale preparation.
2024, 35(12): 109619
doi: 10.1016/j.cclet.2024.109619
摘要:
Patients with oral squamous cell carcinoma (OSCC) encounter challenges in achieving efficient antitumor immunity, primarily due to the inherent pathophysiological characteristics of solid tumors affecting drug accumulation and penetration. Insufficient T-cells and immune escape induced by tumor-associated macrophages (TAMs) further exacerbate these issues. This study utilized M1 macrophage membrane-modified spatial dimension conversion drug delivery systems (SDDDSs) and introduced photosensitizers chlorophyll Pyro and the immune agonist R848. This innovative approach enhanced tumor targeting and accumulation by transforming stimulus-responsive size-reductive SDDDSs into smaller-sized iRGD-Pyro and R848 within the extracellular tumor microenvironment (TME). This facilitated effective drug penetration into deep tumor regions and cellular uptake. The synergistic treatment strategy for OSCC, combining photodynamic therapy (PDT) and tumor immunotherapy, induced tumor cell apoptosis, triggered immunogenic cell death (ICD), polarized TAMs towards the M1 phenotype, promoted sufficient T-cell infiltration, and resulted in significant therapeutic outcomes. This approach offers a promising avenue for future OSCC therapeutic interventions.
Patients with oral squamous cell carcinoma (OSCC) encounter challenges in achieving efficient antitumor immunity, primarily due to the inherent pathophysiological characteristics of solid tumors affecting drug accumulation and penetration. Insufficient T-cells and immune escape induced by tumor-associated macrophages (TAMs) further exacerbate these issues. This study utilized M1 macrophage membrane-modified spatial dimension conversion drug delivery systems (SDDDSs) and introduced photosensitizers chlorophyll Pyro and the immune agonist R848. This innovative approach enhanced tumor targeting and accumulation by transforming stimulus-responsive size-reductive SDDDSs into smaller-sized iRGD-Pyro and R848 within the extracellular tumor microenvironment (TME). This facilitated effective drug penetration into deep tumor regions and cellular uptake. The synergistic treatment strategy for OSCC, combining photodynamic therapy (PDT) and tumor immunotherapy, induced tumor cell apoptosis, triggered immunogenic cell death (ICD), polarized TAMs towards the M1 phenotype, promoted sufficient T-cell infiltration, and resulted in significant therapeutic outcomes. This approach offers a promising avenue for future OSCC therapeutic interventions.
2024, 35(12): 109628
doi: 10.1016/j.cclet.2024.109628
摘要:
Achieving selectivity in cell penetrating peptide (CPP) design is crucial to mitigate systemic toxicity and enable precise targeting based on distinct cellular phenotypes. Herein, we designed an amphiphilic peptide, L17Yp, by incorporating phosphorylated tyrosine into natural occurring M-lycotoxin peptide, known for its potent membrane-lytic activity. This strategic modification induced a conformational shift, as confirmed by circular dichroism spectroscopy, transitioning it from its bioactive α-helix conformation to an inactive random coli configuration, effectively shielding its membrane-penetrating capacity. Upon exposure to alkaline phosphatase, L17Yp undergoes enzymatic dephosphorylation, prompting a conformational shift that restores its membrane-transduction capabilities. This unique property hold promises for selective drug delivery. This work introduces an enzymatic approach for targeted perturbation of the cell membrane, offering promising prospects for precise drug delivery applications.
Achieving selectivity in cell penetrating peptide (CPP) design is crucial to mitigate systemic toxicity and enable precise targeting based on distinct cellular phenotypes. Herein, we designed an amphiphilic peptide, L17Yp, by incorporating phosphorylated tyrosine into natural occurring M-lycotoxin peptide, known for its potent membrane-lytic activity. This strategic modification induced a conformational shift, as confirmed by circular dichroism spectroscopy, transitioning it from its bioactive α-helix conformation to an inactive random coli configuration, effectively shielding its membrane-penetrating capacity. Upon exposure to alkaline phosphatase, L17Yp undergoes enzymatic dephosphorylation, prompting a conformational shift that restores its membrane-transduction capabilities. This unique property hold promises for selective drug delivery. This work introduces an enzymatic approach for targeted perturbation of the cell membrane, offering promising prospects for precise drug delivery applications.
2024, 35(12): 109631
doi: 10.1016/j.cclet.2024.109631
摘要:
Photodynamic therapy (PDT) is a promising cancer treatment modality owing to its high spatiotemporal selectivity and noninvasive nature. However, conventional photosensitizers (PSs) used in PDT are responsive only to visible light, which makes them unsuitable for tissue penetration. In this study, we propose a PS based on hot band absorption (HBA), which can be triggered by anti-Stokes light at 808 nm via a one-photon process. The introduction of selenium (Se) into pentamethine cyanine (Secy5) not only facilitates intersystem crossing for reactive oxygen species (ROS) production but also enhances HBA efficiency, thereby prolonging the excitation wavelength. In addition, Secy5 demonstrates excellent biocompatibility, unlike its I-substituted counterpart (Icy5), and produces not only 1O2 but also O2•−, making it a desirable candidate for treating hypoxic solid tumors. According to the results of in vivo and in vitro experiments, Secy5 can efficiently inhibit cancer cell growth via anti-Stokes activation processes, thereby providing a novel approach to design anti-Stokes excitation PSs for anticancer treatment.
Photodynamic therapy (PDT) is a promising cancer treatment modality owing to its high spatiotemporal selectivity and noninvasive nature. However, conventional photosensitizers (PSs) used in PDT are responsive only to visible light, which makes them unsuitable for tissue penetration. In this study, we propose a PS based on hot band absorption (HBA), which can be triggered by anti-Stokes light at 808 nm via a one-photon process. The introduction of selenium (Se) into pentamethine cyanine (Secy5) not only facilitates intersystem crossing for reactive oxygen species (ROS) production but also enhances HBA efficiency, thereby prolonging the excitation wavelength. In addition, Secy5 demonstrates excellent biocompatibility, unlike its I-substituted counterpart (Icy5), and produces not only 1O2 but also O2•−, making it a desirable candidate for treating hypoxic solid tumors. According to the results of in vivo and in vitro experiments, Secy5 can efficiently inhibit cancer cell growth via anti-Stokes activation processes, thereby providing a novel approach to design anti-Stokes excitation PSs for anticancer treatment.
2024, 35(12): 109632
doi: 10.1016/j.cclet.2024.109632
摘要:
Radiotherapy (RT) is a widely used cancer treatment, and the use of metal-based nano-radiotherapy sensitizers has shown promise in enhancing its efficacy. However, efficient accumulation and deep penetration of these sensitizers within tumors remain challenging. In this study, we present the development of bismuth/manganese biomineralized nanoparticles (BiMn/BSA) with multiple radiosensitizing mechanisms, including high atomic number element-mediated radiation capture, catalase-mimic oxygenation, and activation of the stimulator of interferon genes (STING) pathway. Significantly, we demonstrate that low-dose RT induces the recruitment of macrophages and subsequent upregulation of Matrix metalloproteinases (MMP)-2 and MMP-9 that degrade the extracellular matrix (ECM). This dynamic process facilitates the targeted delivery and deep penetration of BiMn/BSA nanoparticles within tumors, thereby enhancing the effectiveness of RT. By combining low-dose RT with BiMn/BSA nanoparticles, we achieved complete suppression of tumor growth in mice with excellent biocompatibility. This study provides a novel and clinically relevant strategy for targeted nanoparticle delivery to tumors, and establishes a safe and effective sequential radiotherapy approach for cancer treatment. These findings hold great promise for improving the outcomes of RT and advancing the field of nanomedicine in cancer therapy.
Radiotherapy (RT) is a widely used cancer treatment, and the use of metal-based nano-radiotherapy sensitizers has shown promise in enhancing its efficacy. However, efficient accumulation and deep penetration of these sensitizers within tumors remain challenging. In this study, we present the development of bismuth/manganese biomineralized nanoparticles (BiMn/BSA) with multiple radiosensitizing mechanisms, including high atomic number element-mediated radiation capture, catalase-mimic oxygenation, and activation of the stimulator of interferon genes (STING) pathway. Significantly, we demonstrate that low-dose RT induces the recruitment of macrophages and subsequent upregulation of Matrix metalloproteinases (MMP)-2 and MMP-9 that degrade the extracellular matrix (ECM). This dynamic process facilitates the targeted delivery and deep penetration of BiMn/BSA nanoparticles within tumors, thereby enhancing the effectiveness of RT. By combining low-dose RT with BiMn/BSA nanoparticles, we achieved complete suppression of tumor growth in mice with excellent biocompatibility. This study provides a novel and clinically relevant strategy for targeted nanoparticle delivery to tumors, and establishes a safe and effective sequential radiotherapy approach for cancer treatment. These findings hold great promise for improving the outcomes of RT and advancing the field of nanomedicine in cancer therapy.
2024, 35(12): 109638
doi: 10.1016/j.cclet.2024.109638
摘要:
Deoxyribozyme (DNAzyme) and its substrate hybridization are crucial for achieving desirable detection performance in the DNAzyme coupling nanomaterial biosensor system. However, interfacial factors such as electrostatic repulsion, steric hindrance, and nonspecific adsorption from gold nanoparticles make this hybridization process complicated and challenging. Moreover, the DNAzyme structure changes with different application purposes, which might affect the DNAzyme and substrate’s connection. Few studies have focused on the interplay of DNAzyme and interfacial factors in the biosensor field. In this work, three types of DNAzyme variants were designed, and their biosensor performance rules were studied and summarized with the synergistic effect of interfacial factors. Additionally, corresponding biosensor applications, such as multiple modulation functions and miRNA detections, were constructed based on the distinct principles of DNAzyme variants.
Deoxyribozyme (DNAzyme) and its substrate hybridization are crucial for achieving desirable detection performance in the DNAzyme coupling nanomaterial biosensor system. However, interfacial factors such as electrostatic repulsion, steric hindrance, and nonspecific adsorption from gold nanoparticles make this hybridization process complicated and challenging. Moreover, the DNAzyme structure changes with different application purposes, which might affect the DNAzyme and substrate’s connection. Few studies have focused on the interplay of DNAzyme and interfacial factors in the biosensor field. In this work, three types of DNAzyme variants were designed, and their biosensor performance rules were studied and summarized with the synergistic effect of interfacial factors. Additionally, corresponding biosensor applications, such as multiple modulation functions and miRNA detections, were constructed based on the distinct principles of DNAzyme variants.
2024, 35(12): 109644
doi: 10.1016/j.cclet.2024.109644
摘要:
Sonodynamic therapy (SDT) exhibits noninvasive and accuracy in cancer treatment, and has aroused widespread attention. However, the low quantum yield of inorganic sonosensitizers under ultrasound (US) stimulation leads to unsatisfactory efficacy. In this work, an urchin-like piezoelectric ZnSnO3/Cu3P p-n heterojunction was constructed as an efficient sonosensitizer for enhanced SDT. The p-n heterojunction formation narrows the band bandgap and increases the piezoelectric property, which contribute to the promotion of carrier separation and suppression of carrier recombination, resulting in enhanced SDT. Moreover, under tumor microenvironment (TME) with over produced H2O2 and glutathione (GSH), Cu3P NNs induce chemodynamic therapy (CDT) by initiating a Fenton-like reaction and depleting GSH, leading to increased cellular oxidative damage. With the combination effect, the ZnSnO3/Cu3P heterojunction demonstrates a 70% tumor growth inhibition rate in 4T1 tumor mice model. This piezoelectric heterojunction achieves the combined treatment of SDT and CDT, and opens new possibilities for the application of SDT in tumor therapy.
Sonodynamic therapy (SDT) exhibits noninvasive and accuracy in cancer treatment, and has aroused widespread attention. However, the low quantum yield of inorganic sonosensitizers under ultrasound (US) stimulation leads to unsatisfactory efficacy. In this work, an urchin-like piezoelectric ZnSnO3/Cu3P p-n heterojunction was constructed as an efficient sonosensitizer for enhanced SDT. The p-n heterojunction formation narrows the band bandgap and increases the piezoelectric property, which contribute to the promotion of carrier separation and suppression of carrier recombination, resulting in enhanced SDT. Moreover, under tumor microenvironment (TME) with over produced H2O2 and glutathione (GSH), Cu3P NNs induce chemodynamic therapy (CDT) by initiating a Fenton-like reaction and depleting GSH, leading to increased cellular oxidative damage. With the combination effect, the ZnSnO3/Cu3P heterojunction demonstrates a 70% tumor growth inhibition rate in 4T1 tumor mice model. This piezoelectric heterojunction achieves the combined treatment of SDT and CDT, and opens new possibilities for the application of SDT in tumor therapy.
2024, 35(12): 109646
doi: 10.1016/j.cclet.2024.109646
摘要:
Multimodal bioorthogonal small molecule probes play a pivotal role in drug-focused biomedical research. However, existing drug tracking and imaging techniques face obstacles in living organisms, hindering precise drug localization and target protein capture. Herein, we introduced a multimodal probe named 1-(azidomethyl)pyrene-4,5–dione (AMPD). The probe incorporates adjacent dione structures at the pyrene core. AMPD selectively interacts with oxygen-rich alkene-labeled drug molecules under ice-blue LED light exposure, producing specific fluorescence emission and enabling in vivo tracking and flow cytometry sorting. A methyl azide group was also introduced at the pyrene core to help efficiently enrich target proteins via click chemistry with alkyne-functionalized beads. AMPD demonstrates exceptional biocompatibility, rendering it highly suitable for visual photo-triggered tracking studies. Combined with metabolic labeling using an oxygen-rich alkene-tagged drug molecule probe, AMPD is effective for live animal, tissue, cellular, and in-gel imaging, as well as target protein identification through magnetic capture. With its versatile capabilities, AMPD enhances our comprehension of drug-target interactions at the in vivo level and expedites the process of drug discovery.
Multimodal bioorthogonal small molecule probes play a pivotal role in drug-focused biomedical research. However, existing drug tracking and imaging techniques face obstacles in living organisms, hindering precise drug localization and target protein capture. Herein, we introduced a multimodal probe named 1-(azidomethyl)pyrene-4,5–dione (AMPD). The probe incorporates adjacent dione structures at the pyrene core. AMPD selectively interacts with oxygen-rich alkene-labeled drug molecules under ice-blue LED light exposure, producing specific fluorescence emission and enabling in vivo tracking and flow cytometry sorting. A methyl azide group was also introduced at the pyrene core to help efficiently enrich target proteins via click chemistry with alkyne-functionalized beads. AMPD demonstrates exceptional biocompatibility, rendering it highly suitable for visual photo-triggered tracking studies. Combined with metabolic labeling using an oxygen-rich alkene-tagged drug molecule probe, AMPD is effective for live animal, tissue, cellular, and in-gel imaging, as well as target protein identification through magnetic capture. With its versatile capabilities, AMPD enhances our comprehension of drug-target interactions at the in vivo level and expedites the process of drug discovery.
2024, 35(12): 109657
doi: 10.1016/j.cclet.2024.109657
摘要:
The combination of diagnostic and therapeutic agents in the form of theranostic platforms to enhance tumor therapeutic efficacy is receiving increasing attention in recent years. However, simultaneous encapsulation, embedding or conjugation of various agents to traditional theranostic nanocarriers always require intricate synthetic process. Herein, a supramolecular drug-drug self-delivery nanosystem (DSDN) based on a newly developed aggregation-induced emission (AIE) photosensitizer (CBTM) and an anti-tumor tyroservaltide (YSV) was constructed for near-infrared (NIR) fluorescence imaging-guided photodynamic/chemotherapy of tumor. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) confirmed that YSV and CBTM could co-assemble into YSV/CBTM nanoparticles, with regular round-shape morphology and homogeneous size. Inspiringly, YSV/CBTM nanoparticles could effectively overcome the aggregation-caused quenching (ACQ) effect, and enter CT26 tumor cells with a high NIR fluorescence emission, allowing preoperative diagnosis. Meanwhile, the as-prepared YSV/CBTM could efficiently generate reactive oxygen species (ROS) under NIR light irradiation, exhibiting photodynamic ablation of tumor cells. More importantly, the peptide drug of YSV not only improved the availability of CBTM nanoparticles, but also served as a toxic adjuvant to enhance the photodynamic therapy (PDT) efficacy of CBTM. In vitro and in vivo assays revealed that most of colorectal tumor cells and tumor tissues were thoroughly ablated by photodynamic-chemotherapy integrated nanoparticles, resulting in longer survival of tumor-bearing mice. Regarding the advantages of the YSV/CBTM nanosystem, we believe this research could offer valuable guidance for the design of nanodrugs with high performance for cancer theranostics.
The combination of diagnostic and therapeutic agents in the form of theranostic platforms to enhance tumor therapeutic efficacy is receiving increasing attention in recent years. However, simultaneous encapsulation, embedding or conjugation of various agents to traditional theranostic nanocarriers always require intricate synthetic process. Herein, a supramolecular drug-drug self-delivery nanosystem (DSDN) based on a newly developed aggregation-induced emission (AIE) photosensitizer (CBTM) and an anti-tumor tyroservaltide (YSV) was constructed for near-infrared (NIR) fluorescence imaging-guided photodynamic/chemotherapy of tumor. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) confirmed that YSV and CBTM could co-assemble into YSV/CBTM nanoparticles, with regular round-shape morphology and homogeneous size. Inspiringly, YSV/CBTM nanoparticles could effectively overcome the aggregation-caused quenching (ACQ) effect, and enter CT26 tumor cells with a high NIR fluorescence emission, allowing preoperative diagnosis. Meanwhile, the as-prepared YSV/CBTM could efficiently generate reactive oxygen species (ROS) under NIR light irradiation, exhibiting photodynamic ablation of tumor cells. More importantly, the peptide drug of YSV not only improved the availability of CBTM nanoparticles, but also served as a toxic adjuvant to enhance the photodynamic therapy (PDT) efficacy of CBTM. In vitro and in vivo assays revealed that most of colorectal tumor cells and tumor tissues were thoroughly ablated by photodynamic-chemotherapy integrated nanoparticles, resulting in longer survival of tumor-bearing mice. Regarding the advantages of the YSV/CBTM nanosystem, we believe this research could offer valuable guidance for the design of nanodrugs with high performance for cancer theranostics.
2024, 35(12): 109658
doi: 10.1016/j.cclet.2024.109658
摘要:
Lymphoma is a hematological malignancy with an increasing mortality rate. Nevertheless, the treatment strategy against lymphoma remains limited. Doxorubicin (DOX) is a broad-spectrum anti-tumor chemotherapeutic drug, the clinical application of which is limited by serious adverse effects and drug resistance. In this work, biodegradable methoxy poly(ethylene glycol)-block-poly(lactic acid) (mPEG-PLA) nanomicelles co-delivering of DOX and apatinib (AP) (DOX-AP/m) was developed for lymphoma therapy. The average particle size of the self-assembled drug-loaded nano-micelle was 31.94 nm. It is revealed that AP can enhance the uptake of DOX by tumor cells. The in vivo and in vitro experimental results revealed that DOX-AP/m combination therapy could inhibit proliferation and promote apoptosis of lymphoma cells, and greatly suppress tumor growth. Our study indicated that DOX-AP/m might provide new insight and hold great potential in the treatment of lymphoma.
Lymphoma is a hematological malignancy with an increasing mortality rate. Nevertheless, the treatment strategy against lymphoma remains limited. Doxorubicin (DOX) is a broad-spectrum anti-tumor chemotherapeutic drug, the clinical application of which is limited by serious adverse effects and drug resistance. In this work, biodegradable methoxy poly(ethylene glycol)-block-poly(lactic acid) (mPEG-PLA) nanomicelles co-delivering of DOX and apatinib (AP) (DOX-AP/m) was developed for lymphoma therapy. The average particle size of the self-assembled drug-loaded nano-micelle was 31.94 nm. It is revealed that AP can enhance the uptake of DOX by tumor cells. The in vivo and in vitro experimental results revealed that DOX-AP/m combination therapy could inhibit proliferation and promote apoptosis of lymphoma cells, and greatly suppress tumor growth. Our study indicated that DOX-AP/m might provide new insight and hold great potential in the treatment of lymphoma.
2024, 35(12): 109660
doi: 10.1016/j.cclet.2024.109660
摘要:
The combination of nucleic acid and small-molecule drugs in tumor treatment holds significant promise; however, the precise delivery and controlled release of drugs within the cytoplasm encounter substantial obstacles, impeding the advancement of formulations. To surmount the challenges associated with precise drug delivery and controlled release, we have developed a multi-level pH-responsive co-loaded drug lipid nanoplatform. This platform first employs cyclic cell-penetrating peptides to exert a multi-level pH response, thereby enhancing the uptake efficiency of tumor cells and endow the nanosystem with effective endosomal/lysosomal escape. Subsequently, small interferring RNA (siRNA) complexes are formed by compacting siRNA with stearic acid octahistidine, which is capable of responding to the lysosome-to-cytoplasm pH gradient and facilitate siRNA release. The siRNA complexes and docetaxel are simultaneously encapsulated into liposomes, thereby creating a lipid nanoplatform capable of co-delivering nucleic acid and small-molecule drugs. The efficacy of this platform has been validated through both in vitro and in vivo experiments, affirming its significant potential for practical applications in the co-delivery of nucleic acids and small-molecule drugs.
The combination of nucleic acid and small-molecule drugs in tumor treatment holds significant promise; however, the precise delivery and controlled release of drugs within the cytoplasm encounter substantial obstacles, impeding the advancement of formulations. To surmount the challenges associated with precise drug delivery and controlled release, we have developed a multi-level pH-responsive co-loaded drug lipid nanoplatform. This platform first employs cyclic cell-penetrating peptides to exert a multi-level pH response, thereby enhancing the uptake efficiency of tumor cells and endow the nanosystem with effective endosomal/lysosomal escape. Subsequently, small interferring RNA (siRNA) complexes are formed by compacting siRNA with stearic acid octahistidine, which is capable of responding to the lysosome-to-cytoplasm pH gradient and facilitate siRNA release. The siRNA complexes and docetaxel are simultaneously encapsulated into liposomes, thereby creating a lipid nanoplatform capable of co-delivering nucleic acid and small-molecule drugs. The efficacy of this platform has been validated through both in vitro and in vivo experiments, affirming its significant potential for practical applications in the co-delivery of nucleic acids and small-molecule drugs.
2024, 35(12): 109663
doi: 10.1016/j.cclet.2024.109663
摘要:
The prodrug strategy provides an opportunity for improving the therapeutic index of drugs and avoiding their side effects. The main challenge lies in the fast and effective release of the parent drugs at the desired site under specific stimuli. Herein, a cooperative prodrug activation approach with exogenous native enzyme and endogenous tumor small molecule biomarkers was developed. Chemically, precursors of methylene blue (MB) and resorufin (RSF) react with horseradish peroxidase (HRP)/hydrogen peroxide (H2O2) to quickly and quantitatively release parent dyes and drugs containing amines or carboxylic acids. The application of this approach in mammalian cells was demonstrated with cooperative-activated photodynamic therapy based on a precursor of MB. Compared with free MB, much higher selectivity toward cancer cells was achieved with this approach as evaluated by the selectivity index (SI). This study provides a new method for fast and effective targeted prodrug activation with no need for antibody modification compared with traditional enzyme/prodrug therapy.
The prodrug strategy provides an opportunity for improving the therapeutic index of drugs and avoiding their side effects. The main challenge lies in the fast and effective release of the parent drugs at the desired site under specific stimuli. Herein, a cooperative prodrug activation approach with exogenous native enzyme and endogenous tumor small molecule biomarkers was developed. Chemically, precursors of methylene blue (MB) and resorufin (RSF) react with horseradish peroxidase (HRP)/hydrogen peroxide (H2O2) to quickly and quantitatively release parent dyes and drugs containing amines or carboxylic acids. The application of this approach in mammalian cells was demonstrated with cooperative-activated photodynamic therapy based on a precursor of MB. Compared with free MB, much higher selectivity toward cancer cells was achieved with this approach as evaluated by the selectivity index (SI). This study provides a new method for fast and effective targeted prodrug activation with no need for antibody modification compared with traditional enzyme/prodrug therapy.
2024, 35(12): 109665
doi: 10.1016/j.cclet.2024.109665
摘要:
Increasing interests of difluorinated amino acids (DFAAs) have been raised in recent years due to their widespread bio-organic and medical applications. However, to date, only few investigations focused on their asymmetric synthesis. Exploring difluoromethyl reagent to tailor a novel pathway and developing efficient catalytic system are highly desirable for constructing structurally diverse chiral DFAAs. Herein, a copper-catalyzed asymmetric difluorobenzylation of aldimine esters is described. By using α,α-difluorinated benzyltriflones as difluoromethyl reagents, this protocol allows the asymmetric synthesis of α-quaternary DFAAs with wide scope, good yields and excellent enantioselectivities (90%-98% ee). Control experiments and DESI-MS analysis demonstrate the reaction probably proceeds via a key difluorocarbocation intermediate. Moreover, polyfluoroarenes are found efficient candidates to polyfluoroaryl amino acids via C-F activation. Gram-scale experiment, late-stage functionalization, synthesis of difluorinated dipeptides and bioactive molecular analogues revealed the utility of the protocol, thereby largely enriching the structural diversity of FAAs and providing more potential opportunities in drug discovery.
Increasing interests of difluorinated amino acids (DFAAs) have been raised in recent years due to their widespread bio-organic and medical applications. However, to date, only few investigations focused on their asymmetric synthesis. Exploring difluoromethyl reagent to tailor a novel pathway and developing efficient catalytic system are highly desirable for constructing structurally diverse chiral DFAAs. Herein, a copper-catalyzed asymmetric difluorobenzylation of aldimine esters is described. By using α,α-difluorinated benzyltriflones as difluoromethyl reagents, this protocol allows the asymmetric synthesis of α-quaternary DFAAs with wide scope, good yields and excellent enantioselectivities (90%-98% ee). Control experiments and DESI-MS analysis demonstrate the reaction probably proceeds via a key difluorocarbocation intermediate. Moreover, polyfluoroarenes are found efficient candidates to polyfluoroaryl amino acids via C-F activation. Gram-scale experiment, late-stage functionalization, synthesis of difluorinated dipeptides and bioactive molecular analogues revealed the utility of the protocol, thereby largely enriching the structural diversity of FAAs and providing more potential opportunities in drug discovery.
2024, 35(12): 109668
doi: 10.1016/j.cclet.2024.109668
摘要:
Osteoporosis is a disease of bone metabolism homeostasis imbalance with obvious bone loss, damage to bone microstructure, and increased risk of fracture. The occurrence and development of osteoporosis is related to the augmentation of active osteoclasts. Receptor activator of nuclear factor kappa B (RANK) small interfering RNA (siRNA) knockdowns the expression of RANK mRNA to inhibit the osteoclast precursors differentiate into osteoclasts as a treatment in osteoporosis. Salmon calcitonin (sCT) is a commonly used anti-osteoporotic agent that inhibits osteoclast activity and induces osteoclast apoptosis, and it also could promote the osteogenesis by osteoblasts. A cocktail therapy improves the therapeutic effect of osteoporosis between RANK siRNA and sCT. A size-switchable microsphere from micro to nano scale was developed to address the delivery barriers of biomacromolecules with poor stability and frequent administration. RANK siRNA and sCT were incorporated into the microspheres with a nanoparticle/micelle-microsphere double-layer structure to achieve sustained release when the particle size shrunk and dual protection of RANK siRNA and sCT. The size-switchable microspheres MS@(AL-NPs/ARM) had an optimal therapeutic effect and reduced the frequency of administration in glucocorticoid induced osteoporosis (GIOP) mouse model. RANK siRNA and sCT co-delivery system based on size-switchable microsphere is a promising strategy to treat osteoporosis through the controlled release of biomacromolecules.
Osteoporosis is a disease of bone metabolism homeostasis imbalance with obvious bone loss, damage to bone microstructure, and increased risk of fracture. The occurrence and development of osteoporosis is related to the augmentation of active osteoclasts. Receptor activator of nuclear factor kappa B (RANK) small interfering RNA (siRNA) knockdowns the expression of RANK mRNA to inhibit the osteoclast precursors differentiate into osteoclasts as a treatment in osteoporosis. Salmon calcitonin (sCT) is a commonly used anti-osteoporotic agent that inhibits osteoclast activity and induces osteoclast apoptosis, and it also could promote the osteogenesis by osteoblasts. A cocktail therapy improves the therapeutic effect of osteoporosis between RANK siRNA and sCT. A size-switchable microsphere from micro to nano scale was developed to address the delivery barriers of biomacromolecules with poor stability and frequent administration. RANK siRNA and sCT were incorporated into the microspheres with a nanoparticle/micelle-microsphere double-layer structure to achieve sustained release when the particle size shrunk and dual protection of RANK siRNA and sCT. The size-switchable microspheres MS@(AL-NPs/ARM) had an optimal therapeutic effect and reduced the frequency of administration in glucocorticoid induced osteoporosis (GIOP) mouse model. RANK siRNA and sCT co-delivery system based on size-switchable microsphere is a promising strategy to treat osteoporosis through the controlled release of biomacromolecules.
2024, 35(12): 109674
doi: 10.1016/j.cclet.2024.109674
摘要:
2-Deoxy-α-C-Glycosides are a significant class of carbohydrates found in numerous bioactive molecules and medicines. Developing a concise strategy for the assembly of these α-configured C-glycosides is crucial in the field of carbohydrate chemistry. However, current methods are restricted to the utilization of glycosyl radical precursors, which are required for pre-syntheses. Herein, we present a novel approach for the synthesis of 2-deoxy-α-C-glycosides using a nickel-catalyzed stereoselective coupling reaction with commercially available glycals. Notably, this method circumvents the preparation for diverse glycosyl radical precursors. The developed protocol exhibits a broad substrate scope and remarkable stereoselectivity under mild reaction conditions. Furthermore, the raw materials required for this process are readily accessible, eliminating the necessity for pre-functionalization modifications of the glycosyl substrates and ensuring high atomic economy.
2-Deoxy-α-C-Glycosides are a significant class of carbohydrates found in numerous bioactive molecules and medicines. Developing a concise strategy for the assembly of these α-configured C-glycosides is crucial in the field of carbohydrate chemistry. However, current methods are restricted to the utilization of glycosyl radical precursors, which are required for pre-syntheses. Herein, we present a novel approach for the synthesis of 2-deoxy-α-C-glycosides using a nickel-catalyzed stereoselective coupling reaction with commercially available glycals. Notably, this method circumvents the preparation for diverse glycosyl radical precursors. The developed protocol exhibits a broad substrate scope and remarkable stereoselectivity under mild reaction conditions. Furthermore, the raw materials required for this process are readily accessible, eliminating the necessity for pre-functionalization modifications of the glycosyl substrates and ensuring high atomic economy.
2024, 35(12): 109677
doi: 10.1016/j.cclet.2024.109677
摘要:
Pyrroles are important structural units of natural products, drug molecules, biomolecules and functional material molecules. Efficient synthesis of α-functionalized pyrroles with different substituents from easily accessible starting materials is still challenging. Herein, a facile and regioselective coarctate reaction of enynals involving a free carbene intermediate has been developed, which allows the divergent and practical de novo synthesis of various α-furanyl pyrroles and α-cyclopropenyl pyrroles derivatives with good to excellent yields and high efficiency under mild conditions. This approach features readily accessible starting materials, high functional group compatibility, step economy and scalability, which would complement previous methods and support expansion of the toolbox for the synthesis of valuable, but previously inaccessible, highly substituted and electron-rich α-functionalized pyrroles.
Pyrroles are important structural units of natural products, drug molecules, biomolecules and functional material molecules. Efficient synthesis of α-functionalized pyrroles with different substituents from easily accessible starting materials is still challenging. Herein, a facile and regioselective coarctate reaction of enynals involving a free carbene intermediate has been developed, which allows the divergent and practical de novo synthesis of various α-furanyl pyrroles and α-cyclopropenyl pyrroles derivatives with good to excellent yields and high efficiency under mild conditions. This approach features readily accessible starting materials, high functional group compatibility, step economy and scalability, which would complement previous methods and support expansion of the toolbox for the synthesis of valuable, but previously inaccessible, highly substituted and electron-rich α-functionalized pyrroles.
2024, 35(12): 109681
doi: 10.1016/j.cclet.2024.109681
摘要:
Human β-galactosidase (β-gal) is recognized as a crucial biomarker for evaluating senescence at the cellular and tissue levels in humans. However, tools to precisely track the endogenous β-gal are still limited. Herein, we present two novel self-calibrating β-gal probes 7a and 7b which were constructed on a unique green/red dual-emissive fluorescence platform. The two probes inherently exhibited a stable green fluorescence signal impervious to β-gal activity, serving as a reliable internal reference. They also displayed a progressively diminishing red fluorescence signal with the increasing of β-gal expression levels. The dual behavior endows them with self-calibration capacity and then renders excellently selective and sensitive for precisely monitoring β-gal activity. Notably, compared with E. coli β-gal, the two probes are more effectively response to A. oryzae β-gal homologous to human β-gal, indicating their unique species-selectivity. Furthermore, 7a was validated for its effectiveness in determining senescence-associated β-galactosidase (SA-β-gal) expression in senescent NRK-52E and HepG2 cells, underscoring its practical applicability in senescence research.
Human β-galactosidase (β-gal) is recognized as a crucial biomarker for evaluating senescence at the cellular and tissue levels in humans. However, tools to precisely track the endogenous β-gal are still limited. Herein, we present two novel self-calibrating β-gal probes 7a and 7b which were constructed on a unique green/red dual-emissive fluorescence platform. The two probes inherently exhibited a stable green fluorescence signal impervious to β-gal activity, serving as a reliable internal reference. They also displayed a progressively diminishing red fluorescence signal with the increasing of β-gal expression levels. The dual behavior endows them with self-calibration capacity and then renders excellently selective and sensitive for precisely monitoring β-gal activity. Notably, compared with E. coli β-gal, the two probes are more effectively response to A. oryzae β-gal homologous to human β-gal, indicating their unique species-selectivity. Furthermore, 7a was validated for its effectiveness in determining senescence-associated β-galactosidase (SA-β-gal) expression in senescent NRK-52E and HepG2 cells, underscoring its practical applicability in senescence research.
2024, 35(12): 109682
doi: 10.1016/j.cclet.2024.109682
摘要:
Two lindenane-type sesquiterpene (LDS) trimers with unprecedented carbon skeletons, holotrichones A (1) and B (2), were obtained from the whole plant of Chloranthus holostegius var. trichoneurus by a ultra performance liquid chromatography-photodiode array detector-mass spectrometry (UPLC-PDA-MS)-guided isolation strategy. Compound 1 represents the first LDS trimer incorporating a unique 3/5/6/6-fused framework, in which a lindenane-type monomer and the 2-methylbutyryl substituent of an LDS dimer is bridged by a six-membered ring system. Compound 2 is the first hetero-trimer fused by an LDS dimer with a p-benzoquinone-meroterpenoid, featuring an unusual 3/5/6/6/3/5/6/6/6 nonacyclic system fused by the sesquiterpenoid unit and a 2-geranyl-6-methyl-2,5-cyclohexadien-1,4-dione moiety. In compound 2, the dimeric LDS moiety is equipped with a rare oxaspiro[4.5]decane system. Their structures, including absolute configurations, were established by spectroscopic methods, GIAO NMR calculations and DP4+ probability analyses, electronic circular dichroism (ECD) calculations, and single-crystal X-ray diffraction analysis. The plausible biogenetic pathway speculation indicated that hetero- and homo-Diels-Alder additions may dominate the formation of these highly fused polycyclic frameworks. Both compounds 1 and 2 induced the human acute myeloid leukemia MV-4–11 cell death via apoptosis induction, which deserves further investigation on this new chemical class of LDS oligomers for their anti-leukemic potential.
Two lindenane-type sesquiterpene (LDS) trimers with unprecedented carbon skeletons, holotrichones A (1) and B (2), were obtained from the whole plant of Chloranthus holostegius var. trichoneurus by a ultra performance liquid chromatography-photodiode array detector-mass spectrometry (UPLC-PDA-MS)-guided isolation strategy. Compound 1 represents the first LDS trimer incorporating a unique 3/5/6/6-fused framework, in which a lindenane-type monomer and the 2-methylbutyryl substituent of an LDS dimer is bridged by a six-membered ring system. Compound 2 is the first hetero-trimer fused by an LDS dimer with a p-benzoquinone-meroterpenoid, featuring an unusual 3/5/6/6/3/5/6/6/6 nonacyclic system fused by the sesquiterpenoid unit and a 2-geranyl-6-methyl-2,5-cyclohexadien-1,4-dione moiety. In compound 2, the dimeric LDS moiety is equipped with a rare oxaspiro[4.5]decane system. Their structures, including absolute configurations, were established by spectroscopic methods, GIAO NMR calculations and DP4+ probability analyses, electronic circular dichroism (ECD) calculations, and single-crystal X-ray diffraction analysis. The plausible biogenetic pathway speculation indicated that hetero- and homo-Diels-Alder additions may dominate the formation of these highly fused polycyclic frameworks. Both compounds 1 and 2 induced the human acute myeloid leukemia MV-4–11 cell death via apoptosis induction, which deserves further investigation on this new chemical class of LDS oligomers for their anti-leukemic potential.
2024, 35(12): 109688
doi: 10.1016/j.cclet.2024.109688
摘要:
The catalytic asymmetric dipolar cycloaddition reaction is efficient for the construction of various chiral valuable carbo- and heterocycles. Thus, the design and exploration of new dipoles and the subsequent control of their reactivity for various stereoselective cycloadditions are significant aspects of modern organic synthesis. Herein, we have developed a series of vinyl cyclic carbamates containing an oxazolidine-2,4–dione fragment and used them as reactive precursors for in situ generation of amide-based aza-π-allylpalladium 1,3-dipoles, which could be applied to asymmetric decarboxylative 1,3-dipolar cycloaddition with different types of dipolarophiles containing C=C, C=N, and C=O double bonds. This strategy provides an opportunity for the synthesis of previously unusual structures, such as highly functionalized optically pure pyrrolidin-2-ones, imidazolidin-4-ones, and oxazolidin-4-ones. This protocol also has significant features including wide substrate scope, mild reaction conditions, simple operation, and good to excellent results (70 examples, up to 99% yield, >20:1 dr and 99% ee). This unique method significantly expands the reaction range of the amide-based aza-π-allylpalladium 1,3-dipoles compared to the precedents.
The catalytic asymmetric dipolar cycloaddition reaction is efficient for the construction of various chiral valuable carbo- and heterocycles. Thus, the design and exploration of new dipoles and the subsequent control of their reactivity for various stereoselective cycloadditions are significant aspects of modern organic synthesis. Herein, we have developed a series of vinyl cyclic carbamates containing an oxazolidine-2,4–dione fragment and used them as reactive precursors for in situ generation of amide-based aza-π-allylpalladium 1,3-dipoles, which could be applied to asymmetric decarboxylative 1,3-dipolar cycloaddition with different types of dipolarophiles containing C=C, C=N, and C=O double bonds. This strategy provides an opportunity for the synthesis of previously unusual structures, such as highly functionalized optically pure pyrrolidin-2-ones, imidazolidin-4-ones, and oxazolidin-4-ones. This protocol also has significant features including wide substrate scope, mild reaction conditions, simple operation, and good to excellent results (70 examples, up to 99% yield, >20:1 dr and 99% ee). This unique method significantly expands the reaction range of the amide-based aza-π-allylpalladium 1,3-dipoles compared to the precedents.
2024, 35(12): 109689
doi: 10.1016/j.cclet.2024.109689
摘要:
Colorectal cancer is a common cancer worldwide. Traditional chemotherapeutic drugs often face limitations such as poor aqueous solubility and high systemic toxicity, which can lead to adverse side effects and limited therapeutic efficacy. In this study, a library of one kind of biodegradable and biocompatible polymer, leucine based-poly(ester amide)s (Leu-PEAs) was developed and utilized as drug carrier. The structure of Leu-PEAs can be tuned to alter their physicochemical properties, enhancing drug loading capacity and delivery efficiency. Leu-PEAs can self-assemble into nanoparticles by nanoprecipitation and load paclitaxel (PTX) with the diameter of ~108 nm and PTX loading capacity of ~8.5%. PTX-loaded Leu-PEAs nanoparticles (PTX@Leu-PEAs) demonstrated significant inhibition of CT26 cell growth in vitro. In vivo, these nanoparticles exhibited prolonged tumor accumulation and antitumor effects, with no observed toxicity to normal organs. Furthermore, blank Leu-PEAs nanoparticles also showed antitumor effects in vitro and in vivo, which may be attributed to the activation of the mammalian target of rapamycin (mTOR) pathway by leucine. Consequently, this biocompatible Leu-PEAs nano-drug delivery system shows potential as a promising strategy for colorectal cancer treatment, warranting further investigation.
Colorectal cancer is a common cancer worldwide. Traditional chemotherapeutic drugs often face limitations such as poor aqueous solubility and high systemic toxicity, which can lead to adverse side effects and limited therapeutic efficacy. In this study, a library of one kind of biodegradable and biocompatible polymer, leucine based-poly(ester amide)s (Leu-PEAs) was developed and utilized as drug carrier. The structure of Leu-PEAs can be tuned to alter their physicochemical properties, enhancing drug loading capacity and delivery efficiency. Leu-PEAs can self-assemble into nanoparticles by nanoprecipitation and load paclitaxel (PTX) with the diameter of ~108 nm and PTX loading capacity of ~8.5%. PTX-loaded Leu-PEAs nanoparticles (PTX@Leu-PEAs) demonstrated significant inhibition of CT26 cell growth in vitro. In vivo, these nanoparticles exhibited prolonged tumor accumulation and antitumor effects, with no observed toxicity to normal organs. Furthermore, blank Leu-PEAs nanoparticles also showed antitumor effects in vitro and in vivo, which may be attributed to the activation of the mammalian target of rapamycin (mTOR) pathway by leucine. Consequently, this biocompatible Leu-PEAs nano-drug delivery system shows potential as a promising strategy for colorectal cancer treatment, warranting further investigation.
2024, 35(12): 109692
doi: 10.1016/j.cclet.2024.109692
摘要:
Photodynamic therapy has been widely employed as an alternative strategy against bacterial infection. Molecular structure has a profound effect on the antibacterial ability of photosensitizers (PSs). Herein, we designed and synthesized a series of boron dipyrromethene (BODIPY)-based photosensitizers with different alkyl chain lengths, and then their antibacterial activities were compared. Among these BODIPYs, the BODIPY with octyl (BDP-8) exhibits the best antibacterial effect, while the antibacterial performance of BODIPY with dodecyl (BDP-12) is the worst. This work provides instructive information for further development of effective photodynamic antimicrobial agents.
Photodynamic therapy has been widely employed as an alternative strategy against bacterial infection. Molecular structure has a profound effect on the antibacterial ability of photosensitizers (PSs). Herein, we designed and synthesized a series of boron dipyrromethene (BODIPY)-based photosensitizers with different alkyl chain lengths, and then their antibacterial activities were compared. Among these BODIPYs, the BODIPY with octyl (BDP-8) exhibits the best antibacterial effect, while the antibacterial performance of BODIPY with dodecyl (BDP-12) is the worst. This work provides instructive information for further development of effective photodynamic antimicrobial agents.
Quantum dots boost large-view NIR-Ⅱ imaging with high fidelity for fluorescence-guided tumor surgery
2024, 35(12): 109694
doi: 10.1016/j.cclet.2024.109694
摘要:
Owing to the high spatiotemporal resolution, the second near-infrared (NIR-Ⅱ) imaging window can provide high imaging contrast with diminished tissue autofluorescence and suppressed photon scattering to pinpoint the locations for tumor surgery. Due to the unique optical properties and excellent fluorescence performance, quantum dots (QDs) are regarded as ideal nanoprobes for fluorescence-guided surgery (FGS). Moreover, QDs can be excited by a variety of light sources owing to the continuous and wide absorption ranges. Herein, light-emitting diode (LED) was used as the excitation source of QDs-based nanoprobes to realize FGS of tumor with high resolution. Since the LED light could irradiate a large region with consistent light intensity, signal distortion at the edge of imaging field was avoided. The signal intensity of the view edges under LED excitation can be improved by about 5 times compared to laser excitation. Therefore, more micro-vessels and smaller tumors (Vtumor < 5 mm2) could be detected, thus providing more precise guidance for tumor resection surgery.
Owing to the high spatiotemporal resolution, the second near-infrared (NIR-Ⅱ) imaging window can provide high imaging contrast with diminished tissue autofluorescence and suppressed photon scattering to pinpoint the locations for tumor surgery. Due to the unique optical properties and excellent fluorescence performance, quantum dots (QDs) are regarded as ideal nanoprobes for fluorescence-guided surgery (FGS). Moreover, QDs can be excited by a variety of light sources owing to the continuous and wide absorption ranges. Herein, light-emitting diode (LED) was used as the excitation source of QDs-based nanoprobes to realize FGS of tumor with high resolution. Since the LED light could irradiate a large region with consistent light intensity, signal distortion at the edge of imaging field was avoided. The signal intensity of the view edges under LED excitation can be improved by about 5 times compared to laser excitation. Therefore, more micro-vessels and smaller tumors (Vtumor < 5 mm2) could be detected, thus providing more precise guidance for tumor resection surgery.
2024, 35(12): 109696
doi: 10.1016/j.cclet.2024.109696
摘要:
The anti-oxidative characteristic and immunosuppressive microenvironment contribute to a high resistance of tumor to many treatments. In this work, a glutathione (GSH)-responsive metal-coordinated oxidative stress amplifier (designated as CuPA) is fabricated to suppress tumor growth through elevating the cellular level of reactive oxygen species (ROS) and eliminating M2 macrophages. Among which, cooper ion (Cu2+) is capable of coordinating with thioredoxin (Trx) inhibitor of PX-12 and signal transducer and activator of transcription 6 (STAT6) inhibitor of AS1517499 with the assistance of distearoyl phosphoethanolamine-PEG2000 (DSPE-PEG2000), which can extensively increase the stability to enhance drug delivery in vitro and in vivo. Furthermore, CuPA can upregulate intracellular ROS to cause tumor cell death through restraining Trx and degrading GSH. Also, CuPA-mediated STAT6 inhibition results in the elimination of M2 macrophage to reverse the immunosuppressive tumor microenvironment. Finally, the elevated oxidative stress and increased immune activation amplify the synergistic antitumor effect without causing obvious side effect. This work provides a new sight for synergistic tumor suppression through chemo-immunotherapy in consideration of the complex resistant tumor microenvironment.
The anti-oxidative characteristic and immunosuppressive microenvironment contribute to a high resistance of tumor to many treatments. In this work, a glutathione (GSH)-responsive metal-coordinated oxidative stress amplifier (designated as CuPA) is fabricated to suppress tumor growth through elevating the cellular level of reactive oxygen species (ROS) and eliminating M2 macrophages. Among which, cooper ion (Cu2+) is capable of coordinating with thioredoxin (Trx) inhibitor of PX-12 and signal transducer and activator of transcription 6 (STAT6) inhibitor of AS1517499 with the assistance of distearoyl phosphoethanolamine-PEG2000 (DSPE-PEG2000), which can extensively increase the stability to enhance drug delivery in vitro and in vivo. Furthermore, CuPA can upregulate intracellular ROS to cause tumor cell death through restraining Trx and degrading GSH. Also, CuPA-mediated STAT6 inhibition results in the elimination of M2 macrophage to reverse the immunosuppressive tumor microenvironment. Finally, the elevated oxidative stress and increased immune activation amplify the synergistic antitumor effect without causing obvious side effect. This work provides a new sight for synergistic tumor suppression through chemo-immunotherapy in consideration of the complex resistant tumor microenvironment.
2024, 35(12): 109697
doi: 10.1016/j.cclet.2024.109697
摘要:
The utilization of fungicides in plants is very low, emphasizing the need to improve their utilization rates. In this study, the fungicide dimethachlon (Dim) was encapsulated within hollow mesoporous silica (HMSNs), and a coating was formed on the HMSNs surface through the reaction of Na2CO3 and CaCl2, resulting in a pH-responsive delivery system named D/H@CaCO3, proven valuable in preventing sclerotinia diseases in romaine lettuce. When disease-infested romaine lettuce was treated with D/H@CaCO3, it degraded in the acidic microenvironment of Sclerotinia sclerotiorum (S. sclerotiorum), allowing for the pH-responsive release of Dim and effectively killing S. sclerotiorum. Moreover, the degraded CaCO3 coating releases CO2, which enhances the photosynthetic pigment contents, such as chlorophyll a, chlorophyll b, and carotenoids, in turn promoting plant growth. D/H@CaCO3 is biologically safe for plants and is environmentally friendly, as confirmed by assessments involving zebrafish and earthworms. Given their antifungal capabilities, the controlled release of fungicides offers potential for plant protection.
The utilization of fungicides in plants is very low, emphasizing the need to improve their utilization rates. In this study, the fungicide dimethachlon (Dim) was encapsulated within hollow mesoporous silica (HMSNs), and a coating was formed on the HMSNs surface through the reaction of Na2CO3 and CaCl2, resulting in a pH-responsive delivery system named D/H@CaCO3, proven valuable in preventing sclerotinia diseases in romaine lettuce. When disease-infested romaine lettuce was treated with D/H@CaCO3, it degraded in the acidic microenvironment of Sclerotinia sclerotiorum (S. sclerotiorum), allowing for the pH-responsive release of Dim and effectively killing S. sclerotiorum. Moreover, the degraded CaCO3 coating releases CO2, which enhances the photosynthetic pigment contents, such as chlorophyll a, chlorophyll b, and carotenoids, in turn promoting plant growth. D/H@CaCO3 is biologically safe for plants and is environmentally friendly, as confirmed by assessments involving zebrafish and earthworms. Given their antifungal capabilities, the controlled release of fungicides offers potential for plant protection.
2024, 35(12): 109698
doi: 10.1016/j.cclet.2024.109698
摘要:
The insufficient F(III)/Fe(II) cycling rate resulted from high combination of photogenerated carriers severely hinders the photo-Fenton activity. In this work, 0 dimensional α-Fe2O3 nanoclusters decorated TiO2 heterojunction (FT-x) was prepared via in-situ phase transformation strategy. FT-200 exhibited the optimal photo-Fenton activity for 2,4-dichlorophenol degradation with the kinetic rate constant reaching 1.0806 min−1 under low H2O2 dosage (1 mmol/L), which was 126.1 and 202.8 times higher than that of TiO2 and α-Fe2O3. Radical quenching experiments and electron spin resonance spectra proved that ·OH was the leading reactive specie. The enhanced photo-Fenton activity was attributed to the accelerated F(III)/Fe(II) cycling rate induced by the direct Z-Scheme charge transfer mechanism. Benefiting from the abundant ·OH production, the dechlorinate ratios and mineralization ratios of multiple chlorophenol pollutants (2,4-dichlorophenol, 4-chlorophenol, 2,4,6-trichlorophenol) all exceeded 98%. The biotoxicity of chlorophenol wastewater was greatly reduced after the treatment by Light/H2O2/FT-200 system. Overall, this work constructed a low-cost and highly efficient photo-Fenton system for refractory organic wastewater treatment.
The insufficient F(III)/Fe(II) cycling rate resulted from high combination of photogenerated carriers severely hinders the photo-Fenton activity. In this work, 0 dimensional α-Fe2O3 nanoclusters decorated TiO2 heterojunction (FT-x) was prepared via in-situ phase transformation strategy. FT-200 exhibited the optimal photo-Fenton activity for 2,4-dichlorophenol degradation with the kinetic rate constant reaching 1.0806 min−1 under low H2O2 dosage (1 mmol/L), which was 126.1 and 202.8 times higher than that of TiO2 and α-Fe2O3. Radical quenching experiments and electron spin resonance spectra proved that ·OH was the leading reactive specie. The enhanced photo-Fenton activity was attributed to the accelerated F(III)/Fe(II) cycling rate induced by the direct Z-Scheme charge transfer mechanism. Benefiting from the abundant ·OH production, the dechlorinate ratios and mineralization ratios of multiple chlorophenol pollutants (2,4-dichlorophenol, 4-chlorophenol, 2,4,6-trichlorophenol) all exceeded 98%. The biotoxicity of chlorophenol wastewater was greatly reduced after the treatment by Light/H2O2/FT-200 system. Overall, this work constructed a low-cost and highly efficient photo-Fenton system for refractory organic wastewater treatment.
2024, 35(12): 109699
doi: 10.1016/j.cclet.2024.109699
摘要:
In view of widespread existence and toxicity, removal and detection of bisphenols is imperative to assess environmental risks and reduce harm to human health. Although many techniques have been reported, constructing fast and sensitive method remains a challenge. Herein, porous poly(divinylbenzene) polymer was synthesized in-situ on the Fe3O4 particles by means of distillation-precipitation polymerization and functioned as sorbents to extract bisphenols. Employing Fe3O4@poly(divinylbenzene) as sorbent, a magnetic solid-phase extraction coupling with liquid chromatography was developed to detect trace bisphenols in water. This method presented low detection limits (0.01–0.03 ng/mL), high enrichment ability (enrichment factor, 327–343), and good reproducibility. Moreover, the method showed satisfactory recoveries in the detection of lake water (80.60%-116.2%) and egg sample (75.17%-120.0%). Impressively, Fe3O4@PDVB has excellent adsorption capacity, which can realize rapid kinetic adsorption of bisphenols with equilibrium time all less than 10 s. The maximum adsorption capacities reached 1074.8, 1049.7, 1299.1 and 1329.5 mg/g for bisphenol F, bisphenol A, bisphenol B and bisphenol AF with Langmuir isotherm model. The adsorption mechanism of Fe3O4@PDVB to bisphenols was investigated and demonstrated that hydrophobic interactions played a key role, together with assistance of stacking interactions and hydrogen interactions. Overall, this work provides a promising sorbent material with ultra-fast and large adsorption capacities for extraction of bisphenols from water.
In view of widespread existence and toxicity, removal and detection of bisphenols is imperative to assess environmental risks and reduce harm to human health. Although many techniques have been reported, constructing fast and sensitive method remains a challenge. Herein, porous poly(divinylbenzene) polymer was synthesized in-situ on the Fe3O4 particles by means of distillation-precipitation polymerization and functioned as sorbents to extract bisphenols. Employing Fe3O4@poly(divinylbenzene) as sorbent, a magnetic solid-phase extraction coupling with liquid chromatography was developed to detect trace bisphenols in water. This method presented low detection limits (0.01–0.03 ng/mL), high enrichment ability (enrichment factor, 327–343), and good reproducibility. Moreover, the method showed satisfactory recoveries in the detection of lake water (80.60%-116.2%) and egg sample (75.17%-120.0%). Impressively, Fe3O4@PDVB has excellent adsorption capacity, which can realize rapid kinetic adsorption of bisphenols with equilibrium time all less than 10 s. The maximum adsorption capacities reached 1074.8, 1049.7, 1299.1 and 1329.5 mg/g for bisphenol F, bisphenol A, bisphenol B and bisphenol AF with Langmuir isotherm model. The adsorption mechanism of Fe3O4@PDVB to bisphenols was investigated and demonstrated that hydrophobic interactions played a key role, together with assistance of stacking interactions and hydrogen interactions. Overall, this work provides a promising sorbent material with ultra-fast and large adsorption capacities for extraction of bisphenols from water.
2024, 35(12): 109718
doi: 10.1016/j.cclet.2024.109718
摘要:
Bacterial endotoxin (a type of lipopolysaccharide, LPS) that acts as the strongest immune stimulant exhibits high toxicity to human health. The golden standard detection methods rely heavily on the use of a large amount of tachypleus amebocyte lysate (TAL) reagents, extracted from the unique blue blood of legally protected horseshoe crabs. Herein, a cost-effective distance-based lateral flow (D-LAF) sensor is demonstrated for the first time based on the coagulation cascade process of TAL induced by endotoxin, which causes the generation of gel-state TAL. The gelation process can increase the amount of trapped water molecules and shorten the lateral flow distance of the remaining free water on the pH paper. The water flow distance is directly correlated to the concentration of endotoxin. Noteworthy, the D-LAF sensor allows the detection of endotoxin with the reduced dosage of TAL reagents than the golden standard detection methods. The detection limit of endotoxin is calculated to be 0.0742 EU/mL. This method can be applied to the detection of endotoxin in real samples such as household water and clinical injection solution with excellent performance comparable to the commercial ELISA kit.
Bacterial endotoxin (a type of lipopolysaccharide, LPS) that acts as the strongest immune stimulant exhibits high toxicity to human health. The golden standard detection methods rely heavily on the use of a large amount of tachypleus amebocyte lysate (TAL) reagents, extracted from the unique blue blood of legally protected horseshoe crabs. Herein, a cost-effective distance-based lateral flow (D-LAF) sensor is demonstrated for the first time based on the coagulation cascade process of TAL induced by endotoxin, which causes the generation of gel-state TAL. The gelation process can increase the amount of trapped water molecules and shorten the lateral flow distance of the remaining free water on the pH paper. The water flow distance is directly correlated to the concentration of endotoxin. Noteworthy, the D-LAF sensor allows the detection of endotoxin with the reduced dosage of TAL reagents than the golden standard detection methods. The detection limit of endotoxin is calculated to be 0.0742 EU/mL. This method can be applied to the detection of endotoxin in real samples such as household water and clinical injection solution with excellent performance comparable to the commercial ELISA kit.
2024, 35(12): 109723
doi: 10.1016/j.cclet.2024.109723
摘要:
The chemical investigation into the EtOAc extract of the deep-sea-derived fungus Penicillium citrinum W22 yielded three unprecedented citrinin dimers, neo-Dicitrinols A–C (1–3) and a known one, penicitrinone A (4). Their structures were elucidated by extensive analysis of spectroscopic data, electronic circular dichroism (ECD) calculation, X-ray diffraction, and biogenetic consideration. neo-Dicitrinols A–C (1–3), bearing a tetramic acid unit, represent the first example of citrinin analogues as hybrid polyketide synthase-nonribosomal peptide synthase (PKS-NRPS) products. neo-Dicitrinol C (3) significantly inhibited renin-angiotensin system-selective lethal 3 (RSL3)-induced ferroptosis with a half maximal effective concentration (EC50) value of 21.6 µmol/L.
The chemical investigation into the EtOAc extract of the deep-sea-derived fungus Penicillium citrinum W22 yielded three unprecedented citrinin dimers, neo-Dicitrinols A–C (1–3) and a known one, penicitrinone A (4). Their structures were elucidated by extensive analysis of spectroscopic data, electronic circular dichroism (ECD) calculation, X-ray diffraction, and biogenetic consideration. neo-Dicitrinols A–C (1–3), bearing a tetramic acid unit, represent the first example of citrinin analogues as hybrid polyketide synthase-nonribosomal peptide synthase (PKS-NRPS) products. neo-Dicitrinol C (3) significantly inhibited renin-angiotensin system-selective lethal 3 (RSL3)-induced ferroptosis with a half maximal effective concentration (EC50) value of 21.6 µmol/L.
2024, 35(12): 109725
doi: 10.1016/j.cclet.2024.109725
摘要:
To address the pressing global need for carbon-neutral fuels, optimizing the conversion of biomass to bio-oil (bio-chemicals) is crucial. Here, we introduce MXene (Ti3C2Tx) as an innovative catalyst in biomass pyrolysis, exhibiting significant prowess in boosting levoglucosan yields. Py-GC/MS analysis indicated a remarkable 438% enhancement in levoglucosan yield when a 5 wt% catalyst-to-biomass ratio was employed. Laboratory-scale studies achieved an impressive 13.95 wt% levoglucosan in ex-situ fixed-bed catalytic pyrolysis, a yield that is 19.6 times higher than that from pure biomass at 40 wt% catalyst loading. Recycling evaluations affirm the robust stability of the MXene catalyst, validating its potential for multiple use cycles in eco-friendly industrial levoglucosan production.
To address the pressing global need for carbon-neutral fuels, optimizing the conversion of biomass to bio-oil (bio-chemicals) is crucial. Here, we introduce MXene (Ti3C2Tx) as an innovative catalyst in biomass pyrolysis, exhibiting significant prowess in boosting levoglucosan yields. Py-GC/MS analysis indicated a remarkable 438% enhancement in levoglucosan yield when a 5 wt% catalyst-to-biomass ratio was employed. Laboratory-scale studies achieved an impressive 13.95 wt% levoglucosan in ex-situ fixed-bed catalytic pyrolysis, a yield that is 19.6 times higher than that from pure biomass at 40 wt% catalyst loading. Recycling evaluations affirm the robust stability of the MXene catalyst, validating its potential for multiple use cycles in eco-friendly industrial levoglucosan production.
2024, 35(12): 109735
doi: 10.1016/j.cclet.2024.109735
摘要:
Near infrared-II (NIR-II) dyes have unique advantages in biomedical applications owing to the powerful ability in penetrating biological tissues. Herein, NIR-II aza-BODIPY dye, QLD-BDP, was developed with julolidine at 1,7-sites and p-dimethylaminophenyl group at 3,5-sites. According to X-ray analysis, QLD-BDP exhibits significant distortion, and this molecule appears a bowl shaped structure. The photothermal conversion efficiency of the self-assembled QLD-BDP nanoparticles (QLD-BDP-NPs) can reach 50.5%, with maximum emission at 998 nm by the aggregate. QLD-BDP-NPs can cause the complete destruction of 4T1 multicellular spheroids (MCSs), indicating a photothermal therapy (PTT) effect.
Near infrared-II (NIR-II) dyes have unique advantages in biomedical applications owing to the powerful ability in penetrating biological tissues. Herein, NIR-II aza-BODIPY dye, QLD-BDP, was developed with julolidine at 1,7-sites and p-dimethylaminophenyl group at 3,5-sites. According to X-ray analysis, QLD-BDP exhibits significant distortion, and this molecule appears a bowl shaped structure. The photothermal conversion efficiency of the self-assembled QLD-BDP nanoparticles (QLD-BDP-NPs) can reach 50.5%, with maximum emission at 998 nm by the aggregate. QLD-BDP-NPs can cause the complete destruction of 4T1 multicellular spheroids (MCSs), indicating a photothermal therapy (PTT) effect.
2024, 35(12): 109753
doi: 10.1016/j.cclet.2024.109753
摘要:
To efficiently remove perfluorooctanoic acid (PFOA), we developed a composite of magnetic Fe3O4 nanocrystals and MIL-101 (an iron-based metal organic framework). Because of its high surface area, porous structure, and complexation between PFOA as confirmed by experimental results and density functional theory simulation, the magnetic composite showed a Langmuir adsorption capacity of 415 mg/g in the presence of various groundwater components, and thus adsorbed PFOA at environment-relevant concentration within 20 min. The catalyst loaded with PFOA can then be magnetically separated from the synthetic groundwater. This adsorption step concentrated PFOA near MIL-101 and resulted in a fast decomposition rate in the decomposition step, where MIL-101 served as an efficient Fenton agent due to its abundant Fe3+/Fe2+ sites. Meanwhile, the alternative magnetic field was introduced to change the production pathway of reactive oxygen species and superoxide radical anions were produced, which was critical for PFOA degradation. In addition, the inductive heating effect heat the magnetic particles to 445 K through an in-situ approach, which thus further accelerated Fenton reactions rate. In addition, and achieved a complete degradation of PFOA within 30 min. This newly developed Fenton catalyst demonstrates advantages over conventionally heterogeneous and homogeneous catalysts, and thus is promising for practical applications.
To efficiently remove perfluorooctanoic acid (PFOA), we developed a composite of magnetic Fe3O4 nanocrystals and MIL-101 (an iron-based metal organic framework). Because of its high surface area, porous structure, and complexation between PFOA as confirmed by experimental results and density functional theory simulation, the magnetic composite showed a Langmuir adsorption capacity of 415 mg/g in the presence of various groundwater components, and thus adsorbed PFOA at environment-relevant concentration within 20 min. The catalyst loaded with PFOA can then be magnetically separated from the synthetic groundwater. This adsorption step concentrated PFOA near MIL-101 and resulted in a fast decomposition rate in the decomposition step, where MIL-101 served as an efficient Fenton agent due to its abundant Fe3+/Fe2+ sites. Meanwhile, the alternative magnetic field was introduced to change the production pathway of reactive oxygen species and superoxide radical anions were produced, which was critical for PFOA degradation. In addition, the inductive heating effect heat the magnetic particles to 445 K through an in-situ approach, which thus further accelerated Fenton reactions rate. In addition, and achieved a complete degradation of PFOA within 30 min. This newly developed Fenton catalyst demonstrates advantages over conventionally heterogeneous and homogeneous catalysts, and thus is promising for practical applications.
2024, 35(12): 109756
doi: 10.1016/j.cclet.2024.109756
摘要:
The highly desired goal is to employ visible light for the photocatalytic reduction of toxic Cr(VI) to environmentally friendly Cr(III). Metal-organic frameworks (MOFs) are considered one of the most promising materials for the photoreduction of Cr(VI). Nevertheless, developing MOFs with high stability and activity is still challenging. Herein, we report a stable Zn-based MOF (named DZU-64) with an anthracene functionalized ligand, and its reduction of Cr(VI) under sunlight irradiation was investigated. DZU-64 exhibits excellent chemical stability in pH range of 2−14 aqueous solution, and remarkable thermal stability to 570 ℃. For the photoreduction of Cr(VI) under visible light irradiation, DZU-64 gives a record rate constant of 0.467 min−1 and a high Cr(VI) reduction rate of 6.68 mg Cr(VI) gcata−1 min−1 at pH 2. Moreover, under real solar light, DZU-64 can also efficiently reduce Cr(VI) to Cr(III) while retaining its catalytic activity throughout 5 cycles without any notable decline, further demonstrating its great application prospect. By combining the photovoltaic performance tests and electron spin resonance test, the possible photoreduction of Cr(VI) mechanism in DZU-64 was analyzed.
The highly desired goal is to employ visible light for the photocatalytic reduction of toxic Cr(VI) to environmentally friendly Cr(III). Metal-organic frameworks (MOFs) are considered one of the most promising materials for the photoreduction of Cr(VI). Nevertheless, developing MOFs with high stability and activity is still challenging. Herein, we report a stable Zn-based MOF (named DZU-64) with an anthracene functionalized ligand, and its reduction of Cr(VI) under sunlight irradiation was investigated. DZU-64 exhibits excellent chemical stability in pH range of 2−14 aqueous solution, and remarkable thermal stability to 570 ℃. For the photoreduction of Cr(VI) under visible light irradiation, DZU-64 gives a record rate constant of 0.467 min−1 and a high Cr(VI) reduction rate of 6.68 mg Cr(VI) gcata−1 min−1 at pH 2. Moreover, under real solar light, DZU-64 can also efficiently reduce Cr(VI) to Cr(III) while retaining its catalytic activity throughout 5 cycles without any notable decline, further demonstrating its great application prospect. By combining the photovoltaic performance tests and electron spin resonance test, the possible photoreduction of Cr(VI) mechanism in DZU-64 was analyzed.
2024, 35(12): 109761
doi: 10.1016/j.cclet.2024.109761
摘要:
Efficient yield of 1O2 determines the photocatalytic degradation rate of antibiotics, but the regulatory mechanism for 1O2 selective generation in O2 activation is still lacking exploration. Herein, oxygen vacancy (OV) modification strategy of MIL-125 was successfully practiced to promote the selective generation of 1O2. Multiple characterizations including extended X-ray absorption fine structure (EXAFS) and electron paramagnetic resonance spectra (EPR) confirmed the formation of oxygen vacancy in OV-MIL-125. The synthesized OV-MIL-125 exhibited greatly enhanced 1O2 selective (~90%) and antibiotics removal rate in water with high mineralization rate. Dynamics analysis of excitons by transient-steady state fluorescence and phosphorescence, transient absorption spectra (TAS) revealed that oxygen vacancy greatly enhanced the intersystem crossing (ISC) of singlet exciton, promoting triplet exciton generation. Density functional theoretical (DFT) calculation also proved the reduced gap of intersystem (ΔEST) and the modulated highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) population which was conducive to intersystem crossing process. Calculation of transition state further confirmed the lower energy barrier for π* orbital spin flip of O2 adsorbed on OV-MIL-125. The Dexter energy transfer involving triplet annihilation dominated the O2 activation mechanism to generate 1O2 instead of the charge transfer to generate O2•− which happened in MIL-125. This study provides new thinking for photocatalytic activation of molecular oxygen and is expected to guide the design of MOF-based catalysts for water treatment.
Efficient yield of 1O2 determines the photocatalytic degradation rate of antibiotics, but the regulatory mechanism for 1O2 selective generation in O2 activation is still lacking exploration. Herein, oxygen vacancy (OV) modification strategy of MIL-125 was successfully practiced to promote the selective generation of 1O2. Multiple characterizations including extended X-ray absorption fine structure (EXAFS) and electron paramagnetic resonance spectra (EPR) confirmed the formation of oxygen vacancy in OV-MIL-125. The synthesized OV-MIL-125 exhibited greatly enhanced 1O2 selective (~90%) and antibiotics removal rate in water with high mineralization rate. Dynamics analysis of excitons by transient-steady state fluorescence and phosphorescence, transient absorption spectra (TAS) revealed that oxygen vacancy greatly enhanced the intersystem crossing (ISC) of singlet exciton, promoting triplet exciton generation. Density functional theoretical (DFT) calculation also proved the reduced gap of intersystem (ΔEST) and the modulated highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) population which was conducive to intersystem crossing process. Calculation of transition state further confirmed the lower energy barrier for π* orbital spin flip of O2 adsorbed on OV-MIL-125. The Dexter energy transfer involving triplet annihilation dominated the O2 activation mechanism to generate 1O2 instead of the charge transfer to generate O2•− which happened in MIL-125. This study provides new thinking for photocatalytic activation of molecular oxygen and is expected to guide the design of MOF-based catalysts for water treatment.
2024, 35(12): 109767
doi: 10.1016/j.cclet.2024.109767
摘要:
Antibiotics present in surface water have detrimental effects on both human health and the ecosystem. Additionally, they pose a threat to the effectiveness of biological water treatment processes. In this study, a visible photocatalytic system with BiOCl/g-C3N4 heterojunction was developed to remove sulfonamide antibiotic sulfamerazine (SMZ) in water. The removal rate reached 92.77% under visible light irradiation for 80 min. This photocatalyst remained active after 5 cycles of experiments and maintained a relatively stable removal rate of SMZ of over 80%. The ESR tests indicate that the main active species in this photocatalytic system were h+ and •O2−. The enhanced photocatalytic efficiency was mainly ascribed to the formation of a built-in electric field between BiOCl and g-C3N4 through the carrier transport mechanism of the S-scheme heterojunction. This heterojunction facilitated the photogenerated carrier shift and segregation, and improved the interfacial charge transfer efficiency, as confirmed by photoelectrochemical test and Density functional theory (DFT) calculations. The HPLC-QTOF-MS/MS and DFT analysis revealed possible degradation pathways of SMZ may involve deamination, hydroxylation, SO2 extrusion and bond breaking. This novel BiOCl/g-C3N4 heterojunction has proven to be essential for efficient visible-light photocatalysis.
Antibiotics present in surface water have detrimental effects on both human health and the ecosystem. Additionally, they pose a threat to the effectiveness of biological water treatment processes. In this study, a visible photocatalytic system with BiOCl/g-C3N4 heterojunction was developed to remove sulfonamide antibiotic sulfamerazine (SMZ) in water. The removal rate reached 92.77% under visible light irradiation for 80 min. This photocatalyst remained active after 5 cycles of experiments and maintained a relatively stable removal rate of SMZ of over 80%. The ESR tests indicate that the main active species in this photocatalytic system were h+ and •O2−. The enhanced photocatalytic efficiency was mainly ascribed to the formation of a built-in electric field between BiOCl and g-C3N4 through the carrier transport mechanism of the S-scheme heterojunction. This heterojunction facilitated the photogenerated carrier shift and segregation, and improved the interfacial charge transfer efficiency, as confirmed by photoelectrochemical test and Density functional theory (DFT) calculations. The HPLC-QTOF-MS/MS and DFT analysis revealed possible degradation pathways of SMZ may involve deamination, hydroxylation, SO2 extrusion and bond breaking. This novel BiOCl/g-C3N4 heterojunction has proven to be essential for efficient visible-light photocatalysis.
2024, 35(12): 109782
doi: 10.1016/j.cclet.2024.109782
摘要:
Host-guest recognition-based macrocycle in macrocycle to form "Russian doll" assemblies remains an interesting topic in supramolecular chemistry. Herein, a macrocycle-in-macrocycle assembly was studied using cucurbit[10]uril (Q[10]) and the smallest cucurbituril-like macrocycle (TD[4]). X-ray crystal structure analysis revealed that TD[4] was encapsulated in the cavity of Q[10] to form a 1:1 complex. Importantly, competitive guest studies suggested that TD[4] had the highest binding constant with the Q[10] host among the guests used, including Q[5], Me8TD[4], and amantadine molecules in water. Our results provided a new cucurbituril-based Russian-doll structure containing both the largest and smallest cavities of the cucurbiturils, which expanded the family of molecular Russian dolls.
Host-guest recognition-based macrocycle in macrocycle to form "Russian doll" assemblies remains an interesting topic in supramolecular chemistry. Herein, a macrocycle-in-macrocycle assembly was studied using cucurbit[10]uril (Q[10]) and the smallest cucurbituril-like macrocycle (TD[4]). X-ray crystal structure analysis revealed that TD[4] was encapsulated in the cavity of Q[10] to form a 1:1 complex. Importantly, competitive guest studies suggested that TD[4] had the highest binding constant with the Q[10] host among the guests used, including Q[5], Me8TD[4], and amantadine molecules in water. Our results provided a new cucurbituril-based Russian-doll structure containing both the largest and smallest cavities of the cucurbiturils, which expanded the family of molecular Russian dolls.
2024, 35(12): 109783
doi: 10.1016/j.cclet.2024.109783
摘要:
Aromatic aldehydes are the most fundamentally important compounds used in organic synthesis. The development of new synthetic methods for introduction of a formyl group into an organic scaffold is highly desirable. In this report, a nickel-catalyzed reductive coupling between aryl halides and α–chloro N-methoxyphthalimide has been documented for the synthesis of a diverse array of aromatic aldehydes. Because of mild reductive coupling conditions, excellent functional group tolerance, especially for substrates containing free -OH and -NH2, was observed. Due to the simple operation mode, a large library of aromatic aldehydes can be quickly constructed by this process. Moreover, the present protocol is amenable for late-stage functionalization of bioactive compound. A combined computational and experimental investigation suggested the reaction may undergo a reaction mechanism of active Ni(I) catalyst formation and the formation of key formyl radical intermediate under zinc reductive conditions.
Aromatic aldehydes are the most fundamentally important compounds used in organic synthesis. The development of new synthetic methods for introduction of a formyl group into an organic scaffold is highly desirable. In this report, a nickel-catalyzed reductive coupling between aryl halides and α–chloro N-methoxyphthalimide has been documented for the synthesis of a diverse array of aromatic aldehydes. Because of mild reductive coupling conditions, excellent functional group tolerance, especially for substrates containing free -OH and -NH2, was observed. Due to the simple operation mode, a large library of aromatic aldehydes can be quickly constructed by this process. Moreover, the present protocol is amenable for late-stage functionalization of bioactive compound. A combined computational and experimental investigation suggested the reaction may undergo a reaction mechanism of active Ni(I) catalyst formation and the formation of key formyl radical intermediate under zinc reductive conditions.
2024, 35(12): 109788
doi: 10.1016/j.cclet.2024.109788
摘要:
Matrix-assisted laser desorption ionization-mass spectrometry imaging (MALDI-MSI) has shown its capability in visualizing the spatial distribution of various kinds of endogenous metabolites. Nevertheless, high quality mass imaging of low polar metabolites remains challenging. Herein, a platform for sensitive matrix-assisted laser desorption ionization-mass spectrometry imaging of cholesterol and glycerides has been proposed. In the platform, a vacuum promoted on-tissue derivatization strategy was proposed to constantly make the derivatization reaction proceed towards to the direction of products. Compared with traditional on-tissue derivatization procedure, the strategy improved the acquired intensity of derivatized glycerides about 50%. Additionally, the mass spectrometry image reflecting the signal ratio between 3 classes of glycerides was achieved to exploit the metabolic level of glycerides on tissue slice. Finally, the platform was applied to brain slices of Alzheimer's transgenic mice, type 2 diabetes mice and normal mice. Significant difference was found in mass spectrometry images reflecting the signal ratio of multiple endogenous metabolites. The work constructed a promising platform for mapping of glycerides in tissue by mass spectrometry imaging.
Matrix-assisted laser desorption ionization-mass spectrometry imaging (MALDI-MSI) has shown its capability in visualizing the spatial distribution of various kinds of endogenous metabolites. Nevertheless, high quality mass imaging of low polar metabolites remains challenging. Herein, a platform for sensitive matrix-assisted laser desorption ionization-mass spectrometry imaging of cholesterol and glycerides has been proposed. In the platform, a vacuum promoted on-tissue derivatization strategy was proposed to constantly make the derivatization reaction proceed towards to the direction of products. Compared with traditional on-tissue derivatization procedure, the strategy improved the acquired intensity of derivatized glycerides about 50%. Additionally, the mass spectrometry image reflecting the signal ratio between 3 classes of glycerides was achieved to exploit the metabolic level of glycerides on tissue slice. Finally, the platform was applied to brain slices of Alzheimer's transgenic mice, type 2 diabetes mice and normal mice. Significant difference was found in mass spectrometry images reflecting the signal ratio of multiple endogenous metabolites. The work constructed a promising platform for mapping of glycerides in tissue by mass spectrometry imaging.
2024, 35(12): 109789
doi: 10.1016/j.cclet.2024.109789
摘要:
Electrocatalytic reduction of nitrate (NO3−) at low concentrations to ammonia (NH4+) still faces challenges of low NO3− conversion and NH4+ selectivity due to the sluggish mass transfer and insufficient atomic hydrogen (H*) supply. Herein, we propose CuO/NiO heterojunction with the assistance of a built-in electric field to enhance mass transfer and H* provision. The built-in electric field in CuO/NiO is successfully formed as demonstrated by X-ray photoelectron spectroscopy and ultraviolet photoemission spectroscopy. The results reveal that CuO/NiO achieves high NO3− reduction activity (100%) and NH4+ selectivity (100%) under low NO3− concentration conditions (100 mg/L NO3−, ca. 22.6 mg/L NO3−-N), which is superior to that of many recently reported electrocatalysts. Density functional theory calculations further clarify that the built-in electric field triggers the enhanced adsorption of reactants on CuO/NiO heterojunction interface and strong d-p orbital hybridization between reactants and CuO/NiO. Besides, the free energy diagram of hydrogen evolution reaction of CuO/NiO confirms the realization of enhanced H* provision. Moreover, coupling experiments and consecutive cycle tests demonstrate the potential of CuO/NiO in practical applications. This work may open up a new path and guide the development of efficient electrocatalysts for electrocatalytic reduction of NO3− at low concentrations to NH4+.
Electrocatalytic reduction of nitrate (NO3−) at low concentrations to ammonia (NH4+) still faces challenges of low NO3− conversion and NH4+ selectivity due to the sluggish mass transfer and insufficient atomic hydrogen (H*) supply. Herein, we propose CuO/NiO heterojunction with the assistance of a built-in electric field to enhance mass transfer and H* provision. The built-in electric field in CuO/NiO is successfully formed as demonstrated by X-ray photoelectron spectroscopy and ultraviolet photoemission spectroscopy. The results reveal that CuO/NiO achieves high NO3− reduction activity (100%) and NH4+ selectivity (100%) under low NO3− concentration conditions (100 mg/L NO3−, ca. 22.6 mg/L NO3−-N), which is superior to that of many recently reported electrocatalysts. Density functional theory calculations further clarify that the built-in electric field triggers the enhanced adsorption of reactants on CuO/NiO heterojunction interface and strong d-p orbital hybridization between reactants and CuO/NiO. Besides, the free energy diagram of hydrogen evolution reaction of CuO/NiO confirms the realization of enhanced H* provision. Moreover, coupling experiments and consecutive cycle tests demonstrate the potential of CuO/NiO in practical applications. This work may open up a new path and guide the development of efficient electrocatalysts for electrocatalytic reduction of NO3− at low concentrations to NH4+.
2024, 35(12): 109813
doi: 10.1016/j.cclet.2024.109813
摘要:
Ensuring the timely and precise monitoring of severe liver diseases is crucial for guiding effective therapies and significantly extending overall quality of life. However, this remains a worldwide challenge, given the high incidence rate and the presence of strong confounding clinical symptoms. Herein, we applied a convenient and high-yield method to prepare the magnetic mesoporous carbon (MMC-Fe), guided by a composite of resol and triblock copolymer. With the combination of MMC-Fe, high-throughput mass spectrometry, and a simple machine learning algorithm, we extracted N-glycan profiles from various serum samples, including healthy controls, liver cirrhosis, and liver cancer, and from which we screened specific N-glycans. Specifically, the selected N-glycans demonstrate exceptional performance with area under the curve (AUC) values ranging from 0.948 to 0.993 for the detection of liver diseases, including alpha fetoprotein (AFP)-negative liver cancer. Among them, five N-glycans holds potential in monitoring distinctions between liver cirrhosis and AFP-negative liver cancer (AUC values of 0.827–0.842). This study is expected to promote the glycan-based precise monitoring of diseases, not limited to liver disease.
Ensuring the timely and precise monitoring of severe liver diseases is crucial for guiding effective therapies and significantly extending overall quality of life. However, this remains a worldwide challenge, given the high incidence rate and the presence of strong confounding clinical symptoms. Herein, we applied a convenient and high-yield method to prepare the magnetic mesoporous carbon (MMC-Fe), guided by a composite of resol and triblock copolymer. With the combination of MMC-Fe, high-throughput mass spectrometry, and a simple machine learning algorithm, we extracted N-glycan profiles from various serum samples, including healthy controls, liver cirrhosis, and liver cancer, and from which we screened specific N-glycans. Specifically, the selected N-glycans demonstrate exceptional performance with area under the curve (AUC) values ranging from 0.948 to 0.993 for the detection of liver diseases, including alpha fetoprotein (AFP)-negative liver cancer. Among them, five N-glycans holds potential in monitoring distinctions between liver cirrhosis and AFP-negative liver cancer (AUC values of 0.827–0.842). This study is expected to promote the glycan-based precise monitoring of diseases, not limited to liver disease.
2024, 35(12): 109833
doi: 10.1016/j.cclet.2024.109833
摘要:
Fenton-like process based on metal oxide presents one of the most hoping strategies to generate reactive oxygen species to treat refractory pollutants. The introduction of oxygen vacancies (OVs) can enhance the catalytic performance of metal oxides in Fenton-like reaction. In this paper, a one-step all solid-state synthesis strategy is proposed to induce oxygen defects in V2O5, which uses graphene to engineer the crystallization process of V-based crystals. Such approach employs graphene as a solid-catalyst to promote growth of V-based crystals owing to the ions-π interactions between graphene and VCl3. The electron-donor OVs in V2O5@graphene can not only active H2O2 for the •OH generation, but also accelerate the reduction of V5+ and V4+, thereby ensuring defective V2O5@graphene/H2O2 system is 14.3, 28.2, and 17.3 times higher than that of graphene/H2O2, pure V2O5/H2O2 and graphene+V2O5/H2O2 (mechanical mixed system), respectively. Our study provides a novel synthetic strategy to design and prepare OVs-riched transition metal catalysts for developing advanced oxidation technologies toward higher sustainability and practicality.
Fenton-like process based on metal oxide presents one of the most hoping strategies to generate reactive oxygen species to treat refractory pollutants. The introduction of oxygen vacancies (OVs) can enhance the catalytic performance of metal oxides in Fenton-like reaction. In this paper, a one-step all solid-state synthesis strategy is proposed to induce oxygen defects in V2O5, which uses graphene to engineer the crystallization process of V-based crystals. Such approach employs graphene as a solid-catalyst to promote growth of V-based crystals owing to the ions-π interactions between graphene and VCl3. The electron-donor OVs in V2O5@graphene can not only active H2O2 for the •OH generation, but also accelerate the reduction of V5+ and V4+, thereby ensuring defective V2O5@graphene/H2O2 system is 14.3, 28.2, and 17.3 times higher than that of graphene/H2O2, pure V2O5/H2O2 and graphene+V2O5/H2O2 (mechanical mixed system), respectively. Our study provides a novel synthetic strategy to design and prepare OVs-riched transition metal catalysts for developing advanced oxidation technologies toward higher sustainability and practicality.
2024, 35(12): 109837
doi: 10.1016/j.cclet.2024.109837
摘要:
Since the discovery of the Nernst effect in 19th century, it has been an important transverse thermoelectric charge transport phenomenon in solid states. Conjugated polymers have recently attracted great attention as promising optoelectronic materials. However, the Nernst effect is yet to be explored for conducting polymers. Here, we report the first theoretical investigations of the Nernst effect in doped conducting polymers by first-principles calculations under the frame work of Fermi-liquid theory. Specifically, the Nernst coefficients of PBTTT are found to be ranging from 0.0029 to 0.039 µV K−1 T−1. They are monotonically decreased with the doping level due to both much enhanced Fermi energy and the decreased charge mobility at high doping level. Our theoretical findings not only enhance our fundamental understanding of the doping mechanism that controls the charge transport properties of conducting polymers, but more importantly, they also offer initial predictions of the transverse thermoelectric conversion capability of conducting polymers. These predictions are crucial for the development of future flexible thermoelectric applications based on the Nernst effect.
Since the discovery of the Nernst effect in 19th century, it has been an important transverse thermoelectric charge transport phenomenon in solid states. Conjugated polymers have recently attracted great attention as promising optoelectronic materials. However, the Nernst effect is yet to be explored for conducting polymers. Here, we report the first theoretical investigations of the Nernst effect in doped conducting polymers by first-principles calculations under the frame work of Fermi-liquid theory. Specifically, the Nernst coefficients of PBTTT are found to be ranging from 0.0029 to 0.039 µV K−1 T−1. They are monotonically decreased with the doping level due to both much enhanced Fermi energy and the decreased charge mobility at high doping level. Our theoretical findings not only enhance our fundamental understanding of the doping mechanism that controls the charge transport properties of conducting polymers, but more importantly, they also offer initial predictions of the transverse thermoelectric conversion capability of conducting polymers. These predictions are crucial for the development of future flexible thermoelectric applications based on the Nernst effect.
2024, 35(12): 109843
doi: 10.1016/j.cclet.2024.109843
摘要:
β-Amino sulfides hold significant biological importance, motivating the development of several methods for sulfenylamination of alkenes. However, these methods often involve a three-component system with limited alkene substrate range. In this study, we present a pioneering two-component approach utilizing readily accessible sulfenamides as efficient difunctionalization reagents. Key to its success is the careful selection of a suitable photosensitizer, which enables precise modulation of sulfenamides by promoting unprecedented energy transfer rather than traditional single-electron oxidation. This novel strategy leads to the concurrent formation of N- and S-radical species, ensuring high regioselectivity for both electron-neutral and electron-deficient alkenes. As a result, a wide range of valuable β-amino sulfides, including those with congested amine groups, can be readily synthesized. These findings highlight the potential of this method for the efficient synthesis of diverse functionalized β-amino sulfides.
β-Amino sulfides hold significant biological importance, motivating the development of several methods for sulfenylamination of alkenes. However, these methods often involve a three-component system with limited alkene substrate range. In this study, we present a pioneering two-component approach utilizing readily accessible sulfenamides as efficient difunctionalization reagents. Key to its success is the careful selection of a suitable photosensitizer, which enables precise modulation of sulfenamides by promoting unprecedented energy transfer rather than traditional single-electron oxidation. This novel strategy leads to the concurrent formation of N- and S-radical species, ensuring high regioselectivity for both electron-neutral and electron-deficient alkenes. As a result, a wide range of valuable β-amino sulfides, including those with congested amine groups, can be readily synthesized. These findings highlight the potential of this method for the efficient synthesis of diverse functionalized β-amino sulfides.
2024, 35(12): 109847
doi: 10.1016/j.cclet.2024.109847
摘要:
Herein, a diatomite biomorphic Si-O doped carbon-based catalyst (DB-SiOC) was prepared using natural mineral diatomite as the silicon source and porous template. The results showed that the metal-free DB-SiOC catalyst exhibited ultrafast oxidation towards chlorophenol (CP) via peroxymonosulfate (PMS) activation, which was almost one order of magnitudes than most of carbon-based catalysts. The DB-SiOC/PMS system also showed the high ability to resist the interference of environmental matrix. The radicals (•OH and SO4•‒) exhibited a very small contribution to the CP oxidation while the electron transfer processes (ETP) played the major role in the DB-SiOC/PMS system. The electron shuttles from the electron-donating CP molecules to the adjacent DB-SiOC/PMS* could be efficiently triggered via Si-O bonds as bridges, making it possible for ultrafast oxidation of CP. In addition, the hollow-disc shaped DB-SiOC provided the biomorphic DE structures with abundant pores for enriching the PMS and pollutants, thus further accelerating the oxidation reaction. This work provided a new routine for the fabrication of Si-O doped carbon-based catalysts with excellent Fenton-like catalytic activity, which would greatly promote their application prospects in Fenton-like systems.
Herein, a diatomite biomorphic Si-O doped carbon-based catalyst (DB-SiOC) was prepared using natural mineral diatomite as the silicon source and porous template. The results showed that the metal-free DB-SiOC catalyst exhibited ultrafast oxidation towards chlorophenol (CP) via peroxymonosulfate (PMS) activation, which was almost one order of magnitudes than most of carbon-based catalysts. The DB-SiOC/PMS system also showed the high ability to resist the interference of environmental matrix. The radicals (•OH and SO4•‒) exhibited a very small contribution to the CP oxidation while the electron transfer processes (ETP) played the major role in the DB-SiOC/PMS system. The electron shuttles from the electron-donating CP molecules to the adjacent DB-SiOC/PMS* could be efficiently triggered via Si-O bonds as bridges, making it possible for ultrafast oxidation of CP. In addition, the hollow-disc shaped DB-SiOC provided the biomorphic DE structures with abundant pores for enriching the PMS and pollutants, thus further accelerating the oxidation reaction. This work provided a new routine for the fabrication of Si-O doped carbon-based catalysts with excellent Fenton-like catalytic activity, which would greatly promote their application prospects in Fenton-like systems.
2024, 35(12): 109877
doi: 10.1016/j.cclet.2024.109877
摘要:
Carbon nitride, a typical low-dimensional conjugated polymer photocatalyst, features a high exciton binding energy due to the weak dielectric screening and the strong Coulombic attraction of photogenerated electrons and holes. The reduction of the exciton binding energy of carbon nitride to promote the conversion from excitons into free carriers is the first priority for the improvement of charge-transfer-dependent photocatalytic reaction activity. In this paper, by introducing a variety of polar metal cations to carbon nitride, it is demonstrated that the charge distribution of the heptazine ring can be improved by ion polarization, which effectively promotes the dissociation of excitons into electrons and holes. The sodium ion shows the best modification effect, which enhances the rate of both photocatalytic hydrogen and hydrogen peroxide production by about 50%. Characterization shows that the introduction of strongly polar metal cations contributes to the reduction of the exciton dissociation energy of carbon nitride. This study provides a new perspective and a convenient method for the exciton modulation engineering of low-dimensional photocatalysts.
Carbon nitride, a typical low-dimensional conjugated polymer photocatalyst, features a high exciton binding energy due to the weak dielectric screening and the strong Coulombic attraction of photogenerated electrons and holes. The reduction of the exciton binding energy of carbon nitride to promote the conversion from excitons into free carriers is the first priority for the improvement of charge-transfer-dependent photocatalytic reaction activity. In this paper, by introducing a variety of polar metal cations to carbon nitride, it is demonstrated that the charge distribution of the heptazine ring can be improved by ion polarization, which effectively promotes the dissociation of excitons into electrons and holes. The sodium ion shows the best modification effect, which enhances the rate of both photocatalytic hydrogen and hydrogen peroxide production by about 50%. Characterization shows that the introduction of strongly polar metal cations contributes to the reduction of the exciton dissociation energy of carbon nitride. This study provides a new perspective and a convenient method for the exciton modulation engineering of low-dimensional photocatalysts.
2024, 35(12): 109892
doi: 10.1016/j.cclet.2024.109892
摘要:
BiVO4 is a promising semiconducting photoanode for photoelectrochemical (PEC) water splitting due to its suitable bandgap. However, the dissolution of V5+ and sluggish reaction kinetics at the surface in the oxygen evolution reaction (OER) limit its applications. Herein, we report a convenient strategy to change the microenvironment by adding Fe(Ⅲ) into the electrolyte. During the PEC process, Fe(Ⅲ) ions not only improve the current density, but also show excellent stability toward BiVO4. Consequently, the current increases by more than 1.7 times compared to that without Fe(Ⅲ). Photoelectrochemical, morphological, and structural characterizations reveal that the FeOOH co-catalyst produced in situ on the BiVO4 photoanode by cyclical formation of the intermediates at the electrode/electrolyte interface during OER accelerates the OER kinetics and prevents photo-corrosion by suppressing the dissolution of V5+. The results reveal a new strategy for the multifunctional modification of photoanodes for efficient solar conversion.
BiVO4 is a promising semiconducting photoanode for photoelectrochemical (PEC) water splitting due to its suitable bandgap. However, the dissolution of V5+ and sluggish reaction kinetics at the surface in the oxygen evolution reaction (OER) limit its applications. Herein, we report a convenient strategy to change the microenvironment by adding Fe(Ⅲ) into the electrolyte. During the PEC process, Fe(Ⅲ) ions not only improve the current density, but also show excellent stability toward BiVO4. Consequently, the current increases by more than 1.7 times compared to that without Fe(Ⅲ). Photoelectrochemical, morphological, and structural characterizations reveal that the FeOOH co-catalyst produced in situ on the BiVO4 photoanode by cyclical formation of the intermediates at the electrode/electrolyte interface during OER accelerates the OER kinetics and prevents photo-corrosion by suppressing the dissolution of V5+. The results reveal a new strategy for the multifunctional modification of photoanodes for efficient solar conversion.
2024, 35(12): 109900
doi: 10.1016/j.cclet.2024.109900
摘要:
Water pollution caused by Hg(II) and Ag(I) poses deleterious effects to environmental safety. Adsorption is one of the promising methods to decontaminate aqueous metal ions. Herein, polyhydroxyl-capped poly(amidoamine) (PAMAM) dendrimer/silica composites (G1-OH and G2-OH) were prepared for decontaminating aqueous Hg(II) and Ag(I). The maximum adsorption capacity of G1-OH and G2-OH for Hg(II) are 0.45 and 0.76 mmol/g, while that for Ag(I) are 0.66 and 0.81 mmol/g. The optimum solution pH for the adsorption of Hg(II) and Ag(I) are both 6. The adsorption for Hg(II) and Ag(I) can reach equilibrium at 150 and 120 min, respectively. Pseudo-second-order model can be used to describe the adsorption kinetic process and the rate-controlling step is film diffusion process. Adsorption isotherm indicates the adsorption can be promoted by increasing concentration and temperature, and the adsorption process could be described by Langmuir model with chemical mechanism. G1-OH and G2-OH exhibit excellent adsorption selectivity and they can 100% adsorb Hg(II) or Ag(I) with the coexisting of Fe(III), Co(II), Cu(II) or Ni(II). Adsorption mechanism confirms C-N, OH and CONH groups play critical role for the adsorption of the two ions. The work may provide efficient adsorbents for the decontamination of aqueous Hg(II) and Ag(I) with practical value.
Water pollution caused by Hg(II) and Ag(I) poses deleterious effects to environmental safety. Adsorption is one of the promising methods to decontaminate aqueous metal ions. Herein, polyhydroxyl-capped poly(amidoamine) (PAMAM) dendrimer/silica composites (G1-OH and G2-OH) were prepared for decontaminating aqueous Hg(II) and Ag(I). The maximum adsorption capacity of G1-OH and G2-OH for Hg(II) are 0.45 and 0.76 mmol/g, while that for Ag(I) are 0.66 and 0.81 mmol/g. The optimum solution pH for the adsorption of Hg(II) and Ag(I) are both 6. The adsorption for Hg(II) and Ag(I) can reach equilibrium at 150 and 120 min, respectively. Pseudo-second-order model can be used to describe the adsorption kinetic process and the rate-controlling step is film diffusion process. Adsorption isotherm indicates the adsorption can be promoted by increasing concentration and temperature, and the adsorption process could be described by Langmuir model with chemical mechanism. G1-OH and G2-OH exhibit excellent adsorption selectivity and they can 100% adsorb Hg(II) or Ag(I) with the coexisting of Fe(III), Co(II), Cu(II) or Ni(II). Adsorption mechanism confirms C-N, OH and CONH groups play critical role for the adsorption of the two ions. The work may provide efficient adsorbents for the decontamination of aqueous Hg(II) and Ag(I) with practical value.
2024, 35(12): 109909
doi: 10.1016/j.cclet.2024.109909
摘要:
Temperature plays a crucial role in regulating polymorphism in supramolecular polymers. Understanding the mechanism behind temperature-dependent supramolecular polymorphism is crucial as it provides an opportunity to tailor polymorphs for specific properties and applications. In this study, we present our findings on a naphthalimide-substituted benzene-1,3,5-tricarboxamide derivative, R-Nap-1, which exhibits two distinct polymerization pathways at varying temperatures. At 313 K, polymerization results in the formation of an M-chiral polymorph, whereas at 253 K, a P-chiral polymorph is formed. Both polymorphs are notably stable, remaining unchanged for over six months under ambient conditions. Theoretical calculations and experimental investigations allowed us to elucidate the mechanisms underlying these polymorphic transformations. The formation of the M-chiral polymorph at 313 K is attributed to the nucleation and growth of R-Nap-1 monomers once their concentration surpasses a critical threshold. Conversely, at lower temperatures (e.g., 253 K), the monomers undergo facile transformation into dimers due to a lower energy barrier and reduced Gibbs energy compared to the monomeric state. Subsequently, these dimers undergo nucleation-elongation to form the P-chiral polymorph when their concentration exceeds the critical polymerization concentration. The stability and lack of interconversion between the two polymorphs can be attributed to their close thermodynamic stabilities, as evidenced by variable-temperature CD spectra and DFT calculations. These findings highlight the importance of accurate temperature control in supramolecular polymerization processes, making a significant contribution to the understanding of supramolecular polymorphism, thus advancing the field of supramolecular chemistry.
Temperature plays a crucial role in regulating polymorphism in supramolecular polymers. Understanding the mechanism behind temperature-dependent supramolecular polymorphism is crucial as it provides an opportunity to tailor polymorphs for specific properties and applications. In this study, we present our findings on a naphthalimide-substituted benzene-1,3,5-tricarboxamide derivative, R-Nap-1, which exhibits two distinct polymerization pathways at varying temperatures. At 313 K, polymerization results in the formation of an M-chiral polymorph, whereas at 253 K, a P-chiral polymorph is formed. Both polymorphs are notably stable, remaining unchanged for over six months under ambient conditions. Theoretical calculations and experimental investigations allowed us to elucidate the mechanisms underlying these polymorphic transformations. The formation of the M-chiral polymorph at 313 K is attributed to the nucleation and growth of R-Nap-1 monomers once their concentration surpasses a critical threshold. Conversely, at lower temperatures (e.g., 253 K), the monomers undergo facile transformation into dimers due to a lower energy barrier and reduced Gibbs energy compared to the monomeric state. Subsequently, these dimers undergo nucleation-elongation to form the P-chiral polymorph when their concentration exceeds the critical polymerization concentration. The stability and lack of interconversion between the two polymorphs can be attributed to their close thermodynamic stabilities, as evidenced by variable-temperature CD spectra and DFT calculations. These findings highlight the importance of accurate temperature control in supramolecular polymerization processes, making a significant contribution to the understanding of supramolecular polymorphism, thus advancing the field of supramolecular chemistry.
2024, 35(12): 109912
doi: 10.1016/j.cclet.2024.109912
摘要:
2024, 35(12): 109918
doi: 10.1016/j.cclet.2024.109918
摘要:
Organic semiconductors are promising candidates as active layers in flexible and biocompatible electronics owing to their solution processability and molecular design flexibility. However, it remains necessary to establish a green processing approach to acquire desirable electrical properties for scalable industrial applications. Here, a highly efficient and environmentally friendly post-treatment method using liquid nitrogen as a cooling bath is developed to optimize the aggregation structure and electrical performance of organic semiconductors. The carrier mobility has increased by nearly 60% with this treatment, achieving a performance boost comparable to that of traditional annealing methods. This performance improvement is attributable to the denser aggregation structure and enhanced molecular ordering compared with those of as-cast semiconducting polymer films. Impressively, the entire process can be completed within a few minutes without additional vacuum or high-temperature conditions, offering an economical and efficient alternative to traditional methods. Furthermore, the enhancement effect and long-term stability of this treatment are validated across a wide range of organic semiconductors, positioning this green and versatile approach as a promising substitute for conventional post-treatment, thereby facilitating the development of next-generation sustainable electronics.
Organic semiconductors are promising candidates as active layers in flexible and biocompatible electronics owing to their solution processability and molecular design flexibility. However, it remains necessary to establish a green processing approach to acquire desirable electrical properties for scalable industrial applications. Here, a highly efficient and environmentally friendly post-treatment method using liquid nitrogen as a cooling bath is developed to optimize the aggregation structure and electrical performance of organic semiconductors. The carrier mobility has increased by nearly 60% with this treatment, achieving a performance boost comparable to that of traditional annealing methods. This performance improvement is attributable to the denser aggregation structure and enhanced molecular ordering compared with those of as-cast semiconducting polymer films. Impressively, the entire process can be completed within a few minutes without additional vacuum or high-temperature conditions, offering an economical and efficient alternative to traditional methods. Furthermore, the enhancement effect and long-term stability of this treatment are validated across a wide range of organic semiconductors, positioning this green and versatile approach as a promising substitute for conventional post-treatment, thereby facilitating the development of next-generation sustainable electronics.
2024, 35(12): 109921
doi: 10.1016/j.cclet.2024.109921
摘要:
The sequestration of 99Tc represents one of the most challenging tasks in nuclear waste decontamination. In the event of a radioactive waste leak, 99TcO4– (a main form of 99Tc) would spread into the groundwater, a scenario difficult to address with conventional anion exchange materials like resin and inorganic cationic sorbents. Herein, we present a nickel(Ⅱ) metal-organic framework (MOF), TNU-143, featuring 3D four-fold interpenetrated networks. TNU-143 exhibits efficient ReO4– (a nonradioactive analogue of 99TcO4–) removal with fast anion exchange kinetics (< 1 min), high sorption capacity (844 mg/g for ReO4–), and outstanding selectivity over common anions. More importantly, TNU-143 shows superior stability in alkaline solution and can remove 91.6% ReO4– from simulated alkaline high-level waste (HLW) streams with solid-liquid ratio of 40 g/L. The uptake mechanism is elucidated by the single-crystal structure of TNU-143(Re), showing that ReO4– anions are firmly coordinated to nickel cation to result in a 2D layered structures. Density functional theory (DFT) calculations confirm the transformation from TNU-143 to TNU-143(Re) is a thermodynamically favorable process. This work presents a new approach to the removal of ReO4–/99TcO4– from alkaline nulcear fuel using MOF sorbents.
The sequestration of 99Tc represents one of the most challenging tasks in nuclear waste decontamination. In the event of a radioactive waste leak, 99TcO4– (a main form of 99Tc) would spread into the groundwater, a scenario difficult to address with conventional anion exchange materials like resin and inorganic cationic sorbents. Herein, we present a nickel(Ⅱ) metal-organic framework (MOF), TNU-143, featuring 3D four-fold interpenetrated networks. TNU-143 exhibits efficient ReO4– (a nonradioactive analogue of 99TcO4–) removal with fast anion exchange kinetics (< 1 min), high sorption capacity (844 mg/g for ReO4–), and outstanding selectivity over common anions. More importantly, TNU-143 shows superior stability in alkaline solution and can remove 91.6% ReO4– from simulated alkaline high-level waste (HLW) streams with solid-liquid ratio of 40 g/L. The uptake mechanism is elucidated by the single-crystal structure of TNU-143(Re), showing that ReO4– anions are firmly coordinated to nickel cation to result in a 2D layered structures. Density functional theory (DFT) calculations confirm the transformation from TNU-143 to TNU-143(Re) is a thermodynamically favorable process. This work presents a new approach to the removal of ReO4–/99TcO4– from alkaline nulcear fuel using MOF sorbents.
2024, 35(12): 109932
doi: 10.1016/j.cclet.2024.109932
摘要:
Higher initial (de)hydrogenation temperature and sluggish kinetics are the main bottlenecks to develop Mg-based hydrogen storage alloys with high hydrogen capacity. One of the effective methods of solving these problems is introducing additives to enhance (de)hydrogenation kinetics and decrease particle sizes to lower (de)hydrogenation temperatures. In this work, Mg85-Ni10-La4.5-Y0.5 alloy doped with Cu@C nanoparticles is prepared, which could enhance (de)hydrogenation kinetics via introducing Cu nanoparticles as a catalyst and reduce the alloy particle sizes via acting as a grinding agent to lower (de)hydrogenation temperature. The results indicate the dehydrogenation temperature of the modified Mg85-Ni10-La4.5-Y0.5 composite could be decreased to 308.5 ℃, absorb 4.73 wt% H2 at 220 ℃ within 1 min and release 5.01 wt% H2 within 4 min at 300 ℃. Moreover, the capacity retention could be maintained around 98.8% after 10 cycles at 300 ℃, superior than those of Mg85-Ni10-La4.5-Y0.5 and milled-Mg85-Ni10-La4.5-Y0.5. DFT results and characterizations suggest that in-situ formed Mg2Cu could accelerate the dissociation of Mg-H bonds and the presence of amorphous carbon in Mg-Ni-La-Y-Cu system will further synergistically improve the (de)hydrogenation kinetics of Mg85-Ni10-La4.5-Y0.5. Reduced particle sizes under the aid of carbon frameworks also help introduce boundaries of the particles and shorten hydrogen diffusion pathways.
Higher initial (de)hydrogenation temperature and sluggish kinetics are the main bottlenecks to develop Mg-based hydrogen storage alloys with high hydrogen capacity. One of the effective methods of solving these problems is introducing additives to enhance (de)hydrogenation kinetics and decrease particle sizes to lower (de)hydrogenation temperatures. In this work, Mg85-Ni10-La4.5-Y0.5 alloy doped with Cu@C nanoparticles is prepared, which could enhance (de)hydrogenation kinetics via introducing Cu nanoparticles as a catalyst and reduce the alloy particle sizes via acting as a grinding agent to lower (de)hydrogenation temperature. The results indicate the dehydrogenation temperature of the modified Mg85-Ni10-La4.5-Y0.5 composite could be decreased to 308.5 ℃, absorb 4.73 wt% H2 at 220 ℃ within 1 min and release 5.01 wt% H2 within 4 min at 300 ℃. Moreover, the capacity retention could be maintained around 98.8% after 10 cycles at 300 ℃, superior than those of Mg85-Ni10-La4.5-Y0.5 and milled-Mg85-Ni10-La4.5-Y0.5. DFT results and characterizations suggest that in-situ formed Mg2Cu could accelerate the dissociation of Mg-H bonds and the presence of amorphous carbon in Mg-Ni-La-Y-Cu system will further synergistically improve the (de)hydrogenation kinetics of Mg85-Ni10-La4.5-Y0.5. Reduced particle sizes under the aid of carbon frameworks also help introduce boundaries of the particles and shorten hydrogen diffusion pathways.
2024, 35(12): 109990
doi: 10.1016/j.cclet.2024.109990
摘要:
Silicon based (Si-based) materials are considered to be the most promising anode materials for lithium-ion batteries (LIBs) due to their high specific capacity. However, the issues of poor electrical conductivity and volume expansion during cycling have not been effectively addressed. The optimum remedy is to select specific materials to establish an exceptional conductive and volume buffer structure to assist the Si materials to develop its excellent lithium storage properties. Here, Si particles were encapsulated into porous carbon fibers containing ultrafine Co particles (CP) to obtained Si-x@CP-y film. Among them, the addition of Si particles and the void structure was precisely regulated to achieve a superior electrode with a high specific capacity. Subsequently, the two-dimensional conductive material reduced graphene oxide (rGO) nanosheets were further incorporated to obtain Si-2@CP-2@rGO films with core@multi-shell structure. The final electrode was equipped with one-, two-, and three-dimensional electronic pathways to allow rapid electron transport, and featured with multi-layer buffer structure and reserved pores that could effectively mitigate volume changes. As expected, the free-standing Si-2@CP-2@rGO electrode delivered a high specific capacity of 1221.2 mAh/g after 100 cycles at 0.1 A/g in a half cell, and the assembled full cell showed 249.0 mAh/g after 200 cycles at 0.2 A/g, which fulfilled the lightweight requirement for new energy storage devices.
Silicon based (Si-based) materials are considered to be the most promising anode materials for lithium-ion batteries (LIBs) due to their high specific capacity. However, the issues of poor electrical conductivity and volume expansion during cycling have not been effectively addressed. The optimum remedy is to select specific materials to establish an exceptional conductive and volume buffer structure to assist the Si materials to develop its excellent lithium storage properties. Here, Si particles were encapsulated into porous carbon fibers containing ultrafine Co particles (CP) to obtained Si-x@CP-y film. Among them, the addition of Si particles and the void structure was precisely regulated to achieve a superior electrode with a high specific capacity. Subsequently, the two-dimensional conductive material reduced graphene oxide (rGO) nanosheets were further incorporated to obtain Si-2@CP-2@rGO films with core@multi-shell structure. The final electrode was equipped with one-, two-, and three-dimensional electronic pathways to allow rapid electron transport, and featured with multi-layer buffer structure and reserved pores that could effectively mitigate volume changes. As expected, the free-standing Si-2@CP-2@rGO electrode delivered a high specific capacity of 1221.2 mAh/g after 100 cycles at 0.1 A/g in a half cell, and the assembled full cell showed 249.0 mAh/g after 200 cycles at 0.2 A/g, which fulfilled the lightweight requirement for new energy storage devices.
2024, 35(12): 110014
doi: 10.1016/j.cclet.2024.110014
摘要:
The battery energy density can be improved by raising the operating voltage, however, which may lead to rapid capacity decay due to the continuous electrolyte decomposition and the thickening of electrode electrolyte interphases. To address these challenges, we proposed tripropyl phosphate (TPP) as an additive−regulating Li+ solvation structure to construct a stable LiF–rich electrode carbonate−based electrolyte interphases for sustaining 4.6 V Li||LiCoO2 batteries. This optimized interphases could help reduce the resistance and achieve better rate performance and cycling stability. As expected, the Li||LiCoO2 battery retained 79.4% capacity after 100 cycles at 0.5 C, while the Li||Li symmetric cell also kept a stable plating/stripping process over 450 h at the current density of 1.0 mA/cm2 with a deposited amount of 0.5 mAh/cm2.
The battery energy density can be improved by raising the operating voltage, however, which may lead to rapid capacity decay due to the continuous electrolyte decomposition and the thickening of electrode electrolyte interphases. To address these challenges, we proposed tripropyl phosphate (TPP) as an additive−regulating Li+ solvation structure to construct a stable LiF–rich electrode carbonate−based electrolyte interphases for sustaining 4.6 V Li||LiCoO2 batteries. This optimized interphases could help reduce the resistance and achieve better rate performance and cycling stability. As expected, the Li||LiCoO2 battery retained 79.4% capacity after 100 cycles at 0.5 C, while the Li||Li symmetric cell also kept a stable plating/stripping process over 450 h at the current density of 1.0 mA/cm2 with a deposited amount of 0.5 mAh/cm2.
2024, 35(12): 110018
doi: 10.1016/j.cclet.2024.110018
摘要:
Selenium (Se) plays an important role in the development and treatment of lung cancer, yet its specific mechanisms remain elusive. Lower Se level in serum was noted in lung cancer patients compared to normal controls. Therefore, developing effective therapeutic adjuvants containing Se might benefit the treatment of lung cancer patients. This study aimed to investigate the association between Se and the chemotherapeutic efficacy of lung cancer. Lentinan-modified selenium nanoparticles (LET-SeNPs) were created to develop and verify the effectiveness of Se containing adjuvant applied with pemetrexed on lung cancer cells. A synergistic effect was observed between LET-SeNPs and pemetrexed in vitro. The combination of LET-SeNPs and pemetrexed could induce reactive oxygen species overproduction, mitochondrial dysfunction and DNA damage, ultimately leading to cancer cell apoptosis. It is implied that LET-SeNPs might be a promising sensitizer to pemetrexed chemotherapy and could potentially enhance chemotherapy efficiency in non-small cell lung cancer.
Selenium (Se) plays an important role in the development and treatment of lung cancer, yet its specific mechanisms remain elusive. Lower Se level in serum was noted in lung cancer patients compared to normal controls. Therefore, developing effective therapeutic adjuvants containing Se might benefit the treatment of lung cancer patients. This study aimed to investigate the association between Se and the chemotherapeutic efficacy of lung cancer. Lentinan-modified selenium nanoparticles (LET-SeNPs) were created to develop and verify the effectiveness of Se containing adjuvant applied with pemetrexed on lung cancer cells. A synergistic effect was observed between LET-SeNPs and pemetrexed in vitro. The combination of LET-SeNPs and pemetrexed could induce reactive oxygen species overproduction, mitochondrial dysfunction and DNA damage, ultimately leading to cancer cell apoptosis. It is implied that LET-SeNPs might be a promising sensitizer to pemetrexed chemotherapy and could potentially enhance chemotherapy efficiency in non-small cell lung cancer.
2024, 35(12): 110020
doi: 10.1016/j.cclet.2024.110020
摘要:
As the main organ of gas exchange, the lungs are susceptible to various exogenous attacks, and pneumonia is one of the major inflammatory diseases that threaten human health. Generally, pneumonia is a disease that occurs in the alveoli and respiratory bronchioles induced by pathogens and further causes local and systemic inflammatory responses. The development of pneumonia can bring various serious complications, including lung abscess, sepsis, meningitis, brain damage and hearing loss. Over the past few decades, the mortality rate of pneumonia patients has remained high. While lung cancer is another lung-related malignant tumors worldwide, with a low 5 year survival rate. Exploring the mechanisms of their occurrence and interaction between pneumonia and lung cancer is a challenging and meaningful task. The abnormalities of lipid droplets (LDs) polarity have been found strongly accompanied by many diseases, especially cancer, inflammation, and metabolic diseases. However, their exact role is not yet clear. Hence, it is significant to develop a novel detection method to observe the polarity changes of LDs, which would help to reveal the development process of diseases pneumonia and lung cancer. In this work, a new polarity-sensitive LDs-targeted near-infrared probe BFZ up to 712 nm was designed, according to the intramolecular charge transfer mechanism, which displayed high fluorescence intensity in low polarity while showing decreased fluorescence intensity in high-polarity conditions with a significant redshift. The BFZ was successfully applied to the change of LDs polarity in lipopolysaccharide (LPS)-stimulated A549 cells, and a mouse model of lung inflammation. It also tells the polarity differences between normal and tumor cells and between normal and tumor tissues. Moreover, the correlations between pneumonia and polarity changes were observed through the imaging experiments, which may provide an insightful method for the early diagnosis of pneumonia and lung cancer.
As the main organ of gas exchange, the lungs are susceptible to various exogenous attacks, and pneumonia is one of the major inflammatory diseases that threaten human health. Generally, pneumonia is a disease that occurs in the alveoli and respiratory bronchioles induced by pathogens and further causes local and systemic inflammatory responses. The development of pneumonia can bring various serious complications, including lung abscess, sepsis, meningitis, brain damage and hearing loss. Over the past few decades, the mortality rate of pneumonia patients has remained high. While lung cancer is another lung-related malignant tumors worldwide, with a low 5 year survival rate. Exploring the mechanisms of their occurrence and interaction between pneumonia and lung cancer is a challenging and meaningful task. The abnormalities of lipid droplets (LDs) polarity have been found strongly accompanied by many diseases, especially cancer, inflammation, and metabolic diseases. However, their exact role is not yet clear. Hence, it is significant to develop a novel detection method to observe the polarity changes of LDs, which would help to reveal the development process of diseases pneumonia and lung cancer. In this work, a new polarity-sensitive LDs-targeted near-infrared probe BFZ up to 712 nm was designed, according to the intramolecular charge transfer mechanism, which displayed high fluorescence intensity in low polarity while showing decreased fluorescence intensity in high-polarity conditions with a significant redshift. The BFZ was successfully applied to the change of LDs polarity in lipopolysaccharide (LPS)-stimulated A549 cells, and a mouse model of lung inflammation. It also tells the polarity differences between normal and tumor cells and between normal and tumor tissues. Moreover, the correlations between pneumonia and polarity changes were observed through the imaging experiments, which may provide an insightful method for the early diagnosis of pneumonia and lung cancer.
2024, 35(12): 110022
doi: 10.1016/j.cclet.2024.110022
摘要:
In recent years, host-guest interactions of macrocycles have emerged as a promising approach to effectively enhance pure organic room-temperature phosphorescence by inhibiting the nonradiative relaxation while isolating the effects of oxygen and water molecules. In this work, a supramolecular assembly Q[8]-BCPI was constructed by 6-bromoisoquinoline derivative (BCPI) and cucurbit[8]uril (Q[8]). The assembly produced intense green room temperature phosphorescence (RTP) emission and enabled supramolecular recognition and detection of l-tryptophan (L-Trp) and l-tyrosine (L-Tyr). Moreover, the Q[8]-BCPI assembly showed good biocompatibility and low biotoxicity, and had a good staining effect on HeLa cells.
In recent years, host-guest interactions of macrocycles have emerged as a promising approach to effectively enhance pure organic room-temperature phosphorescence by inhibiting the nonradiative relaxation while isolating the effects of oxygen and water molecules. In this work, a supramolecular assembly Q[8]-BCPI was constructed by 6-bromoisoquinoline derivative (BCPI) and cucurbit[8]uril (Q[8]). The assembly produced intense green room temperature phosphorescence (RTP) emission and enabled supramolecular recognition and detection of l-tryptophan (L-Trp) and l-tyrosine (L-Tyr). Moreover, the Q[8]-BCPI assembly showed good biocompatibility and low biotoxicity, and had a good staining effect on HeLa cells.
2024, 35(12): 110025
doi: 10.1016/j.cclet.2024.110025
摘要:
Dendrite growth of zinc (Zn) anode at high current density severely affects the fast-charging performance of aqueous zinc metal batteries (AZMBs). While interfacial modification strategies can optimize Zn performance, challenges such as complicated preparation processes, excessive layer thicknesses, and high voltage hysteresis should be addressed. Herein, we utilize a cost-effective liquid fluorosiloxane, (3,3,3-trifluoropropyl)trimethoxysilane, for scalable modification of Zn foil via drop-casting at room temperature, resulting in an ultra-thin interphase layer of only 20 nm. The Si-O-Zn bonds formed between fluorosiloxane and Zn ensure interfacial stability, and the Si-O-Si bonds between fluorosiloxane molecules help to homogenize the electric field distribution. Additionally, the abundant highly electronegative fluorine atoms on the anode surface act as zincophilic sites, promoting the uniform deposition of Zn2+. Thus, the modified Zn foil (SiFO-Zn) exhibits excellent dendrite suppression, reduced voltage hysteresis, and prolonged cycle life at ultra-high current density (40 mA/cm2), achieving a cumulative areal capacity of 12.9 Ah/cm2. Further, the full cell assembled with 10 µm-thick SiFO-Zn anode and MnO2 cathode achieves 2600 cycles at 5 A/g with minimal capacity degradation, and a large-size (22.5 cm−2) pouch cell powers the light-emitting diode even after reverse bending, demonstrating the potential of AZMBs for fast-charging flexible devices.
Dendrite growth of zinc (Zn) anode at high current density severely affects the fast-charging performance of aqueous zinc metal batteries (AZMBs). While interfacial modification strategies can optimize Zn performance, challenges such as complicated preparation processes, excessive layer thicknesses, and high voltage hysteresis should be addressed. Herein, we utilize a cost-effective liquid fluorosiloxane, (3,3,3-trifluoropropyl)trimethoxysilane, for scalable modification of Zn foil via drop-casting at room temperature, resulting in an ultra-thin interphase layer of only 20 nm. The Si-O-Zn bonds formed between fluorosiloxane and Zn ensure interfacial stability, and the Si-O-Si bonds between fluorosiloxane molecules help to homogenize the electric field distribution. Additionally, the abundant highly electronegative fluorine atoms on the anode surface act as zincophilic sites, promoting the uniform deposition of Zn2+. Thus, the modified Zn foil (SiFO-Zn) exhibits excellent dendrite suppression, reduced voltage hysteresis, and prolonged cycle life at ultra-high current density (40 mA/cm2), achieving a cumulative areal capacity of 12.9 Ah/cm2. Further, the full cell assembled with 10 µm-thick SiFO-Zn anode and MnO2 cathode achieves 2600 cycles at 5 A/g with minimal capacity degradation, and a large-size (22.5 cm−2) pouch cell powers the light-emitting diode even after reverse bending, demonstrating the potential of AZMBs for fast-charging flexible devices.
2024, 35(12): 110030
doi: 10.1016/j.cclet.2024.110030
摘要:
Artificial synapses are essential building blocks for neuromorphic electronics. Here, solid polymer electrolyte-gated artificial synapses (EGASs) were fabricated using ITO fibers as channels, which possess an ultra-high sensitivity of 5 mV and a long-term memory time exceeding 3 min. Notably, digitally printed ITO-fiber arrays exhibit an ultra-high transmittance of approximately 99.67%. Biological synaptic plasticity, such as excitatory postsynaptic current, paired-pulse facilitation, spike frequency-dependent plasticity, and synaptic potentiation and depression, were successfully mimicked using the EGASs. Based on the synaptic properties of the EGASs, an artificial neural network was constructed to perform supervised learning using the Fashion-MNIST dataset, achieving high pattern recognition rate (82.39%) due to the linear and symmetric synaptic plasticity. This work provides insights into high-sensitivity artificial synapses for future neuromorphic computing.
Artificial synapses are essential building blocks for neuromorphic electronics. Here, solid polymer electrolyte-gated artificial synapses (EGASs) were fabricated using ITO fibers as channels, which possess an ultra-high sensitivity of 5 mV and a long-term memory time exceeding 3 min. Notably, digitally printed ITO-fiber arrays exhibit an ultra-high transmittance of approximately 99.67%. Biological synaptic plasticity, such as excitatory postsynaptic current, paired-pulse facilitation, spike frequency-dependent plasticity, and synaptic potentiation and depression, were successfully mimicked using the EGASs. Based on the synaptic properties of the EGASs, an artificial neural network was constructed to perform supervised learning using the Fashion-MNIST dataset, achieving high pattern recognition rate (82.39%) due to the linear and symmetric synaptic plasticity. This work provides insights into high-sensitivity artificial synapses for future neuromorphic computing.
2024, 35(12): 110031
doi: 10.1016/j.cclet.2024.110031
摘要:
Carbon-based materials with single-atom (SA) transition metals coordinated with nitrogen (M-Nx) have attracted extensive attention due to their superior electrochemical CO2 reduction reaction (CO2RR) performance. However, the uncontrolled recombination of metal atoms during the typical high-temperature synthesis process in M-Nx causes deterioration of CO2RR activity. Herein, by using electrospinning, we propose a novel strategy for constructing a highly active and selective SA Fe-modified N-doped porous carbon fiber membrane catalyst (Fe-N-CF). This carbon membrane has an interconnected three-dimensional structure and a hierarchical porous structure, which can not only confine Fe to be single atom as active centers, but also provide a diffusion channel for CO2 molecules. Relying on its special structure and stable mechanical properties, Fe-N-CF is directly used for CO2RR, which presents an excellent selectivity (CO Faradaic efficiency of 97%) and stability. DFT calculations reveals that the synthesized Fe-N4-C can significantly reduce the energy barrier for intermediate COOH* formation and CO desorption. This work highlights the specific advantages of using electrospinning method to prepare the optimal SA catalysts.
Carbon-based materials with single-atom (SA) transition metals coordinated with nitrogen (M-Nx) have attracted extensive attention due to their superior electrochemical CO2 reduction reaction (CO2RR) performance. However, the uncontrolled recombination of metal atoms during the typical high-temperature synthesis process in M-Nx causes deterioration of CO2RR activity. Herein, by using electrospinning, we propose a novel strategy for constructing a highly active and selective SA Fe-modified N-doped porous carbon fiber membrane catalyst (Fe-N-CF). This carbon membrane has an interconnected three-dimensional structure and a hierarchical porous structure, which can not only confine Fe to be single atom as active centers, but also provide a diffusion channel for CO2 molecules. Relying on its special structure and stable mechanical properties, Fe-N-CF is directly used for CO2RR, which presents an excellent selectivity (CO Faradaic efficiency of 97%) and stability. DFT calculations reveals that the synthesized Fe-N4-C can significantly reduce the energy barrier for intermediate COOH* formation and CO desorption. This work highlights the specific advantages of using electrospinning method to prepare the optimal SA catalysts.
2024, 35(12): 110068
doi: 10.1016/j.cclet.2024.110068
摘要:
The rational design of high-performance bifunctional electrocatalysts for overall water splitting (OWS) is the key to popularize hydrogen production technology. The active metal oxyhydroxide (MOOH) formed after surface self-reconfiguration of transition metal sulfide (TMS) electrocatalyst is often regarded as the "actual catalyst" in oxygen evolution reaction (OER). Herein, an Fe doped CoS2/MoS2 hollow TMS polyhedron (Fe-CoS2/MoS2) with rich Mott-Schottky heterojunction is reported and directly utilized as an OWS electrocatalyst. The spontaneous built-in electric field (BEF) at the heterogeneous interface regulates the electronic structure and D-band center of the catalyst. More importantly, the “TMS-MOOH” core-shell structure obtained in the KOH electrolyte shows enhanced OER properties. And the introduction of Fe ions activates the inert basal plane of MoS2, which greatly steps up the performance of HER. Hence, the preferable Fe-CoS2/MoS2–400 presents superior OER activity (η10 = 178 mV, η100 = 375 mV), HER activity (η10 = 92 mV) and ultra-high stability for 50 h. This work has deeply explored the catalytic mechanism of TMS and provided a new idea for the construction of efficient bifunctional catalysts.
The rational design of high-performance bifunctional electrocatalysts for overall water splitting (OWS) is the key to popularize hydrogen production technology. The active metal oxyhydroxide (MOOH) formed after surface self-reconfiguration of transition metal sulfide (TMS) electrocatalyst is often regarded as the "actual catalyst" in oxygen evolution reaction (OER). Herein, an Fe doped CoS2/MoS2 hollow TMS polyhedron (Fe-CoS2/MoS2) with rich Mott-Schottky heterojunction is reported and directly utilized as an OWS electrocatalyst. The spontaneous built-in electric field (BEF) at the heterogeneous interface regulates the electronic structure and D-band center of the catalyst. More importantly, the “TMS-MOOH” core-shell structure obtained in the KOH electrolyte shows enhanced OER properties. And the introduction of Fe ions activates the inert basal plane of MoS2, which greatly steps up the performance of HER. Hence, the preferable Fe-CoS2/MoS2–400 presents superior OER activity (η10 = 178 mV, η100 = 375 mV), HER activity (η10 = 92 mV) and ultra-high stability for 50 h. This work has deeply explored the catalytic mechanism of TMS and provided a new idea for the construction of efficient bifunctional catalysts.
2024, 35(12): 110074
doi: 10.1016/j.cclet.2024.110074
摘要:
Two o-carborane based tetraphenylethene (TPE) cationic cyclophanes O1·4PF6 and O2·4PF6 were synthesized through an SN2 reaction. Their structures were confirmed both possessing Z-shaped cavities in single crystal analysis. The optical properties of these macrocycles were systematically investigated using UV–vis spectroscopy and fluorescence techniques. It is worth noting that the introduction of a methoxy group to the TPE unit enables the synthesis of a near-infrared-emitting macrocycle O2·4PF6. The recognition behaviors of these two macrocycles towards nucleotides were investigated using various techniques including fluorescence titration, UV–vis titration, and transmission electron microscopy (TEM). Interestingly, these cyclophanes exhibited aggregation-induced emission (AIE) effects in water or under the induction of nucleotides.
Two o-carborane based tetraphenylethene (TPE) cationic cyclophanes O1·4PF6 and O2·4PF6 were synthesized through an SN2 reaction. Their structures were confirmed both possessing Z-shaped cavities in single crystal analysis. The optical properties of these macrocycles were systematically investigated using UV–vis spectroscopy and fluorescence techniques. It is worth noting that the introduction of a methoxy group to the TPE unit enables the synthesis of a near-infrared-emitting macrocycle O2·4PF6. The recognition behaviors of these two macrocycles towards nucleotides were investigated using various techniques including fluorescence titration, UV–vis titration, and transmission electron microscopy (TEM). Interestingly, these cyclophanes exhibited aggregation-induced emission (AIE) effects in water or under the induction of nucleotides.
2024, 35(12): 110104
doi: 10.1016/j.cclet.2024.110104
摘要:
The carboxylation of readily available organo halides with CO2 represents a practical strategy to afford valuable carboxylic acids. However, efficient carboxylation of inexpensive unactivated alkyl chlorides is still underdeveloped. Herein, we report the electro-reductive carboxylation of CCl bonds in unactivated chlorides and polyvinyl chloride with CO2. A variety of alkyl carboxylic acids are obtained in moderate to good yields under mild conditions with high chemoselectivity. Importantly, the utility of this electro-reductive carboxylation is demonstrated with great potential in polyvinyl chloride (PVC) upgrading, which could convert discarded PVC from hydrophobic to hydrophilic functional products. Mechanistic experiments support the successive single electron reduction of unactivated chlorides to generate alkyl anion species and following nucleophilic attack on CO2 to give desired products.
The carboxylation of readily available organo halides with CO2 represents a practical strategy to afford valuable carboxylic acids. However, efficient carboxylation of inexpensive unactivated alkyl chlorides is still underdeveloped. Herein, we report the electro-reductive carboxylation of CCl bonds in unactivated chlorides and polyvinyl chloride with CO2. A variety of alkyl carboxylic acids are obtained in moderate to good yields under mild conditions with high chemoselectivity. Importantly, the utility of this electro-reductive carboxylation is demonstrated with great potential in polyvinyl chloride (PVC) upgrading, which could convert discarded PVC from hydrophobic to hydrophilic functional products. Mechanistic experiments support the successive single electron reduction of unactivated chlorides to generate alkyl anion species and following nucleophilic attack on CO2 to give desired products.
2024, 35(12): 110176
doi: 10.1016/j.cclet.2024.110176
摘要:
Constructing synergistic active sites and optimizing the cooperative adsorption energies for hydrogen and hydroxyl based intermediates are two essential strategies to improve the sluggish kinetics of hydrogen evolution reaction (HER) in alkaline medium. However, it is still in its infancy to simultaneously achieve these goals, especially for designing a well-defined carrier with multiple hydroxyl adsorption sites. Herein, the Ni(HCO3)2 nanoplates (NHC) with horizontal interfaces sites of Ni-terminated NiO, NiOOH, NiCOO, and Ni(OH)2 were employed as the hydroxyl adsorption active sites, which could anchor Pt particles with hydrogen adsorption active sites, constructing the synergistic active sites (NHC-Pt) for HER catalysis. Evidenced by X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS), the NHC could affect the chemical state and electronic structure of Pt particles by forming bond of Pt-O which could reduce the reaction energy barriers, facilitate the adsorption of hydrogen and establishment of H–H bond. Furthermore, density functional theory (DFT) theoretical calculation revealed that the related process of hydroxide was the rate-determining step. It is demonstrated the hydroxyl group presents the lowest energy barrier for desorption in the process of HER when the gradual desorption process could be described as a migration from Ni(HCO3)2·OH directly or via other Ni-based systems formed after partial decomposition of nickel hydrocarbonate to Ni(OH)2···OH with following desorption. As a result, the NHC-Pt hierarchical nanostructure demonstrated superior activity towards HER in a pH-universal solution. This enhancement can be attributed to the optimized electronic structure of Pt, the migration of hydroxyl group on NHC substrates, and the synergistic effects between the NHC carrier and Pt particles.
Constructing synergistic active sites and optimizing the cooperative adsorption energies for hydrogen and hydroxyl based intermediates are two essential strategies to improve the sluggish kinetics of hydrogen evolution reaction (HER) in alkaline medium. However, it is still in its infancy to simultaneously achieve these goals, especially for designing a well-defined carrier with multiple hydroxyl adsorption sites. Herein, the Ni(HCO3)2 nanoplates (NHC) with horizontal interfaces sites of Ni-terminated NiO, NiOOH, NiCOO, and Ni(OH)2 were employed as the hydroxyl adsorption active sites, which could anchor Pt particles with hydrogen adsorption active sites, constructing the synergistic active sites (NHC-Pt) for HER catalysis. Evidenced by X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS), the NHC could affect the chemical state and electronic structure of Pt particles by forming bond of Pt-O which could reduce the reaction energy barriers, facilitate the adsorption of hydrogen and establishment of H–H bond. Furthermore, density functional theory (DFT) theoretical calculation revealed that the related process of hydroxide was the rate-determining step. It is demonstrated the hydroxyl group presents the lowest energy barrier for desorption in the process of HER when the gradual desorption process could be described as a migration from Ni(HCO3)2·OH directly or via other Ni-based systems formed after partial decomposition of nickel hydrocarbonate to Ni(OH)2···OH with following desorption. As a result, the NHC-Pt hierarchical nanostructure demonstrated superior activity towards HER in a pH-universal solution. This enhancement can be attributed to the optimized electronic structure of Pt, the migration of hydroxyl group on NHC substrates, and the synergistic effects between the NHC carrier and Pt particles.
2024, 35(12): 110274
doi: 10.1016/j.cclet.2024.110274
摘要:
A dimeric Y(Ⅲ)-containing antimonotungstate [Y4(H2O)8(mal)2(OAc)O(Sb2WⅤ2WⅥ19O72)2]21− (Y4mal2, H3mal = DL-malic acid), resembling a “handshake” configuration, was synthesized and characterized. The polyanion of Y4mal2 consists of two Dawson-derived {Y2Sb2W21} moieties that are further linked by two mal ligands and one μ2-bridging acetate to form an asymmetric polyanion. Notably, the chiral configuration induced by the D- or L-configuration of the mal ligand results in both {Y2Sb2W21} moieties within one polyanion exhibiting identical chirality, leading to the racemate crystallization of Y4mal2. Moreover, Y4mal2 exhibits excellent Lewis acid catalytic activity for environmentally friendly synthesis of imidazoles.
A dimeric Y(Ⅲ)-containing antimonotungstate [Y4(H2O)8(mal)2(OAc)O(Sb2WⅤ2WⅥ19O72)2]21− (Y4mal2, H3mal = DL-malic acid), resembling a “handshake” configuration, was synthesized and characterized. The polyanion of Y4mal2 consists of two Dawson-derived {Y2Sb2W21} moieties that are further linked by two mal ligands and one μ2-bridging acetate to form an asymmetric polyanion. Notably, the chiral configuration induced by the D- or L-configuration of the mal ligand results in both {Y2Sb2W21} moieties within one polyanion exhibiting identical chirality, leading to the racemate crystallization of Y4mal2. Moreover, Y4mal2 exhibits excellent Lewis acid catalytic activity for environmentally friendly synthesis of imidazoles.
2024, 35(12): 110283
doi: 10.1016/j.cclet.2024.110283
摘要:
Diabetic pressure ulcers (DPU) are non-healing due to vascular dysfunction and bacterial infection. Early intervention can delay ulcer progression, such as preventing the formation of full-thickness skin defects. Local administration of deferoxamine (DFO) at wound sites has been shown to promote neovascularization and enhance wound healing. However, since DPU skin wounds are not full-thickness defects and DFO is hydrophilic, enhancing its transdermal delivery is crucial for effective treatment. Photothermal ablation of stratum corneum, generated by copper sulfide nanoparticles (CuS NPs) under near-infrared (NIR) light irradiation, is a promising method to improve transdermal drug delivery. Meanwhile, CuS NPs-induced photothermal therapy offers excellent antibacterial performance. In this study, DFO and CuS NPs were incorporated into a matrix metalloproteinase (MMPs)-sensitive hydrogel. This hydrogel promotes cell adhesion and is degraded by cell-secreted MMPs, a process crucial for the controlled release of encapsulated DFO and CuS NPs. Under NIR irradiation, the stratum corneum is disrupted, facilitating transdermal DFO delivery and simultaneously eliminating infected bacteria. As a result, the essential requirements for DPU treatment, "facilitating transdermal DFO delivery, promoting angiogenesis, and inhibiting bacterial infection", were achieved simultaneously.
Diabetic pressure ulcers (DPU) are non-healing due to vascular dysfunction and bacterial infection. Early intervention can delay ulcer progression, such as preventing the formation of full-thickness skin defects. Local administration of deferoxamine (DFO) at wound sites has been shown to promote neovascularization and enhance wound healing. However, since DPU skin wounds are not full-thickness defects and DFO is hydrophilic, enhancing its transdermal delivery is crucial for effective treatment. Photothermal ablation of stratum corneum, generated by copper sulfide nanoparticles (CuS NPs) under near-infrared (NIR) light irradiation, is a promising method to improve transdermal drug delivery. Meanwhile, CuS NPs-induced photothermal therapy offers excellent antibacterial performance. In this study, DFO and CuS NPs were incorporated into a matrix metalloproteinase (MMPs)-sensitive hydrogel. This hydrogel promotes cell adhesion and is degraded by cell-secreted MMPs, a process crucial for the controlled release of encapsulated DFO and CuS NPs. Under NIR irradiation, the stratum corneum is disrupted, facilitating transdermal DFO delivery and simultaneously eliminating infected bacteria. As a result, the essential requirements for DPU treatment, "facilitating transdermal DFO delivery, promoting angiogenesis, and inhibiting bacterial infection", were achieved simultaneously.
2024, 35(12): 110355
doi: 10.1016/j.cclet.2024.110355
摘要:
Under "green architecture" principles, electrochromic smart windows are employed to adjust optical transmittance and indoor temperature, yet their high costs limit the wide application. Here, an electrochromic window is driven by a redox flow battery (RFB), where TOC and deposition layers are no longer needed. The transmittance of the electrochromic window is modulated by the state of oxidation (SOC) of aqueous posolyte Fe(phen)3Cl2, which is coupled with BTMAP-Vi negolyte in RFB. Under optimized conditions, average CE, VE, and EE reach 93.25%, 92.61%, and 86.35% for RFB with a capacity fading rate of 1.57% per cycle. 88.66% optical modulation and 9.36 cm2/C coloration efficiency are achieved in the electrochromic process, and 72.34% optical modulation is maintained after 12000 s. Essentially, the indoor temperature declines 3 ℃ for posolyte with 100% SOC when compared with the control experiment using circulating water for a model house. This means minimum electricity of 0.0185 kWh is saved when using an air conditioner to cool a 100 m3 house, which corresponds to declined CO2 emission (COE) of 0.0185 kg. This work provides a novel and cost-efficient strategy for modulating indoor comfort via electrochromic windows driven by RFB.
Under "green architecture" principles, electrochromic smart windows are employed to adjust optical transmittance and indoor temperature, yet their high costs limit the wide application. Here, an electrochromic window is driven by a redox flow battery (RFB), where TOC and deposition layers are no longer needed. The transmittance of the electrochromic window is modulated by the state of oxidation (SOC) of aqueous posolyte Fe(phen)3Cl2, which is coupled with BTMAP-Vi negolyte in RFB. Under optimized conditions, average CE, VE, and EE reach 93.25%, 92.61%, and 86.35% for RFB with a capacity fading rate of 1.57% per cycle. 88.66% optical modulation and 9.36 cm2/C coloration efficiency are achieved in the electrochromic process, and 72.34% optical modulation is maintained after 12000 s. Essentially, the indoor temperature declines 3 ℃ for posolyte with 100% SOC when compared with the control experiment using circulating water for a model house. This means minimum electricity of 0.0185 kWh is saved when using an air conditioner to cool a 100 m3 house, which corresponds to declined CO2 emission (COE) of 0.0185 kg. This work provides a novel and cost-efficient strategy for modulating indoor comfort via electrochromic windows driven by RFB.
2024, 35(12): 109598
doi: 10.1016/j.cclet.2024.109598
摘要:
Dopamine, a pivotal excitatory neurotransmitter, plays a crucial role in metabolic, cardiovascular, renal, central nervous, and endocrine systems. Abnormal dopamine within the human body can cause various diseases. Therefore, the precise quantification of dopamine levels, both in vivo and in vitro, holds paramount significance for clinical applications and physiological investigations. Carbon dots (CDs) exhibit a plethora of remarkable properties, including a substantial specific surface area, robust electrical conductivity, commendable biocompatibility, minimal toxicity, and high photostability. Considering these unique characteristics, CDs demonstrate substantial potential for fluorescent sensors, colorimetric sensors, and electrochemical sensors for dopamine detection. This review systematically examined the challenges and prospects for the utilization of CDs-based fluorescent sensors, electrochemical biosensors, and colorimetric sensors for monitoring dopamine levels in recent years. These findings unveil promising avenues for further advancements in the field of dopamine detection.
Dopamine, a pivotal excitatory neurotransmitter, plays a crucial role in metabolic, cardiovascular, renal, central nervous, and endocrine systems. Abnormal dopamine within the human body can cause various diseases. Therefore, the precise quantification of dopamine levels, both in vivo and in vitro, holds paramount significance for clinical applications and physiological investigations. Carbon dots (CDs) exhibit a plethora of remarkable properties, including a substantial specific surface area, robust electrical conductivity, commendable biocompatibility, minimal toxicity, and high photostability. Considering these unique characteristics, CDs demonstrate substantial potential for fluorescent sensors, colorimetric sensors, and electrochemical sensors for dopamine detection. This review systematically examined the challenges and prospects for the utilization of CDs-based fluorescent sensors, electrochemical biosensors, and colorimetric sensors for monitoring dopamine levels in recent years. These findings unveil promising avenues for further advancements in the field of dopamine detection.
Mechanisms and applications: Cargos transport to basolateral membranes in polarized epithelial cells
2024, 35(12): 109673
doi: 10.1016/j.cclet.2024.109673
摘要:
In polarized cells, the differential distribution of proteins results in the formation of apical and basolateral membranes. The basolateral membrane contacts basal lamina and mediates cell-to-cell communication, which is crucial for maintaining homeostasis and enabling drug absorption. To establish and maintain the basolateral domain, intricate mechanisms are necessary to ensure the proper sorting and transportation of molecules. Sorting signals play a crucial role in regulating the distributions of basolateral proteins, determining their trafficking route and final residence. Newly synthesized proteins can be segregated into different carrier vesicles at either trans-Golgi network (TGN) or endosomes. Additionally, understanding basolateral transport in polarized epithelial cells is important for predicting diseases and delivering drugs. This review provides a summary of recent advancements in the mechanisms and applications of basolateral sorting and trafficking.
In polarized cells, the differential distribution of proteins results in the formation of apical and basolateral membranes. The basolateral membrane contacts basal lamina and mediates cell-to-cell communication, which is crucial for maintaining homeostasis and enabling drug absorption. To establish and maintain the basolateral domain, intricate mechanisms are necessary to ensure the proper sorting and transportation of molecules. Sorting signals play a crucial role in regulating the distributions of basolateral proteins, determining their trafficking route and final residence. Newly synthesized proteins can be segregated into different carrier vesicles at either trans-Golgi network (TGN) or endosomes. Additionally, understanding basolateral transport in polarized epithelial cells is important for predicting diseases and delivering drugs. This review provides a summary of recent advancements in the mechanisms and applications of basolateral sorting and trafficking.
2024, 35(12): 109758
doi: 10.1016/j.cclet.2024.109758
摘要:
Zeolites are crystalline porous materials that are used in the chemical industry for adsorption, separation and catalytic reactions. Chiral zeolites have shown promise in enantioselective adsorption and catalytic organic reactions, attracting significant research interest. Recent advances have been made in the rational design, computational prediction and hydrothermal synthesis of using chiral organic structure-directing agents. Additionally, newly developed electron microscopic techniques have been utilized to analyze the structure and determine absolute configuration. The following review aims to provide an overview of the development history of chiral zeolites, examine several prominent chiral zeolite structures discovered so far, discuss the recent progress in characterization methods and explore their potential applications.
Zeolites are crystalline porous materials that are used in the chemical industry for adsorption, separation and catalytic reactions. Chiral zeolites have shown promise in enantioselective adsorption and catalytic organic reactions, attracting significant research interest. Recent advances have been made in the rational design, computational prediction and hydrothermal synthesis of using chiral organic structure-directing agents. Additionally, newly developed electron microscopic techniques have been utilized to analyze the structure and determine absolute configuration. The following review aims to provide an overview of the development history of chiral zeolites, examine several prominent chiral zeolite structures discovered so far, discuss the recent progress in characterization methods and explore their potential applications.
2024, 35(12): 109787
doi: 10.1016/j.cclet.2024.109787
摘要:
The homochiral compounds play an important role in human health and pharmaceutical industry. Currently, the chromatographic enantioseparation has become one of the most effective and practical approach to obtain pure enantiomers. Herein, the exploration of advanced materials, using as chromatographic chiral stationary phases for racemic separation, has attracted great attention. Thanks to their high enantioselectivity and controllable synthesis, the emerging chiral metal-organic frameworks (CMOFs) have been widely studied as the stationary phase in chromatographic technology. In this review, we will summarize the principles of synthetic strategies and mechanism of chiral microenvironment. In particular, the recent progress and research hotspot of CMOFs regarding as the chiral stationary phases in gas chromatography (GC), high-performance liquid chromatography (HPLC), and capillary electrochromatography (CEC), are elucidated systematically according to the published work. Last but not the least, we also highlight the challenges and perspectives of rational design of CMOFs, as well as their corresponding racemic separation. We envision that the review will provide a further understanding of CMOFs and facilitate the development of chromatographic enantioselective applications.
The homochiral compounds play an important role in human health and pharmaceutical industry. Currently, the chromatographic enantioseparation has become one of the most effective and practical approach to obtain pure enantiomers. Herein, the exploration of advanced materials, using as chromatographic chiral stationary phases for racemic separation, has attracted great attention. Thanks to their high enantioselectivity and controllable synthesis, the emerging chiral metal-organic frameworks (CMOFs) have been widely studied as the stationary phase in chromatographic technology. In this review, we will summarize the principles of synthetic strategies and mechanism of chiral microenvironment. In particular, the recent progress and research hotspot of CMOFs regarding as the chiral stationary phases in gas chromatography (GC), high-performance liquid chromatography (HPLC), and capillary electrochromatography (CEC), are elucidated systematically according to the published work. Last but not the least, we also highlight the challenges and perspectives of rational design of CMOFs, as well as their corresponding racemic separation. We envision that the review will provide a further understanding of CMOFs and facilitate the development of chromatographic enantioselective applications.
2024, 35(12): 110055
doi: 10.1016/j.cclet.2024.110055
摘要:
Surface chemistry focuses on the investigation of the adsorption, migration, assembly, activation, reaction, and desorption of atoms and molecules at surfaces. Surface chemistry plays the pivotal roles in both fundamental science and applied technology. This review will summarize the recent progresses on surface assembly, synthesis and catalysis investigated mainly by scanning tunneling microscopy and atomic force microscopy. Surface assemblies of water and small biomolecules, construction of Sierpiński triangles and surface chirality are summarized. On-surface synthesis of conjugated carbo- and heterocycles and other kinds of carbon nanostructures are surveyed. Surface model catalysis, including single-atom catalysis and electrochemical catalysis, are discussed at the single-atom level.
Surface chemistry focuses on the investigation of the adsorption, migration, assembly, activation, reaction, and desorption of atoms and molecules at surfaces. Surface chemistry plays the pivotal roles in both fundamental science and applied technology. This review will summarize the recent progresses on surface assembly, synthesis and catalysis investigated mainly by scanning tunneling microscopy and atomic force microscopy. Surface assemblies of water and small biomolecules, construction of Sierpiński triangles and surface chirality are summarized. On-surface synthesis of conjugated carbo- and heterocycles and other kinds of carbon nanostructures are surveyed. Surface model catalysis, including single-atom catalysis and electrochemical catalysis, are discussed at the single-atom level.
2024, 35(12): 110125
doi: 10.1016/j.cclet.2024.110125
摘要:
Photocatalytic hydrogen peroxide (H2O2) synthesis, driven by solar energy, offers a sustainable and cleaner alternative for producing green H2O2 from water and oxygen. 2D photocatalysts have emerged as powerful materials for this purpose due to their unique physiochemical properties such as a flexible planar structure and large surface area. This review provides a comprehensive overview of the latest advances in 2D photocatalytic materials employed in H2O2 synthesis, including metal oxides, metal chalcogenides, bismuth-based materials, graphitic carbon nitrides (g-C3N4), metal−organic frameworks (MOFs), and covalent organic frameworks (COFs). Beginning with an extensive introduction to possible reaction routes for photocatalytic H2O2 synthesis, we summarize the common methods for H2O2 detection, crucial for obtaining reliable results in H2O2 studies. Additionally, we highlight molecular-level modification strategies for 2D photocatalysts, such as surface modification, ion doping, defect engineering, and heterojunction construction, which promote high-efficiency solar-to-chemical conversion for sustainable H2O2 photosynthesis. Furthermore, we discuss key issues and provide perspective outlooks for the efficient and sustainable generation of H2O2 in scale-up industrial production. This review offers in-depth insights into different reaction pathways of H2O2 synthesis and provides design principles for 2D photocatalysts to enhance H2O2 production, guiding the development of efficient photocatalysts for H2O2 synthesis.
Photocatalytic hydrogen peroxide (H2O2) synthesis, driven by solar energy, offers a sustainable and cleaner alternative for producing green H2O2 from water and oxygen. 2D photocatalysts have emerged as powerful materials for this purpose due to their unique physiochemical properties such as a flexible planar structure and large surface area. This review provides a comprehensive overview of the latest advances in 2D photocatalytic materials employed in H2O2 synthesis, including metal oxides, metal chalcogenides, bismuth-based materials, graphitic carbon nitrides (g-C3N4), metal−organic frameworks (MOFs), and covalent organic frameworks (COFs). Beginning with an extensive introduction to possible reaction routes for photocatalytic H2O2 synthesis, we summarize the common methods for H2O2 detection, crucial for obtaining reliable results in H2O2 studies. Additionally, we highlight molecular-level modification strategies for 2D photocatalysts, such as surface modification, ion doping, defect engineering, and heterojunction construction, which promote high-efficiency solar-to-chemical conversion for sustainable H2O2 photosynthesis. Furthermore, we discuss key issues and provide perspective outlooks for the efficient and sustainable generation of H2O2 in scale-up industrial production. This review offers in-depth insights into different reaction pathways of H2O2 synthesis and provides design principles for 2D photocatalysts to enhance H2O2 production, guiding the development of efficient photocatalysts for H2O2 synthesis.
2024, 35(12): 110302
doi: 10.1016/j.cclet.2024.110302
摘要:
Viral epidemics pose a serious threat to global public health, making it essential to explore virus-host interactions for uncovering the pathogenesis of viral diseases and developing effective antiviral strategies. Traditional in vitro cell infection models struggle to replicate physiological microenvironment, while animal infection models may encounter obstacles such as species gap, high-cost, and ethical issues. Additionally, potential heterogeneous infection outcomes are usually inaccessible by population-based experiments. Microfluidics, as an emerging interdisciplinary platform, has proven to be a powerful tool for inquiring virus-host interactions. In this review, conventional virological methods were introduced first and remarkable advantages of microfluidics in viral cell biology were highlighted. Next, the in-depth applications of microfluidics in analyzing heterogeneity of virus-host interplays, dynamic monitoring of events related to viral life cycle, and modeling of viral infectious diseases were fully elaborated from the perspective of single-cell chip, multi-cell culture chip and organ-on-a-chip (organ chip). Finally, the opportunities and challenges in developing robust microfluidic methods for virology were discussed. Overall, this review aims to provide an overview of microfluidic-based research on virus-host interaction and promote multidisciplinary collaborations for better understanding and responding to viral threats.
Viral epidemics pose a serious threat to global public health, making it essential to explore virus-host interactions for uncovering the pathogenesis of viral diseases and developing effective antiviral strategies. Traditional in vitro cell infection models struggle to replicate physiological microenvironment, while animal infection models may encounter obstacles such as species gap, high-cost, and ethical issues. Additionally, potential heterogeneous infection outcomes are usually inaccessible by population-based experiments. Microfluidics, as an emerging interdisciplinary platform, has proven to be a powerful tool for inquiring virus-host interactions. In this review, conventional virological methods were introduced first and remarkable advantages of microfluidics in viral cell biology were highlighted. Next, the in-depth applications of microfluidics in analyzing heterogeneity of virus-host interplays, dynamic monitoring of events related to viral life cycle, and modeling of viral infectious diseases were fully elaborated from the perspective of single-cell chip, multi-cell culture chip and organ-on-a-chip (organ chip). Finally, the opportunities and challenges in developing robust microfluidic methods for virology were discussed. Overall, this review aims to provide an overview of microfluidic-based research on virus-host interaction and promote multidisciplinary collaborations for better understanding and responding to viral threats.
2024, 35(12): 110089
doi: 10.1016/j.cclet.2024.110089
摘要:
2024, 35(12): 110198
doi: 10.1016/j.cclet.2024.110198
摘要:
2024, 35(12): 110208
doi: 10.1016/j.cclet.2024.110208
摘要:
2024, 35(12): 110210
doi: 10.1016/j.cclet.2024.110210
摘要:
2024, 35(12): 110261
doi: 10.1016/j.cclet.2024.110261
摘要:
2024, 35(8): 109030
doi: 10.1016/j.cclet.2023.109030
摘要:
Under the guidance of the approach which integrates molecular networking, MolNetEnhancer and Network Annotation Propagation (NAP), daphnaltaicanoids A and B (1 and 2) with unprecedented 9-oxa-tetracyclo[6.6.1.02,6.08,13]pentadecane and tetracyclo[5.3.0.12,5.24,11]tridecane central frameworks were isolated from Daphne altaica Pall., representing two types of unparalleled meroterpenoid cores. Their structures were elucidated by extensive spectroscopic analysis, nuclear magnetic resonance (NMR) calculations, DP4+ analysis and electronic circular dichroism (ECD) calculations. The plausible biosynthetic pathways for 1 and 2 were postulated. Biologically, 2 exerted potent neuroprotective activities which were superior to trolox at 12.5 and 25 µmol/L. Moreover, 1 and 2 exhibited more noticeable acetylcholinesterase inhibitory activities than donepezil. Molecular docking simulations were performed to explore the intermolecular interaction of compounds 1 and 2 with acetylcholinesterase. The bioactivity evaluation results highlight the prospects of 1 and 2 as a novel category of neurological agents.
Under the guidance of the approach which integrates molecular networking, MolNetEnhancer and Network Annotation Propagation (NAP), daphnaltaicanoids A and B (1 and 2) with unprecedented 9-oxa-tetracyclo[6.6.1.02,6.08,13]pentadecane and tetracyclo[5.3.0.12,5.24,11]tridecane central frameworks were isolated from Daphne altaica Pall., representing two types of unparalleled meroterpenoid cores. Their structures were elucidated by extensive spectroscopic analysis, nuclear magnetic resonance (NMR) calculations, DP4+ analysis and electronic circular dichroism (ECD) calculations. The plausible biosynthetic pathways for 1 and 2 were postulated. Biologically, 2 exerted potent neuroprotective activities which were superior to trolox at 12.5 and 25 µmol/L. Moreover, 1 and 2 exhibited more noticeable acetylcholinesterase inhibitory activities than donepezil. Molecular docking simulations were performed to explore the intermolecular interaction of compounds 1 and 2 with acetylcholinesterase. The bioactivity evaluation results highlight the prospects of 1 and 2 as a novel category of neurological agents.
2024, 35(8): 109035
doi: 10.1016/j.cclet.2023.109035
摘要:
Citrinsorbicillin A (1), a novel homotrimeric sorbicillinoid, along with two new monomers citrinsorbicillins B (2) and C (3), were isolated from the Coptis chinensis endophyte Trichoderma citrinoviride HT-9 by liquid chromatograph mass spectrometer (LC-MS)-guided strategy. 1 was the first trimeric-example from terrestrial fungi, which possessed a unique carbon skeleton with two bicyclo[2.2.2]octanedione ring connected through an enolated carbon forming by [4 + 2] cycloaddition. Their structures were elucidated by spectroscopic analysis and X-ray diffraction. 1 exhibited moderate cytotoxicity against human colon cancer HT29 cells, and it induced significant cell cycle arrest by reducing the protein expression of cyclin D1.
Citrinsorbicillin A (1), a novel homotrimeric sorbicillinoid, along with two new monomers citrinsorbicillins B (2) and C (3), were isolated from the Coptis chinensis endophyte Trichoderma citrinoviride HT-9 by liquid chromatograph mass spectrometer (LC-MS)-guided strategy. 1 was the first trimeric-example from terrestrial fungi, which possessed a unique carbon skeleton with two bicyclo[2.2.2]octanedione ring connected through an enolated carbon forming by [4 + 2] cycloaddition. Their structures were elucidated by spectroscopic analysis and X-ray diffraction. 1 exhibited moderate cytotoxicity against human colon cancer HT29 cells, and it induced significant cell cycle arrest by reducing the protein expression of cyclin D1.
2024, 35(8): 109048
doi: 10.1016/j.cclet.2023.109048
摘要:
We report here the synthesis and characterization of two new members of the M2E12 family of endohedral Zintl clusters, [Fe2Sn4Bi8]3– and [Cr2Sb12]3–, both of which contain open-shell metal dimers encapsulated inside a triple-decker cluster of main-group atoms. The 75-electron [Fe2Sn4Bi8]3– cluster has a D4h-symmetric structure, while [Cr2Sb12]3–, despite having the same 75-electron count, is strongly distorted to a geometry that resembles a CrSb8 crown capped by a CrSb4 unit. The structural differences between the two are driven by the increasing availability of 3d electron density in the earlier transition metal, which leads, ultimately, to different electronic configurations in the two clusters. The trends precisely mirror those observed in the ME10 and ME12 families containing a single transition metal ion.
We report here the synthesis and characterization of two new members of the M2E12 family of endohedral Zintl clusters, [Fe2Sn4Bi8]3– and [Cr2Sb12]3–, both of which contain open-shell metal dimers encapsulated inside a triple-decker cluster of main-group atoms. The 75-electron [Fe2Sn4Bi8]3– cluster has a D4h-symmetric structure, while [Cr2Sb12]3–, despite having the same 75-electron count, is strongly distorted to a geometry that resembles a CrSb8 crown capped by a CrSb4 unit. The structural differences between the two are driven by the increasing availability of 3d electron density in the earlier transition metal, which leads, ultimately, to different electronic configurations in the two clusters. The trends precisely mirror those observed in the ME10 and ME12 families containing a single transition metal ion.
2024, 35(8): 109052
doi: 10.1016/j.cclet.2023.109052
摘要:
Electron-deficient viologens are widely used as ligands or structure-directing agents (SDAs) to synthesize crystalline X-ray induced photochromic materials. Here, a new rational strategy of anion-directed folding a flexible cation (H2imb)2+ ((H2imb)2+ = di-protonated 2,3-bis(imidazolin-2-yl)-2,3-dimethylbutane) has been developed. Electron-donating Cl− and (ZnCl4)2− are used to direct folding a flexible electron-deficient (H2imb)2+ cation. Three complexes (H2imb)(NO3)2 (1), (H2imb)Cl2·H2O (2), and (H2imb)ZnCl4 (3) have been synthesized in which (H2imb)2+ crystallize in an anti-conformation, 88.8°-gauche, and 51.8°-gauche, respectively. In contrary to X-ray silent complex 1, X-ray induced photochromism has been achieved in both complex 2 and 3. An intermolecular charge-transfer mechanism has been elucidated and the anion directed folding of (H2imb)2+ has been validated to be critical to yield colored long-lived charge-separated states.
Electron-deficient viologens are widely used as ligands or structure-directing agents (SDAs) to synthesize crystalline X-ray induced photochromic materials. Here, a new rational strategy of anion-directed folding a flexible cation (H2imb)2+ ((H2imb)2+ = di-protonated 2,3-bis(imidazolin-2-yl)-2,3-dimethylbutane) has been developed. Electron-donating Cl− and (ZnCl4)2− are used to direct folding a flexible electron-deficient (H2imb)2+ cation. Three complexes (H2imb)(NO3)2 (1), (H2imb)Cl2·H2O (2), and (H2imb)ZnCl4 (3) have been synthesized in which (H2imb)2+ crystallize in an anti-conformation, 88.8°-gauche, and 51.8°-gauche, respectively. In contrary to X-ray silent complex 1, X-ray induced photochromism has been achieved in both complex 2 and 3. An intermolecular charge-transfer mechanism has been elucidated and the anion directed folding of (H2imb)2+ has been validated to be critical to yield colored long-lived charge-separated states.
2024, 35(8): 109061
doi: 10.1016/j.cclet.2023.109061
摘要:
The selective oxidative esterification of aldehydes with alcohols to the corresponding esters has been one of the hot spots in scientific research and industrial synthesis. However, the application of precious metal catalytic systems is limited by their complicated synthetic steps and high cost. Thus a highly efficient, green, recyclable selective synthesis method of esters catalyzed by polyoxovanadate (POV)-based molecular catalysts has been developed in this paper. The results show that supramolecular interaction between POV and 1,3-dibenzylimidazolium bromide (Act2Im) can efficiently convert alcohols and aldehydes to the corresponding esters in high yield under much milder conditions. Mechanistic insight is also provided based on the control experiments, single crystal X-ray diffraction and cyclic voltammetry studies.
The selective oxidative esterification of aldehydes with alcohols to the corresponding esters has been one of the hot spots in scientific research and industrial synthesis. However, the application of precious metal catalytic systems is limited by their complicated synthetic steps and high cost. Thus a highly efficient, green, recyclable selective synthesis method of esters catalyzed by polyoxovanadate (POV)-based molecular catalysts has been developed in this paper. The results show that supramolecular interaction between POV and 1,3-dibenzylimidazolium bromide (Act2Im) can efficiently convert alcohols and aldehydes to the corresponding esters in high yield under much milder conditions. Mechanistic insight is also provided based on the control experiments, single crystal X-ray diffraction and cyclic voltammetry studies.
2024, 35(8): 109063
doi: 10.1016/j.cclet.2023.109063
摘要:
The development of circularly polarized luminescence (CPL) materials with high performance is significantly important. Herein, we develop a facial strategy for fabricating a CPL-active system by employing an achiral luminescent metal-organic cage (MOC) and chiral boron dipyrromethene (BODIPY) molecules. CPL is achieved by taking advantage of the radiative energy transfer process, in which BODIPY molecules act as energy acceptors and MOCs act as donors. The CPL performance (maximum luminescence dissymmetry factor up to ± 1.5 × 10−3) can be tuned by adjusting the ratio between MOCs and BODIPY. White-light emission with the CPL feature is obtained by using a ternary system including MOC, chiral BODIPY, and Rhodamine B. The present work provides a facile and universal strategy to construct a CPL-active system by integrating achiral luminophores and chiral molecules.
The development of circularly polarized luminescence (CPL) materials with high performance is significantly important. Herein, we develop a facial strategy for fabricating a CPL-active system by employing an achiral luminescent metal-organic cage (MOC) and chiral boron dipyrromethene (BODIPY) molecules. CPL is achieved by taking advantage of the radiative energy transfer process, in which BODIPY molecules act as energy acceptors and MOCs act as donors. The CPL performance (maximum luminescence dissymmetry factor up to ± 1.5 × 10−3) can be tuned by adjusting the ratio between MOCs and BODIPY. White-light emission with the CPL feature is obtained by using a ternary system including MOC, chiral BODIPY, and Rhodamine B. The present work provides a facile and universal strategy to construct a CPL-active system by integrating achiral luminophores and chiral molecules.
2024, 35(8): 109082
doi: 10.1016/j.cclet.2023.109082
摘要:
Concise chemistry leads to a family of heptanuclear CoⅡ-clusters, [Co7(N3)12(CH3CN)12] [Y2(NO3)4(piv)4]·2CH3CN (DC1) (pivH = pivalic acid), [Co7(N3)12(CH3CN)10(NO3)0.4 (Cl)1.6]·4CH3CN (DC2) and [Co7(N3)12(CH3CN)10(NO3)2]·4CH3CN (DC3), in which the metal ions are exclusively bridged by end-on azido ligands to stabilize a beautiful disk-like topology. The resulting clusters exhibit interesting structural transformations and thermodynamically-distinct steady states verified by theoretical calculations. Magnetic studies reveal the first observation of zero-field SMM behaviour in disk-like heptanuclear CoⅡ complexes.
Concise chemistry leads to a family of heptanuclear CoⅡ-clusters, [Co7(N3)12(CH3CN)12] [Y2(NO3)4(piv)4]·2CH3CN (DC1) (pivH = pivalic acid), [Co7(N3)12(CH3CN)10(NO3)0.4 (Cl)1.6]·4CH3CN (DC2) and [Co7(N3)12(CH3CN)10(NO3)2]·4CH3CN (DC3), in which the metal ions are exclusively bridged by end-on azido ligands to stabilize a beautiful disk-like topology. The resulting clusters exhibit interesting structural transformations and thermodynamically-distinct steady states verified by theoretical calculations. Magnetic studies reveal the first observation of zero-field SMM behaviour in disk-like heptanuclear CoⅡ complexes.
2024, 35(8): 109083
doi: 10.1016/j.cclet.2023.109083
摘要:
Palladium-based alloy catalysts have been employed as one of the potential candidates for oxygen reduction reaction (ORR), but the dissolution of transition metal hinders their application. Herein, structure ordered PdTe intermetallic with Pd shell (o-PdTe@Pd) are synthesized via an electrochemical etching driven surface reconstruction strategy. The surface reconstruction could tune the electronic structure, weaken the adsorption energy of reaction intermediates on o-PdTe@Pd, resulting in enhanced electrocatalytic activity for ORR. The mass activity of o-PdTe@Pd is about 3.3 and 2.7 times higher than that of Pd/C in acid and alkaline, respectively. Besides, the half-potentials for ORR decay only about 44 mV and 12 mV after 30 k cycles accelerated durability test in acid and alkaline media, respectively. The enhanced durability originates from the resistance of Te atoms dissolve in the ordered PdTe intermetallic core and the core-shell structure. When assembled in a Zn-air battery, o-PdTe@Pd electrode delivers a higher specific capacity (794 mAh/g) and better cycling stability than Pt/C.
Palladium-based alloy catalysts have been employed as one of the potential candidates for oxygen reduction reaction (ORR), but the dissolution of transition metal hinders their application. Herein, structure ordered PdTe intermetallic with Pd shell (o-PdTe@Pd) are synthesized via an electrochemical etching driven surface reconstruction strategy. The surface reconstruction could tune the electronic structure, weaken the adsorption energy of reaction intermediates on o-PdTe@Pd, resulting in enhanced electrocatalytic activity for ORR. The mass activity of o-PdTe@Pd is about 3.3 and 2.7 times higher than that of Pd/C in acid and alkaline, respectively. Besides, the half-potentials for ORR decay only about 44 mV and 12 mV after 30 k cycles accelerated durability test in acid and alkaline media, respectively. The enhanced durability originates from the resistance of Te atoms dissolve in the ordered PdTe intermetallic core and the core-shell structure. When assembled in a Zn-air battery, o-PdTe@Pd electrode delivers a higher specific capacity (794 mAh/g) and better cycling stability than Pt/C.
2024, 35(8): 109085
doi: 10.1016/j.cclet.2023.109085
摘要:
Recently, organic-inorganic hybrid metal halides (HMHs) have attracted extensive attention as promising multifunctional materials by virtue of their structural diversity and tunable photophysical properties. However, it remains a challenge to design HMHs with specific functions on demand. Herein, by introducing R/S-methylbenzylamine (R/S-MBA) and doping Sb3+, we have achieved both second harmonic generation (SHG) and circularly polarized luminescence (CPL) properties in lead-free indium halides. The introduction of chiral organic cations can break the symmetry and induce the indium halides to crystallize in the chiral space group. The Sb3+ with ns2 electronic configuration can serve as the dopants to promote the formation of self-trapped excitons, so as to activate highly efficient luminescence. As a result, the as-prepared Sb3+ doped (R/S-MBA)3InCl6 show not only SHG responses but also CPL signals with luminescence dissymmetry factor of −5.3 × 10−3 and 4.7 × 10−3. This work provides a new inspiration for the exploitation of chiral multifunctional materials.
Recently, organic-inorganic hybrid metal halides (HMHs) have attracted extensive attention as promising multifunctional materials by virtue of their structural diversity and tunable photophysical properties. However, it remains a challenge to design HMHs with specific functions on demand. Herein, by introducing R/S-methylbenzylamine (R/S-MBA) and doping Sb3+, we have achieved both second harmonic generation (SHG) and circularly polarized luminescence (CPL) properties in lead-free indium halides. The introduction of chiral organic cations can break the symmetry and induce the indium halides to crystallize in the chiral space group. The Sb3+ with ns2 electronic configuration can serve as the dopants to promote the formation of self-trapped excitons, so as to activate highly efficient luminescence. As a result, the as-prepared Sb3+ doped (R/S-MBA)3InCl6 show not only SHG responses but also CPL signals with luminescence dissymmetry factor of −5.3 × 10−3 and 4.7 × 10−3. This work provides a new inspiration for the exploitation of chiral multifunctional materials.
Tailored ionically conductive graphene oxide-encased metal ions for ultrasensitive cadaverine sensor
2024, 35(8): 109102
doi: 10.1016/j.cclet.2023.109102
摘要:
Intelligent chemical sensors have been extensively used in food safety and environmental assessment, while limited sensitivity and homogeneity bring about huge obstacles to their practical application. Herein, novel ionically conductive sensitive materials were elaborately designed based on metal ion decorated graphene oxide (GO) via a facile and general in-situ spin-coating strategy, where the abundant functional groups (-OH and -COOH) of GO layer could provide natural binding sites for various bivalent metal cations (such as Cu2+, Ni2+, Zn2+, Co2+, and Mg2+) through coordination and electrostatic interaction. The intercalated metal cations on the layered GO nanosheets can be regarded as charge carriers and complexation with targeted gas (cadaverine, Cad), which is a typical metabolites production and food degradants. By contrast, the designed GO@Cu(Ⅱ) sensor exhibited the optimal sensing performance toward Cad molecules at room temperature, including ultra-low detection limit (ca. 3 nL), excellent sensitivity, and rapid low concentration detection rate (only 16 s). Interestingly, the sensor exhibited an irreversible and specific response toward Cad, while it showed a transient and reversible response to other interfering gases, implying its outstanding selectivity. In addition, the GO@Cu(Ⅱ) sensor enabled real-time monitoring of the decay progression of cheese, and it exhibited great potential for large-scale production via its excellent homogeneity. It provides an efficient approach to tailoring intelligent chemical sensors for real-time food safety monitoring and human health warning.
Intelligent chemical sensors have been extensively used in food safety and environmental assessment, while limited sensitivity and homogeneity bring about huge obstacles to their practical application. Herein, novel ionically conductive sensitive materials were elaborately designed based on metal ion decorated graphene oxide (GO) via a facile and general in-situ spin-coating strategy, where the abundant functional groups (-OH and -COOH) of GO layer could provide natural binding sites for various bivalent metal cations (such as Cu2+, Ni2+, Zn2+, Co2+, and Mg2+) through coordination and electrostatic interaction. The intercalated metal cations on the layered GO nanosheets can be regarded as charge carriers and complexation with targeted gas (cadaverine, Cad), which is a typical metabolites production and food degradants. By contrast, the designed GO@Cu(Ⅱ) sensor exhibited the optimal sensing performance toward Cad molecules at room temperature, including ultra-low detection limit (ca. 3 nL), excellent sensitivity, and rapid low concentration detection rate (only 16 s). Interestingly, the sensor exhibited an irreversible and specific response toward Cad, while it showed a transient and reversible response to other interfering gases, implying its outstanding selectivity. In addition, the GO@Cu(Ⅱ) sensor enabled real-time monitoring of the decay progression of cheese, and it exhibited great potential for large-scale production via its excellent homogeneity. It provides an efficient approach to tailoring intelligent chemical sensors for real-time food safety monitoring and human health warning.
2024, 35(8): 109120
doi: 10.1016/j.cclet.2023.109120
摘要:
Metal-organic frameworks (MOFs) functionalized with open metal sites (OMSs) have received widespread attention in various applications due to their fascinating electronic properties and unique interactions with guest molecules. However, rational tailoring of the coordination environment of metal nodes during the synthesis of MOFs remains a great challenge due to their tendency of saturated coordination with linkers. Herein, we reported the construction of three new MOFs featuring unsaturated Cu(Ⅱ) sites, namely [Cu(HCOO)(pzta)]n (HL-1), {[Cu(PTA)0.5(pzta)(H2O)]·2H2O}n (HL-2) and [Cu(NA)0.5(pzta)]n (HL-3) (Hpzta = 3-pyrazinyl-1,2,4-triazole; PTA = terephthalic acid; NA = 1,4-naphthalene dicarboxylic acid), based on the mixed-linker strategy via specific selection of versatile Hpzta ligand and carboxylate ligands. Remarkably, the obtained MOFs exhibited excellent activity and good recyclability for the catalytic reduction of nitroaromatics under mild conditions (25 ℃ and 1 atm). In particular, the complete conversion of 4-nitrophenol (4-NP) took only 30 s on HL-2, reaching a record-high TOF value compared with previously reported metal catalysts. The combined experimental and theoretical studies on HL-2 revealed that the open Cu site with positive-charged nature could improve the adsorption and subsequent electron transport between the substrates, and was responsible for the outstanding performance. This work shined lights on the further enhancement of performance for MOFs through rational OMSs construction.
Metal-organic frameworks (MOFs) functionalized with open metal sites (OMSs) have received widespread attention in various applications due to their fascinating electronic properties and unique interactions with guest molecules. However, rational tailoring of the coordination environment of metal nodes during the synthesis of MOFs remains a great challenge due to their tendency of saturated coordination with linkers. Herein, we reported the construction of three new MOFs featuring unsaturated Cu(Ⅱ) sites, namely [Cu(HCOO)(pzta)]n (HL-1), {[Cu(PTA)0.5(pzta)(H2O)]·2H2O}n (HL-2) and [Cu(NA)0.5(pzta)]n (HL-3) (Hpzta = 3-pyrazinyl-1,2,4-triazole; PTA = terephthalic acid; NA = 1,4-naphthalene dicarboxylic acid), based on the mixed-linker strategy via specific selection of versatile Hpzta ligand and carboxylate ligands. Remarkably, the obtained MOFs exhibited excellent activity and good recyclability for the catalytic reduction of nitroaromatics under mild conditions (25 ℃ and 1 atm). In particular, the complete conversion of 4-nitrophenol (4-NP) took only 30 s on HL-2, reaching a record-high TOF value compared with previously reported metal catalysts. The combined experimental and theoretical studies on HL-2 revealed that the open Cu site with positive-charged nature could improve the adsorption and subsequent electron transport between the substrates, and was responsible for the outstanding performance. This work shined lights on the further enhancement of performance for MOFs through rational OMSs construction.
2024, 35(8): 109122
doi: 10.1016/j.cclet.2023.109122
摘要:
In the development of 3D conductive frameworks for lithium metal anode (LMA), two models have been proposed: top growth model and bottom-up growth model. However, Li tends to accumulate on the top of these 3D frameworks with homogenous lithiophilicity (top growth) and Li dendrite still forms. To address this issue, some researchers have focused on developing 3D frameworks with gradient lithiophilicity, which realized bottom-up growth of Li. Nevertheless, partial Li nucleation sites on the top of these frameworks were missed. Inspired by the two models talked above, this work firstly proposed a novel intermittent lithiophilic model for lithium deposition. To demonstrate the feasibility of this model, a bimetallic metal-organic frameworks derived ZnMn2O4-MnO nanoparticles were grown on carbon cloth for LMA. It can cycle stably under ultra-high current and areal capacity (10 mA/cm2, 10 mAh/cm2). The in-situ optical microscopy (OM) was conducted to observe the Li deposition behavior, no dendrite was found during 80 h in ester-based electrolyte while the pure Li only cycled for 2 h. What is more, it can also be well-coupled with LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode and solid-state electrolyte, which further prove the advantages of the intermittent model for the development of LMAs with high safety and high energy density.
In the development of 3D conductive frameworks for lithium metal anode (LMA), two models have been proposed: top growth model and bottom-up growth model. However, Li tends to accumulate on the top of these 3D frameworks with homogenous lithiophilicity (top growth) and Li dendrite still forms. To address this issue, some researchers have focused on developing 3D frameworks with gradient lithiophilicity, which realized bottom-up growth of Li. Nevertheless, partial Li nucleation sites on the top of these frameworks were missed. Inspired by the two models talked above, this work firstly proposed a novel intermittent lithiophilic model for lithium deposition. To demonstrate the feasibility of this model, a bimetallic metal-organic frameworks derived ZnMn2O4-MnO nanoparticles were grown on carbon cloth for LMA. It can cycle stably under ultra-high current and areal capacity (10 mA/cm2, 10 mAh/cm2). The in-situ optical microscopy (OM) was conducted to observe the Li deposition behavior, no dendrite was found during 80 h in ester-based electrolyte while the pure Li only cycled for 2 h. What is more, it can also be well-coupled with LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode and solid-state electrolyte, which further prove the advantages of the intermittent model for the development of LMAs with high safety and high energy density.
2024, 35(8): 109123
doi: 10.1016/j.cclet.2023.109123
摘要:
Safety and energy density are significant for lithium-ion batteries (LIBs), and the flammable organic electrolyte is one of the most critical causes of the safety problem of LIBs. Although LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode with high capacity can improve the energy density, the interface stability between NCM811 cathode and electrolytes needs to be improved. Herein, we report a multifunctional additive, diethyl(2-(triethoxysilyl)ethyl)phosphonate (DETSP), which can suppress the flammability of the electrolyte and enhance the cycling stability of NCM811 cathode with a capacity retention of 89.9% after 400 cycles at 1 C, while that of the blank electrolyte is merely 61.3%. In addition, DETSP is compatible well with the graphite anode without impairing the electrochemical performances. Significantly, the performance and safety of NCM811/graphite full cells are also improved. Experimental and theoretical results demonstrate that DETSP can scavenge acidic byproducts and is beneficial to form a stable cathode-electrolyte interface (CEI). Accordingly, DETSP can potentially be an effective solution to ameliorating the safety of the commercial electrolyte and improving the stability of high-voltage cathodes.
Safety and energy density are significant for lithium-ion batteries (LIBs), and the flammable organic electrolyte is one of the most critical causes of the safety problem of LIBs. Although LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode with high capacity can improve the energy density, the interface stability between NCM811 cathode and electrolytes needs to be improved. Herein, we report a multifunctional additive, diethyl(2-(triethoxysilyl)ethyl)phosphonate (DETSP), which can suppress the flammability of the electrolyte and enhance the cycling stability of NCM811 cathode with a capacity retention of 89.9% after 400 cycles at 1 C, while that of the blank electrolyte is merely 61.3%. In addition, DETSP is compatible well with the graphite anode without impairing the electrochemical performances. Significantly, the performance and safety of NCM811/graphite full cells are also improved. Experimental and theoretical results demonstrate that DETSP can scavenge acidic byproducts and is beneficial to form a stable cathode-electrolyte interface (CEI). Accordingly, DETSP can potentially be an effective solution to ameliorating the safety of the commercial electrolyte and improving the stability of high-voltage cathodes.
2024, 35(8): 109146
doi: 10.1016/j.cclet.2023.109146
摘要:
Weakly-solvated electrolytes (WSEs) utilizing solvents with weak coordination ability offer advantages for low-potential graphite anode owing to their facile desolvation process and anions-derived inorganic-rich solid electrolyte interphase (SEI) film. However, these electrolytes face challenges in achieving a balance between the weak solvation affinity and high ionic conductivity, as well as between rigid inorganic-rich SEI and flexible SEI for long-term stability. Herein, we introduce 1,3-dioxolane (DOL) and lithium bis(trifluoromethanesulfonyl)-imide (LiTFSI) as functional additives into a WSE based on nonpolar cyclic ether (1,4-dioxane). The well-formulated WSE not only preserves the weakly solvated features and anion-dominated solvation sheath, but also utilizes DOL to contribute organic species for stabilizing the SEI layer. Benefitting from these merits, the optimized electrolyte enables graphite anode with excellent fast-charging performance (210 mAh/g at 5 C) and outstanding cycling stability (600 cycles with a capacity retention of 82.0% at room temperature and 400 cycles with a capacity retention of 80.4% at high temperature). Furthermore, the fabricated LiNi0.8Co0.1Mn0.1O2||graphite full cells demonstrate stable operation for 140 cycles with high capacity retention of 80.3%. This work highlights the potential of tailoring solvation sheath and interphase properties in WSEs for advanced electrolyte design in graphite-based lithium-ion batteries.
Weakly-solvated electrolytes (WSEs) utilizing solvents with weak coordination ability offer advantages for low-potential graphite anode owing to their facile desolvation process and anions-derived inorganic-rich solid electrolyte interphase (SEI) film. However, these electrolytes face challenges in achieving a balance between the weak solvation affinity and high ionic conductivity, as well as between rigid inorganic-rich SEI and flexible SEI for long-term stability. Herein, we introduce 1,3-dioxolane (DOL) and lithium bis(trifluoromethanesulfonyl)-imide (LiTFSI) as functional additives into a WSE based on nonpolar cyclic ether (1,4-dioxane). The well-formulated WSE not only preserves the weakly solvated features and anion-dominated solvation sheath, but also utilizes DOL to contribute organic species for stabilizing the SEI layer. Benefitting from these merits, the optimized electrolyte enables graphite anode with excellent fast-charging performance (210 mAh/g at 5 C) and outstanding cycling stability (600 cycles with a capacity retention of 82.0% at room temperature and 400 cycles with a capacity retention of 80.4% at high temperature). Furthermore, the fabricated LiNi0.8Co0.1Mn0.1O2||graphite full cells demonstrate stable operation for 140 cycles with high capacity retention of 80.3%. This work highlights the potential of tailoring solvation sheath and interphase properties in WSEs for advanced electrolyte design in graphite-based lithium-ion batteries.
2024, 35(8): 109148
doi: 10.1016/j.cclet.2023.109148
摘要:
The widespread application of phenolic substances in the field of food, medicine and industry, is harmful to the environment and human health. Therefore, it is very important to develop a convenient and effective method to detect and degrade phenolic compounds. Herein, we report a new keggin-type polyoxometallate-based metal-organic complex self-assembled under solvothermal condition, {[Cu(dap)(3-PA)]4(SiW12O40)(H2O)2}·2H2O (1, dap = 1,2-diaminopropane, 3-HPA = 3-pyridineacrylic acid). 1 shows an interesting 1D ladder-like structure. As a bifunctional catalyst, 1 can be employed as a colorimetric sensor toward phenol with the relatively low detection limit (LOD) of 0.36 µmol/L (S/N = 3) in the wide range (0.001–0.1 mmol/L). The title colorimetric sensor is applied to determine phenol in various water environment with good recoveries ranging from 95%–105%. In addition, 1 also exhibits excellent photocatalytic degradation toward phenol under visible light with the highest removal efficiency at 96% for 100 min and wide pH universality. The selectivity, stability and reliability of the detection of 1 towards phenol, as well as the detection for 4-chlorophenol, o-cresol, 4-nitrophenol and phloroglucinol were studied. Furthermore, the photocatalytic reaction kinetics and the mechanisms of photodegradation of phenol were also investigated in detail.
The widespread application of phenolic substances in the field of food, medicine and industry, is harmful to the environment and human health. Therefore, it is very important to develop a convenient and effective method to detect and degrade phenolic compounds. Herein, we report a new keggin-type polyoxometallate-based metal-organic complex self-assembled under solvothermal condition, {[Cu(dap)(3-PA)]4(SiW12O40)(H2O)2}·2H2O (1, dap = 1,2-diaminopropane, 3-HPA = 3-pyridineacrylic acid). 1 shows an interesting 1D ladder-like structure. As a bifunctional catalyst, 1 can be employed as a colorimetric sensor toward phenol with the relatively low detection limit (LOD) of 0.36 µmol/L (S/N = 3) in the wide range (0.001–0.1 mmol/L). The title colorimetric sensor is applied to determine phenol in various water environment with good recoveries ranging from 95%–105%. In addition, 1 also exhibits excellent photocatalytic degradation toward phenol under visible light with the highest removal efficiency at 96% for 100 min and wide pH universality. The selectivity, stability and reliability of the detection of 1 towards phenol, as well as the detection for 4-chlorophenol, o-cresol, 4-nitrophenol and phloroglucinol were studied. Furthermore, the photocatalytic reaction kinetics and the mechanisms of photodegradation of phenol were also investigated in detail.
2024, 35(8): 109166
doi: 10.1016/j.cclet.2023.109166
摘要:
For treatment of sulfion-containing wastewater, coupling the electrochemical sulfion oxidation reaction (SOR) with hydrogen evolution reaction (HER) can be an ideal way for sulfur and H2 resources recovery. Herein, we synthesize a metal-modified carbon nanotube arrays electrode (Co@NCNTs/CC) for SOR and HER. This electrode has excellent performance for SOR and HER attributed to the unique array structure. It can achieve 99.36 mA/cm2 at 0.6 V for SOR, and 10 mA/cm2 at 0.067 V for HER. Density functional theory calculations verify that metal modification is able to regulate the electronic structure of carbon nanotube, which is able to optimize the adsorption of intermediates. Employed Co@NCNTs/CC as bifunctional electrodes to establish a hybrid electrolytic cell can reduce about 67% of energy consumption compared with the traditional water splitting electrolytic cell. Finally, the hybrid electrolytic cell is used to treat actual sulfion-containing wastewater, achieving the sulfur yield of 30 mg h−1 cm−2 and the hydrogen production of 0.64 mL/min.
For treatment of sulfion-containing wastewater, coupling the electrochemical sulfion oxidation reaction (SOR) with hydrogen evolution reaction (HER) can be an ideal way for sulfur and H2 resources recovery. Herein, we synthesize a metal-modified carbon nanotube arrays electrode (Co@NCNTs/CC) for SOR and HER. This electrode has excellent performance for SOR and HER attributed to the unique array structure. It can achieve 99.36 mA/cm2 at 0.6 V for SOR, and 10 mA/cm2 at 0.067 V for HER. Density functional theory calculations verify that metal modification is able to regulate the electronic structure of carbon nanotube, which is able to optimize the adsorption of intermediates. Employed Co@NCNTs/CC as bifunctional electrodes to establish a hybrid electrolytic cell can reduce about 67% of energy consumption compared with the traditional water splitting electrolytic cell. Finally, the hybrid electrolytic cell is used to treat actual sulfion-containing wastewater, achieving the sulfur yield of 30 mg h−1 cm−2 and the hydrogen production of 0.64 mL/min.
2024, 35(8): 109170
doi: 10.1016/j.cclet.2023.109170
摘要:
Traditional therapies such as surgery and endocrine therapy no longer meet the clinical needs in prostate cancer treatment, and more effective treatments are urgently required. Recent studies have reported that targeted inhibition of the transcription factor cyclin dependent kinase 7 (CDK7) could effectively suppress prostate cancer progression. However, the toxicity of CDK7 inhibitors such as THZ1 is the main limitation of the clinical application. In this work, we synthesized Cys8E (C8E) nanoparticles (NPs) loaded with THZ1 (C8E@THZ1), a novel GSH-targeting and stimuli-responsive nano-delivery platform, and investigated its anti-tumor potential and biosafety properties. In vitro, C8E@THZ1 potently inhibited the proliferation and promoted the apoptosis of prostate cancer cells. On tumor-bearing mice, C8E@THZ1 inhibited tumors by up to 85%, while the damage of THZ1 to liver function was effectively avoided. These results confirmed that inhibition of CDK7 can effectively block the progression of prostate cancer, and that Cys8E NPs is a highly prospective delivery platform to promote the clinical application of CDK7 inhibitors.
Traditional therapies such as surgery and endocrine therapy no longer meet the clinical needs in prostate cancer treatment, and more effective treatments are urgently required. Recent studies have reported that targeted inhibition of the transcription factor cyclin dependent kinase 7 (CDK7) could effectively suppress prostate cancer progression. However, the toxicity of CDK7 inhibitors such as THZ1 is the main limitation of the clinical application. In this work, we synthesized Cys8E (C8E) nanoparticles (NPs) loaded with THZ1 (C8E@THZ1), a novel GSH-targeting and stimuli-responsive nano-delivery platform, and investigated its anti-tumor potential and biosafety properties. In vitro, C8E@THZ1 potently inhibited the proliferation and promoted the apoptosis of prostate cancer cells. On tumor-bearing mice, C8E@THZ1 inhibited tumors by up to 85%, while the damage of THZ1 to liver function was effectively avoided. These results confirmed that inhibition of CDK7 can effectively block the progression of prostate cancer, and that Cys8E NPs is a highly prospective delivery platform to promote the clinical application of CDK7 inhibitors.
2024, 35(8): 109180
doi: 10.1016/j.cclet.2023.109180
摘要:
The purification of low-grade coal-bed methane is extremely important, but challenging, due to the very similar physical properties of CH4 and N2. Herein, we proposed a dual polarization strategy by employing triazine and polyfluoride sites to construct polar pores in COF materials, achieving the efficient separation of CH4 from N2. As expected, the dual polarized F-CTF-1 and F-CTF-2 exhibit higher CH4 adsorption capacity and CH4/N2 selectivity than CTF-1 and CTF-2, respectively. Especially, the CH4 uptake capacity and CH4/N2 selectivity of F-CTF-2 is 1.76 and 1.42 times than that of CTF-2. This work not only developed promising COF materials for CH4/N2 separation, but also provided important guidance for the separation of other adsorbates with similar properties.
The purification of low-grade coal-bed methane is extremely important, but challenging, due to the very similar physical properties of CH4 and N2. Herein, we proposed a dual polarization strategy by employing triazine and polyfluoride sites to construct polar pores in COF materials, achieving the efficient separation of CH4 from N2. As expected, the dual polarized F-CTF-1 and F-CTF-2 exhibit higher CH4 adsorption capacity and CH4/N2 selectivity than CTF-1 and CTF-2, respectively. Especially, the CH4 uptake capacity and CH4/N2 selectivity of F-CTF-2 is 1.76 and 1.42 times than that of CTF-2. This work not only developed promising COF materials for CH4/N2 separation, but also provided important guidance for the separation of other adsorbates with similar properties.
2024, 35(8): 109181
doi: 10.1016/j.cclet.2023.109181
摘要:
Searching for efficient nonprecious metal-based catalysts toward oxygen evolution reaction (OER) are of significance for seawater electrolysis. Herein, a core–shell-structured hybrid of cobalt phosphide nanowires@NiFe layered double hydroxide nanosheets grown on conductive nickel foam (CoP@NiFe LDH/NF) is prepared by a feasible approach at low temperature. The charming structure can provide numerous phosphide/hydroxide heterogenous interfaces, expose abundant active sites, and boost electron/mass transfer, synergistically enhancing catalytic OER activity. When employed as an electrocatalyst toward the OER, the resultant CoP@NiFe LDH/NF only requires a small overpotential of 287 mV to provide 300 mA/cm2 current density as well as long-time durability in 1.0 mol/L KOH seawater. The regulation of electronic states and surface reconstruction synergistically contribute to highly efficient seawater oxidation. This work provides an opportunity to construct efficient and inexpensive electrocatalysts for hydrogen production.
Searching for efficient nonprecious metal-based catalysts toward oxygen evolution reaction (OER) are of significance for seawater electrolysis. Herein, a core–shell-structured hybrid of cobalt phosphide nanowires@NiFe layered double hydroxide nanosheets grown on conductive nickel foam (CoP@NiFe LDH/NF) is prepared by a feasible approach at low temperature. The charming structure can provide numerous phosphide/hydroxide heterogenous interfaces, expose abundant active sites, and boost electron/mass transfer, synergistically enhancing catalytic OER activity. When employed as an electrocatalyst toward the OER, the resultant CoP@NiFe LDH/NF only requires a small overpotential of 287 mV to provide 300 mA/cm2 current density as well as long-time durability in 1.0 mol/L KOH seawater. The regulation of electronic states and surface reconstruction synergistically contribute to highly efficient seawater oxidation. This work provides an opportunity to construct efficient and inexpensive electrocatalysts for hydrogen production.
2024, 35(8): 109182
doi: 10.1016/j.cclet.2023.109182
摘要:
Satisfactory ionic conductivity, excellent mechanical stability, and high-temperature resistance are the prerequisites for the safe application of solid polymer electrolytes (SPEs) in all-solid-state lithium metal batteries (ASSLMBs). In this study, a novel poly(m-phenylene isophthalamide) (PMIA)-core/poly(ethylene oxide) (PEO)-shell nanofiber membrane and the functional Li6.4La3Zr1.4Ta0.6O12 (LLZTO) ceramic nanoparticle are simultaneously introduced into the PEO-based SPEs to prepare composite polymer electrolytes (CPEs). The core PMIA layer of composite nanofibers can greatly improve the mechanical strength and thermal stability of the CPEs, while the shell PEO layer can provide the 3D continuous transport channels for lithium ions. In addition, the introduction of functional LLZTO nanoparticle not only reduces the crystallinity of PEO, but also promotes the dissociation of lithium salts and releases more Li+ ions through its interaction with the Lewis acid-base of anions, thereby overall improving the transport of lithium ions. Consequently, the optimized CPEs present high ionic conductivity of 1.38×10−4 S/cm at 30 ℃, significantly improved mechanical strength (8.5 MPa), remarkable thermal stability (without obvious shrinkage at 150 ℃), and conspicuous Li dendrites blocking ability (> 1800 h). The CPEs also both have good compatibility and cyclic stability with LiFePO4 (> 2000 cycles) and high-voltage LiNi0.8Mn0.1Co0.1O2 (NMC811) (> 500 cycles) cathodes. In addition, even at low temperature (40 ℃), the assembled LiFePO4/CPEs/Li battery still can cycle stably. The novel design can provide an effective way to exploit high-performance solid-state electrolytes.
Satisfactory ionic conductivity, excellent mechanical stability, and high-temperature resistance are the prerequisites for the safe application of solid polymer electrolytes (SPEs) in all-solid-state lithium metal batteries (ASSLMBs). In this study, a novel poly(m-phenylene isophthalamide) (PMIA)-core/poly(ethylene oxide) (PEO)-shell nanofiber membrane and the functional Li6.4La3Zr1.4Ta0.6O12 (LLZTO) ceramic nanoparticle are simultaneously introduced into the PEO-based SPEs to prepare composite polymer electrolytes (CPEs). The core PMIA layer of composite nanofibers can greatly improve the mechanical strength and thermal stability of the CPEs, while the shell PEO layer can provide the 3D continuous transport channels for lithium ions. In addition, the introduction of functional LLZTO nanoparticle not only reduces the crystallinity of PEO, but also promotes the dissociation of lithium salts and releases more Li+ ions through its interaction with the Lewis acid-base of anions, thereby overall improving the transport of lithium ions. Consequently, the optimized CPEs present high ionic conductivity of 1.38×10−4 S/cm at 30 ℃, significantly improved mechanical strength (8.5 MPa), remarkable thermal stability (without obvious shrinkage at 150 ℃), and conspicuous Li dendrites blocking ability (> 1800 h). The CPEs also both have good compatibility and cyclic stability with LiFePO4 (> 2000 cycles) and high-voltage LiNi0.8Mn0.1Co0.1O2 (NMC811) (> 500 cycles) cathodes. In addition, even at low temperature (40 ℃), the assembled LiFePO4/CPEs/Li battery still can cycle stably. The novel design can provide an effective way to exploit high-performance solid-state electrolytes.
2024, 35(8): 109187
doi: 10.1016/j.cclet.2023.109187
摘要:
Tumor vascular normalization has emerged as a promising strategy for synergistic therapy recently. Based on the strategy of “fluorescence turn on-controllable release”, a novel bifunctional candidate was constructed based on previous developed vascular normalization inducer QDAU5, which could self-assemble to form functional enzyme infrared QDAU5 nanoparticles (FEIRQ NPs). Subsequently, biological evaluation demonstrated that the FEIRQ NPs could induce ferroptosis, endoplasmic reticulum stress, and antigen preconditioning and maturation of dendritic cells and CD8+ T cells, leading to excellent antitumor efficacy in the absence of cytotoxic drugs. Additionally, FEIRQ NPs show high fluorescence intensity upon exposure to the β-galactosidase (β-Gal) enzyme expressed in ovarian cancer, enabling real-time monitoring of therapeutic effects. Overall, our findings suggest a prospering strategy to early diagnosis and efficient therapy for ovarian cancer without cytotoxicity.
Tumor vascular normalization has emerged as a promising strategy for synergistic therapy recently. Based on the strategy of “fluorescence turn on-controllable release”, a novel bifunctional candidate was constructed based on previous developed vascular normalization inducer QDAU5, which could self-assemble to form functional enzyme infrared QDAU5 nanoparticles (FEIRQ NPs). Subsequently, biological evaluation demonstrated that the FEIRQ NPs could induce ferroptosis, endoplasmic reticulum stress, and antigen preconditioning and maturation of dendritic cells and CD8+ T cells, leading to excellent antitumor efficacy in the absence of cytotoxic drugs. Additionally, FEIRQ NPs show high fluorescence intensity upon exposure to the β-galactosidase (β-Gal) enzyme expressed in ovarian cancer, enabling real-time monitoring of therapeutic effects. Overall, our findings suggest a prospering strategy to early diagnosis and efficient therapy for ovarian cancer without cytotoxicity.
2024, 35(8): 109190
doi: 10.1016/j.cclet.2023.109190
摘要:
Photodynamic therapy (PDT) has emerged as a significant cancer therapy option. Currently, cation-based organic small molecule aggregation-induced emission (AIE) photosensitizers (PSs) attract the wide attention of many scientists, due to improved reactive oxygen species (ROS) production after cationization. However, such PSs tend to localize only the mitochondria, limiting the death way of tumor cells (usually apoptosis) during PDT process, which may affect the therapeutic effect under some circumstances. Herein, we designed a novel water-soluble three positive charge PS, TPAN-18F, which could be distributed uniformly in cell cytoplasm and had distribution in different sub-organelles (mitochondria, endoplasmic reticulum, lysosome). The experimental results showed that TPAN-18F-based PDT process can not only disrupt mitochondrial functions (reducing ATP production and destroying mitochondrial membrane potential), but also elevate the intracellular lipid peroxides (LPOs) level, which evoke the non-apoptotic death manner of tumor cells. Further, in vivo studies showed that TPAN-18F-based PDT could effectively inhibit tumor growth. Accordingly, we believe that the construction of TPAN-18F is suggestive for tumor non-apoptotic therapy.
Photodynamic therapy (PDT) has emerged as a significant cancer therapy option. Currently, cation-based organic small molecule aggregation-induced emission (AIE) photosensitizers (PSs) attract the wide attention of many scientists, due to improved reactive oxygen species (ROS) production after cationization. However, such PSs tend to localize only the mitochondria, limiting the death way of tumor cells (usually apoptosis) during PDT process, which may affect the therapeutic effect under some circumstances. Herein, we designed a novel water-soluble three positive charge PS, TPAN-18F, which could be distributed uniformly in cell cytoplasm and had distribution in different sub-organelles (mitochondria, endoplasmic reticulum, lysosome). The experimental results showed that TPAN-18F-based PDT process can not only disrupt mitochondrial functions (reducing ATP production and destroying mitochondrial membrane potential), but also elevate the intracellular lipid peroxides (LPOs) level, which evoke the non-apoptotic death manner of tumor cells. Further, in vivo studies showed that TPAN-18F-based PDT could effectively inhibit tumor growth. Accordingly, we believe that the construction of TPAN-18F is suggestive for tumor non-apoptotic therapy.
2024, 35(8): 109191
doi: 10.1016/j.cclet.2023.109191
摘要:
KTi2(PO4)3 is a promising anode material for potassium storage, but suffers from low conductivity and difficult balance between high capacity and good structural stability. Herein, the Ti3C2T MXene is used as a multifunctional binder to fabricate the KTi2(PO4)3 electrode by the traditional homogenizing-coating method. The MXene nanosheets, together with the conductive agent super P nanoparticles, construct a multiple conductive network for fast electron/ion transfer and high electrochemical kinetics. Moreover, the network ensures the structural stability of the KTi2(PO4)3 electrode during the de-intercalation/intercalation of 4 K+ ions, which is beneficial for simultaneously achieving high capacity and good cycle performance. Therefore, the MXene-bonded KTi2(PO4)3 electrode delivers a reversible capacity of 255.2 mAh/g at 50 mA/g, outstanding rate capability with 132.3 mAh/g at 2 A/g, and excellent cycle performance with 151.6 mAh/g at 1 A/g after 2000 cycles. This work not only suggests a high-performance anode material for potassium-ion batteries, but also demonstrates that the MXene is a promising binder material for constructing conductive electrodes in rechargeable batteries.
KTi2(PO4)3 is a promising anode material for potassium storage, but suffers from low conductivity and difficult balance between high capacity and good structural stability. Herein, the Ti3C2T MXene is used as a multifunctional binder to fabricate the KTi2(PO4)3 electrode by the traditional homogenizing-coating method. The MXene nanosheets, together with the conductive agent super P nanoparticles, construct a multiple conductive network for fast electron/ion transfer and high electrochemical kinetics. Moreover, the network ensures the structural stability of the KTi2(PO4)3 electrode during the de-intercalation/intercalation of 4 K+ ions, which is beneficial for simultaneously achieving high capacity and good cycle performance. Therefore, the MXene-bonded KTi2(PO4)3 electrode delivers a reversible capacity of 255.2 mAh/g at 50 mA/g, outstanding rate capability with 132.3 mAh/g at 2 A/g, and excellent cycle performance with 151.6 mAh/g at 1 A/g after 2000 cycles. This work not only suggests a high-performance anode material for potassium-ion batteries, but also demonstrates that the MXene is a promising binder material for constructing conductive electrodes in rechargeable batteries.
2024, 35(8): 109196
doi: 10.1016/j.cclet.2023.109196
摘要:
There is increasing evidence shows that either electrical stimulation (ES) or metal ion is an effective way to accelerate ulcerative wound healing. However, less attention is paid to investigating the synergistic effect between them. Herein, we explore the combined effects of ES and multiple metal ions on diabetic wound healing assisted by a triboelectric nanogenerator (TENG). Firstly, the novel Eggshell@CuFe2O4 nanocomposites (NCs) are prepared, which show unique structure and intrinsic antimicrobial properties. Subsequently, the as-prepared nanocomposites are embedded in oxidized starch hydrogel to form a multifunctional composite gel, which is further assembled into a wearable ionic triboelectric nanogenerator (iTENG) patch with polydimethylsiloxane (PDMS). It can convert the mechanical energy produced by a human body motion to electric energy and mediate the sequential release of metal ions (Fe2+/Ca2+/Cu2+), thereby resulting in the "cocktail effect" on impaired tissue. Under their effects, a satisfying healing result in diabetic mouse is identified, which can effectively accelerate wound healing process by relieving inflammation, promoting angiogenesis and collagen deposition. The work puts forward the cocktail effect of electric simulation coupled with the multiple metal ions, and opens up a new perspective in designing iTENG patch towards repair of hard-to-heal wounds.
There is increasing evidence shows that either electrical stimulation (ES) or metal ion is an effective way to accelerate ulcerative wound healing. However, less attention is paid to investigating the synergistic effect between them. Herein, we explore the combined effects of ES and multiple metal ions on diabetic wound healing assisted by a triboelectric nanogenerator (TENG). Firstly, the novel Eggshell@CuFe2O4 nanocomposites (NCs) are prepared, which show unique structure and intrinsic antimicrobial properties. Subsequently, the as-prepared nanocomposites are embedded in oxidized starch hydrogel to form a multifunctional composite gel, which is further assembled into a wearable ionic triboelectric nanogenerator (iTENG) patch with polydimethylsiloxane (PDMS). It can convert the mechanical energy produced by a human body motion to electric energy and mediate the sequential release of metal ions (Fe2+/Ca2+/Cu2+), thereby resulting in the "cocktail effect" on impaired tissue. Under their effects, a satisfying healing result in diabetic mouse is identified, which can effectively accelerate wound healing process by relieving inflammation, promoting angiogenesis and collagen deposition. The work puts forward the cocktail effect of electric simulation coupled with the multiple metal ions, and opens up a new perspective in designing iTENG patch towards repair of hard-to-heal wounds.
2024, 35(8): 109199
doi: 10.1016/j.cclet.2023.109199
摘要:
Bladder cancer is a common malignant tumor of the urinary system with the potential to be treated by nano drug delivery system. The current work describes the synthesis and characterization of a novel nanomaterial to construct a nano-carrier based on 1-palmitoyl-2-oleoyl-sn-glycerol-3-phosphatecholine (POPC) loaded doxorubicin (DOX) and embedded with gold nanoparticles and poly(N-isopropyl acrylamide) (PNIPAM) (GNPS@PNIPAM-POPC-DOX, GPPD). The dual-sensitive nanosystem gives simultaneous photothermal treatment and chemotherapy for bladder cancer. In vitro and in vivo properties were assessed using bladder cancer cell lines and mice and GPPD system distribution, tumor inhibition, and biocompatibility are reported. The system had favorable stability, low biological toxicity, controlled release efficiency, photothermal synergistic action, efficient photothermal transition, and favorable tumor suppressive effects. As a result, GPPD is a potential therapeutic approach for bladder cancer.
Bladder cancer is a common malignant tumor of the urinary system with the potential to be treated by nano drug delivery system. The current work describes the synthesis and characterization of a novel nanomaterial to construct a nano-carrier based on 1-palmitoyl-2-oleoyl-sn-glycerol-3-phosphatecholine (POPC) loaded doxorubicin (DOX) and embedded with gold nanoparticles and poly(N-isopropyl acrylamide) (PNIPAM) (GNPS@PNIPAM-POPC-DOX, GPPD). The dual-sensitive nanosystem gives simultaneous photothermal treatment and chemotherapy for bladder cancer. In vitro and in vivo properties were assessed using bladder cancer cell lines and mice and GPPD system distribution, tumor inhibition, and biocompatibility are reported. The system had favorable stability, low biological toxicity, controlled release efficiency, photothermal synergistic action, efficient photothermal transition, and favorable tumor suppressive effects. As a result, GPPD is a potential therapeutic approach for bladder cancer.
2024, 35(8): 109223
doi: 10.1016/j.cclet.2023.109223
摘要:
Focused on the performance promotion of organic small molecular dyes based photothermal agents via non-chemical modification, we found that heat-assisted binding of human serum albumin (HSA) to the dye causes shrinkage of the protein and encapsulate the dye to form nanoparticles. This revolutionizes the photostability of small molecule dyes which further improves their photothermal conversion efficiency and tumor ablation performance as photothermal agents significantly. In this work, the obtained photothermal agent named HSA-P2-T could accumulate in tumor and induce 22 ℃ enhancement of the tumor in xenograft models upon ultra-low dose (0.1 W/cm2) laser irradiation, which, as far as we know, is the lowest laser dose used in vivo photothermal therapy. Utilizing HSA-P2-T, we realized tumor ablation upon twice intravenous injections of the nanoparticles and four photothermal treatments.
Focused on the performance promotion of organic small molecular dyes based photothermal agents via non-chemical modification, we found that heat-assisted binding of human serum albumin (HSA) to the dye causes shrinkage of the protein and encapsulate the dye to form nanoparticles. This revolutionizes the photostability of small molecule dyes which further improves their photothermal conversion efficiency and tumor ablation performance as photothermal agents significantly. In this work, the obtained photothermal agent named HSA-P2-T could accumulate in tumor and induce 22 ℃ enhancement of the tumor in xenograft models upon ultra-low dose (0.1 W/cm2) laser irradiation, which, as far as we know, is the lowest laser dose used in vivo photothermal therapy. Utilizing HSA-P2-T, we realized tumor ablation upon twice intravenous injections of the nanoparticles and four photothermal treatments.
2024, 35(8): 109226
doi: 10.1016/j.cclet.2023.109226
摘要:
Here, we present a novel bioorthogonal platform that enables precise positioning of attached moieties in close proximity, thereby facilitating the discovery and optimization of biocompatible reactions. Using this platform, we achieve a Horner-Wadsworth-Emmons (HWE) reaction under physiological conditions, generating a fluorophore in situ with a yield of up to 93%. This proximity platform should facilitate the discovery of various types of biocompatible reactions, making it a versatile tool for biomedical applications.
Here, we present a novel bioorthogonal platform that enables precise positioning of attached moieties in close proximity, thereby facilitating the discovery and optimization of biocompatible reactions. Using this platform, we achieve a Horner-Wadsworth-Emmons (HWE) reaction under physiological conditions, generating a fluorophore in situ with a yield of up to 93%. This proximity platform should facilitate the discovery of various types of biocompatible reactions, making it a versatile tool for biomedical applications.
2024, 35(8): 109227
doi: 10.1016/j.cclet.2023.109227
摘要:
Cyclooctatetraene (COT) attachment to fluorophores (“self-healing” dyes) is known for quenching reactive triplet states via triplet-state energy transfer (TET), enhancing photostability. However, COT’s impact on singlet states remains unclear. Quantum calculations reveal that COT induces energy transfer to dark states in deep blue dyes while promoting photoinduced electron transfer (PET) and intersystem crossing (ISC) in visible dyes, potentially compromising brightness and/or photostability. To address this, we propose the use of ΔE descriptor to optimize COT’s effects. Our findings uncover COT’s multifaceted impact. These insights will guide the development of superior triplet state quenchers and photostable dyes.
Cyclooctatetraene (COT) attachment to fluorophores (“self-healing” dyes) is known for quenching reactive triplet states via triplet-state energy transfer (TET), enhancing photostability. However, COT’s impact on singlet states remains unclear. Quantum calculations reveal that COT induces energy transfer to dark states in deep blue dyes while promoting photoinduced electron transfer (PET) and intersystem crossing (ISC) in visible dyes, potentially compromising brightness and/or photostability. To address this, we propose the use of ΔE descriptor to optimize COT’s effects. Our findings uncover COT’s multifaceted impact. These insights will guide the development of superior triplet state quenchers and photostable dyes.
2024, 35(8): 109241
doi: 10.1016/j.cclet.2023.109241
摘要:
Recently, the utilization of nonsteroidal anti-inflammatory drugs (NSAIDs) to sensitize cisplatin (CDDP) has gained substantial traction in the treatment of ovarian cancer (OC). However, even widely employed NSAIDs such as celecoxib and naproxen carry an elevated risk of cardiovascular events, notably thrombosis. Furthermore, the diminished sensitivity to CDDP therapy in OC is multifactorial, rendering the application of NSAIDs only partially effective due to their cyclooxygenase-2 (COX-2) inhibiting mechanism. Hence, in this study, reactive oxygen species (ROS)-responsive composite nano-hydrangeas loaded with the Chinese medicine small molecule allicin and platinum(Ⅳ) prodrug (DTP@AP NPs) were prepared to achieve comprehensive chemosensitization. On one front, allicin achieved COX-2 blocking therapy, encompassing the inhibition of proliferation, angiogenesis and endothelial mesenchymal transition (EMT), thereby mitigating the adverse impacts of CDDP chemotherapy. Simultaneously, synergistic chemosensitization was achieved from multifaceted mechanisms by decreasing CDDP inactivation, damaging mitochondria and inhibiting DNA repair. In essence, these findings provided an optimized approach for synergizing CDDP with COX-2 inhibitors, offering a promising avenue for enhancing OC treatment outcomes.
Recently, the utilization of nonsteroidal anti-inflammatory drugs (NSAIDs) to sensitize cisplatin (CDDP) has gained substantial traction in the treatment of ovarian cancer (OC). However, even widely employed NSAIDs such as celecoxib and naproxen carry an elevated risk of cardiovascular events, notably thrombosis. Furthermore, the diminished sensitivity to CDDP therapy in OC is multifactorial, rendering the application of NSAIDs only partially effective due to their cyclooxygenase-2 (COX-2) inhibiting mechanism. Hence, in this study, reactive oxygen species (ROS)-responsive composite nano-hydrangeas loaded with the Chinese medicine small molecule allicin and platinum(Ⅳ) prodrug (DTP@AP NPs) were prepared to achieve comprehensive chemosensitization. On one front, allicin achieved COX-2 blocking therapy, encompassing the inhibition of proliferation, angiogenesis and endothelial mesenchymal transition (EMT), thereby mitigating the adverse impacts of CDDP chemotherapy. Simultaneously, synergistic chemosensitization was achieved from multifaceted mechanisms by decreasing CDDP inactivation, damaging mitochondria and inhibiting DNA repair. In essence, these findings provided an optimized approach for synergizing CDDP with COX-2 inhibitors, offering a promising avenue for enhancing OC treatment outcomes.
2024, 35(8): 109243
doi: 10.1016/j.cclet.2023.109243
摘要:
Fe(II) is an essential trace element for anaerobic ammonium oxidation bacteria (AAOB) metabolism, and can improve the nitrogen removal efficiency of anaerobic ammonia oxidation (Anammox). Here we operated two identical expanded granular sludge bed (EGSB) reactors at low temperature (15 ± 3 ℃) for 154 days. Reactor 1 (R1) received additional Fe(II) (0.12 mmol/L) during the late startup phase, while reactor 0 (R0) served as the control and did not receive extra Fe(II). Nitrogen removal in R1 became stable at 55 d of operation, ten days earlier than R0. The nitrogen removal rate (NRR) of R1 was 1.64 kg N m−3 d−1 and its TN removal rate was as high as 89%, while R0 only reached 75%. The addition of Fe(II) was further beneficial to aggregation and stability of the granular sludge, and the used sludge of both reactors showed enrichment for AAOB populations compared to the inoculum, for instance, increased abundance of Candidatus-Kuenenia and in particular of Candidatus-Brocadia (from 0.17% to 10.10% in R0 and 7.79% in R1). Diverse microbial species and complex microbial network structure in R1 compared to R0 promoted the coupled denitrogenation by Anammox, dissimilatory nitrate reduction to ammonium (DNRA), nitrate-dependent Fe oxidation (NDFO), and ferric ammonium oxidation (Feammox). In addition, the microbial community in R1 was more resistant to short-term low temperature (2–7 ℃) starvation, illustrating a further positive effect of adding Fe(II) during the startup phase of an Anammox reactor.
Fe(II) is an essential trace element for anaerobic ammonium oxidation bacteria (AAOB) metabolism, and can improve the nitrogen removal efficiency of anaerobic ammonia oxidation (Anammox). Here we operated two identical expanded granular sludge bed (EGSB) reactors at low temperature (15 ± 3 ℃) for 154 days. Reactor 1 (R1) received additional Fe(II) (0.12 mmol/L) during the late startup phase, while reactor 0 (R0) served as the control and did not receive extra Fe(II). Nitrogen removal in R1 became stable at 55 d of operation, ten days earlier than R0. The nitrogen removal rate (NRR) of R1 was 1.64 kg N m−3 d−1 and its TN removal rate was as high as 89%, while R0 only reached 75%. The addition of Fe(II) was further beneficial to aggregation and stability of the granular sludge, and the used sludge of both reactors showed enrichment for AAOB populations compared to the inoculum, for instance, increased abundance of Candidatus-Kuenenia and in particular of Candidatus-Brocadia (from 0.17% to 10.10% in R0 and 7.79% in R1). Diverse microbial species and complex microbial network structure in R1 compared to R0 promoted the coupled denitrogenation by Anammox, dissimilatory nitrate reduction to ammonium (DNRA), nitrate-dependent Fe oxidation (NDFO), and ferric ammonium oxidation (Feammox). In addition, the microbial community in R1 was more resistant to short-term low temperature (2–7 ℃) starvation, illustrating a further positive effect of adding Fe(II) during the startup phase of an Anammox reactor.
2024, 35(8): 109248
doi: 10.1016/j.cclet.2023.109248
摘要:
Idiopathic pulmonary fibrosis (IPF) is a chronic and fatal lung disease characterized by pulmonary inflammation, oxidative stress, and excessive extracellular matrix (ECM) deposition. Current anti-fibrotic drugs for IPF treatment in the clinic lack selectivity and demonstrate unsatisfactory efficacy, highlighting the urgent necessity for a novel therapeutic strategy. Taraxasterol (TA), which has biological activities against lung injury induced by various factors, is a potential anti-IPF drug due to its anti-inflammatory, antioxidant and lung-protective effects. However, the protective effect of TA on IPF has not been confirmed, and its clinical application is limited due to its poor aqueous solubility. In this study, we demonstrated that TA could inhibit epithelial-mesenchymal transition (EMT) and migration of A549 cells by inhibiting the transforming growth factor-β1 (TGF-β1)/Smad signaling pathway. To improve the aqueous solubility and pulmonary administration performance of TA, we prepared TA loaded methoxy poly(ethylene glycol)-poly(d, l-lactide) (mPEG-PLA)/d-α-tocopheryl polyethylene glycol succinate (TPGS) mixed polymeric micelles (TA-PM). Then a MicroSprayerⓇ Aerosolizer was used to deliver TA-PM once every two days for three weeks to evaluate their therapeutic effects on bleomycin (BLM)-induced IPF mice. Our results demonstrated that inhaled TA-PM significantly inhibited BLM-induced inflammation, oxidative stress and fibrosis in lung tissue. Furthermore, TA-PM exhibited high pulmonary deposition and retention by pulmonary administration, along with a favorable safety profile. Overall, this study emphasizes the potential of inhaled TA-PM as a promising treatment for IPF, providing a new opportunity for their clinical application.
Idiopathic pulmonary fibrosis (IPF) is a chronic and fatal lung disease characterized by pulmonary inflammation, oxidative stress, and excessive extracellular matrix (ECM) deposition. Current anti-fibrotic drugs for IPF treatment in the clinic lack selectivity and demonstrate unsatisfactory efficacy, highlighting the urgent necessity for a novel therapeutic strategy. Taraxasterol (TA), which has biological activities against lung injury induced by various factors, is a potential anti-IPF drug due to its anti-inflammatory, antioxidant and lung-protective effects. However, the protective effect of TA on IPF has not been confirmed, and its clinical application is limited due to its poor aqueous solubility. In this study, we demonstrated that TA could inhibit epithelial-mesenchymal transition (EMT) and migration of A549 cells by inhibiting the transforming growth factor-β1 (TGF-β1)/Smad signaling pathway. To improve the aqueous solubility and pulmonary administration performance of TA, we prepared TA loaded methoxy poly(ethylene glycol)-poly(d, l-lactide) (mPEG-PLA)/d-α-tocopheryl polyethylene glycol succinate (TPGS) mixed polymeric micelles (TA-PM). Then a MicroSprayerⓇ Aerosolizer was used to deliver TA-PM once every two days for three weeks to evaluate their therapeutic effects on bleomycin (BLM)-induced IPF mice. Our results demonstrated that inhaled TA-PM significantly inhibited BLM-induced inflammation, oxidative stress and fibrosis in lung tissue. Furthermore, TA-PM exhibited high pulmonary deposition and retention by pulmonary administration, along with a favorable safety profile. Overall, this study emphasizes the potential of inhaled TA-PM as a promising treatment for IPF, providing a new opportunity for their clinical application.
2024, 35(8): 109251
doi: 10.1016/j.cclet.2023.109251
摘要:
The selective 2e− ORR reaction on polymeric carbon nitride framework is one of the most promising approaches for solar-driven hydrogen peroxide production. Poly(heptazine imide) (PHI) as a class of K+-incorporated crystalline carbon nitride framework, is highly active for photocatalytic H2O2 production. An upgrade on the H2O2 photoproduction performance of PHI is realized and the mechanistic insights are revealed in this work. By photochemical reaction, the electron withdrawing groups of hydroxyl group and cyano group are grafted on the surface of PHI frameworks. The dual polarization sites on the surface contribute significantly to the enhancement of the exciton dissociation. The optimized PHI with dual polarization sites exhibits a remarkable photocatalytic H2O2 production performance, which is 2 times of the active pristine PHI. Most importantly, the photochemical reaction method is generally applicable to improve the exciton dissociation of a wide range of polymeric carbon nitride frameworks with various structure and compositions; and the thiourea-derived polymeric carbon nitride framework with dual surface polarization sites exhibits a remarkable photocatalytic performance with a high H2O2 production rate of 40.5 mmol h−1 g−1.
The selective 2e− ORR reaction on polymeric carbon nitride framework is one of the most promising approaches for solar-driven hydrogen peroxide production. Poly(heptazine imide) (PHI) as a class of K+-incorporated crystalline carbon nitride framework, is highly active for photocatalytic H2O2 production. An upgrade on the H2O2 photoproduction performance of PHI is realized and the mechanistic insights are revealed in this work. By photochemical reaction, the electron withdrawing groups of hydroxyl group and cyano group are grafted on the surface of PHI frameworks. The dual polarization sites on the surface contribute significantly to the enhancement of the exciton dissociation. The optimized PHI with dual polarization sites exhibits a remarkable photocatalytic H2O2 production performance, which is 2 times of the active pristine PHI. Most importantly, the photochemical reaction method is generally applicable to improve the exciton dissociation of a wide range of polymeric carbon nitride frameworks with various structure and compositions; and the thiourea-derived polymeric carbon nitride framework with dual surface polarization sites exhibits a remarkable photocatalytic performance with a high H2O2 production rate of 40.5 mmol h−1 g−1.
2024, 35(8): 109254
doi: 10.1016/j.cclet.2023.109254
摘要:
Oxidative therapies receive a limited antitumor efficiency due to the insufficient reactive oxygen species (ROS) levels at focal sites and the evolvement of antioxidant defense systems. Herein, we develop an albumin-based nanomedicine to co-deliver chlorin e6 (Ce6) and COH-SR4 (CS), which can simultaneously enhance the yield and lethality of intracellular ROS for amplified photodynamic therapy (PDT). In which, CS acts as both an activator of AMP-activated protein kinase (AMPK) and an inhibitor of glutathione S-transferases (GSTs). Benefiting from it, the prepared HSA-Ce6@COH-SR4 (HCCS) enables positive feedback uptake by promoting AMPK phosphorylation, leading to rapid and extensive tumor accumulation of drugs. As a result, HCCS obviously increases the ROS production to elevate intracellular oxidative stress. Furthermore, HCCS can inhibit GSTs to disturb the antioxidant defense system of tumor cells, intensifying the oxidative damage of ROS. Ultimately, the PDT of HCCS is significantly strengthened by improving the ROS yield and lethality, which greatly declines the proliferation of breast cancer in vivo. This study may open a window in the development of drug co-delivery system for enhanced oxidative therapy of tumors.
Oxidative therapies receive a limited antitumor efficiency due to the insufficient reactive oxygen species (ROS) levels at focal sites and the evolvement of antioxidant defense systems. Herein, we develop an albumin-based nanomedicine to co-deliver chlorin e6 (Ce6) and COH-SR4 (CS), which can simultaneously enhance the yield and lethality of intracellular ROS for amplified photodynamic therapy (PDT). In which, CS acts as both an activator of AMP-activated protein kinase (AMPK) and an inhibitor of glutathione S-transferases (GSTs). Benefiting from it, the prepared HSA-Ce6@COH-SR4 (HCCS) enables positive feedback uptake by promoting AMPK phosphorylation, leading to rapid and extensive tumor accumulation of drugs. As a result, HCCS obviously increases the ROS production to elevate intracellular oxidative stress. Furthermore, HCCS can inhibit GSTs to disturb the antioxidant defense system of tumor cells, intensifying the oxidative damage of ROS. Ultimately, the PDT of HCCS is significantly strengthened by improving the ROS yield and lethality, which greatly declines the proliferation of breast cancer in vivo. This study may open a window in the development of drug co-delivery system for enhanced oxidative therapy of tumors.
2024, 35(8): 109259
doi: 10.1016/j.cclet.2023.109259
摘要:
Sleep deprivation (SD) is a widespread issue that disrupts the lives of millions of people. These effects initiate as changes within neurons, specifically at the DNA and RNA level, leading to disruptions in neuronal plasticity and the dysregulation of various cognitive functions, such as learning and memory. Nucleic acid epigenetic modifications that could regulate gene expression have been reported to play crucial roles in this process. However, there is a lack of comprehensive research on the correlation of SD with nucleic acid epigenetic modifications. In the current study, we aimed to systematically investigate the landscape of modifications in DNA as well as in small RNA molecules across multiple tissues, including the heart, liver, kidney, lung, hippocampus, and spleen, in response to chronic sleep deprivation (CSD). Using liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis, we characterized the dynamic changes in DNA and RNA modification profiles in different tissues of mice under CSD stress. Specifically, we observed a significant decrease in the level of 5-methylcytosine (5mC) and a significant increase in the level of 5-hydroxymethylcytosine (5hmC) in the kidney in CSD group. Regarding RNA modifications, we observed an overall increased trend for most of these significantly changed modifications across six tissues in CSD group. Our study sheds light on the significance of DNA and RNA modifications as crucial epigenetic markers in the context of CSD-induced stress.
Sleep deprivation (SD) is a widespread issue that disrupts the lives of millions of people. These effects initiate as changes within neurons, specifically at the DNA and RNA level, leading to disruptions in neuronal plasticity and the dysregulation of various cognitive functions, such as learning and memory. Nucleic acid epigenetic modifications that could regulate gene expression have been reported to play crucial roles in this process. However, there is a lack of comprehensive research on the correlation of SD with nucleic acid epigenetic modifications. In the current study, we aimed to systematically investigate the landscape of modifications in DNA as well as in small RNA molecules across multiple tissues, including the heart, liver, kidney, lung, hippocampus, and spleen, in response to chronic sleep deprivation (CSD). Using liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis, we characterized the dynamic changes in DNA and RNA modification profiles in different tissues of mice under CSD stress. Specifically, we observed a significant decrease in the level of 5-methylcytosine (5mC) and a significant increase in the level of 5-hydroxymethylcytosine (5hmC) in the kidney in CSD group. Regarding RNA modifications, we observed an overall increased trend for most of these significantly changed modifications across six tissues in CSD group. Our study sheds light on the significance of DNA and RNA modifications as crucial epigenetic markers in the context of CSD-induced stress.
2024, 35(8): 109260
doi: 10.1016/j.cclet.2023.109260
摘要:
Bioprinting is emerging as an advanced tool in tissue engineering. However, there is still a lack of bioinks able to form hydrogels with desirable bioactivities that support positive cell behaviors. In this study, modified plasma proteins capable of forming hydrogels with multiple biological functions are developed as bioinks for digital light processing (DLP) printing. The Plasma-MA (BM) was synthesized via a one-pot method through the reaction between the fresh frozen plasma and methacrylic anhydride. The methacrylated levels were observed to influence the physical properties of BM hydrogels including mechanical properties, swelling, and degradation. The photo-crosslinked BM hydrogels can sustainedly release vascular endothelial growth factor (VEGF) and exhibit positive biological effects on cell adhesion and proliferation, and cell functionality such as tube formation of human umbilical vein endothelial cells (HUVECs), and neurite elongation of rat pheochromocytoma cells (PC12). Meanwhile, BM hydrogels can also induce cell infiltration, modulate immune response, and promote angiogenesis in vivo. Moreover, the plasma bioinks can be used to fabricate customized scaffolds with complex structures through a DLP printing process. These findings implicate that the modified plasma with growth factor release is a promising candidate for bioprinting in autologous and personalized tissue engineering.
Bioprinting is emerging as an advanced tool in tissue engineering. However, there is still a lack of bioinks able to form hydrogels with desirable bioactivities that support positive cell behaviors. In this study, modified plasma proteins capable of forming hydrogels with multiple biological functions are developed as bioinks for digital light processing (DLP) printing. The Plasma-MA (BM) was synthesized via a one-pot method through the reaction between the fresh frozen plasma and methacrylic anhydride. The methacrylated levels were observed to influence the physical properties of BM hydrogels including mechanical properties, swelling, and degradation. The photo-crosslinked BM hydrogels can sustainedly release vascular endothelial growth factor (VEGF) and exhibit positive biological effects on cell adhesion and proliferation, and cell functionality such as tube formation of human umbilical vein endothelial cells (HUVECs), and neurite elongation of rat pheochromocytoma cells (PC12). Meanwhile, BM hydrogels can also induce cell infiltration, modulate immune response, and promote angiogenesis in vivo. Moreover, the plasma bioinks can be used to fabricate customized scaffolds with complex structures through a DLP printing process. These findings implicate that the modified plasma with growth factor release is a promising candidate for bioprinting in autologous and personalized tissue engineering.
2024, 35(8): 109262
doi: 10.1016/j.cclet.2023.109262
摘要:
Recently, a novel 2-electron oxygen reduction reaction (ORR) based electro-oxidation (EO) system was developed, which utilizes a H2O2 generation cathode instead of H2 evolution cathode. A Ti-based Ni-Sb co-doped SnO2 (Ti/NATO) anode was selected for efficient degradation of refractory organics and O3 production. The synergistic reaction of O3/H2O2 further accelerated the generation of hydroxyl radicals (•OH) in the ORR-EO system. However, the catalytic activity and long-term effectiveness of the Ti/NATO anode limited the large-scale application of the ORR-EO process. In this study, a blue TiO2 nanotube array (blue-TiO2-NTA) inter-layer was introduced into the fabrication process between the Ti substrate and NATO catalyst layer. Compared to the Ti/NATO anode, the Ti/blue-TiO2-NTA/NATO anode achieved higher efficiency of organic removal and O3 generation. Additionally, the accelerated lifetime of the Ti/blue-TiO2-NTA/NATO anode was increased by 7 times compared to the Ti/NATO anode. When combined with CNTs-C/PTFE air cathode in ORR-EO system, all anodic oxidation and O3/H2O2 processes achieved higher •OH production. Over 92% of TOC in leachate bio-effluent was effectively eliminated with a relatively low energy cost of 45 kWh/t.
Recently, a novel 2-electron oxygen reduction reaction (ORR) based electro-oxidation (EO) system was developed, which utilizes a H2O2 generation cathode instead of H2 evolution cathode. A Ti-based Ni-Sb co-doped SnO2 (Ti/NATO) anode was selected for efficient degradation of refractory organics and O3 production. The synergistic reaction of O3/H2O2 further accelerated the generation of hydroxyl radicals (•OH) in the ORR-EO system. However, the catalytic activity and long-term effectiveness of the Ti/NATO anode limited the large-scale application of the ORR-EO process. In this study, a blue TiO2 nanotube array (blue-TiO2-NTA) inter-layer was introduced into the fabrication process between the Ti substrate and NATO catalyst layer. Compared to the Ti/NATO anode, the Ti/blue-TiO2-NTA/NATO anode achieved higher efficiency of organic removal and O3 generation. Additionally, the accelerated lifetime of the Ti/blue-TiO2-NTA/NATO anode was increased by 7 times compared to the Ti/NATO anode. When combined with CNTs-C/PTFE air cathode in ORR-EO system, all anodic oxidation and O3/H2O2 processes achieved higher •OH production. Over 92% of TOC in leachate bio-effluent was effectively eliminated with a relatively low energy cost of 45 kWh/t.
2024, 35(8): 109264
doi: 10.1016/j.cclet.2023.109264
摘要:
Hexokinase 2 (HK2) is the rate-limiting enzyme in the first step of glycolysis, catalyzing glucose to glucose-6-phosphate, and overexpressed in most cancer cells. HK2 also binds to voltage-dependent anion channel (VDAC) to stabilize the mitochondrial outer membrane, which inhibits cancer cell apoptosis. Therefore, HK2 has become a potential target for cancer treatment. Proteolysis targeting chimeras (PROTACs) are hetero-bifunctional molecules that recruit an E3 ubiquitin ligase to a given substrate protein resulting in its targeted degradation. Many potent and specific PROTACs targeting dissimilar targets have been developed. In this study, an HK2 PROTAC, 4H-5P-M, was developed and induced the degradation of HK2 relying on the ubiquitin-proteasome system. It was found that 4H-5P-M as an effective HK2 degrader induced HK2 degradation in a dose- and time-dependent manner and suppressed the growth of SW480 cells. 4H-5P-M selectively induced HK2 degradation at a lower concentration than other hexokinase isozymes. Moreover, it could suppress glycolysis and accelerate the apoptosis of cancer cells. Therefore, it provided a new insight into the development of anti-tumor drugs.
Hexokinase 2 (HK2) is the rate-limiting enzyme in the first step of glycolysis, catalyzing glucose to glucose-6-phosphate, and overexpressed in most cancer cells. HK2 also binds to voltage-dependent anion channel (VDAC) to stabilize the mitochondrial outer membrane, which inhibits cancer cell apoptosis. Therefore, HK2 has become a potential target for cancer treatment. Proteolysis targeting chimeras (PROTACs) are hetero-bifunctional molecules that recruit an E3 ubiquitin ligase to a given substrate protein resulting in its targeted degradation. Many potent and specific PROTACs targeting dissimilar targets have been developed. In this study, an HK2 PROTAC, 4H-5P-M, was developed and induced the degradation of HK2 relying on the ubiquitin-proteasome system. It was found that 4H-5P-M as an effective HK2 degrader induced HK2 degradation in a dose- and time-dependent manner and suppressed the growth of SW480 cells. 4H-5P-M selectively induced HK2 degradation at a lower concentration than other hexokinase isozymes. Moreover, it could suppress glycolysis and accelerate the apoptosis of cancer cells. Therefore, it provided a new insight into the development of anti-tumor drugs.
2024, 35(8): 109270
doi: 10.1016/j.cclet.2023.109270
摘要:
The monkeypox virus (MPXV) outbreak, declared a Public Health Emergency of International Concern (PHEIC) by the World Health Organization (WHO) in 2022, continues to pose a significant threat due to the absence of vaccines or drugs for MPXV infection. In this study, we developed an mRNA vaccine that expressing the A29L antigen, a specific protein of the intracellular mature virus. Our vaccine utilizes a thermostable ionizable lipid nanoparticle (iLNP) platform and has been administered to mice. Our findings demonstrate that the MPXV A29L mRNA vaccine candidate induces robust cross-neutralizing immune responses against both vaccinia virus (VACV) and MPXV live virus. Furthermore, immunization with the vaccine candidate provided protection against the VACV challenge in mice. These findings underscore the potential of mRNA-LNP vaccines as safe and effective candidates against monkeypox epidemics. Given the current absence of specific interventions for MPXV infection, our study represents a significant step forward in developing a viable solution to combat this ongoing public health threat.
The monkeypox virus (MPXV) outbreak, declared a Public Health Emergency of International Concern (PHEIC) by the World Health Organization (WHO) in 2022, continues to pose a significant threat due to the absence of vaccines or drugs for MPXV infection. In this study, we developed an mRNA vaccine that expressing the A29L antigen, a specific protein of the intracellular mature virus. Our vaccine utilizes a thermostable ionizable lipid nanoparticle (iLNP) platform and has been administered to mice. Our findings demonstrate that the MPXV A29L mRNA vaccine candidate induces robust cross-neutralizing immune responses against both vaccinia virus (VACV) and MPXV live virus. Furthermore, immunization with the vaccine candidate provided protection against the VACV challenge in mice. These findings underscore the potential of mRNA-LNP vaccines as safe and effective candidates against monkeypox epidemics. Given the current absence of specific interventions for MPXV infection, our study represents a significant step forward in developing a viable solution to combat this ongoing public health threat.
2024, 35(8): 109275
doi: 10.1016/j.cclet.2023.109275
摘要:
Essential amino acids (EAAs) deprivation is a potential antitumor approach because EAAs are critical for tumor growth. To efficiently inhibit tumor growth, continuous deprivation of EAAs is required, however, continuous deprivation without precise control will introduce toxicity to normal cells. Herein, a programmable double-unlock nanocomplex (ROCK) was prepared, which could self-supply phenylalanine ammonia-lyase (PAL) to tumor cells for phenylalanine (Phe) deprivation. ROCK was double-locked in physiological conditions when administered systemically. While ROCK actively targeted to tumor cells by integrin αvβ3/5 and CD44, ROCK was firstly unlocked by cleavage of protease on tumor cell membrane, exposing CendR and R8 to enhance endocytosis. Then, hyaluronic acid was digested by hyaluronidase overexpressed in endo/lysosome of tumor cells, in which ROCK was secondly unlocked, resulting in promoting endo/lysosome escape and PAL plasmid (pPAL) release. Released pPAL could sustainably express PAL in host tumor cells until the self-supplied PAL precisely and successfully deprived Phe, thereby blocking the protein synthesis and killing tumor cells specifically. Overall, our precise Phe deprivation strategy effectively inhibited tumor growth with no observable toxicity to normal cells, providing new insights to efficiently remove intratumoral nutrition for cancer therapy.
Essential amino acids (EAAs) deprivation is a potential antitumor approach because EAAs are critical for tumor growth. To efficiently inhibit tumor growth, continuous deprivation of EAAs is required, however, continuous deprivation without precise control will introduce toxicity to normal cells. Herein, a programmable double-unlock nanocomplex (ROCK) was prepared, which could self-supply phenylalanine ammonia-lyase (PAL) to tumor cells for phenylalanine (Phe) deprivation. ROCK was double-locked in physiological conditions when administered systemically. While ROCK actively targeted to tumor cells by integrin αvβ3/5 and CD44, ROCK was firstly unlocked by cleavage of protease on tumor cell membrane, exposing CendR and R8 to enhance endocytosis. Then, hyaluronic acid was digested by hyaluronidase overexpressed in endo/lysosome of tumor cells, in which ROCK was secondly unlocked, resulting in promoting endo/lysosome escape and PAL plasmid (pPAL) release. Released pPAL could sustainably express PAL in host tumor cells until the self-supplied PAL precisely and successfully deprived Phe, thereby blocking the protein synthesis and killing tumor cells specifically. Overall, our precise Phe deprivation strategy effectively inhibited tumor growth with no observable toxicity to normal cells, providing new insights to efficiently remove intratumoral nutrition for cancer therapy.
2024, 35(8): 109278
doi: 10.1016/j.cclet.2023.109278
摘要:
Facile and efficient method for constructing carbon dots (CDs) with narrow full width at half maximum (FWHM) is a major challenge in the field, and researches on regulating the FWHM of CDs are also rare and scarce. In this work, we delved into the synthesis of CDs with narrow fluorescence emission FWHM (NFEF-CDs) in the m-phenylenediamine (m-PD)/ethanol system, utilizing solid superacid resin as catalyst with solvothermal method. The resulting NFEF-CDs exhibit a photoluminescent (PL) emission peak at 521 nm with a narrow FWHM of 41 nm, an absolute PL quantum yield (QY) of 80%, and display excitation-independent PL behavior. Through comprehensive characterization, we identified the protonation of edge amino on NFEF-CDs as the key factor in achieving the narrow FWHM. Subsequently, we validated the broad applicability of solid superacid resins as catalysts for synthesizing CDs with narrow FWHM in the m-PD/ethanol system. Finally, we utilized a self-leveling method to prepare NFEF-CDs film on the surface of poly(methyl methacrylate) (PMMA) substrate and investigated the solid-state fluorescence properties of NFEF-CDs as well as their performance as luminescence solar concentrator (LSC) for photovoltaic conversion. The results revealed that the as-prepared LSC exhibit an internal quantum efficiency (ηint) of 42.39% and an optical efficiency (ηopt) of 0.68%. These findings demonstrate the promising prospects of NFEF-CDs in the field of LSCs and provide a theoretical basis for their application in photovoltaic conversion.
Facile and efficient method for constructing carbon dots (CDs) with narrow full width at half maximum (FWHM) is a major challenge in the field, and researches on regulating the FWHM of CDs are also rare and scarce. In this work, we delved into the synthesis of CDs with narrow fluorescence emission FWHM (NFEF-CDs) in the m-phenylenediamine (m-PD)/ethanol system, utilizing solid superacid resin as catalyst with solvothermal method. The resulting NFEF-CDs exhibit a photoluminescent (PL) emission peak at 521 nm with a narrow FWHM of 41 nm, an absolute PL quantum yield (QY) of 80%, and display excitation-independent PL behavior. Through comprehensive characterization, we identified the protonation of edge amino on NFEF-CDs as the key factor in achieving the narrow FWHM. Subsequently, we validated the broad applicability of solid superacid resins as catalysts for synthesizing CDs with narrow FWHM in the m-PD/ethanol system. Finally, we utilized a self-leveling method to prepare NFEF-CDs film on the surface of poly(methyl methacrylate) (PMMA) substrate and investigated the solid-state fluorescence properties of NFEF-CDs as well as their performance as luminescence solar concentrator (LSC) for photovoltaic conversion. The results revealed that the as-prepared LSC exhibit an internal quantum efficiency (ηint) of 42.39% and an optical efficiency (ηopt) of 0.68%. These findings demonstrate the promising prospects of NFEF-CDs in the field of LSCs and provide a theoretical basis for their application in photovoltaic conversion.
2024, 35(8): 109291
doi: 10.1016/j.cclet.2023.109291
摘要:
Intracellular ATP is an emerging biomarker for cancer early diagnosis because it is a key messenger for regulating the proliferation and migration of cancer cells. However, the conventional ATP biosensing strategy is often limited by the undesired on-target off-tumor interference. Here, we reported a novel strategy to design enzymatically controlled DNA tetrahedron nanoprobes (En-DT) for biosensing and imaging ATP in tumor cells. The En-DT was designed via rational engineering of structure-switching aptamers with the incorporation of an enzyme-activatable site and further conjugation on the DNA tetrahedron. The En-DT could be catalytically activated by apurinic/apyrimidinic endonuclease 1 (APE1) in cancer cells, but they did not respond to ATP in normal cells, thereby enabling cancer-specific ATP biosensing and imaging in vitro and in vivo with improved tumor specificity. This strategy would facilitate the precise detection of a broad range of biomarker in tumors and may promote the development of smart probes for cancer diagnosis.
Intracellular ATP is an emerging biomarker for cancer early diagnosis because it is a key messenger for regulating the proliferation and migration of cancer cells. However, the conventional ATP biosensing strategy is often limited by the undesired on-target off-tumor interference. Here, we reported a novel strategy to design enzymatically controlled DNA tetrahedron nanoprobes (En-DT) for biosensing and imaging ATP in tumor cells. The En-DT was designed via rational engineering of structure-switching aptamers with the incorporation of an enzyme-activatable site and further conjugation on the DNA tetrahedron. The En-DT could be catalytically activated by apurinic/apyrimidinic endonuclease 1 (APE1) in cancer cells, but they did not respond to ATP in normal cells, thereby enabling cancer-specific ATP biosensing and imaging in vitro and in vivo with improved tumor specificity. This strategy would facilitate the precise detection of a broad range of biomarker in tumors and may promote the development of smart probes for cancer diagnosis.
2024, 35(8): 109301
doi: 10.1016/j.cclet.2023.109301
摘要:
Metal-nanocluster materials have gradually become a promising electrode candidate for supercapacitor application. The high-efficient and rational architecture of these metal-nanocluster electrode materials with satisfied supercapacitive performance are full of challenges. Herein, Fe-nanocluster anchored porous carbon (FAPC) nanosheets were constructed through a facile and low-cost impregnation-activation strategy. Various characterization methods documented that FAPC nanosheets possessed a mesopore-dominated structure with large surface area and abundant Fe-N4 active sites, which are crucial for supercapacitive energy storage. The optimal FAPC electrode exhibited a high specific capacitance of 378 F/g at a specific current of 1 A/g and an excellent rate capability (271 F/g at 10 A/g), which are comparable or even superior to that of most reported carbon candidates. Furthermore, the FAPC-based device achieved a desired specific energy of 14.8 Wh/kg at a specific power of 700 W/kg. This work opens a new avenue to design metal-nanocluster materials for high-performance biomass waste-based supercapacitors.
Metal-nanocluster materials have gradually become a promising electrode candidate for supercapacitor application. The high-efficient and rational architecture of these metal-nanocluster electrode materials with satisfied supercapacitive performance are full of challenges. Herein, Fe-nanocluster anchored porous carbon (FAPC) nanosheets were constructed through a facile and low-cost impregnation-activation strategy. Various characterization methods documented that FAPC nanosheets possessed a mesopore-dominated structure with large surface area and abundant Fe-N4 active sites, which are crucial for supercapacitive energy storage. The optimal FAPC electrode exhibited a high specific capacitance of 378 F/g at a specific current of 1 A/g and an excellent rate capability (271 F/g at 10 A/g), which are comparable or even superior to that of most reported carbon candidates. Furthermore, the FAPC-based device achieved a desired specific energy of 14.8 Wh/kg at a specific power of 700 W/kg. This work opens a new avenue to design metal-nanocluster materials for high-performance biomass waste-based supercapacitors.
2024, 35(8): 109325
doi: 10.1016/j.cclet.2023.109325
摘要:
Flow-electrode capacitive deionization (FCDI) represents a promising approach for ion separation from aqueous solutions. However, the optimization of spacer, particularly for nitrate-contaminated groundwater systems, has often been overlooked. This research comprehensively investigates the influence of using a conductive (carbon cloth, CC) spacer on nitrate removal performance within FCDI system, comparing it to a non-conductive (nylon net, NN) spacer. In both CC and NN FCDI systems, it is unsurprisingly that nitrate removal efficiency improved notably with the increasing current density and hydraulic retention time (HRT). Interestingly, the specific energy consumption (SEC) for nitrate removal did not show obvious fluctuations when the current density and HRT varied in both systems. Under the auspiciously optimized process parameters, CC-FCDI attained a 20% superior nitrate removal efficiency relative to NN-FCDI, accompanied by a notably diminished SEC for CC-FCDI, registering at a mere 28% of NN-FCDI. This great improvement can be primarily attributed to the decrement in FCDI internal resistance after using conductive spacer, which further confirmed by electrochemical tests such as linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). Upon prolonged continuous nitrate removal at the optimized conditions, the CC-FCDI system achieved a consistent 90% nitrate removal efficiency with a low SEC of 2.7–7.8 kWh/kg NO3-N, underscoring its steady performance. Overall, this study highlights the pivotal importance of careful spacer design and optimization in realizing energy-efficient groundwater treatment via FCDI.
Flow-electrode capacitive deionization (FCDI) represents a promising approach for ion separation from aqueous solutions. However, the optimization of spacer, particularly for nitrate-contaminated groundwater systems, has often been overlooked. This research comprehensively investigates the influence of using a conductive (carbon cloth, CC) spacer on nitrate removal performance within FCDI system, comparing it to a non-conductive (nylon net, NN) spacer. In both CC and NN FCDI systems, it is unsurprisingly that nitrate removal efficiency improved notably with the increasing current density and hydraulic retention time (HRT). Interestingly, the specific energy consumption (SEC) for nitrate removal did not show obvious fluctuations when the current density and HRT varied in both systems. Under the auspiciously optimized process parameters, CC-FCDI attained a 20% superior nitrate removal efficiency relative to NN-FCDI, accompanied by a notably diminished SEC for CC-FCDI, registering at a mere 28% of NN-FCDI. This great improvement can be primarily attributed to the decrement in FCDI internal resistance after using conductive spacer, which further confirmed by electrochemical tests such as linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). Upon prolonged continuous nitrate removal at the optimized conditions, the CC-FCDI system achieved a consistent 90% nitrate removal efficiency with a low SEC of 2.7–7.8 kWh/kg NO3-N, underscoring its steady performance. Overall, this study highlights the pivotal importance of careful spacer design and optimization in realizing energy-efficient groundwater treatment via FCDI.
2024, 35(8): 109327
doi: 10.1016/j.cclet.2023.109327
摘要:
Electrochemical-nitrate-reduction-reaction (eNitRR) synthesis of ammonia is an effective way to treat nitrate wastewater and alleviate the pressure of the Haber-Bosch ammonia production industry. How to develop effective catalysts to electrochemically reduce nitrate to ammonia and purify sewage under complex environmental conditions is the focus of current research. Herein, the dopamine polymerization process and the [(C12H8N2)2Cu]2+ complex embedding process were run simultaneously in time and space, and ultrafine Cu nanoparticles (Cu/CN) were effectively loaded on nitrogen-doped carbon after heat treatment. Using Cu/CN as the catalyst, the ammonia yield rate and Faradaic efficiency of the electrochemical conversion of to NH3 are highly 8984.0 µg h−1 mgcat.−1 and 95.6%, respectively. Even in the face of complex water environments, such as neutral media, acidic media, coexisting ions, and actual nitrate wastewater, nitrate wastewater can be effectively purified to form high value-added ammonia. The strategy of simultaneous embedding increases the exposure rate of Cu sites, and the support of CN is also beneficial to reduce the energy barrier of *NO3 activation. This study rationally designed catalysts that are beneficial to eNitRR, and considered the situation faced by practical applications during the research stage, reducing the performance gap between laboratory exploration and industrial applications.
Electrochemical-nitrate-reduction-reaction (eNitRR) synthesis of ammonia is an effective way to treat nitrate wastewater and alleviate the pressure of the Haber-Bosch ammonia production industry. How to develop effective catalysts to electrochemically reduce nitrate to ammonia and purify sewage under complex environmental conditions is the focus of current research. Herein, the dopamine polymerization process and the [(C12H8N2)2Cu]2+ complex embedding process were run simultaneously in time and space, and ultrafine Cu nanoparticles (Cu/CN) were effectively loaded on nitrogen-doped carbon after heat treatment. Using Cu/CN as the catalyst, the ammonia yield rate and Faradaic efficiency of the electrochemical conversion of to NH3 are highly 8984.0 µg h−1 mgcat.−1 and 95.6%, respectively. Even in the face of complex water environments, such as neutral media, acidic media, coexisting ions, and actual nitrate wastewater, nitrate wastewater can be effectively purified to form high value-added ammonia. The strategy of simultaneous embedding increases the exposure rate of Cu sites, and the support of CN is also beneficial to reduce the energy barrier of *NO3 activation. This study rationally designed catalysts that are beneficial to eNitRR, and considered the situation faced by practical applications during the research stage, reducing the performance gap between laboratory exploration and industrial applications.
2024, 35(8): 109331
doi: 10.1016/j.cclet.2023.109331
摘要:
In Fenton-like oxidation, the catalyst directly influences the reaction mechanism for the degradation of pollutants from water. Here, a α-MnO2 catalyst (OAm-1) was synthesized via a self-assembly method with the assistance of a surfactant. OAm-1 possessed a large specific surface area of 221 m2/g, abundant mesoporous structures and a large proportion of Mn(Ⅲ). Further characterization exhibited that OAm-1 had abundant oxygen vacancies and excellent reducibility and conductivity. The adsorption and catalytic ability of OAm-1 were studied in the degradation of oxytetracycline (OTC) via the activation of hydrogen peroxide (H2O2). Through the radical quenching experiments, electron resonance spectroscopy (EPR), X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FT-IR) analysis, Mn(Ⅲ) of OAm-1 was proved to be the active sites for the chemisorption of OTC. Systematic electrochemical experiments and analysis have shown that a process of electron transfer mediated by OAm-1 occurred between the pollutant and H2O2 during a Fenton-like reaction. This work experimentally verifies the electron transfer process dominated nonradical mechanism over α-MnO2, which is helpful for understanding the catalytic mechanism of the Fenton-like oxidation.
In Fenton-like oxidation, the catalyst directly influences the reaction mechanism for the degradation of pollutants from water. Here, a α-MnO2 catalyst (OAm-1) was synthesized via a self-assembly method with the assistance of a surfactant. OAm-1 possessed a large specific surface area of 221 m2/g, abundant mesoporous structures and a large proportion of Mn(Ⅲ). Further characterization exhibited that OAm-1 had abundant oxygen vacancies and excellent reducibility and conductivity. The adsorption and catalytic ability of OAm-1 were studied in the degradation of oxytetracycline (OTC) via the activation of hydrogen peroxide (H2O2). Through the radical quenching experiments, electron resonance spectroscopy (EPR), X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FT-IR) analysis, Mn(Ⅲ) of OAm-1 was proved to be the active sites for the chemisorption of OTC. Systematic electrochemical experiments and analysis have shown that a process of electron transfer mediated by OAm-1 occurred between the pollutant and H2O2 during a Fenton-like reaction. This work experimentally verifies the electron transfer process dominated nonradical mechanism over α-MnO2, which is helpful for understanding the catalytic mechanism of the Fenton-like oxidation.
2024, 35(8): 109334
doi: 10.1016/j.cclet.2023.109334
摘要:
Herein, a modified metal-free acetylene black (MMF-AB) catalyst was synthesized by a simple solvothermal-calcination method and designed successfully to activate peroxodisulfate (PDS) for the degradation of sulfisoxazole (SIZ). Due to the doping of N, S and O metal-free elements, the modified catalyst showed excellent catalytic performance with 100% SIZ removal within 30 min. Pseudo first-order reaction rate constants (evaluating catalytic efficiencies and activity) of MMF-AB (kobs = 0.105 min−1) was 3 times higher than pure-AB (kobs = 0.029 min−1). Interestingly, it was demonstrated that the reaction system is based on the transfer of electrons from SIZ to PDS to realize an electron-transfer-based mechanism by the evidence of premixing, electron paramagnetic resonance (EPR) spectroscopy, salt-bridge experiments and electrochemical analyses. The introduction of recyclable filtration device solved the secondary pollution caused by the dispersion of the powdered catalyst in the treated water, which further proved the practicality and superiority of the MMF-AB catalyst.
Herein, a modified metal-free acetylene black (MMF-AB) catalyst was synthesized by a simple solvothermal-calcination method and designed successfully to activate peroxodisulfate (PDS) for the degradation of sulfisoxazole (SIZ). Due to the doping of N, S and O metal-free elements, the modified catalyst showed excellent catalytic performance with 100% SIZ removal within 30 min. Pseudo first-order reaction rate constants (evaluating catalytic efficiencies and activity) of MMF-AB (kobs = 0.105 min−1) was 3 times higher than pure-AB (kobs = 0.029 min−1). Interestingly, it was demonstrated that the reaction system is based on the transfer of electrons from SIZ to PDS to realize an electron-transfer-based mechanism by the evidence of premixing, electron paramagnetic resonance (EPR) spectroscopy, salt-bridge experiments and electrochemical analyses. The introduction of recyclable filtration device solved the secondary pollution caused by the dispersion of the powdered catalyst in the treated water, which further proved the practicality and superiority of the MMF-AB catalyst.
2024, 35(8): 109336
doi: 10.1016/j.cclet.2023.109336
摘要:
In this study, three-dimensional microspherical CQDs/Bi2MoO6 heterostructures were synthesized using a simple alcohol-thermal method. It was found that the CQDs/Bi2MoO6 had a large specific surface area of 56.0 m2/g, and the introduction of CQDs extended the light absorption spectrum from 480 nm to 496 nm. When utilizing the synthesized CQDs/Bi2MoO6 composite for photocatalytic degradation of antibiotic norfloxacin in a water environment, complete decay of norfloxacin and effective removal of total organic carbon (TOC) were achieved within 30 min. Through the optimization of material synthesis and experimental conditions, the optimal CQDs loading amount was determined as 200 µL, the optimal CQDs/Bi2MoO6 dosage was 0.8 g/L. Moreover, the CQDs/Bi2MoO6 worked well under a wide pH range of 4.4–10.8. The coexistence of HCO3− enhanced the norfloxacin decay, while the presence of Cl−, NO3−, and SO42− slightly retarded it. The synthesized CQDs/Bi2MoO6 had the great potential in removing and mineralizing norfloxacin in real aquatic environments.
In this study, three-dimensional microspherical CQDs/Bi2MoO6 heterostructures were synthesized using a simple alcohol-thermal method. It was found that the CQDs/Bi2MoO6 had a large specific surface area of 56.0 m2/g, and the introduction of CQDs extended the light absorption spectrum from 480 nm to 496 nm. When utilizing the synthesized CQDs/Bi2MoO6 composite for photocatalytic degradation of antibiotic norfloxacin in a water environment, complete decay of norfloxacin and effective removal of total organic carbon (TOC) were achieved within 30 min. Through the optimization of material synthesis and experimental conditions, the optimal CQDs loading amount was determined as 200 µL, the optimal CQDs/Bi2MoO6 dosage was 0.8 g/L. Moreover, the CQDs/Bi2MoO6 worked well under a wide pH range of 4.4–10.8. The coexistence of HCO3− enhanced the norfloxacin decay, while the presence of Cl−, NO3−, and SO42− slightly retarded it. The synthesized CQDs/Bi2MoO6 had the great potential in removing and mineralizing norfloxacin in real aquatic environments.
2024, 35(8): 109338
doi: 10.1016/j.cclet.2023.109338
摘要:
Owing to the serious potential side-effects on the environment and human health, the rapid detection and removal of antibiotics have become an important research focus. In this work, four zinc-based metal-organic frameworks (MOFs) with different functional groups, i.e., Zn-MOF, Zn-MOF-CH3, Zn-MOF-NO2, Zn-MOF-COOH, were utilized for the construction of LDO/MOF composite materials with a nickel-iron-cobalt-based layered double oxide, NiFeCo-LDO. The results showed that the LDO/MOF composites not only had high sensitivity in detecting sulfonamide and quinolone antibiotics, but also had an appreciable ability to adsorb them from wastewater. The maximum adsorption capacities of all the four types of LDO@Zn-MOFs to all antibiotics can at least reach 150 mg/g, and the limits of detection in relation to all four antibiotics were at least as low as 100 µg/L. Our work suggested the dual-function extraction performance can be attributed to the synergistic effects between the LDO and the MOFs. Moreover, the strong ferromagnetism derived from the LDO provided great convenience for the separation and regeneration of the LDO/MOF composites.
Owing to the serious potential side-effects on the environment and human health, the rapid detection and removal of antibiotics have become an important research focus. In this work, four zinc-based metal-organic frameworks (MOFs) with different functional groups, i.e., Zn-MOF, Zn-MOF-CH3, Zn-MOF-NO2, Zn-MOF-COOH, were utilized for the construction of LDO/MOF composite materials with a nickel-iron-cobalt-based layered double oxide, NiFeCo-LDO. The results showed that the LDO/MOF composites not only had high sensitivity in detecting sulfonamide and quinolone antibiotics, but also had an appreciable ability to adsorb them from wastewater. The maximum adsorption capacities of all the four types of LDO@Zn-MOFs to all antibiotics can at least reach 150 mg/g, and the limits of detection in relation to all four antibiotics were at least as low as 100 µg/L. Our work suggested the dual-function extraction performance can be attributed to the synergistic effects between the LDO and the MOFs. Moreover, the strong ferromagnetism derived from the LDO provided great convenience for the separation and regeneration of the LDO/MOF composites.
2024, 35(8): 109361
doi: 10.1016/j.cclet.2023.109361
摘要:
Transition-metal-catalyzed remote sp2C—H functionalization of aryl sulfonic acids was hardly ever realized owing to competitive ortho-C—H functionalization of aryl sulfonates and electron-deficient nature of phenyl ring. Herein, with the assistance of a practical biaryl indolyl directing template, palladium-catalyzed remote sp2C—H alkylation of aryl sulfonic acids have been achieved in moderate to good yields with exclusive meta selectivity. Moreover, remote meta-selective C—H alkynylation of aryl sulfonic acids was also accomplished with a rhodium catalyst. These meta-C—H functionalized products proved to be the superior synthetic precursors, which are difficult to access using the conventional strategy.
Transition-metal-catalyzed remote sp2C—H functionalization of aryl sulfonic acids was hardly ever realized owing to competitive ortho-C—H functionalization of aryl sulfonates and electron-deficient nature of phenyl ring. Herein, with the assistance of a practical biaryl indolyl directing template, palladium-catalyzed remote sp2C—H alkylation of aryl sulfonic acids have been achieved in moderate to good yields with exclusive meta selectivity. Moreover, remote meta-selective C—H alkynylation of aryl sulfonic acids was also accomplished with a rhodium catalyst. These meta-C—H functionalized products proved to be the superior synthetic precursors, which are difficult to access using the conventional strategy.
2024, 35(8): 109362
doi: 10.1016/j.cclet.2023.109362
摘要:
In this contribution, we describe the preparation and recognition characteristics of a novel tetrapodal benzene cage (1). The cage can express a wide recognition range without losing selectivity for the object of appropriate size and functional groups. The key to obtaining the desired structural isomer of 1 is the synthesis and isolation of the o-bis(bromomethyl)benzene precursor (5). Three distinct guests, F− (extremely small size), D-lactate (appropriate size) and L-Asp (branched shape), were selected as examples to demonstrate the recognition characteristics of 1. By NMR titration studies, they all expressed good binding affinity (K > 105 L/mol) in competitive medium (10% DMSO/THF), indicating that 1 has a wide recognition scope. The highest binding constant was observed for D-lactate, revealing that 1 has good selectivity for D-lactate versus F− and L-Asp. Moreover, the NMR titration study of F− in DMSO indicates 1 can achieve different binding modes (1:1 and 2:1 guest-host) for small-sized guests, which allows for the further development of binary binding properties and thereafter applications in the field of catalysis.
In this contribution, we describe the preparation and recognition characteristics of a novel tetrapodal benzene cage (1). The cage can express a wide recognition range without losing selectivity for the object of appropriate size and functional groups. The key to obtaining the desired structural isomer of 1 is the synthesis and isolation of the o-bis(bromomethyl)benzene precursor (5). Three distinct guests, F− (extremely small size), D-lactate (appropriate size) and L-Asp (branched shape), were selected as examples to demonstrate the recognition characteristics of 1. By NMR titration studies, they all expressed good binding affinity (K > 105 L/mol) in competitive medium (10% DMSO/THF), indicating that 1 has a wide recognition scope. The highest binding constant was observed for D-lactate, revealing that 1 has good selectivity for D-lactate versus F− and L-Asp. Moreover, the NMR titration study of F− in DMSO indicates 1 can achieve different binding modes (1:1 and 2:1 guest-host) for small-sized guests, which allows for the further development of binary binding properties and thereafter applications in the field of catalysis.
2024, 35(8): 109365
doi: 10.1016/j.cclet.2023.109365
摘要:
Organic lasers with broad emission bands in near-infrared (NIR) region are crucial for their applications in laser communication, night-vision as well as bioimaging owing to the abundance of selectable lasing wavelengths. However, for most organic gain materials, gain regions are limited in a small wavelength range because of the fixed energy level systems. Herein, we design a strategy to realize NIR organic lasers with broad emission bands based on tunable energy level systems induced by cascaded excited-state intramolecular proton transfer (ESIPT). A novel gain material named DHNN was developed, which can undergo a cascaded double-ESIPT process supporting four-level and six-level systems simultaneously. By doping DHNN into polystyrene microspheres, NIR lasers with tunable emission bands can be achieved based on the careful modulation of microcavities. Finally, organic lasers with an ultra-broad emission band ranging from 700 nm to 900 nm was successfully achieved by harnessing four-level and six-level systems simultaneously.
Organic lasers with broad emission bands in near-infrared (NIR) region are crucial for their applications in laser communication, night-vision as well as bioimaging owing to the abundance of selectable lasing wavelengths. However, for most organic gain materials, gain regions are limited in a small wavelength range because of the fixed energy level systems. Herein, we design a strategy to realize NIR organic lasers with broad emission bands based on tunable energy level systems induced by cascaded excited-state intramolecular proton transfer (ESIPT). A novel gain material named DHNN was developed, which can undergo a cascaded double-ESIPT process supporting four-level and six-level systems simultaneously. By doping DHNN into polystyrene microspheres, NIR lasers with tunable emission bands can be achieved based on the careful modulation of microcavities. Finally, organic lasers with an ultra-broad emission band ranging from 700 nm to 900 nm was successfully achieved by harnessing four-level and six-level systems simultaneously.
2024, 35(8): 109402
doi: 10.1016/j.cclet.2023.109402
摘要:
The extraction of radioactive minor actinides (An(Ⅲ)) from lanthanides (Ln(Ⅲ)) is an extremely important step in nuclear waste reprocessing. Designing ligands with high-performance actinide-selectivity remains an essential task. Recent works have reported that some polyazole based ligands exhibit good An(Ⅲ)/Ln(Ⅲ) separation performance. Herein, we first evaluated the effects of different polyazole side chains on the Am(Ⅲ)/Eu(Ⅲ) selectivity by exploring three pyridine-derived polyazole ligands L1, L2 and L3 with 1,2,4-triazole, 1,2,3-triazole, and pyrazole side chains, respectively, using scalar relativistic theoretical methods. The coordination structures, bonding properties and thermodynamic behaviors of AmL(NO3)3 and EuL(NO3)3 complexes were investigated, which clarifies that the side chains do affect the electronic structure of ligand and its selectivity for Am(Ⅲ)/Eu(Ⅲ) ions. Moreover, L1 with 1,2,4-triazole side chains exhibited the highest selectivity for Am(Ⅲ) over Eu(Ⅲ) while the lowest complexation ability for metal ions among the three pyridine-derived polyazole ligands. Subsequently, we designed a new ligand L4 containing 1,2,4-triazole side chains and a preorganized phenanthroline backbone. Theoretically, such a new ligand was verified to show stronger complexation ability and higher selectivity for Am(Ⅲ)/Eu(Ⅲ) ions than L1. This work clarifies the complexation nature of polyazole based ligands with Am(Ⅲ)/Eu(Ⅲ) ions and provides design strategies for highly efficient polyazole based ligands for An(Ⅲ)/Ln(Ⅲ) separation.
The extraction of radioactive minor actinides (An(Ⅲ)) from lanthanides (Ln(Ⅲ)) is an extremely important step in nuclear waste reprocessing. Designing ligands with high-performance actinide-selectivity remains an essential task. Recent works have reported that some polyazole based ligands exhibit good An(Ⅲ)/Ln(Ⅲ) separation performance. Herein, we first evaluated the effects of different polyazole side chains on the Am(Ⅲ)/Eu(Ⅲ) selectivity by exploring three pyridine-derived polyazole ligands L1, L2 and L3 with 1,2,4-triazole, 1,2,3-triazole, and pyrazole side chains, respectively, using scalar relativistic theoretical methods. The coordination structures, bonding properties and thermodynamic behaviors of AmL(NO3)3 and EuL(NO3)3 complexes were investigated, which clarifies that the side chains do affect the electronic structure of ligand and its selectivity for Am(Ⅲ)/Eu(Ⅲ) ions. Moreover, L1 with 1,2,4-triazole side chains exhibited the highest selectivity for Am(Ⅲ) over Eu(Ⅲ) while the lowest complexation ability for metal ions among the three pyridine-derived polyazole ligands. Subsequently, we designed a new ligand L4 containing 1,2,4-triazole side chains and a preorganized phenanthroline backbone. Theoretically, such a new ligand was verified to show stronger complexation ability and higher selectivity for Am(Ⅲ)/Eu(Ⅲ) ions than L1. This work clarifies the complexation nature of polyazole based ligands with Am(Ⅲ)/Eu(Ⅲ) ions and provides design strategies for highly efficient polyazole based ligands for An(Ⅲ)/Ln(Ⅲ) separation.
2024, 35(8): 109403
doi: 10.1016/j.cclet.2023.109403
摘要:
A photochromic molecular rotor based on stiff-stilbene (SSB-FMR) was handily prepared through coupled reaction, and further self-assembled with cucurbit[8]uril (CB[8]) to form a 2:2 quaternary supramolecular complex (SSB-FMR/CB[8]). Significantly, the intervention of CB[8] on SSB-FMR achieved dual functions that assembly-induced emission enhancement and assembly-induced improvement of photoisomerized performance (especially reversibility) of stiff-stilbene molecular photoswitch. The supramolecular strategy further facilitated the assembly as a photoresponsive fluorescence switch with outstanding fatigue resistance, which was expediently applied in high-security-level QR code anti-counterfeiting and controllable lysosome targeted imaging. The study unprecedentedly provides a supramolecular method for highly efficiently improving photoisomerized performance especially reversibility of molecular photoswitches based on stiff-stilbene, and is of vital significance for the construction of intelligent materials with excellent capability.
A photochromic molecular rotor based on stiff-stilbene (SSB-FMR) was handily prepared through coupled reaction, and further self-assembled with cucurbit[8]uril (CB[8]) to form a 2:2 quaternary supramolecular complex (SSB-FMR/CB[8]). Significantly, the intervention of CB[8] on SSB-FMR achieved dual functions that assembly-induced emission enhancement and assembly-induced improvement of photoisomerized performance (especially reversibility) of stiff-stilbene molecular photoswitch. The supramolecular strategy further facilitated the assembly as a photoresponsive fluorescence switch with outstanding fatigue resistance, which was expediently applied in high-security-level QR code anti-counterfeiting and controllable lysosome targeted imaging. The study unprecedentedly provides a supramolecular method for highly efficiently improving photoisomerized performance especially reversibility of molecular photoswitches based on stiff-stilbene, and is of vital significance for the construction of intelligent materials with excellent capability.
2024, 35(8): 109404
doi: 10.1016/j.cclet.2023.109404
摘要:
The self-assembled structures of H3BDA molecule with multiple meta-dicarboxylic groups and their stimulus responses to the guest molecules (COR and T4PT) are thoroughly investigated by scanning tunneling microscopy (STM). STM observations display that two kinds of nanostructures are fabricated by H3BDA molecules through intermolecular hydrogen bonds, in which a linear structure is formed at a higher concentration and a flower-like structure is obtained at a lower concentration. After the addition of COR and T4PT, H3BDA appears different responsiveness resulting in different co-assembled structures, respectively. The linear structure is regulated into a flower-like structure by COR and COR molecules are trapped in the cavities. When the pyridine derivative (T4PT) is introduced, a new bicomponent porous structure emerges via the hydrogen bond formed between the carboxyl group and the pyridine. Furthermore, the deposition of additional COR to the H3BDA/T4PT system results in the breakdown of the porous structure and the generation of H3BDA/COR host–guest system. Combined with density functional theory (DFT) calculations and molecular dynamics (MD) simulations, the transformation phenomenon of bi-component nanostructure induced by guest molecules is formulated. The results are expected to understand the modification effect of guest molecules on the host network, which is of great significance for the design and construction of multi-component nanostructures and crystal engineering.
The self-assembled structures of H3BDA molecule with multiple meta-dicarboxylic groups and their stimulus responses to the guest molecules (COR and T4PT) are thoroughly investigated by scanning tunneling microscopy (STM). STM observations display that two kinds of nanostructures are fabricated by H3BDA molecules through intermolecular hydrogen bonds, in which a linear structure is formed at a higher concentration and a flower-like structure is obtained at a lower concentration. After the addition of COR and T4PT, H3BDA appears different responsiveness resulting in different co-assembled structures, respectively. The linear structure is regulated into a flower-like structure by COR and COR molecules are trapped in the cavities. When the pyridine derivative (T4PT) is introduced, a new bicomponent porous structure emerges via the hydrogen bond formed between the carboxyl group and the pyridine. Furthermore, the deposition of additional COR to the H3BDA/T4PT system results in the breakdown of the porous structure and the generation of H3BDA/COR host–guest system. Combined with density functional theory (DFT) calculations and molecular dynamics (MD) simulations, the transformation phenomenon of bi-component nanostructure induced by guest molecules is formulated. The results are expected to understand the modification effect of guest molecules on the host network, which is of great significance for the design and construction of multi-component nanostructures and crystal engineering.
2024, 35(8): 109408
doi: 10.1016/j.cclet.2023.109408
摘要:
Heterocycle-braced cyclic peptides have demonstrated enhanced metabolic stability, increased potency and selectivity. Here, we present a rapid synthesis method for constructing Trp(C7)-alkene(E)-crosslinked cyclic peptides with potent anti-proliferative activities against cancer cells, through C-H alkenylation and macrolactamization. This report addresses critical challenges associated with the installation and removal of the directing group N-Piv, configuration selectivity of the olefin, and intramolecular cyclization. Notably, this method exhibits mild reaction conditions, traceless removal of the directing group, and high configuration selectivity.
Heterocycle-braced cyclic peptides have demonstrated enhanced metabolic stability, increased potency and selectivity. Here, we present a rapid synthesis method for constructing Trp(C7)-alkene(E)-crosslinked cyclic peptides with potent anti-proliferative activities against cancer cells, through C-H alkenylation and macrolactamization. This report addresses critical challenges associated with the installation and removal of the directing group N-Piv, configuration selectivity of the olefin, and intramolecular cyclization. Notably, this method exhibits mild reaction conditions, traceless removal of the directing group, and high configuration selectivity.
2024, 35(8): 109433
doi: 10.1016/j.cclet.2023.109433
摘要:
The dynamic kinetic asymmetric transformation of racemic propargylic ammonium salts with prochiral aldimine esters through a stereodivergent propargylation is catalyzed by dual nickel and copper catalysis. Thus, a diverse range of optically active α-quaternary amino esters were produced via CN bond cleavage with high reaction efficiency and stereoselectivity (up to > 99% ee). By selection of the appropriate pairwise combination of catalyst configurational isomers, all four possible stereoisomers of the corresponding propargylation products are obtained in high yields with excellent regio-, diastereo-, and enantioselectivities.
The dynamic kinetic asymmetric transformation of racemic propargylic ammonium salts with prochiral aldimine esters through a stereodivergent propargylation is catalyzed by dual nickel and copper catalysis. Thus, a diverse range of optically active α-quaternary amino esters were produced via CN bond cleavage with high reaction efficiency and stereoselectivity (up to > 99% ee). By selection of the appropriate pairwise combination of catalyst configurational isomers, all four possible stereoisomers of the corresponding propargylation products are obtained in high yields with excellent regio-, diastereo-, and enantioselectivities.
2024, 35(8): 109434
doi: 10.1016/j.cclet.2023.109434
摘要:
This study presents an unexpected finding that the cis isomer of β-thio-Asp exhibits higher ligation activity than the trans isomer. This discovery sheds light on the intricate nature of native chemical ligation and highlights the importance of factors beyond the steric effects of the side chain in modulating ligation activity.
This study presents an unexpected finding that the cis isomer of β-thio-Asp exhibits higher ligation activity than the trans isomer. This discovery sheds light on the intricate nature of native chemical ligation and highlights the importance of factors beyond the steric effects of the side chain in modulating ligation activity.
2024, 35(8): 109443
doi: 10.1016/j.cclet.2023.109443
摘要:
This work describes intermolecular acylfluorination of gem-difluoroenynes using acyl fluorides as both acyl source and fluorine source. Trifluoromethyl-substituted allenones or furans could be selectively achieved via phosphine and silver catalysis. These approaches exhibit high regioselectivity, atom economy and broad functionality tolerance.
This work describes intermolecular acylfluorination of gem-difluoroenynes using acyl fluorides as both acyl source and fluorine source. Trifluoromethyl-substituted allenones or furans could be selectively achieved via phosphine and silver catalysis. These approaches exhibit high regioselectivity, atom economy and broad functionality tolerance.
2024, 35(8): 109457
doi: 10.1016/j.cclet.2023.109457
摘要:
Delayed or non-healing of diabetic wounds is a significant complication, often attributed to high glucose-induced M1 macrophage accumulation, impaired angiogenesis, and reactive oxygen species (ROS) buildup. Addressing this, we introduced a strontium polyphenol network microneedle patch (SrC-MPNs@MN-PP) for percutaneous drug delivery. This patch, formulated with polymer poly(γ-glutamic acid) (γ-PGA) and epsilon-poly-L-lysine (ε-PLL), incorporates strontium polyphenol networks (SrC-MPNs). The release of chlorogenic acid (CGA) from SrC-MPNs not only neutralizes ROS, but strontium ions also foster angiogenesis. Consequently, SrC-MPNs@MN-PP can ameliorate the diabetic wound microenvironment and expedite healing.
Delayed or non-healing of diabetic wounds is a significant complication, often attributed to high glucose-induced M1 macrophage accumulation, impaired angiogenesis, and reactive oxygen species (ROS) buildup. Addressing this, we introduced a strontium polyphenol network microneedle patch (SrC-MPNs@MN-PP) for percutaneous drug delivery. This patch, formulated with polymer poly(γ-glutamic acid) (γ-PGA) and epsilon-poly-L-lysine (ε-PLL), incorporates strontium polyphenol networks (SrC-MPNs). The release of chlorogenic acid (CGA) from SrC-MPNs not only neutralizes ROS, but strontium ions also foster angiogenesis. Consequently, SrC-MPNs@MN-PP can ameliorate the diabetic wound microenvironment and expedite healing.
2024, 35(8): 109467
doi: 10.1016/j.cclet.2023.109467
摘要:
Sulphur (S)-template method based on conventional slurry-casting method has been developed to produce porous silicon (Si) electrodes. The facile fabrication technology is suitable for current production line and expected to be widely applied to various electrode materials under large volume change during operation. Specifically, S particles as template agent are mixed with active material Si, carbon conductor and binder forming uniform slurry. After casting and drying, the electrodes are immersed in carbon disulfide solution to remove S particles rapidly, generating pores in-situ at the original position of S particles. Electrochemical analysis shows that the pores inside electrodes are able to shorten lithium ion diffusion paths, reduce normal expansion rate and decrease formation of cracks in the Si electrode (2 mgSi/cm2), demonstrating a reversible capacity of 951 mAh/g at 0.5 A/g after 100 cycles (with a capacity retention of 99.5%) and a capacity of ~826 mAh/g at 2 A/g.
Sulphur (S)-template method based on conventional slurry-casting method has been developed to produce porous silicon (Si) electrodes. The facile fabrication technology is suitable for current production line and expected to be widely applied to various electrode materials under large volume change during operation. Specifically, S particles as template agent are mixed with active material Si, carbon conductor and binder forming uniform slurry. After casting and drying, the electrodes are immersed in carbon disulfide solution to remove S particles rapidly, generating pores in-situ at the original position of S particles. Electrochemical analysis shows that the pores inside electrodes are able to shorten lithium ion diffusion paths, reduce normal expansion rate and decrease formation of cracks in the Si electrode (2 mgSi/cm2), demonstrating a reversible capacity of 951 mAh/g at 0.5 A/g after 100 cycles (with a capacity retention of 99.5%) and a capacity of ~826 mAh/g at 2 A/g.
2024, 35(8): 109514
doi: 10.1016/j.cclet.2024.109514
摘要:
An eco-friendly and practical method for the clean preparation of 5-amino-1,2,4-thiadiazoles was developed. With WS2 as the semiconductor photocatalyst, both TEMPO and O2 (in air) as the redox catalysts, a variety of thiadiazoles were semi-heterogeneously formed in high to quantitative yields and could be easily collected by CPME extraction and rinsing. Furthermore, the catalytic system can be reusable for at least 5 reaction runs.
An eco-friendly and practical method for the clean preparation of 5-amino-1,2,4-thiadiazoles was developed. With WS2 as the semiconductor photocatalyst, both TEMPO and O2 (in air) as the redox catalysts, a variety of thiadiazoles were semi-heterogeneously formed in high to quantitative yields and could be easily collected by CPME extraction and rinsing. Furthermore, the catalytic system can be reusable for at least 5 reaction runs.
2024, 35(8): 109518
doi: 10.1016/j.cclet.2024.109518
摘要:
The development of low-cost, earth-abundant and environmentally benign transition metal catalysts, which can catalyze multiple different types of asymmetric reactions, is an important objective in modern asymmetric catalysis. Herein we demonstrate that a chiral Ni/P-Phos catalyst achieves three types of asymmetric reactions: allenylic substitution of racemic allenic ethers, 1,4-hydroalkylation of prochiral 1,3-enynes and double alkylation of newly designed enynyl ether reagents. Three methods complement each other and produce various axially chiral allene derivatives bearing a pyrazolidine-3,5-dione unit, which is widely present in drugs and biologically active molecules with versatile pharmacological activities.
The development of low-cost, earth-abundant and environmentally benign transition metal catalysts, which can catalyze multiple different types of asymmetric reactions, is an important objective in modern asymmetric catalysis. Herein we demonstrate that a chiral Ni/P-Phos catalyst achieves three types of asymmetric reactions: allenylic substitution of racemic allenic ethers, 1,4-hydroalkylation of prochiral 1,3-enynes and double alkylation of newly designed enynyl ether reagents. Three methods complement each other and produce various axially chiral allene derivatives bearing a pyrazolidine-3,5-dione unit, which is widely present in drugs and biologically active molecules with versatile pharmacological activities.
2024, 35(8): 109737
doi: 10.1016/j.cclet.2024.109737
摘要:
Highly branched poly(β-amino ester)s (HPAEs) have emerged as a safe and efficient type of non-viral gene delivery vectors. However, the presence of inactive terminal secondary amine groups compromises their gene transfection capability. In this study, HPAEs with similar topological structures and chemical compositions but varying numbers of terminal secondary 4-amino-1-butanol (S4) and secondary/tertiary 3-morpholinopropylamine (MPA) groups were synthesized. The results demonstrate that an increased number of secondary/tertiary MPA groups in-situ significantly enhances the DNA binding capability of HPAEs, leading to the formation of smaller HPAE/DNA polyplexes with higher zeta potential, ultimately resulting in superior gene transfection efficiency in bladder epithelial cells. This study establishes a simple yet effective strategy to maximize the gene transfection potency of HPAEs by converting the inactive terminal groups in-situ without the need for complex modifications to their topological structure and chemical composition.
Highly branched poly(β-amino ester)s (HPAEs) have emerged as a safe and efficient type of non-viral gene delivery vectors. However, the presence of inactive terminal secondary amine groups compromises their gene transfection capability. In this study, HPAEs with similar topological structures and chemical compositions but varying numbers of terminal secondary 4-amino-1-butanol (S4) and secondary/tertiary 3-morpholinopropylamine (MPA) groups were synthesized. The results demonstrate that an increased number of secondary/tertiary MPA groups in-situ significantly enhances the DNA binding capability of HPAEs, leading to the formation of smaller HPAE/DNA polyplexes with higher zeta potential, ultimately resulting in superior gene transfection efficiency in bladder epithelial cells. This study establishes a simple yet effective strategy to maximize the gene transfection potency of HPAEs by converting the inactive terminal groups in-situ without the need for complex modifications to their topological structure and chemical composition.
2024, 35(8): 109745
doi: 10.1016/j.cclet.2024.109745
摘要:
Diradical polycyclic hydrocarbons (PHs) have unique open-shell structures and interesting physical properties. However, owing to high reactivity of unpaired electrons, such open-shell organic diradicaloids are usually less stable than closed-shell systems, limiting their practical applications. In this study, we report P=O-attaching of diradical PHs as a new strategy to enhance their stability while maintaining diradical properties. Three P=O-attached PHs containing the indeno[1,2-b]fluorene, fluoreno[3,2-b]fluorene and indeno[2,1-b]fluorene π-skeletons, respectively, were designed and synthesized. As theoretically and experimentally proved, two of them have the relatively large diradical characters and open-shell singlet diradical nature. In comparison to their all-carbon analogues, the attached electron-withdrawing P=O groups endow them with much lower LUMO/HOMO energy levels but preserved magnetic activities and physical properties, such as thermally accessible triplet species and multi-redox ability. Moreover, the P=O groups effectively decrease their oxidation activities and thereby lead to their remarkably excellent ambient stabilities. Thus, this P=O-attaching strategy will be applicable to other diradical PH systems and may promote the generation of stable organic diradicaloids for radical chemistry and materials.
Diradical polycyclic hydrocarbons (PHs) have unique open-shell structures and interesting physical properties. However, owing to high reactivity of unpaired electrons, such open-shell organic diradicaloids are usually less stable than closed-shell systems, limiting their practical applications. In this study, we report P=O-attaching of diradical PHs as a new strategy to enhance their stability while maintaining diradical properties. Three P=O-attached PHs containing the indeno[1,2-b]fluorene, fluoreno[3,2-b]fluorene and indeno[2,1-b]fluorene π-skeletons, respectively, were designed and synthesized. As theoretically and experimentally proved, two of them have the relatively large diradical characters and open-shell singlet diradical nature. In comparison to their all-carbon analogues, the attached electron-withdrawing P=O groups endow them with much lower LUMO/HOMO energy levels but preserved magnetic activities and physical properties, such as thermally accessible triplet species and multi-redox ability. Moreover, the P=O groups effectively decrease their oxidation activities and thereby lead to their remarkably excellent ambient stabilities. Thus, this P=O-attaching strategy will be applicable to other diradical PH systems and may promote the generation of stable organic diradicaloids for radical chemistry and materials.
2024, 35(8): 109806
doi: 10.1016/j.cclet.2024.109806
摘要:
Electrocatalytic synthesis of urea through CN bond formation, converting carbon dioxide (CO2) and nitrate (NO3–), presents a promising, less energy-intensive alternative to industrial urea production process. In this communication, we report the application of Mo2C nanosheets-decorated carbon sheets (Mo2C/C) as a highly efficient electrocatalyst for facilitating CN coupling in ambient urea electrosynthesis. In CO2-saturated 0.2 mol/L Na2SO4 solution containing 0.05 mol/L NO3–, the Mo2C/C catalyst achieves an impressive urea yield of 579.13 µg h–1 mg–1 with high Faradaic efficiency of 44.80% at –0.5 V versus the reversible hydrogen electrode. Further theoretical calculations reveal that the multiple Mo active sites enhance the formation of *CO and *NH2 intermediates and facilitate their CN coupling. This research propels the use of Mo2C-based electrodes in electrocatalysis and accentuates the capabilities of binary metal-based catalysts in CN coupling reactions.
Electrocatalytic synthesis of urea through CN bond formation, converting carbon dioxide (CO2) and nitrate (NO3–), presents a promising, less energy-intensive alternative to industrial urea production process. In this communication, we report the application of Mo2C nanosheets-decorated carbon sheets (Mo2C/C) as a highly efficient electrocatalyst for facilitating CN coupling in ambient urea electrosynthesis. In CO2-saturated 0.2 mol/L Na2SO4 solution containing 0.05 mol/L NO3–, the Mo2C/C catalyst achieves an impressive urea yield of 579.13 µg h–1 mg–1 with high Faradaic efficiency of 44.80% at –0.5 V versus the reversible hydrogen electrode. Further theoretical calculations reveal that the multiple Mo active sites enhance the formation of *CO and *NH2 intermediates and facilitate their CN coupling. This research propels the use of Mo2C-based electrodes in electrocatalysis and accentuates the capabilities of binary metal-based catalysts in CN coupling reactions.
2024, 35(8): 109886
doi: 10.1016/j.cclet.2024.109886
摘要:
Photocatalytic synthesis of hydrogen peroxide has gradually become a promising method for in-situ production of hydrogen peroxide, which relies on sustainable solar energy. However, the commonly used photocatalyst, i.e., carbon nitride (CN), still suffers from the drawbacks of narrow light absorption range and fast charge recombination. Here, we report a facile method to introduce nitrogen defects into carbon nitride together with sodium ion. By adjusting the ratio of sodium dicyandiamide, the band gap of carbon nitride can be controlled, while the carrier separation and transfer ability of carbon nitride is improved. The modified CN with sodium doping and nitrogen defect (SD-CN) demonstrates outstanding H2O2 production performance (H2O2 yield rate of 297.2 µmol L−1 h−1) under visible light irradiation, which is approximately 9.8 times higher than that of pristine CN. This work deepens the understanding of the coordinated effect of structural defect and element doping of carbon nitride on the photocatalytic H2O2 production performance, and provides new insight into the design of photocatalytic system for efficient production of H2O2.
Photocatalytic synthesis of hydrogen peroxide has gradually become a promising method for in-situ production of hydrogen peroxide, which relies on sustainable solar energy. However, the commonly used photocatalyst, i.e., carbon nitride (CN), still suffers from the drawbacks of narrow light absorption range and fast charge recombination. Here, we report a facile method to introduce nitrogen defects into carbon nitride together with sodium ion. By adjusting the ratio of sodium dicyandiamide, the band gap of carbon nitride can be controlled, while the carrier separation and transfer ability of carbon nitride is improved. The modified CN with sodium doping and nitrogen defect (SD-CN) demonstrates outstanding H2O2 production performance (H2O2 yield rate of 297.2 µmol L−1 h−1) under visible light irradiation, which is approximately 9.8 times higher than that of pristine CN. This work deepens the understanding of the coordinated effect of structural defect and element doping of carbon nitride on the photocatalytic H2O2 production performance, and provides new insight into the design of photocatalytic system for efficient production of H2O2.
2024, 35(8): 109894
doi: 10.1016/j.cclet.2024.109894
摘要:
Herein, we constructed defective UiO-66 with rich Zr vacancy structure model, in which the defective structure was verified by various characterizations. Also, the Pb adsorption experiments affirmed that defective UiO-66 could display better adsorption and selective adsorption ability than that of perfect UiO-66. The results of partial density of states (PDOS) and Mulliken charge population indicated that the blue shift of O 2p and Zr 4d orbit induced the electron rearrangement of atoms closed to the bonding sites, while the positive charge number of Zr atoms decreased than before. Combining with the expansion of pore size, Pb atom was more inclined to transfer and bond with unsaturated coordination oxygens. More significantly, quantitative structure-activity relationships (QSARs) demonstrated that selective capture of Pb instead of Zn, Cu, Cd and Hg displayed by defective UiO-66 was determined jointly by bond strength, adsorption energy and electron transfer. This work provided some theoretical direction for the purpose of the fabrication of adsorbent and the investigation of mechanism.
Herein, we constructed defective UiO-66 with rich Zr vacancy structure model, in which the defective structure was verified by various characterizations. Also, the Pb adsorption experiments affirmed that defective UiO-66 could display better adsorption and selective adsorption ability than that of perfect UiO-66. The results of partial density of states (PDOS) and Mulliken charge population indicated that the blue shift of O 2p and Zr 4d orbit induced the electron rearrangement of atoms closed to the bonding sites, while the positive charge number of Zr atoms decreased than before. Combining with the expansion of pore size, Pb atom was more inclined to transfer and bond with unsaturated coordination oxygens. More significantly, quantitative structure-activity relationships (QSARs) demonstrated that selective capture of Pb instead of Zn, Cu, Cd and Hg displayed by defective UiO-66 was determined jointly by bond strength, adsorption energy and electron transfer. This work provided some theoretical direction for the purpose of the fabrication of adsorbent and the investigation of mechanism.
2024, 35(8): 109105
doi: 10.1016/j.cclet.2023.109105
摘要:
Electrocatalysis is a surface-sensitive process, in which the catalytic activity of electrocatalyst highly relates to the surface adsorption/desorption behaviors of the reactants/intermediates/products on the catalytically active sites. Surface chemical microenvironment engineering via organic molecules functionalization is a promising strategy to tune the electrocatalytic activity since it can well modify the electrode/electrolyte interface and alter the reaction pathways. In this review, we summarize the recent progress of surface microenvironment engineering of electrocatalysts induced by organic molecules functionalization, with the special focus on the organic molecule-assisted growth mechanism and unique electronic effect. More importantly, the applications of organic molecule functionalized catalysts in various electrocatalytic reactions are also systematically summarized, along with a deep discussion on the conclusion and perspective. This work will open a new avenue for the construction and modification of advanced electrocatalysts based on organic molecule-mediated interface engineering.
Electrocatalysis is a surface-sensitive process, in which the catalytic activity of electrocatalyst highly relates to the surface adsorption/desorption behaviors of the reactants/intermediates/products on the catalytically active sites. Surface chemical microenvironment engineering via organic molecules functionalization is a promising strategy to tune the electrocatalytic activity since it can well modify the electrode/electrolyte interface and alter the reaction pathways. In this review, we summarize the recent progress of surface microenvironment engineering of electrocatalysts induced by organic molecules functionalization, with the special focus on the organic molecule-assisted growth mechanism and unique electronic effect. More importantly, the applications of organic molecule functionalized catalysts in various electrocatalytic reactions are also systematically summarized, along with a deep discussion on the conclusion and perspective. This work will open a new avenue for the construction and modification of advanced electrocatalysts based on organic molecule-mediated interface engineering.
2024, 35(8): 109141
doi: 10.1016/j.cclet.2023.109141
摘要:
Catalyst with high performance has drawn increasing attention recently due to its significant advantages in chemical reactions such as speeding up the reaction, lowering the reaction temperature or pressure, and proceeding without itself being consumed. Despite the superior catalytic performance of precious metal catalysts, transition metal oxides offer a promising route for substitution of precious metals in catalysis arising from their low cost, intrinsic activity and sufficient stability. Mullite-type oxide SmMn2O5 exhibits a unique crystal structure containing double crystalline fields, and nowadays is used widely as the catalyst in different chemical reactions, including the reactions of vehicle emissions reduction and oxygen evolution reaction, gas sensors, and metal-air batteries, promoting attention in catalytic performance enhancement. To our knowledge, there is no review article covering the comprehensive information of SmMn2O5 and its applications. Here we review the recent progress in understanding of the crystal structure of SmMn2O5 and its basic physical properties. We then summarize the catalytic sources of SmMn2O5 and reaction mechanisms, while the strategies to improve catalytic performance of SmMn2O5 are further presented. Finally, we provide a perspective on how to make further progress in catalytic applications.
Catalyst with high performance has drawn increasing attention recently due to its significant advantages in chemical reactions such as speeding up the reaction, lowering the reaction temperature or pressure, and proceeding without itself being consumed. Despite the superior catalytic performance of precious metal catalysts, transition metal oxides offer a promising route for substitution of precious metals in catalysis arising from their low cost, intrinsic activity and sufficient stability. Mullite-type oxide SmMn2O5 exhibits a unique crystal structure containing double crystalline fields, and nowadays is used widely as the catalyst in different chemical reactions, including the reactions of vehicle emissions reduction and oxygen evolution reaction, gas sensors, and metal-air batteries, promoting attention in catalytic performance enhancement. To our knowledge, there is no review article covering the comprehensive information of SmMn2O5 and its applications. Here we review the recent progress in understanding of the crystal structure of SmMn2O5 and its basic physical properties. We then summarize the catalytic sources of SmMn2O5 and reaction mechanisms, while the strategies to improve catalytic performance of SmMn2O5 are further presented. Finally, we provide a perspective on how to make further progress in catalytic applications.
2024, 35(8): 109142
doi: 10.1016/j.cclet.2023.109142
摘要:
Climate change is an important issue facing the world today and carbon reduction has become the focus of attention for all countries. Alternative bio-fuels are an important means to achieve carbon emission reduction. The production of jet fuel precursors from biomass by hydrothermal liquefaction (HTL) has received a lot of attention due to its mild conditions and environmental friendliness. Lignocellulosic biomass and algal biomass are considered as the second and the third generation biomasses as promising raw materials for alternative fuel preparation. Among them, lignocellulosic biomass has been extensively studied due to its wide range of sources and can be divided into one-step HTL and stepwise HTL according to the process method. Algal biomass has been extensively studied experimentally due to its short growth cycle and the fact that it can sequester large amounts of carbon without taking up arable land. In this paper, the feedstock composition of different biomasses is reviewed for the HTL of biomass. A detailed review of the process characteristics, reaction pathways and influencing factors for the HTL production of jet fuel precursors from lignocellulosic biomass and algal biomass is also presented. Theoretical references are provided for further process optimization and bio-crude quality upgrading.
Climate change is an important issue facing the world today and carbon reduction has become the focus of attention for all countries. Alternative bio-fuels are an important means to achieve carbon emission reduction. The production of jet fuel precursors from biomass by hydrothermal liquefaction (HTL) has received a lot of attention due to its mild conditions and environmental friendliness. Lignocellulosic biomass and algal biomass are considered as the second and the third generation biomasses as promising raw materials for alternative fuel preparation. Among them, lignocellulosic biomass has been extensively studied due to its wide range of sources and can be divided into one-step HTL and stepwise HTL according to the process method. Algal biomass has been extensively studied experimentally due to its short growth cycle and the fact that it can sequester large amounts of carbon without taking up arable land. In this paper, the feedstock composition of different biomasses is reviewed for the HTL of biomass. A detailed review of the process characteristics, reaction pathways and influencing factors for the HTL production of jet fuel precursors from lignocellulosic biomass and algal biomass is also presented. Theoretical references are provided for further process optimization and bio-crude quality upgrading.
2024, 35(8): 109143
doi: 10.1016/j.cclet.2023.109143
摘要:
With the low cost, excellent safety and high theoretical specific capacity, aqueous zinc-ion batteries (AZIBs) are considered as a potential rival for lithium-ion batteries to promote the sustainable development of large-scale energy storage technologies. However, the notorious Zn dendrites and low Coulombic efficiency (CE) limit further development of AZIBs, due to the unstable electrochemical deposition/stripping behavior of Zn anode in aqueous zinc ion electrolytes. In this review, critical issues and advances are summarized in electrolyte engineering strategies. These strategies are focused on active water molecules during electrochemical process, including high-concentration electrolytes, ionic liquids, gel-polymer electrolytes and functional additives. With suppressed active water molecules, the solvation and de-solvation behavior of Zn2+ can be regulated, thereby modulating the electrochemical performance of Zn anode. Finally, the inherent problems of these strategies are discussed, and some promising directions are provided on electrolytes engineering for high performance Zn anode in AZIBs.
With the low cost, excellent safety and high theoretical specific capacity, aqueous zinc-ion batteries (AZIBs) are considered as a potential rival for lithium-ion batteries to promote the sustainable development of large-scale energy storage technologies. However, the notorious Zn dendrites and low Coulombic efficiency (CE) limit further development of AZIBs, due to the unstable electrochemical deposition/stripping behavior of Zn anode in aqueous zinc ion electrolytes. In this review, critical issues and advances are summarized in electrolyte engineering strategies. These strategies are focused on active water molecules during electrochemical process, including high-concentration electrolytes, ionic liquids, gel-polymer electrolytes and functional additives. With suppressed active water molecules, the solvation and de-solvation behavior of Zn2+ can be regulated, thereby modulating the electrochemical performance of Zn anode. Finally, the inherent problems of these strategies are discussed, and some promising directions are provided on electrolytes engineering for high performance Zn anode in AZIBs.
2024, 35(8): 109147
doi: 10.1016/j.cclet.2023.109147
摘要:
Urea is extensively used in agriculture and chemical industry, and it is produced on an industrial scale from CO2 and Haber–Bosch NH3 under relatively high temperature and high pressure conditions, which demands high energy input and generates masses of carbon footprint. The conversion of CO2 and N sources (such as NO2−, NO3−, and N2) through electrocatalytic reactions under ambient conditions is a promising alternative to realize efficient urea synthesis. Of note, the design of electrocatalyst is one of the key factors that can improve the efficiency and selectivity of C–N coupling reactions. Defect engineering is an intriguing strategy for regulating the electronic structure and charge density of electrocatalysts, which endows electrocatalysts with excellent physicochemical properties and optimized adsorption energy of the reaction intermediates to reduce the kinetic barriers. In this minireview, recent advances of defect engineered electrocatalysts in urea electrosynthesis from CO2 and various N reactants are firstly introduced. Mechanistic discussions of C–N coupling in these advances are presented, with the aim of directing future investigations on improving the urea yield. Finally, the prospects and challenges of defect engineered electrocatalysts for urea synthesis are discussed. This overview is expected to provide in-depth understanding of structure–reactivity relationship and shed light on future electrocatalytic C–N coupling reactions.
Urea is extensively used in agriculture and chemical industry, and it is produced on an industrial scale from CO2 and Haber–Bosch NH3 under relatively high temperature and high pressure conditions, which demands high energy input and generates masses of carbon footprint. The conversion of CO2 and N sources (such as NO2−, NO3−, and N2) through electrocatalytic reactions under ambient conditions is a promising alternative to realize efficient urea synthesis. Of note, the design of electrocatalyst is one of the key factors that can improve the efficiency and selectivity of C–N coupling reactions. Defect engineering is an intriguing strategy for regulating the electronic structure and charge density of electrocatalysts, which endows electrocatalysts with excellent physicochemical properties and optimized adsorption energy of the reaction intermediates to reduce the kinetic barriers. In this minireview, recent advances of defect engineered electrocatalysts in urea electrosynthesis from CO2 and various N reactants are firstly introduced. Mechanistic discussions of C–N coupling in these advances are presented, with the aim of directing future investigations on improving the urea yield. Finally, the prospects and challenges of defect engineered electrocatalysts for urea synthesis are discussed. This overview is expected to provide in-depth understanding of structure–reactivity relationship and shed light on future electrocatalytic C–N coupling reactions.
2024, 35(8): 109192
doi: 10.1016/j.cclet.2023.109192
摘要:
Small molecule inhibitors have dominated the pharmaceutical landscape for a long time as the primary therapeutic paradigm targeting pathogenic proteins. However, their efficacy heavily relies on the amino acid composition and spatial constitution of proteins, rendering them susceptible to drug resistance and failing to target undruggable proteins. In recent years, the advent of targeted protein degradation (TPD) technology has captured substantial attention from both industry and academia. Employing an event-driven mode, TPD offers a novel approach to eliminate pathogenic proteins by promoting their degradation, thus circumventing the limitations associated with traditional small molecule inhibitors. Hydrophobic tag tethering degrader (HyTTD) technology represents one such TPD approach that is currently in the burgeoning stage. HyTTDs employ endogenous protein degradation systems to induce the degradation of target proteins through the proteasome pathway, which displays significant potential for medical value. In this review, we provide a comprehensive overview of the development history and the reported mechanism of action of HyTTDs. Additionally, we delve into the physiological roles, structure-activity relationships, and medical implications of HyTTDs targeting various disease-associated proteins. Moreover, we propose insights into the challenges that necessitate resolution for the successful development of HyTTDs, with the ultimate goal of initiating a new age of clinical treatment leveraging the immense potential of HyTTDs.
Small molecule inhibitors have dominated the pharmaceutical landscape for a long time as the primary therapeutic paradigm targeting pathogenic proteins. However, their efficacy heavily relies on the amino acid composition and spatial constitution of proteins, rendering them susceptible to drug resistance and failing to target undruggable proteins. In recent years, the advent of targeted protein degradation (TPD) technology has captured substantial attention from both industry and academia. Employing an event-driven mode, TPD offers a novel approach to eliminate pathogenic proteins by promoting their degradation, thus circumventing the limitations associated with traditional small molecule inhibitors. Hydrophobic tag tethering degrader (HyTTD) technology represents one such TPD approach that is currently in the burgeoning stage. HyTTDs employ endogenous protein degradation systems to induce the degradation of target proteins through the proteasome pathway, which displays significant potential for medical value. In this review, we provide a comprehensive overview of the development history and the reported mechanism of action of HyTTDs. Additionally, we delve into the physiological roles, structure-activity relationships, and medical implications of HyTTDs targeting various disease-associated proteins. Moreover, we propose insights into the challenges that necessitate resolution for the successful development of HyTTDs, with the ultimate goal of initiating a new age of clinical treatment leveraging the immense potential of HyTTDs.
2024, 35(8): 109225
doi: 10.1016/j.cclet.2023.109225
摘要:
Radiotherapy (RT) is a crucial treatment for cancer; however, its effectiveness is limited by adverse effects on normal tissues, radioresistance, and tumor recurrence. To overcome these challenges, hydrogels have been employed for delivery of radiosensitizers and other therapeutic agents. This review summarizes recent advancements in the application of hydrogel-based local drug delivery systems for improving the therapeutic efficacy of RT in cancer treatment. Firstly, we introduce the classification and properties of hydrogels. Next, we detail hydrogel-based platforms designed to enhance both external beam radiation therapy and brachytherapy. We also discuss hydrogels used in combination therapy involving RT and immunotherapy. Lastly, we highlight the challenges that hydrogels face in RT. By surveying the latest developments in hydrogel applications for RT, this review aims to provide insights into the development of more effective and targeted cancer therapies.
Radiotherapy (RT) is a crucial treatment for cancer; however, its effectiveness is limited by adverse effects on normal tissues, radioresistance, and tumor recurrence. To overcome these challenges, hydrogels have been employed for delivery of radiosensitizers and other therapeutic agents. This review summarizes recent advancements in the application of hydrogel-based local drug delivery systems for improving the therapeutic efficacy of RT in cancer treatment. Firstly, we introduce the classification and properties of hydrogels. Next, we detail hydrogel-based platforms designed to enhance both external beam radiation therapy and brachytherapy. We also discuss hydrogels used in combination therapy involving RT and immunotherapy. Lastly, we highlight the challenges that hydrogels face in RT. By surveying the latest developments in hydrogel applications for RT, this review aims to provide insights into the development of more effective and targeted cancer therapies.
2024, 35(8): 109249
doi: 10.1016/j.cclet.2023.109249
摘要:
The concentration of metallic elements is closely associated with overall health. However, the discharge of untreated industrial wastewater can lead to metal-containing pollutants entering the human body through the food chain, disrupting the organism's homeostasis and posing a risk to human health. Covalent organic framework materials (COFs) have emerged as a novel porous material for detecting or adsorbing metal ions due to their unique pore structure, topological structure and flexible design. This paper summarizes the role, toxicity, and sources of metal ions related to human health, as well as the design, synthesis and performance of COFs fluorescent materials for detecting these elements. The interaction mechanism of different fluorescent COFs and metal ions are discussed. Additionally, the remaining challenges and prospects of COFs fluorescence sensors are provided. We believe this review will be useful in directing the development of fluorescent COFs towards metal ions.
The concentration of metallic elements is closely associated with overall health. However, the discharge of untreated industrial wastewater can lead to metal-containing pollutants entering the human body through the food chain, disrupting the organism's homeostasis and posing a risk to human health. Covalent organic framework materials (COFs) have emerged as a novel porous material for detecting or adsorbing metal ions due to their unique pore structure, topological structure and flexible design. This paper summarizes the role, toxicity, and sources of metal ions related to human health, as well as the design, synthesis and performance of COFs fluorescent materials for detecting these elements. The interaction mechanism of different fluorescent COFs and metal ions are discussed. Additionally, the remaining challenges and prospects of COFs fluorescence sensors are provided. We believe this review will be useful in directing the development of fluorescent COFs towards metal ions.
2024, 35(8): 109276
doi: 10.1016/j.cclet.2023.109276
摘要:
Metabolism encompasses a series of intricate biochemical processes that are vital for the sustenance of life in organisms. Metabolomics, an essential scientific discipline, is a field of study within the broader domain of systems biology that focuses on the comprehensive analysis of small molecules, known as metabolites including lipids, coenzymes, etc., which are synthesized during metabolism. With the continuous development of metabolomics, the multiple biological functions of metabolites are constantly being discovered, encompassing signal transduction and enzyme stimulation, while concurrently exhibiting associations with afflictions like cancer and diabetes. The comprehension of metabolite functionalities and their intricate interplay with disease conditions assumes paramount importance in both disease-focused research endeavors and the development of diagnostic tools. This scholarly exposition undertakes an extensive review of recent advancements in the investigation of functional roles assumed by metabolites, with specific emphasis on metabolites in lipid synthesis, glucose metabolism and exogenous metabolites.
Metabolism encompasses a series of intricate biochemical processes that are vital for the sustenance of life in organisms. Metabolomics, an essential scientific discipline, is a field of study within the broader domain of systems biology that focuses on the comprehensive analysis of small molecules, known as metabolites including lipids, coenzymes, etc., which are synthesized during metabolism. With the continuous development of metabolomics, the multiple biological functions of metabolites are constantly being discovered, encompassing signal transduction and enzyme stimulation, while concurrently exhibiting associations with afflictions like cancer and diabetes. The comprehension of metabolite functionalities and their intricate interplay with disease conditions assumes paramount importance in both disease-focused research endeavors and the development of diagnostic tools. This scholarly exposition undertakes an extensive review of recent advancements in the investigation of functional roles assumed by metabolites, with specific emphasis on metabolites in lipid synthesis, glucose metabolism and exogenous metabolites.
2024, 35(8): 109277
doi: 10.1016/j.cclet.2023.109277
摘要:
The advancement of energy storage technology has paved the way for the application of electrochemical processes in achieving low-carbon and precise environmental pollution reduction. Electrodes play a crucial role in efficiently removing organic pollutants and heavy metals. To implement electrochemical pollution control technology in practical engineering, flexible electrode preparation is vital. This review highlights recent progress in flexible electrode research, focusing on the selection and structural design of flexible electrode materials. It summarizes the latest advancements in current collectors, active materials, and preparation methods to enhance conductivity, flexibility, and cycle stability. The application of flexible electrodes in water pollution control is categorized into three aspects: Organic pollutants, inorganic pollutants, and composite pollutants. Finally, the challenges and research requirements for enhancing electrode flexibility in environmental governance are discussed, along with prospects for their future applications.
The advancement of energy storage technology has paved the way for the application of electrochemical processes in achieving low-carbon and precise environmental pollution reduction. Electrodes play a crucial role in efficiently removing organic pollutants and heavy metals. To implement electrochemical pollution control technology in practical engineering, flexible electrode preparation is vital. This review highlights recent progress in flexible electrode research, focusing on the selection and structural design of flexible electrode materials. It summarizes the latest advancements in current collectors, active materials, and preparation methods to enhance conductivity, flexibility, and cycle stability. The application of flexible electrodes in water pollution control is categorized into three aspects: Organic pollutants, inorganic pollutants, and composite pollutants. Finally, the challenges and research requirements for enhancing electrode flexibility in environmental governance are discussed, along with prospects for their future applications.
2024, 35(8): 109329
doi: 10.1016/j.cclet.2023.109329
摘要:
Hydrogen (H2) is a promising renewable energy which finds wide applications as the world gears toward low-carbon economy. However, current H2 production via steam methane reforming of natural gas or gasification of coal are laden with high CO2 footprints. Recently, methane (CH4) pyrolysis has emerged as a potential technology to generate low-carbon H2 and solid carbon. In this review, the current state-of-art and recent progress of H2 production from CH4 pyrolysis are reviewed in detail. Aspects such as fundamental mechanism and chemistry involved, effect of process parameters on the conversion efficiency and reaction kinetics for various reaction media and catalysts are elucidated and critically discussed. Temperature, among other factors, plays the most critical influence on the methane pyrolysis reaction. Molten metal/salt could lower the operating temperature of methane pyrolysis to < 1000 ℃, whereas plasma technology usually operates in the regime of > 1000 ℃. Based on the reaction kinetics, metal-based catalysts were more efficient in lowering the activation energy of the reaction to 29.5–88 kJ/mol from that of uncatalyzed reaction (147–420.7 kJ/mol). Besides, the current techno-economic performance of the process reveals that the levelized cost of H2 is directly influenced by the sales price of carbon (by-product) generated, which could offset the overall cost. Lastly, the main challenges of reactor design for efficient product separation and retrieval, as well as catalyst deactivation/poisoning need to be debottlenecked.
Hydrogen (H2) is a promising renewable energy which finds wide applications as the world gears toward low-carbon economy. However, current H2 production via steam methane reforming of natural gas or gasification of coal are laden with high CO2 footprints. Recently, methane (CH4) pyrolysis has emerged as a potential technology to generate low-carbon H2 and solid carbon. In this review, the current state-of-art and recent progress of H2 production from CH4 pyrolysis are reviewed in detail. Aspects such as fundamental mechanism and chemistry involved, effect of process parameters on the conversion efficiency and reaction kinetics for various reaction media and catalysts are elucidated and critically discussed. Temperature, among other factors, plays the most critical influence on the methane pyrolysis reaction. Molten metal/salt could lower the operating temperature of methane pyrolysis to < 1000 ℃, whereas plasma technology usually operates in the regime of > 1000 ℃. Based on the reaction kinetics, metal-based catalysts were more efficient in lowering the activation energy of the reaction to 29.5–88 kJ/mol from that of uncatalyzed reaction (147–420.7 kJ/mol). Besides, the current techno-economic performance of the process reveals that the levelized cost of H2 is directly influenced by the sales price of carbon (by-product) generated, which could offset the overall cost. Lastly, the main challenges of reactor design for efficient product separation and retrieval, as well as catalyst deactivation/poisoning need to be debottlenecked.
2024, 35(8): 109342
doi: 10.1016/j.cclet.2023.109342
摘要:
As a powerful noninvasive imaging technology, positron emission tomography (PET) has been playing an important role in disease theranostics and drug discovery. The successful application of PET relies on not only the biological properties of PET tracers but also the availability of facile and efficient radiochemical reactions to enable practical production and widespread use of PET tracers. Most recently, photochemistry is emerging as a novel, mild and efficient approach to generating PET agents. In this review, we focus on the recent advances in newly developed photocatalytic radiochemical reactions, innovation on automated photochemical radiosynthesis modules, as well as implementation in late-stage radiolabeling and radiopharmaceutical synthesis for PET imaging. We believe that this review will inspire the development of more promising radiolabeling protocols for the preparation of clinically useful PET agents.
As a powerful noninvasive imaging technology, positron emission tomography (PET) has been playing an important role in disease theranostics and drug discovery. The successful application of PET relies on not only the biological properties of PET tracers but also the availability of facile and efficient radiochemical reactions to enable practical production and widespread use of PET tracers. Most recently, photochemistry is emerging as a novel, mild and efficient approach to generating PET agents. In this review, we focus on the recent advances in newly developed photocatalytic radiochemical reactions, innovation on automated photochemical radiosynthesis modules, as well as implementation in late-stage radiolabeling and radiopharmaceutical synthesis for PET imaging. We believe that this review will inspire the development of more promising radiolabeling protocols for the preparation of clinically useful PET agents.
2024, 35(8): 109363
doi: 10.1016/j.cclet.2023.109363
摘要:
New fabrication method of nanostructures is of great importance for the applications of nanoscience and nanotechnology. This review summarizes cucurbit[n]uril (CB[n])-based nanostructure fabrication and modification approaches. These strategies include the use of CB[n]s as building blocks and supramolecular crosslinkers to fabricate nanostructures, to surface modify nanostructures, and as gatekeepers to control the release of encapsulated cargo. These nanostructures are used for drug delivery, bioimaging, chemical sensing, catalysis and other applications. CB[n]s often play a vital role in the fabrication of these nanostructures, and the realization of the applications.
New fabrication method of nanostructures is of great importance for the applications of nanoscience and nanotechnology. This review summarizes cucurbit[n]uril (CB[n])-based nanostructure fabrication and modification approaches. These strategies include the use of CB[n]s as building blocks and supramolecular crosslinkers to fabricate nanostructures, to surface modify nanostructures, and as gatekeepers to control the release of encapsulated cargo. These nanostructures are used for drug delivery, bioimaging, chemical sensing, catalysis and other applications. CB[n]s often play a vital role in the fabrication of these nanostructures, and the realization of the applications.
2024, 35(8): 109417
doi: 10.1016/j.cclet.2023.109417
摘要:
The atom-economical C-F insertion chemistry is emerged as a promising technology for the synthesis of various fluorinated scaffolds, which have wide applications both in the academic and the industrial communities. The past three years have witnessed rapid developments in this field. This highlight provides an overview on the evolution according to the fluorinating agents used.
The atom-economical C-F insertion chemistry is emerged as a promising technology for the synthesis of various fluorinated scaffolds, which have wide applications both in the academic and the industrial communities. The past three years have witnessed rapid developments in this field. This highlight provides an overview on the evolution according to the fluorinating agents used.
2024, 35(8): 109472
doi: 10.1016/j.cclet.2023.109472
摘要:
Heterogeneous porous carbon (PC) materials have gained unique importance in the catalysis community due to their captivating properties, including high specific surface area, tunable porosity, and functionality. PC can play a prominent role in the sustainable synthesis of functional heterocycles, as they are a low-cost alternative while being an efficient and user-friendly material. This review examines the preparation and applicability of these carbonaceous materials used as catalysts or support for biologically active heterocycles synthesis, including hydrogenation, oxidation, oxidative dehydrogenation, cross-coupling, and other organic reactions. Moreover, the challenges, potential future development directions, and opportunities in the synthesis of potent bioactive heterocycles over PC materials have been addressed. This review will inspire further research to explore novel PC materials and their implications in heterocyclization.
Heterogeneous porous carbon (PC) materials have gained unique importance in the catalysis community due to their captivating properties, including high specific surface area, tunable porosity, and functionality. PC can play a prominent role in the sustainable synthesis of functional heterocycles, as they are a low-cost alternative while being an efficient and user-friendly material. This review examines the preparation and applicability of these carbonaceous materials used as catalysts or support for biologically active heterocycles synthesis, including hydrogenation, oxidation, oxidative dehydrogenation, cross-coupling, and other organic reactions. Moreover, the challenges, potential future development directions, and opportunities in the synthesis of potent bioactive heterocycles over PC materials have been addressed. This review will inspire further research to explore novel PC materials and their implications in heterocyclization.
2024, 35(8): 109749
doi: 10.1016/j.cclet.2024.109749
摘要:
Organic thermoelectric (OTE) materials and devices have garnered significant attention in the past decade for flexible and wearable electronics. Due to the numerous combinations of different backbones, side chains, and functional groups for polymer molecules, further efficient developments of high performance OTEs rely on reverse and rational molecular design as well as fundamental understanding to the structure-property relationship, which both require precise theoretical input. Recently, many theoretical efforts and progresses have been made to predict TE properties and develop high performance OTE materials. Here, we present first the general methods and principles for OTE theoretical calculations. Subsequently, the latest theoretical advances regarding the effects of molecular design, chemical doping, ambipolar charge transport etc., to TE conversion are carefully reviewed. These theoretical advances not only significantly deepen the fundamental understanding of OTEs, but also provide precise guidance to the molecular design of OTE materials. Finally, we propose several perspectives for future theoretical investigations of OTEs.
Organic thermoelectric (OTE) materials and devices have garnered significant attention in the past decade for flexible and wearable electronics. Due to the numerous combinations of different backbones, side chains, and functional groups for polymer molecules, further efficient developments of high performance OTEs rely on reverse and rational molecular design as well as fundamental understanding to the structure-property relationship, which both require precise theoretical input. Recently, many theoretical efforts and progresses have been made to predict TE properties and develop high performance OTE materials. Here, we present first the general methods and principles for OTE theoretical calculations. Subsequently, the latest theoretical advances regarding the effects of molecular design, chemical doping, ambipolar charge transport etc., to TE conversion are carefully reviewed. These theoretical advances not only significantly deepen the fundamental understanding of OTEs, but also provide precise guidance to the molecular design of OTE materials. Finally, we propose several perspectives for future theoretical investigations of OTEs.
2024, 35(8): 109754
doi: 10.1016/j.cclet.2024.109754
摘要:
The isolation of circulating tumor cells (CTCs) from complex biological samples is of paramount significance for advancing cancer diagnosis, prognosis, and treatment. However, the low concentration of CTCs and nonspecific adhesion of white blood cells (WBCs) present challenges that hinder the efficiency and purity of captured CTCs. Microfluidic-based strategies utilize precise fluid control at the micron level to incorporate specific micro/nanostructures or recognition molecules, enabling effective CTCs separation. Moreover, by employing surface modification designs that exhibit exceptional anti-adhesion properties against WBCs, the purity of isolated CTCs can be further enhanced. This review offers an in-depth exploration of recent advancements, challenges, and opportunities associated with microfluidic-based CTCs isolation from biological samples. Firstly, we will comprehensively introduce the microfluidic-based strategies for achieving high-efficiency CTCs isolation, which includes the morphological design of microchannels for physical force-based CTCs isolation and the specific modification of microchannel surfaces for affinity-based CTCs isolation. Subsequently, a review of recent research advances in microfluidic-based high-purity CTCs isolation is presented, focusing on strategies that decrease the nonspecific adhesion of WBCs through surface micro-/nanostructure construction or chemical and biological modification. Finally, we will summarize the article by providing the prospective opportunities and challenges for the future development of microfluidic-based CTCs isolation.
The isolation of circulating tumor cells (CTCs) from complex biological samples is of paramount significance for advancing cancer diagnosis, prognosis, and treatment. However, the low concentration of CTCs and nonspecific adhesion of white blood cells (WBCs) present challenges that hinder the efficiency and purity of captured CTCs. Microfluidic-based strategies utilize precise fluid control at the micron level to incorporate specific micro/nanostructures or recognition molecules, enabling effective CTCs separation. Moreover, by employing surface modification designs that exhibit exceptional anti-adhesion properties against WBCs, the purity of isolated CTCs can be further enhanced. This review offers an in-depth exploration of recent advancements, challenges, and opportunities associated with microfluidic-based CTCs isolation from biological samples. Firstly, we will comprehensively introduce the microfluidic-based strategies for achieving high-efficiency CTCs isolation, which includes the morphological design of microchannels for physical force-based CTCs isolation and the specific modification of microchannel surfaces for affinity-based CTCs isolation. Subsequently, a review of recent research advances in microfluidic-based high-purity CTCs isolation is presented, focusing on strategies that decrease the nonspecific adhesion of WBCs through surface micro-/nanostructure construction or chemical and biological modification. Finally, we will summarize the article by providing the prospective opportunities and challenges for the future development of microfluidic-based CTCs isolation.
2024, 35(8): 109743
doi: 10.1016/j.cclet.2024.109743
摘要:
2024, 35(8): 109899
doi: 10.1016/j.cclet.2024.109899
摘要:
