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2024 Volume 35 Issue 12
2024, 35(12): 109507
doi: 10.1016/j.cclet.2024.109507
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
2024, 35(12): 109918
doi: 10.1016/j.cclet.2024.109918
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
2024, 35(12): 110198
doi: 10.1016/j.cclet.2024.110198
Abstract:
2024, 35(12): 110208
doi: 10.1016/j.cclet.2024.110208
Abstract:
2024, 35(12): 110210
doi: 10.1016/j.cclet.2024.110210
Abstract:
