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Chinese Chemical Letters
Chinese Chemical Letters
主管 : 中国科学技术协会
刊期 : 月刊主编 : 钱旭红
语种 : 英文主办 : 中国化学会、中国医学科学院药物研究所
ISSN : 1001-8417 CN : 11-2710/O6本刊创办于1990年7月，是由中国化学会主办，中国医学科学院药物研究所承办的核心期刊。本刊由著名化学家梁晓天院士任主编，其内容涵盖化学研究的各个领域，及时报道我国化学界各个研究领域的最新进展及世界上一些化学研究的热点问题。本刊自1993年起为SCI、CA、日本科技文献速报等收录，2000年美国化学文摘引用中国期刊频次中位列第四。展开 > - 影响因子: 6.779
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Synthesis of a new ratiometric emission Ca2+ indicator for in vivo bioimaging
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Synthesis of a water-soluble macromolecular light stabilizer containing hindered amine structures
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Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation
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Superiority of poly(L-lactic acid) microspheres as dermal fillers
2024, 35(10): 109343
doi: 10.1016/j.cclet.2023.109343
摘要:
A novel Ce-containing poly(tungstobismuthate) Cs18Na8H20[Ce3(H2O)10W8Bi4O28(B-α-BiW9 O33)4]2·64H2O (1) has been synthesized by a facile one-pot self-assembly reaction strategy. Its structural characterization is realized by virtue of single-crystal X-ray diffraction, infrared spectroscopy, powder X-ray diffraction and thermogravimetric analysis. The polyoxoanion of 1 is an octameric architecture consisting of two tetrameric entities [Ce3(H2O)10W8Bi4O28(B-α-BiW9O33)4]23− linked by two CeOW bonds, and adjacent polyoxoanions are further combined together by means of Ce3+ linkers, resulting in an infinite 1D chain architecture. Compound 1 is the currently largest tungstobismuthate, and also represents the first example of lanthanide-encapsulated tungstobismuthate exhibiting an extended structure. Furthermore, compound 1 as a heterogeneous catalyst, exhibits high activity for the oxidative decontamination of a sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES) into 2-chloroethyl ethyl sulfoxide (CEESO).
A novel Ce-containing poly(tungstobismuthate) Cs18Na8H20[Ce3(H2O)10W8Bi4O28(B-α-BiW9 O33)4]2·64H2O (1) has been synthesized by a facile one-pot self-assembly reaction strategy. Its structural characterization is realized by virtue of single-crystal X-ray diffraction, infrared spectroscopy, powder X-ray diffraction and thermogravimetric analysis. The polyoxoanion of 1 is an octameric architecture consisting of two tetrameric entities [Ce3(H2O)10W8Bi4O28(B-α-BiW9O33)4]23− linked by two CeOW bonds, and adjacent polyoxoanions are further combined together by means of Ce3+ linkers, resulting in an infinite 1D chain architecture. Compound 1 is the currently largest tungstobismuthate, and also represents the first example of lanthanide-encapsulated tungstobismuthate exhibiting an extended structure. Furthermore, compound 1 as a heterogeneous catalyst, exhibits high activity for the oxidative decontamination of a sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES) into 2-chloroethyl ethyl sulfoxide (CEESO).
2024, 35(10): 109345
doi: 10.1016/j.cclet.2023.109345
摘要:
In core-shell silver nanoclusters, the control of core structure presents a more formidable challenge compared to that of the shell structure. Here, we report the successful synthesis and characterization of four distinct silver thiolate nanoclusters [MS4@Ag12@Ag46S24(dppb)12] (M = Mo or W), each incorporating a cup-like [MS4@Ag12]2+ kernel. These nanoclusters were meticulously prepared using (NH4)2MoS4 or (NH4)2WS4 as both a template and a controlled source of S2− ions. Remarkably, we have observed a unique configuration within these eight-electron superatomic Ag58 nanoclusters, where the zero-valent Ag atoms reside exclusively within the inner [MS4@Ag12]2+ kernel. This stands in contrast to other superatomic clusters possessing an Ag(0) core. Notably, the introduction of phenyl-containing compounds during the synthesis process induced a transformation in the space group symmetry from C2/c to I4. This transformative effect was found to originate from the interplay between adjacent 1,4-bis(diphenylphosphino)butane (dppb) ligands, which facilitated enhanced emission through aggregation-induced intermolecular interactions, specifically C−H···π interactions. Collectively, our findings contribute substantively to the understanding of the intricate relationship between nanocluster structures and their corresponding properties, shedding light on the crucial roles played by templates and diphosphine ligands in this context.
In core-shell silver nanoclusters, the control of core structure presents a more formidable challenge compared to that of the shell structure. Here, we report the successful synthesis and characterization of four distinct silver thiolate nanoclusters [MS4@Ag12@Ag46S24(dppb)12] (M = Mo or W), each incorporating a cup-like [MS4@Ag12]2+ kernel. These nanoclusters were meticulously prepared using (NH4)2MoS4 or (NH4)2WS4 as both a template and a controlled source of S2− ions. Remarkably, we have observed a unique configuration within these eight-electron superatomic Ag58 nanoclusters, where the zero-valent Ag atoms reside exclusively within the inner [MS4@Ag12]2+ kernel. This stands in contrast to other superatomic clusters possessing an Ag(0) core. Notably, the introduction of phenyl-containing compounds during the synthesis process induced a transformation in the space group symmetry from C2/c to I4. This transformative effect was found to originate from the interplay between adjacent 1,4-bis(diphenylphosphino)butane (dppb) ligands, which facilitated enhanced emission through aggregation-induced intermolecular interactions, specifically C−H···π interactions. Collectively, our findings contribute substantively to the understanding of the intricate relationship between nanocluster structures and their corresponding properties, shedding light on the crucial roles played by templates and diphosphine ligands in this context.
2024, 35(10): 109352
doi: 10.1016/j.cclet.2023.109352
摘要:
Understanding the role of perovskite surface passivators in hot carriers transfer dynamics is important to develop highly efficient perovskite solar cells (PSCs). In this work, we have designed and synthesized a naphthalimide-based organic small molecule (NCN) for perovskite surface defect passivator. We reveal that the introduction of NCN not only reduces the density of perovskite defect-state, but also promotes hot carriers (HCs) cooling in perovskite through the transient absorption spectroscopy measurements. Fast HCs cooling permits HCs transfer from perovskite layer into NCN layer, thus resulting in the decreased charge-carrier recombination in NCN-treated device. As expected, the power conversion efficiency (PCE) of PSCs with NCN is enhanced to 22.02% from 19.95% for the control device. The findings are relevant for developing highly efficient PSCs.
Understanding the role of perovskite surface passivators in hot carriers transfer dynamics is important to develop highly efficient perovskite solar cells (PSCs). In this work, we have designed and synthesized a naphthalimide-based organic small molecule (NCN) for perovskite surface defect passivator. We reveal that the introduction of NCN not only reduces the density of perovskite defect-state, but also promotes hot carriers (HCs) cooling in perovskite through the transient absorption spectroscopy measurements. Fast HCs cooling permits HCs transfer from perovskite layer into NCN layer, thus resulting in the decreased charge-carrier recombination in NCN-treated device. As expected, the power conversion efficiency (PCE) of PSCs with NCN is enhanced to 22.02% from 19.95% for the control device. The findings are relevant for developing highly efficient PSCs.
2024, 35(10): 109355
doi: 10.1016/j.cclet.2023.109355
摘要:
Since the appearance of Rochelle salt, ferroelectrics have received extensive attention from researchers due to they are playing an important role in sensors, memories, mechanical actuation, and so on. In recent years, with the rapid development of molecular ferroelectrics, high-performance molecular ferroelectrics have become effective complement to inorganic ferroelectrics. However, compared with inorganic ferroelectrics, the family of molecular ferroelectrics is relatively scarce, and exploring high-performance ferroelectric materials through new synthesis strategies has become the trend of molecular ferroelectrics. Here, we successfully transformed non-polar material 1 (2-H2PCA)2(H2O)CdCl6 (2-H2PCA = 2-picolylamine cation) into polar material 2 (2-H2PCA)2CdCl6 by single-crystal to single-crystal transformation (SCSCT). Meanwhile, 2 exhibits clear ferroelectricity with a high-temperature Tc of 378 K, a Ps of 1.18 µC/cm2 at 300 K. This work not only realizes the purpose of synthesizing ferroelectrics by forming polar structures by SCSCT, but also realizes the reversibility of SCSCT, which provides ideas for the construction and exploration of new molecular ferroelectrics.
Since the appearance of Rochelle salt, ferroelectrics have received extensive attention from researchers due to they are playing an important role in sensors, memories, mechanical actuation, and so on. In recent years, with the rapid development of molecular ferroelectrics, high-performance molecular ferroelectrics have become effective complement to inorganic ferroelectrics. However, compared with inorganic ferroelectrics, the family of molecular ferroelectrics is relatively scarce, and exploring high-performance ferroelectric materials through new synthesis strategies has become the trend of molecular ferroelectrics. Here, we successfully transformed non-polar material 1 (2-H2PCA)2(H2O)CdCl6 (2-H2PCA = 2-picolylamine cation) into polar material 2 (2-H2PCA)2CdCl6 by single-crystal to single-crystal transformation (SCSCT). Meanwhile, 2 exhibits clear ferroelectricity with a high-temperature Tc of 378 K, a Ps of 1.18 µC/cm2 at 300 K. This work not only realizes the purpose of synthesizing ferroelectrics by forming polar structures by SCSCT, but also realizes the reversibility of SCSCT, which provides ideas for the construction and exploration of new molecular ferroelectrics.
2024, 35(10): 109377
doi: 10.1016/j.cclet.2023.109377
摘要:
Recently, non-centrosymmetric (NCS) Hg-based chalcogenides have garnered significant interest due to their strong second-harmonic-generation intensities (deff), making them attractive candidates for infrared nonlinear optical (IR-NLO) application. However, achieving both wide band gaps (Eg) and large phase-matched deff simultaneously in these materials remains a challenge due to their inherent constraints on each other. In this research, we have successfully obtained two quaternary NCS Hg-based chalcogenides, Rb2HgGe3S8 and Cs2HgGe3S8, by implementing a bandgap engineering strategy that involves alkali metal introduction and Hg/Ge ratio regulation. Both compounds consist of 2D [HgGe3S8]2– anionic layers made of 1D [HgGeS6]6– chains and dimeric [Ge2S6]4– polyhedra arranged alternately, and the charge-balanced Rb+/Cs+ cations located between these layers. Remarkably, Rb2HgGe3S8 and Cs2HgGe3S8 exhibit overall properties required for promising IR-NLO materials, including sufficient PM deff (0.55–0.70 × AgGaS2@2050 nm), large Eg (3.27–3.41 eV), giant laser-induced damage thresholds (17.4–19.7 × AgGaS2@1064 nm), broad optical transmission intervals (0.32–17.5 µm), and suitable theoretical birefringence (0.069–0.086@2050 nm). Furthermore, in-depth theoretical analysis reveals that the exceptional IR-NLO performance is attributed to the synergy effects of distorted [HgS4] and [GeS4] tetrahedra. Our study provides a useful strategy for enhancing the Eg and advancing Hg-based IR-NLO materials, which is expected to extended and implemented in other chalcogenide systems.
Recently, non-centrosymmetric (NCS) Hg-based chalcogenides have garnered significant interest due to their strong second-harmonic-generation intensities (deff), making them attractive candidates for infrared nonlinear optical (IR-NLO) application. However, achieving both wide band gaps (Eg) and large phase-matched deff simultaneously in these materials remains a challenge due to their inherent constraints on each other. In this research, we have successfully obtained two quaternary NCS Hg-based chalcogenides, Rb2HgGe3S8 and Cs2HgGe3S8, by implementing a bandgap engineering strategy that involves alkali metal introduction and Hg/Ge ratio regulation. Both compounds consist of 2D [HgGe3S8]2– anionic layers made of 1D [HgGeS6]6– chains and dimeric [Ge2S6]4– polyhedra arranged alternately, and the charge-balanced Rb+/Cs+ cations located between these layers. Remarkably, Rb2HgGe3S8 and Cs2HgGe3S8 exhibit overall properties required for promising IR-NLO materials, including sufficient PM deff (0.55–0.70 × AgGaS2@2050 nm), large Eg (3.27–3.41 eV), giant laser-induced damage thresholds (17.4–19.7 × AgGaS2@1064 nm), broad optical transmission intervals (0.32–17.5 µm), and suitable theoretical birefringence (0.069–0.086@2050 nm). Furthermore, in-depth theoretical analysis reveals that the exceptional IR-NLO performance is attributed to the synergy effects of distorted [HgS4] and [GeS4] tetrahedra. Our study provides a useful strategy for enhancing the Eg and advancing Hg-based IR-NLO materials, which is expected to extended and implemented in other chalcogenide systems.
2024, 35(10): 109380
doi: 10.1016/j.cclet.2023.109380
摘要:
Post-synthetic installation strategy is an effective approach to improve the functions of metal-organic frameworks (MOFs). Herein, a pair of chiral MOFs is successfully constructed through solvothermal subcomponent self-assembly and exhibit circularly polarized luminescence (CPL). These MOFs contain coordinatively unsaturated Zn sites and channels, which allow the installation of pyridyl-terminated pillars into the original structure. Such a post-synthetic installation process reinforces the MOFs' rigidity and increases the photoluminescence quantum yields (PLQYs). Furthermore, the luminescence dissymmetry factors (glum) of these post-modified MOFs are amplified after installing the pillars. This work provides an appealing strategy for boosting the CPL performance of chiral MOFs.
Post-synthetic installation strategy is an effective approach to improve the functions of metal-organic frameworks (MOFs). Herein, a pair of chiral MOFs is successfully constructed through solvothermal subcomponent self-assembly and exhibit circularly polarized luminescence (CPL). These MOFs contain coordinatively unsaturated Zn sites and channels, which allow the installation of pyridyl-terminated pillars into the original structure. Such a post-synthetic installation process reinforces the MOFs' rigidity and increases the photoluminescence quantum yields (PLQYs). Furthermore, the luminescence dissymmetry factors (glum) of these post-modified MOFs are amplified after installing the pillars. This work provides an appealing strategy for boosting the CPL performance of chiral MOFs.
2024, 35(10): 109387
doi: 10.1016/j.cclet.2023.109387
摘要:
Lithium argyrodites Li6PS5X (X = Cl, Br, I) show great potential as solid electrolytes for solid-state lithium batteries due to their high Li-ion conductivities and excellent electrode compatibility. However, the relatively low conductivity of Li6PS5I (10−6 mS/cm) compared to the other two compositions limits its applications. Herein, Si-doped Li6.5P0.5Si0.5S5I electrolyte is designed and synthesized with superior high conductivity of 3.6 mS/cm. Structural characterization proves the increase due to the anion disorder and volume expansion caused by Si-doping. However, the poor interfacial stability between layered oxide cathode LiNi0.6Co0.2Mn0.2O2 and Li6.5P0.5Si0.5S5I inhibits its battery performance. By introducing Li3InCl6 electrolyte in the configuration, the corresponding battery delivers high initial discharge capacity of 150.2 mAh/g and superior cyclability during 250 cycles at 0.5 C. This work offers design strategy to obtain Li6PS5I-based electrolytes for high performance solid-state batteries.
Lithium argyrodites Li6PS5X (X = Cl, Br, I) show great potential as solid electrolytes for solid-state lithium batteries due to their high Li-ion conductivities and excellent electrode compatibility. However, the relatively low conductivity of Li6PS5I (10−6 mS/cm) compared to the other two compositions limits its applications. Herein, Si-doped Li6.5P0.5Si0.5S5I electrolyte is designed and synthesized with superior high conductivity of 3.6 mS/cm. Structural characterization proves the increase due to the anion disorder and volume expansion caused by Si-doping. However, the poor interfacial stability between layered oxide cathode LiNi0.6Co0.2Mn0.2O2 and Li6.5P0.5Si0.5S5I inhibits its battery performance. By introducing Li3InCl6 electrolyte in the configuration, the corresponding battery delivers high initial discharge capacity of 150.2 mAh/g and superior cyclability during 250 cycles at 0.5 C. This work offers design strategy to obtain Li6PS5I-based electrolytes for high performance solid-state batteries.
2024, 35(10): 109388
doi: 10.1016/j.cclet.2023.109388
摘要:
Aqueous alkaline zinc batteries (AZBs) exhibit great potential due to their high capacity, high safety and low cost. However, despite these advantages, the lack of high stability and high utilization rate makes the search for high-performance cathode materials a great challenge. Here, an amorphous nickel boride/rGO (NiB/rGO) complex structure was designed. As a result of abundant unsaturated active sites and synergistic electronic effects, amorphous NiB exhibits excellent energy storage properties. As well as having high electrical conductivity, rGO avoids aggregation of NiB nanoparticles, ensuring that NiB/rGO electrodes have a high energy storage capacity. The structure has a strong adhesion between NiB and rGO, which protects its stable structure and extends its life. More importantly, the NiB/rGO//Zn full battery shows remarkable capacity (228.4 mAh/g at 2 A/g), extraordinary cycle durability (93.7% retained after 1000 cycles) and strong energy density 399.7 Wh/kg, when coupled with NiB/rGO cathode. This work will also shed light on other nickel-zinc batteries in order to achieve super durability and capacity.
Aqueous alkaline zinc batteries (AZBs) exhibit great potential due to their high capacity, high safety and low cost. However, despite these advantages, the lack of high stability and high utilization rate makes the search for high-performance cathode materials a great challenge. Here, an amorphous nickel boride/rGO (NiB/rGO) complex structure was designed. As a result of abundant unsaturated active sites and synergistic electronic effects, amorphous NiB exhibits excellent energy storage properties. As well as having high electrical conductivity, rGO avoids aggregation of NiB nanoparticles, ensuring that NiB/rGO electrodes have a high energy storage capacity. The structure has a strong adhesion between NiB and rGO, which protects its stable structure and extends its life. More importantly, the NiB/rGO//Zn full battery shows remarkable capacity (228.4 mAh/g at 2 A/g), extraordinary cycle durability (93.7% retained after 1000 cycles) and strong energy density 399.7 Wh/kg, when coupled with NiB/rGO cathode. This work will also shed light on other nickel-zinc batteries in order to achieve super durability and capacity.
2024, 35(10): 109391
doi: 10.1016/j.cclet.2023.109391
摘要:
Magnesium rechargeable batteries (MRBs) present opportunities for grid-scale energy storage applications as a complement to Li-ion batteries (LIBS). The major challenges are the low reversible capacity, inferior cycling stability and unsatisfactory energy densities. Na3VCr0.5Fe0.5(PO4)3 with a well-defined NASION-type structure is used as cathode in Mg cell. Two-electrons reaction (~116 mAh/g), 1.5 V average voltage and 65% of capacity retention over 100 cycles are accomplished. Mg is inserted by a biphasic reaction with the participation of V3+/V4+/V5+ redox couples in the electrochemical reaction while the non-active redox couples such as Cr3+/Cr4+ and Fe2+/Fe3+ served as stabilizer to buffer the volume variation. A thermal stability up to ~412 ℃ is also exhibited. Therefore, incorporating a mixture of three transition metal (V/Cr/Fe) in this type of structures will broaden new perspectives for realizing high performance cathodes for MRBs.
Magnesium rechargeable batteries (MRBs) present opportunities for grid-scale energy storage applications as a complement to Li-ion batteries (LIBS). The major challenges are the low reversible capacity, inferior cycling stability and unsatisfactory energy densities. Na3VCr0.5Fe0.5(PO4)3 with a well-defined NASION-type structure is used as cathode in Mg cell. Two-electrons reaction (~116 mAh/g), 1.5 V average voltage and 65% of capacity retention over 100 cycles are accomplished. Mg is inserted by a biphasic reaction with the participation of V3+/V4+/V5+ redox couples in the electrochemical reaction while the non-active redox couples such as Cr3+/Cr4+ and Fe2+/Fe3+ served as stabilizer to buffer the volume variation. A thermal stability up to ~412 ℃ is also exhibited. Therefore, incorporating a mixture of three transition metal (V/Cr/Fe) in this type of structures will broaden new perspectives for realizing high performance cathodes for MRBs.
2024, 35(10): 109405
doi: 10.1016/j.cclet.2023.109405
摘要:
Na-ion cathode materials with a fast charge and discharge behavior are needed to develop future high-energy sodium-ion batteries (SIBs). However, inevitably complicated phase transitions and sluggish kinetics during insertion and removal of Na+ in P2-type layered transition metal oxides generate structural instability and severe capacity decay. To get rid of such a dilemma, we report a structural optimization strategy to promote P2-type layered transition metal oxides with more (010) active planes as an efficient cathode for SIBs. As a result, as-prepared hexagonal-prism P2-type layered Na0.71Ni0.16Li0.09Co0.16Mn0.6O2 cathode with more (010) active planes delivers a reversible capacity of 120.1 mAh/g at 0.1 C, impressive rate capability of 52.7 mAh/g at 10 C, and long-term cycling stability (capacity retention of 95.6% over 200 cycles). The outstanding electrochemical performance benefited from the unique hexagonal-prism with more (010) active facets, which can effectively shorten the diffusion distances of Na+, increase the Na-ion migration dynamics and nanostructural stability during cycling verified by morphology characterization, Rietveld refinement, GITT, density functional theory calculations and operando XRD.
Na-ion cathode materials with a fast charge and discharge behavior are needed to develop future high-energy sodium-ion batteries (SIBs). However, inevitably complicated phase transitions and sluggish kinetics during insertion and removal of Na+ in P2-type layered transition metal oxides generate structural instability and severe capacity decay. To get rid of such a dilemma, we report a structural optimization strategy to promote P2-type layered transition metal oxides with more (010) active planes as an efficient cathode for SIBs. As a result, as-prepared hexagonal-prism P2-type layered Na0.71Ni0.16Li0.09Co0.16Mn0.6O2 cathode with more (010) active planes delivers a reversible capacity of 120.1 mAh/g at 0.1 C, impressive rate capability of 52.7 mAh/g at 10 C, and long-term cycling stability (capacity retention of 95.6% over 200 cycles). The outstanding electrochemical performance benefited from the unique hexagonal-prism with more (010) active facets, which can effectively shorten the diffusion distances of Na+, increase the Na-ion migration dynamics and nanostructural stability during cycling verified by morphology characterization, Rietveld refinement, GITT, density functional theory calculations and operando XRD.
2024, 35(10): 109407
doi: 10.1016/j.cclet.2023.109407
摘要:
Metronidazole (MNZ) is a type of antibiotic that can help people and animals cure bacterial infections, however, abuse of MNZ has posed a threat to human health. Hence, portable and visual detection of MNZ is meaningful for food safety and rational administration of drugs, but full of challenges. Hence, a porous three-dimensional Tb-based metal-organic framework (MOF) {(CH3)2NH2·[Tb5(TDA)8(H2O)2]·6DMF·2C2H5OH}n (TDA-Tb) with good solvent and pH stabilities was prepared, and the framework possesses one-dimensional channels with a diameter of 12 Å along the c-axis. Experiment results suggest that the synthesized TDA-Tb can selectively and sensitively detect MNZ in water, and the limit of detection (LOD) is as low as 4.1 × 10−7 mol/L. Moreover, a flexible sensor TDA-Tb-M was also constructed by incorporating TDA-Tb into membrane materials for convenient usage. And the TDA-Tb-M firstly realized portable and visual detection of MNZ through smartphone scanning, which may inspire more probes with wide application ranges.
Metronidazole (MNZ) is a type of antibiotic that can help people and animals cure bacterial infections, however, abuse of MNZ has posed a threat to human health. Hence, portable and visual detection of MNZ is meaningful for food safety and rational administration of drugs, but full of challenges. Hence, a porous three-dimensional Tb-based metal-organic framework (MOF) {(CH3)2NH2·[Tb5(TDA)8(H2O)2]·6DMF·2C2H5OH}n (TDA-Tb) with good solvent and pH stabilities was prepared, and the framework possesses one-dimensional channels with a diameter of 12 Å along the c-axis. Experiment results suggest that the synthesized TDA-Tb can selectively and sensitively detect MNZ in water, and the limit of detection (LOD) is as low as 4.1 × 10−7 mol/L. Moreover, a flexible sensor TDA-Tb-M was also constructed by incorporating TDA-Tb into membrane materials for convenient usage. And the TDA-Tb-M firstly realized portable and visual detection of MNZ through smartphone scanning, which may inspire more probes with wide application ranges.
2024, 35(10): 109415
doi: 10.1016/j.cclet.2023.109415
摘要:
The combination of interface engineering and defect engineering is a promising strategy for developing new semiconducting surface-enhanced Raman scattering (SERS) substrate. Herein, an organic/inorganic hybrid g-C3N4/TiO2-X heterojunction with synchronous generation of strong interface effect and abundant surface oxygen vacancy (OV) defect was prepared by a simple sol-hydrothermal procedure with a help of urea. Due to the improved substrate-to-molecule charge transfer (CT) from joint contribution of high-efficiency carrier separation induced by strong interface coupling effect and multiple CT paths derived from abundant surface OV, g-C3N4/TiO2-X substrate exhibits greatly enhanced SERS effect for non-resonant 4-mercaptobenzoic acid (4-MBA) probe. The enhancement factor of g-C3N4/TiO2-X substrate for 4-MBA is as high as 5.57 × 106, and the substrate exhibits ultra-high stability and excellent spectral reproducibility. More meaningfully, the developed g-C3N4/TiO2-X heterojunction can be used to execute an ultrasensitive detection for antibiotic residues in real water system, even comprehensive evaluation of multi-component residues.
The combination of interface engineering and defect engineering is a promising strategy for developing new semiconducting surface-enhanced Raman scattering (SERS) substrate. Herein, an organic/inorganic hybrid g-C3N4/TiO2-X heterojunction with synchronous generation of strong interface effect and abundant surface oxygen vacancy (OV) defect was prepared by a simple sol-hydrothermal procedure with a help of urea. Due to the improved substrate-to-molecule charge transfer (CT) from joint contribution of high-efficiency carrier separation induced by strong interface coupling effect and multiple CT paths derived from abundant surface OV, g-C3N4/TiO2-X substrate exhibits greatly enhanced SERS effect for non-resonant 4-mercaptobenzoic acid (4-MBA) probe. The enhancement factor of g-C3N4/TiO2-X substrate for 4-MBA is as high as 5.57 × 106, and the substrate exhibits ultra-high stability and excellent spectral reproducibility. More meaningfully, the developed g-C3N4/TiO2-X heterojunction can be used to execute an ultrasensitive detection for antibiotic residues in real water system, even comprehensive evaluation of multi-component residues.
2024, 35(10): 109423
doi: 10.1016/j.cclet.2023.109423
摘要:
The efficient energy conversion of fuel cells is greatly constrained by the slow oxygen reduction reaction (ORR) kinetics, which necessitates the use of highly active metal catalysts such as platinum (Pt). The critical challenge limiting large-scale usage of Pt is the capital cost that can be addressed through a prototypical approach by embedding metal nanoparticles (NPs), e.g., Pt NPs, in the conductive framework. However, previously reported embedding approaches are sophisticated and suffer from limited yields, leading to higher chemical process costs and remaining distant from commercial viability. Here, we report a facile, cost-effective and time-efficient structural tuning approach to synthesizing ultrafine Pt NPs impregnated within a conductive and highly porous carbon framework via a microwave-assisted polyol reduction method. Pt NPs with a uniform size of ~2.27 nm can be successfully integrated within the pores of the carbon framework, enabling homogeneous dispersion. Benefiting from these highly dispersed and ultrafine Pt NPs, the electrochemical surface area (ECSA) is improved to 142.98 m²/gPt, 2.25 times higher than that of the commercial counterpart (63.52 m²/gPt). Furthermore, our structurally optimized catalyst composite features a remarkably catalytic activity with a high half-wave potential (E1/2) of 0.895 V and an improved mass activity (MA) of 0.2289 A/mgPt, 2.39-fold improvement compared to the commercial counterpart. In addition, orthogonal experiments were designed to identify the key process parameters for fabricating Pt/C catalysts, offering insights for scaled-up and industrial production.
The efficient energy conversion of fuel cells is greatly constrained by the slow oxygen reduction reaction (ORR) kinetics, which necessitates the use of highly active metal catalysts such as platinum (Pt). The critical challenge limiting large-scale usage of Pt is the capital cost that can be addressed through a prototypical approach by embedding metal nanoparticles (NPs), e.g., Pt NPs, in the conductive framework. However, previously reported embedding approaches are sophisticated and suffer from limited yields, leading to higher chemical process costs and remaining distant from commercial viability. Here, we report a facile, cost-effective and time-efficient structural tuning approach to synthesizing ultrafine Pt NPs impregnated within a conductive and highly porous carbon framework via a microwave-assisted polyol reduction method. Pt NPs with a uniform size of ~2.27 nm can be successfully integrated within the pores of the carbon framework, enabling homogeneous dispersion. Benefiting from these highly dispersed and ultrafine Pt NPs, the electrochemical surface area (ECSA) is improved to 142.98 m²/gPt, 2.25 times higher than that of the commercial counterpart (63.52 m²/gPt). Furthermore, our structurally optimized catalyst composite features a remarkably catalytic activity with a high half-wave potential (E1/2) of 0.895 V and an improved mass activity (MA) of 0.2289 A/mgPt, 2.39-fold improvement compared to the commercial counterpart. In addition, orthogonal experiments were designed to identify the key process parameters for fabricating Pt/C catalysts, offering insights for scaled-up and industrial production.
2024, 35(10): 109425
doi: 10.1016/j.cclet.2023.109425
摘要:
Defects at the surface and grain boundaries of the perovskite films are extremely detrimental to both the efficiency and stability of perovskite solar cells (PSCs). Herein, a simple and stable quaternary ammonium halide, named chlormequat chloride (i.e., chlorinated choline chloride, CCC), is introduced to regulate the upper surface chemical environment of perovskite films. The anion (Cl−) and cation [ClCH2CH2N(CH3)3]+ in CCC could effectively self-search and passivate positively and negatively charged ionic defects in perovskites, respectively, which contributes to inhibited nonradiative recombination and reduced energy loss in PSCs. As a result, the champion power conversion efficiency (PCE) of PSCs can be significantly enhanced from 22.82% to 24.07%. Moreover, the unencapsulated device with CCC modification retains 92.0% of its original PCE even subject to thermal aging at 85 ℃ for 2496 h. This work provides guidance for the rational design of functional molecules as defect passivators in PSCs, which is beneficial for the improvements in both device performance and stability.
Defects at the surface and grain boundaries of the perovskite films are extremely detrimental to both the efficiency and stability of perovskite solar cells (PSCs). Herein, a simple and stable quaternary ammonium halide, named chlormequat chloride (i.e., chlorinated choline chloride, CCC), is introduced to regulate the upper surface chemical environment of perovskite films. The anion (Cl−) and cation [ClCH2CH2N(CH3)3]+ in CCC could effectively self-search and passivate positively and negatively charged ionic defects in perovskites, respectively, which contributes to inhibited nonradiative recombination and reduced energy loss in PSCs. As a result, the champion power conversion efficiency (PCE) of PSCs can be significantly enhanced from 22.82% to 24.07%. Moreover, the unencapsulated device with CCC modification retains 92.0% of its original PCE even subject to thermal aging at 85 ℃ for 2496 h. This work provides guidance for the rational design of functional molecules as defect passivators in PSCs, which is beneficial for the improvements in both device performance and stability.
2024, 35(10): 109426
doi: 10.1016/j.cclet.2023.109426
摘要:
Zinc metal is regarded as one of the most promising anodes for Zn-based batteries in next-generation energy storage systems. However, the dendrite growth and interfacial corrosion lead to poor reversibility and cycle life of Zn anodes. Herein, we synthesize a 2-phosphate-1,2,4-butane tricarboxylic acid modified hyperbranched polyamidoamine containing rich terminal groups of phosphate and carboxyl (HPC) as modified layer for the Zn anodes. Importantly, the in situ acid-etching promotes the exposure of (002)Zn plane and the generated salt-polymer complexes could be adhered to the Zn anodes tightly. This greatly favors the uniform deposition of Zn and inhibits interfacial corrosion. Consequently, stable HPC@Zn anode plating/stripping for over 1200 h at a high areal capacity of 4 mAh/cm2 and a current density of 4 mA/cm2 is obtained. This study provides a new avenue of hyperbranched polymer in interfacial design for highly reversible and stable Zn metal anodes.
Zinc metal is regarded as one of the most promising anodes for Zn-based batteries in next-generation energy storage systems. However, the dendrite growth and interfacial corrosion lead to poor reversibility and cycle life of Zn anodes. Herein, we synthesize a 2-phosphate-1,2,4-butane tricarboxylic acid modified hyperbranched polyamidoamine containing rich terminal groups of phosphate and carboxyl (HPC) as modified layer for the Zn anodes. Importantly, the in situ acid-etching promotes the exposure of (002)Zn plane and the generated salt-polymer complexes could be adhered to the Zn anodes tightly. This greatly favors the uniform deposition of Zn and inhibits interfacial corrosion. Consequently, stable HPC@Zn anode plating/stripping for over 1200 h at a high areal capacity of 4 mAh/cm2 and a current density of 4 mA/cm2 is obtained. This study provides a new avenue of hyperbranched polymer in interfacial design for highly reversible and stable Zn metal anodes.
2024, 35(10): 109430
doi: 10.1016/j.cclet.2023.109430
摘要:
Carbon dots (CDs), as a solid-state phosphor, have great potential for application in a new solid-state lighting device—laser diode (LD). For high efficiency LD devices, both high photoluminescence quantum yield (PLQY) and high photothermal stability of CDs are essential. Herein, yellow CDs@ZIF-8 composites with high structural stability were prepared by encapsulating CDs in zeolitic imidazolate framework-8 (ZIF-8) through electrostatic adsorption between CDs and ZIF-8, in which CDs with amino groups on the surface were used as luminescent feeders and ZIF-8 was used as a protective layer matrix. The as-prepared CDs@ZIF-8 not only possess a high PLQY of up to 81.17%, but also maintain a high fluorescence intensity of 100% and 80% under long-term illumination (60 min) and high temperature (478 K), respectively. The hydrogen bonding between CDs and ZIF-8 in the encapsulated structure can enhance the degree of electron cloud delocalization, which can improve the PLQY of CDs@ZIF-8. Meanwhile, CDs@ZIF-8 has high photothermal stability due to the binding effect of ZIF-8 on CDs and high thermal stability of ZIF-8. The white LD device, fabricated from CDs@ZIF-8 as a phosphor in combination with 450 nm blue LD, has a color coordinate of (0.37, 0.33), a color temperature of 3762 K, and a high color rendering index of 86. This study provides a new strategy for the construction of solid-state phosphors with high PLQY and high photothermal performance.
Carbon dots (CDs), as a solid-state phosphor, have great potential for application in a new solid-state lighting device—laser diode (LD). For high efficiency LD devices, both high photoluminescence quantum yield (PLQY) and high photothermal stability of CDs are essential. Herein, yellow CDs@ZIF-8 composites with high structural stability were prepared by encapsulating CDs in zeolitic imidazolate framework-8 (ZIF-8) through electrostatic adsorption between CDs and ZIF-8, in which CDs with amino groups on the surface were used as luminescent feeders and ZIF-8 was used as a protective layer matrix. The as-prepared CDs@ZIF-8 not only possess a high PLQY of up to 81.17%, but also maintain a high fluorescence intensity of 100% and 80% under long-term illumination (60 min) and high temperature (478 K), respectively. The hydrogen bonding between CDs and ZIF-8 in the encapsulated structure can enhance the degree of electron cloud delocalization, which can improve the PLQY of CDs@ZIF-8. Meanwhile, CDs@ZIF-8 has high photothermal stability due to the binding effect of ZIF-8 on CDs and high thermal stability of ZIF-8. The white LD device, fabricated from CDs@ZIF-8 as a phosphor in combination with 450 nm blue LD, has a color coordinate of (0.37, 0.33), a color temperature of 3762 K, and a high color rendering index of 86. This study provides a new strategy for the construction of solid-state phosphors with high PLQY and high photothermal performance.
2024, 35(10): 109446
doi: 10.1016/j.cclet.2023.109446
摘要:
Spin-orbit, charge-transfer intersystem crossing (SOCT-ISC) can directly overcome the disadvantages of the traditional heavy-atom effect and improve the generation efficiency of reactive oxygen species (ROS). Since orthogonal molecular orbitals of donor-acceptor (D-A) pairs favor the SOCT-ISC transition, herein aza-borondipyrromethenes (aza-BODIPYs) with 1,7-di-anthracyl groups (An-azaBDP) was successfully prepared, owing to steric hindrance to produce a big dihedral angle between the two molecular orbital (MO) planes. Moreover, according to density functional theory (DFT) and time-dependent density functional theory (TDDFT), the energy difference between the S1-T1 orbitals of An-azaBDP is small and more inclined towards ISC. An-azaBDP can effectively generate singlet oxygen under light irradiation. An-azaBDP with light irradiation can induce apoptosis in SW620 cells, and can serve as a potential candidate for the treatment of cancer cells and tumors.
Spin-orbit, charge-transfer intersystem crossing (SOCT-ISC) can directly overcome the disadvantages of the traditional heavy-atom effect and improve the generation efficiency of reactive oxygen species (ROS). Since orthogonal molecular orbitals of donor-acceptor (D-A) pairs favor the SOCT-ISC transition, herein aza-borondipyrromethenes (aza-BODIPYs) with 1,7-di-anthracyl groups (An-azaBDP) was successfully prepared, owing to steric hindrance to produce a big dihedral angle between the two molecular orbital (MO) planes. Moreover, according to density functional theory (DFT) and time-dependent density functional theory (TDDFT), the energy difference between the S1-T1 orbitals of An-azaBDP is small and more inclined towards ISC. An-azaBDP can effectively generate singlet oxygen under light irradiation. An-azaBDP with light irradiation can induce apoptosis in SW620 cells, and can serve as a potential candidate for the treatment of cancer cells and tumors.
2024, 35(10): 109448
doi: 10.1016/j.cclet.2023.109448
摘要:
Solid polymer electrolytes (SPEs) are considered to be one of the most promising systems applied in all-solid-state lithium metal batteries (ASSLMBs) on account of their chemical and electrochemical robustness, mechanical stability, cost-effective and scalable manufacturing techniques. Lately, significant endeavors have been directed towards mitigating the formation of the Li dendrite in SPE-based ASSLMBs, while research on the inactive lithium in the forms of the solid-electrolyte interface has been rarely reported. Herein, a bi-functional GaI3 additive is developed for in-situ generating Li3Ga alloy for suppressing Li dendrite growth, as well as I3− in recovering dead lithium. Relying on the density functional theory (DFT) results, the Li atom prefers to deposit on the Li3Ga surface and then guide uniform Li deposition, while the I3 species features a relatively lower lowest unoccupied molecular orbital (LUMO) energy level (-2.12 eV), meaning a higher electron affinity, which is beneficial for reviving inactive lithium to counterbalance the loss of lithium. As a result, in comparison to cells employing pure PEGDME-based electrolytes, the Li-Li symmetric cells utilizing GaI3-containing solid-state electrolyte exhibited a cycling life nearly 30 times longer at a current density/capacity of 0.2 mA/cm2, 0.2 mAh/cm2. The full batteries of LFP//1%GaI3-SPE//40 µm Li delivered a noteworthy capacity retention of 82% after 1300 cycles at a rate of 1 C.
Solid polymer electrolytes (SPEs) are considered to be one of the most promising systems applied in all-solid-state lithium metal batteries (ASSLMBs) on account of their chemical and electrochemical robustness, mechanical stability, cost-effective and scalable manufacturing techniques. Lately, significant endeavors have been directed towards mitigating the formation of the Li dendrite in SPE-based ASSLMBs, while research on the inactive lithium in the forms of the solid-electrolyte interface has been rarely reported. Herein, a bi-functional GaI3 additive is developed for in-situ generating Li3Ga alloy for suppressing Li dendrite growth, as well as I3− in recovering dead lithium. Relying on the density functional theory (DFT) results, the Li atom prefers to deposit on the Li3Ga surface and then guide uniform Li deposition, while the I3 species features a relatively lower lowest unoccupied molecular orbital (LUMO) energy level (-2.12 eV), meaning a higher electron affinity, which is beneficial for reviving inactive lithium to counterbalance the loss of lithium. As a result, in comparison to cells employing pure PEGDME-based electrolytes, the Li-Li symmetric cells utilizing GaI3-containing solid-state electrolyte exhibited a cycling life nearly 30 times longer at a current density/capacity of 0.2 mA/cm2, 0.2 mAh/cm2. The full batteries of LFP//1%GaI3-SPE//40 µm Li delivered a noteworthy capacity retention of 82% after 1300 cycles at a rate of 1 C.
2024, 35(10): 109450
doi: 10.1016/j.cclet.2023.109450
摘要:
The occurrence of acquired resistance to cisplatin (DDP) that induces the toxic drug effects has always been a huge challenge and urgently needs to be resolved in the cancer treatment. The combination of anticancer drugs with different mechanisms can remarkably improve the chemotherapeutic efficiency. Given that glutathione (GSH) plays as the driving factors in the resistance of DDP, here we have firstly proposed a “three birds, one stone” based nanoplatform to achieve triple synergetic effects simultaneously addressing DDP resistance in non-small cell lung cancer (NSCLC). Specifically, we initially designed and synthesized a DDP prodrug [Pt(Ⅳ)] bridged silsesquioxane precursor (Pt-Si). Then Pt-Si and bis[3-(triethoxysilyl)propyl]diselenide (BTESePD) were integrated into the framework of mesoporous organosilica nanoparticles (MONs) to obtain a nanocarrier MONPt/Se. After loading with norcantharidin (NCTD) and modifying with the aptamer AS1411 based G-quadruplex (Apt), the Apt@NCTD@MONPt/Se exhibit impressive tumor homing capability. Once being endocytosed, (Ⅰ) the diselenide and -O-Pt(Ⅳ)-O- rich scaffold can be reduced by the excessive GSH, followed by (Ⅱ) breaking the redox homeostasis via GSH depletion and precise release of the DDP. Next, the encapsulated NCTD is also released along with the degradation of the nanocarriers thereby (Ⅲ) achieving the GSH depletion and synergistic anti-tumor effect of NCTD and DDP. Taken together, we believe this “one stone, three birds” strategy may be a promising paradigm to conquer drug resistance for clinical care.
The occurrence of acquired resistance to cisplatin (DDP) that induces the toxic drug effects has always been a huge challenge and urgently needs to be resolved in the cancer treatment. The combination of anticancer drugs with different mechanisms can remarkably improve the chemotherapeutic efficiency. Given that glutathione (GSH) plays as the driving factors in the resistance of DDP, here we have firstly proposed a “three birds, one stone” based nanoplatform to achieve triple synergetic effects simultaneously addressing DDP resistance in non-small cell lung cancer (NSCLC). Specifically, we initially designed and synthesized a DDP prodrug [Pt(Ⅳ)] bridged silsesquioxane precursor (Pt-Si). Then Pt-Si and bis[3-(triethoxysilyl)propyl]diselenide (BTESePD) were integrated into the framework of mesoporous organosilica nanoparticles (MONs) to obtain a nanocarrier MONPt/Se. After loading with norcantharidin (NCTD) and modifying with the aptamer AS1411 based G-quadruplex (Apt), the Apt@NCTD@MONPt/Se exhibit impressive tumor homing capability. Once being endocytosed, (Ⅰ) the diselenide and -O-Pt(Ⅳ)-O- rich scaffold can be reduced by the excessive GSH, followed by (Ⅱ) breaking the redox homeostasis via GSH depletion and precise release of the DDP. Next, the encapsulated NCTD is also released along with the degradation of the nanocarriers thereby (Ⅲ) achieving the GSH depletion and synergistic anti-tumor effect of NCTD and DDP. Taken together, we believe this “one stone, three birds” strategy may be a promising paradigm to conquer drug resistance for clinical care.
2024, 35(10): 109451
doi: 10.1016/j.cclet.2023.109451
摘要:
Hidden natural products are representative of defensive strategies produced in vivo in diseased plants, a process that is induced by the plant immune system. The first transcriptome library of uninfected and pathogen infected Hibiscus tiliaceus stems was constructed by transcriptome sequencing technology, genes related to cadinene-type sesquiterpenoid biosynthesis were screened and combined with ultra-performance liquid chromatography-quadrupole-time of flight mass spectrometry (UPLC-QTOF-MS) analysis data, which indicated pathological tissue had potential to produce novel carbon skeletons of cadinane sesquiterpenoid dimers. Successfully, two cadinane-derived sesquiterpenoid dimers with unprecedented carbon skeletons, hibisceusanols A (1) and B (2) were isolated for the first time from the stems of H. tiliaceus induced by plant-microbial interactions. Their structures and absolute configurations were unambiguously established by spectroscopy, advanced chemistry development (ACD) and electronic circular dichroism (ECD) methods. Compounds 1 and 2 exhibited significant antitumor activity in vitro with half maximal inhibitory concentration (IC50) values of 2.3–7.2 µmol/L. The anticancer effect was generated via the induction of HepG2 cell apoptosis by inhibiting the phosphatidylinositol 3-kinase (PI3K) pathway.
Hidden natural products are representative of defensive strategies produced in vivo in diseased plants, a process that is induced by the plant immune system. The first transcriptome library of uninfected and pathogen infected Hibiscus tiliaceus stems was constructed by transcriptome sequencing technology, genes related to cadinene-type sesquiterpenoid biosynthesis were screened and combined with ultra-performance liquid chromatography-quadrupole-time of flight mass spectrometry (UPLC-QTOF-MS) analysis data, which indicated pathological tissue had potential to produce novel carbon skeletons of cadinane sesquiterpenoid dimers. Successfully, two cadinane-derived sesquiterpenoid dimers with unprecedented carbon skeletons, hibisceusanols A (1) and B (2) were isolated for the first time from the stems of H. tiliaceus induced by plant-microbial interactions. Their structures and absolute configurations were unambiguously established by spectroscopy, advanced chemistry development (ACD) and electronic circular dichroism (ECD) methods. Compounds 1 and 2 exhibited significant antitumor activity in vitro with half maximal inhibitory concentration (IC50) values of 2.3–7.2 µmol/L. The anticancer effect was generated via the induction of HepG2 cell apoptosis by inhibiting the phosphatidylinositol 3-kinase (PI3K) pathway.
2024, 35(10): 109452
doi: 10.1016/j.cclet.2023.109452
摘要:
Clinical phototheranostic agents suffer from low absorption in near-infrared (NIR) region, decreasing singlet oxygen quantum yield (1O2 QY) caused by aggregation in water, and low photothermal conversion efficiency (PCE), all of which are factors weakening their phototheranostic efficacy. Herein, we designed and synthesized a donor-acceptor-donor (D-A-D) structured boron-dipyrromethene derivative (B-2TPA) which exhibited NIR absorption and fluorescence. After being encapsulated in amphiphilic distearoyl phosphoethanolamine polyethyleneglycol 2000 (DSPE-PEG-2000), the water-soluble B-2TPA nanoparticles (NPs) had increasing 1O2 QY (6.7%) due to the intermolecular aggregation-induced decrease in the energy gap between singlet and triplet excited states. Moreover, the quenched fluorescence and stable twisted intramolecular charge transfer in aggregates further increased the PCE of B-2TPA NPs to 60.1%. In vitro and in vivo studies confirmed that B-2TPA NPs could be used in NIR fluorescence and photoacoustic imaging-guided synergistic photodynamic and photothermal therapy in tumor treatment.
Clinical phototheranostic agents suffer from low absorption in near-infrared (NIR) region, decreasing singlet oxygen quantum yield (1O2 QY) caused by aggregation in water, and low photothermal conversion efficiency (PCE), all of which are factors weakening their phototheranostic efficacy. Herein, we designed and synthesized a donor-acceptor-donor (D-A-D) structured boron-dipyrromethene derivative (B-2TPA) which exhibited NIR absorption and fluorescence. After being encapsulated in amphiphilic distearoyl phosphoethanolamine polyethyleneglycol 2000 (DSPE-PEG-2000), the water-soluble B-2TPA nanoparticles (NPs) had increasing 1O2 QY (6.7%) due to the intermolecular aggregation-induced decrease in the energy gap between singlet and triplet excited states. Moreover, the quenched fluorescence and stable twisted intramolecular charge transfer in aggregates further increased the PCE of B-2TPA NPs to 60.1%. In vitro and in vivo studies confirmed that B-2TPA NPs could be used in NIR fluorescence and photoacoustic imaging-guided synergistic photodynamic and photothermal therapy in tumor treatment.
2024, 35(10): 109456
doi: 10.1016/j.cclet.2023.109456
摘要:
Three highly oxidized hybrid flavonoids neosophoflavonoids A–C (1, 2a, and 2b) were isolated from the roots of Sophora flavescens. Neosophoflavonoid A possesses a unique highly oxidized heptacyclic 6/6/6/6/6/6/5 system. Neosophoflavonoids B and C are isomers and share the same highly oxidized hexacyclic 6/6/6/6/6/6 systems. Their planar structures were elucidated from 1D/2D nuclear magnetic resonance (NMR), ultraviolet spectroscopy (UV), infrared spectroscopy (IR), and high resolution electrospray ionization mass spectroscopy (HRESIMS) data. Their absolute configurations were determined by thorough GIAO 13C NMR (DP4+) calculation protocol and electronic circular dichroism (ECD) calculation method. The plausible biosynthetic routes for the compounds were also proposed. All compounds exhibited significant protein tyrosine phosphatase-1B (PTP1B) inhibitory activity with half maximal inhibitory concentration (IC50) values 3.94 ± 0.01, 0.38 ± 0.13, and 0.70 ± 0.01 µmol/L, respectively. In addition, compared to a positive control fenofibrate (Feno) at 20 µmol/L, compounds 2a and 2b exhibited stronger inhibitory effects on lipid accumulation in the oleic acid (OA)-induced cell model at 5 and 10 µmol/L.
Three highly oxidized hybrid flavonoids neosophoflavonoids A–C (1, 2a, and 2b) were isolated from the roots of Sophora flavescens. Neosophoflavonoid A possesses a unique highly oxidized heptacyclic 6/6/6/6/6/6/5 system. Neosophoflavonoids B and C are isomers and share the same highly oxidized hexacyclic 6/6/6/6/6/6 systems. Their planar structures were elucidated from 1D/2D nuclear magnetic resonance (NMR), ultraviolet spectroscopy (UV), infrared spectroscopy (IR), and high resolution electrospray ionization mass spectroscopy (HRESIMS) data. Their absolute configurations were determined by thorough GIAO 13C NMR (DP4+) calculation protocol and electronic circular dichroism (ECD) calculation method. The plausible biosynthetic routes for the compounds were also proposed. All compounds exhibited significant protein tyrosine phosphatase-1B (PTP1B) inhibitory activity with half maximal inhibitory concentration (IC50) values 3.94 ± 0.01, 0.38 ± 0.13, and 0.70 ± 0.01 µmol/L, respectively. In addition, compared to a positive control fenofibrate (Feno) at 20 µmol/L, compounds 2a and 2b exhibited stronger inhibitory effects on lipid accumulation in the oleic acid (OA)-induced cell model at 5 and 10 µmol/L.
2024, 35(10): 109458
doi: 10.1016/j.cclet.2023.109458
摘要:
Monosescinol A (1), the first example of sesquiterpene–polycyclic polyprenylated acylphloroglucinol (PPAP) adduct, which represented a new subclass of PPAP-type natural products, along with two new congeners with normal spiro 6/6/5 tricyclic architecture, were isolated from Hypericum longistylum. Monosescinol A possessed an unprecedented 6/5/5/6/6 pentacyclic carbon skeleton that might be assembled from the 6/6/5 carbon skeleton, via the splitting decomposition of C-3/C-14, and the attack from the C-3 in the PPAP core to C-28 in sesquiterpene section. In addition, we have firstly confirmed that 24R configuration was existed in sec–Bu containing PPAPs by single crystal diffraction data analysis of monosescinol B (2), that might provide an enlightenment in the configurational determination of sec–Bu containing PPAPs. Significantly, further pharmacological research has found that compound 1 exhibited remarkable pharmacological effects against acute myeloid leukemia (AML) cell lines, with direct inhibition of mitochondrial complex Ⅴ and an increase in mitochondrial membrane potential, and led to an induction of oxidative stress, endogenous inflammation, and apoptosis of AML cells.
Monosescinol A (1), the first example of sesquiterpene–polycyclic polyprenylated acylphloroglucinol (PPAP) adduct, which represented a new subclass of PPAP-type natural products, along with two new congeners with normal spiro 6/6/5 tricyclic architecture, were isolated from Hypericum longistylum. Monosescinol A possessed an unprecedented 6/5/5/6/6 pentacyclic carbon skeleton that might be assembled from the 6/6/5 carbon skeleton, via the splitting decomposition of C-3/C-14, and the attack from the C-3 in the PPAP core to C-28 in sesquiterpene section. In addition, we have firstly confirmed that 24R configuration was existed in sec–Bu containing PPAPs by single crystal diffraction data analysis of monosescinol B (2), that might provide an enlightenment in the configurational determination of sec–Bu containing PPAPs. Significantly, further pharmacological research has found that compound 1 exhibited remarkable pharmacological effects against acute myeloid leukemia (AML) cell lines, with direct inhibition of mitochondrial complex Ⅴ and an increase in mitochondrial membrane potential, and led to an induction of oxidative stress, endogenous inflammation, and apoptosis of AML cells.
2024, 35(10): 109459
doi: 10.1016/j.cclet.2023.109459
摘要:
Infections frequently occur after skin injuries, posing a significant challenge in current clinical care. Frequently changing dressings to minimize wound infections and adhesions results in large amounts of medical waste. Therefore, developing environmentally friendly multifunctional dressings has considerable application and translational significance. This study aimed to prepare a wound dressing with favorable antimicrobial properties and biosafety by grafting a natural antimicrobial peptide, polylysine, onto a traditional cotton textile dressing. The cotton textile dressing offers excellent moisture absorption and softness, while polylysine provides excellent biocompatibility, a broad antimicrobial spectrum, and high stability. Furthermore, both materials are natural and biodegradable, making them ideal for environmentally friendly wound dressings.
Infections frequently occur after skin injuries, posing a significant challenge in current clinical care. Frequently changing dressings to minimize wound infections and adhesions results in large amounts of medical waste. Therefore, developing environmentally friendly multifunctional dressings has considerable application and translational significance. This study aimed to prepare a wound dressing with favorable antimicrobial properties and biosafety by grafting a natural antimicrobial peptide, polylysine, onto a traditional cotton textile dressing. The cotton textile dressing offers excellent moisture absorption and softness, while polylysine provides excellent biocompatibility, a broad antimicrobial spectrum, and high stability. Furthermore, both materials are natural and biodegradable, making them ideal for environmentally friendly wound dressings.
2024, 35(10): 109464
doi: 10.1016/j.cclet.2023.109464
摘要:
Dual-state emission (DSE) molecules displayed conspicuous fluorescent performance both in solid and solution states. However, the construction of DSE molecules and the regulation of their emission wavelengths remains a great challenge. Based on the structure-function relationship of quinolinonitrile-type fluorophores, this work proposed a feasible strategy for modulating their fluorescent properties into DSE via limiting the torsion angle between the quinoline ring and C=C bond in the range of 4.7° to 30°. Based on this strategy, 53 compounds were obtained which displayed tunable emission wavelengths from 397 nm to 740 nm in solid-state and from 360 nm to 672 nm in solution. The feasibility of the strategy was supported by a series of theoretical calculations, optical characterizations, and crystal analysis, suggesting the compounds have great potential in imaging living cells and tissues with desired wavelengths.
Dual-state emission (DSE) molecules displayed conspicuous fluorescent performance both in solid and solution states. However, the construction of DSE molecules and the regulation of their emission wavelengths remains a great challenge. Based on the structure-function relationship of quinolinonitrile-type fluorophores, this work proposed a feasible strategy for modulating their fluorescent properties into DSE via limiting the torsion angle between the quinoline ring and C=C bond in the range of 4.7° to 30°. Based on this strategy, 53 compounds were obtained which displayed tunable emission wavelengths from 397 nm to 740 nm in solid-state and from 360 nm to 672 nm in solution. The feasibility of the strategy was supported by a series of theoretical calculations, optical characterizations, and crystal analysis, suggesting the compounds have great potential in imaging living cells and tissues with desired wavelengths.
2024, 35(10): 109489
doi: 10.1016/j.cclet.2024.109489
摘要:
Constructing a smart polymer film with favorable lithium (Li) transport capability and mechanical flexibility for suppressing Li dendrite growth is an effective strategy. Unfortunately, the porosity and the swelling of the polymer membrane cannot completely prevent liquid electrolyte from sweeping through the artificial protection film, severely deteriorating the cyclic performance. Herein, we propose a defect-free hybrid film that consists of Li+ conductive lithium polyacrylate (LiPAA) polymer interface layer and Li-Zn alloy patch to tackle the critical problems of traditional polymer composite passivation film. The pinhole leaks of the polymer matrix are self-filled by Li-Zn alloy patches, enhancing the integrity of LiPAA film. Consequently, a defect-free hybrid film is nailed flat against the Li metal anode, exhibiting extraordinary stability in the liquid electrolyte and enabling perfect protection effect. This facile strategy produces a promising anode for next generation Li batteries.
Constructing a smart polymer film with favorable lithium (Li) transport capability and mechanical flexibility for suppressing Li dendrite growth is an effective strategy. Unfortunately, the porosity and the swelling of the polymer membrane cannot completely prevent liquid electrolyte from sweeping through the artificial protection film, severely deteriorating the cyclic performance. Herein, we propose a defect-free hybrid film that consists of Li+ conductive lithium polyacrylate (LiPAA) polymer interface layer and Li-Zn alloy patch to tackle the critical problems of traditional polymer composite passivation film. The pinhole leaks of the polymer matrix are self-filled by Li-Zn alloy patches, enhancing the integrity of LiPAA film. Consequently, a defect-free hybrid film is nailed flat against the Li metal anode, exhibiting extraordinary stability in the liquid electrolyte and enabling perfect protection effect. This facile strategy produces a promising anode for next generation Li batteries.
2024, 35(10): 109491
doi: 10.1016/j.cclet.2024.109491
摘要:
Foods are often contaminated by multiple foodborne pathogens, which threatens human health. In this work, we developed a microfluidic biosensor for multiplex immunoassay of foodborne bacteria with agitation driven by programmed audio signals. This agitation, powered by the vibration of a speaker cone during music playing, accelerated the mass transport in the incubation process to form bacterial complexes within 10 min. Immunoassay reagents of the two target bacteria (Escherichia coli O157:H7 and Salmonella typhimurium) were preloaded into the corresponding fore-vacuum storage chamber on the chip, and released to participate in the subsequent immune analysis process by piercing the chambers. All the detection processes were integrated into a single microfluidic chip and controlled by a smartphone through Bluetooth. Under selected conditions, wide linear ranges and low limits of detection (LODs < 2 CFU/mL) were obtained, and real food samples were successfully determined within 30 min. This biosensing method can be extended to wide-ranging applications by loading different recognizing reagents.
Foods are often contaminated by multiple foodborne pathogens, which threatens human health. In this work, we developed a microfluidic biosensor for multiplex immunoassay of foodborne bacteria with agitation driven by programmed audio signals. This agitation, powered by the vibration of a speaker cone during music playing, accelerated the mass transport in the incubation process to form bacterial complexes within 10 min. Immunoassay reagents of the two target bacteria (Escherichia coli O157:H7 and Salmonella typhimurium) were preloaded into the corresponding fore-vacuum storage chamber on the chip, and released to participate in the subsequent immune analysis process by piercing the chambers. All the detection processes were integrated into a single microfluidic chip and controlled by a smartphone through Bluetooth. Under selected conditions, wide linear ranges and low limits of detection (LODs < 2 CFU/mL) were obtained, and real food samples were successfully determined within 30 min. This biosensing method can be extended to wide-ranging applications by loading different recognizing reagents.
2024, 35(10): 109497
doi: 10.1016/j.cclet.2024.109497
摘要:
Histone H3K79 modifications are essential to regulate chromatin structure and gene transcription, but understanding of the molecular mechanisms is limited. Because H3K79 is at globular domain, short histone peptide cannot mimic H3K79 in chromatin. Instead, reconstituted nucleosome-based chemical tools are ideally used to investigate H3K79 modifications. In consequence, H3K79-modified histone H3 with additional chemical handles are required, but such synthesis is challenging and laborious. Here we report a facile semisynthesis method that enables multifunctional histone H3 readily available. H3K79-containing fragment is short for straight peptide synthesis that was later ligated to recombinant expressed H3 fragments for full-length product in large scale. As a result, nucleosomes with H3K79 modifications as well as photo-reactive group and affinity tag were obtained to investigate potential binding proteins. We believe this method that enhances synthetic accessibility of nucleosome probes will accelerate understanding of the underexplored H3K79 modifications.
Histone H3K79 modifications are essential to regulate chromatin structure and gene transcription, but understanding of the molecular mechanisms is limited. Because H3K79 is at globular domain, short histone peptide cannot mimic H3K79 in chromatin. Instead, reconstituted nucleosome-based chemical tools are ideally used to investigate H3K79 modifications. In consequence, H3K79-modified histone H3 with additional chemical handles are required, but such synthesis is challenging and laborious. Here we report a facile semisynthesis method that enables multifunctional histone H3 readily available. H3K79-containing fragment is short for straight peptide synthesis that was later ligated to recombinant expressed H3 fragments for full-length product in large scale. As a result, nucleosomes with H3K79 modifications as well as photo-reactive group and affinity tag were obtained to investigate potential binding proteins. We believe this method that enhances synthetic accessibility of nucleosome probes will accelerate understanding of the underexplored H3K79 modifications.
2024, 35(10): 109499
doi: 10.1016/j.cclet.2024.109499
摘要:
Sodium percarbonate (Na2CO3·1.5H2O2, SPC) has been extensively employed as a solid substitute of H2O2 for Fenton process in water treatment, because of its high stability during the production, transport, storage and usage. In addition, SPC can be applied in a wider range of work pH, it is also applied as a buffer in Fenton reaction for preventing a drop in pH. Herein, we have synthesized basic copper molybdate (BCM) nanoblocks with the molecular formula of Cu3(MoO4)2(OH)2 as an efficient and heterogeneous catalyst for antibiotics degradation via percarbonate activation. First, fully physical characterizations confirmed BCM nanocomposite exhibited a structure of nanoblocks. We also found that BCM/SPC system could work in a much wider pH range, compared with H2O2. Then, BCM/SPC system presented a good anti-interference ability for natural organic matter in OTC degradation. EPR results and Quenching tests confirmed that the co-presence of ·CO3−, ·O2−, 1O2 and ·OH in BCM/SPC system.
Sodium percarbonate (Na2CO3·1.5H2O2, SPC) has been extensively employed as a solid substitute of H2O2 for Fenton process in water treatment, because of its high stability during the production, transport, storage and usage. In addition, SPC can be applied in a wider range of work pH, it is also applied as a buffer in Fenton reaction for preventing a drop in pH. Herein, we have synthesized basic copper molybdate (BCM) nanoblocks with the molecular formula of Cu3(MoO4)2(OH)2 as an efficient and heterogeneous catalyst for antibiotics degradation via percarbonate activation. First, fully physical characterizations confirmed BCM nanocomposite exhibited a structure of nanoblocks. We also found that BCM/SPC system could work in a much wider pH range, compared with H2O2. Then, BCM/SPC system presented a good anti-interference ability for natural organic matter in OTC degradation. EPR results and Quenching tests confirmed that the co-presence of ·CO3−, ·O2−, 1O2 and ·OH in BCM/SPC system.
2024, 35(10): 109504
doi: 10.1016/j.cclet.2024.109504
摘要:
Polyketide synthases (PKSs) are megasynthases with multiple autonomously folding domains, which operate cooperatively in the PKS assemblies to synthesize specific polyketide scaffolds. Any nonreactive intermediates tethered to acyl carrier protein (ACP) domain in the PKS will block the elongation process of polyketide chains. In this study, we systematically elucidate the editing function of fungal type Ⅱ thioesterases (TEIIs) to hydrolyze ACP domain-bounded nonreactive acyl groups, which are uploaded by substrate promiscuous fungal phosphopantetheinyl transferase. Thereof, the TEIIs encoded in gene clusters of nonreducing PKS with reductase domain exhibit universal editing function. Besides, editing function was also found for TEIIs encoded in gene clusters of highly-reducing PKS with condensation domain. Hence, the editing TEIIs with function of recovery PKS are applied to improve the yield of the fungal polyketides in vivo. Our study provides valuable insights into the editing process of fungal PKSs, highlights the crucial role of TEIIs in enhancing polyketide production and introduces a novel metabolic engineering strategy for fungal polyketide biosynthesis by leveraging the editing function of TEIIs.
Polyketide synthases (PKSs) are megasynthases with multiple autonomously folding domains, which operate cooperatively in the PKS assemblies to synthesize specific polyketide scaffolds. Any nonreactive intermediates tethered to acyl carrier protein (ACP) domain in the PKS will block the elongation process of polyketide chains. In this study, we systematically elucidate the editing function of fungal type Ⅱ thioesterases (TEIIs) to hydrolyze ACP domain-bounded nonreactive acyl groups, which are uploaded by substrate promiscuous fungal phosphopantetheinyl transferase. Thereof, the TEIIs encoded in gene clusters of nonreducing PKS with reductase domain exhibit universal editing function. Besides, editing function was also found for TEIIs encoded in gene clusters of highly-reducing PKS with condensation domain. Hence, the editing TEIIs with function of recovery PKS are applied to improve the yield of the fungal polyketides in vivo. Our study provides valuable insights into the editing process of fungal PKSs, highlights the crucial role of TEIIs in enhancing polyketide production and introduces a novel metabolic engineering strategy for fungal polyketide biosynthesis by leveraging the editing function of TEIIs.
2024, 35(10): 109506
doi: 10.1016/j.cclet.2024.109506
摘要:
The development of resistance against most of the available antibiotics has made Acinetobacter baumannii (A. baumannii) a pathogen of high risk. In this study, thirty novel berberine derivatives are rationally designed, synthesized, and evaluated for their synergistic antibacterial activities against A. baumannii. Among them, compound 2d shows the most potent synergetic effect to aztreonam against A. baumannii, including carbapenem-resistant and extended-spectrum β-lactamases-producing strains. Moreover, synergistic effects were observed for the combinations of 2d and different antibacterial used in clinical practices, indicating its potent broad-spectrum antibiotic-sensitizing effects against A. baumannii. The combination of 2d and aztreonam significantly improves the survival rates of G. mellonella larvae compared with aztreonam treatment alone. Mechanism studies indicate that 2d inhibits the drug efflux and iron acquisition of the bacteria by targeting the AdeB transporter protein, thus achieving a synergistic antimicrobial efficacy with different antibacterial agents. Therefore, berberine derivatives represent a new family of antimicrobial adjuvants against A. baumannii, with the advantage of dual-function antibacterial effect, and are worthy of further investigation.
The development of resistance against most of the available antibiotics has made Acinetobacter baumannii (A. baumannii) a pathogen of high risk. In this study, thirty novel berberine derivatives are rationally designed, synthesized, and evaluated for their synergistic antibacterial activities against A. baumannii. Among them, compound 2d shows the most potent synergetic effect to aztreonam against A. baumannii, including carbapenem-resistant and extended-spectrum β-lactamases-producing strains. Moreover, synergistic effects were observed for the combinations of 2d and different antibacterial used in clinical practices, indicating its potent broad-spectrum antibiotic-sensitizing effects against A. baumannii. The combination of 2d and aztreonam significantly improves the survival rates of G. mellonella larvae compared with aztreonam treatment alone. Mechanism studies indicate that 2d inhibits the drug efflux and iron acquisition of the bacteria by targeting the AdeB transporter protein, thus achieving a synergistic antimicrobial efficacy with different antibacterial agents. Therefore, berberine derivatives represent a new family of antimicrobial adjuvants against A. baumannii, with the advantage of dual-function antibacterial effect, and are worthy of further investigation.
2024, 35(10): 109512
doi: 10.1016/j.cclet.2024.109512
摘要:
As a promising imaging technology, the low sensitivity of fluorine-19 magnetic resonance imaging (19F MRI) severely hinders its biomedical applications. Herein, we have developed an unprecedented rotaxane-based strategy to improve the sensitivity of 19F MRI agents. By threading the fluorinated macrocycle into 2-blade pinwheel [2]rotaxanes, the 19F longitudinal relaxation rate R1 was dramatically increased, resulting in a significant 19F MRI signal intensity enhancement of up to 79%. Through comparative molecular dynamics studies using a series of solution and solid-state 1H/19F nuclear magnetic resonance (1H/19F NMR) and molecular dynamics simulations, it was found that the formation of mechanical bonds dramatically restricts the motion of the wheel fluorines and thus increasing the R1 for higher 19F MRI sensitivity. Besides a novel strategy for improving 19F MRI sensitivity, this study has established 19F NMR/MRI as a valuable technology for monitoring the molecular dynamics of rotaxanes, which may shed new light on high-performance 19F MRI agents and molecular devices.
As a promising imaging technology, the low sensitivity of fluorine-19 magnetic resonance imaging (19F MRI) severely hinders its biomedical applications. Herein, we have developed an unprecedented rotaxane-based strategy to improve the sensitivity of 19F MRI agents. By threading the fluorinated macrocycle into 2-blade pinwheel [2]rotaxanes, the 19F longitudinal relaxation rate R1 was dramatically increased, resulting in a significant 19F MRI signal intensity enhancement of up to 79%. Through comparative molecular dynamics studies using a series of solution and solid-state 1H/19F nuclear magnetic resonance (1H/19F NMR) and molecular dynamics simulations, it was found that the formation of mechanical bonds dramatically restricts the motion of the wheel fluorines and thus increasing the R1 for higher 19F MRI sensitivity. Besides a novel strategy for improving 19F MRI sensitivity, this study has established 19F NMR/MRI as a valuable technology for monitoring the molecular dynamics of rotaxanes, which may shed new light on high-performance 19F MRI agents and molecular devices.
2024, 35(10): 109519
doi: 10.1016/j.cclet.2024.109519
摘要:
Hepatocellular carcinoma is a common and fatal malignancy for which there is no effective systemic therapeutic strategy. Dihydroartemisinin (DHA), a derivative of artemisinin, has been shown to exert anti-tumor effects through the production of reactive oxygen species (ROS) and resultant mitochondrial damage. However, clinical translation is limited by several drawbacks, such as insolubility, instability and low bioavailability. Here, based on a nanomedicine-based delivery strategy, we fabricated mitochondria-targeted carrier-free nanoparticles coupling DHA and triphenylphosphonium (TPP), aiming to improve bioavailability and mitochondrial targeting. DHA-TPP nanoparticles can be passively delivered to the tumor site by enhanced penetration and retention and then internalized. Flow cytometry and Western blot analysis showed that DHA-TPP nanoparticles increased intracellular ROS, which increased mitochondrial stress and in turn upregulated the downstream Bcl-2 pathway, leading to apoptosis. In vivo experiments showed that DHA-TPP nanoparticles exhibited anti-tumor effects in a mouse model of hepatocellular carcinoma. These findings suggest carrier-free DHA-TPP nanoparticles as a potential therapeutic strategy for hepatocellular carcinoma.
Hepatocellular carcinoma is a common and fatal malignancy for which there is no effective systemic therapeutic strategy. Dihydroartemisinin (DHA), a derivative of artemisinin, has been shown to exert anti-tumor effects through the production of reactive oxygen species (ROS) and resultant mitochondrial damage. However, clinical translation is limited by several drawbacks, such as insolubility, instability and low bioavailability. Here, based on a nanomedicine-based delivery strategy, we fabricated mitochondria-targeted carrier-free nanoparticles coupling DHA and triphenylphosphonium (TPP), aiming to improve bioavailability and mitochondrial targeting. DHA-TPP nanoparticles can be passively delivered to the tumor site by enhanced penetration and retention and then internalized. Flow cytometry and Western blot analysis showed that DHA-TPP nanoparticles increased intracellular ROS, which increased mitochondrial stress and in turn upregulated the downstream Bcl-2 pathway, leading to apoptosis. In vivo experiments showed that DHA-TPP nanoparticles exhibited anti-tumor effects in a mouse model of hepatocellular carcinoma. These findings suggest carrier-free DHA-TPP nanoparticles as a potential therapeutic strategy for hepatocellular carcinoma.
2024, 35(10): 109521
doi: 10.1016/j.cclet.2024.109521
摘要:
Photodynamic therapy (PDT) has garnered significant attention as a promising approach to cancer therapy, harnessing the combined benefits of localized light treatment and the accompanying host immune response. In this study, we engineered an immuno-enhanced PDT nanoplatform, denoted as HM@p-MOF (hybrid membrane@porphyrin-metal organic framework). The core porphyrin-MOF was cloaked with a hybrid membrane derived from B16F10 cancer cells and NK cells, resulting in enhanced stability. In both in vitro and in vivo experiments, our finding demonstrated that the hybrid membrane conferred dual targeting capabilities to the nanoplatform, leveraging the unique properties of the B16F10 membrane and NK membrane to augment immunogenic cell death (ICD) induced by photodynamic effects. Additionally, in conjunction with the immunomodulatory functions of the NK cell membrane, we observed an expansion of in situ immune infiltration leading to a systemic immune response. The HM@p-MOF nanoplatform exhibited the capacity to not only inhibit the growth of mouse melanoma but also suppress metastasis. This innovative HM@p-MOF nanoplatform present a viable strategy to enhance phototherapeutic efficacy for both localized and metastatic tumors. It provides a direction for the fabrication of biomimetic nanomedicines possessing immuno-modulatory function.
Photodynamic therapy (PDT) has garnered significant attention as a promising approach to cancer therapy, harnessing the combined benefits of localized light treatment and the accompanying host immune response. In this study, we engineered an immuno-enhanced PDT nanoplatform, denoted as HM@p-MOF (hybrid membrane@porphyrin-metal organic framework). The core porphyrin-MOF was cloaked with a hybrid membrane derived from B16F10 cancer cells and NK cells, resulting in enhanced stability. In both in vitro and in vivo experiments, our finding demonstrated that the hybrid membrane conferred dual targeting capabilities to the nanoplatform, leveraging the unique properties of the B16F10 membrane and NK membrane to augment immunogenic cell death (ICD) induced by photodynamic effects. Additionally, in conjunction with the immunomodulatory functions of the NK cell membrane, we observed an expansion of in situ immune infiltration leading to a systemic immune response. The HM@p-MOF nanoplatform exhibited the capacity to not only inhibit the growth of mouse melanoma but also suppress metastasis. This innovative HM@p-MOF nanoplatform present a viable strategy to enhance phototherapeutic efficacy for both localized and metastatic tumors. It provides a direction for the fabrication of biomimetic nanomedicines possessing immuno-modulatory function.
2024, 35(10): 109523
doi: 10.1016/j.cclet.2024.109523
摘要:
Long-term fluorescence monitoring of subcellular organelles is crucial for cellular physiology and pathology studies. Lipid droplets (LDs) are increasingly recognized for their involvement in various biological processes, to influence disease development through diverse behaviors However, existing LD probes face challenges in achieving high targeting and long-term monitoring due to poor photostability and long-term phototoxicity. Carbon quantum dots (CQDs) have gained prominence due to their exceptional fluorescence properties, but their prevalent blue excitation wavelength presents difficulties for long-term imaging. Herein, we synthesized red-emissive carbon quantum dot (R-CQDs) with superior photobleaching resistance and red-emission, thus enabling harmlessly fluorescence monitoring of cells longer than 3 h. In addition, R-CQD exhibits suitable amphiphilicity and remarkable solvatochromic effect, allowing rapid targeting to LDs for immediate imaging without cumbersome washing steps. Hence, R-CQD shows high performance for extended observation of dynamic LD behavior in various biological processes, which is confirmed by documenting the course of LDs during starvation as well as lipotoxicity. Compared to commercial probes, R-CQD extends live cell imaging time by at least 9-fold, facilitating the study of LD behavioral characteristics under diverse physiological or pathological conditions. This work provides a reliable fluorescence tool for tracking intercellular microenvironment dynamically thus to understand the divers biological or disease mechanism.
Long-term fluorescence monitoring of subcellular organelles is crucial for cellular physiology and pathology studies. Lipid droplets (LDs) are increasingly recognized for their involvement in various biological processes, to influence disease development through diverse behaviors However, existing LD probes face challenges in achieving high targeting and long-term monitoring due to poor photostability and long-term phototoxicity. Carbon quantum dots (CQDs) have gained prominence due to their exceptional fluorescence properties, but their prevalent blue excitation wavelength presents difficulties for long-term imaging. Herein, we synthesized red-emissive carbon quantum dot (R-CQDs) with superior photobleaching resistance and red-emission, thus enabling harmlessly fluorescence monitoring of cells longer than 3 h. In addition, R-CQD exhibits suitable amphiphilicity and remarkable solvatochromic effect, allowing rapid targeting to LDs for immediate imaging without cumbersome washing steps. Hence, R-CQD shows high performance for extended observation of dynamic LD behavior in various biological processes, which is confirmed by documenting the course of LDs during starvation as well as lipotoxicity. Compared to commercial probes, R-CQD extends live cell imaging time by at least 9-fold, facilitating the study of LD behavioral characteristics under diverse physiological or pathological conditions. This work provides a reliable fluorescence tool for tracking intercellular microenvironment dynamically thus to understand the divers biological or disease mechanism.
2024, 35(10): 109524
doi: 10.1016/j.cclet.2024.109524
摘要:
Deep oxidation of NO molecules to nitrate species by photocatalysis with virtually no toxic byproduct NO2 generation is a challenging task. In this study, TiO2 in-situ grows based on NH2−MIL-125(Ti) (NM-125) not only inhibited TiO2 agglomeration, but also contacted more tightly to obtain efficient interfacial effects, thus displaying excellent photocatalytic NO removal activity (68.08%). The formation of TiO2 is directly confirmed by characterizations such as X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS). Meanwhile, UV–vis, photoluminescence, and photoelectrochemical analysis indicate that TiO2 formation effectively improves the optical properties. Moreover, the strong electron interaction and electron transport direction between NM-125 and TiO2 are investigated by density functional theoretical (DFT) calculation. Finally, combined with the results of electron spin resonance (ESR) and in-situ FT-IR test, the intermediate processes of NO adsorption and photocatalytic oxidation reaction are discussed in depth, where the production of reactive oxygen species (ROS) under light is the key factor in the successful degradation of NO. Compared with NM-125 which can only produce •OH through photogenerated electrons since the lower valence band position, NMT-2 can directly produce •OH through photogenerated holes, thereby relieving the pressure on photogenerated electrons and producing more ROS. This study will provide reasonable guidance for the modification of NM-125 for photocatalytic removal of ppb-level NO.
Deep oxidation of NO molecules to nitrate species by photocatalysis with virtually no toxic byproduct NO2 generation is a challenging task. In this study, TiO2 in-situ grows based on NH2−MIL-125(Ti) (NM-125) not only inhibited TiO2 agglomeration, but also contacted more tightly to obtain efficient interfacial effects, thus displaying excellent photocatalytic NO removal activity (68.08%). The formation of TiO2 is directly confirmed by characterizations such as X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS). Meanwhile, UV–vis, photoluminescence, and photoelectrochemical analysis indicate that TiO2 formation effectively improves the optical properties. Moreover, the strong electron interaction and electron transport direction between NM-125 and TiO2 are investigated by density functional theoretical (DFT) calculation. Finally, combined with the results of electron spin resonance (ESR) and in-situ FT-IR test, the intermediate processes of NO adsorption and photocatalytic oxidation reaction are discussed in depth, where the production of reactive oxygen species (ROS) under light is the key factor in the successful degradation of NO. Compared with NM-125 which can only produce •OH through photogenerated electrons since the lower valence band position, NMT-2 can directly produce •OH through photogenerated holes, thereby relieving the pressure on photogenerated electrons and producing more ROS. This study will provide reasonable guidance for the modification of NM-125 for photocatalytic removal of ppb-level NO.
2024, 35(10): 109526
doi: 10.1016/j.cclet.2024.109526
摘要:
Solar-driven H2O2 production and emerging organic pollutants (EOPs) elimination are of great significance from the perspective of environmental sustainability. The efficiency of the photocatalytic reaction system is the key challenge to be addressed. In this work, the strategy of constructing surface ionic local polarization centers to enhance the exciton dissociation of the polymeric photocatalytic is demonstrated. Selected bipyridinium cation (TMAP) is complexed on a K+-incorporated carbon nitride (CNK) framework, and the combination of local polarization centers both on the surface (bipyridinium cation) and bulk (K+ cation) contributes to a superior photocatalytic H2O2 production performance, affording a remarkable H2O2 generation rate of 46.8 µmol h−1 mg−1 and a high apparent quantum yield (AQY) value of 77.5% under irradiation of 405 nm photons. As substantiated experimentally by steady state/transient spectroscopy techniques, the surface local polarization centers increase the population of the long-lived trapped electrons, and thereby promote the interfacial charge transfer process for chemical conversion reaction. The strategy is potentially applicable to the design of a wide range of efficient solar-to-chemical conversion systems.
Solar-driven H2O2 production and emerging organic pollutants (EOPs) elimination are of great significance from the perspective of environmental sustainability. The efficiency of the photocatalytic reaction system is the key challenge to be addressed. In this work, the strategy of constructing surface ionic local polarization centers to enhance the exciton dissociation of the polymeric photocatalytic is demonstrated. Selected bipyridinium cation (TMAP) is complexed on a K+-incorporated carbon nitride (CNK) framework, and the combination of local polarization centers both on the surface (bipyridinium cation) and bulk (K+ cation) contributes to a superior photocatalytic H2O2 production performance, affording a remarkable H2O2 generation rate of 46.8 µmol h−1 mg−1 and a high apparent quantum yield (AQY) value of 77.5% under irradiation of 405 nm photons. As substantiated experimentally by steady state/transient spectroscopy techniques, the surface local polarization centers increase the population of the long-lived trapped electrons, and thereby promote the interfacial charge transfer process for chemical conversion reaction. The strategy is potentially applicable to the design of a wide range of efficient solar-to-chemical conversion systems.
2024, 35(10): 109533
doi: 10.1016/j.cclet.2024.109533
摘要:
Rhodium-catalyzed C4aryl−H activation and ring-retentive annulation of 2H-imidazoles with internal alkynes to build imidazo[5,1-a]isoquinolinium salts with high yields and broad scope has been disclosed. These novel salts serve as new full-color emissive fluorophores (433−633 nm), just by simply modifying the substituents on C3 and C4 positions of isoquinoline ring. Furthermore, these salts can undergo ring-opening C5aryl−H activation/annulation with a different alkyne to form non-symmetric and AIE-active 1,1′-biisoquinolines, where NH4OAc plays an indispensable role that accounts for Hofmann elimination and imine formation, leading to an unprecedented imine dance: cyclic imine → N-alkenyl imine → NH imine. The 15N labelling experiments indicate that the 2nd annulation includes two pathways: N-exchange (major) and N-retention (minor).
Rhodium-catalyzed C4aryl−H activation and ring-retentive annulation of 2H-imidazoles with internal alkynes to build imidazo[5,1-a]isoquinolinium salts with high yields and broad scope has been disclosed. These novel salts serve as new full-color emissive fluorophores (433−633 nm), just by simply modifying the substituents on C3 and C4 positions of isoquinoline ring. Furthermore, these salts can undergo ring-opening C5aryl−H activation/annulation with a different alkyne to form non-symmetric and AIE-active 1,1′-biisoquinolines, where NH4OAc plays an indispensable role that accounts for Hofmann elimination and imine formation, leading to an unprecedented imine dance: cyclic imine → N-alkenyl imine → NH imine. The 15N labelling experiments indicate that the 2nd annulation includes two pathways: N-exchange (major) and N-retention (minor).
2024, 35(10): 109538
doi: 10.1016/j.cclet.2024.109538
摘要:
Chemotherapy has been recommended as the standard protocol for triple-negative breast cancer (TNBC) at the advanced stage. However, the current treatment is unsatisfactory due to inefficient drug accumulation and rapid chemo-resistance. Thus, rational design of advanced drug delivery systems that can induce multiple cell death pathways is a promising strategy to combat TNBC. Ferroptosis is a powerful non-apoptotic cell death modality, showing potential in tumor inhibition. Herein, we propose a binary prodrug nanoassemblies that combines chemotherapy with ferroptosis for TNBC treatment. In this system, paclitaxel is linked with paracetamol (ferroptosis activator) by a disulfide linkage to construct self-assembly prodrug. Meanwhile, 2-distearoyl-sn-glycerol-3-phosphoethanolamine-N-methyl(polyethylene glycol)-2000-tyrosine (DSPE-PEG2k-tyrosine) is applied for large neutral amino acid transporter 1 (LAT1) targeting, which is highly expressed in TNBC. The prodrug nanoassemblies exhibit good stability and a glutathione (GSH)-responsive release profile. Furthermore, the LAT1-targeted nanoassemblies show stronger cytotoxicity, higher cellular uptake, and more obvious ferroptosis activation than non-decorated ones. In a TNBC mice model, the prodrug nanoassemblies demonstrate strong anti-tumor efficacy. The application of ferroptosis-assisting chemotherapy may provide a promising strategy for TNBC therapy.
Chemotherapy has been recommended as the standard protocol for triple-negative breast cancer (TNBC) at the advanced stage. However, the current treatment is unsatisfactory due to inefficient drug accumulation and rapid chemo-resistance. Thus, rational design of advanced drug delivery systems that can induce multiple cell death pathways is a promising strategy to combat TNBC. Ferroptosis is a powerful non-apoptotic cell death modality, showing potential in tumor inhibition. Herein, we propose a binary prodrug nanoassemblies that combines chemotherapy with ferroptosis for TNBC treatment. In this system, paclitaxel is linked with paracetamol (ferroptosis activator) by a disulfide linkage to construct self-assembly prodrug. Meanwhile, 2-distearoyl-sn-glycerol-3-phosphoethanolamine-N-methyl(polyethylene glycol)-2000-tyrosine (DSPE-PEG2k-tyrosine) is applied for large neutral amino acid transporter 1 (LAT1) targeting, which is highly expressed in TNBC. The prodrug nanoassemblies exhibit good stability and a glutathione (GSH)-responsive release profile. Furthermore, the LAT1-targeted nanoassemblies show stronger cytotoxicity, higher cellular uptake, and more obvious ferroptosis activation than non-decorated ones. In a TNBC mice model, the prodrug nanoassemblies demonstrate strong anti-tumor efficacy. The application of ferroptosis-assisting chemotherapy may provide a promising strategy for TNBC therapy.
2024, 35(10): 109539
doi: 10.1016/j.cclet.2024.109539
摘要:
Using hydrogen-bonded organic frameworks (HOFs) as photosensitizers to perform photocatalytic oxidation reactions under green and mild conditions is still a challenge for the application of HOFs materials. This study presents a novel approach that exploits HOFs to enhance the efficiency of photocatalytic oxidation for achieving visible light catalytic oxidation of styrene and its derivatives in the aqueous environment. By using 1,3,6,8-tetrakis(p-benzoic acid)pyrene (H4TBAPy) as the monomer, a pyrene-based hydrogen-bonded organic framework (PFC-1) with a microporous structure was successfully prepared. Compared with monomer H4TBAPy, due to the exciton effect and the interlayer confinement of HOFs, the singlet oxygen (1O2) production efficiency is significantly improved, which has great potential in photocatalytic oxidation reactions. Subsequently, the practicality of PFC-1 as a photocatalyst was studied, and the photocatalytic oxidation of styrene and its derivatives in aqueous solution was achieved under visible light with high catalytic efficiency, indicating that PFC-1 has significant potential to promote photocatalytic oxidation reactions under mild conditions. The utilization of HOFs as photosensitizers in this straightforward approach enables the attainment of green photocatalytic oxidation, hence expanding the potential applications of HOFs materials within the realm of photocatalysis.
Using hydrogen-bonded organic frameworks (HOFs) as photosensitizers to perform photocatalytic oxidation reactions under green and mild conditions is still a challenge for the application of HOFs materials. This study presents a novel approach that exploits HOFs to enhance the efficiency of photocatalytic oxidation for achieving visible light catalytic oxidation of styrene and its derivatives in the aqueous environment. By using 1,3,6,8-tetrakis(p-benzoic acid)pyrene (H4TBAPy) as the monomer, a pyrene-based hydrogen-bonded organic framework (PFC-1) with a microporous structure was successfully prepared. Compared with monomer H4TBAPy, due to the exciton effect and the interlayer confinement of HOFs, the singlet oxygen (1O2) production efficiency is significantly improved, which has great potential in photocatalytic oxidation reactions. Subsequently, the practicality of PFC-1 as a photocatalyst was studied, and the photocatalytic oxidation of styrene and its derivatives in aqueous solution was achieved under visible light with high catalytic efficiency, indicating that PFC-1 has significant potential to promote photocatalytic oxidation reactions under mild conditions. The utilization of HOFs as photosensitizers in this straightforward approach enables the attainment of green photocatalytic oxidation, hence expanding the potential applications of HOFs materials within the realm of photocatalysis.
2024, 35(10): 109540
doi: 10.1016/j.cclet.2024.109540
摘要:
Oligo[n]rotaxanes are one of the most extensively studied categories of mechanically bonded macromolecules. In this study, a supramolecular oligo[2]rotaxane is successfully constructed driven by platinum(Ⅱ) metallacycle and pillar[5]arene-based host–guest interactions in an orthogonal way. The supramolecular oligo[2]rotaxane is further applied in fabricating a light harvesting system.
Oligo[n]rotaxanes are one of the most extensively studied categories of mechanically bonded macromolecules. In this study, a supramolecular oligo[2]rotaxane is successfully constructed driven by platinum(Ⅱ) metallacycle and pillar[5]arene-based host–guest interactions in an orthogonal way. The supramolecular oligo[2]rotaxane is further applied in fabricating a light harvesting system.
2024, 35(10): 109544
doi: 10.1016/j.cclet.2024.109544
摘要:
A rhodium-catalyzed desymmetrization reaction for enantioselective methyl C−H arylation is achieved by utilizing an in situ arylating reagent via nucleophilic cyclization of o-aminoaryl alkyne. The reaction results in chiral indoles containing all-carbon quaternary stereocenters under atmospheric conditions, with a wide range of substrates exhibiting good enantioselectivity (44 examples). Mechnism and DFT studies show that the stereocontrol is reasonably achieved through the collaborative control of a large silicon substituted chiral ligand and C−H···π, LP···π interactions between aryl rings of the carboxylate group and the substrate. Control experiments demonstrate that Rh-aryl bond formation via in situ nucleophilic cyclization is more critical for reaction efficiency than via C−H activation of the nucleophilic cyclization byproduct.
A rhodium-catalyzed desymmetrization reaction for enantioselective methyl C−H arylation is achieved by utilizing an in situ arylating reagent via nucleophilic cyclization of o-aminoaryl alkyne. The reaction results in chiral indoles containing all-carbon quaternary stereocenters under atmospheric conditions, with a wide range of substrates exhibiting good enantioselectivity (44 examples). Mechnism and DFT studies show that the stereocontrol is reasonably achieved through the collaborative control of a large silicon substituted chiral ligand and C−H···π, LP···π interactions between aryl rings of the carboxylate group and the substrate. Control experiments demonstrate that Rh-aryl bond formation via in situ nucleophilic cyclization is more critical for reaction efficiency than via C−H activation of the nucleophilic cyclization byproduct.
2024, 35(10): 109548
doi: 10.1016/j.cclet.2024.109548
摘要:
Molecular-based ferroelastics with dielectric switching properties are highly desirable for their applications on microelectronic dielectric switches, sensors, data storage, and so on. However, the current reports mostly focus on organic-inorganic hybrids containing toxic heavy metal atoms, and the relatively low phase transition temperature limits their application. In this paper, low-toxic organic salt ferroelastic enantiomers (R/S)-4-fluoro-1-azabicyclo[3.2.1]octonium chloride [(R/S)-F-321] were designed and synthesized under the introducing chirality strategy. They undergo a 432F422-type ferroelastic phase transition with a high Curie temperature (Tc) of 470 K, simultaneously exhibiting excellent dielectric switching characteristics. In addition to the ordered-disordered movement of cations, the significant displacement of anions is also responsible for such high Tc and large dielectric switching ratios, which is very rare in molecular-based switching materials. This work enriches the development of molecular ferroelastic switching materials and gives inspiration for the exploration of environmentally friendly high Tc organic salt ferroelastics with prominent switching performances.
Molecular-based ferroelastics with dielectric switching properties are highly desirable for their applications on microelectronic dielectric switches, sensors, data storage, and so on. However, the current reports mostly focus on organic-inorganic hybrids containing toxic heavy metal atoms, and the relatively low phase transition temperature limits their application. In this paper, low-toxic organic salt ferroelastic enantiomers (R/S)-4-fluoro-1-azabicyclo[3.2.1]octonium chloride [(R/S)-F-321] were designed and synthesized under the introducing chirality strategy. They undergo a 432F422-type ferroelastic phase transition with a high Curie temperature (Tc) of 470 K, simultaneously exhibiting excellent dielectric switching characteristics. In addition to the ordered-disordered movement of cations, the significant displacement of anions is also responsible for such high Tc and large dielectric switching ratios, which is very rare in molecular-based switching materials. This work enriches the development of molecular ferroelastic switching materials and gives inspiration for the exploration of environmentally friendly high Tc organic salt ferroelastics with prominent switching performances.
2024, 35(10): 109554
doi: 10.1016/j.cclet.2024.109554
摘要:
Triphenylamine (TPA)-containing 2-(2′-hydroxyphenyl)benzoxazoles (2a-2c) have been synthesized via a highly efficient rhodium-catalyzed C–H/C–H cross-coupling reaction. Compound 2a is a novel mechanofluorochromic material with blue-shifted mechanochromic properties. Compounds 2b and 2c presented opposite mechanochromic trends. For 2b, the enol-form emission enhanced, and the keto-form emission blue-shift after grinding. In contrast, 2c exhibited the weak enol-form emission disappeared and the keto-form emission slightly red-shift after grinding treatments. The estrone-containing 2b-based water-dispersed nanoparticles (NPs) exhibit apparent dual-emission and were applied for fluorescence images. In addition, bis(TPA)-containing 2c-based devices exhibit dual-emission with good performance and a singlet exciton yield of 92%, which breaks through the theoretical upper limit of 25% in conventional fluorescent OLEDs. This is one of the highest exciton utilization values recorded for the ESIPT molecules with a dual emission system.
Triphenylamine (TPA)-containing 2-(2′-hydroxyphenyl)benzoxazoles (2a-2c) have been synthesized via a highly efficient rhodium-catalyzed C–H/C–H cross-coupling reaction. Compound 2a is a novel mechanofluorochromic material with blue-shifted mechanochromic properties. Compounds 2b and 2c presented opposite mechanochromic trends. For 2b, the enol-form emission enhanced, and the keto-form emission blue-shift after grinding. In contrast, 2c exhibited the weak enol-form emission disappeared and the keto-form emission slightly red-shift after grinding treatments. The estrone-containing 2b-based water-dispersed nanoparticles (NPs) exhibit apparent dual-emission and were applied for fluorescence images. In addition, bis(TPA)-containing 2c-based devices exhibit dual-emission with good performance and a singlet exciton yield of 92%, which breaks through the theoretical upper limit of 25% in conventional fluorescent OLEDs. This is one of the highest exciton utilization values recorded for the ESIPT molecules with a dual emission system.
2024, 35(10): 109560
doi: 10.1016/j.cclet.2024.109560
摘要:
Reliable and selective sensing of dopamine (DA) is essential for early diagnosis of mental diseases. Among the various potential methods, nanozyme-based sensing systems have demonstrated promising sensitivity and reliability. However, owing to the lack of substrate specificity, it is challenging to selectively detect DA using nanozymes. Herein, based on the reactivity of the DA oxidation intermediates, we report a cascade colorimetric sensing system for the selective detection of DA using only a single nanozyme. It was disclosed that the oxidation product of DA catalyzed by Co-N-doped carbon sheets (Co-N-C, a common oxidase-like nanozyme), dopamine quinone (DAQ), showed significant biocatalytic electron-donating activity in the reduction of O2 to generate O2•−. Further using O2•− to oxidize 3,3′,5,5′-tetramethylbenzidine (TMB), a colorimetric sensing platform for DA was constructed with a linear detection range of 50 nmol/L to 50 µmol/L and a low limit of detection of 4 nmol/L. Thanks to the reactivity of the oxidation product, without any biometric units (such as nucleic acids, enzymes, and antibodies/antigens), the reaction selectivity of DA against other interferences (e.g., ascorbic acid, adrenaline, 5-hydroxytryptamine, and glutathione) was enhanced up to 71-fold. Beyond complicated cascade systems requiring at least two nanozymes, sophisticated artificial recognition via multiple interactions was simplified by exploiting the oxidative properties of product intermediates; thus, only a single common oxidase-like nanozyme was needed. This work offers a new strategy to enhance the selectivity of nanozymes for bioanalytical applications.
Reliable and selective sensing of dopamine (DA) is essential for early diagnosis of mental diseases. Among the various potential methods, nanozyme-based sensing systems have demonstrated promising sensitivity and reliability. However, owing to the lack of substrate specificity, it is challenging to selectively detect DA using nanozymes. Herein, based on the reactivity of the DA oxidation intermediates, we report a cascade colorimetric sensing system for the selective detection of DA using only a single nanozyme. It was disclosed that the oxidation product of DA catalyzed by Co-N-doped carbon sheets (Co-N-C, a common oxidase-like nanozyme), dopamine quinone (DAQ), showed significant biocatalytic electron-donating activity in the reduction of O2 to generate O2•−. Further using O2•− to oxidize 3,3′,5,5′-tetramethylbenzidine (TMB), a colorimetric sensing platform for DA was constructed with a linear detection range of 50 nmol/L to 50 µmol/L and a low limit of detection of 4 nmol/L. Thanks to the reactivity of the oxidation product, without any biometric units (such as nucleic acids, enzymes, and antibodies/antigens), the reaction selectivity of DA against other interferences (e.g., ascorbic acid, adrenaline, 5-hydroxytryptamine, and glutathione) was enhanced up to 71-fold. Beyond complicated cascade systems requiring at least two nanozymes, sophisticated artificial recognition via multiple interactions was simplified by exploiting the oxidative properties of product intermediates; thus, only a single common oxidase-like nanozyme was needed. This work offers a new strategy to enhance the selectivity of nanozymes for bioanalytical applications.
2024, 35(10): 109565
doi: 10.1016/j.cclet.2024.109565
摘要:
An oxidative annulation of 2-arylidene-1,3-indanediones with Meldrum's acid has been developed for the divergent syntheses of spirolactones with a spirocenter located at the γ-position with respect to the carbonyl group. This heteroannulation protocol tolerates various functional groups and delivers moderate-to-good product yields. Interestingly, the reaction outcomes are exclusively controlled by the reaction oxidant/medium. This annulation strategy can also be executed in the flow system with decent product yields. Control experiments revealed that the reaction proceeds via a radical tandem annulation pathway.
An oxidative annulation of 2-arylidene-1,3-indanediones with Meldrum's acid has been developed for the divergent syntheses of spirolactones with a spirocenter located at the γ-position with respect to the carbonyl group. This heteroannulation protocol tolerates various functional groups and delivers moderate-to-good product yields. Interestingly, the reaction outcomes are exclusively controlled by the reaction oxidant/medium. This annulation strategy can also be executed in the flow system with decent product yields. Control experiments revealed that the reaction proceeds via a radical tandem annulation pathway.
2024, 35(10): 109567
doi: 10.1016/j.cclet.2024.109567
摘要:
Silicon-based anodes including Si, SiOx and SiO2 could deliver ultra-large capacities, but degrade fast owing to huge volume change and low conductivity. Generally, large amounts of elastic binder and conductive additives were composited with nanosized silicon-based materials to yield reasonable cycling stability, which nevertheless not only decrease specific capacity but also induce inhomogeneous lithiation/delithiation as well as uneven stress variations. Artificial nanolattice has exhibited superior mechanical properties which could be ideal structure for silicon-based anodes, but yet faces challenges in integration of chemical reactivity, conductivity and mechanical stability. Herein, we fabricate artificial SiO2 honeycomb nanolattice consisting of numerous nanoscale SiO2 cells interconnected by through-holes, and conformal coating of highly graphitic carbon on the nanolattice is achieved through in situ catalytic graphitization. Moreover, the nanolattice is firmly bonded on Cu substrate through atomic interdiffusion irrespective of surface roughness. This unique structure allows fast charge transportation and homogeneous lithiation/delithiation throughout the micron-meter nanolattice, which results in excellent stability and large reversible capacity over 500 cycles at 1 A/g. The results highlight design and constructing artificial nanolattice can be an effective way to prevent chemo-mechanical degradation of silicon-based anode materials.
Silicon-based anodes including Si, SiOx and SiO2 could deliver ultra-large capacities, but degrade fast owing to huge volume change and low conductivity. Generally, large amounts of elastic binder and conductive additives were composited with nanosized silicon-based materials to yield reasonable cycling stability, which nevertheless not only decrease specific capacity but also induce inhomogeneous lithiation/delithiation as well as uneven stress variations. Artificial nanolattice has exhibited superior mechanical properties which could be ideal structure for silicon-based anodes, but yet faces challenges in integration of chemical reactivity, conductivity and mechanical stability. Herein, we fabricate artificial SiO2 honeycomb nanolattice consisting of numerous nanoscale SiO2 cells interconnected by through-holes, and conformal coating of highly graphitic carbon on the nanolattice is achieved through in situ catalytic graphitization. Moreover, the nanolattice is firmly bonded on Cu substrate through atomic interdiffusion irrespective of surface roughness. This unique structure allows fast charge transportation and homogeneous lithiation/delithiation throughout the micron-meter nanolattice, which results in excellent stability and large reversible capacity over 500 cycles at 1 A/g. The results highlight design and constructing artificial nanolattice can be an effective way to prevent chemo-mechanical degradation of silicon-based anode materials.
2024, 35(10): 109571
doi: 10.1016/j.cclet.2024.109571
摘要:
The topology of conjugated macrocycles had significant impacts on their photo-physical and photo-chemical properties. Herein, a series of π-conjugated macrocycles with diverse topology were synthesized via intramolecular McMurry coupling. Their chemical structure and macrocyclic topology were unambiguously confirmed via NMR, MALDI-TOF mass spectra, crystal analysis and scanning tunneling microscopy (STM). Depending on the structural topology and structural rigidity, these cyclic compounds display obviously distinctive emission behavior and photochemical reactions in the solution and in the solid state. Monocyclic phenylene vinylene macrocycle (denoted as MST) exhibiting aggregation-induced emission behavior, was more vulnerable to photo-cyclization in solution and triplet sensitizer promoted photo-dimerization due to lower strain and more flourishing intramolecular motions. After UV light irradiation, relatively more flexible MST could yield the anti-dimer via triplet excimer on the HOPG surface confirmed by STM investigation. By contrast, highly constrained bicyclic analogue (named as DMTPE) with central tetraphenylethene core, displayed high emission quantum yields of 68% both in solution and in the solid state, and was relatively inert to photochemical reactions and yield syn-dimer on the surface via singlet excimer involved [2 + 2] photo-dimerization. Based on the solution-mediated photo-polymerization of MST moiety, multicyclic porous carbon-rich ribbon connected with four-membered ring was successfully constructed and validated via STM imaging.
The topology of conjugated macrocycles had significant impacts on their photo-physical and photo-chemical properties. Herein, a series of π-conjugated macrocycles with diverse topology were synthesized via intramolecular McMurry coupling. Their chemical structure and macrocyclic topology were unambiguously confirmed via NMR, MALDI-TOF mass spectra, crystal analysis and scanning tunneling microscopy (STM). Depending on the structural topology and structural rigidity, these cyclic compounds display obviously distinctive emission behavior and photochemical reactions in the solution and in the solid state. Monocyclic phenylene vinylene macrocycle (denoted as MST) exhibiting aggregation-induced emission behavior, was more vulnerable to photo-cyclization in solution and triplet sensitizer promoted photo-dimerization due to lower strain and more flourishing intramolecular motions. After UV light irradiation, relatively more flexible MST could yield the anti-dimer via triplet excimer on the HOPG surface confirmed by STM investigation. By contrast, highly constrained bicyclic analogue (named as DMTPE) with central tetraphenylethene core, displayed high emission quantum yields of 68% both in solution and in the solid state, and was relatively inert to photochemical reactions and yield syn-dimer on the surface via singlet excimer involved [2 + 2] photo-dimerization. Based on the solution-mediated photo-polymerization of MST moiety, multicyclic porous carbon-rich ribbon connected with four-membered ring was successfully constructed and validated via STM imaging.
2024, 35(10): 109572
doi: 10.1016/j.cclet.2024.109572
摘要:
Epilepsy, as a chronic neurological disease of the brain, is closely related to oxidative stress, and the peroxynitrite (ONOO−) significantly rise up in this event. Therefore, ONOO− is considered as a potential biomarker for early prediction of epilepsy. However, some potential diagnostic reagents for epilepsy are hindered by the blood-brain barrier (BBB). Meanwhile, “drug repurposing” is attracting a growing interest. Edaravone (EDA), as a first-line drug in the clinical treatment of cerebral ischemia, plays antioxidant roles in scavenging free radicals, promising potential antiepileptic activity. Thus, it is imperative to develop fluorescent probes for monitoring ONOO− fluctuations in the epileptic brain. Hence, we proposed a novel fluorescent probe with the thiocarbonate as the promising recognition unit for ONOO− and dicyanoisophorone derivative as the fluorophore. Moreover, by the “three-in-one” strategy, the introduction of trifluoromethyl into DCI-ONOO-3 can extend the emission wavelength of the fluorophore, shorten the response and increase lipophilicity. Consequently, DCI-ONOO-3 was used for monitoring ONOO− fluxes in brain of epileptic mice and evaluating the antiepileptic efficacy of EDA. It opens up a new way for the design of BBB permeable fluorescent probes, and provides a convincing new method for the diagnosis and treatment of epilepsy.
Epilepsy, as a chronic neurological disease of the brain, is closely related to oxidative stress, and the peroxynitrite (ONOO−) significantly rise up in this event. Therefore, ONOO− is considered as a potential biomarker for early prediction of epilepsy. However, some potential diagnostic reagents for epilepsy are hindered by the blood-brain barrier (BBB). Meanwhile, “drug repurposing” is attracting a growing interest. Edaravone (EDA), as a first-line drug in the clinical treatment of cerebral ischemia, plays antioxidant roles in scavenging free radicals, promising potential antiepileptic activity. Thus, it is imperative to develop fluorescent probes for monitoring ONOO− fluctuations in the epileptic brain. Hence, we proposed a novel fluorescent probe with the thiocarbonate as the promising recognition unit for ONOO− and dicyanoisophorone derivative as the fluorophore. Moreover, by the “three-in-one” strategy, the introduction of trifluoromethyl into DCI-ONOO-3 can extend the emission wavelength of the fluorophore, shorten the response and increase lipophilicity. Consequently, DCI-ONOO-3 was used for monitoring ONOO− fluxes in brain of epileptic mice and evaluating the antiepileptic efficacy of EDA. It opens up a new way for the design of BBB permeable fluorescent probes, and provides a convincing new method for the diagnosis and treatment of epilepsy.
2024, 35(10): 109575
doi: 10.1016/j.cclet.2024.109575
摘要:
Trifluoroacetic acid (TFA) catalyzed condensation reaction between tetraaminooxacalix[4]arene and N-alkylcarbazole-3,6-dicarbaldehyde in CH2Cl2 afforded a single product in 87%–89% yield. Well-defined yet undissolvable 1H NMR spectra suggested formation of robust and discrete structures in solution. X-ray single crystal analysis further revealed a giant twisted double-layer chiral macrocycle in the solid state, which was formed from [4 + 8] condensation of the two reactants via 16 imine bonds. DFT calculations discovered that only the [4 + 8] twisted product is thermodynamically favorable, which accounts for its highly selective and efficient formation out of a library of many other combinations.
Trifluoroacetic acid (TFA) catalyzed condensation reaction between tetraaminooxacalix[4]arene and N-alkylcarbazole-3,6-dicarbaldehyde in CH2Cl2 afforded a single product in 87%–89% yield. Well-defined yet undissolvable 1H NMR spectra suggested formation of robust and discrete structures in solution. X-ray single crystal analysis further revealed a giant twisted double-layer chiral macrocycle in the solid state, which was formed from [4 + 8] condensation of the two reactants via 16 imine bonds. DFT calculations discovered that only the [4 + 8] twisted product is thermodynamically favorable, which accounts for its highly selective and efficient formation out of a library of many other combinations.
2024, 35(10): 109581
doi: 10.1016/j.cclet.2024.109581
摘要:
Post-synthetic modifications (PSM) have drawn great attention as a vigoroso tool to tune or enhance the performance of metal-organic frameworks (MOFs). However, the current PSM method usually have to sacrifice the porosity of MOFs to enrich their functionality, such as pore space partition (PSP) and post-synthetic elimination and insertion (PSE&I), causing a trade-off in this aspect. To address this issue, we herein propose a new PSM strategy of using the size-matching ligands as the bolts to lock MOFs’ pores, which could be anchored onto open metal sites (OMSs) after guest loading through a stepwise manipulation. As a result, the loaded cargoes undergo a controlled releasing process with respect to different bolt ligands. Our proposed strategy provides a promising way to balance the functionality and porosity of MOFs.
Post-synthetic modifications (PSM) have drawn great attention as a vigoroso tool to tune or enhance the performance of metal-organic frameworks (MOFs). However, the current PSM method usually have to sacrifice the porosity of MOFs to enrich their functionality, such as pore space partition (PSP) and post-synthetic elimination and insertion (PSE&I), causing a trade-off in this aspect. To address this issue, we herein propose a new PSM strategy of using the size-matching ligands as the bolts to lock MOFs’ pores, which could be anchored onto open metal sites (OMSs) after guest loading through a stepwise manipulation. As a result, the loaded cargoes undergo a controlled releasing process with respect to different bolt ligands. Our proposed strategy provides a promising way to balance the functionality and porosity of MOFs.
2024, 35(10): 109582
doi: 10.1016/j.cclet.2024.109582
摘要:
The first example of metal Sn-fused perylene diimides (PDI) derivative (Sn-PDI) was designed, synthesized, and investigated. To obtain this type compound, a simple one-pot synthesis, named stannylative cycloaddition reaction, has been successfully developed via a palladium-based catalyst system. The novel mechanism exhibits that the reaction experiences oxidative addition, Pd-cyclization, stannylation, Pd-Sn-cyclization, and reductive elimination processes successively. This stannylative cycloaddition does realize unique σ-π hyperconjugation effect and therefore significantly influencing on the photophysical, electrochemical and excited state properties. Compared with those of PDI, both of the absorption and fluorescence spectra of Sn-PDI display large red-shifts over 20 nm. The electron energy levels of Sn-PDI have changed with an uncommon regulation. And Sn-PDI gives a considerably raised highest occupied molecular orbital (HOMO) level of -6.00 eV More importantly, the singlet excitons of Sn-PDI could efficiently intersystem cross (ISC) into triplet state with a long lifetime of 17.8 µs, which is far longer than that (4.4 ns) of PDI.
The first example of metal Sn-fused perylene diimides (PDI) derivative (Sn-PDI) was designed, synthesized, and investigated. To obtain this type compound, a simple one-pot synthesis, named stannylative cycloaddition reaction, has been successfully developed via a palladium-based catalyst system. The novel mechanism exhibits that the reaction experiences oxidative addition, Pd-cyclization, stannylation, Pd-Sn-cyclization, and reductive elimination processes successively. This stannylative cycloaddition does realize unique σ-π hyperconjugation effect and therefore significantly influencing on the photophysical, electrochemical and excited state properties. Compared with those of PDI, both of the absorption and fluorescence spectra of Sn-PDI display large red-shifts over 20 nm. The electron energy levels of Sn-PDI have changed with an uncommon regulation. And Sn-PDI gives a considerably raised highest occupied molecular orbital (HOMO) level of -6.00 eV More importantly, the singlet excitons of Sn-PDI could efficiently intersystem cross (ISC) into triplet state with a long lifetime of 17.8 µs, which is far longer than that (4.4 ns) of PDI.
2024, 35(10): 109583
doi: 10.1016/j.cclet.2024.109583
摘要:
Activated pancreatic stellate cells (PSCs) are the main source of collagen layer deposition and the key target in pancreatic fibrosis. However, no effective treatment specific to pancreatic fibrosis clinically, owing to the drug accumulation blocked by the collagen barrier and thus it is difficult to inhibit activated PSCs precisely. Herein, a PSCs-targeting nano-system based on “nanodrill” strategy (LA-PC) was designed to enhance the accumulation of all-trans retinoic acid (ATRA) in PSCs, relying on the platelet-derived growth factor receptor beta (PDGFRβ)-targeting peptide (pPB: C*SRNLIDC*) and collagenase (Col). After being injected into fibrotic mice via tail vein, the Col modified on LA-PC can remove the excess collagen layer, and the drug delivery efficiency through pPB targeting peptide was more than 5 times higher than that of free ATRA, as well as the degree of fibrosis significantly reduced. Notably, this nano-system effectively inhibited platelet-derived growth factor subunit B (PDGF-BB)/PDGFRβ axis on PSCs via a down-regulated extracellular signal-regulated protein kinase (ERK) pathway, and accordingly reduced the level of PDGF-BB. Thus, the smart platform provided a promising strategy for the treatment of pancreatic fibrosis to achieve the precise regulation of PSCs.
Activated pancreatic stellate cells (PSCs) are the main source of collagen layer deposition and the key target in pancreatic fibrosis. However, no effective treatment specific to pancreatic fibrosis clinically, owing to the drug accumulation blocked by the collagen barrier and thus it is difficult to inhibit activated PSCs precisely. Herein, a PSCs-targeting nano-system based on “nanodrill” strategy (LA-PC) was designed to enhance the accumulation of all-trans retinoic acid (ATRA) in PSCs, relying on the platelet-derived growth factor receptor beta (PDGFRβ)-targeting peptide (pPB: C*SRNLIDC*) and collagenase (Col). After being injected into fibrotic mice via tail vein, the Col modified on LA-PC can remove the excess collagen layer, and the drug delivery efficiency through pPB targeting peptide was more than 5 times higher than that of free ATRA, as well as the degree of fibrosis significantly reduced. Notably, this nano-system effectively inhibited platelet-derived growth factor subunit B (PDGF-BB)/PDGFRβ axis on PSCs via a down-regulated extracellular signal-regulated protein kinase (ERK) pathway, and accordingly reduced the level of PDGF-BB. Thus, the smart platform provided a promising strategy for the treatment of pancreatic fibrosis to achieve the precise regulation of PSCs.
2024, 35(10): 109599
doi: 10.1016/j.cclet.2024.109599
摘要:
Tetracycline (TC) as a typical emerging pollutant is becoming a serious threat to the environment and human health. A combined advanced oxidation technology of UV/Ozone (O3)/peroxydisulfate (PDS) process was developed to explore an efficient and economic treatment process of TC in wastewater. Furthermore, the reactive sites and transformation pathways of TC were explored and the toxicity of the intermediates was quantified with a quantitative structure-activity relationship (QSAR) assessment. The degradation performance of TC was substantially enhanced in UV/O3/PDS process with a kobs of 0.0949 min−1, which was 2.3 times higher than UV/O3 and 3.2 times than sole UV. The results demonstrated that there was a superior synergistic effect of PDS on UV/O3 processes for the degradation of TC. Electron paramagnetic resonance (EPR) analysis and quenching experiments show that •OH, SO4•−, O2•− and 1O2 all contributed to TC degradation in the UV/O3/PDS process and exhibited a synergistic effect, which inhibited the generation of harmful products. In addition, the UV/O3/PDS system can effectively degrade TC in a wide range of substrate concentrations and pH, and also showed excellent adaptability to various concentrations of anions (Cl− and HCO3−). This study proves the feasibility of UV/O3/PDS process for treating TC contaminated wastewater with complicated water matrix.
Tetracycline (TC) as a typical emerging pollutant is becoming a serious threat to the environment and human health. A combined advanced oxidation technology of UV/Ozone (O3)/peroxydisulfate (PDS) process was developed to explore an efficient and economic treatment process of TC in wastewater. Furthermore, the reactive sites and transformation pathways of TC were explored and the toxicity of the intermediates was quantified with a quantitative structure-activity relationship (QSAR) assessment. The degradation performance of TC was substantially enhanced in UV/O3/PDS process with a kobs of 0.0949 min−1, which was 2.3 times higher than UV/O3 and 3.2 times than sole UV. The results demonstrated that there was a superior synergistic effect of PDS on UV/O3 processes for the degradation of TC. Electron paramagnetic resonance (EPR) analysis and quenching experiments show that •OH, SO4•−, O2•− and 1O2 all contributed to TC degradation in the UV/O3/PDS process and exhibited a synergistic effect, which inhibited the generation of harmful products. In addition, the UV/O3/PDS system can effectively degrade TC in a wide range of substrate concentrations and pH, and also showed excellent adaptability to various concentrations of anions (Cl− and HCO3−). This study proves the feasibility of UV/O3/PDS process for treating TC contaminated wastewater with complicated water matrix.
2024, 35(10): 109618
doi: 10.1016/j.cclet.2024.109618
摘要:
The existence of adsorbed water and structural water in the crystal structure of attapulgite (ATP) endows it with poor capability to store lithium ions. Herein, the chloride molten salt method was developed to function ATP materials based on theoretical calculations, which exhibit ground-breaking electrochemical performance. After the modification process, the metal ions in chloride molten salt occupy the vertices of the Mg-O octahedral structure from the liberation of structural water and hydroxyl groups in ATP, forming MaMgbAlcSixOy (M = Li, Na, or K). Using LiCl molten salt-modified ATP (Li-ATP) as a proof-of-concept, the detailed phase transition, physicochemical properties, and lithium storage capacity were investigated. Compared to the original ATP, Li-ATP achieves a nearly 7-fold increase in lithium storage capacity (498 mAh/g), featuring a promising low-cost polyanionic type anode material.
The existence of adsorbed water and structural water in the crystal structure of attapulgite (ATP) endows it with poor capability to store lithium ions. Herein, the chloride molten salt method was developed to function ATP materials based on theoretical calculations, which exhibit ground-breaking electrochemical performance. After the modification process, the metal ions in chloride molten salt occupy the vertices of the Mg-O octahedral structure from the liberation of structural water and hydroxyl groups in ATP, forming MaMgbAlcSixOy (M = Li, Na, or K). Using LiCl molten salt-modified ATP (Li-ATP) as a proof-of-concept, the detailed phase transition, physicochemical properties, and lithium storage capacity were investigated. Compared to the original ATP, Li-ATP achieves a nearly 7-fold increase in lithium storage capacity (498 mAh/g), featuring a promising low-cost polyanionic type anode material.
2024, 35(10): 109625
doi: 10.1016/j.cclet.2024.109625
摘要:
When zero-valent iron (ZVI) is prepared and applied under neutral conditions, it is easy to form oxides or hydroxides on its surface, which hinders the electron release of ZVI. To this end, a nucleophile was introduced into the ZVI system to inhibit the precipitation of iron ions, improve the conductivity of the solution, and promote the removal efficiency of electrophilic functional groups in organic compounds. In this study, the addition of nucleophiles such as ethylenediamine, methylamine and dimethylamine to the ZVI/H2O2 system resulted in an enhanced removal efficiency of tetracycline (TC) under neutral condition, while electrophiles such as EDTA-2Na and oxalic acid dihydrate impeded the removal of TC. Experimental results demonstrated that the presence of nucleophiles could effectively promote the release of iron ions and increase the proportion of ferrous in both aqueous solution and solid surface of ZVI. Experimental and theoretical calculation results revealed that the electrophilic functional group was eliminated in the TC molecule, and the toxicity of the treated solution was reduced significantly. Overall, this work provides a selection of the conditions and pollutants applicable to ZVI under neutral pH conditions.
When zero-valent iron (ZVI) is prepared and applied under neutral conditions, it is easy to form oxides or hydroxides on its surface, which hinders the electron release of ZVI. To this end, a nucleophile was introduced into the ZVI system to inhibit the precipitation of iron ions, improve the conductivity of the solution, and promote the removal efficiency of electrophilic functional groups in organic compounds. In this study, the addition of nucleophiles such as ethylenediamine, methylamine and dimethylamine to the ZVI/H2O2 system resulted in an enhanced removal efficiency of tetracycline (TC) under neutral condition, while electrophiles such as EDTA-2Na and oxalic acid dihydrate impeded the removal of TC. Experimental results demonstrated that the presence of nucleophiles could effectively promote the release of iron ions and increase the proportion of ferrous in both aqueous solution and solid surface of ZVI. Experimental and theoretical calculation results revealed that the electrophilic functional group was eliminated in the TC molecule, and the toxicity of the treated solution was reduced significantly. Overall, this work provides a selection of the conditions and pollutants applicable to ZVI under neutral pH conditions.
2024, 35(10): 109635
doi: 10.1016/j.cclet.2024.109635
摘要:
A novel biodegradable material, Se@PLA, was designed and prepared via the selenization reaction of polylactic acid using NaHSe as the selenization reagent. This material shows excellent antibacterial activity (EC50 = 13.38 µg/mL) against Xanthomonas oryzae pv. Oryzae, which is a highly destructive pathogen responsible for rice bacterial blight. Se@PLA induces oxidative stress in bacteria, leading to the rupture of bacterial cell membranes and eventual death. Moreover, Se@PLA can significantly inhibit the motility of bacteria and is low toxic to soil and aquatic organisms. This work provides an effective method for preventing and controlling rice bacterial blight, and reveals the great potential of using Se@PLA as an alternative next generation plant bactericide.
A novel biodegradable material, Se@PLA, was designed and prepared via the selenization reaction of polylactic acid using NaHSe as the selenization reagent. This material shows excellent antibacterial activity (EC50 = 13.38 µg/mL) against Xanthomonas oryzae pv. Oryzae, which is a highly destructive pathogen responsible for rice bacterial blight. Se@PLA induces oxidative stress in bacteria, leading to the rupture of bacterial cell membranes and eventual death. Moreover, Se@PLA can significantly inhibit the motility of bacteria and is low toxic to soil and aquatic organisms. This work provides an effective method for preventing and controlling rice bacterial blight, and reveals the great potential of using Se@PLA as an alternative next generation plant bactericide.
2024, 35(10): 109645
doi: 10.1016/j.cclet.2024.109645
摘要:
In recent years, multicolor cascade supramolecular assemblies with controllable topological morphology have become a research hotspot due to their wide application in light-emitting materials, cell imaging and other fields. Herein, several kinds of macrocycles including cucurbiturils, calixarene and cyclodextrins are used as building blocks to construct fluorescent assemblies with anthryl-conjugated phenylpyridine (G), wherein cucurbit[8]uril (CB[8]) and G can form nanowires at a stoichiometric ratio of n: n through host-guest encapsulation to form a non-covalent heterodimer. Significantly, the macrocycle confinement effect drastically enhances the fluorescence emission of G and emission peak generated bathochromic shift from 500 nm to 600 nm. When the supramolecular polymer is further assembled with amphiphilic calix[4]arene (SC4A8), the fluorescence emission of G⊂CB[8] further increases to 1.4 times, accompanied by the morphological transformation from linear structure to nanorod structure. Subsequently, a very small amount of dye Cy5 is added to the assembly solution as an energy receptor, and the negatively charged G⊂CB[8]@SC4A8 system is regarded as an energy donor. The efficient energy transfer process enables near-infrared (NIR) emission at 675 nm with 71% energy transfer efficiency (ΦET) at a donor/receptor ratio of 100:1. Finally, the cascade supramolecular assembly has been successfully applied to targeted imaging in the nucleus of HeLa and A549 cancer cells.
In recent years, multicolor cascade supramolecular assemblies with controllable topological morphology have become a research hotspot due to their wide application in light-emitting materials, cell imaging and other fields. Herein, several kinds of macrocycles including cucurbiturils, calixarene and cyclodextrins are used as building blocks to construct fluorescent assemblies with anthryl-conjugated phenylpyridine (G), wherein cucurbit[8]uril (CB[8]) and G can form nanowires at a stoichiometric ratio of n: n through host-guest encapsulation to form a non-covalent heterodimer. Significantly, the macrocycle confinement effect drastically enhances the fluorescence emission of G and emission peak generated bathochromic shift from 500 nm to 600 nm. When the supramolecular polymer is further assembled with amphiphilic calix[4]arene (SC4A8), the fluorescence emission of G⊂CB[8] further increases to 1.4 times, accompanied by the morphological transformation from linear structure to nanorod structure. Subsequently, a very small amount of dye Cy5 is added to the assembly solution as an energy receptor, and the negatively charged G⊂CB[8]@SC4A8 system is regarded as an energy donor. The efficient energy transfer process enables near-infrared (NIR) emission at 675 nm with 71% energy transfer efficiency (ΦET) at a donor/receptor ratio of 100:1. Finally, the cascade supramolecular assembly has been successfully applied to targeted imaging in the nucleus of HeLa and A549 cancer cells.
2024, 35(10): 109648
doi: 10.1016/j.cclet.2024.109648
摘要:
Sequential C-H bond addition with two different coupling partners is a powerful method for the rapid and modular construction of complex molecules based on simple starting materials. Herein, an efficient ruthenium-catalysed multicomponent long-range C-H functionalization of 2H-imidazoles was developed. This protocol showed good substrate suitability and yielded alkyl arylation products with potential biological activity.
Sequential C-H bond addition with two different coupling partners is a powerful method for the rapid and modular construction of complex molecules based on simple starting materials. Herein, an efficient ruthenium-catalysed multicomponent long-range C-H functionalization of 2H-imidazoles was developed. This protocol showed good substrate suitability and yielded alkyl arylation products with potential biological activity.
2024, 35(10): 109652
doi: 10.1016/j.cclet.2024.109652
摘要:
The adsorption of peroxymonosulfate (PMS) is crucial for PMS activation in the heterogeneous advanced oxidation processes. However, the investigation of PMS adsorption on the piezocatalysts still remains insufficient. In this work, bismuth oxychloride (BiOCl) nanosheets were prepared as the piezocatalysts for PMS activation under ultrasonic vibration to remove carbamazepine (CBZ) in aqueous solutions. Up to 92.5% of CBZ was degraded for 40 min in BiOCl piezo-activated PMS system with the reaction rate constant of 0.0741 min−1, being 1.63 times that of the sum of BiOCl piezocatalysis, BiOCl-activated PMS, and vibration-activated PMS. PMS adsorption on the surface of BiOCl was specifically studied by comparing the microscopic structure change of the fresh and used BiOCl. The results suggested that the piezoelectric field of BiOCl was able to promote the tight adsorption of PMS on the surface, thus facilitating the fast activation of PMS through electrons transfer to produce reactive species (HO•, SO4•−, O2•−, 1O2). This work presents an in-depth understanding for the role of piezoelectric effect on the adsorption and activation of PMS.
The adsorption of peroxymonosulfate (PMS) is crucial for PMS activation in the heterogeneous advanced oxidation processes. However, the investigation of PMS adsorption on the piezocatalysts still remains insufficient. In this work, bismuth oxychloride (BiOCl) nanosheets were prepared as the piezocatalysts for PMS activation under ultrasonic vibration to remove carbamazepine (CBZ) in aqueous solutions. Up to 92.5% of CBZ was degraded for 40 min in BiOCl piezo-activated PMS system with the reaction rate constant of 0.0741 min−1, being 1.63 times that of the sum of BiOCl piezocatalysis, BiOCl-activated PMS, and vibration-activated PMS. PMS adsorption on the surface of BiOCl was specifically studied by comparing the microscopic structure change of the fresh and used BiOCl. The results suggested that the piezoelectric field of BiOCl was able to promote the tight adsorption of PMS on the surface, thus facilitating the fast activation of PMS through electrons transfer to produce reactive species (HO•, SO4•−, O2•−, 1O2). This work presents an in-depth understanding for the role of piezoelectric effect on the adsorption and activation of PMS.
2024, 35(10): 109792
doi: 10.1016/j.cclet.2024.109792
摘要:
GPCRs are dominant targets for approved drugs and the discovery of lead compound targeting them is still challengeable. Affinity-based screening technique is a promising platform to uncover GPCR ligands. However, the intrinsic activities of them are seldom simultaneously determined during the screening. Taking beta2-adrenoceptor (β2AR) as a probe, this work created a strategy for screening GPCR ligands with simultaneous characterization of their downstream G protein binding responses associated with GTP. The strategy included (ⅰ) the design and expression of a protein miniature formed by β2AR and G protein α-subunit (Gαs) using circularly permuted HaloTag (cpHalo) as a flexible linker; (ⅱ) immobilization of the miniature onto silica gel by a click dehalogenation reaction; (ⅲ) systematic characterization of the immobilized miniature by fluorescent and chromatographic studies, and (ⅳ) simulating of ligand-induced β2AR-Gαs signaling cascade by chromatographic assays using GTP as an indicator. The immobilized miniature exhibited specificity to β2AR and Gαs antibodies and ligands. The specificity is stable at least within fifteen days with the variation less than 1%. The intrinsic activities of β2AR ligands were distinguished by the changes of GTP chromatographic behaviors on Gαs-cpHalo-β2AR column. Agonists strengthened the binding affinity and kinetics of GTP with Gαs, while antagonist did not give any effect on them. With the intrinsic activity evaluation, we believe, it will improve the attributes of chromatographic methods for drug discovery efforts with minimizing false-positive results.
GPCRs are dominant targets for approved drugs and the discovery of lead compound targeting them is still challengeable. Affinity-based screening technique is a promising platform to uncover GPCR ligands. However, the intrinsic activities of them are seldom simultaneously determined during the screening. Taking beta2-adrenoceptor (β2AR) as a probe, this work created a strategy for screening GPCR ligands with simultaneous characterization of their downstream G protein binding responses associated with GTP. The strategy included (ⅰ) the design and expression of a protein miniature formed by β2AR and G protein α-subunit (Gαs) using circularly permuted HaloTag (cpHalo) as a flexible linker; (ⅱ) immobilization of the miniature onto silica gel by a click dehalogenation reaction; (ⅲ) systematic characterization of the immobilized miniature by fluorescent and chromatographic studies, and (ⅳ) simulating of ligand-induced β2AR-Gαs signaling cascade by chromatographic assays using GTP as an indicator. The immobilized miniature exhibited specificity to β2AR and Gαs antibodies and ligands. The specificity is stable at least within fifteen days with the variation less than 1%. The intrinsic activities of β2AR ligands were distinguished by the changes of GTP chromatographic behaviors on Gαs-cpHalo-β2AR column. Agonists strengthened the binding affinity and kinetics of GTP with Gαs, while antagonist did not give any effect on them. With the intrinsic activity evaluation, we believe, it will improve the attributes of chromatographic methods for drug discovery efforts with minimizing false-positive results.
2024, 35(10): 109805
doi: 10.1016/j.cclet.2024.109805
摘要:
Directed self-assembly has been used to create micro-nano scale patterns, including chiral periodic structures of organic molecules, for potential applications in optics, photonics, metamaterials, and medical and sensing technologies. This study presents a straightforward approach for fabricating large-scale chiral grating porphyrin assemblies through template-assisted techniques. The solution of tetrakis(4-sulfonatophenyl)porphyrin (TPPS) was induced by chiral amino acids (L/D-arginine and L/D-serine) to self-assemble into highly ordered chiral grating structures with the assistance of sodium dodecyl sulfate (SDS). The structures show precise line widths (5.5 µm) and gaps (18 µm). Using in situ optical microscopy and second harmonic generation (SHG) microscopy, the chiral characteristics and dynamic evolution of the template-assisted self-assembly are investigated. It is found that the chirality of amino acids induced TPPS self-assembled into chiral structures and the liquid contraction interface significantly enhanced the chirality of the assemblies. This study is significant for understanding the mechanism of chiral evolution and designing novel micro-nano materials with predetermined chiral properties.
Directed self-assembly has been used to create micro-nano scale patterns, including chiral periodic structures of organic molecules, for potential applications in optics, photonics, metamaterials, and medical and sensing technologies. This study presents a straightforward approach for fabricating large-scale chiral grating porphyrin assemblies through template-assisted techniques. The solution of tetrakis(4-sulfonatophenyl)porphyrin (TPPS) was induced by chiral amino acids (L/D-arginine and L/D-serine) to self-assemble into highly ordered chiral grating structures with the assistance of sodium dodecyl sulfate (SDS). The structures show precise line widths (5.5 µm) and gaps (18 µm). Using in situ optical microscopy and second harmonic generation (SHG) microscopy, the chiral characteristics and dynamic evolution of the template-assisted self-assembly are investigated. It is found that the chirality of amino acids induced TPPS self-assembled into chiral structures and the liquid contraction interface significantly enhanced the chirality of the assemblies. This study is significant for understanding the mechanism of chiral evolution and designing novel micro-nano materials with predetermined chiral properties.
2024, 35(10): 109808
doi: 10.1016/j.cclet.2024.109808
摘要:
Charge-transfer (CT) stoichiometric cocrystals are promising choice of organic materials for unveiling the structure-property relationship. However, due to the contradiction between large CT degree required for strong NIR absorption and flexible molecular stacking, construction of stoichiomorphism-based cocystals with near-infrared (NIR) photothermal property remains challenging. Herein, the first example of stoichiomorphism-based photothermal cocrystals were accomplished through the adaptive assembly of 3,3′,5,5′-tetramethylbenzidine (TMB) donor and 1,2,4,5-tetracyanobenzene (TCNB) acceptor. The selective cocrystallization could be controlled by varying the donor-acceptor stoichiometries via a surfactant-assisted method, resulting in two cocrystals with 1:1 (T1C1) and 1:2 (T2C1) stoichiometries. The absorbance intensity of T1C1 at 808 nm was nearly twice that of T2C1, while the photothermal conversion efficiency (PCE) of the former was 60.3% ± 0.6%, approximately 80% of that for the latter (75.5% ± 2.6%), which might be caused by the different intermolecular interactions in distinct molecular stacking patterns. Notably, both excellent PCEs of stoichiometric cocrystals were attributed to the nonradiative transition process, including internal conversion and charge dissociation processes, as elucidated by femtosecond transient absorption spectroscopy measurements. Furthermore, T1C1 was used as an NIR heater for preparing agarose-based photothermal hydrogel, showing great potential for light-controlled in-situ gelation. This strategy of balancing the CT degree and molecular packing orientation not only uncovered the relationship between stoichiometric stacking and photothermal property, but also provided an opportunity to develop advanced organic optoelectronic materials.
Charge-transfer (CT) stoichiometric cocrystals are promising choice of organic materials for unveiling the structure-property relationship. However, due to the contradiction between large CT degree required for strong NIR absorption and flexible molecular stacking, construction of stoichiomorphism-based cocystals with near-infrared (NIR) photothermal property remains challenging. Herein, the first example of stoichiomorphism-based photothermal cocrystals were accomplished through the adaptive assembly of 3,3′,5,5′-tetramethylbenzidine (TMB) donor and 1,2,4,5-tetracyanobenzene (TCNB) acceptor. The selective cocrystallization could be controlled by varying the donor-acceptor stoichiometries via a surfactant-assisted method, resulting in two cocrystals with 1:1 (T1C1) and 1:2 (T2C1) stoichiometries. The absorbance intensity of T1C1 at 808 nm was nearly twice that of T2C1, while the photothermal conversion efficiency (PCE) of the former was 60.3% ± 0.6%, approximately 80% of that for the latter (75.5% ± 2.6%), which might be caused by the different intermolecular interactions in distinct molecular stacking patterns. Notably, both excellent PCEs of stoichiometric cocrystals were attributed to the nonradiative transition process, including internal conversion and charge dissociation processes, as elucidated by femtosecond transient absorption spectroscopy measurements. Furthermore, T1C1 was used as an NIR heater for preparing agarose-based photothermal hydrogel, showing great potential for light-controlled in-situ gelation. This strategy of balancing the CT degree and molecular packing orientation not only uncovered the relationship between stoichiometric stacking and photothermal property, but also provided an opportunity to develop advanced organic optoelectronic materials.
2024, 35(10): 109809
doi: 10.1016/j.cclet.2024.109809
摘要:
Deep-blue emitter with high photoluminescence efficiency (PLQY) is highly desirable in ultra-high definition displays and white solid-state lightings. In this work, two deep-blue phenanthro[9,10]imidazole derivatives, PPIS and PPPIS, with hot exciton property are successfully developed. Compared to PPIS, the embedded phenyl bridge in PPPIS is able to effectively increase the overlap of frontier molecular orbitals. In consequence, PPPIS shows higher oscillator strength and significantly enhanced PLQY. PPPIS also achieves better electroluminescence performance in non-doped device, showing deep-blue emission with Commission International de l'Eclairage (CIE) coordinates of (0.153, 0.087) and the maximum external quantum efficiency (EQEmax) of 8.5% with minuscule efficiency roll-off. Meanwhile, when PPPIS serves as the host for phosphor PO-01, high-efficiency orange phosphorescent device is obtained with high EQEmax of 29.8% and negligible efficiency roll-off at 1000 cd/m2. Further, efficient single-emissive-layer white device is assembled via utilizing PPPIS as a blue emitter as well as the host for PO-01 simultaneously, providing warm-white emission with CIE coordinates of (0.429, 0.433) at 1000 cd/m2, the forward-viewing EQEmax of 27.2% and maximum power efficiency (PEmax) of 80.1 lm/W, respectively. Our studies can establish a viable design strategy for deep-blue emitters in high-performance non-doped blue OLEDs and hybrid WOLEDs.
Deep-blue emitter with high photoluminescence efficiency (PLQY) is highly desirable in ultra-high definition displays and white solid-state lightings. In this work, two deep-blue phenanthro[9,10]imidazole derivatives, PPIS and PPPIS, with hot exciton property are successfully developed. Compared to PPIS, the embedded phenyl bridge in PPPIS is able to effectively increase the overlap of frontier molecular orbitals. In consequence, PPPIS shows higher oscillator strength and significantly enhanced PLQY. PPPIS also achieves better electroluminescence performance in non-doped device, showing deep-blue emission with Commission International de l'Eclairage (CIE) coordinates of (0.153, 0.087) and the maximum external quantum efficiency (EQEmax) of 8.5% with minuscule efficiency roll-off. Meanwhile, when PPPIS serves as the host for phosphor PO-01, high-efficiency orange phosphorescent device is obtained with high EQEmax of 29.8% and negligible efficiency roll-off at 1000 cd/m2. Further, efficient single-emissive-layer white device is assembled via utilizing PPPIS as a blue emitter as well as the host for PO-01 simultaneously, providing warm-white emission with CIE coordinates of (0.429, 0.433) at 1000 cd/m2, the forward-viewing EQEmax of 27.2% and maximum power efficiency (PEmax) of 80.1 lm/W, respectively. Our studies can establish a viable design strategy for deep-blue emitters in high-performance non-doped blue OLEDs and hybrid WOLEDs.
2024, 35(10): 109821
doi: 10.1016/j.cclet.2024.109821
摘要:
It has been widely recognized that hole transporting materials (HTMs) play a key role in the rapid progress of perovskite solar cells (PVSCs). However, common organic HTMs such as spiro-OMeTAD not only suffer from high synthetic costs, but also usually require the additional chemical doping process to improve their hole transport ability, which unfortunately induces the terrible stability issue. Therefore, it is urgent to develop low-cost dopant-free HTMs for efficient and stable PVSCs. In this work, we have successfully developed a new class of efficient dopant-free fluoranthene-based HTMs (TPF1–5) with quite low lab synthetic costs by combining donor-acceptor and branched structure designs. The detailed structure-property study revealed that tuning the twisted arms at different substitution sites would regulate the intermolecular interactions and film-forming ability, thereby significantly affecting the performance of the HTMs. By applying these HTMs in conventional PVSCs, the dopant-free TPF1-based devices not only achieved the best efficiency of 21.76%, which is comparable to that of the doped spiro-OMeTAD control devices, but also showed much better operational stability, which maintained over 87% of the initial efficiency under maximum power point tracking after 1038 h.
It has been widely recognized that hole transporting materials (HTMs) play a key role in the rapid progress of perovskite solar cells (PVSCs). However, common organic HTMs such as spiro-OMeTAD not only suffer from high synthetic costs, but also usually require the additional chemical doping process to improve their hole transport ability, which unfortunately induces the terrible stability issue. Therefore, it is urgent to develop low-cost dopant-free HTMs for efficient and stable PVSCs. In this work, we have successfully developed a new class of efficient dopant-free fluoranthene-based HTMs (TPF1–5) with quite low lab synthetic costs by combining donor-acceptor and branched structure designs. The detailed structure-property study revealed that tuning the twisted arms at different substitution sites would regulate the intermolecular interactions and film-forming ability, thereby significantly affecting the performance of the HTMs. By applying these HTMs in conventional PVSCs, the dopant-free TPF1-based devices not only achieved the best efficiency of 21.76%, which is comparable to that of the doped spiro-OMeTAD control devices, but also showed much better operational stability, which maintained over 87% of the initial efficiency under maximum power point tracking after 1038 h.
2024, 35(10): 109838
doi: 10.1016/j.cclet.2024.109838
摘要:
As a hydrolase, chymotrypsin (CHT) is involved in many physiological activities, and its abnormal activity is closely related to diabetes, pancreatic fibrosis, chronic pancreatitis and pancreatic cancer. In this work, an innovative long-wavelength emission fluorescent probe TCF-CHT was designed and synthesized for the high specificity detection of CHT, which utilized TCF-OH and a mimetic peptide substrate 4-bromobutyryl as chromogenic group and recognition group, respectively. TCF-CHT exhibited excellent selectivity and eye-catching sensitivity (8.91 ng/mL) towards CHT, "off-on" long-wavelength emission at 670 nm and large Stokes shift (140 nm). Furthermore, the successful fulfillment and perfect performance in imaging endogenous CHT in complex organisms (P815 cells, HepG2 cells, zebrafish and tumor-bearing mice) verified its potential as a powerful tool for the recognition of CHT in complicated biological environments.
As a hydrolase, chymotrypsin (CHT) is involved in many physiological activities, and its abnormal activity is closely related to diabetes, pancreatic fibrosis, chronic pancreatitis and pancreatic cancer. In this work, an innovative long-wavelength emission fluorescent probe TCF-CHT was designed and synthesized for the high specificity detection of CHT, which utilized TCF-OH and a mimetic peptide substrate 4-bromobutyryl as chromogenic group and recognition group, respectively. TCF-CHT exhibited excellent selectivity and eye-catching sensitivity (8.91 ng/mL) towards CHT, "off-on" long-wavelength emission at 670 nm and large Stokes shift (140 nm). Furthermore, the successful fulfillment and perfect performance in imaging endogenous CHT in complex organisms (P815 cells, HepG2 cells, zebrafish and tumor-bearing mice) verified its potential as a powerful tool for the recognition of CHT in complicated biological environments.
2024, 35(10): 109862
doi: 10.1016/j.cclet.2024.109862
摘要:
A novel and readily available binaphthyl-based fluorescent probe (S)-1 was designed and synthesized. (S)-1 can be used to not only chemoselectively discriminate 3 basic amino acids out of common amino acids, but also enantioselectively recognize histidine. Encouragingly, enantioselective imaging of histidine in cells was achieved for the first time by the probe (S)-1. These performances endowed it potential application in the chiral analysis of basic amino acids in asymmetric synthesis and cell imaging for diagnosis of diseases caused by racemization of histidine. Nuclear magnetic resonance (NMR) and mass spectrometry investigations suggested that different reaction extent of (S)-1 with l/d-histidine and different product structures generated the observed enantioselective fluorescent response. The molecular structures and thermodynamic stability of the complexes, formed from (S)-1 + Zn2+ and enantiomers of histidine, were calculated by Gaussian 16 based on density functional theory (DFT) to validate the above action mechanism.
A novel and readily available binaphthyl-based fluorescent probe (S)-1 was designed and synthesized. (S)-1 can be used to not only chemoselectively discriminate 3 basic amino acids out of common amino acids, but also enantioselectively recognize histidine. Encouragingly, enantioselective imaging of histidine in cells was achieved for the first time by the probe (S)-1. These performances endowed it potential application in the chiral analysis of basic amino acids in asymmetric synthesis and cell imaging for diagnosis of diseases caused by racemization of histidine. Nuclear magnetic resonance (NMR) and mass spectrometry investigations suggested that different reaction extent of (S)-1 with l/d-histidine and different product structures generated the observed enantioselective fluorescent response. The molecular structures and thermodynamic stability of the complexes, formed from (S)-1 + Zn2+ and enantiomers of histidine, were calculated by Gaussian 16 based on density functional theory (DFT) to validate the above action mechanism.
2024, 35(10): 109863
doi: 10.1016/j.cclet.2024.109863
摘要:
The development of efficient and stable bifunctional overall water-splitting is a crucial goal for clean and renewable energy, which is a challenging task. Herein, we report an Mn-incorporated RuO2 (Mn-RuO2) catalyst for highly efficient electrocatalytic oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in acid and alkaline media. Benefiting from a more electrochemical active area with the incorporation of Mn, the Mn-RuO2 required an overpotential of 200 mV to attain a current density of 10 mA/cm2 for OER in acid. DFT result indicates that the doping of Mn into RuO2 can enhance the OER activity. An acidic overall water-splitting electrolyzer with good stability constructed by bifunctional Mn-RuO2 only requires a cell voltage of 1.50 V to afford 10 mA/cm2 and can operate stably for 50 h at 50 mA/cm2, which is better than the state-of-the-art Ru-based catalyst. Additionally, the Mn-RuO2 exhibits excellent HER and OER activity in alkaline media, and it shows superior activity and durability for overall water-splitting, only needing a cell voltage of 1.49 V to attain 10 mA/cm2. The present work provides an efficient approach to designing and constructing efficient Ru-based electrocatalysts for overall water-splitting.
The development of efficient and stable bifunctional overall water-splitting is a crucial goal for clean and renewable energy, which is a challenging task. Herein, we report an Mn-incorporated RuO2 (Mn-RuO2) catalyst for highly efficient electrocatalytic oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in acid and alkaline media. Benefiting from a more electrochemical active area with the incorporation of Mn, the Mn-RuO2 required an overpotential of 200 mV to attain a current density of 10 mA/cm2 for OER in acid. DFT result indicates that the doping of Mn into RuO2 can enhance the OER activity. An acidic overall water-splitting electrolyzer with good stability constructed by bifunctional Mn-RuO2 only requires a cell voltage of 1.50 V to afford 10 mA/cm2 and can operate stably for 50 h at 50 mA/cm2, which is better than the state-of-the-art Ru-based catalyst. Additionally, the Mn-RuO2 exhibits excellent HER and OER activity in alkaline media, and it shows superior activity and durability for overall water-splitting, only needing a cell voltage of 1.49 V to attain 10 mA/cm2. The present work provides an efficient approach to designing and constructing efficient Ru-based electrocatalysts for overall water-splitting.
2024, 35(10): 110038
doi: 10.1016/j.cclet.2024.110038
摘要:
The first example of sono-photocatalytic bond formation was reported. With both visible light and ultrasound wave as the energy, various 3-aminoquinoxalin-2(1H)-ones were efficiently obtained with good functional group tolerance in the absence of any additive or external photocatalyst. Compared with the conventional photocatalysis, sono-photocatalysis not only dramatically improved the reaction rates and yields, but also reduced energy consumption.
The first example of sono-photocatalytic bond formation was reported. With both visible light and ultrasound wave as the energy, various 3-aminoquinoxalin-2(1H)-ones were efficiently obtained with good functional group tolerance in the absence of any additive or external photocatalyst. Compared with the conventional photocatalysis, sono-photocatalysis not only dramatically improved the reaction rates and yields, but also reduced energy consumption.
2024, 35(10): 109347
doi: 10.1016/j.cclet.2023.109347
摘要:
Polymeric carbon nitride (PCN) has garnered increasing attention as a metal-free photocatalyst with a suitable band gap. In efforts to enhance its photocatalytic performance, researchers have examined various PCN materials, including poly(heptazine imide) (PHI) and poly(triazine imide) (PTI), two isomers within the PCN family that exhibit distinct and superior photocatalytic activity compared to other forms. The challenge, however, lies in the common practice among researchers to categorize PHI and PTI along with other PCN types under the overarching term "g-C3N4, " which significantly impedes optimization efforts. The objective of this review is to provide comprehensive insights into the structural features, photoelectrochemical properties, and effective characterization methods employed for distinguishing between PHI and PTI materials. The review also summarizes various optimization strategies, such as crystallinity adjustments, defect engineering, morphology control, constructing heterojunction, and atomic-level metal loading dispersion, to elevate the photocatalytic activity of PHI and PTI, in addition to summarizing the history of carbon nitride development. Furthermore, this review highlights the primary applications of PHI and PTI, encompassing nitrogen fixation, biomass conversion, organic synthesis, CO2 reduction, pollutant degradation, H2O2 production, and photocatalytic water splitting. Lastly, the prospects and challenges associated with further advancing PHI and PTI are thoroughly examined.
Polymeric carbon nitride (PCN) has garnered increasing attention as a metal-free photocatalyst with a suitable band gap. In efforts to enhance its photocatalytic performance, researchers have examined various PCN materials, including poly(heptazine imide) (PHI) and poly(triazine imide) (PTI), two isomers within the PCN family that exhibit distinct and superior photocatalytic activity compared to other forms. The challenge, however, lies in the common practice among researchers to categorize PHI and PTI along with other PCN types under the overarching term "g-C3N4, " which significantly impedes optimization efforts. The objective of this review is to provide comprehensive insights into the structural features, photoelectrochemical properties, and effective characterization methods employed for distinguishing between PHI and PTI materials. The review also summarizes various optimization strategies, such as crystallinity adjustments, defect engineering, morphology control, constructing heterojunction, and atomic-level metal loading dispersion, to elevate the photocatalytic activity of PHI and PTI, in addition to summarizing the history of carbon nitride development. Furthermore, this review highlights the primary applications of PHI and PTI, encompassing nitrogen fixation, biomass conversion, organic synthesis, CO2 reduction, pollutant degradation, H2O2 production, and photocatalytic water splitting. Lastly, the prospects and challenges associated with further advancing PHI and PTI are thoroughly examined.
2024, 35(10): 109416
doi: 10.1016/j.cclet.2023.109416
摘要:
Water splitting with proton exchange membrane water electrolyzers (PEMWE) is regarded as a promising pathway for sustainable hydrogen conversion. Additionally, oxygen evolution reaction (OER) is considered as the dominant factor during the whole process due to the sluggish kinetics. Among the catalysts, Ru-based catalysts draw special attention because of their excellent activity and relatively low price. However, the limited stability impedes their further commercialization and tremendous efforts have been devoted to overcome this challenge. This review firstly introduces the basic mechanisms of OER. Then the evaluation protocols and techniques to investigate the stability of Ru-based catalysts are summarized. A detailed elucidation of the possible degradation mechanisms is also critically analyzed. Furthermore, effective strategies to design durable Ru-based catalysts for acidic OER are discussed. Such as heteroatom doping, phase and facet engineering, heterostructure building and support optimization. Finally, promises, perspectives and challenges in developing highly durable Ru-based catalysts for acidic OER are outlined.
Water splitting with proton exchange membrane water electrolyzers (PEMWE) is regarded as a promising pathway for sustainable hydrogen conversion. Additionally, oxygen evolution reaction (OER) is considered as the dominant factor during the whole process due to the sluggish kinetics. Among the catalysts, Ru-based catalysts draw special attention because of their excellent activity and relatively low price. However, the limited stability impedes their further commercialization and tremendous efforts have been devoted to overcome this challenge. This review firstly introduces the basic mechanisms of OER. Then the evaluation protocols and techniques to investigate the stability of Ru-based catalysts are summarized. A detailed elucidation of the possible degradation mechanisms is also critically analyzed. Furthermore, effective strategies to design durable Ru-based catalysts for acidic OER are discussed. Such as heteroatom doping, phase and facet engineering, heterostructure building and support optimization. Finally, promises, perspectives and challenges in developing highly durable Ru-based catalysts for acidic OER are outlined.
2024, 35(10): 109420
doi: 10.1016/j.cclet.2023.109420
摘要:
For a significant duration, enhancing the efficacy of cancer therapy has remained a critical concern. Magnetotactic bacteria (MTB), often likened to micro-robots, hold substantial promise as a drug delivery system. MTB, classified as anaerobic, aquatic, and gram-negative microorganisms, exhibit remarkable motility and precise control over their internal biomineralization processes. This unique ability results in the formation of magnetic nanoparticles arranged along filamentous structures in a catenary fashion, enclosed within a membrane. These bacteria possess distinctive biochemical properties that facilitate their precise positioning within complex environments. By harnessing these biochemical attributes, MTB could potentially offer substantial advantages in the realm of cancer therapy. This article reviews the drug delivery capabilities of MTB in tumor treatment and explores various applications based on their inherent properties. The objective is to provide a comprehensive understanding of MTB-driven drug delivery and stimulate innovative insights in this field.
For a significant duration, enhancing the efficacy of cancer therapy has remained a critical concern. Magnetotactic bacteria (MTB), often likened to micro-robots, hold substantial promise as a drug delivery system. MTB, classified as anaerobic, aquatic, and gram-negative microorganisms, exhibit remarkable motility and precise control over their internal biomineralization processes. This unique ability results in the formation of magnetic nanoparticles arranged along filamentous structures in a catenary fashion, enclosed within a membrane. These bacteria possess distinctive biochemical properties that facilitate their precise positioning within complex environments. By harnessing these biochemical attributes, MTB could potentially offer substantial advantages in the realm of cancer therapy. This article reviews the drug delivery capabilities of MTB in tumor treatment and explores various applications based on their inherent properties. The objective is to provide a comprehensive understanding of MTB-driven drug delivery and stimulate innovative insights in this field.
2024, 35(10): 109442
doi: 10.1016/j.cclet.2023.109442
摘要:
Natural hydrogels have emerged as a pivotal innovation in wound care, offering a unique combination of high absorbency, biocompatibility, and versatility. However, due to the complexity of wound healing, the physiological state of the wound varies dynamically, and the mechanism of natural hydrogels that boost wound healing is still unclear. In this review, we firstly provide a comprehensive introduction to the biological process of wound healing, emphasizing the critical stages and factors affecting healing. This work concludes the composition and properties of natural hydrogels, including collagen, gelatin, hyaluronic acid, chitosan, alginates, cellulose, and fibroin, highlighting their biocompatibility and biodegradability. The focus shifts to the various crosslinking strategies employed to enhance the structural integrity and functionality of natural hydrogels. This review further investigates the biological effects of natural hydrogels in wound healing, detailing their antibacterial, antioxidant, anti-inflammatory, adhesive, and hemostatic functions. Furthermore, we propose the challenges and future perspectives of natural hydrogels in practical applications. This review offers a comprehensive overview of the current state and potential future advancements in natural hydrogel dressings for wound care, highlighting their critical role in addressing complex and hard-to-heal wounds.
Natural hydrogels have emerged as a pivotal innovation in wound care, offering a unique combination of high absorbency, biocompatibility, and versatility. However, due to the complexity of wound healing, the physiological state of the wound varies dynamically, and the mechanism of natural hydrogels that boost wound healing is still unclear. In this review, we firstly provide a comprehensive introduction to the biological process of wound healing, emphasizing the critical stages and factors affecting healing. This work concludes the composition and properties of natural hydrogels, including collagen, gelatin, hyaluronic acid, chitosan, alginates, cellulose, and fibroin, highlighting their biocompatibility and biodegradability. The focus shifts to the various crosslinking strategies employed to enhance the structural integrity and functionality of natural hydrogels. This review further investigates the biological effects of natural hydrogels in wound healing, detailing their antibacterial, antioxidant, anti-inflammatory, adhesive, and hemostatic functions. Furthermore, we propose the challenges and future perspectives of natural hydrogels in practical applications. This review offers a comprehensive overview of the current state and potential future advancements in natural hydrogel dressings for wound care, highlighting their critical role in addressing complex and hard-to-heal wounds.
2024, 35(10): 109492
doi: 10.1016/j.cclet.2024.109492
摘要:
Amorphous alloys, with unique atomic structures and metastable nature, are treated as superior candidates for environmental wastewater remediation due to their superior catalytic capabilities. Given the strong demand for environmental protection, the field of amorphous alloys in wastewater treatment has great development prospects, and numerous research results have been published in recent years. As a promising catalyst, it was demonstrated that amorphous alloys could exhibit many excellent properties in wastewater treatment, such as high catalytic efficiency, easily adjustable parameters and reliable sustainability. This paper aims to summarize recent research trends regarding amorphous alloys in the field of catalysis, focusing on the preparation methods, physical performance, catalytic mechanisms and environmental application. Meanwhile, this review also investigates the challenges encountered and future perspectives of amorphous alloys, offering new research opportunities to enlarge their applicability spectra.
Amorphous alloys, with unique atomic structures and metastable nature, are treated as superior candidates for environmental wastewater remediation due to their superior catalytic capabilities. Given the strong demand for environmental protection, the field of amorphous alloys in wastewater treatment has great development prospects, and numerous research results have been published in recent years. As a promising catalyst, it was demonstrated that amorphous alloys could exhibit many excellent properties in wastewater treatment, such as high catalytic efficiency, easily adjustable parameters and reliable sustainability. This paper aims to summarize recent research trends regarding amorphous alloys in the field of catalysis, focusing on the preparation methods, physical performance, catalytic mechanisms and environmental application. Meanwhile, this review also investigates the challenges encountered and future perspectives of amorphous alloys, offering new research opportunities to enlarge their applicability spectra.
2024, 35(10): 109503
doi: 10.1016/j.cclet.2024.109503
摘要:
Air pollution, including airborne pathogens and particulate matter (PM), has become a prominent issue affecting human health and safety. Conventional air filtration materials do not meet the requirements for efficient PM capture or do not instantly kill pathogens, leading to increased risk of direct/indirect contact transmission and infection due to the accumulation of pathogens during filtration. Electrospun nanofibrous membranes have emerged as a promising platform due to their rich porous structure, finer fiber diameters, good internal connectivity, and the ability to easily incorporate active chemicals for antimicrobial function. In this review, antimicrobial mechanisms of nanofibrous membranes for air filtration and PM capture mechanisms of nanofibers were firstly investigated, and various types of electrospun nanofibrous membranes with different antimicrobial agents for efficient air filtration were described in detail, including organic antimicrobial agents, inorganic antimicrobial agents and metal−organic frameworks. We hope this work could provide a better practical insight for designing novel electrospun nanofibrous membranes with antimicrobial efficacy for efficient air filtration.
Air pollution, including airborne pathogens and particulate matter (PM), has become a prominent issue affecting human health and safety. Conventional air filtration materials do not meet the requirements for efficient PM capture or do not instantly kill pathogens, leading to increased risk of direct/indirect contact transmission and infection due to the accumulation of pathogens during filtration. Electrospun nanofibrous membranes have emerged as a promising platform due to their rich porous structure, finer fiber diameters, good internal connectivity, and the ability to easily incorporate active chemicals for antimicrobial function. In this review, antimicrobial mechanisms of nanofibrous membranes for air filtration and PM capture mechanisms of nanofibers were firstly investigated, and various types of electrospun nanofibrous membranes with different antimicrobial agents for efficient air filtration were described in detail, including organic antimicrobial agents, inorganic antimicrobial agents and metal−organic frameworks. We hope this work could provide a better practical insight for designing novel electrospun nanofibrous membranes with antimicrobial efficacy for efficient air filtration.
2024, 35(10): 109511
doi: 10.1016/j.cclet.2024.109511
摘要:
The application of nanotechnologies in formulation has significantly promoted the development of modern medical and pharmacological science, especially for nanoparticle-based drug delivery, bioimaging, and theranostics. The advancement of engineering particle design and fabrication is largely supported by a better understanding of how their apparent characteristics (e.g., size and size distribution, surface morphology, colloidal stability, chemical composition) influence their in vivo biological performance, which raises an urgent need for practical nanoformulation methods. Based on turbulent flow mixing and the self-assembly of molecules in fluids, flash technologies emerged as effective bottom-up fabrication strategies for effective nanoformulation. Among the flash technology family, flash nanocomplexation (FNC) is considered a novel and promising candidate that can promote and optimize formulation processes in a precise spatiotemporal manner, thus obtaining excellent fabrication efficiency, reproducibility and expandability. This review presents an overview of recent advances in fabricating drug-delivery nanoparticles using FNC platforms. Firstly, brief introductions to the basic principles of FNC technology were carried out, followed by descriptions of turbulent microvolume mixers that have significantly promoted the efficiency of FNC-based fabrications. Applications of real formulation cases were then categorized according to the self-assembly-driven interactions (including electrostatic interaction, coordination interaction, hydrogen bonding and hydrophobic interaction) and discussed to reveal the progressiveness of fabricating nanoparticles and discuss how its flexibility will provide advances and replenish the philosophy of nanomedicine formulation. In the end, the commercial potential, current limitations, and prospects of FNC technology for nanoformulation will be summarized and discussed.
The application of nanotechnologies in formulation has significantly promoted the development of modern medical and pharmacological science, especially for nanoparticle-based drug delivery, bioimaging, and theranostics. The advancement of engineering particle design and fabrication is largely supported by a better understanding of how their apparent characteristics (e.g., size and size distribution, surface morphology, colloidal stability, chemical composition) influence their in vivo biological performance, which raises an urgent need for practical nanoformulation methods. Based on turbulent flow mixing and the self-assembly of molecules in fluids, flash technologies emerged as effective bottom-up fabrication strategies for effective nanoformulation. Among the flash technology family, flash nanocomplexation (FNC) is considered a novel and promising candidate that can promote and optimize formulation processes in a precise spatiotemporal manner, thus obtaining excellent fabrication efficiency, reproducibility and expandability. This review presents an overview of recent advances in fabricating drug-delivery nanoparticles using FNC platforms. Firstly, brief introductions to the basic principles of FNC technology were carried out, followed by descriptions of turbulent microvolume mixers that have significantly promoted the efficiency of FNC-based fabrications. Applications of real formulation cases were then categorized according to the self-assembly-driven interactions (including electrostatic interaction, coordination interaction, hydrogen bonding and hydrophobic interaction) and discussed to reveal the progressiveness of fabricating nanoparticles and discuss how its flexibility will provide advances and replenish the philosophy of nanomedicine formulation. In the end, the commercial potential, current limitations, and prospects of FNC technology for nanoformulation will be summarized and discussed.
2024, 35(10): 109527
doi: 10.1016/j.cclet.2024.109527
摘要:
Photothermal hydrogels with excellent photo responsive and thermal conversion ability had attract a great deal of attention from researchers to explore their biological applications. This review aimed to provide a comprehensive overview of photothermal hydrogels, focusing on their design principles, various functions, and biological applications. Firstly, several classifications of photothermal hydrogels were given according to different photothermal agents (metal, metal sulfide/oxide, MXene, carbon-based, dyes, black phosphorus, and polymer) utilized in hydrogel construction. The photothermal conversion mechanism and hydrogel fabrication were also discussed in detail. Then, the relationship between their photothermal conversion property and functions, together with some indispensable property such as biocompatibility, adhesion, mechanical properties, and self-healing properties was fully introduced. Furthermore, the applications of photothermal hydrogels in the biomedical (i.e., wound healing, antibacterial treatments, controlled drug release, bone repair, and tumor treatment) was summarized. Finally, the future opportunities and challenges of photothermal hydrogels were proposed. We believe that this review could provide a new horizon for further preparation of photothermal hydrogels, and could promote their applications in wider fields.
Photothermal hydrogels with excellent photo responsive and thermal conversion ability had attract a great deal of attention from researchers to explore their biological applications. This review aimed to provide a comprehensive overview of photothermal hydrogels, focusing on their design principles, various functions, and biological applications. Firstly, several classifications of photothermal hydrogels were given according to different photothermal agents (metal, metal sulfide/oxide, MXene, carbon-based, dyes, black phosphorus, and polymer) utilized in hydrogel construction. The photothermal conversion mechanism and hydrogel fabrication were also discussed in detail. Then, the relationship between their photothermal conversion property and functions, together with some indispensable property such as biocompatibility, adhesion, mechanical properties, and self-healing properties was fully introduced. Furthermore, the applications of photothermal hydrogels in the biomedical (i.e., wound healing, antibacterial treatments, controlled drug release, bone repair, and tumor treatment) was summarized. Finally, the future opportunities and challenges of photothermal hydrogels were proposed. We believe that this review could provide a new horizon for further preparation of photothermal hydrogels, and could promote their applications in wider fields.
2024, 35(10): 109541
doi: 10.1016/j.cclet.2024.109541
摘要:
Antibiotics, as widely used antibacterial drug, exist in various environmental media. Antibiotic residues can affect biological metabolism and lead to bacterial resistance and the formation of antibiotic-resistance genes, posing a threat to human health and ecological safety. Establishing efficient detection methods for antibiotics and antibiotic-resistance genes has great environmental significance. Fluorescence detection methods, due to their fast response, high sensitivity and specificity, and low-cost, are widely used in chemical and biological sensing. This review first summarizes the pre-treatment methods for different types of environmental samples, and then focuses on the recent advances of fluorescence methods for the detection of antibiotics and antibiotic-resistance genes. Finally, main challenges and future research directions of fluorescence methods for antibiotic and antibiotic-resistance genes detection are discussed. This review highlights the promising prospect of fluorescence methods in-situ detection and monitoring of antibiotics and antibiotic-resistance genes, and provides guidance for the construction of overall risk assessment system of environmental media.
Antibiotics, as widely used antibacterial drug, exist in various environmental media. Antibiotic residues can affect biological metabolism and lead to bacterial resistance and the formation of antibiotic-resistance genes, posing a threat to human health and ecological safety. Establishing efficient detection methods for antibiotics and antibiotic-resistance genes has great environmental significance. Fluorescence detection methods, due to their fast response, high sensitivity and specificity, and low-cost, are widely used in chemical and biological sensing. This review first summarizes the pre-treatment methods for different types of environmental samples, and then focuses on the recent advances of fluorescence methods for the detection of antibiotics and antibiotic-resistance genes. Finally, main challenges and future research directions of fluorescence methods for antibiotic and antibiotic-resistance genes detection are discussed. This review highlights the promising prospect of fluorescence methods in-situ detection and monitoring of antibiotics and antibiotic-resistance genes, and provides guidance for the construction of overall risk assessment system of environmental media.
2024, 35(10): 109558
doi: 10.1016/j.cclet.2024.109558
摘要:
DNA-based hydrogels are exceptional materials for biological applications because of their numerous advantages such as biodegradability, biocompatibility, hydrophilicity, super absorbency, porosity, and swelling. Among these advantages, the ability of DNA-based hydrogels to respond to specific physical and chemical triggers and undergo reversible phase transitions has garnered significant attention in the fields of disease diagnosis (biosensors) and treatment (drug delivery). This article focuses on the recent advancements in the research of DNA-based hydrogels and discusses the different types of these hydrogels, the synthetic methods, their unique properties, and their applications in biosensors and drug delivery. The types of DNA hydrogels are categorized based on their building blocks, and the process of synthesis as well as the unique characteristics of DNA-based hydrogels are described. Then, DNA-based responsive hydrogels utilized as intelligent materials for the development of biosensors are reviewed. Furthermore, this article also presents the current status of DNA-based responsive hydrogels in drug delivery for cancer treatment, wound healing, and other therapeutic applications. Ultimately, this paper discusses the current challenges in expanding the practical application of DNA-based hydrogels.
DNA-based hydrogels are exceptional materials for biological applications because of their numerous advantages such as biodegradability, biocompatibility, hydrophilicity, super absorbency, porosity, and swelling. Among these advantages, the ability of DNA-based hydrogels to respond to specific physical and chemical triggers and undergo reversible phase transitions has garnered significant attention in the fields of disease diagnosis (biosensors) and treatment (drug delivery). This article focuses on the recent advancements in the research of DNA-based hydrogels and discusses the different types of these hydrogels, the synthetic methods, their unique properties, and their applications in biosensors and drug delivery. The types of DNA hydrogels are categorized based on their building blocks, and the process of synthesis as well as the unique characteristics of DNA-based hydrogels are described. Then, DNA-based responsive hydrogels utilized as intelligent materials for the development of biosensors are reviewed. Furthermore, this article also presents the current status of DNA-based responsive hydrogels in drug delivery for cancer treatment, wound healing, and other therapeutic applications. Ultimately, this paper discusses the current challenges in expanding the practical application of DNA-based hydrogels.
2024, 35(10): 109579
doi: 10.1016/j.cclet.2024.109579
摘要:
Reactive oxygen species (ROSs) in Fenton process are of great importance in treating contaminants in wastewater. It is crucial to understand their chemical properties, formation, and reaction mechanisms with contaminants. This review summarizes the reactive oxygen species in Fenton process, including hydroxyl radical (•OH), superoxide radical (O2•−), singlet oxygen (1O2), hydroperoxyl radical (HO2•), and high-valent iron. •OH shows a trend to react with chemistry groups with abundant electrons through H-atom abstraction, radical adduct formation and single electron transfer. Electron transfer is discovered to be an important pathway when 1O2 degrades organic pollutants. Ring-opening and β-scission are proposed to be the possible ways of 1O2 to certain contaminants. Proton abstraction, nucleophilic substitution, and single electron transfer are proposed to explain how O2•− degrade pollutants. As the conjugated acid of O2•−, radical adduct formation and H-atom abstraction are reported for the reaction mechanisms of hydroperoxyl radical. High-valent iron in Fenton, namely Fe(Ⅳ), reacts with certain pollutants via single- or two-electron transfer. This review is important for researchers to understand the ROSs produced in Fenton and how they react with pollutants.
Reactive oxygen species (ROSs) in Fenton process are of great importance in treating contaminants in wastewater. It is crucial to understand their chemical properties, formation, and reaction mechanisms with contaminants. This review summarizes the reactive oxygen species in Fenton process, including hydroxyl radical (•OH), superoxide radical (O2•−), singlet oxygen (1O2), hydroperoxyl radical (HO2•), and high-valent iron. •OH shows a trend to react with chemistry groups with abundant electrons through H-atom abstraction, radical adduct formation and single electron transfer. Electron transfer is discovered to be an important pathway when 1O2 degrades organic pollutants. Ring-opening and β-scission are proposed to be the possible ways of 1O2 to certain contaminants. Proton abstraction, nucleophilic substitution, and single electron transfer are proposed to explain how O2•− degrade pollutants. As the conjugated acid of O2•−, radical adduct formation and H-atom abstraction are reported for the reaction mechanisms of hydroperoxyl radical. High-valent iron in Fenton, namely Fe(Ⅳ), reacts with certain pollutants via single- or two-electron transfer. This review is important for researchers to understand the ROSs produced in Fenton and how they react with pollutants.
2024, 35(10): 109727
doi: 10.1016/j.cclet.2024.109727
摘要:
Sonodynamic therapy (SDT) exhibits promising clinical applications in cancer treatment owing to its advantages, including ultrasonic cavitation effect, mechanical effect, and deep tissue penetration. Titanium dioxide (TiO2) nanomaterials, recognized as excellent sonosensitizers, have been extensively studied in cancer SDT. This review first outlines the mechanism of TiO2-based SDT, then systematically discusses the regulation of TiO2 sonosensitivity, covering aspects such as morphology, particle size, element doping, defect engineering, heterojunction structure, and interactions with the tumor microenvironment. Furthermore, the review generalizes ultrasound-responsive TiO2-based therapeutic modalities for tumor treatment, including SDT, SDT combined with chemotherapy, chemodynamic therapy, photothermal therapy, immunotherapy, and treatment visualization. Finally, the review navigates the ongoing challenges and prospects in TiO2-based cancer SDT.
Sonodynamic therapy (SDT) exhibits promising clinical applications in cancer treatment owing to its advantages, including ultrasonic cavitation effect, mechanical effect, and deep tissue penetration. Titanium dioxide (TiO2) nanomaterials, recognized as excellent sonosensitizers, have been extensively studied in cancer SDT. This review first outlines the mechanism of TiO2-based SDT, then systematically discusses the regulation of TiO2 sonosensitivity, covering aspects such as morphology, particle size, element doping, defect engineering, heterojunction structure, and interactions with the tumor microenvironment. Furthermore, the review generalizes ultrasound-responsive TiO2-based therapeutic modalities for tumor treatment, including SDT, SDT combined with chemotherapy, chemodynamic therapy, photothermal therapy, immunotherapy, and treatment visualization. Finally, the review navigates the ongoing challenges and prospects in TiO2-based cancer SDT.
2024, 35(10): 109810
doi: 10.1016/j.cclet.2024.109810
摘要:
Bioelectronics have gained substantial research attention owing to their potential applications in health monitoring and diagnose, and greatly promoted the development of biomedicine. Recently, poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) hydrogels have arose as a promising candidate for the next-generation bioelectronic interface due to its high-conductivity, versatility, flexibility and biocompatibility. In this review, we highlight the recent advances of PEDOT:PSS hydrogels, including the gelation methods and modification strategies, and summarize their wide applications in different type of sensors and tissue engineering in detail. We expect that this work will provide valuable information regarding the functionalizations and applications of PEDOT:PSS hydrogels.
Bioelectronics have gained substantial research attention owing to their potential applications in health monitoring and diagnose, and greatly promoted the development of biomedicine. Recently, poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) hydrogels have arose as a promising candidate for the next-generation bioelectronic interface due to its high-conductivity, versatility, flexibility and biocompatibility. In this review, we highlight the recent advances of PEDOT:PSS hydrogels, including the gelation methods and modification strategies, and summarize their wide applications in different type of sensors and tissue engineering in detail. We expect that this work will provide valuable information regarding the functionalizations and applications of PEDOT:PSS hydrogels.
2024, 35(10): 109550
doi: 10.1016/j.cclet.2024.109550
摘要:
2024, 35(10): 110026
doi: 10.1016/j.cclet.2024.110026
摘要:
2024, 35(10): 110060
doi: 10.1016/j.cclet.2024.110060
摘要:
2024, 35(10): 110061
doi: 10.1016/j.cclet.2024.110061
摘要:
2024, 35(10): 110115
doi: 10.1016/j.cclet.2024.110115
摘要:
2024, 35(8): 109030
doi: 10.1016/j.cclet.2023.109030
摘要:
Under the guidance of the approach which integrates molecular networking, MolNetEnhancer and Network Annotation Propagation (NAP), daphnaltaicanoids A and B (1 and 2) with unprecedented 9-oxa-tetracyclo[6.6.1.02,6.08,13]pentadecane and tetracyclo[5.3.0.12,5.24,11]tridecane central frameworks were isolated from Daphne altaica Pall., representing two types of unparalleled meroterpenoid cores. Their structures were elucidated by extensive spectroscopic analysis, nuclear magnetic resonance (NMR) calculations, DP4+ analysis and electronic circular dichroism (ECD) calculations. The plausible biosynthetic pathways for 1 and 2 were postulated. Biologically, 2 exerted potent neuroprotective activities which were superior to trolox at 12.5 and 25 µmol/L. Moreover, 1 and 2 exhibited more noticeable acetylcholinesterase inhibitory activities than donepezil. Molecular docking simulations were performed to explore the intermolecular interaction of compounds 1 and 2 with acetylcholinesterase. The bioactivity evaluation results highlight the prospects of 1 and 2 as a novel category of neurological agents.
Under the guidance of the approach which integrates molecular networking, MolNetEnhancer and Network Annotation Propagation (NAP), daphnaltaicanoids A and B (1 and 2) with unprecedented 9-oxa-tetracyclo[6.6.1.02,6.08,13]pentadecane and tetracyclo[5.3.0.12,5.24,11]tridecane central frameworks were isolated from Daphne altaica Pall., representing two types of unparalleled meroterpenoid cores. Their structures were elucidated by extensive spectroscopic analysis, nuclear magnetic resonance (NMR) calculations, DP4+ analysis and electronic circular dichroism (ECD) calculations. The plausible biosynthetic pathways for 1 and 2 were postulated. Biologically, 2 exerted potent neuroprotective activities which were superior to trolox at 12.5 and 25 µmol/L. Moreover, 1 and 2 exhibited more noticeable acetylcholinesterase inhibitory activities than donepezil. Molecular docking simulations were performed to explore the intermolecular interaction of compounds 1 and 2 with acetylcholinesterase. The bioactivity evaluation results highlight the prospects of 1 and 2 as a novel category of neurological agents.
2024, 35(8): 109035
doi: 10.1016/j.cclet.2023.109035
摘要:
Citrinsorbicillin A (1), a novel homotrimeric sorbicillinoid, along with two new monomers citrinsorbicillins B (2) and C (3), were isolated from the Coptis chinensis endophyte Trichoderma citrinoviride HT-9 by liquid chromatograph mass spectrometer (LC-MS)-guided strategy. 1 was the first trimeric-example from terrestrial fungi, which possessed a unique carbon skeleton with two bicyclo[2.2.2]octanedione ring connected through an enolated carbon forming by [4 + 2] cycloaddition. Their structures were elucidated by spectroscopic analysis and X-ray diffraction. 1 exhibited moderate cytotoxicity against human colon cancer HT29 cells, and it induced significant cell cycle arrest by reducing the protein expression of cyclin D1.
Citrinsorbicillin A (1), a novel homotrimeric sorbicillinoid, along with two new monomers citrinsorbicillins B (2) and C (3), were isolated from the Coptis chinensis endophyte Trichoderma citrinoviride HT-9 by liquid chromatograph mass spectrometer (LC-MS)-guided strategy. 1 was the first trimeric-example from terrestrial fungi, which possessed a unique carbon skeleton with two bicyclo[2.2.2]octanedione ring connected through an enolated carbon forming by [4 + 2] cycloaddition. Their structures were elucidated by spectroscopic analysis and X-ray diffraction. 1 exhibited moderate cytotoxicity against human colon cancer HT29 cells, and it induced significant cell cycle arrest by reducing the protein expression of cyclin D1.
2024, 35(8): 109048
doi: 10.1016/j.cclet.2023.109048
摘要:
We report here the synthesis and characterization of two new members of the M2E12 family of endohedral Zintl clusters, [Fe2Sn4Bi8]3– and [Cr2Sb12]3–, both of which contain open-shell metal dimers encapsulated inside a triple-decker cluster of main-group atoms. The 75-electron [Fe2Sn4Bi8]3– cluster has a D4h-symmetric structure, while [Cr2Sb12]3–, despite having the same 75-electron count, is strongly distorted to a geometry that resembles a CrSb8 crown capped by a CrSb4 unit. The structural differences between the two are driven by the increasing availability of 3d electron density in the earlier transition metal, which leads, ultimately, to different electronic configurations in the two clusters. The trends precisely mirror those observed in the ME10 and ME12 families containing a single transition metal ion.
We report here the synthesis and characterization of two new members of the M2E12 family of endohedral Zintl clusters, [Fe2Sn4Bi8]3– and [Cr2Sb12]3–, both of which contain open-shell metal dimers encapsulated inside a triple-decker cluster of main-group atoms. The 75-electron [Fe2Sn4Bi8]3– cluster has a D4h-symmetric structure, while [Cr2Sb12]3–, despite having the same 75-electron count, is strongly distorted to a geometry that resembles a CrSb8 crown capped by a CrSb4 unit. The structural differences between the two are driven by the increasing availability of 3d electron density in the earlier transition metal, which leads, ultimately, to different electronic configurations in the two clusters. The trends precisely mirror those observed in the ME10 and ME12 families containing a single transition metal ion.
2024, 35(8): 109052
doi: 10.1016/j.cclet.2023.109052
摘要:
Electron-deficient viologens are widely used as ligands or structure-directing agents (SDAs) to synthesize crystalline X-ray induced photochromic materials. Here, a new rational strategy of anion-directed folding a flexible cation (H2imb)2+ ((H2imb)2+ = di-protonated 2,3-bis(imidazolin-2-yl)-2,3-dimethylbutane) has been developed. Electron-donating Cl− and (ZnCl4)2− are used to direct folding a flexible electron-deficient (H2imb)2+ cation. Three complexes (H2imb)(NO3)2 (1), (H2imb)Cl2·H2O (2), and (H2imb)ZnCl4 (3) have been synthesized in which (H2imb)2+ crystallize in an anti-conformation, 88.8°-gauche, and 51.8°-gauche, respectively. In contrary to X-ray silent complex 1, X-ray induced photochromism has been achieved in both complex 2 and 3. An intermolecular charge-transfer mechanism has been elucidated and the anion directed folding of (H2imb)2+ has been validated to be critical to yield colored long-lived charge-separated states.
Electron-deficient viologens are widely used as ligands or structure-directing agents (SDAs) to synthesize crystalline X-ray induced photochromic materials. Here, a new rational strategy of anion-directed folding a flexible cation (H2imb)2+ ((H2imb)2+ = di-protonated 2,3-bis(imidazolin-2-yl)-2,3-dimethylbutane) has been developed. Electron-donating Cl− and (ZnCl4)2− are used to direct folding a flexible electron-deficient (H2imb)2+ cation. Three complexes (H2imb)(NO3)2 (1), (H2imb)Cl2·H2O (2), and (H2imb)ZnCl4 (3) have been synthesized in which (H2imb)2+ crystallize in an anti-conformation, 88.8°-gauche, and 51.8°-gauche, respectively. In contrary to X-ray silent complex 1, X-ray induced photochromism has been achieved in both complex 2 and 3. An intermolecular charge-transfer mechanism has been elucidated and the anion directed folding of (H2imb)2+ has been validated to be critical to yield colored long-lived charge-separated states.
2024, 35(8): 109061
doi: 10.1016/j.cclet.2023.109061
摘要:
The selective oxidative esterification of aldehydes with alcohols to the corresponding esters has been one of the hot spots in scientific research and industrial synthesis. However, the application of precious metal catalytic systems is limited by their complicated synthetic steps and high cost. Thus a highly efficient, green, recyclable selective synthesis method of esters catalyzed by polyoxovanadate (POV)-based molecular catalysts has been developed in this paper. The results show that supramolecular interaction between POV and 1,3-dibenzylimidazolium bromide (Act2Im) can efficiently convert alcohols and aldehydes to the corresponding esters in high yield under much milder conditions. Mechanistic insight is also provided based on the control experiments, single crystal X-ray diffraction and cyclic voltammetry studies.
The selective oxidative esterification of aldehydes with alcohols to the corresponding esters has been one of the hot spots in scientific research and industrial synthesis. However, the application of precious metal catalytic systems is limited by their complicated synthetic steps and high cost. Thus a highly efficient, green, recyclable selective synthesis method of esters catalyzed by polyoxovanadate (POV)-based molecular catalysts has been developed in this paper. The results show that supramolecular interaction between POV and 1,3-dibenzylimidazolium bromide (Act2Im) can efficiently convert alcohols and aldehydes to the corresponding esters in high yield under much milder conditions. Mechanistic insight is also provided based on the control experiments, single crystal X-ray diffraction and cyclic voltammetry studies.
2024, 35(8): 109063
doi: 10.1016/j.cclet.2023.109063
摘要:
The development of circularly polarized luminescence (CPL) materials with high performance is significantly important. Herein, we develop a facial strategy for fabricating a CPL-active system by employing an achiral luminescent metal-organic cage (MOC) and chiral boron dipyrromethene (BODIPY) molecules. CPL is achieved by taking advantage of the radiative energy transfer process, in which BODIPY molecules act as energy acceptors and MOCs act as donors. The CPL performance (maximum luminescence dissymmetry factor up to ± 1.5 × 10−3) can be tuned by adjusting the ratio between MOCs and BODIPY. White-light emission with the CPL feature is obtained by using a ternary system including MOC, chiral BODIPY, and Rhodamine B. The present work provides a facile and universal strategy to construct a CPL-active system by integrating achiral luminophores and chiral molecules.
The development of circularly polarized luminescence (CPL) materials with high performance is significantly important. Herein, we develop a facial strategy for fabricating a CPL-active system by employing an achiral luminescent metal-organic cage (MOC) and chiral boron dipyrromethene (BODIPY) molecules. CPL is achieved by taking advantage of the radiative energy transfer process, in which BODIPY molecules act as energy acceptors and MOCs act as donors. The CPL performance (maximum luminescence dissymmetry factor up to ± 1.5 × 10−3) can be tuned by adjusting the ratio between MOCs and BODIPY. White-light emission with the CPL feature is obtained by using a ternary system including MOC, chiral BODIPY, and Rhodamine B. The present work provides a facile and universal strategy to construct a CPL-active system by integrating achiral luminophores and chiral molecules.
2024, 35(8): 109082
doi: 10.1016/j.cclet.2023.109082
摘要:
Concise chemistry leads to a family of heptanuclear CoⅡ-clusters, [Co7(N3)12(CH3CN)12] [Y2(NO3)4(piv)4]·2CH3CN (DC1) (pivH = pivalic acid), [Co7(N3)12(CH3CN)10(NO3)0.4 (Cl)1.6]·4CH3CN (DC2) and [Co7(N3)12(CH3CN)10(NO3)2]·4CH3CN (DC3), in which the metal ions are exclusively bridged by end-on azido ligands to stabilize a beautiful disk-like topology. The resulting clusters exhibit interesting structural transformations and thermodynamically-distinct steady states verified by theoretical calculations. Magnetic studies reveal the first observation of zero-field SMM behaviour in disk-like heptanuclear CoⅡ complexes.
Concise chemistry leads to a family of heptanuclear CoⅡ-clusters, [Co7(N3)12(CH3CN)12] [Y2(NO3)4(piv)4]·2CH3CN (DC1) (pivH = pivalic acid), [Co7(N3)12(CH3CN)10(NO3)0.4 (Cl)1.6]·4CH3CN (DC2) and [Co7(N3)12(CH3CN)10(NO3)2]·4CH3CN (DC3), in which the metal ions are exclusively bridged by end-on azido ligands to stabilize a beautiful disk-like topology. The resulting clusters exhibit interesting structural transformations and thermodynamically-distinct steady states verified by theoretical calculations. Magnetic studies reveal the first observation of zero-field SMM behaviour in disk-like heptanuclear CoⅡ complexes.
2024, 35(8): 109083
doi: 10.1016/j.cclet.2023.109083
摘要:
Palladium-based alloy catalysts have been employed as one of the potential candidates for oxygen reduction reaction (ORR), but the dissolution of transition metal hinders their application. Herein, structure ordered PdTe intermetallic with Pd shell (o-PdTe@Pd) are synthesized via an electrochemical etching driven surface reconstruction strategy. The surface reconstruction could tune the electronic structure, weaken the adsorption energy of reaction intermediates on o-PdTe@Pd, resulting in enhanced electrocatalytic activity for ORR. The mass activity of o-PdTe@Pd is about 3.3 and 2.7 times higher than that of Pd/C in acid and alkaline, respectively. Besides, the half-potentials for ORR decay only about 44 mV and 12 mV after 30 k cycles accelerated durability test in acid and alkaline media, respectively. The enhanced durability originates from the resistance of Te atoms dissolve in the ordered PdTe intermetallic core and the core-shell structure. When assembled in a Zn-air battery, o-PdTe@Pd electrode delivers a higher specific capacity (794 mAh/g) and better cycling stability than Pt/C.
Palladium-based alloy catalysts have been employed as one of the potential candidates for oxygen reduction reaction (ORR), but the dissolution of transition metal hinders their application. Herein, structure ordered PdTe intermetallic with Pd shell (o-PdTe@Pd) are synthesized via an electrochemical etching driven surface reconstruction strategy. The surface reconstruction could tune the electronic structure, weaken the adsorption energy of reaction intermediates on o-PdTe@Pd, resulting in enhanced electrocatalytic activity for ORR. The mass activity of o-PdTe@Pd is about 3.3 and 2.7 times higher than that of Pd/C in acid and alkaline, respectively. Besides, the half-potentials for ORR decay only about 44 mV and 12 mV after 30 k cycles accelerated durability test in acid and alkaline media, respectively. The enhanced durability originates from the resistance of Te atoms dissolve in the ordered PdTe intermetallic core and the core-shell structure. When assembled in a Zn-air battery, o-PdTe@Pd electrode delivers a higher specific capacity (794 mAh/g) and better cycling stability than Pt/C.
2024, 35(8): 109085
doi: 10.1016/j.cclet.2023.109085
摘要:
Recently, organic-inorganic hybrid metal halides (HMHs) have attracted extensive attention as promising multifunctional materials by virtue of their structural diversity and tunable photophysical properties. However, it remains a challenge to design HMHs with specific functions on demand. Herein, by introducing R/S-methylbenzylamine (R/S-MBA) and doping Sb3+, we have achieved both second harmonic generation (SHG) and circularly polarized luminescence (CPL) properties in lead-free indium halides. The introduction of chiral organic cations can break the symmetry and induce the indium halides to crystallize in the chiral space group. The Sb3+ with ns2 electronic configuration can serve as the dopants to promote the formation of self-trapped excitons, so as to activate highly efficient luminescence. As a result, the as-prepared Sb3+ doped (R/S-MBA)3InCl6 show not only SHG responses but also CPL signals with luminescence dissymmetry factor of −5.3 × 10−3 and 4.7 × 10−3. This work provides a new inspiration for the exploitation of chiral multifunctional materials.
Recently, organic-inorganic hybrid metal halides (HMHs) have attracted extensive attention as promising multifunctional materials by virtue of their structural diversity and tunable photophysical properties. However, it remains a challenge to design HMHs with specific functions on demand. Herein, by introducing R/S-methylbenzylamine (R/S-MBA) and doping Sb3+, we have achieved both second harmonic generation (SHG) and circularly polarized luminescence (CPL) properties in lead-free indium halides. The introduction of chiral organic cations can break the symmetry and induce the indium halides to crystallize in the chiral space group. The Sb3+ with ns2 electronic configuration can serve as the dopants to promote the formation of self-trapped excitons, so as to activate highly efficient luminescence. As a result, the as-prepared Sb3+ doped (R/S-MBA)3InCl6 show not only SHG responses but also CPL signals with luminescence dissymmetry factor of −5.3 × 10−3 and 4.7 × 10−3. This work provides a new inspiration for the exploitation of chiral multifunctional materials.
Tailored ionically conductive graphene oxide-encased metal ions for ultrasensitive cadaverine sensor
2024, 35(8): 109102
doi: 10.1016/j.cclet.2023.109102
摘要:
Intelligent chemical sensors have been extensively used in food safety and environmental assessment, while limited sensitivity and homogeneity bring about huge obstacles to their practical application. Herein, novel ionically conductive sensitive materials were elaborately designed based on metal ion decorated graphene oxide (GO) via a facile and general in-situ spin-coating strategy, where the abundant functional groups (-OH and -COOH) of GO layer could provide natural binding sites for various bivalent metal cations (such as Cu2+, Ni2+, Zn2+, Co2+, and Mg2+) through coordination and electrostatic interaction. The intercalated metal cations on the layered GO nanosheets can be regarded as charge carriers and complexation with targeted gas (cadaverine, Cad), which is a typical metabolites production and food degradants. By contrast, the designed GO@Cu(Ⅱ) sensor exhibited the optimal sensing performance toward Cad molecules at room temperature, including ultra-low detection limit (ca. 3 nL), excellent sensitivity, and rapid low concentration detection rate (only 16 s). Interestingly, the sensor exhibited an irreversible and specific response toward Cad, while it showed a transient and reversible response to other interfering gases, implying its outstanding selectivity. In addition, the GO@Cu(Ⅱ) sensor enabled real-time monitoring of the decay progression of cheese, and it exhibited great potential for large-scale production via its excellent homogeneity. It provides an efficient approach to tailoring intelligent chemical sensors for real-time food safety monitoring and human health warning.
Intelligent chemical sensors have been extensively used in food safety and environmental assessment, while limited sensitivity and homogeneity bring about huge obstacles to their practical application. Herein, novel ionically conductive sensitive materials were elaborately designed based on metal ion decorated graphene oxide (GO) via a facile and general in-situ spin-coating strategy, where the abundant functional groups (-OH and -COOH) of GO layer could provide natural binding sites for various bivalent metal cations (such as Cu2+, Ni2+, Zn2+, Co2+, and Mg2+) through coordination and electrostatic interaction. The intercalated metal cations on the layered GO nanosheets can be regarded as charge carriers and complexation with targeted gas (cadaverine, Cad), which is a typical metabolites production and food degradants. By contrast, the designed GO@Cu(Ⅱ) sensor exhibited the optimal sensing performance toward Cad molecules at room temperature, including ultra-low detection limit (ca. 3 nL), excellent sensitivity, and rapid low concentration detection rate (only 16 s). Interestingly, the sensor exhibited an irreversible and specific response toward Cad, while it showed a transient and reversible response to other interfering gases, implying its outstanding selectivity. In addition, the GO@Cu(Ⅱ) sensor enabled real-time monitoring of the decay progression of cheese, and it exhibited great potential for large-scale production via its excellent homogeneity. It provides an efficient approach to tailoring intelligent chemical sensors for real-time food safety monitoring and human health warning.
2024, 35(8): 109120
doi: 10.1016/j.cclet.2023.109120
摘要:
Metal-organic frameworks (MOFs) functionalized with open metal sites (OMSs) have received widespread attention in various applications due to their fascinating electronic properties and unique interactions with guest molecules. However, rational tailoring of the coordination environment of metal nodes during the synthesis of MOFs remains a great challenge due to their tendency of saturated coordination with linkers. Herein, we reported the construction of three new MOFs featuring unsaturated Cu(Ⅱ) sites, namely [Cu(HCOO)(pzta)]n (HL-1), {[Cu(PTA)0.5(pzta)(H2O)]·2H2O}n (HL-2) and [Cu(NA)0.5(pzta)]n (HL-3) (Hpzta = 3-pyrazinyl-1,2,4-triazole; PTA = terephthalic acid; NA = 1,4-naphthalene dicarboxylic acid), based on the mixed-linker strategy via specific selection of versatile Hpzta ligand and carboxylate ligands. Remarkably, the obtained MOFs exhibited excellent activity and good recyclability for the catalytic reduction of nitroaromatics under mild conditions (25 ℃ and 1 atm). In particular, the complete conversion of 4-nitrophenol (4-NP) took only 30 s on HL-2, reaching a record-high TOF value compared with previously reported metal catalysts. The combined experimental and theoretical studies on HL-2 revealed that the open Cu site with positive-charged nature could improve the adsorption and subsequent electron transport between the substrates, and was responsible for the outstanding performance. This work shined lights on the further enhancement of performance for MOFs through rational OMSs construction.
Metal-organic frameworks (MOFs) functionalized with open metal sites (OMSs) have received widespread attention in various applications due to their fascinating electronic properties and unique interactions with guest molecules. However, rational tailoring of the coordination environment of metal nodes during the synthesis of MOFs remains a great challenge due to their tendency of saturated coordination with linkers. Herein, we reported the construction of three new MOFs featuring unsaturated Cu(Ⅱ) sites, namely [Cu(HCOO)(pzta)]n (HL-1), {[Cu(PTA)0.5(pzta)(H2O)]·2H2O}n (HL-2) and [Cu(NA)0.5(pzta)]n (HL-3) (Hpzta = 3-pyrazinyl-1,2,4-triazole; PTA = terephthalic acid; NA = 1,4-naphthalene dicarboxylic acid), based on the mixed-linker strategy via specific selection of versatile Hpzta ligand and carboxylate ligands. Remarkably, the obtained MOFs exhibited excellent activity and good recyclability for the catalytic reduction of nitroaromatics under mild conditions (25 ℃ and 1 atm). In particular, the complete conversion of 4-nitrophenol (4-NP) took only 30 s on HL-2, reaching a record-high TOF value compared with previously reported metal catalysts. The combined experimental and theoretical studies on HL-2 revealed that the open Cu site with positive-charged nature could improve the adsorption and subsequent electron transport between the substrates, and was responsible for the outstanding performance. This work shined lights on the further enhancement of performance for MOFs through rational OMSs construction.
2024, 35(8): 109122
doi: 10.1016/j.cclet.2023.109122
摘要:
In the development of 3D conductive frameworks for lithium metal anode (LMA), two models have been proposed: top growth model and bottom-up growth model. However, Li tends to accumulate on the top of these 3D frameworks with homogenous lithiophilicity (top growth) and Li dendrite still forms. To address this issue, some researchers have focused on developing 3D frameworks with gradient lithiophilicity, which realized bottom-up growth of Li. Nevertheless, partial Li nucleation sites on the top of these frameworks were missed. Inspired by the two models talked above, this work firstly proposed a novel intermittent lithiophilic model for lithium deposition. To demonstrate the feasibility of this model, a bimetallic metal-organic frameworks derived ZnMn2O4-MnO nanoparticles were grown on carbon cloth for LMA. It can cycle stably under ultra-high current and areal capacity (10 mA/cm2, 10 mAh/cm2). The in-situ optical microscopy (OM) was conducted to observe the Li deposition behavior, no dendrite was found during 80 h in ester-based electrolyte while the pure Li only cycled for 2 h. What is more, it can also be well-coupled with LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode and solid-state electrolyte, which further prove the advantages of the intermittent model for the development of LMAs with high safety and high energy density.
In the development of 3D conductive frameworks for lithium metal anode (LMA), two models have been proposed: top growth model and bottom-up growth model. However, Li tends to accumulate on the top of these 3D frameworks with homogenous lithiophilicity (top growth) and Li dendrite still forms. To address this issue, some researchers have focused on developing 3D frameworks with gradient lithiophilicity, which realized bottom-up growth of Li. Nevertheless, partial Li nucleation sites on the top of these frameworks were missed. Inspired by the two models talked above, this work firstly proposed a novel intermittent lithiophilic model for lithium deposition. To demonstrate the feasibility of this model, a bimetallic metal-organic frameworks derived ZnMn2O4-MnO nanoparticles were grown on carbon cloth for LMA. It can cycle stably under ultra-high current and areal capacity (10 mA/cm2, 10 mAh/cm2). The in-situ optical microscopy (OM) was conducted to observe the Li deposition behavior, no dendrite was found during 80 h in ester-based electrolyte while the pure Li only cycled for 2 h. What is more, it can also be well-coupled with LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode and solid-state electrolyte, which further prove the advantages of the intermittent model for the development of LMAs with high safety and high energy density.
2024, 35(8): 109123
doi: 10.1016/j.cclet.2023.109123
摘要:
Safety and energy density are significant for lithium-ion batteries (LIBs), and the flammable organic electrolyte is one of the most critical causes of the safety problem of LIBs. Although LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode with high capacity can improve the energy density, the interface stability between NCM811 cathode and electrolytes needs to be improved. Herein, we report a multifunctional additive, diethyl(2-(triethoxysilyl)ethyl)phosphonate (DETSP), which can suppress the flammability of the electrolyte and enhance the cycling stability of NCM811 cathode with a capacity retention of 89.9% after 400 cycles at 1 C, while that of the blank electrolyte is merely 61.3%. In addition, DETSP is compatible well with the graphite anode without impairing the electrochemical performances. Significantly, the performance and safety of NCM811/graphite full cells are also improved. Experimental and theoretical results demonstrate that DETSP can scavenge acidic byproducts and is beneficial to form a stable cathode-electrolyte interface (CEI). Accordingly, DETSP can potentially be an effective solution to ameliorating the safety of the commercial electrolyte and improving the stability of high-voltage cathodes.
Safety and energy density are significant for lithium-ion batteries (LIBs), and the flammable organic electrolyte is one of the most critical causes of the safety problem of LIBs. Although LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode with high capacity can improve the energy density, the interface stability between NCM811 cathode and electrolytes needs to be improved. Herein, we report a multifunctional additive, diethyl(2-(triethoxysilyl)ethyl)phosphonate (DETSP), which can suppress the flammability of the electrolyte and enhance the cycling stability of NCM811 cathode with a capacity retention of 89.9% after 400 cycles at 1 C, while that of the blank electrolyte is merely 61.3%. In addition, DETSP is compatible well with the graphite anode without impairing the electrochemical performances. Significantly, the performance and safety of NCM811/graphite full cells are also improved. Experimental and theoretical results demonstrate that DETSP can scavenge acidic byproducts and is beneficial to form a stable cathode-electrolyte interface (CEI). Accordingly, DETSP can potentially be an effective solution to ameliorating the safety of the commercial electrolyte and improving the stability of high-voltage cathodes.
2024, 35(8): 109146
doi: 10.1016/j.cclet.2023.109146
摘要:
Weakly-solvated electrolytes (WSEs) utilizing solvents with weak coordination ability offer advantages for low-potential graphite anode owing to their facile desolvation process and anions-derived inorganic-rich solid electrolyte interphase (SEI) film. However, these electrolytes face challenges in achieving a balance between the weak solvation affinity and high ionic conductivity, as well as between rigid inorganic-rich SEI and flexible SEI for long-term stability. Herein, we introduce 1,3-dioxolane (DOL) and lithium bis(trifluoromethanesulfonyl)-imide (LiTFSI) as functional additives into a WSE based on nonpolar cyclic ether (1,4-dioxane). The well-formulated WSE not only preserves the weakly solvated features and anion-dominated solvation sheath, but also utilizes DOL to contribute organic species for stabilizing the SEI layer. Benefitting from these merits, the optimized electrolyte enables graphite anode with excellent fast-charging performance (210 mAh/g at 5 C) and outstanding cycling stability (600 cycles with a capacity retention of 82.0% at room temperature and 400 cycles with a capacity retention of 80.4% at high temperature). Furthermore, the fabricated LiNi0.8Co0.1Mn0.1O2||graphite full cells demonstrate stable operation for 140 cycles with high capacity retention of 80.3%. This work highlights the potential of tailoring solvation sheath and interphase properties in WSEs for advanced electrolyte design in graphite-based lithium-ion batteries.
Weakly-solvated electrolytes (WSEs) utilizing solvents with weak coordination ability offer advantages for low-potential graphite anode owing to their facile desolvation process and anions-derived inorganic-rich solid electrolyte interphase (SEI) film. However, these electrolytes face challenges in achieving a balance between the weak solvation affinity and high ionic conductivity, as well as between rigid inorganic-rich SEI and flexible SEI for long-term stability. Herein, we introduce 1,3-dioxolane (DOL) and lithium bis(trifluoromethanesulfonyl)-imide (LiTFSI) as functional additives into a WSE based on nonpolar cyclic ether (1,4-dioxane). The well-formulated WSE not only preserves the weakly solvated features and anion-dominated solvation sheath, but also utilizes DOL to contribute organic species for stabilizing the SEI layer. Benefitting from these merits, the optimized electrolyte enables graphite anode with excellent fast-charging performance (210 mAh/g at 5 C) and outstanding cycling stability (600 cycles with a capacity retention of 82.0% at room temperature and 400 cycles with a capacity retention of 80.4% at high temperature). Furthermore, the fabricated LiNi0.8Co0.1Mn0.1O2||graphite full cells demonstrate stable operation for 140 cycles with high capacity retention of 80.3%. This work highlights the potential of tailoring solvation sheath and interphase properties in WSEs for advanced electrolyte design in graphite-based lithium-ion batteries.
2024, 35(8): 109148
doi: 10.1016/j.cclet.2023.109148
摘要:
The widespread application of phenolic substances in the field of food, medicine and industry, is harmful to the environment and human health. Therefore, it is very important to develop a convenient and effective method to detect and degrade phenolic compounds. Herein, we report a new keggin-type polyoxometallate-based metal-organic complex self-assembled under solvothermal condition, {[Cu(dap)(3-PA)]4(SiW12O40)(H2O)2}·2H2O (1, dap = 1,2-diaminopropane, 3-HPA = 3-pyridineacrylic acid). 1 shows an interesting 1D ladder-like structure. As a bifunctional catalyst, 1 can be employed as a colorimetric sensor toward phenol with the relatively low detection limit (LOD) of 0.36 µmol/L (S/N = 3) in the wide range (0.001–0.1 mmol/L). The title colorimetric sensor is applied to determine phenol in various water environment with good recoveries ranging from 95%–105%. In addition, 1 also exhibits excellent photocatalytic degradation toward phenol under visible light with the highest removal efficiency at 96% for 100 min and wide pH universality. The selectivity, stability and reliability of the detection of 1 towards phenol, as well as the detection for 4-chlorophenol, o-cresol, 4-nitrophenol and phloroglucinol were studied. Furthermore, the photocatalytic reaction kinetics and the mechanisms of photodegradation of phenol were also investigated in detail.
The widespread application of phenolic substances in the field of food, medicine and industry, is harmful to the environment and human health. Therefore, it is very important to develop a convenient and effective method to detect and degrade phenolic compounds. Herein, we report a new keggin-type polyoxometallate-based metal-organic complex self-assembled under solvothermal condition, {[Cu(dap)(3-PA)]4(SiW12O40)(H2O)2}·2H2O (1, dap = 1,2-diaminopropane, 3-HPA = 3-pyridineacrylic acid). 1 shows an interesting 1D ladder-like structure. As a bifunctional catalyst, 1 can be employed as a colorimetric sensor toward phenol with the relatively low detection limit (LOD) of 0.36 µmol/L (S/N = 3) in the wide range (0.001–0.1 mmol/L). The title colorimetric sensor is applied to determine phenol in various water environment with good recoveries ranging from 95%–105%. In addition, 1 also exhibits excellent photocatalytic degradation toward phenol under visible light with the highest removal efficiency at 96% for 100 min and wide pH universality. The selectivity, stability and reliability of the detection of 1 towards phenol, as well as the detection for 4-chlorophenol, o-cresol, 4-nitrophenol and phloroglucinol were studied. Furthermore, the photocatalytic reaction kinetics and the mechanisms of photodegradation of phenol were also investigated in detail.
2024, 35(8): 109166
doi: 10.1016/j.cclet.2023.109166
摘要:
For treatment of sulfion-containing wastewater, coupling the electrochemical sulfion oxidation reaction (SOR) with hydrogen evolution reaction (HER) can be an ideal way for sulfur and H2 resources recovery. Herein, we synthesize a metal-modified carbon nanotube arrays electrode (Co@NCNTs/CC) for SOR and HER. This electrode has excellent performance for SOR and HER attributed to the unique array structure. It can achieve 99.36 mA/cm2 at 0.6 V for SOR, and 10 mA/cm2 at 0.067 V for HER. Density functional theory calculations verify that metal modification is able to regulate the electronic structure of carbon nanotube, which is able to optimize the adsorption of intermediates. Employed Co@NCNTs/CC as bifunctional electrodes to establish a hybrid electrolytic cell can reduce about 67% of energy consumption compared with the traditional water splitting electrolytic cell. Finally, the hybrid electrolytic cell is used to treat actual sulfion-containing wastewater, achieving the sulfur yield of 30 mg h−1 cm−2 and the hydrogen production of 0.64 mL/min.
For treatment of sulfion-containing wastewater, coupling the electrochemical sulfion oxidation reaction (SOR) with hydrogen evolution reaction (HER) can be an ideal way for sulfur and H2 resources recovery. Herein, we synthesize a metal-modified carbon nanotube arrays electrode (Co@NCNTs/CC) for SOR and HER. This electrode has excellent performance for SOR and HER attributed to the unique array structure. It can achieve 99.36 mA/cm2 at 0.6 V for SOR, and 10 mA/cm2 at 0.067 V for HER. Density functional theory calculations verify that metal modification is able to regulate the electronic structure of carbon nanotube, which is able to optimize the adsorption of intermediates. Employed Co@NCNTs/CC as bifunctional electrodes to establish a hybrid electrolytic cell can reduce about 67% of energy consumption compared with the traditional water splitting electrolytic cell. Finally, the hybrid electrolytic cell is used to treat actual sulfion-containing wastewater, achieving the sulfur yield of 30 mg h−1 cm−2 and the hydrogen production of 0.64 mL/min.
2024, 35(8): 109170
doi: 10.1016/j.cclet.2023.109170
摘要:
Traditional therapies such as surgery and endocrine therapy no longer meet the clinical needs in prostate cancer treatment, and more effective treatments are urgently required. Recent studies have reported that targeted inhibition of the transcription factor cyclin dependent kinase 7 (CDK7) could effectively suppress prostate cancer progression. However, the toxicity of CDK7 inhibitors such as THZ1 is the main limitation of the clinical application. In this work, we synthesized Cys8E (C8E) nanoparticles (NPs) loaded with THZ1 (C8E@THZ1), a novel GSH-targeting and stimuli-responsive nano-delivery platform, and investigated its anti-tumor potential and biosafety properties. In vitro, C8E@THZ1 potently inhibited the proliferation and promoted the apoptosis of prostate cancer cells. On tumor-bearing mice, C8E@THZ1 inhibited tumors by up to 85%, while the damage of THZ1 to liver function was effectively avoided. These results confirmed that inhibition of CDK7 can effectively block the progression of prostate cancer, and that Cys8E NPs is a highly prospective delivery platform to promote the clinical application of CDK7 inhibitors.
Traditional therapies such as surgery and endocrine therapy no longer meet the clinical needs in prostate cancer treatment, and more effective treatments are urgently required. Recent studies have reported that targeted inhibition of the transcription factor cyclin dependent kinase 7 (CDK7) could effectively suppress prostate cancer progression. However, the toxicity of CDK7 inhibitors such as THZ1 is the main limitation of the clinical application. In this work, we synthesized Cys8E (C8E) nanoparticles (NPs) loaded with THZ1 (C8E@THZ1), a novel GSH-targeting and stimuli-responsive nano-delivery platform, and investigated its anti-tumor potential and biosafety properties. In vitro, C8E@THZ1 potently inhibited the proliferation and promoted the apoptosis of prostate cancer cells. On tumor-bearing mice, C8E@THZ1 inhibited tumors by up to 85%, while the damage of THZ1 to liver function was effectively avoided. These results confirmed that inhibition of CDK7 can effectively block the progression of prostate cancer, and that Cys8E NPs is a highly prospective delivery platform to promote the clinical application of CDK7 inhibitors.
2024, 35(8): 109180
doi: 10.1016/j.cclet.2023.109180
摘要:
The purification of low-grade coal-bed methane is extremely important, but challenging, due to the very similar physical properties of CH4 and N2. Herein, we proposed a dual polarization strategy by employing triazine and polyfluoride sites to construct polar pores in COF materials, achieving the efficient separation of CH4 from N2. As expected, the dual polarized F-CTF-1 and F-CTF-2 exhibit higher CH4 adsorption capacity and CH4/N2 selectivity than CTF-1 and CTF-2, respectively. Especially, the CH4 uptake capacity and CH4/N2 selectivity of F-CTF-2 is 1.76 and 1.42 times than that of CTF-2. This work not only developed promising COF materials for CH4/N2 separation, but also provided important guidance for the separation of other adsorbates with similar properties.
The purification of low-grade coal-bed methane is extremely important, but challenging, due to the very similar physical properties of CH4 and N2. Herein, we proposed a dual polarization strategy by employing triazine and polyfluoride sites to construct polar pores in COF materials, achieving the efficient separation of CH4 from N2. As expected, the dual polarized F-CTF-1 and F-CTF-2 exhibit higher CH4 adsorption capacity and CH4/N2 selectivity than CTF-1 and CTF-2, respectively. Especially, the CH4 uptake capacity and CH4/N2 selectivity of F-CTF-2 is 1.76 and 1.42 times than that of CTF-2. This work not only developed promising COF materials for CH4/N2 separation, but also provided important guidance for the separation of other adsorbates with similar properties.
2024, 35(8): 109181
doi: 10.1016/j.cclet.2023.109181
摘要:
Searching for efficient nonprecious metal-based catalysts toward oxygen evolution reaction (OER) are of significance for seawater electrolysis. Herein, a core–shell-structured hybrid of cobalt phosphide nanowires@NiFe layered double hydroxide nanosheets grown on conductive nickel foam (CoP@NiFe LDH/NF) is prepared by a feasible approach at low temperature. The charming structure can provide numerous phosphide/hydroxide heterogenous interfaces, expose abundant active sites, and boost electron/mass transfer, synergistically enhancing catalytic OER activity. When employed as an electrocatalyst toward the OER, the resultant CoP@NiFe LDH/NF only requires a small overpotential of 287 mV to provide 300 mA/cm2 current density as well as long-time durability in 1.0 mol/L KOH seawater. The regulation of electronic states and surface reconstruction synergistically contribute to highly efficient seawater oxidation. This work provides an opportunity to construct efficient and inexpensive electrocatalysts for hydrogen production.
Searching for efficient nonprecious metal-based catalysts toward oxygen evolution reaction (OER) are of significance for seawater electrolysis. Herein, a core–shell-structured hybrid of cobalt phosphide nanowires@NiFe layered double hydroxide nanosheets grown on conductive nickel foam (CoP@NiFe LDH/NF) is prepared by a feasible approach at low temperature. The charming structure can provide numerous phosphide/hydroxide heterogenous interfaces, expose abundant active sites, and boost electron/mass transfer, synergistically enhancing catalytic OER activity. When employed as an electrocatalyst toward the OER, the resultant CoP@NiFe LDH/NF only requires a small overpotential of 287 mV to provide 300 mA/cm2 current density as well as long-time durability in 1.0 mol/L KOH seawater. The regulation of electronic states and surface reconstruction synergistically contribute to highly efficient seawater oxidation. This work provides an opportunity to construct efficient and inexpensive electrocatalysts for hydrogen production.
2024, 35(8): 109182
doi: 10.1016/j.cclet.2023.109182
摘要:
Satisfactory ionic conductivity, excellent mechanical stability, and high-temperature resistance are the prerequisites for the safe application of solid polymer electrolytes (SPEs) in all-solid-state lithium metal batteries (ASSLMBs). In this study, a novel poly(m-phenylene isophthalamide) (PMIA)-core/poly(ethylene oxide) (PEO)-shell nanofiber membrane and the functional Li6.4La3Zr1.4Ta0.6O12 (LLZTO) ceramic nanoparticle are simultaneously introduced into the PEO-based SPEs to prepare composite polymer electrolytes (CPEs). The core PMIA layer of composite nanofibers can greatly improve the mechanical strength and thermal stability of the CPEs, while the shell PEO layer can provide the 3D continuous transport channels for lithium ions. In addition, the introduction of functional LLZTO nanoparticle not only reduces the crystallinity of PEO, but also promotes the dissociation of lithium salts and releases more Li+ ions through its interaction with the Lewis acid-base of anions, thereby overall improving the transport of lithium ions. Consequently, the optimized CPEs present high ionic conductivity of 1.38×10−4 S/cm at 30 ℃, significantly improved mechanical strength (8.5 MPa), remarkable thermal stability (without obvious shrinkage at 150 ℃), and conspicuous Li dendrites blocking ability (> 1800 h). The CPEs also both have good compatibility and cyclic stability with LiFePO4 (> 2000 cycles) and high-voltage LiNi0.8Mn0.1Co0.1O2 (NMC811) (> 500 cycles) cathodes. In addition, even at low temperature (40 ℃), the assembled LiFePO4/CPEs/Li battery still can cycle stably. The novel design can provide an effective way to exploit high-performance solid-state electrolytes.
Satisfactory ionic conductivity, excellent mechanical stability, and high-temperature resistance are the prerequisites for the safe application of solid polymer electrolytes (SPEs) in all-solid-state lithium metal batteries (ASSLMBs). In this study, a novel poly(m-phenylene isophthalamide) (PMIA)-core/poly(ethylene oxide) (PEO)-shell nanofiber membrane and the functional Li6.4La3Zr1.4Ta0.6O12 (LLZTO) ceramic nanoparticle are simultaneously introduced into the PEO-based SPEs to prepare composite polymer electrolytes (CPEs). The core PMIA layer of composite nanofibers can greatly improve the mechanical strength and thermal stability of the CPEs, while the shell PEO layer can provide the 3D continuous transport channels for lithium ions. In addition, the introduction of functional LLZTO nanoparticle not only reduces the crystallinity of PEO, but also promotes the dissociation of lithium salts and releases more Li+ ions through its interaction with the Lewis acid-base of anions, thereby overall improving the transport of lithium ions. Consequently, the optimized CPEs present high ionic conductivity of 1.38×10−4 S/cm at 30 ℃, significantly improved mechanical strength (8.5 MPa), remarkable thermal stability (without obvious shrinkage at 150 ℃), and conspicuous Li dendrites blocking ability (> 1800 h). The CPEs also both have good compatibility and cyclic stability with LiFePO4 (> 2000 cycles) and high-voltage LiNi0.8Mn0.1Co0.1O2 (NMC811) (> 500 cycles) cathodes. In addition, even at low temperature (40 ℃), the assembled LiFePO4/CPEs/Li battery still can cycle stably. The novel design can provide an effective way to exploit high-performance solid-state electrolytes.
2024, 35(8): 109187
doi: 10.1016/j.cclet.2023.109187
摘要:
Tumor vascular normalization has emerged as a promising strategy for synergistic therapy recently. Based on the strategy of “fluorescence turn on-controllable release”, a novel bifunctional candidate was constructed based on previous developed vascular normalization inducer QDAU5, which could self-assemble to form functional enzyme infrared QDAU5 nanoparticles (FEIRQ NPs). Subsequently, biological evaluation demonstrated that the FEIRQ NPs could induce ferroptosis, endoplasmic reticulum stress, and antigen preconditioning and maturation of dendritic cells and CD8+ T cells, leading to excellent antitumor efficacy in the absence of cytotoxic drugs. Additionally, FEIRQ NPs show high fluorescence intensity upon exposure to the β-galactosidase (β-Gal) enzyme expressed in ovarian cancer, enabling real-time monitoring of therapeutic effects. Overall, our findings suggest a prospering strategy to early diagnosis and efficient therapy for ovarian cancer without cytotoxicity.
Tumor vascular normalization has emerged as a promising strategy for synergistic therapy recently. Based on the strategy of “fluorescence turn on-controllable release”, a novel bifunctional candidate was constructed based on previous developed vascular normalization inducer QDAU5, which could self-assemble to form functional enzyme infrared QDAU5 nanoparticles (FEIRQ NPs). Subsequently, biological evaluation demonstrated that the FEIRQ NPs could induce ferroptosis, endoplasmic reticulum stress, and antigen preconditioning and maturation of dendritic cells and CD8+ T cells, leading to excellent antitumor efficacy in the absence of cytotoxic drugs. Additionally, FEIRQ NPs show high fluorescence intensity upon exposure to the β-galactosidase (β-Gal) enzyme expressed in ovarian cancer, enabling real-time monitoring of therapeutic effects. Overall, our findings suggest a prospering strategy to early diagnosis and efficient therapy for ovarian cancer without cytotoxicity.
2024, 35(8): 109190
doi: 10.1016/j.cclet.2023.109190
摘要:
Photodynamic therapy (PDT) has emerged as a significant cancer therapy option. Currently, cation-based organic small molecule aggregation-induced emission (AIE) photosensitizers (PSs) attract the wide attention of many scientists, due to improved reactive oxygen species (ROS) production after cationization. However, such PSs tend to localize only the mitochondria, limiting the death way of tumor cells (usually apoptosis) during PDT process, which may affect the therapeutic effect under some circumstances. Herein, we designed a novel water-soluble three positive charge PS, TPAN-18F, which could be distributed uniformly in cell cytoplasm and had distribution in different sub-organelles (mitochondria, endoplasmic reticulum, lysosome). The experimental results showed that TPAN-18F-based PDT process can not only disrupt mitochondrial functions (reducing ATP production and destroying mitochondrial membrane potential), but also elevate the intracellular lipid peroxides (LPOs) level, which evoke the non-apoptotic death manner of tumor cells. Further, in vivo studies showed that TPAN-18F-based PDT could effectively inhibit tumor growth. Accordingly, we believe that the construction of TPAN-18F is suggestive for tumor non-apoptotic therapy.
Photodynamic therapy (PDT) has emerged as a significant cancer therapy option. Currently, cation-based organic small molecule aggregation-induced emission (AIE) photosensitizers (PSs) attract the wide attention of many scientists, due to improved reactive oxygen species (ROS) production after cationization. However, such PSs tend to localize only the mitochondria, limiting the death way of tumor cells (usually apoptosis) during PDT process, which may affect the therapeutic effect under some circumstances. Herein, we designed a novel water-soluble three positive charge PS, TPAN-18F, which could be distributed uniformly in cell cytoplasm and had distribution in different sub-organelles (mitochondria, endoplasmic reticulum, lysosome). The experimental results showed that TPAN-18F-based PDT process can not only disrupt mitochondrial functions (reducing ATP production and destroying mitochondrial membrane potential), but also elevate the intracellular lipid peroxides (LPOs) level, which evoke the non-apoptotic death manner of tumor cells. Further, in vivo studies showed that TPAN-18F-based PDT could effectively inhibit tumor growth. Accordingly, we believe that the construction of TPAN-18F is suggestive for tumor non-apoptotic therapy.
2024, 35(8): 109191
doi: 10.1016/j.cclet.2023.109191
摘要:
KTi2(PO4)3 is a promising anode material for potassium storage, but suffers from low conductivity and difficult balance between high capacity and good structural stability. Herein, the Ti3C2T MXene is used as a multifunctional binder to fabricate the KTi2(PO4)3 electrode by the traditional homogenizing-coating method. The MXene nanosheets, together with the conductive agent super P nanoparticles, construct a multiple conductive network for fast electron/ion transfer and high electrochemical kinetics. Moreover, the network ensures the structural stability of the KTi2(PO4)3 electrode during the de-intercalation/intercalation of 4 K+ ions, which is beneficial for simultaneously achieving high capacity and good cycle performance. Therefore, the MXene-bonded KTi2(PO4)3 electrode delivers a reversible capacity of 255.2 mAh/g at 50 mA/g, outstanding rate capability with 132.3 mAh/g at 2 A/g, and excellent cycle performance with 151.6 mAh/g at 1 A/g after 2000 cycles. This work not only suggests a high-performance anode material for potassium-ion batteries, but also demonstrates that the MXene is a promising binder material for constructing conductive electrodes in rechargeable batteries.
KTi2(PO4)3 is a promising anode material for potassium storage, but suffers from low conductivity and difficult balance between high capacity and good structural stability. Herein, the Ti3C2T MXene is used as a multifunctional binder to fabricate the KTi2(PO4)3 electrode by the traditional homogenizing-coating method. The MXene nanosheets, together with the conductive agent super P nanoparticles, construct a multiple conductive network for fast electron/ion transfer and high electrochemical kinetics. Moreover, the network ensures the structural stability of the KTi2(PO4)3 electrode during the de-intercalation/intercalation of 4 K+ ions, which is beneficial for simultaneously achieving high capacity and good cycle performance. Therefore, the MXene-bonded KTi2(PO4)3 electrode delivers a reversible capacity of 255.2 mAh/g at 50 mA/g, outstanding rate capability with 132.3 mAh/g at 2 A/g, and excellent cycle performance with 151.6 mAh/g at 1 A/g after 2000 cycles. This work not only suggests a high-performance anode material for potassium-ion batteries, but also demonstrates that the MXene is a promising binder material for constructing conductive electrodes in rechargeable batteries.
2024, 35(8): 109196
doi: 10.1016/j.cclet.2023.109196
摘要:
There is increasing evidence shows that either electrical stimulation (ES) or metal ion is an effective way to accelerate ulcerative wound healing. However, less attention is paid to investigating the synergistic effect between them. Herein, we explore the combined effects of ES and multiple metal ions on diabetic wound healing assisted by a triboelectric nanogenerator (TENG). Firstly, the novel Eggshell@CuFe2O4 nanocomposites (NCs) are prepared, which show unique structure and intrinsic antimicrobial properties. Subsequently, the as-prepared nanocomposites are embedded in oxidized starch hydrogel to form a multifunctional composite gel, which is further assembled into a wearable ionic triboelectric nanogenerator (iTENG) patch with polydimethylsiloxane (PDMS). It can convert the mechanical energy produced by a human body motion to electric energy and mediate the sequential release of metal ions (Fe2+/Ca2+/Cu2+), thereby resulting in the "cocktail effect" on impaired tissue. Under their effects, a satisfying healing result in diabetic mouse is identified, which can effectively accelerate wound healing process by relieving inflammation, promoting angiogenesis and collagen deposition. The work puts forward the cocktail effect of electric simulation coupled with the multiple metal ions, and opens up a new perspective in designing iTENG patch towards repair of hard-to-heal wounds.
There is increasing evidence shows that either electrical stimulation (ES) or metal ion is an effective way to accelerate ulcerative wound healing. However, less attention is paid to investigating the synergistic effect between them. Herein, we explore the combined effects of ES and multiple metal ions on diabetic wound healing assisted by a triboelectric nanogenerator (TENG). Firstly, the novel Eggshell@CuFe2O4 nanocomposites (NCs) are prepared, which show unique structure and intrinsic antimicrobial properties. Subsequently, the as-prepared nanocomposites are embedded in oxidized starch hydrogel to form a multifunctional composite gel, which is further assembled into a wearable ionic triboelectric nanogenerator (iTENG) patch with polydimethylsiloxane (PDMS). It can convert the mechanical energy produced by a human body motion to electric energy and mediate the sequential release of metal ions (Fe2+/Ca2+/Cu2+), thereby resulting in the "cocktail effect" on impaired tissue. Under their effects, a satisfying healing result in diabetic mouse is identified, which can effectively accelerate wound healing process by relieving inflammation, promoting angiogenesis and collagen deposition. The work puts forward the cocktail effect of electric simulation coupled with the multiple metal ions, and opens up a new perspective in designing iTENG patch towards repair of hard-to-heal wounds.
2024, 35(8): 109199
doi: 10.1016/j.cclet.2023.109199
摘要:
Bladder cancer is a common malignant tumor of the urinary system with the potential to be treated by nano drug delivery system. The current work describes the synthesis and characterization of a novel nanomaterial to construct a nano-carrier based on 1-palmitoyl-2-oleoyl-sn-glycerol-3-phosphatecholine (POPC) loaded doxorubicin (DOX) and embedded with gold nanoparticles and poly(N-isopropyl acrylamide) (PNIPAM) (GNPS@PNIPAM-POPC-DOX, GPPD). The dual-sensitive nanosystem gives simultaneous photothermal treatment and chemotherapy for bladder cancer. In vitro and in vivo properties were assessed using bladder cancer cell lines and mice and GPPD system distribution, tumor inhibition, and biocompatibility are reported. The system had favorable stability, low biological toxicity, controlled release efficiency, photothermal synergistic action, efficient photothermal transition, and favorable tumor suppressive effects. As a result, GPPD is a potential therapeutic approach for bladder cancer.
Bladder cancer is a common malignant tumor of the urinary system with the potential to be treated by nano drug delivery system. The current work describes the synthesis and characterization of a novel nanomaterial to construct a nano-carrier based on 1-palmitoyl-2-oleoyl-sn-glycerol-3-phosphatecholine (POPC) loaded doxorubicin (DOX) and embedded with gold nanoparticles and poly(N-isopropyl acrylamide) (PNIPAM) (GNPS@PNIPAM-POPC-DOX, GPPD). The dual-sensitive nanosystem gives simultaneous photothermal treatment and chemotherapy for bladder cancer. In vitro and in vivo properties were assessed using bladder cancer cell lines and mice and GPPD system distribution, tumor inhibition, and biocompatibility are reported. The system had favorable stability, low biological toxicity, controlled release efficiency, photothermal synergistic action, efficient photothermal transition, and favorable tumor suppressive effects. As a result, GPPD is a potential therapeutic approach for bladder cancer.
2024, 35(8): 109223
doi: 10.1016/j.cclet.2023.109223
摘要:
Focused on the performance promotion of organic small molecular dyes based photothermal agents via non-chemical modification, we found that heat-assisted binding of human serum albumin (HSA) to the dye causes shrinkage of the protein and encapsulate the dye to form nanoparticles. This revolutionizes the photostability of small molecule dyes which further improves their photothermal conversion efficiency and tumor ablation performance as photothermal agents significantly. In this work, the obtained photothermal agent named HSA-P2-T could accumulate in tumor and induce 22 ℃ enhancement of the tumor in xenograft models upon ultra-low dose (0.1 W/cm2) laser irradiation, which, as far as we know, is the lowest laser dose used in vivo photothermal therapy. Utilizing HSA-P2-T, we realized tumor ablation upon twice intravenous injections of the nanoparticles and four photothermal treatments.
Focused on the performance promotion of organic small molecular dyes based photothermal agents via non-chemical modification, we found that heat-assisted binding of human serum albumin (HSA) to the dye causes shrinkage of the protein and encapsulate the dye to form nanoparticles. This revolutionizes the photostability of small molecule dyes which further improves their photothermal conversion efficiency and tumor ablation performance as photothermal agents significantly. In this work, the obtained photothermal agent named HSA-P2-T could accumulate in tumor and induce 22 ℃ enhancement of the tumor in xenograft models upon ultra-low dose (0.1 W/cm2) laser irradiation, which, as far as we know, is the lowest laser dose used in vivo photothermal therapy. Utilizing HSA-P2-T, we realized tumor ablation upon twice intravenous injections of the nanoparticles and four photothermal treatments.
2024, 35(8): 109226
doi: 10.1016/j.cclet.2023.109226
摘要:
Here, we present a novel bioorthogonal platform that enables precise positioning of attached moieties in close proximity, thereby facilitating the discovery and optimization of biocompatible reactions. Using this platform, we achieve a Horner-Wadsworth-Emmons (HWE) reaction under physiological conditions, generating a fluorophore in situ with a yield of up to 93%. This proximity platform should facilitate the discovery of various types of biocompatible reactions, making it a versatile tool for biomedical applications.
Here, we present a novel bioorthogonal platform that enables precise positioning of attached moieties in close proximity, thereby facilitating the discovery and optimization of biocompatible reactions. Using this platform, we achieve a Horner-Wadsworth-Emmons (HWE) reaction under physiological conditions, generating a fluorophore in situ with a yield of up to 93%. This proximity platform should facilitate the discovery of various types of biocompatible reactions, making it a versatile tool for biomedical applications.
2024, 35(8): 109227
doi: 10.1016/j.cclet.2023.109227
摘要:
Cyclooctatetraene (COT) attachment to fluorophores (“self-healing” dyes) is known for quenching reactive triplet states via triplet-state energy transfer (TET), enhancing photostability. However, COT’s impact on singlet states remains unclear. Quantum calculations reveal that COT induces energy transfer to dark states in deep blue dyes while promoting photoinduced electron transfer (PET) and intersystem crossing (ISC) in visible dyes, potentially compromising brightness and/or photostability. To address this, we propose the use of ΔE descriptor to optimize COT’s effects. Our findings uncover COT’s multifaceted impact. These insights will guide the development of superior triplet state quenchers and photostable dyes.
Cyclooctatetraene (COT) attachment to fluorophores (“self-healing” dyes) is known for quenching reactive triplet states via triplet-state energy transfer (TET), enhancing photostability. However, COT’s impact on singlet states remains unclear. Quantum calculations reveal that COT induces energy transfer to dark states in deep blue dyes while promoting photoinduced electron transfer (PET) and intersystem crossing (ISC) in visible dyes, potentially compromising brightness and/or photostability. To address this, we propose the use of ΔE descriptor to optimize COT’s effects. Our findings uncover COT’s multifaceted impact. These insights will guide the development of superior triplet state quenchers and photostable dyes.
2024, 35(8): 109241
doi: 10.1016/j.cclet.2023.109241
摘要:
Recently, the utilization of nonsteroidal anti-inflammatory drugs (NSAIDs) to sensitize cisplatin (CDDP) has gained substantial traction in the treatment of ovarian cancer (OC). However, even widely employed NSAIDs such as celecoxib and naproxen carry an elevated risk of cardiovascular events, notably thrombosis. Furthermore, the diminished sensitivity to CDDP therapy in OC is multifactorial, rendering the application of NSAIDs only partially effective due to their cyclooxygenase-2 (COX-2) inhibiting mechanism. Hence, in this study, reactive oxygen species (ROS)-responsive composite nano-hydrangeas loaded with the Chinese medicine small molecule allicin and platinum(Ⅳ) prodrug (DTP@AP NPs) were prepared to achieve comprehensive chemosensitization. On one front, allicin achieved COX-2 blocking therapy, encompassing the inhibition of proliferation, angiogenesis and endothelial mesenchymal transition (EMT), thereby mitigating the adverse impacts of CDDP chemotherapy. Simultaneously, synergistic chemosensitization was achieved from multifaceted mechanisms by decreasing CDDP inactivation, damaging mitochondria and inhibiting DNA repair. In essence, these findings provided an optimized approach for synergizing CDDP with COX-2 inhibitors, offering a promising avenue for enhancing OC treatment outcomes.
Recently, the utilization of nonsteroidal anti-inflammatory drugs (NSAIDs) to sensitize cisplatin (CDDP) has gained substantial traction in the treatment of ovarian cancer (OC). However, even widely employed NSAIDs such as celecoxib and naproxen carry an elevated risk of cardiovascular events, notably thrombosis. Furthermore, the diminished sensitivity to CDDP therapy in OC is multifactorial, rendering the application of NSAIDs only partially effective due to their cyclooxygenase-2 (COX-2) inhibiting mechanism. Hence, in this study, reactive oxygen species (ROS)-responsive composite nano-hydrangeas loaded with the Chinese medicine small molecule allicin and platinum(Ⅳ) prodrug (DTP@AP NPs) were prepared to achieve comprehensive chemosensitization. On one front, allicin achieved COX-2 blocking therapy, encompassing the inhibition of proliferation, angiogenesis and endothelial mesenchymal transition (EMT), thereby mitigating the adverse impacts of CDDP chemotherapy. Simultaneously, synergistic chemosensitization was achieved from multifaceted mechanisms by decreasing CDDP inactivation, damaging mitochondria and inhibiting DNA repair. In essence, these findings provided an optimized approach for synergizing CDDP with COX-2 inhibitors, offering a promising avenue for enhancing OC treatment outcomes.
2024, 35(8): 109243
doi: 10.1016/j.cclet.2023.109243
摘要:
Fe(II) is an essential trace element for anaerobic ammonium oxidation bacteria (AAOB) metabolism, and can improve the nitrogen removal efficiency of anaerobic ammonia oxidation (Anammox). Here we operated two identical expanded granular sludge bed (EGSB) reactors at low temperature (15 ± 3 ℃) for 154 days. Reactor 1 (R1) received additional Fe(II) (0.12 mmol/L) during the late startup phase, while reactor 0 (R0) served as the control and did not receive extra Fe(II). Nitrogen removal in R1 became stable at 55 d of operation, ten days earlier than R0. The nitrogen removal rate (NRR) of R1 was 1.64 kg N m−3 d−1 and its TN removal rate was as high as 89%, while R0 only reached 75%. The addition of Fe(II) was further beneficial to aggregation and stability of the granular sludge, and the used sludge of both reactors showed enrichment for AAOB populations compared to the inoculum, for instance, increased abundance of Candidatus-Kuenenia and in particular of Candidatus-Brocadia (from 0.17% to 10.10% in R0 and 7.79% in R1). Diverse microbial species and complex microbial network structure in R1 compared to R0 promoted the coupled denitrogenation by Anammox, dissimilatory nitrate reduction to ammonium (DNRA), nitrate-dependent Fe oxidation (NDFO), and ferric ammonium oxidation (Feammox). In addition, the microbial community in R1 was more resistant to short-term low temperature (2–7 ℃) starvation, illustrating a further positive effect of adding Fe(II) during the startup phase of an Anammox reactor.
Fe(II) is an essential trace element for anaerobic ammonium oxidation bacteria (AAOB) metabolism, and can improve the nitrogen removal efficiency of anaerobic ammonia oxidation (Anammox). Here we operated two identical expanded granular sludge bed (EGSB) reactors at low temperature (15 ± 3 ℃) for 154 days. Reactor 1 (R1) received additional Fe(II) (0.12 mmol/L) during the late startup phase, while reactor 0 (R0) served as the control and did not receive extra Fe(II). Nitrogen removal in R1 became stable at 55 d of operation, ten days earlier than R0. The nitrogen removal rate (NRR) of R1 was 1.64 kg N m−3 d−1 and its TN removal rate was as high as 89%, while R0 only reached 75%. The addition of Fe(II) was further beneficial to aggregation and stability of the granular sludge, and the used sludge of both reactors showed enrichment for AAOB populations compared to the inoculum, for instance, increased abundance of Candidatus-Kuenenia and in particular of Candidatus-Brocadia (from 0.17% to 10.10% in R0 and 7.79% in R1). Diverse microbial species and complex microbial network structure in R1 compared to R0 promoted the coupled denitrogenation by Anammox, dissimilatory nitrate reduction to ammonium (DNRA), nitrate-dependent Fe oxidation (NDFO), and ferric ammonium oxidation (Feammox). In addition, the microbial community in R1 was more resistant to short-term low temperature (2–7 ℃) starvation, illustrating a further positive effect of adding Fe(II) during the startup phase of an Anammox reactor.
2024, 35(8): 109248
doi: 10.1016/j.cclet.2023.109248
摘要:
Idiopathic pulmonary fibrosis (IPF) is a chronic and fatal lung disease characterized by pulmonary inflammation, oxidative stress, and excessive extracellular matrix (ECM) deposition. Current anti-fibrotic drugs for IPF treatment in the clinic lack selectivity and demonstrate unsatisfactory efficacy, highlighting the urgent necessity for a novel therapeutic strategy. Taraxasterol (TA), which has biological activities against lung injury induced by various factors, is a potential anti-IPF drug due to its anti-inflammatory, antioxidant and lung-protective effects. However, the protective effect of TA on IPF has not been confirmed, and its clinical application is limited due to its poor aqueous solubility. In this study, we demonstrated that TA could inhibit epithelial-mesenchymal transition (EMT) and migration of A549 cells by inhibiting the transforming growth factor-β1 (TGF-β1)/Smad signaling pathway. To improve the aqueous solubility and pulmonary administration performance of TA, we prepared TA loaded methoxy poly(ethylene glycol)-poly(d, l-lactide) (mPEG-PLA)/d-α-tocopheryl polyethylene glycol succinate (TPGS) mixed polymeric micelles (TA-PM). Then a MicroSprayerⓇ Aerosolizer was used to deliver TA-PM once every two days for three weeks to evaluate their therapeutic effects on bleomycin (BLM)-induced IPF mice. Our results demonstrated that inhaled TA-PM significantly inhibited BLM-induced inflammation, oxidative stress and fibrosis in lung tissue. Furthermore, TA-PM exhibited high pulmonary deposition and retention by pulmonary administration, along with a favorable safety profile. Overall, this study emphasizes the potential of inhaled TA-PM as a promising treatment for IPF, providing a new opportunity for their clinical application.
Idiopathic pulmonary fibrosis (IPF) is a chronic and fatal lung disease characterized by pulmonary inflammation, oxidative stress, and excessive extracellular matrix (ECM) deposition. Current anti-fibrotic drugs for IPF treatment in the clinic lack selectivity and demonstrate unsatisfactory efficacy, highlighting the urgent necessity for a novel therapeutic strategy. Taraxasterol (TA), which has biological activities against lung injury induced by various factors, is a potential anti-IPF drug due to its anti-inflammatory, antioxidant and lung-protective effects. However, the protective effect of TA on IPF has not been confirmed, and its clinical application is limited due to its poor aqueous solubility. In this study, we demonstrated that TA could inhibit epithelial-mesenchymal transition (EMT) and migration of A549 cells by inhibiting the transforming growth factor-β1 (TGF-β1)/Smad signaling pathway. To improve the aqueous solubility and pulmonary administration performance of TA, we prepared TA loaded methoxy poly(ethylene glycol)-poly(d, l-lactide) (mPEG-PLA)/d-α-tocopheryl polyethylene glycol succinate (TPGS) mixed polymeric micelles (TA-PM). Then a MicroSprayerⓇ Aerosolizer was used to deliver TA-PM once every two days for three weeks to evaluate their therapeutic effects on bleomycin (BLM)-induced IPF mice. Our results demonstrated that inhaled TA-PM significantly inhibited BLM-induced inflammation, oxidative stress and fibrosis in lung tissue. Furthermore, TA-PM exhibited high pulmonary deposition and retention by pulmonary administration, along with a favorable safety profile. Overall, this study emphasizes the potential of inhaled TA-PM as a promising treatment for IPF, providing a new opportunity for their clinical application.
2024, 35(8): 109251
doi: 10.1016/j.cclet.2023.109251
摘要:
The selective 2e− ORR reaction on polymeric carbon nitride framework is one of the most promising approaches for solar-driven hydrogen peroxide production. Poly(heptazine imide) (PHI) as a class of K+-incorporated crystalline carbon nitride framework, is highly active for photocatalytic H2O2 production. An upgrade on the H2O2 photoproduction performance of PHI is realized and the mechanistic insights are revealed in this work. By photochemical reaction, the electron withdrawing groups of hydroxyl group and cyano group are grafted on the surface of PHI frameworks. The dual polarization sites on the surface contribute significantly to the enhancement of the exciton dissociation. The optimized PHI with dual polarization sites exhibits a remarkable photocatalytic H2O2 production performance, which is 2 times of the active pristine PHI. Most importantly, the photochemical reaction method is generally applicable to improve the exciton dissociation of a wide range of polymeric carbon nitride frameworks with various structure and compositions; and the thiourea-derived polymeric carbon nitride framework with dual surface polarization sites exhibits a remarkable photocatalytic performance with a high H2O2 production rate of 40.5 mmol h−1 g−1.
The selective 2e− ORR reaction on polymeric carbon nitride framework is one of the most promising approaches for solar-driven hydrogen peroxide production. Poly(heptazine imide) (PHI) as a class of K+-incorporated crystalline carbon nitride framework, is highly active for photocatalytic H2O2 production. An upgrade on the H2O2 photoproduction performance of PHI is realized and the mechanistic insights are revealed in this work. By photochemical reaction, the electron withdrawing groups of hydroxyl group and cyano group are grafted on the surface of PHI frameworks. The dual polarization sites on the surface contribute significantly to the enhancement of the exciton dissociation. The optimized PHI with dual polarization sites exhibits a remarkable photocatalytic H2O2 production performance, which is 2 times of the active pristine PHI. Most importantly, the photochemical reaction method is generally applicable to improve the exciton dissociation of a wide range of polymeric carbon nitride frameworks with various structure and compositions; and the thiourea-derived polymeric carbon nitride framework with dual surface polarization sites exhibits a remarkable photocatalytic performance with a high H2O2 production rate of 40.5 mmol h−1 g−1.
2024, 35(8): 109254
doi: 10.1016/j.cclet.2023.109254
摘要:
Oxidative therapies receive a limited antitumor efficiency due to the insufficient reactive oxygen species (ROS) levels at focal sites and the evolvement of antioxidant defense systems. Herein, we develop an albumin-based nanomedicine to co-deliver chlorin e6 (Ce6) and COH-SR4 (CS), which can simultaneously enhance the yield and lethality of intracellular ROS for amplified photodynamic therapy (PDT). In which, CS acts as both an activator of AMP-activated protein kinase (AMPK) and an inhibitor of glutathione S-transferases (GSTs). Benefiting from it, the prepared HSA-Ce6@COH-SR4 (HCCS) enables positive feedback uptake by promoting AMPK phosphorylation, leading to rapid and extensive tumor accumulation of drugs. As a result, HCCS obviously increases the ROS production to elevate intracellular oxidative stress. Furthermore, HCCS can inhibit GSTs to disturb the antioxidant defense system of tumor cells, intensifying the oxidative damage of ROS. Ultimately, the PDT of HCCS is significantly strengthened by improving the ROS yield and lethality, which greatly declines the proliferation of breast cancer in vivo. This study may open a window in the development of drug co-delivery system for enhanced oxidative therapy of tumors.
Oxidative therapies receive a limited antitumor efficiency due to the insufficient reactive oxygen species (ROS) levels at focal sites and the evolvement of antioxidant defense systems. Herein, we develop an albumin-based nanomedicine to co-deliver chlorin e6 (Ce6) and COH-SR4 (CS), which can simultaneously enhance the yield and lethality of intracellular ROS for amplified photodynamic therapy (PDT). In which, CS acts as both an activator of AMP-activated protein kinase (AMPK) and an inhibitor of glutathione S-transferases (GSTs). Benefiting from it, the prepared HSA-Ce6@COH-SR4 (HCCS) enables positive feedback uptake by promoting AMPK phosphorylation, leading to rapid and extensive tumor accumulation of drugs. As a result, HCCS obviously increases the ROS production to elevate intracellular oxidative stress. Furthermore, HCCS can inhibit GSTs to disturb the antioxidant defense system of tumor cells, intensifying the oxidative damage of ROS. Ultimately, the PDT of HCCS is significantly strengthened by improving the ROS yield and lethality, which greatly declines the proliferation of breast cancer in vivo. This study may open a window in the development of drug co-delivery system for enhanced oxidative therapy of tumors.
2024, 35(8): 109259
doi: 10.1016/j.cclet.2023.109259
摘要:
Sleep deprivation (SD) is a widespread issue that disrupts the lives of millions of people. These effects initiate as changes within neurons, specifically at the DNA and RNA level, leading to disruptions in neuronal plasticity and the dysregulation of various cognitive functions, such as learning and memory. Nucleic acid epigenetic modifications that could regulate gene expression have been reported to play crucial roles in this process. However, there is a lack of comprehensive research on the correlation of SD with nucleic acid epigenetic modifications. In the current study, we aimed to systematically investigate the landscape of modifications in DNA as well as in small RNA molecules across multiple tissues, including the heart, liver, kidney, lung, hippocampus, and spleen, in response to chronic sleep deprivation (CSD). Using liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis, we characterized the dynamic changes in DNA and RNA modification profiles in different tissues of mice under CSD stress. Specifically, we observed a significant decrease in the level of 5-methylcytosine (5mC) and a significant increase in the level of 5-hydroxymethylcytosine (5hmC) in the kidney in CSD group. Regarding RNA modifications, we observed an overall increased trend for most of these significantly changed modifications across six tissues in CSD group. Our study sheds light on the significance of DNA and RNA modifications as crucial epigenetic markers in the context of CSD-induced stress.
Sleep deprivation (SD) is a widespread issue that disrupts the lives of millions of people. These effects initiate as changes within neurons, specifically at the DNA and RNA level, leading to disruptions in neuronal plasticity and the dysregulation of various cognitive functions, such as learning and memory. Nucleic acid epigenetic modifications that could regulate gene expression have been reported to play crucial roles in this process. However, there is a lack of comprehensive research on the correlation of SD with nucleic acid epigenetic modifications. In the current study, we aimed to systematically investigate the landscape of modifications in DNA as well as in small RNA molecules across multiple tissues, including the heart, liver, kidney, lung, hippocampus, and spleen, in response to chronic sleep deprivation (CSD). Using liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis, we characterized the dynamic changes in DNA and RNA modification profiles in different tissues of mice under CSD stress. Specifically, we observed a significant decrease in the level of 5-methylcytosine (5mC) and a significant increase in the level of 5-hydroxymethylcytosine (5hmC) in the kidney in CSD group. Regarding RNA modifications, we observed an overall increased trend for most of these significantly changed modifications across six tissues in CSD group. Our study sheds light on the significance of DNA and RNA modifications as crucial epigenetic markers in the context of CSD-induced stress.
2024, 35(8): 109260
doi: 10.1016/j.cclet.2023.109260
摘要:
Bioprinting is emerging as an advanced tool in tissue engineering. However, there is still a lack of bioinks able to form hydrogels with desirable bioactivities that support positive cell behaviors. In this study, modified plasma proteins capable of forming hydrogels with multiple biological functions are developed as bioinks for digital light processing (DLP) printing. The Plasma-MA (BM) was synthesized via a one-pot method through the reaction between the fresh frozen plasma and methacrylic anhydride. The methacrylated levels were observed to influence the physical properties of BM hydrogels including mechanical properties, swelling, and degradation. The photo-crosslinked BM hydrogels can sustainedly release vascular endothelial growth factor (VEGF) and exhibit positive biological effects on cell adhesion and proliferation, and cell functionality such as tube formation of human umbilical vein endothelial cells (HUVECs), and neurite elongation of rat pheochromocytoma cells (PC12). Meanwhile, BM hydrogels can also induce cell infiltration, modulate immune response, and promote angiogenesis in vivo. Moreover, the plasma bioinks can be used to fabricate customized scaffolds with complex structures through a DLP printing process. These findings implicate that the modified plasma with growth factor release is a promising candidate for bioprinting in autologous and personalized tissue engineering.
Bioprinting is emerging as an advanced tool in tissue engineering. However, there is still a lack of bioinks able to form hydrogels with desirable bioactivities that support positive cell behaviors. In this study, modified plasma proteins capable of forming hydrogels with multiple biological functions are developed as bioinks for digital light processing (DLP) printing. The Plasma-MA (BM) was synthesized via a one-pot method through the reaction between the fresh frozen plasma and methacrylic anhydride. The methacrylated levels were observed to influence the physical properties of BM hydrogels including mechanical properties, swelling, and degradation. The photo-crosslinked BM hydrogels can sustainedly release vascular endothelial growth factor (VEGF) and exhibit positive biological effects on cell adhesion and proliferation, and cell functionality such as tube formation of human umbilical vein endothelial cells (HUVECs), and neurite elongation of rat pheochromocytoma cells (PC12). Meanwhile, BM hydrogels can also induce cell infiltration, modulate immune response, and promote angiogenesis in vivo. Moreover, the plasma bioinks can be used to fabricate customized scaffolds with complex structures through a DLP printing process. These findings implicate that the modified plasma with growth factor release is a promising candidate for bioprinting in autologous and personalized tissue engineering.
2024, 35(8): 109262
doi: 10.1016/j.cclet.2023.109262
摘要:
Recently, a novel 2-electron oxygen reduction reaction (ORR) based electro-oxidation (EO) system was developed, which utilizes a H2O2 generation cathode instead of H2 evolution cathode. A Ti-based Ni-Sb co-doped SnO2 (Ti/NATO) anode was selected for efficient degradation of refractory organics and O3 production. The synergistic reaction of O3/H2O2 further accelerated the generation of hydroxyl radicals (•OH) in the ORR-EO system. However, the catalytic activity and long-term effectiveness of the Ti/NATO anode limited the large-scale application of the ORR-EO process. In this study, a blue TiO2 nanotube array (blue-TiO2-NTA) inter-layer was introduced into the fabrication process between the Ti substrate and NATO catalyst layer. Compared to the Ti/NATO anode, the Ti/blue-TiO2-NTA/NATO anode achieved higher efficiency of organic removal and O3 generation. Additionally, the accelerated lifetime of the Ti/blue-TiO2-NTA/NATO anode was increased by 7 times compared to the Ti/NATO anode. When combined with CNTs-C/PTFE air cathode in ORR-EO system, all anodic oxidation and O3/H2O2 processes achieved higher •OH production. Over 92% of TOC in leachate bio-effluent was effectively eliminated with a relatively low energy cost of 45 kWh/t.
Recently, a novel 2-electron oxygen reduction reaction (ORR) based electro-oxidation (EO) system was developed, which utilizes a H2O2 generation cathode instead of H2 evolution cathode. A Ti-based Ni-Sb co-doped SnO2 (Ti/NATO) anode was selected for efficient degradation of refractory organics and O3 production. The synergistic reaction of O3/H2O2 further accelerated the generation of hydroxyl radicals (•OH) in the ORR-EO system. However, the catalytic activity and long-term effectiveness of the Ti/NATO anode limited the large-scale application of the ORR-EO process. In this study, a blue TiO2 nanotube array (blue-TiO2-NTA) inter-layer was introduced into the fabrication process between the Ti substrate and NATO catalyst layer. Compared to the Ti/NATO anode, the Ti/blue-TiO2-NTA/NATO anode achieved higher efficiency of organic removal and O3 generation. Additionally, the accelerated lifetime of the Ti/blue-TiO2-NTA/NATO anode was increased by 7 times compared to the Ti/NATO anode. When combined with CNTs-C/PTFE air cathode in ORR-EO system, all anodic oxidation and O3/H2O2 processes achieved higher •OH production. Over 92% of TOC in leachate bio-effluent was effectively eliminated with a relatively low energy cost of 45 kWh/t.
2024, 35(8): 109264
doi: 10.1016/j.cclet.2023.109264
摘要:
Hexokinase 2 (HK2) is the rate-limiting enzyme in the first step of glycolysis, catalyzing glucose to glucose-6-phosphate, and overexpressed in most cancer cells. HK2 also binds to voltage-dependent anion channel (VDAC) to stabilize the mitochondrial outer membrane, which inhibits cancer cell apoptosis. Therefore, HK2 has become a potential target for cancer treatment. Proteolysis targeting chimeras (PROTACs) are hetero-bifunctional molecules that recruit an E3 ubiquitin ligase to a given substrate protein resulting in its targeted degradation. Many potent and specific PROTACs targeting dissimilar targets have been developed. In this study, an HK2 PROTAC, 4H-5P-M, was developed and induced the degradation of HK2 relying on the ubiquitin-proteasome system. It was found that 4H-5P-M as an effective HK2 degrader induced HK2 degradation in a dose- and time-dependent manner and suppressed the growth of SW480 cells. 4H-5P-M selectively induced HK2 degradation at a lower concentration than other hexokinase isozymes. Moreover, it could suppress glycolysis and accelerate the apoptosis of cancer cells. Therefore, it provided a new insight into the development of anti-tumor drugs.
Hexokinase 2 (HK2) is the rate-limiting enzyme in the first step of glycolysis, catalyzing glucose to glucose-6-phosphate, and overexpressed in most cancer cells. HK2 also binds to voltage-dependent anion channel (VDAC) to stabilize the mitochondrial outer membrane, which inhibits cancer cell apoptosis. Therefore, HK2 has become a potential target for cancer treatment. Proteolysis targeting chimeras (PROTACs) are hetero-bifunctional molecules that recruit an E3 ubiquitin ligase to a given substrate protein resulting in its targeted degradation. Many potent and specific PROTACs targeting dissimilar targets have been developed. In this study, an HK2 PROTAC, 4H-5P-M, was developed and induced the degradation of HK2 relying on the ubiquitin-proteasome system. It was found that 4H-5P-M as an effective HK2 degrader induced HK2 degradation in a dose- and time-dependent manner and suppressed the growth of SW480 cells. 4H-5P-M selectively induced HK2 degradation at a lower concentration than other hexokinase isozymes. Moreover, it could suppress glycolysis and accelerate the apoptosis of cancer cells. Therefore, it provided a new insight into the development of anti-tumor drugs.
2024, 35(8): 109270
doi: 10.1016/j.cclet.2023.109270
摘要:
The monkeypox virus (MPXV) outbreak, declared a Public Health Emergency of International Concern (PHEIC) by the World Health Organization (WHO) in 2022, continues to pose a significant threat due to the absence of vaccines or drugs for MPXV infection. In this study, we developed an mRNA vaccine that expressing the A29L antigen, a specific protein of the intracellular mature virus. Our vaccine utilizes a thermostable ionizable lipid nanoparticle (iLNP) platform and has been administered to mice. Our findings demonstrate that the MPXV A29L mRNA vaccine candidate induces robust cross-neutralizing immune responses against both vaccinia virus (VACV) and MPXV live virus. Furthermore, immunization with the vaccine candidate provided protection against the VACV challenge in mice. These findings underscore the potential of mRNA-LNP vaccines as safe and effective candidates against monkeypox epidemics. Given the current absence of specific interventions for MPXV infection, our study represents a significant step forward in developing a viable solution to combat this ongoing public health threat.
The monkeypox virus (MPXV) outbreak, declared a Public Health Emergency of International Concern (PHEIC) by the World Health Organization (WHO) in 2022, continues to pose a significant threat due to the absence of vaccines or drugs for MPXV infection. In this study, we developed an mRNA vaccine that expressing the A29L antigen, a specific protein of the intracellular mature virus. Our vaccine utilizes a thermostable ionizable lipid nanoparticle (iLNP) platform and has been administered to mice. Our findings demonstrate that the MPXV A29L mRNA vaccine candidate induces robust cross-neutralizing immune responses against both vaccinia virus (VACV) and MPXV live virus. Furthermore, immunization with the vaccine candidate provided protection against the VACV challenge in mice. These findings underscore the potential of mRNA-LNP vaccines as safe and effective candidates against monkeypox epidemics. Given the current absence of specific interventions for MPXV infection, our study represents a significant step forward in developing a viable solution to combat this ongoing public health threat.
2024, 35(8): 109275
doi: 10.1016/j.cclet.2023.109275
摘要:
Essential amino acids (EAAs) deprivation is a potential antitumor approach because EAAs are critical for tumor growth. To efficiently inhibit tumor growth, continuous deprivation of EAAs is required, however, continuous deprivation without precise control will introduce toxicity to normal cells. Herein, a programmable double-unlock nanocomplex (ROCK) was prepared, which could self-supply phenylalanine ammonia-lyase (PAL) to tumor cells for phenylalanine (Phe) deprivation. ROCK was double-locked in physiological conditions when administered systemically. While ROCK actively targeted to tumor cells by integrin αvβ3/5 and CD44, ROCK was firstly unlocked by cleavage of protease on tumor cell membrane, exposing CendR and R8 to enhance endocytosis. Then, hyaluronic acid was digested by hyaluronidase overexpressed in endo/lysosome of tumor cells, in which ROCK was secondly unlocked, resulting in promoting endo/lysosome escape and PAL plasmid (pPAL) release. Released pPAL could sustainably express PAL in host tumor cells until the self-supplied PAL precisely and successfully deprived Phe, thereby blocking the protein synthesis and killing tumor cells specifically. Overall, our precise Phe deprivation strategy effectively inhibited tumor growth with no observable toxicity to normal cells, providing new insights to efficiently remove intratumoral nutrition for cancer therapy.
Essential amino acids (EAAs) deprivation is a potential antitumor approach because EAAs are critical for tumor growth. To efficiently inhibit tumor growth, continuous deprivation of EAAs is required, however, continuous deprivation without precise control will introduce toxicity to normal cells. Herein, a programmable double-unlock nanocomplex (ROCK) was prepared, which could self-supply phenylalanine ammonia-lyase (PAL) to tumor cells for phenylalanine (Phe) deprivation. ROCK was double-locked in physiological conditions when administered systemically. While ROCK actively targeted to tumor cells by integrin αvβ3/5 and CD44, ROCK was firstly unlocked by cleavage of protease on tumor cell membrane, exposing CendR and R8 to enhance endocytosis. Then, hyaluronic acid was digested by hyaluronidase overexpressed in endo/lysosome of tumor cells, in which ROCK was secondly unlocked, resulting in promoting endo/lysosome escape and PAL plasmid (pPAL) release. Released pPAL could sustainably express PAL in host tumor cells until the self-supplied PAL precisely and successfully deprived Phe, thereby blocking the protein synthesis and killing tumor cells specifically. Overall, our precise Phe deprivation strategy effectively inhibited tumor growth with no observable toxicity to normal cells, providing new insights to efficiently remove intratumoral nutrition for cancer therapy.
2024, 35(8): 109278
doi: 10.1016/j.cclet.2023.109278
摘要:
Facile and efficient method for constructing carbon dots (CDs) with narrow full width at half maximum (FWHM) is a major challenge in the field, and researches on regulating the FWHM of CDs are also rare and scarce. In this work, we delved into the synthesis of CDs with narrow fluorescence emission FWHM (NFEF-CDs) in the m-phenylenediamine (m-PD)/ethanol system, utilizing solid superacid resin as catalyst with solvothermal method. The resulting NFEF-CDs exhibit a photoluminescent (PL) emission peak at 521 nm with a narrow FWHM of 41 nm, an absolute PL quantum yield (QY) of 80%, and display excitation-independent PL behavior. Through comprehensive characterization, we identified the protonation of edge amino on NFEF-CDs as the key factor in achieving the narrow FWHM. Subsequently, we validated the broad applicability of solid superacid resins as catalysts for synthesizing CDs with narrow FWHM in the m-PD/ethanol system. Finally, we utilized a self-leveling method to prepare NFEF-CDs film on the surface of poly(methyl methacrylate) (PMMA) substrate and investigated the solid-state fluorescence properties of NFEF-CDs as well as their performance as luminescence solar concentrator (LSC) for photovoltaic conversion. The results revealed that the as-prepared LSC exhibit an internal quantum efficiency (ηint) of 42.39% and an optical efficiency (ηopt) of 0.68%. These findings demonstrate the promising prospects of NFEF-CDs in the field of LSCs and provide a theoretical basis for their application in photovoltaic conversion.
Facile and efficient method for constructing carbon dots (CDs) with narrow full width at half maximum (FWHM) is a major challenge in the field, and researches on regulating the FWHM of CDs are also rare and scarce. In this work, we delved into the synthesis of CDs with narrow fluorescence emission FWHM (NFEF-CDs) in the m-phenylenediamine (m-PD)/ethanol system, utilizing solid superacid resin as catalyst with solvothermal method. The resulting NFEF-CDs exhibit a photoluminescent (PL) emission peak at 521 nm with a narrow FWHM of 41 nm, an absolute PL quantum yield (QY) of 80%, and display excitation-independent PL behavior. Through comprehensive characterization, we identified the protonation of edge amino on NFEF-CDs as the key factor in achieving the narrow FWHM. Subsequently, we validated the broad applicability of solid superacid resins as catalysts for synthesizing CDs with narrow FWHM in the m-PD/ethanol system. Finally, we utilized a self-leveling method to prepare NFEF-CDs film on the surface of poly(methyl methacrylate) (PMMA) substrate and investigated the solid-state fluorescence properties of NFEF-CDs as well as their performance as luminescence solar concentrator (LSC) for photovoltaic conversion. The results revealed that the as-prepared LSC exhibit an internal quantum efficiency (ηint) of 42.39% and an optical efficiency (ηopt) of 0.68%. These findings demonstrate the promising prospects of NFEF-CDs in the field of LSCs and provide a theoretical basis for their application in photovoltaic conversion.
2024, 35(8): 109291
doi: 10.1016/j.cclet.2023.109291
摘要:
Intracellular ATP is an emerging biomarker for cancer early diagnosis because it is a key messenger for regulating the proliferation and migration of cancer cells. However, the conventional ATP biosensing strategy is often limited by the undesired on-target off-tumor interference. Here, we reported a novel strategy to design enzymatically controlled DNA tetrahedron nanoprobes (En-DT) for biosensing and imaging ATP in tumor cells. The En-DT was designed via rational engineering of structure-switching aptamers with the incorporation of an enzyme-activatable site and further conjugation on the DNA tetrahedron. The En-DT could be catalytically activated by apurinic/apyrimidinic endonuclease 1 (APE1) in cancer cells, but they did not respond to ATP in normal cells, thereby enabling cancer-specific ATP biosensing and imaging in vitro and in vivo with improved tumor specificity. This strategy would facilitate the precise detection of a broad range of biomarker in tumors and may promote the development of smart probes for cancer diagnosis.
Intracellular ATP is an emerging biomarker for cancer early diagnosis because it is a key messenger for regulating the proliferation and migration of cancer cells. However, the conventional ATP biosensing strategy is often limited by the undesired on-target off-tumor interference. Here, we reported a novel strategy to design enzymatically controlled DNA tetrahedron nanoprobes (En-DT) for biosensing and imaging ATP in tumor cells. The En-DT was designed via rational engineering of structure-switching aptamers with the incorporation of an enzyme-activatable site and further conjugation on the DNA tetrahedron. The En-DT could be catalytically activated by apurinic/apyrimidinic endonuclease 1 (APE1) in cancer cells, but they did not respond to ATP in normal cells, thereby enabling cancer-specific ATP biosensing and imaging in vitro and in vivo with improved tumor specificity. This strategy would facilitate the precise detection of a broad range of biomarker in tumors and may promote the development of smart probes for cancer diagnosis.
2024, 35(8): 109301
doi: 10.1016/j.cclet.2023.109301
摘要:
Metal-nanocluster materials have gradually become a promising electrode candidate for supercapacitor application. The high-efficient and rational architecture of these metal-nanocluster electrode materials with satisfied supercapacitive performance are full of challenges. Herein, Fe-nanocluster anchored porous carbon (FAPC) nanosheets were constructed through a facile and low-cost impregnation-activation strategy. Various characterization methods documented that FAPC nanosheets possessed a mesopore-dominated structure with large surface area and abundant Fe-N4 active sites, which are crucial for supercapacitive energy storage. The optimal FAPC electrode exhibited a high specific capacitance of 378 F/g at a specific current of 1 A/g and an excellent rate capability (271 F/g at 10 A/g), which are comparable or even superior to that of most reported carbon candidates. Furthermore, the FAPC-based device achieved a desired specific energy of 14.8 Wh/kg at a specific power of 700 W/kg. This work opens a new avenue to design metal-nanocluster materials for high-performance biomass waste-based supercapacitors.
Metal-nanocluster materials have gradually become a promising electrode candidate for supercapacitor application. The high-efficient and rational architecture of these metal-nanocluster electrode materials with satisfied supercapacitive performance are full of challenges. Herein, Fe-nanocluster anchored porous carbon (FAPC) nanosheets were constructed through a facile and low-cost impregnation-activation strategy. Various characterization methods documented that FAPC nanosheets possessed a mesopore-dominated structure with large surface area and abundant Fe-N4 active sites, which are crucial for supercapacitive energy storage. The optimal FAPC electrode exhibited a high specific capacitance of 378 F/g at a specific current of 1 A/g and an excellent rate capability (271 F/g at 10 A/g), which are comparable or even superior to that of most reported carbon candidates. Furthermore, the FAPC-based device achieved a desired specific energy of 14.8 Wh/kg at a specific power of 700 W/kg. This work opens a new avenue to design metal-nanocluster materials for high-performance biomass waste-based supercapacitors.
2024, 35(8): 109325
doi: 10.1016/j.cclet.2023.109325
摘要:
Flow-electrode capacitive deionization (FCDI) represents a promising approach for ion separation from aqueous solutions. However, the optimization of spacer, particularly for nitrate-contaminated groundwater systems, has often been overlooked. This research comprehensively investigates the influence of using a conductive (carbon cloth, CC) spacer on nitrate removal performance within FCDI system, comparing it to a non-conductive (nylon net, NN) spacer. In both CC and NN FCDI systems, it is unsurprisingly that nitrate removal efficiency improved notably with the increasing current density and hydraulic retention time (HRT). Interestingly, the specific energy consumption (SEC) for nitrate removal did not show obvious fluctuations when the current density and HRT varied in both systems. Under the auspiciously optimized process parameters, CC-FCDI attained a 20% superior nitrate removal efficiency relative to NN-FCDI, accompanied by a notably diminished SEC for CC-FCDI, registering at a mere 28% of NN-FCDI. This great improvement can be primarily attributed to the decrement in FCDI internal resistance after using conductive spacer, which further confirmed by electrochemical tests such as linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). Upon prolonged continuous nitrate removal at the optimized conditions, the CC-FCDI system achieved a consistent 90% nitrate removal efficiency with a low SEC of 2.7–7.8 kWh/kg NO3-N, underscoring its steady performance. Overall, this study highlights the pivotal importance of careful spacer design and optimization in realizing energy-efficient groundwater treatment via FCDI.
Flow-electrode capacitive deionization (FCDI) represents a promising approach for ion separation from aqueous solutions. However, the optimization of spacer, particularly for nitrate-contaminated groundwater systems, has often been overlooked. This research comprehensively investigates the influence of using a conductive (carbon cloth, CC) spacer on nitrate removal performance within FCDI system, comparing it to a non-conductive (nylon net, NN) spacer. In both CC and NN FCDI systems, it is unsurprisingly that nitrate removal efficiency improved notably with the increasing current density and hydraulic retention time (HRT). Interestingly, the specific energy consumption (SEC) for nitrate removal did not show obvious fluctuations when the current density and HRT varied in both systems. Under the auspiciously optimized process parameters, CC-FCDI attained a 20% superior nitrate removal efficiency relative to NN-FCDI, accompanied by a notably diminished SEC for CC-FCDI, registering at a mere 28% of NN-FCDI. This great improvement can be primarily attributed to the decrement in FCDI internal resistance after using conductive spacer, which further confirmed by electrochemical tests such as linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). Upon prolonged continuous nitrate removal at the optimized conditions, the CC-FCDI system achieved a consistent 90% nitrate removal efficiency with a low SEC of 2.7–7.8 kWh/kg NO3-N, underscoring its steady performance. Overall, this study highlights the pivotal importance of careful spacer design and optimization in realizing energy-efficient groundwater treatment via FCDI.
2024, 35(8): 109327
doi: 10.1016/j.cclet.2023.109327
摘要:
Electrochemical-nitrate-reduction-reaction (eNitRR) synthesis of ammonia is an effective way to treat nitrate wastewater and alleviate the pressure of the Haber-Bosch ammonia production industry. How to develop effective catalysts to electrochemically reduce nitrate to ammonia and purify sewage under complex environmental conditions is the focus of current research. Herein, the dopamine polymerization process and the [(C12H8N2)2Cu]2+ complex embedding process were run simultaneously in time and space, and ultrafine Cu nanoparticles (Cu/CN) were effectively loaded on nitrogen-doped carbon after heat treatment. Using Cu/CN as the catalyst, the ammonia yield rate and Faradaic efficiency of the electrochemical conversion of to NH3 are highly 8984.0 µg h−1 mgcat.−1 and 95.6%, respectively. Even in the face of complex water environments, such as neutral media, acidic media, coexisting ions, and actual nitrate wastewater, nitrate wastewater can be effectively purified to form high value-added ammonia. The strategy of simultaneous embedding increases the exposure rate of Cu sites, and the support of CN is also beneficial to reduce the energy barrier of *NO3 activation. This study rationally designed catalysts that are beneficial to eNitRR, and considered the situation faced by practical applications during the research stage, reducing the performance gap between laboratory exploration and industrial applications.
Electrochemical-nitrate-reduction-reaction (eNitRR) synthesis of ammonia is an effective way to treat nitrate wastewater and alleviate the pressure of the Haber-Bosch ammonia production industry. How to develop effective catalysts to electrochemically reduce nitrate to ammonia and purify sewage under complex environmental conditions is the focus of current research. Herein, the dopamine polymerization process and the [(C12H8N2)2Cu]2+ complex embedding process were run simultaneously in time and space, and ultrafine Cu nanoparticles (Cu/CN) were effectively loaded on nitrogen-doped carbon after heat treatment. Using Cu/CN as the catalyst, the ammonia yield rate and Faradaic efficiency of the electrochemical conversion of to NH3 are highly 8984.0 µg h−1 mgcat.−1 and 95.6%, respectively. Even in the face of complex water environments, such as neutral media, acidic media, coexisting ions, and actual nitrate wastewater, nitrate wastewater can be effectively purified to form high value-added ammonia. The strategy of simultaneous embedding increases the exposure rate of Cu sites, and the support of CN is also beneficial to reduce the energy barrier of *NO3 activation. This study rationally designed catalysts that are beneficial to eNitRR, and considered the situation faced by practical applications during the research stage, reducing the performance gap between laboratory exploration and industrial applications.
2024, 35(8): 109331
doi: 10.1016/j.cclet.2023.109331
摘要:
In Fenton-like oxidation, the catalyst directly influences the reaction mechanism for the degradation of pollutants from water. Here, a α-MnO2 catalyst (OAm-1) was synthesized via a self-assembly method with the assistance of a surfactant. OAm-1 possessed a large specific surface area of 221 m2/g, abundant mesoporous structures and a large proportion of Mn(Ⅲ). Further characterization exhibited that OAm-1 had abundant oxygen vacancies and excellent reducibility and conductivity. The adsorption and catalytic ability of OAm-1 were studied in the degradation of oxytetracycline (OTC) via the activation of hydrogen peroxide (H2O2). Through the radical quenching experiments, electron resonance spectroscopy (EPR), X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FT-IR) analysis, Mn(Ⅲ) of OAm-1 was proved to be the active sites for the chemisorption of OTC. Systematic electrochemical experiments and analysis have shown that a process of electron transfer mediated by OAm-1 occurred between the pollutant and H2O2 during a Fenton-like reaction. This work experimentally verifies the electron transfer process dominated nonradical mechanism over α-MnO2, which is helpful for understanding the catalytic mechanism of the Fenton-like oxidation.
In Fenton-like oxidation, the catalyst directly influences the reaction mechanism for the degradation of pollutants from water. Here, a α-MnO2 catalyst (OAm-1) was synthesized via a self-assembly method with the assistance of a surfactant. OAm-1 possessed a large specific surface area of 221 m2/g, abundant mesoporous structures and a large proportion of Mn(Ⅲ). Further characterization exhibited that OAm-1 had abundant oxygen vacancies and excellent reducibility and conductivity. The adsorption and catalytic ability of OAm-1 were studied in the degradation of oxytetracycline (OTC) via the activation of hydrogen peroxide (H2O2). Through the radical quenching experiments, electron resonance spectroscopy (EPR), X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FT-IR) analysis, Mn(Ⅲ) of OAm-1 was proved to be the active sites for the chemisorption of OTC. Systematic electrochemical experiments and analysis have shown that a process of electron transfer mediated by OAm-1 occurred between the pollutant and H2O2 during a Fenton-like reaction. This work experimentally verifies the electron transfer process dominated nonradical mechanism over α-MnO2, which is helpful for understanding the catalytic mechanism of the Fenton-like oxidation.
2024, 35(8): 109334
doi: 10.1016/j.cclet.2023.109334
摘要:
Herein, a modified metal-free acetylene black (MMF-AB) catalyst was synthesized by a simple solvothermal-calcination method and designed successfully to activate peroxodisulfate (PDS) for the degradation of sulfisoxazole (SIZ). Due to the doping of N, S and O metal-free elements, the modified catalyst showed excellent catalytic performance with 100% SIZ removal within 30 min. Pseudo first-order reaction rate constants (evaluating catalytic efficiencies and activity) of MMF-AB (kobs = 0.105 min−1) was 3 times higher than pure-AB (kobs = 0.029 min−1). Interestingly, it was demonstrated that the reaction system is based on the transfer of electrons from SIZ to PDS to realize an electron-transfer-based mechanism by the evidence of premixing, electron paramagnetic resonance (EPR) spectroscopy, salt-bridge experiments and electrochemical analyses. The introduction of recyclable filtration device solved the secondary pollution caused by the dispersion of the powdered catalyst in the treated water, which further proved the practicality and superiority of the MMF-AB catalyst.
Herein, a modified metal-free acetylene black (MMF-AB) catalyst was synthesized by a simple solvothermal-calcination method and designed successfully to activate peroxodisulfate (PDS) for the degradation of sulfisoxazole (SIZ). Due to the doping of N, S and O metal-free elements, the modified catalyst showed excellent catalytic performance with 100% SIZ removal within 30 min. Pseudo first-order reaction rate constants (evaluating catalytic efficiencies and activity) of MMF-AB (kobs = 0.105 min−1) was 3 times higher than pure-AB (kobs = 0.029 min−1). Interestingly, it was demonstrated that the reaction system is based on the transfer of electrons from SIZ to PDS to realize an electron-transfer-based mechanism by the evidence of premixing, electron paramagnetic resonance (EPR) spectroscopy, salt-bridge experiments and electrochemical analyses. The introduction of recyclable filtration device solved the secondary pollution caused by the dispersion of the powdered catalyst in the treated water, which further proved the practicality and superiority of the MMF-AB catalyst.
2024, 35(8): 109336
doi: 10.1016/j.cclet.2023.109336
摘要:
In this study, three-dimensional microspherical CQDs/Bi2MoO6 heterostructures were synthesized using a simple alcohol-thermal method. It was found that the CQDs/Bi2MoO6 had a large specific surface area of 56.0 m2/g, and the introduction of CQDs extended the light absorption spectrum from 480 nm to 496 nm. When utilizing the synthesized CQDs/Bi2MoO6 composite for photocatalytic degradation of antibiotic norfloxacin in a water environment, complete decay of norfloxacin and effective removal of total organic carbon (TOC) were achieved within 30 min. Through the optimization of material synthesis and experimental conditions, the optimal CQDs loading amount was determined as 200 µL, the optimal CQDs/Bi2MoO6 dosage was 0.8 g/L. Moreover, the CQDs/Bi2MoO6 worked well under a wide pH range of 4.4–10.8. The coexistence of HCO3− enhanced the norfloxacin decay, while the presence of Cl−, NO3−, and SO42− slightly retarded it. The synthesized CQDs/Bi2MoO6 had the great potential in removing and mineralizing norfloxacin in real aquatic environments.
In this study, three-dimensional microspherical CQDs/Bi2MoO6 heterostructures were synthesized using a simple alcohol-thermal method. It was found that the CQDs/Bi2MoO6 had a large specific surface area of 56.0 m2/g, and the introduction of CQDs extended the light absorption spectrum from 480 nm to 496 nm. When utilizing the synthesized CQDs/Bi2MoO6 composite for photocatalytic degradation of antibiotic norfloxacin in a water environment, complete decay of norfloxacin and effective removal of total organic carbon (TOC) were achieved within 30 min. Through the optimization of material synthesis and experimental conditions, the optimal CQDs loading amount was determined as 200 µL, the optimal CQDs/Bi2MoO6 dosage was 0.8 g/L. Moreover, the CQDs/Bi2MoO6 worked well under a wide pH range of 4.4–10.8. The coexistence of HCO3− enhanced the norfloxacin decay, while the presence of Cl−, NO3−, and SO42− slightly retarded it. The synthesized CQDs/Bi2MoO6 had the great potential in removing and mineralizing norfloxacin in real aquatic environments.
2024, 35(8): 109338
doi: 10.1016/j.cclet.2023.109338
摘要:
Owing to the serious potential side-effects on the environment and human health, the rapid detection and removal of antibiotics have become an important research focus. In this work, four zinc-based metal-organic frameworks (MOFs) with different functional groups, i.e., Zn-MOF, Zn-MOF-CH3, Zn-MOF-NO2, Zn-MOF-COOH, were utilized for the construction of LDO/MOF composite materials with a nickel-iron-cobalt-based layered double oxide, NiFeCo-LDO. The results showed that the LDO/MOF composites not only had high sensitivity in detecting sulfonamide and quinolone antibiotics, but also had an appreciable ability to adsorb them from wastewater. The maximum adsorption capacities of all the four types of LDO@Zn-MOFs to all antibiotics can at least reach 150 mg/g, and the limits of detection in relation to all four antibiotics were at least as low as 100 µg/L. Our work suggested the dual-function extraction performance can be attributed to the synergistic effects between the LDO and the MOFs. Moreover, the strong ferromagnetism derived from the LDO provided great convenience for the separation and regeneration of the LDO/MOF composites.
Owing to the serious potential side-effects on the environment and human health, the rapid detection and removal of antibiotics have become an important research focus. In this work, four zinc-based metal-organic frameworks (MOFs) with different functional groups, i.e., Zn-MOF, Zn-MOF-CH3, Zn-MOF-NO2, Zn-MOF-COOH, were utilized for the construction of LDO/MOF composite materials with a nickel-iron-cobalt-based layered double oxide, NiFeCo-LDO. The results showed that the LDO/MOF composites not only had high sensitivity in detecting sulfonamide and quinolone antibiotics, but also had an appreciable ability to adsorb them from wastewater. The maximum adsorption capacities of all the four types of LDO@Zn-MOFs to all antibiotics can at least reach 150 mg/g, and the limits of detection in relation to all four antibiotics were at least as low as 100 µg/L. Our work suggested the dual-function extraction performance can be attributed to the synergistic effects between the LDO and the MOFs. Moreover, the strong ferromagnetism derived from the LDO provided great convenience for the separation and regeneration of the LDO/MOF composites.
2024, 35(8): 109361
doi: 10.1016/j.cclet.2023.109361
摘要:
Transition-metal-catalyzed remote sp2C—H functionalization of aryl sulfonic acids was hardly ever realized owing to competitive ortho-C—H functionalization of aryl sulfonates and electron-deficient nature of phenyl ring. Herein, with the assistance of a practical biaryl indolyl directing template, palladium-catalyzed remote sp2C—H alkylation of aryl sulfonic acids have been achieved in moderate to good yields with exclusive meta selectivity. Moreover, remote meta-selective C—H alkynylation of aryl sulfonic acids was also accomplished with a rhodium catalyst. These meta-C—H functionalized products proved to be the superior synthetic precursors, which are difficult to access using the conventional strategy.
Transition-metal-catalyzed remote sp2C—H functionalization of aryl sulfonic acids was hardly ever realized owing to competitive ortho-C—H functionalization of aryl sulfonates and electron-deficient nature of phenyl ring. Herein, with the assistance of a practical biaryl indolyl directing template, palladium-catalyzed remote sp2C—H alkylation of aryl sulfonic acids have been achieved in moderate to good yields with exclusive meta selectivity. Moreover, remote meta-selective C—H alkynylation of aryl sulfonic acids was also accomplished with a rhodium catalyst. These meta-C—H functionalized products proved to be the superior synthetic precursors, which are difficult to access using the conventional strategy.
2024, 35(8): 109362
doi: 10.1016/j.cclet.2023.109362
摘要:
In this contribution, we describe the preparation and recognition characteristics of a novel tetrapodal benzene cage (1). The cage can express a wide recognition range without losing selectivity for the object of appropriate size and functional groups. The key to obtaining the desired structural isomer of 1 is the synthesis and isolation of the o-bis(bromomethyl)benzene precursor (5). Three distinct guests, F− (extremely small size), D-lactate (appropriate size) and L-Asp (branched shape), were selected as examples to demonstrate the recognition characteristics of 1. By NMR titration studies, they all expressed good binding affinity (K > 105 L/mol) in competitive medium (10% DMSO/THF), indicating that 1 has a wide recognition scope. The highest binding constant was observed for D-lactate, revealing that 1 has good selectivity for D-lactate versus F− and L-Asp. Moreover, the NMR titration study of F− in DMSO indicates 1 can achieve different binding modes (1:1 and 2:1 guest-host) for small-sized guests, which allows for the further development of binary binding properties and thereafter applications in the field of catalysis.
In this contribution, we describe the preparation and recognition characteristics of a novel tetrapodal benzene cage (1). The cage can express a wide recognition range without losing selectivity for the object of appropriate size and functional groups. The key to obtaining the desired structural isomer of 1 is the synthesis and isolation of the o-bis(bromomethyl)benzene precursor (5). Three distinct guests, F− (extremely small size), D-lactate (appropriate size) and L-Asp (branched shape), were selected as examples to demonstrate the recognition characteristics of 1. By NMR titration studies, they all expressed good binding affinity (K > 105 L/mol) in competitive medium (10% DMSO/THF), indicating that 1 has a wide recognition scope. The highest binding constant was observed for D-lactate, revealing that 1 has good selectivity for D-lactate versus F− and L-Asp. Moreover, the NMR titration study of F− in DMSO indicates 1 can achieve different binding modes (1:1 and 2:1 guest-host) for small-sized guests, which allows for the further development of binary binding properties and thereafter applications in the field of catalysis.
2024, 35(8): 109365
doi: 10.1016/j.cclet.2023.109365
摘要:
Organic lasers with broad emission bands in near-infrared (NIR) region are crucial for their applications in laser communication, night-vision as well as bioimaging owing to the abundance of selectable lasing wavelengths. However, for most organic gain materials, gain regions are limited in a small wavelength range because of the fixed energy level systems. Herein, we design a strategy to realize NIR organic lasers with broad emission bands based on tunable energy level systems induced by cascaded excited-state intramolecular proton transfer (ESIPT). A novel gain material named DHNN was developed, which can undergo a cascaded double-ESIPT process supporting four-level and six-level systems simultaneously. By doping DHNN into polystyrene microspheres, NIR lasers with tunable emission bands can be achieved based on the careful modulation of microcavities. Finally, organic lasers with an ultra-broad emission band ranging from 700 nm to 900 nm was successfully achieved by harnessing four-level and six-level systems simultaneously.
Organic lasers with broad emission bands in near-infrared (NIR) region are crucial for their applications in laser communication, night-vision as well as bioimaging owing to the abundance of selectable lasing wavelengths. However, for most organic gain materials, gain regions are limited in a small wavelength range because of the fixed energy level systems. Herein, we design a strategy to realize NIR organic lasers with broad emission bands based on tunable energy level systems induced by cascaded excited-state intramolecular proton transfer (ESIPT). A novel gain material named DHNN was developed, which can undergo a cascaded double-ESIPT process supporting four-level and six-level systems simultaneously. By doping DHNN into polystyrene microspheres, NIR lasers with tunable emission bands can be achieved based on the careful modulation of microcavities. Finally, organic lasers with an ultra-broad emission band ranging from 700 nm to 900 nm was successfully achieved by harnessing four-level and six-level systems simultaneously.
2024, 35(8): 109402
doi: 10.1016/j.cclet.2023.109402
摘要:
The extraction of radioactive minor actinides (An(Ⅲ)) from lanthanides (Ln(Ⅲ)) is an extremely important step in nuclear waste reprocessing. Designing ligands with high-performance actinide-selectivity remains an essential task. Recent works have reported that some polyazole based ligands exhibit good An(Ⅲ)/Ln(Ⅲ) separation performance. Herein, we first evaluated the effects of different polyazole side chains on the Am(Ⅲ)/Eu(Ⅲ) selectivity by exploring three pyridine-derived polyazole ligands L1, L2 and L3 with 1,2,4-triazole, 1,2,3-triazole, and pyrazole side chains, respectively, using scalar relativistic theoretical methods. The coordination structures, bonding properties and thermodynamic behaviors of AmL(NO3)3 and EuL(NO3)3 complexes were investigated, which clarifies that the side chains do affect the electronic structure of ligand and its selectivity for Am(Ⅲ)/Eu(Ⅲ) ions. Moreover, L1 with 1,2,4-triazole side chains exhibited the highest selectivity for Am(Ⅲ) over Eu(Ⅲ) while the lowest complexation ability for metal ions among the three pyridine-derived polyazole ligands. Subsequently, we designed a new ligand L4 containing 1,2,4-triazole side chains and a preorganized phenanthroline backbone. Theoretically, such a new ligand was verified to show stronger complexation ability and higher selectivity for Am(Ⅲ)/Eu(Ⅲ) ions than L1. This work clarifies the complexation nature of polyazole based ligands with Am(Ⅲ)/Eu(Ⅲ) ions and provides design strategies for highly efficient polyazole based ligands for An(Ⅲ)/Ln(Ⅲ) separation.
The extraction of radioactive minor actinides (An(Ⅲ)) from lanthanides (Ln(Ⅲ)) is an extremely important step in nuclear waste reprocessing. Designing ligands with high-performance actinide-selectivity remains an essential task. Recent works have reported that some polyazole based ligands exhibit good An(Ⅲ)/Ln(Ⅲ) separation performance. Herein, we first evaluated the effects of different polyazole side chains on the Am(Ⅲ)/Eu(Ⅲ) selectivity by exploring three pyridine-derived polyazole ligands L1, L2 and L3 with 1,2,4-triazole, 1,2,3-triazole, and pyrazole side chains, respectively, using scalar relativistic theoretical methods. The coordination structures, bonding properties and thermodynamic behaviors of AmL(NO3)3 and EuL(NO3)3 complexes were investigated, which clarifies that the side chains do affect the electronic structure of ligand and its selectivity for Am(Ⅲ)/Eu(Ⅲ) ions. Moreover, L1 with 1,2,4-triazole side chains exhibited the highest selectivity for Am(Ⅲ) over Eu(Ⅲ) while the lowest complexation ability for metal ions among the three pyridine-derived polyazole ligands. Subsequently, we designed a new ligand L4 containing 1,2,4-triazole side chains and a preorganized phenanthroline backbone. Theoretically, such a new ligand was verified to show stronger complexation ability and higher selectivity for Am(Ⅲ)/Eu(Ⅲ) ions than L1. This work clarifies the complexation nature of polyazole based ligands with Am(Ⅲ)/Eu(Ⅲ) ions and provides design strategies for highly efficient polyazole based ligands for An(Ⅲ)/Ln(Ⅲ) separation.
2024, 35(8): 109403
doi: 10.1016/j.cclet.2023.109403
摘要:
A photochromic molecular rotor based on stiff-stilbene (SSB-FMR) was handily prepared through coupled reaction, and further self-assembled with cucurbit[8]uril (CB[8]) to form a 2:2 quaternary supramolecular complex (SSB-FMR/CB[8]). Significantly, the intervention of CB[8] on SSB-FMR achieved dual functions that assembly-induced emission enhancement and assembly-induced improvement of photoisomerized performance (especially reversibility) of stiff-stilbene molecular photoswitch. The supramolecular strategy further facilitated the assembly as a photoresponsive fluorescence switch with outstanding fatigue resistance, which was expediently applied in high-security-level QR code anti-counterfeiting and controllable lysosome targeted imaging. The study unprecedentedly provides a supramolecular method for highly efficiently improving photoisomerized performance especially reversibility of molecular photoswitches based on stiff-stilbene, and is of vital significance for the construction of intelligent materials with excellent capability.
A photochromic molecular rotor based on stiff-stilbene (SSB-FMR) was handily prepared through coupled reaction, and further self-assembled with cucurbit[8]uril (CB[8]) to form a 2:2 quaternary supramolecular complex (SSB-FMR/CB[8]). Significantly, the intervention of CB[8] on SSB-FMR achieved dual functions that assembly-induced emission enhancement and assembly-induced improvement of photoisomerized performance (especially reversibility) of stiff-stilbene molecular photoswitch. The supramolecular strategy further facilitated the assembly as a photoresponsive fluorescence switch with outstanding fatigue resistance, which was expediently applied in high-security-level QR code anti-counterfeiting and controllable lysosome targeted imaging. The study unprecedentedly provides a supramolecular method for highly efficiently improving photoisomerized performance especially reversibility of molecular photoswitches based on stiff-stilbene, and is of vital significance for the construction of intelligent materials with excellent capability.
2024, 35(8): 109404
doi: 10.1016/j.cclet.2023.109404
摘要:
The self-assembled structures of H3BDA molecule with multiple meta-dicarboxylic groups and their stimulus responses to the guest molecules (COR and T4PT) are thoroughly investigated by scanning tunneling microscopy (STM). STM observations display that two kinds of nanostructures are fabricated by H3BDA molecules through intermolecular hydrogen bonds, in which a linear structure is formed at a higher concentration and a flower-like structure is obtained at a lower concentration. After the addition of COR and T4PT, H3BDA appears different responsiveness resulting in different co-assembled structures, respectively. The linear structure is regulated into a flower-like structure by COR and COR molecules are trapped in the cavities. When the pyridine derivative (T4PT) is introduced, a new bicomponent porous structure emerges via the hydrogen bond formed between the carboxyl group and the pyridine. Furthermore, the deposition of additional COR to the H3BDA/T4PT system results in the breakdown of the porous structure and the generation of H3BDA/COR host–guest system. Combined with density functional theory (DFT) calculations and molecular dynamics (MD) simulations, the transformation phenomenon of bi-component nanostructure induced by guest molecules is formulated. The results are expected to understand the modification effect of guest molecules on the host network, which is of great significance for the design and construction of multi-component nanostructures and crystal engineering.
The self-assembled structures of H3BDA molecule with multiple meta-dicarboxylic groups and their stimulus responses to the guest molecules (COR and T4PT) are thoroughly investigated by scanning tunneling microscopy (STM). STM observations display that two kinds of nanostructures are fabricated by H3BDA molecules through intermolecular hydrogen bonds, in which a linear structure is formed at a higher concentration and a flower-like structure is obtained at a lower concentration. After the addition of COR and T4PT, H3BDA appears different responsiveness resulting in different co-assembled structures, respectively. The linear structure is regulated into a flower-like structure by COR and COR molecules are trapped in the cavities. When the pyridine derivative (T4PT) is introduced, a new bicomponent porous structure emerges via the hydrogen bond formed between the carboxyl group and the pyridine. Furthermore, the deposition of additional COR to the H3BDA/T4PT system results in the breakdown of the porous structure and the generation of H3BDA/COR host–guest system. Combined with density functional theory (DFT) calculations and molecular dynamics (MD) simulations, the transformation phenomenon of bi-component nanostructure induced by guest molecules is formulated. The results are expected to understand the modification effect of guest molecules on the host network, which is of great significance for the design and construction of multi-component nanostructures and crystal engineering.
2024, 35(8): 109408
doi: 10.1016/j.cclet.2023.109408
摘要:
Heterocycle-braced cyclic peptides have demonstrated enhanced metabolic stability, increased potency and selectivity. Here, we present a rapid synthesis method for constructing Trp(C7)-alkene(E)-crosslinked cyclic peptides with potent anti-proliferative activities against cancer cells, through C-H alkenylation and macrolactamization. This report addresses critical challenges associated with the installation and removal of the directing group N-Piv, configuration selectivity of the olefin, and intramolecular cyclization. Notably, this method exhibits mild reaction conditions, traceless removal of the directing group, and high configuration selectivity.
Heterocycle-braced cyclic peptides have demonstrated enhanced metabolic stability, increased potency and selectivity. Here, we present a rapid synthesis method for constructing Trp(C7)-alkene(E)-crosslinked cyclic peptides with potent anti-proliferative activities against cancer cells, through C-H alkenylation and macrolactamization. This report addresses critical challenges associated with the installation and removal of the directing group N-Piv, configuration selectivity of the olefin, and intramolecular cyclization. Notably, this method exhibits mild reaction conditions, traceless removal of the directing group, and high configuration selectivity.
2024, 35(8): 109433
doi: 10.1016/j.cclet.2023.109433
摘要:
The dynamic kinetic asymmetric transformation of racemic propargylic ammonium salts with prochiral aldimine esters through a stereodivergent propargylation is catalyzed by dual nickel and copper catalysis. Thus, a diverse range of optically active α-quaternary amino esters were produced via CN bond cleavage with high reaction efficiency and stereoselectivity (up to > 99% ee). By selection of the appropriate pairwise combination of catalyst configurational isomers, all four possible stereoisomers of the corresponding propargylation products are obtained in high yields with excellent regio-, diastereo-, and enantioselectivities.
The dynamic kinetic asymmetric transformation of racemic propargylic ammonium salts with prochiral aldimine esters through a stereodivergent propargylation is catalyzed by dual nickel and copper catalysis. Thus, a diverse range of optically active α-quaternary amino esters were produced via CN bond cleavage with high reaction efficiency and stereoselectivity (up to > 99% ee). By selection of the appropriate pairwise combination of catalyst configurational isomers, all four possible stereoisomers of the corresponding propargylation products are obtained in high yields with excellent regio-, diastereo-, and enantioselectivities.
2024, 35(8): 109434
doi: 10.1016/j.cclet.2023.109434
摘要:
This study presents an unexpected finding that the cis isomer of β-thio-Asp exhibits higher ligation activity than the trans isomer. This discovery sheds light on the intricate nature of native chemical ligation and highlights the importance of factors beyond the steric effects of the side chain in modulating ligation activity.
This study presents an unexpected finding that the cis isomer of β-thio-Asp exhibits higher ligation activity than the trans isomer. This discovery sheds light on the intricate nature of native chemical ligation and highlights the importance of factors beyond the steric effects of the side chain in modulating ligation activity.
2024, 35(8): 109443
doi: 10.1016/j.cclet.2023.109443
摘要:
This work describes intermolecular acylfluorination of gem-difluoroenynes using acyl fluorides as both acyl source and fluorine source. Trifluoromethyl-substituted allenones or furans could be selectively achieved via phosphine and silver catalysis. These approaches exhibit high regioselectivity, atom economy and broad functionality tolerance.
This work describes intermolecular acylfluorination of gem-difluoroenynes using acyl fluorides as both acyl source and fluorine source. Trifluoromethyl-substituted allenones or furans could be selectively achieved via phosphine and silver catalysis. These approaches exhibit high regioselectivity, atom economy and broad functionality tolerance.
2024, 35(8): 109457
doi: 10.1016/j.cclet.2023.109457
摘要:
Delayed or non-healing of diabetic wounds is a significant complication, often attributed to high glucose-induced M1 macrophage accumulation, impaired angiogenesis, and reactive oxygen species (ROS) buildup. Addressing this, we introduced a strontium polyphenol network microneedle patch (SrC-MPNs@MN-PP) for percutaneous drug delivery. This patch, formulated with polymer poly(γ-glutamic acid) (γ-PGA) and epsilon-poly-L-lysine (ε-PLL), incorporates strontium polyphenol networks (SrC-MPNs). The release of chlorogenic acid (CGA) from SrC-MPNs not only neutralizes ROS, but strontium ions also foster angiogenesis. Consequently, SrC-MPNs@MN-PP can ameliorate the diabetic wound microenvironment and expedite healing.
Delayed or non-healing of diabetic wounds is a significant complication, often attributed to high glucose-induced M1 macrophage accumulation, impaired angiogenesis, and reactive oxygen species (ROS) buildup. Addressing this, we introduced a strontium polyphenol network microneedle patch (SrC-MPNs@MN-PP) for percutaneous drug delivery. This patch, formulated with polymer poly(γ-glutamic acid) (γ-PGA) and epsilon-poly-L-lysine (ε-PLL), incorporates strontium polyphenol networks (SrC-MPNs). The release of chlorogenic acid (CGA) from SrC-MPNs not only neutralizes ROS, but strontium ions also foster angiogenesis. Consequently, SrC-MPNs@MN-PP can ameliorate the diabetic wound microenvironment and expedite healing.
2024, 35(8): 109467
doi: 10.1016/j.cclet.2023.109467
摘要:
Sulphur (S)-template method based on conventional slurry-casting method has been developed to produce porous silicon (Si) electrodes. The facile fabrication technology is suitable for current production line and expected to be widely applied to various electrode materials under large volume change during operation. Specifically, S particles as template agent are mixed with active material Si, carbon conductor and binder forming uniform slurry. After casting and drying, the electrodes are immersed in carbon disulfide solution to remove S particles rapidly, generating pores in-situ at the original position of S particles. Electrochemical analysis shows that the pores inside electrodes are able to shorten lithium ion diffusion paths, reduce normal expansion rate and decrease formation of cracks in the Si electrode (2 mgSi/cm2), demonstrating a reversible capacity of 951 mAh/g at 0.5 A/g after 100 cycles (with a capacity retention of 99.5%) and a capacity of ~826 mAh/g at 2 A/g.
Sulphur (S)-template method based on conventional slurry-casting method has been developed to produce porous silicon (Si) electrodes. The facile fabrication technology is suitable for current production line and expected to be widely applied to various electrode materials under large volume change during operation. Specifically, S particles as template agent are mixed with active material Si, carbon conductor and binder forming uniform slurry. After casting and drying, the electrodes are immersed in carbon disulfide solution to remove S particles rapidly, generating pores in-situ at the original position of S particles. Electrochemical analysis shows that the pores inside electrodes are able to shorten lithium ion diffusion paths, reduce normal expansion rate and decrease formation of cracks in the Si electrode (2 mgSi/cm2), demonstrating a reversible capacity of 951 mAh/g at 0.5 A/g after 100 cycles (with a capacity retention of 99.5%) and a capacity of ~826 mAh/g at 2 A/g.
2024, 35(8): 109514
doi: 10.1016/j.cclet.2024.109514
摘要:
An eco-friendly and practical method for the clean preparation of 5-amino-1,2,4-thiadiazoles was developed. With WS2 as the semiconductor photocatalyst, both TEMPO and O2 (in air) as the redox catalysts, a variety of thiadiazoles were semi-heterogeneously formed in high to quantitative yields and could be easily collected by CPME extraction and rinsing. Furthermore, the catalytic system can be reusable for at least 5 reaction runs.
An eco-friendly and practical method for the clean preparation of 5-amino-1,2,4-thiadiazoles was developed. With WS2 as the semiconductor photocatalyst, both TEMPO and O2 (in air) as the redox catalysts, a variety of thiadiazoles were semi-heterogeneously formed in high to quantitative yields and could be easily collected by CPME extraction and rinsing. Furthermore, the catalytic system can be reusable for at least 5 reaction runs.
2024, 35(8): 109518
doi: 10.1016/j.cclet.2024.109518
摘要:
The development of low-cost, earth-abundant and environmentally benign transition metal catalysts, which can catalyze multiple different types of asymmetric reactions, is an important objective in modern asymmetric catalysis. Herein we demonstrate that a chiral Ni/P-Phos catalyst achieves three types of asymmetric reactions: allenylic substitution of racemic allenic ethers, 1,4-hydroalkylation of prochiral 1,3-enynes and double alkylation of newly designed enynyl ether reagents. Three methods complement each other and produce various axially chiral allene derivatives bearing a pyrazolidine-3,5-dione unit, which is widely present in drugs and biologically active molecules with versatile pharmacological activities.
The development of low-cost, earth-abundant and environmentally benign transition metal catalysts, which can catalyze multiple different types of asymmetric reactions, is an important objective in modern asymmetric catalysis. Herein we demonstrate that a chiral Ni/P-Phos catalyst achieves three types of asymmetric reactions: allenylic substitution of racemic allenic ethers, 1,4-hydroalkylation of prochiral 1,3-enynes and double alkylation of newly designed enynyl ether reagents. Three methods complement each other and produce various axially chiral allene derivatives bearing a pyrazolidine-3,5-dione unit, which is widely present in drugs and biologically active molecules with versatile pharmacological activities.
2024, 35(8): 109737
doi: 10.1016/j.cclet.2024.109737
摘要:
Highly branched poly(β-amino ester)s (HPAEs) have emerged as a safe and efficient type of non-viral gene delivery vectors. However, the presence of inactive terminal secondary amine groups compromises their gene transfection capability. In this study, HPAEs with similar topological structures and chemical compositions but varying numbers of terminal secondary 4-amino-1-butanol (S4) and secondary/tertiary 3-morpholinopropylamine (MPA) groups were synthesized. The results demonstrate that an increased number of secondary/tertiary MPA groups in-situ significantly enhances the DNA binding capability of HPAEs, leading to the formation of smaller HPAE/DNA polyplexes with higher zeta potential, ultimately resulting in superior gene transfection efficiency in bladder epithelial cells. This study establishes a simple yet effective strategy to maximize the gene transfection potency of HPAEs by converting the inactive terminal groups in-situ without the need for complex modifications to their topological structure and chemical composition.
Highly branched poly(β-amino ester)s (HPAEs) have emerged as a safe and efficient type of non-viral gene delivery vectors. However, the presence of inactive terminal secondary amine groups compromises their gene transfection capability. In this study, HPAEs with similar topological structures and chemical compositions but varying numbers of terminal secondary 4-amino-1-butanol (S4) and secondary/tertiary 3-morpholinopropylamine (MPA) groups were synthesized. The results demonstrate that an increased number of secondary/tertiary MPA groups in-situ significantly enhances the DNA binding capability of HPAEs, leading to the formation of smaller HPAE/DNA polyplexes with higher zeta potential, ultimately resulting in superior gene transfection efficiency in bladder epithelial cells. This study establishes a simple yet effective strategy to maximize the gene transfection potency of HPAEs by converting the inactive terminal groups in-situ without the need for complex modifications to their topological structure and chemical composition.
2024, 35(8): 109745
doi: 10.1016/j.cclet.2024.109745
摘要:
Diradical polycyclic hydrocarbons (PHs) have unique open-shell structures and interesting physical properties. However, owing to high reactivity of unpaired electrons, such open-shell organic diradicaloids are usually less stable than closed-shell systems, limiting their practical applications. In this study, we report P=O-attaching of diradical PHs as a new strategy to enhance their stability while maintaining diradical properties. Three P=O-attached PHs containing the indeno[1,2-b]fluorene, fluoreno[3,2-b]fluorene and indeno[2,1-b]fluorene π-skeletons, respectively, were designed and synthesized. As theoretically and experimentally proved, two of them have the relatively large diradical characters and open-shell singlet diradical nature. In comparison to their all-carbon analogues, the attached electron-withdrawing P=O groups endow them with much lower LUMO/HOMO energy levels but preserved magnetic activities and physical properties, such as thermally accessible triplet species and multi-redox ability. Moreover, the P=O groups effectively decrease their oxidation activities and thereby lead to their remarkably excellent ambient stabilities. Thus, this P=O-attaching strategy will be applicable to other diradical PH systems and may promote the generation of stable organic diradicaloids for radical chemistry and materials.
Diradical polycyclic hydrocarbons (PHs) have unique open-shell structures and interesting physical properties. However, owing to high reactivity of unpaired electrons, such open-shell organic diradicaloids are usually less stable than closed-shell systems, limiting their practical applications. In this study, we report P=O-attaching of diradical PHs as a new strategy to enhance their stability while maintaining diradical properties. Three P=O-attached PHs containing the indeno[1,2-b]fluorene, fluoreno[3,2-b]fluorene and indeno[2,1-b]fluorene π-skeletons, respectively, were designed and synthesized. As theoretically and experimentally proved, two of them have the relatively large diradical characters and open-shell singlet diradical nature. In comparison to their all-carbon analogues, the attached electron-withdrawing P=O groups endow them with much lower LUMO/HOMO energy levels but preserved magnetic activities and physical properties, such as thermally accessible triplet species and multi-redox ability. Moreover, the P=O groups effectively decrease their oxidation activities and thereby lead to their remarkably excellent ambient stabilities. Thus, this P=O-attaching strategy will be applicable to other diradical PH systems and may promote the generation of stable organic diradicaloids for radical chemistry and materials.
2024, 35(8): 109806
doi: 10.1016/j.cclet.2024.109806
摘要:
Electrocatalytic synthesis of urea through CN bond formation, converting carbon dioxide (CO2) and nitrate (NO3–), presents a promising, less energy-intensive alternative to industrial urea production process. In this communication, we report the application of Mo2C nanosheets-decorated carbon sheets (Mo2C/C) as a highly efficient electrocatalyst for facilitating CN coupling in ambient urea electrosynthesis. In CO2-saturated 0.2 mol/L Na2SO4 solution containing 0.05 mol/L NO3–, the Mo2C/C catalyst achieves an impressive urea yield of 579.13 µg h–1 mg–1 with high Faradaic efficiency of 44.80% at –0.5 V versus the reversible hydrogen electrode. Further theoretical calculations reveal that the multiple Mo active sites enhance the formation of *CO and *NH2 intermediates and facilitate their CN coupling. This research propels the use of Mo2C-based electrodes in electrocatalysis and accentuates the capabilities of binary metal-based catalysts in CN coupling reactions.
Electrocatalytic synthesis of urea through CN bond formation, converting carbon dioxide (CO2) and nitrate (NO3–), presents a promising, less energy-intensive alternative to industrial urea production process. In this communication, we report the application of Mo2C nanosheets-decorated carbon sheets (Mo2C/C) as a highly efficient electrocatalyst for facilitating CN coupling in ambient urea electrosynthesis. In CO2-saturated 0.2 mol/L Na2SO4 solution containing 0.05 mol/L NO3–, the Mo2C/C catalyst achieves an impressive urea yield of 579.13 µg h–1 mg–1 with high Faradaic efficiency of 44.80% at –0.5 V versus the reversible hydrogen electrode. Further theoretical calculations reveal that the multiple Mo active sites enhance the formation of *CO and *NH2 intermediates and facilitate their CN coupling. This research propels the use of Mo2C-based electrodes in electrocatalysis and accentuates the capabilities of binary metal-based catalysts in CN coupling reactions.
2024, 35(8): 109886
doi: 10.1016/j.cclet.2024.109886
摘要:
Photocatalytic synthesis of hydrogen peroxide has gradually become a promising method for in-situ production of hydrogen peroxide, which relies on sustainable solar energy. However, the commonly used photocatalyst, i.e., carbon nitride (CN), still suffers from the drawbacks of narrow light absorption range and fast charge recombination. Here, we report a facile method to introduce nitrogen defects into carbon nitride together with sodium ion. By adjusting the ratio of sodium dicyandiamide, the band gap of carbon nitride can be controlled, while the carrier separation and transfer ability of carbon nitride is improved. The modified CN with sodium doping and nitrogen defect (SD-CN) demonstrates outstanding H2O2 production performance (H2O2 yield rate of 297.2 µmol L−1 h−1) under visible light irradiation, which is approximately 9.8 times higher than that of pristine CN. This work deepens the understanding of the coordinated effect of structural defect and element doping of carbon nitride on the photocatalytic H2O2 production performance, and provides new insight into the design of photocatalytic system for efficient production of H2O2.
Photocatalytic synthesis of hydrogen peroxide has gradually become a promising method for in-situ production of hydrogen peroxide, which relies on sustainable solar energy. However, the commonly used photocatalyst, i.e., carbon nitride (CN), still suffers from the drawbacks of narrow light absorption range and fast charge recombination. Here, we report a facile method to introduce nitrogen defects into carbon nitride together with sodium ion. By adjusting the ratio of sodium dicyandiamide, the band gap of carbon nitride can be controlled, while the carrier separation and transfer ability of carbon nitride is improved. The modified CN with sodium doping and nitrogen defect (SD-CN) demonstrates outstanding H2O2 production performance (H2O2 yield rate of 297.2 µmol L−1 h−1) under visible light irradiation, which is approximately 9.8 times higher than that of pristine CN. This work deepens the understanding of the coordinated effect of structural defect and element doping of carbon nitride on the photocatalytic H2O2 production performance, and provides new insight into the design of photocatalytic system for efficient production of H2O2.
2024, 35(8): 109894
doi: 10.1016/j.cclet.2024.109894
摘要:
Herein, we constructed defective UiO-66 with rich Zr vacancy structure model, in which the defective structure was verified by various characterizations. Also, the Pb adsorption experiments affirmed that defective UiO-66 could display better adsorption and selective adsorption ability than that of perfect UiO-66. The results of partial density of states (PDOS) and Mulliken charge population indicated that the blue shift of O 2p and Zr 4d orbit induced the electron rearrangement of atoms closed to the bonding sites, while the positive charge number of Zr atoms decreased than before. Combining with the expansion of pore size, Pb atom was more inclined to transfer and bond with unsaturated coordination oxygens. More significantly, quantitative structure-activity relationships (QSARs) demonstrated that selective capture of Pb instead of Zn, Cu, Cd and Hg displayed by defective UiO-66 was determined jointly by bond strength, adsorption energy and electron transfer. This work provided some theoretical direction for the purpose of the fabrication of adsorbent and the investigation of mechanism.
Herein, we constructed defective UiO-66 with rich Zr vacancy structure model, in which the defective structure was verified by various characterizations. Also, the Pb adsorption experiments affirmed that defective UiO-66 could display better adsorption and selective adsorption ability than that of perfect UiO-66. The results of partial density of states (PDOS) and Mulliken charge population indicated that the blue shift of O 2p and Zr 4d orbit induced the electron rearrangement of atoms closed to the bonding sites, while the positive charge number of Zr atoms decreased than before. Combining with the expansion of pore size, Pb atom was more inclined to transfer and bond with unsaturated coordination oxygens. More significantly, quantitative structure-activity relationships (QSARs) demonstrated that selective capture of Pb instead of Zn, Cu, Cd and Hg displayed by defective UiO-66 was determined jointly by bond strength, adsorption energy and electron transfer. This work provided some theoretical direction for the purpose of the fabrication of adsorbent and the investigation of mechanism.
2024, 35(8): 109105
doi: 10.1016/j.cclet.2023.109105
摘要:
Electrocatalysis is a surface-sensitive process, in which the catalytic activity of electrocatalyst highly relates to the surface adsorption/desorption behaviors of the reactants/intermediates/products on the catalytically active sites. Surface chemical microenvironment engineering via organic molecules functionalization is a promising strategy to tune the electrocatalytic activity since it can well modify the electrode/electrolyte interface and alter the reaction pathways. In this review, we summarize the recent progress of surface microenvironment engineering of electrocatalysts induced by organic molecules functionalization, with the special focus on the organic molecule-assisted growth mechanism and unique electronic effect. More importantly, the applications of organic molecule functionalized catalysts in various electrocatalytic reactions are also systematically summarized, along with a deep discussion on the conclusion and perspective. This work will open a new avenue for the construction and modification of advanced electrocatalysts based on organic molecule-mediated interface engineering.
Electrocatalysis is a surface-sensitive process, in which the catalytic activity of electrocatalyst highly relates to the surface adsorption/desorption behaviors of the reactants/intermediates/products on the catalytically active sites. Surface chemical microenvironment engineering via organic molecules functionalization is a promising strategy to tune the electrocatalytic activity since it can well modify the electrode/electrolyte interface and alter the reaction pathways. In this review, we summarize the recent progress of surface microenvironment engineering of electrocatalysts induced by organic molecules functionalization, with the special focus on the organic molecule-assisted growth mechanism and unique electronic effect. More importantly, the applications of organic molecule functionalized catalysts in various electrocatalytic reactions are also systematically summarized, along with a deep discussion on the conclusion and perspective. This work will open a new avenue for the construction and modification of advanced electrocatalysts based on organic molecule-mediated interface engineering.
2024, 35(8): 109141
doi: 10.1016/j.cclet.2023.109141
摘要:
Catalyst with high performance has drawn increasing attention recently due to its significant advantages in chemical reactions such as speeding up the reaction, lowering the reaction temperature or pressure, and proceeding without itself being consumed. Despite the superior catalytic performance of precious metal catalysts, transition metal oxides offer a promising route for substitution of precious metals in catalysis arising from their low cost, intrinsic activity and sufficient stability. Mullite-type oxide SmMn2O5 exhibits a unique crystal structure containing double crystalline fields, and nowadays is used widely as the catalyst in different chemical reactions, including the reactions of vehicle emissions reduction and oxygen evolution reaction, gas sensors, and metal-air batteries, promoting attention in catalytic performance enhancement. To our knowledge, there is no review article covering the comprehensive information of SmMn2O5 and its applications. Here we review the recent progress in understanding of the crystal structure of SmMn2O5 and its basic physical properties. We then summarize the catalytic sources of SmMn2O5 and reaction mechanisms, while the strategies to improve catalytic performance of SmMn2O5 are further presented. Finally, we provide a perspective on how to make further progress in catalytic applications.
Catalyst with high performance has drawn increasing attention recently due to its significant advantages in chemical reactions such as speeding up the reaction, lowering the reaction temperature or pressure, and proceeding without itself being consumed. Despite the superior catalytic performance of precious metal catalysts, transition metal oxides offer a promising route for substitution of precious metals in catalysis arising from their low cost, intrinsic activity and sufficient stability. Mullite-type oxide SmMn2O5 exhibits a unique crystal structure containing double crystalline fields, and nowadays is used widely as the catalyst in different chemical reactions, including the reactions of vehicle emissions reduction and oxygen evolution reaction, gas sensors, and metal-air batteries, promoting attention in catalytic performance enhancement. To our knowledge, there is no review article covering the comprehensive information of SmMn2O5 and its applications. Here we review the recent progress in understanding of the crystal structure of SmMn2O5 and its basic physical properties. We then summarize the catalytic sources of SmMn2O5 and reaction mechanisms, while the strategies to improve catalytic performance of SmMn2O5 are further presented. Finally, we provide a perspective on how to make further progress in catalytic applications.
2024, 35(8): 109142
doi: 10.1016/j.cclet.2023.109142
摘要:
Climate change is an important issue facing the world today and carbon reduction has become the focus of attention for all countries. Alternative bio-fuels are an important means to achieve carbon emission reduction. The production of jet fuel precursors from biomass by hydrothermal liquefaction (HTL) has received a lot of attention due to its mild conditions and environmental friendliness. Lignocellulosic biomass and algal biomass are considered as the second and the third generation biomasses as promising raw materials for alternative fuel preparation. Among them, lignocellulosic biomass has been extensively studied due to its wide range of sources and can be divided into one-step HTL and stepwise HTL according to the process method. Algal biomass has been extensively studied experimentally due to its short growth cycle and the fact that it can sequester large amounts of carbon without taking up arable land. In this paper, the feedstock composition of different biomasses is reviewed for the HTL of biomass. A detailed review of the process characteristics, reaction pathways and influencing factors for the HTL production of jet fuel precursors from lignocellulosic biomass and algal biomass is also presented. Theoretical references are provided for further process optimization and bio-crude quality upgrading.
Climate change is an important issue facing the world today and carbon reduction has become the focus of attention for all countries. Alternative bio-fuels are an important means to achieve carbon emission reduction. The production of jet fuel precursors from biomass by hydrothermal liquefaction (HTL) has received a lot of attention due to its mild conditions and environmental friendliness. Lignocellulosic biomass and algal biomass are considered as the second and the third generation biomasses as promising raw materials for alternative fuel preparation. Among them, lignocellulosic biomass has been extensively studied due to its wide range of sources and can be divided into one-step HTL and stepwise HTL according to the process method. Algal biomass has been extensively studied experimentally due to its short growth cycle and the fact that it can sequester large amounts of carbon without taking up arable land. In this paper, the feedstock composition of different biomasses is reviewed for the HTL of biomass. A detailed review of the process characteristics, reaction pathways and influencing factors for the HTL production of jet fuel precursors from lignocellulosic biomass and algal biomass is also presented. Theoretical references are provided for further process optimization and bio-crude quality upgrading.
2024, 35(8): 109143
doi: 10.1016/j.cclet.2023.109143
摘要:
With the low cost, excellent safety and high theoretical specific capacity, aqueous zinc-ion batteries (AZIBs) are considered as a potential rival for lithium-ion batteries to promote the sustainable development of large-scale energy storage technologies. However, the notorious Zn dendrites and low Coulombic efficiency (CE) limit further development of AZIBs, due to the unstable electrochemical deposition/stripping behavior of Zn anode in aqueous zinc ion electrolytes. In this review, critical issues and advances are summarized in electrolyte engineering strategies. These strategies are focused on active water molecules during electrochemical process, including high-concentration electrolytes, ionic liquids, gel-polymer electrolytes and functional additives. With suppressed active water molecules, the solvation and de-solvation behavior of Zn2+ can be regulated, thereby modulating the electrochemical performance of Zn anode. Finally, the inherent problems of these strategies are discussed, and some promising directions are provided on electrolytes engineering for high performance Zn anode in AZIBs.
With the low cost, excellent safety and high theoretical specific capacity, aqueous zinc-ion batteries (AZIBs) are considered as a potential rival for lithium-ion batteries to promote the sustainable development of large-scale energy storage technologies. However, the notorious Zn dendrites and low Coulombic efficiency (CE) limit further development of AZIBs, due to the unstable electrochemical deposition/stripping behavior of Zn anode in aqueous zinc ion electrolytes. In this review, critical issues and advances are summarized in electrolyte engineering strategies. These strategies are focused on active water molecules during electrochemical process, including high-concentration electrolytes, ionic liquids, gel-polymer electrolytes and functional additives. With suppressed active water molecules, the solvation and de-solvation behavior of Zn2+ can be regulated, thereby modulating the electrochemical performance of Zn anode. Finally, the inherent problems of these strategies are discussed, and some promising directions are provided on electrolytes engineering for high performance Zn anode in AZIBs.
2024, 35(8): 109147
doi: 10.1016/j.cclet.2023.109147
摘要:
Urea is extensively used in agriculture and chemical industry, and it is produced on an industrial scale from CO2 and Haber–Bosch NH3 under relatively high temperature and high pressure conditions, which demands high energy input and generates masses of carbon footprint. The conversion of CO2 and N sources (such as NO2−, NO3−, and N2) through electrocatalytic reactions under ambient conditions is a promising alternative to realize efficient urea synthesis. Of note, the design of electrocatalyst is one of the key factors that can improve the efficiency and selectivity of C–N coupling reactions. Defect engineering is an intriguing strategy for regulating the electronic structure and charge density of electrocatalysts, which endows electrocatalysts with excellent physicochemical properties and optimized adsorption energy of the reaction intermediates to reduce the kinetic barriers. In this minireview, recent advances of defect engineered electrocatalysts in urea electrosynthesis from CO2 and various N reactants are firstly introduced. Mechanistic discussions of C–N coupling in these advances are presented, with the aim of directing future investigations on improving the urea yield. Finally, the prospects and challenges of defect engineered electrocatalysts for urea synthesis are discussed. This overview is expected to provide in-depth understanding of structure–reactivity relationship and shed light on future electrocatalytic C–N coupling reactions.
Urea is extensively used in agriculture and chemical industry, and it is produced on an industrial scale from CO2 and Haber–Bosch NH3 under relatively high temperature and high pressure conditions, which demands high energy input and generates masses of carbon footprint. The conversion of CO2 and N sources (such as NO2−, NO3−, and N2) through electrocatalytic reactions under ambient conditions is a promising alternative to realize efficient urea synthesis. Of note, the design of electrocatalyst is one of the key factors that can improve the efficiency and selectivity of C–N coupling reactions. Defect engineering is an intriguing strategy for regulating the electronic structure and charge density of electrocatalysts, which endows electrocatalysts with excellent physicochemical properties and optimized adsorption energy of the reaction intermediates to reduce the kinetic barriers. In this minireview, recent advances of defect engineered electrocatalysts in urea electrosynthesis from CO2 and various N reactants are firstly introduced. Mechanistic discussions of C–N coupling in these advances are presented, with the aim of directing future investigations on improving the urea yield. Finally, the prospects and challenges of defect engineered electrocatalysts for urea synthesis are discussed. This overview is expected to provide in-depth understanding of structure–reactivity relationship and shed light on future electrocatalytic C–N coupling reactions.
2024, 35(8): 109192
doi: 10.1016/j.cclet.2023.109192
摘要:
Small molecule inhibitors have dominated the pharmaceutical landscape for a long time as the primary therapeutic paradigm targeting pathogenic proteins. However, their efficacy heavily relies on the amino acid composition and spatial constitution of proteins, rendering them susceptible to drug resistance and failing to target undruggable proteins. In recent years, the advent of targeted protein degradation (TPD) technology has captured substantial attention from both industry and academia. Employing an event-driven mode, TPD offers a novel approach to eliminate pathogenic proteins by promoting their degradation, thus circumventing the limitations associated with traditional small molecule inhibitors. Hydrophobic tag tethering degrader (HyTTD) technology represents one such TPD approach that is currently in the burgeoning stage. HyTTDs employ endogenous protein degradation systems to induce the degradation of target proteins through the proteasome pathway, which displays significant potential for medical value. In this review, we provide a comprehensive overview of the development history and the reported mechanism of action of HyTTDs. Additionally, we delve into the physiological roles, structure-activity relationships, and medical implications of HyTTDs targeting various disease-associated proteins. Moreover, we propose insights into the challenges that necessitate resolution for the successful development of HyTTDs, with the ultimate goal of initiating a new age of clinical treatment leveraging the immense potential of HyTTDs.
Small molecule inhibitors have dominated the pharmaceutical landscape for a long time as the primary therapeutic paradigm targeting pathogenic proteins. However, their efficacy heavily relies on the amino acid composition and spatial constitution of proteins, rendering them susceptible to drug resistance and failing to target undruggable proteins. In recent years, the advent of targeted protein degradation (TPD) technology has captured substantial attention from both industry and academia. Employing an event-driven mode, TPD offers a novel approach to eliminate pathogenic proteins by promoting their degradation, thus circumventing the limitations associated with traditional small molecule inhibitors. Hydrophobic tag tethering degrader (HyTTD) technology represents one such TPD approach that is currently in the burgeoning stage. HyTTDs employ endogenous protein degradation systems to induce the degradation of target proteins through the proteasome pathway, which displays significant potential for medical value. In this review, we provide a comprehensive overview of the development history and the reported mechanism of action of HyTTDs. Additionally, we delve into the physiological roles, structure-activity relationships, and medical implications of HyTTDs targeting various disease-associated proteins. Moreover, we propose insights into the challenges that necessitate resolution for the successful development of HyTTDs, with the ultimate goal of initiating a new age of clinical treatment leveraging the immense potential of HyTTDs.
2024, 35(8): 109225
doi: 10.1016/j.cclet.2023.109225
摘要:
Radiotherapy (RT) is a crucial treatment for cancer; however, its effectiveness is limited by adverse effects on normal tissues, radioresistance, and tumor recurrence. To overcome these challenges, hydrogels have been employed for delivery of radiosensitizers and other therapeutic agents. This review summarizes recent advancements in the application of hydrogel-based local drug delivery systems for improving the therapeutic efficacy of RT in cancer treatment. Firstly, we introduce the classification and properties of hydrogels. Next, we detail hydrogel-based platforms designed to enhance both external beam radiation therapy and brachytherapy. We also discuss hydrogels used in combination therapy involving RT and immunotherapy. Lastly, we highlight the challenges that hydrogels face in RT. By surveying the latest developments in hydrogel applications for RT, this review aims to provide insights into the development of more effective and targeted cancer therapies.
Radiotherapy (RT) is a crucial treatment for cancer; however, its effectiveness is limited by adverse effects on normal tissues, radioresistance, and tumor recurrence. To overcome these challenges, hydrogels have been employed for delivery of radiosensitizers and other therapeutic agents. This review summarizes recent advancements in the application of hydrogel-based local drug delivery systems for improving the therapeutic efficacy of RT in cancer treatment. Firstly, we introduce the classification and properties of hydrogels. Next, we detail hydrogel-based platforms designed to enhance both external beam radiation therapy and brachytherapy. We also discuss hydrogels used in combination therapy involving RT and immunotherapy. Lastly, we highlight the challenges that hydrogels face in RT. By surveying the latest developments in hydrogel applications for RT, this review aims to provide insights into the development of more effective and targeted cancer therapies.
2024, 35(8): 109249
doi: 10.1016/j.cclet.2023.109249
摘要:
The concentration of metallic elements is closely associated with overall health. However, the discharge of untreated industrial wastewater can lead to metal-containing pollutants entering the human body through the food chain, disrupting the organism's homeostasis and posing a risk to human health. Covalent organic framework materials (COFs) have emerged as a novel porous material for detecting or adsorbing metal ions due to their unique pore structure, topological structure and flexible design. This paper summarizes the role, toxicity, and sources of metal ions related to human health, as well as the design, synthesis and performance of COFs fluorescent materials for detecting these elements. The interaction mechanism of different fluorescent COFs and metal ions are discussed. Additionally, the remaining challenges and prospects of COFs fluorescence sensors are provided. We believe this review will be useful in directing the development of fluorescent COFs towards metal ions.
The concentration of metallic elements is closely associated with overall health. However, the discharge of untreated industrial wastewater can lead to metal-containing pollutants entering the human body through the food chain, disrupting the organism's homeostasis and posing a risk to human health. Covalent organic framework materials (COFs) have emerged as a novel porous material for detecting or adsorbing metal ions due to their unique pore structure, topological structure and flexible design. This paper summarizes the role, toxicity, and sources of metal ions related to human health, as well as the design, synthesis and performance of COFs fluorescent materials for detecting these elements. The interaction mechanism of different fluorescent COFs and metal ions are discussed. Additionally, the remaining challenges and prospects of COFs fluorescence sensors are provided. We believe this review will be useful in directing the development of fluorescent COFs towards metal ions.
2024, 35(8): 109276
doi: 10.1016/j.cclet.2023.109276
摘要:
Metabolism encompasses a series of intricate biochemical processes that are vital for the sustenance of life in organisms. Metabolomics, an essential scientific discipline, is a field of study within the broader domain of systems biology that focuses on the comprehensive analysis of small molecules, known as metabolites including lipids, coenzymes, etc., which are synthesized during metabolism. With the continuous development of metabolomics, the multiple biological functions of metabolites are constantly being discovered, encompassing signal transduction and enzyme stimulation, while concurrently exhibiting associations with afflictions like cancer and diabetes. The comprehension of metabolite functionalities and their intricate interplay with disease conditions assumes paramount importance in both disease-focused research endeavors and the development of diagnostic tools. This scholarly exposition undertakes an extensive review of recent advancements in the investigation of functional roles assumed by metabolites, with specific emphasis on metabolites in lipid synthesis, glucose metabolism and exogenous metabolites.
Metabolism encompasses a series of intricate biochemical processes that are vital for the sustenance of life in organisms. Metabolomics, an essential scientific discipline, is a field of study within the broader domain of systems biology that focuses on the comprehensive analysis of small molecules, known as metabolites including lipids, coenzymes, etc., which are synthesized during metabolism. With the continuous development of metabolomics, the multiple biological functions of metabolites are constantly being discovered, encompassing signal transduction and enzyme stimulation, while concurrently exhibiting associations with afflictions like cancer and diabetes. The comprehension of metabolite functionalities and their intricate interplay with disease conditions assumes paramount importance in both disease-focused research endeavors and the development of diagnostic tools. This scholarly exposition undertakes an extensive review of recent advancements in the investigation of functional roles assumed by metabolites, with specific emphasis on metabolites in lipid synthesis, glucose metabolism and exogenous metabolites.
2024, 35(8): 109277
doi: 10.1016/j.cclet.2023.109277
摘要:
The advancement of energy storage technology has paved the way for the application of electrochemical processes in achieving low-carbon and precise environmental pollution reduction. Electrodes play a crucial role in efficiently removing organic pollutants and heavy metals. To implement electrochemical pollution control technology in practical engineering, flexible electrode preparation is vital. This review highlights recent progress in flexible electrode research, focusing on the selection and structural design of flexible electrode materials. It summarizes the latest advancements in current collectors, active materials, and preparation methods to enhance conductivity, flexibility, and cycle stability. The application of flexible electrodes in water pollution control is categorized into three aspects: Organic pollutants, inorganic pollutants, and composite pollutants. Finally, the challenges and research requirements for enhancing electrode flexibility in environmental governance are discussed, along with prospects for their future applications.
The advancement of energy storage technology has paved the way for the application of electrochemical processes in achieving low-carbon and precise environmental pollution reduction. Electrodes play a crucial role in efficiently removing organic pollutants and heavy metals. To implement electrochemical pollution control technology in practical engineering, flexible electrode preparation is vital. This review highlights recent progress in flexible electrode research, focusing on the selection and structural design of flexible electrode materials. It summarizes the latest advancements in current collectors, active materials, and preparation methods to enhance conductivity, flexibility, and cycle stability. The application of flexible electrodes in water pollution control is categorized into three aspects: Organic pollutants, inorganic pollutants, and composite pollutants. Finally, the challenges and research requirements for enhancing electrode flexibility in environmental governance are discussed, along with prospects for their future applications.
2024, 35(8): 109329
doi: 10.1016/j.cclet.2023.109329
摘要:
Hydrogen (H2) is a promising renewable energy which finds wide applications as the world gears toward low-carbon economy. However, current H2 production via steam methane reforming of natural gas or gasification of coal are laden with high CO2 footprints. Recently, methane (CH4) pyrolysis has emerged as a potential technology to generate low-carbon H2 and solid carbon. In this review, the current state-of-art and recent progress of H2 production from CH4 pyrolysis are reviewed in detail. Aspects such as fundamental mechanism and chemistry involved, effect of process parameters on the conversion efficiency and reaction kinetics for various reaction media and catalysts are elucidated and critically discussed. Temperature, among other factors, plays the most critical influence on the methane pyrolysis reaction. Molten metal/salt could lower the operating temperature of methane pyrolysis to < 1000 ℃, whereas plasma technology usually operates in the regime of > 1000 ℃. Based on the reaction kinetics, metal-based catalysts were more efficient in lowering the activation energy of the reaction to 29.5–88 kJ/mol from that of uncatalyzed reaction (147–420.7 kJ/mol). Besides, the current techno-economic performance of the process reveals that the levelized cost of H2 is directly influenced by the sales price of carbon (by-product) generated, which could offset the overall cost. Lastly, the main challenges of reactor design for efficient product separation and retrieval, as well as catalyst deactivation/poisoning need to be debottlenecked.
Hydrogen (H2) is a promising renewable energy which finds wide applications as the world gears toward low-carbon economy. However, current H2 production via steam methane reforming of natural gas or gasification of coal are laden with high CO2 footprints. Recently, methane (CH4) pyrolysis has emerged as a potential technology to generate low-carbon H2 and solid carbon. In this review, the current state-of-art and recent progress of H2 production from CH4 pyrolysis are reviewed in detail. Aspects such as fundamental mechanism and chemistry involved, effect of process parameters on the conversion efficiency and reaction kinetics for various reaction media and catalysts are elucidated and critically discussed. Temperature, among other factors, plays the most critical influence on the methane pyrolysis reaction. Molten metal/salt could lower the operating temperature of methane pyrolysis to < 1000 ℃, whereas plasma technology usually operates in the regime of > 1000 ℃. Based on the reaction kinetics, metal-based catalysts were more efficient in lowering the activation energy of the reaction to 29.5–88 kJ/mol from that of uncatalyzed reaction (147–420.7 kJ/mol). Besides, the current techno-economic performance of the process reveals that the levelized cost of H2 is directly influenced by the sales price of carbon (by-product) generated, which could offset the overall cost. Lastly, the main challenges of reactor design for efficient product separation and retrieval, as well as catalyst deactivation/poisoning need to be debottlenecked.
2024, 35(8): 109342
doi: 10.1016/j.cclet.2023.109342
摘要:
As a powerful noninvasive imaging technology, positron emission tomography (PET) has been playing an important role in disease theranostics and drug discovery. The successful application of PET relies on not only the biological properties of PET tracers but also the availability of facile and efficient radiochemical reactions to enable practical production and widespread use of PET tracers. Most recently, photochemistry is emerging as a novel, mild and efficient approach to generating PET agents. In this review, we focus on the recent advances in newly developed photocatalytic radiochemical reactions, innovation on automated photochemical radiosynthesis modules, as well as implementation in late-stage radiolabeling and radiopharmaceutical synthesis for PET imaging. We believe that this review will inspire the development of more promising radiolabeling protocols for the preparation of clinically useful PET agents.
As a powerful noninvasive imaging technology, positron emission tomography (PET) has been playing an important role in disease theranostics and drug discovery. The successful application of PET relies on not only the biological properties of PET tracers but also the availability of facile and efficient radiochemical reactions to enable practical production and widespread use of PET tracers. Most recently, photochemistry is emerging as a novel, mild and efficient approach to generating PET agents. In this review, we focus on the recent advances in newly developed photocatalytic radiochemical reactions, innovation on automated photochemical radiosynthesis modules, as well as implementation in late-stage radiolabeling and radiopharmaceutical synthesis for PET imaging. We believe that this review will inspire the development of more promising radiolabeling protocols for the preparation of clinically useful PET agents.
2024, 35(8): 109363
doi: 10.1016/j.cclet.2023.109363
摘要:
New fabrication method of nanostructures is of great importance for the applications of nanoscience and nanotechnology. This review summarizes cucurbit[n]uril (CB[n])-based nanostructure fabrication and modification approaches. These strategies include the use of CB[n]s as building blocks and supramolecular crosslinkers to fabricate nanostructures, to surface modify nanostructures, and as gatekeepers to control the release of encapsulated cargo. These nanostructures are used for drug delivery, bioimaging, chemical sensing, catalysis and other applications. CB[n]s often play a vital role in the fabrication of these nanostructures, and the realization of the applications.
New fabrication method of nanostructures is of great importance for the applications of nanoscience and nanotechnology. This review summarizes cucurbit[n]uril (CB[n])-based nanostructure fabrication and modification approaches. These strategies include the use of CB[n]s as building blocks and supramolecular crosslinkers to fabricate nanostructures, to surface modify nanostructures, and as gatekeepers to control the release of encapsulated cargo. These nanostructures are used for drug delivery, bioimaging, chemical sensing, catalysis and other applications. CB[n]s often play a vital role in the fabrication of these nanostructures, and the realization of the applications.
2024, 35(8): 109417
doi: 10.1016/j.cclet.2023.109417
摘要:
The atom-economical C-F insertion chemistry is emerged as a promising technology for the synthesis of various fluorinated scaffolds, which have wide applications both in the academic and the industrial communities. The past three years have witnessed rapid developments in this field. This highlight provides an overview on the evolution according to the fluorinating agents used.
The atom-economical C-F insertion chemistry is emerged as a promising technology for the synthesis of various fluorinated scaffolds, which have wide applications both in the academic and the industrial communities. The past three years have witnessed rapid developments in this field. This highlight provides an overview on the evolution according to the fluorinating agents used.
2024, 35(8): 109472
doi: 10.1016/j.cclet.2023.109472
摘要:
Heterogeneous porous carbon (PC) materials have gained unique importance in the catalysis community due to their captivating properties, including high specific surface area, tunable porosity, and functionality. PC can play a prominent role in the sustainable synthesis of functional heterocycles, as they are a low-cost alternative while being an efficient and user-friendly material. This review examines the preparation and applicability of these carbonaceous materials used as catalysts or support for biologically active heterocycles synthesis, including hydrogenation, oxidation, oxidative dehydrogenation, cross-coupling, and other organic reactions. Moreover, the challenges, potential future development directions, and opportunities in the synthesis of potent bioactive heterocycles over PC materials have been addressed. This review will inspire further research to explore novel PC materials and their implications in heterocyclization.
Heterogeneous porous carbon (PC) materials have gained unique importance in the catalysis community due to their captivating properties, including high specific surface area, tunable porosity, and functionality. PC can play a prominent role in the sustainable synthesis of functional heterocycles, as they are a low-cost alternative while being an efficient and user-friendly material. This review examines the preparation and applicability of these carbonaceous materials used as catalysts or support for biologically active heterocycles synthesis, including hydrogenation, oxidation, oxidative dehydrogenation, cross-coupling, and other organic reactions. Moreover, the challenges, potential future development directions, and opportunities in the synthesis of potent bioactive heterocycles over PC materials have been addressed. This review will inspire further research to explore novel PC materials and their implications in heterocyclization.
2024, 35(8): 109749
doi: 10.1016/j.cclet.2024.109749
摘要:
Organic thermoelectric (OTE) materials and devices have garnered significant attention in the past decade for flexible and wearable electronics. Due to the numerous combinations of different backbones, side chains, and functional groups for polymer molecules, further efficient developments of high performance OTEs rely on reverse and rational molecular design as well as fundamental understanding to the structure-property relationship, which both require precise theoretical input. Recently, many theoretical efforts and progresses have been made to predict TE properties and develop high performance OTE materials. Here, we present first the general methods and principles for OTE theoretical calculations. Subsequently, the latest theoretical advances regarding the effects of molecular design, chemical doping, ambipolar charge transport etc., to TE conversion are carefully reviewed. These theoretical advances not only significantly deepen the fundamental understanding of OTEs, but also provide precise guidance to the molecular design of OTE materials. Finally, we propose several perspectives for future theoretical investigations of OTEs.
Organic thermoelectric (OTE) materials and devices have garnered significant attention in the past decade for flexible and wearable electronics. Due to the numerous combinations of different backbones, side chains, and functional groups for polymer molecules, further efficient developments of high performance OTEs rely on reverse and rational molecular design as well as fundamental understanding to the structure-property relationship, which both require precise theoretical input. Recently, many theoretical efforts and progresses have been made to predict TE properties and develop high performance OTE materials. Here, we present first the general methods and principles for OTE theoretical calculations. Subsequently, the latest theoretical advances regarding the effects of molecular design, chemical doping, ambipolar charge transport etc., to TE conversion are carefully reviewed. These theoretical advances not only significantly deepen the fundamental understanding of OTEs, but also provide precise guidance to the molecular design of OTE materials. Finally, we propose several perspectives for future theoretical investigations of OTEs.
2024, 35(8): 109754
doi: 10.1016/j.cclet.2024.109754
摘要:
The isolation of circulating tumor cells (CTCs) from complex biological samples is of paramount significance for advancing cancer diagnosis, prognosis, and treatment. However, the low concentration of CTCs and nonspecific adhesion of white blood cells (WBCs) present challenges that hinder the efficiency and purity of captured CTCs. Microfluidic-based strategies utilize precise fluid control at the micron level to incorporate specific micro/nanostructures or recognition molecules, enabling effective CTCs separation. Moreover, by employing surface modification designs that exhibit exceptional anti-adhesion properties against WBCs, the purity of isolated CTCs can be further enhanced. This review offers an in-depth exploration of recent advancements, challenges, and opportunities associated with microfluidic-based CTCs isolation from biological samples. Firstly, we will comprehensively introduce the microfluidic-based strategies for achieving high-efficiency CTCs isolation, which includes the morphological design of microchannels for physical force-based CTCs isolation and the specific modification of microchannel surfaces for affinity-based CTCs isolation. Subsequently, a review of recent research advances in microfluidic-based high-purity CTCs isolation is presented, focusing on strategies that decrease the nonspecific adhesion of WBCs through surface micro-/nanostructure construction or chemical and biological modification. Finally, we will summarize the article by providing the prospective opportunities and challenges for the future development of microfluidic-based CTCs isolation.
The isolation of circulating tumor cells (CTCs) from complex biological samples is of paramount significance for advancing cancer diagnosis, prognosis, and treatment. However, the low concentration of CTCs and nonspecific adhesion of white blood cells (WBCs) present challenges that hinder the efficiency and purity of captured CTCs. Microfluidic-based strategies utilize precise fluid control at the micron level to incorporate specific micro/nanostructures or recognition molecules, enabling effective CTCs separation. Moreover, by employing surface modification designs that exhibit exceptional anti-adhesion properties against WBCs, the purity of isolated CTCs can be further enhanced. This review offers an in-depth exploration of recent advancements, challenges, and opportunities associated with microfluidic-based CTCs isolation from biological samples. Firstly, we will comprehensively introduce the microfluidic-based strategies for achieving high-efficiency CTCs isolation, which includes the morphological design of microchannels for physical force-based CTCs isolation and the specific modification of microchannel surfaces for affinity-based CTCs isolation. Subsequently, a review of recent research advances in microfluidic-based high-purity CTCs isolation is presented, focusing on strategies that decrease the nonspecific adhesion of WBCs through surface micro-/nanostructure construction or chemical and biological modification. Finally, we will summarize the article by providing the prospective opportunities and challenges for the future development of microfluidic-based CTCs isolation.
2024, 35(8): 109743
doi: 10.1016/j.cclet.2024.109743
摘要:
2024, 35(8): 109899
doi: 10.1016/j.cclet.2024.109899
摘要:
