Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynam...Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.展开更多
We report an immobilized enzyme-catalyzed batch and continuous-flow synthesis of optically pure ethyl(R)-pantothenate((R)-PaOEt),the direct precursor of d-pantothenic acid.Firstly,a ketoreductase mutant designated as ...We report an immobilized enzyme-catalyzed batch and continuous-flow synthesis of optically pure ethyl(R)-pantothenate((R)-PaOEt),the direct precursor of d-pantothenic acid.Firstly,a ketoreductase mutant designated as M2,carrying two-point mutations of F97L and M242F relative to the wild-type SSCR,was constructed by site-directed mutagenesis,exhibited simultaneously improved activity toward ethyl 2′-ketopantothenate(K-PaOEt)and isopropanol,and could effectively catalyze the stereoselective reduction of K-PaOEt to(R)-PaOEt by using isopropanol as the sacrificial co-substrate to regenerate NADPH.After screening six commercially available carriers,an amino resin LXTE-700 was identified as the best solid support for the immobilization of M2 via the glutaraldehyde activation method.Upon optimization of the immobilization process and reaction conditions,the fabricated immobilized enzyme M2@amino resin demonstrated excellent recyclability and reusability,with the complete conversion of K-PaOEt to(R)-PaOEt being still realized after 12 cycles of reuse.Finally,M2@amino resin-catalyzed synthesis of(R)-PaOEt was successfully implemented in continuous-flow,accomplishing a 6.3 times higher space-time yield than that with the batch synthesis(529.2 versus 84 g L^(-1) d^(-1)).Our developed flow biocatalysis system also features an outstanding operational stability,as evidenced by the 100%conversion rate achieved after 15 consecutive days of operation.展开更多
The hydrated tricyclohexyltin theophylline-7-acetic acid(tpH)complex[Sn(C_(6)H_(11))_(3)(tp)(H_(2)O)]was synthesized via an ethanol solvothermal method using tricyclohexyltin hydroxide and tpH in a 1∶1 molar ratio.Th...The hydrated tricyclohexyltin theophylline-7-acetic acid(tpH)complex[Sn(C_(6)H_(11))_(3)(tp)(H_(2)O)]was synthesized via an ethanol solvothermal method using tricyclohexyltin hydroxide and tpH in a 1∶1 molar ratio.The complex was characterized by IR,^(1)H(^(13)C)NMR,elemental analysis,and powder X-ray diffraction,and the crystal structure was determined by single-crystal X-ray diffraction.The crystal belongs to the orthorhombic system with space group Iba2,and the central tin atom is in a five-coordinated trigonal bipyramidal configuration.Quantum chemistry ab initio calculations were performed to investigate the stability,molecular orbital energy,and frontier molecular orbital characteristics of the complex.Additionally,its thermal stability,electrochemical properties,and in vitro anticancer activity were evaluated.CCDC:2380308.展开更多
The significant medicinal values associated with C19-hydroxylated steroids dictate a growing demand for new synthetic strategies that would provide facile access to these challenging targets.This review will encapsula...The significant medicinal values associated with C19-hydroxylated steroids dictate a growing demand for new synthetic strategies that would provide facile access to these challenging targets.This review will encapsulate the key synthetic strategies for C19-hydroxylated steroids,which include indirect C–H oxidation and direct C–H oxidation in semi-synthesis as well as total synthesis.展开更多
ADPr-ATP is a natural nucleotide with three sugar rings and five pentavalent phosphorus,and can be produced through TIR-catalyzed ADP-ribosylation reactions for plant immunity.Here,we report the first total synthesis ...ADPr-ATP is a natural nucleotide with three sugar rings and five pentavalent phosphorus,and can be produced through TIR-catalyzed ADP-ribosylation reactions for plant immunity.Here,we report the first total synthesis of ADPr-ATP(1)with a total yield of 6.4%through 14 steps,featuring late-stage P(V)−N activation reaction of pyrophosphate(4)and 5′-phosphoromorpholidate(25).The protected adenosine 5′-phosphoromorpholidate(24)was prepared on the basis of a scalable to adenosine 5′′-monophosphate(2).The construction of P(V)−N bond in phosphoramidate is esteemed as a critical step as they are sufficiently stable in deprotection reactions.The chemical synthesis of ADPr-ATP can offer an appealing alternative to traditional enzymatic synthesis and fractionation methods.Furthermore,the pRib-AMP and its prodrug are also synthesized to evaluate cytotoxicity and anti-influenza activity in vitro.展开更多
Synthetic dyes,particularly azo dyes,pose significant environmental and health risks due to their persistence,toxicity,and potential carcinogenicity.Zinc oxide(ZnO)is a promising photocatalyst for wastewater remediati...Synthetic dyes,particularly azo dyes,pose significant environmental and health risks due to their persistence,toxicity,and potential carcinogenicity.Zinc oxide(ZnO)is a promising photocatalyst for wastewater remediation,but its wide bandgap and rapid charge recombination limit its practical efficacy.Furthermore,conventional doping methods often rely on hazardous chemical precursors,undermining the sustainability of the overall approach.This review introduces a novel and sustainable paradigm:the utilization of biomass-derived precursors as green reagents for the in-situ synthesis and simultaneous phosphorus-nitrogen(P-N)co-doping of ZnO nanoparticles.We critically analyze how the intrinsic biochemical composition of biomass,rich in P,N,and other heteroatoms,facilitates this one-pot,eco-friendly functionalization.This integrated strategy merges the performance enhancement offered by advanced co-doping,such as extended visible-light absorption and suppressed charge recombination,with the core principles of green chemistry and circular economy.It offers a dual benefit:creating highly effective photocatalysts for the degradation of persistent pollutants and valorizing abundant agricultural or biological waste streams.Our comprehensive evaluation goes beyond description to critically assess the underlying mechanisms,comparative efficacy,scalability challenges,and future research directions of this emerging field.This review underscores the unique contribution of biomass-mediated synthesis to advancing sustainable nanotechnology for environmental applications.展开更多
Circularly polarized luminescence perovskite nanocrystals(NCs)hold great potential in the field of information encryption,3D display and spintronics.However,the synthesis of the chiral perovskites is still confronted ...Circularly polarized luminescence perovskite nanocrystals(NCs)hold great potential in the field of information encryption,3D display and spintronics.However,the synthesis of the chiral perovskites is still confronted with various problems,such as cumbersome synthesis process,poor compatibility and limited processability,which impede their further implementation.In this study,a one-step wet-ball-milling method is proposed for the scale-up synthesis(up to 500 mL)of chiral perovskite ink,where the chiral molecule R-/S-1,2-diphenylethylenediamine(R-/S-DPEM)are introduced as chiral initiator.Chiral R-/S-DPEM molecules can endow the chirality to perovskite NCs through the strong coupling with perovskite surface.Specifically,ethyl cellulose is incorporated as passivating agents and structural supporting molecules,which can not only passivate the perovskite NCs and improve their stability,but also enable the chiral ink to possess better processability.The obtained ink is compatible with multiple substrates,which can be directly processed into various luminescent patterns by means of screen printing,writing,impregnation,laser engraving,etc.These patterns demonstrate high storage stability,flexibility and water resistance,fulfilling the requirements of a wide range of occasions in the future.This work provides a feasible solution for scalable synthesis of chiral perovskite inks,which offer promising prospects in optical anti-counterfeiting,information encryption and wearable optoelectronic devices.展开更多
The single-atom replacement strategy is a typical approach which just converts elements in lead compounds into their analogues with very small chemical changes.In this research,we implemented this strategy to modify t...The single-atom replacement strategy is a typical approach which just converts elements in lead compounds into their analogues with very small chemical changes.In this research,we implemented this strategy to modify the sulfonamide scaffold identified in our previous work,and resulting in the synthesis of 40 novel sulfonamide derivatives not previously reported in the literature.The insecticidal activities of these compounds against the Mythimna separata and Plutella xylostella were assessed.Our findings indicate that the pyridine sulfonamide structure significantly enhances insecticidal efficacy.Specifically,compound 7c exhibited LC 50 values of 0.157 and 0.256 mg/mL against the M.separata and P.xylostella,which significantly increased 97-and 41-fold compared to celangulin V,respectively.The experimental results revealed that pyridine sulfonamide analogues could serve as potential green insecticides.展开更多
Five novel sulfur-containing benzyl metabolites, designated as gastrabenzylsulfoxides A and B(1 and 2), gastrabenzylsulfinate A(3) and gastrabenzylsulfides A and B(4 and 5), along with four known compounds(6-9), were ...Five novel sulfur-containing benzyl metabolites, designated as gastrabenzylsulfoxides A and B(1 and 2), gastrabenzylsulfinate A(3) and gastrabenzylsulfides A and B(4 and 5), along with four known compounds(6-9), were isolated from the aqueous extracts of Gastrodia elata.Compounds 1 and 4 are 4-hydroxy-3-(4′-hydroxybenzyl)benzyl-substituted sulfoxide and sulfide, respectively, which are unprecedented in natural products. Compound 3 represents a rare sulfinate. Several isolates and their sulfone and disulfide analogs(10-13) were synthesized to evaluate their anti-inflammatory activity. Notably, the synthesized sulfone 10 demonstrated significant alleviation of symptoms in multiple in vivo inflammatory models.展开更多
Peptide-and drug-protected gold nanoclusters(Au NCs)with atomic precision have attracted research attention in the last few years owing to their ultrasmall size(<2 nm),well-defined structures,tunable photoluminesce...Peptide-and drug-protected gold nanoclusters(Au NCs)with atomic precision have attracted research attention in the last few years owing to their ultrasmall size(<2 nm),well-defined structures,tunable photoluminescence from the visible to near-infrared range,water solubility,and good biocompatibility.These features,combined with low toxicity and efficient renal clearance,make such Au NCs promising candidates for biomedical use,including diagnosis,therapy,and theranostic.The incorporation of peptides or drugs into Au NCs enhances the stability,targeting specificity,cellular uptake,and prolonged circulation,enabling precise modulation of biological responses.Despite notable advances in achieving atomic precision employing complex ligands such as peptides or drugs,the synthetic methods of this new class of NCs remain a challenge.Careful control of molar ratio(Au:peptide/drug),reducing agent,temperature,and reaction time is required,because these factors directly influence the cluster size,optical properties,and in vivo performance.In this review,we highlight different synthetic approaches of atomically precise peptide-and drug-protected Au NCs,emphasizing the role of rational ligand design and reaction conditions,as well as the challenges associated with structural determination.We further discuss the optical and photoluminescence properties of peptide-protected Au NCs-the mostly explored features for biomedical applications.Finally,we conclude by outlining the current challenges,opportunities for scale-up synthesis,and future design perspectives for these emerging nanomaterials.展开更多
The study explores the feasibility of producing ruthenium catalysts supported on char through a one-pot synthesis,an original approach for the preparation of noble metal-based catalysts in this field.This method combi...The study explores the feasibility of producing ruthenium catalysts supported on char through a one-pot synthesis,an original approach for the preparation of noble metal-based catalysts in this field.This method combines high-temperature stages,such as catalytic support carburization and catalyst activation,in a single step.The innovation represents a significant advancement in utilizing cellulose as a model of waste biomass,enhancing its value,and reducing catalyst production costs.The one-pot catalysts were successfully tested in the hydrogenation reaction of sugar mixtures(L-Arabinose and D-Galactose)under mild conditions,achieving full selectivities.The research also introduces for the first time in that reaction a structural sensitivity analysis of the reaction,comparing experimental results with a theoretical model.The findings reveal a direct correlation between catalytic activity and the{0001}exposed face of hcp ruthenium nanoclusters.This discovery opens new avenues for industrial-scale catalyst development,promising substantial reductions in energy and production costs,and emphasizing the economic appeal of the process.展开更多
Conjugated microporous polymers(CMPs)are a unique class of organic porous materials characterized byπ-conjugated structures and permanent micropores,distinguishing them from non-porous polymers and conventionalπ-con...Conjugated microporous polymers(CMPs)are a unique class of organic porous materials characterized byπ-conjugated structures and permanent micropores,distinguishing them from non-porous polymers and conventionalπ-conjugated polymers.CMPs offer extensive versatility in synthetic approaches,enabling the synthesis of cross-linked and mesoporous structures.Advances in chemical processes,structural design,and synthesis methodologies have been developed,resulting in a diverse range of CMPs with unique configurations and properties,contributing to the fast expansion of the field.CMPs are particularly notable for their ability to enable the competitive utilization ofπ-conjugated structures within mesoporous configurations,making them valuable for investigations across various domains.They have shown considerable promise in addressing fuel and environmental challenges,demonstrated by their exceptional performance in applications such as vapor adsorption,heterogeneous catalysis,light emission,light harvesting,and energy generation.This review examines the chemical engineering principles underlying CMPs,including synthesis approaches,systemic research advancements,multifunctional investigations boundaries,potential applications,and progress in synthesis,dimensionality,and morphology studies.Specifically,it offers a comparative analysis of CMPs and linear polymeric materials,aiding in the development of functional polymers.Furthermore,this review explores the primary fundamental limitations of CMPs in fuel-related domains and discusses alternative strategies,including novel synthesis methods incorporating interactions and morphologies,to address these challenges.Ultimately,this assessment aims to provide a valuable and inspiring resource for professionals in the field of fuel management,guiding future research and development efforts.展开更多
In the future power-electronics-dominated power systems,grid-forming(GFM)converters have been regarded as important devices to actively establish frequency and voltage,so as to provide essential grid support.However,d...In the future power-electronics-dominated power systems,grid-forming(GFM)converters have been regarded as important devices to actively establish frequency and voltage,so as to provide essential grid support.However,due to their voltage source behavior and emulated swing dynamics,GFM converters may encounter low-frequency oscillations(LFOs)when connected to strong grids,which belongs to the self-stability problem of GFM converters.Moreover,GFM converters will also interact with grid-following(GFL)converters and thus impact the mid-frequency oscillations(MFOs)induced by phase-locked loops(PLLs).It has been preliminarily shown in the literature that GFM converters can help stabilize the PLL-induced MFOs,but currently,there is a lack of systematic design methods to coordinate the self-stability and stabilizing ability of GFM converters.This paper addresses this gap by revisiting the impedance model of a typical GFM converter and briefly analyze the oscillations caused by converters.Based on our analysis,we propose a frequency-partitioned synthesis design framework to enable dynamic virtual impedance(DVI)in GFM converters,aiming to enhance their self-stability and stabilizing ability simultaneously.Particularly,a self-stabilizing module is designed to ensure robust device-level damping,with control parameters auto-tuned using H∞methods.In parallel,a stabilizing module is introduced to stabilize GFL converters and enhance the system-level stability,which utilizes a perceive-and-optimize tuning strategy.Simulation results validate the effectiveness of the proposed synthesis DVI framework.展开更多
α-Chiral amides are common in pharmaceuticals,agrochemicals,natural products,and peptides,prompting the need for new synthetic methods.Here,we introduce a nickel-catalyzed asymmetric reductive amidation method to syn...α-Chiral amides are common in pharmaceuticals,agrochemicals,natural products,and peptides,prompting the need for new synthetic methods.Here,we introduce a nickel-catalyzed asymmetric reductive amidation method to synthesizeα-chiral amides from benzyl ammonium salts and isocyanates.The key to success is using a chiral 2,2-bipyridine ligand(-)-Ph-SBpy,enabling high yield(up to 95%)and enantiomeric ratio(up to 98:2 er)under mild conditions.Addition of phenol prevents isocyanate polymerization by reversibly forming a carbamate intermediate,enhancing selectivity and efficiency.The synthetic utility is showcased through transformations of the enantioenriched amides,and the mechanism and enantioselectivity are supported by experimental and computational studies.展开更多
Background This study was conducted to investigate the impact of varying degrees of heat stress on milk protein synthesis in dairy cows using comprehensive analyses of metabolomics and proteomics.Eighteen dairy cows w...Background This study was conducted to investigate the impact of varying degrees of heat stress on milk protein synthesis in dairy cows using comprehensive analyses of metabolomics and proteomics.Eighteen dairy cows were subjected to no heat stress(No-HS),mild heat stress(Mild-HS),and moderate heat stress(Mod-HS).Blood and milk samples were collected to determine the content and composition of amino acids(AA),and milk samples were used for metabolomic and proteomic analyses.Results Milk protein yield was significantly lower under Mild-HS and Mod-HS than No-HS(P<0.001).During Mild-HS,no significant difference was found in total AA concentration in both arterial(P=0.545)and venous blood(P=0.057),but arterial AA supply to the mammary gland significantly increased(P=0.045)when compared with No-HS.Under Mod-HS,the supply(P<0.001)and uptake(P=0.001)of total AA in the mammary gland decreased significantly,affecting the availability of precursors necessary for milk protein synthesis.Milk metabolomic analysis revealed that Mod-HS significantly impacted nucleotide metabolism,energy metabolism,and protein synthesis processes including translation,folding,and transport.Milk proteomic analysis showed significant downregulation of ribosomal and heat shock proteins which are crucial for protein synthesis and folding.Conclusions These findings suggest that heat stress disrupts AA utilization and energy metabolism in the mammary gland,leading to the reduced efficiency in milk protein synthesis and lowered milk protein yield.This study offers valuable insights into the metabolic and proteomic changes in dairy cows under heat stress,highlighting potential strategies to mitigate the adverse effects of heat stress on dairy production and milk quality.展开更多
Structural engineering of Pt-based nanoalloys is crucial for the rational design and manufacturing of high-performance and low-cost electrocatalysts for hydrogen evolution reaction(HER).Here,we reported PtNi nanoparti...Structural engineering of Pt-based nanoalloys is crucial for the rational design and manufacturing of high-performance and low-cost electrocatalysts for hydrogen evolution reaction(HER).Here,we reported PtNi nanoparticles with a refined size of 2.71 nm and regular strains loaded on carbon black,synthesized using the high-temperature liquid shock(HTLS)method.This approach offers significant advantages over conventional synthesis methods,including high scalability,rapid reaction rates,and precise control over the size and shape of nanocrystals.Importantly,the synthesized PtNi electrocatalysts demonstrate outstanding catalytic activity and long-term stability for HER,achieving low overpotentials of 19 and 203 mV at current densities of 10 and 1000 mA/cm^(2),respectively.The superior performance can be attributed to the combination of a refined particle size,lattice strains,and synergistic effects between Pt and Ni.This rapid liquid-state synthesis demonstrated here holds great potential for scalable and industrial manufacturing of micro-/nano-catalysts.展开更多
We report for the first time the combination of directed evolution focused on enhancing and reversing the stereoselectivity of an enzyme with Cu(I)-mediated click chemistry(CuAAC),providing an asymmetric click approac...We report for the first time the combination of directed evolution focused on enhancing and reversing the stereoselectivity of an enzyme with Cu(I)-mediated click chemistry(CuAAC),providing an asymmetric click approach for versatile chiral triazoles products.In this study,the halohydrin dehalogenase HheG was used as the enzyme which was evolved to induce a stereoselective ring-opening reaction of cyclic epoxides in the presence of NaN3 with the formation of chiral azido products.Two mutants of opposite stereopreference were generated,which convert cyclohexene oxide as well as cycloheptene oxide to(1S,2S)-2-azidocyclohexanol,(1R,2R)-2-azidocyclohexanol,(1S,2S)-2-azidocycloheptanol and(1R,2R)-2-azidocycloheptanol with essentially high stereoselectivity.The chiral products were then subjected to CuAAC in reactions with structurally different alkynes.Since HheG was found to be compatible with Cu(I),the process was also performed successfully in a unique 2-step one-pot process leading to various chiral triazoles.In order to understand the enhancement and reversal of the evolved enantioselectivity,QM and MD computations were performed.This approach harnesses the modifiability and high stereoselectivity of the evolved biocatalysts in combination with click chemistry.It holds great potential for diverse fields,particularly in the area of pharmaceuticals.展开更多
The deuterium labeling has garnered significant interest in drug discovery due to its critical role on improving pharmacokinetic and metabolic properties.However,despite its pharmaceutical value,the general and rapid ...The deuterium labeling has garnered significant interest in drug discovery due to its critical role on improving pharmacokinetic and metabolic properties.However,despite its pharmaceutical value,the general and rapid syntheses of aromatic scaffolds that contains deuterium remain an important yet elusive task.State-of-the-art approaches mainly relied on the transition metal-catalyzed C-H deuteration via the assistance of directing groups(DGs),which often suffered from over-deuteration and lengthy step counts required for installation and/or removal of DG.Herein,we report a generalizable synthetic linchpin strategy for the facile preparation of the ortho-deuterated aromatic core.Through capture of aryne-derived 1,3-zwitterion with heavy water,we synthesized an array of ortho-deuterated aryl sulfonium salts.These novel linchpins not only participated the transition metal catalyzed cross-coupling reaction as nucleophiles,but also served as aryl radical reservoirs under photochemical or electrochemical conditions,enabling facile and precise access to structurally diverse deuterated aromatics.Moreover,we have disclosed a novel EDA complex enabled direct arylation of phosphines under visible-light irradiation,further expanding the utility of our platform approach.展开更多
As the core of cathode materials,sensitive metals play important roles in the optimization of acetate production from carbon dioxide(CO_(2))in microbial electrochemical system(MES).In this work,iron(Fe),copper(Cu),and...As the core of cathode materials,sensitive metals play important roles in the optimization of acetate production from carbon dioxide(CO_(2))in microbial electrochemical system(MES).In this work,iron(Fe),copper(Cu),and nickel(Ni)as sensitive metal cathode materials were evaluated for CO_(2) conversion in MES.The MES with Feelectrode as a promising electrode material demonstrated a superior CO_(2) reduction performance with a maximum acetate accumulation of 417.9±39.2 mg/L,which was 1.5 and 1.7 folds higher than that in the Ni-electrode and Cu-electrode groups,respectively.Furthermore,an outstanding electron recovery efficiency of 67.7%was shown in the Fe-electrode group.The electron transfer between electrode-suspended sludge was systematically cross-evaluated by the electrochemical behavior and extracellular polymeric substances.The Fe-electrode group had the highest electron transfer rate with 0.194 s-1(k_(app)),which was 17.6 and 21.5 times higher than that of the Cu-and Ni-electrode groups,respectively.Fe-electrode was beneficial for reducing electrochemical impedance between the electrode and suspended sludge.Additionally,redox substances in extracellular polymeric substances of the Fe-electrode group were increased,implying more favorable electron transport dynamics.Simultaneously,enrichments of functional bacteria Acetoanerobium and increased key enzymes involved in the carbonyl pathway of the Fe-electrode group were observed,which also promoted CO_(2) conversion in MES.This study provides a perspective on evaluating the promising sensitive metal electrode material for the process of CO_(2) valorization in MES and offers a reference for the subsequent electrode modification.展开更多
Rare earth(RE)Y-type zeolite was synthesized in situ by acidic co-hydrolysis route and hydrothermal method.The key process parameters were optimized based on the RE utilization rate.The effect of inducing a rotating p...Rare earth(RE)Y-type zeolite was synthesized in situ by acidic co-hydrolysis route and hydrothermal method.The key process parameters were optimized based on the RE utilization rate.The effect of inducing a rotating packed bed(RPB)in premixing and crystallization on crystallinity and RE utilization rate was further investigated.The results indicate that lanthanide(La)cations are successfully introduced into the sodalite cage of Y-type zeolite.The optimized conditions are that the molar ratio of Si/La is 150,premixing for 5 h,crystallization at 90℃ for 18 h,and calcination at 550℃ for 3.5 h.At this stage,the RE utilization rate reaches 74.5%.Compared with the conventional stirred tank reactor(STR),RPB can effectively shorten the premixing time and crystallization time by 4.3 h and 6 h,improve the crystallinity by 23%and RE utilization rate by 7.5%.The RE utilization rate is more than 80%by RPB,surpassing the effectiveness of using the one-exchange one-calcination process in the traditional liquid ion exchange process.It is expected to provide a reference for the in-situ efficient and green synthesis of RE zeolite.展开更多
基金Supported by the National Natural Science Foundation of China(Nos.52293472,22473096 and 22471164)。
文摘Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.
基金the Science and Technology R&D Major Project of Jiangxi Province(No.20244AFI92001)the National Natural Science Foundation of China(Nos.22071033 and 21801047)for the financial supports.
文摘We report an immobilized enzyme-catalyzed batch and continuous-flow synthesis of optically pure ethyl(R)-pantothenate((R)-PaOEt),the direct precursor of d-pantothenic acid.Firstly,a ketoreductase mutant designated as M2,carrying two-point mutations of F97L and M242F relative to the wild-type SSCR,was constructed by site-directed mutagenesis,exhibited simultaneously improved activity toward ethyl 2′-ketopantothenate(K-PaOEt)and isopropanol,and could effectively catalyze the stereoselective reduction of K-PaOEt to(R)-PaOEt by using isopropanol as the sacrificial co-substrate to regenerate NADPH.After screening six commercially available carriers,an amino resin LXTE-700 was identified as the best solid support for the immobilization of M2 via the glutaraldehyde activation method.Upon optimization of the immobilization process and reaction conditions,the fabricated immobilized enzyme M2@amino resin demonstrated excellent recyclability and reusability,with the complete conversion of K-PaOEt to(R)-PaOEt being still realized after 12 cycles of reuse.Finally,M2@amino resin-catalyzed synthesis of(R)-PaOEt was successfully implemented in continuous-flow,accomplishing a 6.3 times higher space-time yield than that with the batch synthesis(529.2 versus 84 g L^(-1) d^(-1)).Our developed flow biocatalysis system also features an outstanding operational stability,as evidenced by the 100%conversion rate achieved after 15 consecutive days of operation.
文摘The hydrated tricyclohexyltin theophylline-7-acetic acid(tpH)complex[Sn(C_(6)H_(11))_(3)(tp)(H_(2)O)]was synthesized via an ethanol solvothermal method using tricyclohexyltin hydroxide and tpH in a 1∶1 molar ratio.The complex was characterized by IR,^(1)H(^(13)C)NMR,elemental analysis,and powder X-ray diffraction,and the crystal structure was determined by single-crystal X-ray diffraction.The crystal belongs to the orthorhombic system with space group Iba2,and the central tin atom is in a five-coordinated trigonal bipyramidal configuration.Quantum chemistry ab initio calculations were performed to investigate the stability,molecular orbital energy,and frontier molecular orbital characteristics of the complex.Additionally,its thermal stability,electrochemical properties,and in vitro anticancer activity were evaluated.CCDC:2380308.
基金the National Natural Science Foundation of China(No.22325106)the start-up funding from Wuhan University for financial support.We thank Prof.
文摘The significant medicinal values associated with C19-hydroxylated steroids dictate a growing demand for new synthetic strategies that would provide facile access to these challenging targets.This review will encapsulate the key synthetic strategies for C19-hydroxylated steroids,which include indirect C–H oxidation and direct C–H oxidation in semi-synthesis as well as total synthesis.
基金supported by the National Natural Science Foundation of China(Nos.82204209 and 82130103)Natural Science Foundation of Henna Province(No.242300421084).
文摘ADPr-ATP is a natural nucleotide with three sugar rings and five pentavalent phosphorus,and can be produced through TIR-catalyzed ADP-ribosylation reactions for plant immunity.Here,we report the first total synthesis of ADPr-ATP(1)with a total yield of 6.4%through 14 steps,featuring late-stage P(V)−N activation reaction of pyrophosphate(4)and 5′-phosphoromorpholidate(25).The protected adenosine 5′-phosphoromorpholidate(24)was prepared on the basis of a scalable to adenosine 5′′-monophosphate(2).The construction of P(V)−N bond in phosphoramidate is esteemed as a critical step as they are sufficiently stable in deprotection reactions.The chemical synthesis of ADPr-ATP can offer an appealing alternative to traditional enzymatic synthesis and fractionation methods.Furthermore,the pRib-AMP and its prodrug are also synthesized to evaluate cytotoxicity and anti-influenza activity in vitro.
文摘Synthetic dyes,particularly azo dyes,pose significant environmental and health risks due to their persistence,toxicity,and potential carcinogenicity.Zinc oxide(ZnO)is a promising photocatalyst for wastewater remediation,but its wide bandgap and rapid charge recombination limit its practical efficacy.Furthermore,conventional doping methods often rely on hazardous chemical precursors,undermining the sustainability of the overall approach.This review introduces a novel and sustainable paradigm:the utilization of biomass-derived precursors as green reagents for the in-situ synthesis and simultaneous phosphorus-nitrogen(P-N)co-doping of ZnO nanoparticles.We critically analyze how the intrinsic biochemical composition of biomass,rich in P,N,and other heteroatoms,facilitates this one-pot,eco-friendly functionalization.This integrated strategy merges the performance enhancement offered by advanced co-doping,such as extended visible-light absorption and suppressed charge recombination,with the core principles of green chemistry and circular economy.It offers a dual benefit:creating highly effective photocatalysts for the degradation of persistent pollutants and valorizing abundant agricultural or biological waste streams.Our comprehensive evaluation goes beyond description to critically assess the underlying mechanisms,comparative efficacy,scalability challenges,and future research directions of this emerging field.This review underscores the unique contribution of biomass-mediated synthesis to advancing sustainable nanotechnology for environmental applications.
基金supported by National Natural Science Foundation of China(Grant Nos.52572185,12204427 and 52272166)Natural Science Foundation of Henan Province of China(Grant Nos.242300421217,and 222300420299).
文摘Circularly polarized luminescence perovskite nanocrystals(NCs)hold great potential in the field of information encryption,3D display and spintronics.However,the synthesis of the chiral perovskites is still confronted with various problems,such as cumbersome synthesis process,poor compatibility and limited processability,which impede their further implementation.In this study,a one-step wet-ball-milling method is proposed for the scale-up synthesis(up to 500 mL)of chiral perovskite ink,where the chiral molecule R-/S-1,2-diphenylethylenediamine(R-/S-DPEM)are introduced as chiral initiator.Chiral R-/S-DPEM molecules can endow the chirality to perovskite NCs through the strong coupling with perovskite surface.Specifically,ethyl cellulose is incorporated as passivating agents and structural supporting molecules,which can not only passivate the perovskite NCs and improve their stability,but also enable the chiral ink to possess better processability.The obtained ink is compatible with multiple substrates,which can be directly processed into various luminescent patterns by means of screen printing,writing,impregnation,laser engraving,etc.These patterns demonstrate high storage stability,flexibility and water resistance,fulfilling the requirements of a wide range of occasions in the future.This work provides a feasible solution for scalable synthesis of chiral perovskite inks,which offer promising prospects in optical anti-counterfeiting,information encryption and wearable optoelectronic devices.
基金supported by the National Natural Science Foundation of China[Grant No.21977083].
文摘The single-atom replacement strategy is a typical approach which just converts elements in lead compounds into their analogues with very small chemical changes.In this research,we implemented this strategy to modify the sulfonamide scaffold identified in our previous work,and resulting in the synthesis of 40 novel sulfonamide derivatives not previously reported in the literature.The insecticidal activities of these compounds against the Mythimna separata and Plutella xylostella were assessed.Our findings indicate that the pyridine sulfonamide structure significantly enhances insecticidal efficacy.Specifically,compound 7c exhibited LC 50 values of 0.157 and 0.256 mg/mL against the M.separata and P.xylostella,which significantly increased 97-and 41-fold compared to celangulin V,respectively.The experimental results revealed that pyridine sulfonamide analogues could serve as potential green insecticides.
基金supported by the National Natural Science Foundation of China (No. 82293680)the National Science and CAMS Innovation Fund for Medical Science (No. 2021-I2M-1-028)the Nonprofit Central Research Institute Fund of Chinese Academy of Medical Sciences (No. 2021-RC350-009)。
文摘Five novel sulfur-containing benzyl metabolites, designated as gastrabenzylsulfoxides A and B(1 and 2), gastrabenzylsulfinate A(3) and gastrabenzylsulfides A and B(4 and 5), along with four known compounds(6-9), were isolated from the aqueous extracts of Gastrodia elata.Compounds 1 and 4 are 4-hydroxy-3-(4′-hydroxybenzyl)benzyl-substituted sulfoxide and sulfide, respectively, which are unprecedented in natural products. Compound 3 represents a rare sulfinate. Several isolates and their sulfone and disulfide analogs(10-13) were synthesized to evaluate their anti-inflammatory activity. Notably, the synthesized sulfone 10 demonstrated significant alleviation of symptoms in multiple in vivo inflammatory models.
基金RGM is grateful to CNPq for the PDE fellowship(200437/2025-9),MTM acknowledges CNPq research scholarship(314470/2023-9)FAPESP fundings(2022/01825-22025/063196).
文摘Peptide-and drug-protected gold nanoclusters(Au NCs)with atomic precision have attracted research attention in the last few years owing to their ultrasmall size(<2 nm),well-defined structures,tunable photoluminescence from the visible to near-infrared range,water solubility,and good biocompatibility.These features,combined with low toxicity and efficient renal clearance,make such Au NCs promising candidates for biomedical use,including diagnosis,therapy,and theranostic.The incorporation of peptides or drugs into Au NCs enhances the stability,targeting specificity,cellular uptake,and prolonged circulation,enabling precise modulation of biological responses.Despite notable advances in achieving atomic precision employing complex ligands such as peptides or drugs,the synthetic methods of this new class of NCs remain a challenge.Careful control of molar ratio(Au:peptide/drug),reducing agent,temperature,and reaction time is required,because these factors directly influence the cluster size,optical properties,and in vivo performance.In this review,we highlight different synthetic approaches of atomically precise peptide-and drug-protected Au NCs,emphasizing the role of rational ligand design and reaction conditions,as well as the challenges associated with structural determination.We further discuss the optical and photoluminescence properties of peptide-protected Au NCs-the mostly explored features for biomedical applications.Finally,we conclude by outlining the current challenges,opportunities for scale-up synthesis,and future design perspectives for these emerging nanomaterials.
基金support for this work was obtained from Spanish Ministerio de Ciencia e Innovación(No.MCIN/AEI(10.13039/501100011033)/FEDER Funds una manera de hacer Europa)Project PID2020-113809RB-C32 and Junta de Andalucía via Consejería de EconómTransformación ica,Industria,Conocimiento y Universidades and its PAIDI 2020 program(No.P18-RT-3405)all co-financed by FEDER funds from the European Union.
文摘The study explores the feasibility of producing ruthenium catalysts supported on char through a one-pot synthesis,an original approach for the preparation of noble metal-based catalysts in this field.This method combines high-temperature stages,such as catalytic support carburization and catalyst activation,in a single step.The innovation represents a significant advancement in utilizing cellulose as a model of waste biomass,enhancing its value,and reducing catalyst production costs.The one-pot catalysts were successfully tested in the hydrogenation reaction of sugar mixtures(L-Arabinose and D-Galactose)under mild conditions,achieving full selectivities.The research also introduces for the first time in that reaction a structural sensitivity analysis of the reaction,comparing experimental results with a theoretical model.The findings reveal a direct correlation between catalytic activity and the{0001}exposed face of hcp ruthenium nanoclusters.This discovery opens new avenues for industrial-scale catalyst development,promising substantial reductions in energy and production costs,and emphasizing the economic appeal of the process.
基金supported by the King Khalid University,Abha,Saudi Arabiathe Deanship of Scientific Research at King Khalid University for funding this work through Large Groups Project under grant number(R.G.P.2/335/46)the Guangdong Office of Research Projects at the Provincial University(No.2024KCXTD064)。
文摘Conjugated microporous polymers(CMPs)are a unique class of organic porous materials characterized byπ-conjugated structures and permanent micropores,distinguishing them from non-porous polymers and conventionalπ-conjugated polymers.CMPs offer extensive versatility in synthetic approaches,enabling the synthesis of cross-linked and mesoporous structures.Advances in chemical processes,structural design,and synthesis methodologies have been developed,resulting in a diverse range of CMPs with unique configurations and properties,contributing to the fast expansion of the field.CMPs are particularly notable for their ability to enable the competitive utilization ofπ-conjugated structures within mesoporous configurations,making them valuable for investigations across various domains.They have shown considerable promise in addressing fuel and environmental challenges,demonstrated by their exceptional performance in applications such as vapor adsorption,heterogeneous catalysis,light emission,light harvesting,and energy generation.This review examines the chemical engineering principles underlying CMPs,including synthesis approaches,systemic research advancements,multifunctional investigations boundaries,potential applications,and progress in synthesis,dimensionality,and morphology studies.Specifically,it offers a comparative analysis of CMPs and linear polymeric materials,aiding in the development of functional polymers.Furthermore,this review explores the primary fundamental limitations of CMPs in fuel-related domains and discusses alternative strategies,including novel synthesis methods incorporating interactions and morphologies,to address these challenges.Ultimately,this assessment aims to provide a valuable and inspiring resource for professionals in the field of fuel management,guiding future research and development efforts.
基金supported by National Natural Science Foundation of China(U24B6008,U22B6008)State Grid Zhejiang Electric Power Co.,Ltd.Science,and Technology Project(B311DS240015).
文摘In the future power-electronics-dominated power systems,grid-forming(GFM)converters have been regarded as important devices to actively establish frequency and voltage,so as to provide essential grid support.However,due to their voltage source behavior and emulated swing dynamics,GFM converters may encounter low-frequency oscillations(LFOs)when connected to strong grids,which belongs to the self-stability problem of GFM converters.Moreover,GFM converters will also interact with grid-following(GFL)converters and thus impact the mid-frequency oscillations(MFOs)induced by phase-locked loops(PLLs).It has been preliminarily shown in the literature that GFM converters can help stabilize the PLL-induced MFOs,but currently,there is a lack of systematic design methods to coordinate the self-stability and stabilizing ability of GFM converters.This paper addresses this gap by revisiting the impedance model of a typical GFM converter and briefly analyze the oscillations caused by converters.Based on our analysis,we propose a frequency-partitioned synthesis design framework to enable dynamic virtual impedance(DVI)in GFM converters,aiming to enhance their self-stability and stabilizing ability simultaneously.Particularly,a self-stabilizing module is designed to ensure robust device-level damping,with control parameters auto-tuned using H∞methods.In parallel,a stabilizing module is introduced to stabilize GFL converters and enhance the system-level stability,which utilizes a perceive-and-optimize tuning strategy.Simulation results validate the effectiveness of the proposed synthesis DVI framework.
基金the National Natural Science Foundation of China(Nos.22150410339,W2432012,22301233 and 22171218)the Ministry of Science and Technology China(No.wgxz2022188)。
文摘α-Chiral amides are common in pharmaceuticals,agrochemicals,natural products,and peptides,prompting the need for new synthetic methods.Here,we introduce a nickel-catalyzed asymmetric reductive amidation method to synthesizeα-chiral amides from benzyl ammonium salts and isocyanates.The key to success is using a chiral 2,2-bipyridine ligand(-)-Ph-SBpy,enabling high yield(up to 95%)and enantiomeric ratio(up to 98:2 er)under mild conditions.Addition of phenol prevents isocyanate polymerization by reversibly forming a carbamate intermediate,enhancing selectivity and efficiency.The synthetic utility is showcased through transformations of the enantioenriched amides,and the mechanism and enantioselectivity are supported by experimental and computational studies.
基金funded by grants from the National Nature Science Foundation(Grant number:U23A20231)。
文摘Background This study was conducted to investigate the impact of varying degrees of heat stress on milk protein synthesis in dairy cows using comprehensive analyses of metabolomics and proteomics.Eighteen dairy cows were subjected to no heat stress(No-HS),mild heat stress(Mild-HS),and moderate heat stress(Mod-HS).Blood and milk samples were collected to determine the content and composition of amino acids(AA),and milk samples were used for metabolomic and proteomic analyses.Results Milk protein yield was significantly lower under Mild-HS and Mod-HS than No-HS(P<0.001).During Mild-HS,no significant difference was found in total AA concentration in both arterial(P=0.545)and venous blood(P=0.057),but arterial AA supply to the mammary gland significantly increased(P=0.045)when compared with No-HS.Under Mod-HS,the supply(P<0.001)and uptake(P=0.001)of total AA in the mammary gland decreased significantly,affecting the availability of precursors necessary for milk protein synthesis.Milk metabolomic analysis revealed that Mod-HS significantly impacted nucleotide metabolism,energy metabolism,and protein synthesis processes including translation,folding,and transport.Milk proteomic analysis showed significant downregulation of ribosomal and heat shock proteins which are crucial for protein synthesis and folding.Conclusions These findings suggest that heat stress disrupts AA utilization and energy metabolism in the mammary gland,leading to the reduced efficiency in milk protein synthesis and lowered milk protein yield.This study offers valuable insights into the metabolic and proteomic changes in dairy cows under heat stress,highlighting potential strategies to mitigate the adverse effects of heat stress on dairy production and milk quality.
基金the staff of beamline BL13SSW at Shanghai Synchrotron Radiation Facility for experiments supports. This study was financially supported by the National Natural Science Foundation of China (No. 12205165)Hebei Province Innovation Ability Improvement Plan Project (No. 225676111H).
文摘Structural engineering of Pt-based nanoalloys is crucial for the rational design and manufacturing of high-performance and low-cost electrocatalysts for hydrogen evolution reaction(HER).Here,we reported PtNi nanoparticles with a refined size of 2.71 nm and regular strains loaded on carbon black,synthesized using the high-temperature liquid shock(HTLS)method.This approach offers significant advantages over conventional synthesis methods,including high scalability,rapid reaction rates,and precise control over the size and shape of nanocrystals.Importantly,the synthesized PtNi electrocatalysts demonstrate outstanding catalytic activity and long-term stability for HER,achieving low overpotentials of 19 and 203 mV at current densities of 10 and 1000 mA/cm^(2),respectively.The superior performance can be attributed to the combination of a refined particle size,lattice strains,and synergistic effects between Pt and Ni.This rapid liquid-state synthesis demonstrated here holds great potential for scalable and industrial manufacturing of micro-/nano-catalysts.
基金support from the National Key Research and Development Program of China(No.2023YFA0914100/2023YFA0914102)the National Natural Science Foundation of China(Nos.22077029 and 22034002)+2 种基金the Science Fund for Distinguished Young Scholars of Hunan Province(No.2021JJ10034)support from the National Natural Science Foundation of China(No.22276049)M.M.acknowledge the support from the National Natural Science Foundation of China(No.22276050).
文摘We report for the first time the combination of directed evolution focused on enhancing and reversing the stereoselectivity of an enzyme with Cu(I)-mediated click chemistry(CuAAC),providing an asymmetric click approach for versatile chiral triazoles products.In this study,the halohydrin dehalogenase HheG was used as the enzyme which was evolved to induce a stereoselective ring-opening reaction of cyclic epoxides in the presence of NaN3 with the formation of chiral azido products.Two mutants of opposite stereopreference were generated,which convert cyclohexene oxide as well as cycloheptene oxide to(1S,2S)-2-azidocyclohexanol,(1R,2R)-2-azidocyclohexanol,(1S,2S)-2-azidocycloheptanol and(1R,2R)-2-azidocycloheptanol with essentially high stereoselectivity.The chiral products were then subjected to CuAAC in reactions with structurally different alkynes.Since HheG was found to be compatible with Cu(I),the process was also performed successfully in a unique 2-step one-pot process leading to various chiral triazoles.In order to understand the enhancement and reversal of the evolved enantioselectivity,QM and MD computations were performed.This approach harnesses the modifiability and high stereoselectivity of the evolved biocatalysts in combination with click chemistry.It holds great potential for diverse fields,particularly in the area of pharmaceuticals.
基金supported by the National Natural Science Foundation of China (Nos.22271010 and 21702013)。
文摘The deuterium labeling has garnered significant interest in drug discovery due to its critical role on improving pharmacokinetic and metabolic properties.However,despite its pharmaceutical value,the general and rapid syntheses of aromatic scaffolds that contains deuterium remain an important yet elusive task.State-of-the-art approaches mainly relied on the transition metal-catalyzed C-H deuteration via the assistance of directing groups(DGs),which often suffered from over-deuteration and lengthy step counts required for installation and/or removal of DG.Herein,we report a generalizable synthetic linchpin strategy for the facile preparation of the ortho-deuterated aromatic core.Through capture of aryne-derived 1,3-zwitterion with heavy water,we synthesized an array of ortho-deuterated aryl sulfonium salts.These novel linchpins not only participated the transition metal catalyzed cross-coupling reaction as nucleophiles,but also served as aryl radical reservoirs under photochemical or electrochemical conditions,enabling facile and precise access to structurally diverse deuterated aromatics.Moreover,we have disclosed a novel EDA complex enabled direct arylation of phosphines under visible-light irradiation,further expanding the utility of our platform approach.
基金supported by the Science and Technology Commission of Shanghai Municipality Foundation(No.22230710500)the Interdisciplinary joint research project of Tongji University(No.2023-3-YB-07).
文摘As the core of cathode materials,sensitive metals play important roles in the optimization of acetate production from carbon dioxide(CO_(2))in microbial electrochemical system(MES).In this work,iron(Fe),copper(Cu),and nickel(Ni)as sensitive metal cathode materials were evaluated for CO_(2) conversion in MES.The MES with Feelectrode as a promising electrode material demonstrated a superior CO_(2) reduction performance with a maximum acetate accumulation of 417.9±39.2 mg/L,which was 1.5 and 1.7 folds higher than that in the Ni-electrode and Cu-electrode groups,respectively.Furthermore,an outstanding electron recovery efficiency of 67.7%was shown in the Fe-electrode group.The electron transfer between electrode-suspended sludge was systematically cross-evaluated by the electrochemical behavior and extracellular polymeric substances.The Fe-electrode group had the highest electron transfer rate with 0.194 s-1(k_(app)),which was 17.6 and 21.5 times higher than that of the Cu-and Ni-electrode groups,respectively.Fe-electrode was beneficial for reducing electrochemical impedance between the electrode and suspended sludge.Additionally,redox substances in extracellular polymeric substances of the Fe-electrode group were increased,implying more favorable electron transport dynamics.Simultaneously,enrichments of functional bacteria Acetoanerobium and increased key enzymes involved in the carbonyl pathway of the Fe-electrode group were observed,which also promoted CO_(2) conversion in MES.This study provides a perspective on evaluating the promising sensitive metal electrode material for the process of CO_(2) valorization in MES and offers a reference for the subsequent electrode modification.
基金supported by the NationalKey Research and Development Program of China(2023YFA1507701)National Natural Science Foundation of China(U22B6011,22288102)“Announcement and Challenge”Science and Technology Project of Xinjiang Uygur Autonomous Region(XJKJTJBGS-2023).
文摘Rare earth(RE)Y-type zeolite was synthesized in situ by acidic co-hydrolysis route and hydrothermal method.The key process parameters were optimized based on the RE utilization rate.The effect of inducing a rotating packed bed(RPB)in premixing and crystallization on crystallinity and RE utilization rate was further investigated.The results indicate that lanthanide(La)cations are successfully introduced into the sodalite cage of Y-type zeolite.The optimized conditions are that the molar ratio of Si/La is 150,premixing for 5 h,crystallization at 90℃ for 18 h,and calcination at 550℃ for 3.5 h.At this stage,the RE utilization rate reaches 74.5%.Compared with the conventional stirred tank reactor(STR),RPB can effectively shorten the premixing time and crystallization time by 4.3 h and 6 h,improve the crystallinity by 23%and RE utilization rate by 7.5%.The RE utilization rate is more than 80%by RPB,surpassing the effectiveness of using the one-exchange one-calcination process in the traditional liquid ion exchange process.It is expected to provide a reference for the in-situ efficient and green synthesis of RE zeolite.
