A simple and efficient method has been developed for the synthesis ofα-amino nitriles from aldehydes,amines and trimethylsilyl cyanide（Me_3SiCN） in the presence of a catalytic amount of cyanuric acid at room temper...A simple and efficient method has been developed for the synthesis ofα-amino nitriles from aldehydes,amines and trimethylsilyl cyanide（Me_3SiCN） in the presence of a catalytic amount of cyanuric acid at room temperature.展开更多
A series of new hexahydroimidazo[1,2-a]pyridine derivatives were synthesized via convenient and practical three-component reactions. Preliminary bioassays showed that majority of the target compounds exhibited moderat...A series of new hexahydroimidazo[1,2-a]pyridine derivatives were synthesized via convenient and practical three-component reactions. Preliminary bioassays showed that majority of the target compounds exhibited moderate to excellent insecticidal activity against cowpea aphids （Aphis craccivora）. Among them, compound 91 demonstrated significant activity with LCso value of 0.00918 mmol/L which was about 3.8-fold higher than that of imidacloprid （IMI）. Furthermore, the study of stereostructure-activity relationship of four isomers of 9k indicated that configuration played a key role in insecticidal activity of these compounds.展开更多
A general, mild and efficient protocol for the synthesis of ethyl 4-methyl-2-（thiophen）-2,5-dihydro-1,5- benzodiazepine-3-carboxylate is achieved for first time using H3PMo12O40 in ethanol at 0 ℃ by a one- pot, th...A general, mild and efficient protocol for the synthesis of ethyl 4-methyl-2-（thiophen）-2,5-dihydro-1,5- benzodiazepine-3-carboxylate is achieved for first time using H3PMo12O40 in ethanol at 0 ℃ by a one- pot, three-component condensation of various thiophene aldehydes, substituted o-phenylenediamines and ethyl acetoacetate. Compared with the conventional synthesis method, this procedure has the advantages of convenient operation, excellent yields, and environmentally benign. A plausible formation mechanism has been proposed. The structure of the products is characterized by1H NMR, IR, MS and elemental analysis.展开更多
Bismuth（Ⅲ） nitrate pentahydrate catalyzed the three-component condensation ofβ-naphthol,aldehydes and amines/urea under solvent-free conditions to afford the corresponding amidoalkyl naphthols in excellent yields.
The development of the three-component catalytic system for constructing isoindolinones from simple feedstocks is both significant and challenging.In this study,a unique tartrate-linked dimeric samarium-antimonotungst...The development of the three-component catalytic system for constructing isoindolinones from simple feedstocks is both significant and challenging.In this study,a unique tartrate-linked dimeric samarium-antimonotungstate[Sm_(2)(H_(2)O)_(6)(tar)(Sb_(2)W_(21)O_(72))]_(2)^(20-)(Sm_(4)tar_(2),H_(4)tar=tartaric acid)was synthesized via a one-step method at room temperature using an acetate buffer solution.The dimeric polyanion of Sm4tar2shows a centrosymmetric structure with a parallelogram-like arrangement and comprises two enantiomeric{Sm_(2)(H_(2)O)_(6)(Sb_(2)W_(21)O_(72))}moieties connected by two enantiomeric tar ligands.Sm_(4)tar_(2)demonstrates efficient catalytic activity in the three-component reaction involving 2-acylbenzoic acids,primary amines,and phosphine oxides to form 3,3-disubstituted isoindolinones.The advantages of this catalytic system include simple feedstocks,green and reusable catalyst,and operational simplicity with water as the sole by-product.This finding enables an effective molecular fragment assembly strategy for synthesizing isoindolinone drug precursor skeletons.展开更多
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
Metallic copper nanoparticles are a promising alternative to gold and silver in printed electronics due to their excellent electrical and thermal conductivity.However,their synthesis is often hindered by rapid oxidati...Metallic copper nanoparticles are a promising alternative to gold and silver in printed electronics due to their excellent electrical and thermal conductivity.However,their synthesis is often hindered by rapid oxidation and limited scalability.This work presents a microwave-assisted polyol process for the rapid and scalable production of metallic Cu micro-and nanoparticles,performed in air without the need for an inert atmosphere.Ethylene glycol acts as both solvent and reducing agent,while lignin serves as a renewable capping agent.Reaction time is reduced to 10 min in batch mode,and the process is scaled up to a continuous-flow microwave system,achieving production rates of~5gh^(-1).Particle sizes range from 800 to 40 nm depending on lignin content and metal seeding.After pressure or low-temperature(150℃)treatment,the materials reach conductivities between 30 and 100 lΩcm.These metallic copper nanoparticles show strong potential for use in sustainable conductive inks for flexible and printed electronics.展开更多
Renewable energy is critical to building a sustainable society,but its true potential can only be unlocked by developing efficient,environmentally friendly energy storage systems.Advances in storage technologies,inclu...Renewable energy is critical to building a sustainable society,but its true potential can only be unlocked by developing efficient,environmentally friendly energy storage systems.Advances in storage technologies,including cost-effective and green materials,are quickly becoming the cornerstone of sustainable energy solutions.The most effective battery technology available now is lithium-ion batteries(LIBs).However,the sustainability of battery material production and the degradation of LIB functionality at subzero temperatures pose significant challenges,highlighting the urgent need for alternative and sustainable low-temperature(LT)electrode materials.To overcome these issues,a green synthesis approach is proposed to fabricate SnO_(2) nanoparticles using an aqueous extract of banana peel,while the leftover peel serves as a carbon precursor to produce a SnO_(2)/hard carbon composite.The optimized SnO_(2)/hard carbon(7:3)composite was used as the anode and showcased a remarkable reversible capacity of 1110 mAh g^(-1) at room temperature and retained about 660 mAh g^(-1) at-20℃ and 100 mA g^(-1) after 100 cycles,with a capacity of 383 mAh g^(-1) even at-30℃.Stable cycling performance was achieved by the synergistic interaction of SnO_(2) and hard carbon,which improved lithium-ion diffusion and mitigated volume expansion.This eco-friendly and scalable approach shows great promise for developing high-performance anodes for the next generation of LT LIBs.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
文摘A simple and efficient method has been developed for the synthesis ofα-amino nitriles from aldehydes,amines and trimethylsilyl cyanide（Me_3SiCN） in the presence of a catalytic amount of cyanuric acid at room temperature.
基金supported by National Key Technology R&D Program of China(No.2011BAE06B01)
文摘A series of new hexahydroimidazo[1,2-a]pyridine derivatives were synthesized via convenient and practical three-component reactions. Preliminary bioassays showed that majority of the target compounds exhibited moderate to excellent insecticidal activity against cowpea aphids （Aphis craccivora）. Among them, compound 91 demonstrated significant activity with LCso value of 0.00918 mmol/L which was about 3.8-fold higher than that of imidacloprid （IMI）. Furthermore, the study of stereostructure-activity relationship of four isomers of 9k indicated that configuration played a key role in insecticidal activity of these compounds.
基金financial support from the National Natural Science Foundation of China(No.21276064)the Natural Science Foundation of Hebei Education Department(No.2008320)the Science Foundation of Hebei Normal University(No.2011Y04)
文摘A general, mild and efficient protocol for the synthesis of ethyl 4-methyl-2-（thiophen）-2,5-dihydro-1,5- benzodiazepine-3-carboxylate is achieved for first time using H3PMo12O40 in ethanol at 0 ℃ by a one- pot, three-component condensation of various thiophene aldehydes, substituted o-phenylenediamines and ethyl acetoacetate. Compared with the conventional synthesis method, this procedure has the advantages of convenient operation, excellent yields, and environmentally benign. A plausible formation mechanism has been proposed. The structure of the products is characterized by1H NMR, IR, MS and elemental analysis.
文摘Bismuth（Ⅲ） nitrate pentahydrate catalyzed the three-component condensation ofβ-naphthol,aldehydes and amines/urea under solvent-free conditions to afford the corresponding amidoalkyl naphthols in excellent yields.
基金financially supported by the National Natural Science Foundation of China(No.22301033)Jiangxi Provincial Natural Science Foundation(No.20232ACB213005 and 20212BAB213001)。
文摘The development of the three-component catalytic system for constructing isoindolinones from simple feedstocks is both significant and challenging.In this study,a unique tartrate-linked dimeric samarium-antimonotungstate[Sm_(2)(H_(2)O)_(6)(tar)(Sb_(2)W_(21)O_(72))]_(2)^(20-)(Sm_(4)tar_(2),H_(4)tar=tartaric acid)was synthesized via a one-step method at room temperature using an acetate buffer solution.The dimeric polyanion of Sm4tar2shows a centrosymmetric structure with a parallelogram-like arrangement and comprises two enantiomeric{Sm_(2)(H_(2)O)_(6)(Sb_(2)W_(21)O_(72))}moieties connected by two enantiomeric tar ligands.Sm_(4)tar_(2)demonstrates efficient catalytic activity in the three-component reaction involving 2-acylbenzoic acids,primary amines,and phosphine oxides to form 3,3-disubstituted isoindolinones.The advantages of this catalytic system include simple feedstocks,green and reusable catalyst,and operational simplicity with water as the sole by-product.This finding enables an effective molecular fragment assembly strategy for synthesizing isoindolinone drug precursor skeletons.
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.
文摘Metallic copper nanoparticles are a promising alternative to gold and silver in printed electronics due to their excellent electrical and thermal conductivity.However,their synthesis is often hindered by rapid oxidation and limited scalability.This work presents a microwave-assisted polyol process for the rapid and scalable production of metallic Cu micro-and nanoparticles,performed in air without the need for an inert atmosphere.Ethylene glycol acts as both solvent and reducing agent,while lignin serves as a renewable capping agent.Reaction time is reduced to 10 min in batch mode,and the process is scaled up to a continuous-flow microwave system,achieving production rates of~5gh^(-1).Particle sizes range from 800 to 40 nm depending on lignin content and metal seeding.After pressure or low-temperature(150℃)treatment,the materials reach conductivities between 30 and 100 lΩcm.These metallic copper nanoparticles show strong potential for use in sustainable conductive inks for flexible and printed electronics.
基金funded by the projects AP19578472“Electrophoretic deposition of composite multilayer gel-polymer electrolyte for 3D lithium-ion batteries”the Research Targeted Programs BR24992766“Development of methods and technologies for environmentally friendly“green”processing of polymer waste for energy storage”from the Ministry of ScienceHigher Education of the Republic of Kazakhstan and 111024CRP2010 and 20122022FD4135 from Nazarbayev University。
文摘Renewable energy is critical to building a sustainable society,but its true potential can only be unlocked by developing efficient,environmentally friendly energy storage systems.Advances in storage technologies,including cost-effective and green materials,are quickly becoming the cornerstone of sustainable energy solutions.The most effective battery technology available now is lithium-ion batteries(LIBs).However,the sustainability of battery material production and the degradation of LIB functionality at subzero temperatures pose significant challenges,highlighting the urgent need for alternative and sustainable low-temperature(LT)electrode materials.To overcome these issues,a green synthesis approach is proposed to fabricate SnO_(2) nanoparticles using an aqueous extract of banana peel,while the leftover peel serves as a carbon precursor to produce a SnO_(2)/hard carbon composite.The optimized SnO_(2)/hard carbon(7:3)composite was used as the anode and showcased a remarkable reversible capacity of 1110 mAh g^(-1) at room temperature and retained about 660 mAh g^(-1) at-20℃ and 100 mA g^(-1) after 100 cycles,with a capacity of 383 mAh g^(-1) even at-30℃.Stable cycling performance was achieved by the synergistic interaction of SnO_(2) and hard carbon,which improved lithium-ion diffusion and mitigated volume expansion.This eco-friendly and scalable approach shows great promise for developing high-performance anodes for the next generation of LT LIBs.
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.
