A facile "click chemistry" approach to functionalize 2D macromolecules of graphene oxide nanosheets with poly(ethylene glycol) of different molecular weights,polystyrene,palmitic acid and various amino acids...A facile "click chemistry" approach to functionalize 2D macromolecules of graphene oxide nanosheets with poly(ethylene glycol) of different molecular weights,polystyrene,palmitic acid and various amino acids was presented.FTIR,TGA,Raman spectroscopy,XPS,XRD,TEM,AFM and SEM were utilized to characterize the products.High degree of functionalization was achieved on the flat surfaces of graphene oxide,affording polymer-grafted 2D brushes and amino acids-immobilized nanosheets,which show improved solubility in organic solvents.The click chemistry strategy reported herein provides a facile and general method for functionalization of graphene oxide with macromolecules and desired biomolecules.展开更多
In this study, a novel approach by combining base-catalyzed epoxide ring-opening and thiol-ene click chemistry is presented for the side-chain modification of dextran. The vinyl-modified dextran is prepared by a basic...In this study, a novel approach by combining base-catalyzed epoxide ring-opening and thiol-ene click chemistry is presented for the side-chain modification of dextran. The vinyl-modified dextran is prepared by a basic epoxide ring opening reaction of allyl glycidyl ether in 0.1 mol/L NaOH, followed by thiol-addition click reaction of three model sulfhydryl compounds using water-soluble Irgacure 2959 as the photoinitiator, leading to side-chain functionalized dextran modified with carboxyl, bidentate dicarboxyl or amino groups. This is the first example of combining epoxide ring-opening and thiol- ene click chemistry for side-chain modification of dextran in aqueous media. Importantly, it may also be extended as a convenient and efficient method for the side-chain modification of other polysaccharides.展开更多
Since the sulfur(Ⅵ)fluoride exchange reaction(SuFEx)was introduced by Sharpless and co-workers in 2014,this new-generation click chemistry has emerged as an efficient and reliable tool for creating modular intermolec...Since the sulfur(Ⅵ)fluoride exchange reaction(SuFEx)was introduced by Sharpless and co-workers in 2014,this new-generation click chemistry has emerged as an efficient and reliable tool for creating modular intermolecular connections.Sulfonyl fluorides,one of the most important sulfur(Ⅵ)fluoride species,have attracted enormous attention in diverse fields,ranging from organic synthesis and material science,to chemical biology and drug discovery.This review aims to introduce seminal and recent progresses on the synthetic methods of sulfonyl fluorides,which include aromatic,aliphatic,alkenyl,and alkynyl sulfonyl fluorides.While not meant to be exhaustive,the purpose is to give a timely overview and insight in this field,and stimulate the development of more efficient synthetic methods of sulfonyl fluorides.展开更多
Click chemistry was applied to immobilize L-proline derivative onto azide-modified silica gel to give a novel chiral stationary phase （denoted as click-CSP） for ligand exchange chromatography. The developed protocol...Click chemistry was applied to immobilize L-proline derivative onto azide-modified silica gel to give a novel chiral stationary phase （denoted as click-CSP） for ligand exchange chromatography. The developed protocol combines the benefits of operational simplicity, exceptionally mild conditions and high surface loadings. The enantioselectivity α of some DL-arnino acids on the click- CSP were found to be in the range from 1.13 to 3.46. The chromatographic resolutions of some DL-amino acids and the stability study firmly illustrate the potential of click chemistry for preparation chiral stationary phase for ligand exchange chromatography.展开更多
This research work discloses the preparation of polyurethane coatings from cardanol modified using thiolene chemistry,wherein unsaturated long alkyl chain of cardanol was successfully utilized via thiol-ene click reac...This research work discloses the preparation of polyurethane coatings from cardanol modified using thiolene chemistry,wherein unsaturated long alkyl chain of cardanol was successfully utilized via thiol-ene click reaction to synthesize polyol.For this purpose,cardanol and thioglycerol was reacted in the presence of Irgacure 184(photoinitiator)and 1,8-Diazabicyclo[5.4.0]undec-7-ene(catalyst)and exposed to UV light for 12 h at 80℃.One mole of thioglycerol was successfully added across the double bond of fatty chain of cardanol and confirmed by chemical and spectroscopic analysis.Further,the polyol thus prepared was cured with various polyisocyanates,viz.,N-75(HDI based),L-67/BA(TDI based),Z-4470(IPDI based)and corresponding polyurethane coatings were developed.The coatings were then analyzed for mechanical,chemical,optical,thermal and anticorrosive properties.It was observed that cardanol-based PU coatings exhibited excellent mechanical,chemical and thermal and anticorrosive properties as compared to that of commercial acrylic-PU coatings.展开更多
Inorganic polyhedral oligomeric silsesquioxane （POSS） was used as the core for the synthesis of poly（t- lysine） peptide dendrimer via copper-catalyzed azide-alkyne click chemistry. The inorganic/organic composite ...Inorganic polyhedral oligomeric silsesquioxane （POSS） was used as the core for the synthesis of poly（t- lysine） peptide dendrimer via copper-catalyzed azide-alkyne click chemistry. The inorganic/organic composite dendrimer was characterized by MS, 1H NMR, FTIR, GPC and DLS.展开更多
Novel hybrid molecules 8a-8o were designed and synthesized by connecting indole ring with N- hydroxyarylamide through alkyl substituted triazole, and their in vitro biological activities were evaluated. It was discove...Novel hybrid molecules 8a-8o were designed and synthesized by connecting indole ring with N- hydroxyarylamide through alkyl substituted triazole, and their in vitro biological activities were evaluated. It was discovered that most of target compounds showed promising anticancer activities, particularly for 8n, which had a significant HDACs inhibitory and antiproliferative activities comparable to or slightly stronger than SAHA against human carcinoma cells. Furthermore, compound 8n exhibited much better selectivity for HDAC1 over HDAC6 and HDAC8 than SAHA. In addition, compound 8n also could dose-dependently induce cancer cell cycling arrest at G0/G1 phase and promote the expression of the acetylation for histone H3 and tubulin in vitro. Therefore, our novel findings may provide a new framework for the design of new selective HDAC inhibitor for the treatment of cancer.展开更多
A novel octazido substituted nanobuilding precursor, octakis[dimethy（p-azidomethylene）siloxyl]octasilsesquioxane （ODA）, was prepared by the conventional diazo-transfer reaction of octalds[dimethy（p-chloromethylen...A novel octazido substituted nanobuilding precursor, octakis[dimethy（p-azidomethylene）siloxyl]octasilsesquioxane （ODA）, was prepared by the conventional diazo-transfer reaction of octalds[dimethy（p-chloromethylene）silyl]octasilsesquioxane （ODC） with NAN3, and its structure was characterized by FT-IR, 1H, a3C, 29Si NMR and MALDI-TOF MS, respectively. The structural rearrangement of POSS core in the synthesis strategy of ODA developed in this work was effectively prohibited in comparison with traditionary azidization process. The resultant ODA was not only soluble in common solvents such as CHC13, THF, toluene, DMF and DMSO, but also could effectively serve as a versatile nanobuilding precursor for the architecture of well-defined organic- inorganic hybrids via click chemistry.展开更多
Although the concept of click chemistry was proposed more than twenty years ago,the research progress of click chemistry has emerged with great vitality,and this year's Nobel Prize in chemistry has once again high...Although the concept of click chemistry was proposed more than twenty years ago,the research progress of click chemistry has emerged with great vitality,and this year's Nobel Prize in chemistry has once again highlighted the importance of the field of click chemistry.Click chemistry is a reaction in which a variety of molecules are quickly and reliably synthesized by piecing together small units.In particular,it emphasizes the development of new combinatorial chemistry methods based on the synthesis of carbon-heteroatomic bonds and the simple and efficient acquisition of molecular diversity through these reactions.Based on the superior reaction characteristics of click chemistry,click chemistry methods for production are advancing toward precision,simplicity,and high returns,especially in producing polymer materials and some bright biomedical applications.Here,we describe the development logic of typical click reactions with different substrates and catalysts.The latest technologies of click chemistry in the structure control and functional properties of polymers,as well as in the field of biomedicine and its expanding applications,are discussed.Finally,we identify the challenges of click chemistry in reaction mechanisms and engineering applications,and suggest potential future development directions in the future.展开更多
A new bis(aroylacetylene) containing tfiazole and fluorene moieties is synthesized by click chemistry. Polycyclotrimerization of the monomer is catalyzed by piperidine in refluxed dioxane,furnishing a regioregular pol...A new bis(aroylacetylene) containing tfiazole and fluorene moieties is synthesized by click chemistry. Polycyclotrimerization of the monomer is catalyzed by piperidine in refluxed dioxane,furnishing a regioregular poly(aroylarylene) in a satisfactory yield.The hyperbranched structure of the polymer is characterized spectroscopically with satisfactory results.The polymer enjoys no metal detriment and is soluble in common organic solvents such as tetrahydrofuran (THF),chloroform,dichloromethane (DCM),and N,N-...展开更多
Click chemistry was applied to immobilize three kinds of alkyne-carboxylic acids onto azide-modified silica gel to prepare three novel stationary phases for weak cation exchange chromatography（WCX）.The developed pro...Click chemistry was applied to immobilize three kinds of alkyne-carboxylic acids onto azide-modified silica gel to prepare three novel stationary phases for weak cation exchange chromatography（WCX）.The developed protocol combines the benefits of operational simplicity,exceptionally mild conditions and high surface loadings.Six kinds of standard proteins were separated completely on the novel packings.Compared with commercial WCX columns,the three kinds of novel WCX packings prepared by click chemistry approach have better resolution and selectivity.Lysozyme was purified successfully from egg white with the novel WCX column by one step.The purity was more than 97%and a high specific activity was achieved to be 81,435 U/mg.The results illustrate the potential of click chemistry for preparation of stationary phase for IEC.展开更多
The issue about how outstanding scientists obtained innovative findings has drawn the interest of researchers in science, policy and scientometrics. Here, we attempt to address this question by using computational met...The issue about how outstanding scientists obtained innovative findings has drawn the interest of researchers in science, policy and scientometrics. Here, we attempt to address this question by using computational methods to measure the cognitive content and concepts of K. Barry Sharpless’ research and estimate the knowledge flow of his click chemistry to other fields. First, we traced Sharpless’ conceptual journey over time through topic modeling approach, mapping and clustering of the epistemic network from distant reading his publications. We find that connectivity and functions, the core features of click chemistry, are embodied in his constant search for simplicity. What makes simplicity possible is his continuous work with collaborators on reactivity and reaction mechanisms. Moreover, citation and link analysis show that click chemistry had a much richer impact on other research fields than what is generally acknowledged, and drew solutions to significant and practical questions back to chemistry from biology.Together with these findings, we propose that the click chemistry philosophy follows the way that values nature’s principle. Chemistry has a clear-cut epistemic domain in modeling Nature. Thus, click chemistry as a concept on doing science beyond a connective technology goes across the boundaries between disciplines and impacts many other fields.展开更多
The 2022 Nobel Prize in Chemistry was awarded to American scientists Carolyn Bertozzi,K.Barry Sharpless,and Danish scientist Morten P.Merdahl for their contributions to the development of click chemistry and bioorthog...The 2022 Nobel Prize in Chemistry was awarded to American scientists Carolyn Bertozzi,K.Barry Sharpless,and Danish scientist Morten P.Merdahl for their contributions to the development of click chemistry and bioorthogonal chemistry.展开更多
Functionalized poly（phthalazinone ether sulfone ketone） was synthesized by successive chloromethylation and azidation, followed by curing reaction with the propargyl end-groups of various molecular weight crosslinki...Functionalized poly（phthalazinone ether sulfone ketone） was synthesized by successive chloromethylation and azidation, followed by curing reaction with the propargyl end-groups of various molecular weight crosslinking agents in the presence of Cu（I） catalyst via the azide-alkyne click reaction. The influences of the chain length of crosslinking agents on the poly（phthalazinone ether sulfone ketone） system were studied. FTIR and DSC tests demonstrated certain crosslinking by azide-alkyne reaction with the formation of triazole ring. DSC results showed that curing temperature shifted to lower temperatures considerably in the presence of Cu（I） catalyst. TGA showed cured polymers were of much higher thermal stability, including higher thermal decomposition temperatures and higher char-yielding properties. After being cured, the polymers became insoluble in organic solvents and the gel fraction of the cured polymers exceeded 71%. Wide-angle X-ray diffraction results indicated there was a short distance order in the poly（ether sulfone） （PES） main chain except for the azido methyl poly（phthalazinone ether sulfone ketone） and 4,4＇-bis（2-propynyloxy） biphenyl （AMPPESK-BP） system.展开更多
To improve shrink-proofing performance and hydrophilicity of wool fabrics, the wool fibers were modified by poly(ethylene glycol) dimethacrylate(PEGDMA) through thiol-ene click chemistry reaction. Firstly, wool fabric...To improve shrink-proofing performance and hydrophilicity of wool fabrics, the wool fibers were modified by poly(ethylene glycol) dimethacrylate(PEGDMA) through thiol-ene click chemistry reaction. Firstly, wool fabrics were reduced at room temperature with a high-efficiency disulfide bond reducing agent, tris(2-carbonxyethyl) phosphine hydrochloride(TCEP). Then the thiol-ene click chemistry reaction was initiated by dimethyl 2, 2’-azobis(2-methylpropionate)(AIBME) through the heating method. Fourier transform infrared(FTIR) spectroscopy, Raman spectroscopy, and scanning electron microscopy test results all showed that PEGDMA was successfully grafted onto wool fabric surface. Physical properties, hydrophilicity, and shrink-proofing performance were assessed. The wetting time of PEGDMA grafted wool fabrics decreased to about 3 s. After being grafted with PEGDMA, the felting shrinkage of wool fabrics rapidly decreased to about 8%. The anti-pilling properties of wool fabrics were also greatly improved to 5 class after 2 000 times of friction. Meanwhile, the load retention rate of fabrics could reach 90%. It provides a method of wool modification to improve hydrophilicity and anti-felting performance.展开更多
Poly[（mercaptopropyl）methylsiloxane] （PMMS）-based antibacterial polymer coatings have been prepared through a two-step sequential thiol-ene click chemistry utilizing 1-allyl-3-decylimidazolium bromide （ADIm） as ...Poly[（mercaptopropyl）methylsiloxane] （PMMS）-based antibacterial polymer coatings have been prepared through a two-step sequential thiol-ene click chemistry utilizing 1-allyl-3-decylimidazolium bromide （ADIm） as antibacterial monomer and triallyl cyanurate （TAC） as the crosslinker. These films with different content of ADIm were characterized by thermogravimetric analysis （TGA）, dynamic mechanical analysis （DMA） and pencil hardness. It was found that the mechanical and thermal properties of these films were largely influenced by the content of ADIm in the films. Films with imidazolium bromide groups displayed excellent antimicrobial activity against Staphylococcus aureus with 100% killing efficiency.展开更多
Click chemistry is a rapid,reliable,and powerful function and a highly selective organic reaction that facilitates the efficient synthesis of various molecules by joining small units.This approach has found widespread...Click chemistry is a rapid,reliable,and powerful function and a highly selective organic reaction that facilitates the efficient synthesis of various molecules by joining small units.This approach has found widespread applications in fields such as drug development,chemical synthesis,and molecular biology.In recent years,the reaction of alkali-catalyzed polymerization of thiol and sulfur has been employed to prepare various sulfur-containing polymers,which are applied as electrochemical active electrode materials in the pursuit of good performance.In this study,it is surprising to find that the reaction mechanism exhibits characteristics of both the alkali-catalyzed sulfhydryl Micheal addition reaction and thiol-epoxy click chemistry;for the first time,thiol-sulfur click chemistry is defined in detail,providing a comprehensive description of its underlying scientific principles.The introduction of this new reaction pathway holds significant potential for advancing research and the development of sulfur-containing polymers.Based on this novel click chemistry,a new sulfur-containing polymer,polydivinylthioether hexasulfide,has been designed and successfully applied as a cathode material in lithium-organosulfide batteries.This material demonstrates excellent electrochemical performance,achieving an initial capacity that reaches 790.5 mAh g−1(82.6%of theoretical capacity),and in a long-term cycle test,the capacity decay rate is only 0.063%after 1,000 cycles.展开更多
Comprehensive Summary:The reactions of potassium diazaphospholidinyl diazomethylide with phenylacetylene,acetonitrile,adamantyl phosphaalkyne,and styrene promptly form pyrazolide,triazolide,diazaphospholide,and pyrazo...Comprehensive Summary:The reactions of potassium diazaphospholidinyl diazomethylide with phenylacetylene,acetonitrile,adamantyl phosphaalkyne,and styrene promptly form pyrazolide,triazolide,diazaphospholide,and pyrazolinide,respectively.The reaction mechanisms have been studied using DFT calculations.While the reactions with phenylacetylene and styrene proceed via stepwise pathways,those with acetonitrile and adamantyl phosphaalkyne follow concerted pathways.Additionally,the pyrazolide product readily undergoes N-functionalization,yielding methyl pyrazole,germanyl pyrazole,and copper pyrazolide complexes.展开更多
Pear fruit typically contains abundant highly lignified cells,known as stone cells,which have a negative impact on the fruit's edibility and processing quality.Despite extensive physiological and molecular researc...Pear fruit typically contains abundant highly lignified cells,known as stone cells,which have a negative impact on the fruit's edibility and processing quality.Despite extensive physiological and molecular research,there remains a limited understanding of the precise spatiotemporal aspects of lignification in flesh cells during pear devel-opment,particularly regarding the initiation of lignification and expansion of stone cell clusters.Here,an emerging bioorthogonal chemistry-based imaging technique was employed to in vivo visualize cell lignification dynamics in developing pear fruit.Specific identification of active sites undergoing lignification revealed that initial lignification of flesh cells occurred at 10 days after full bloom(DAFB),resulting in the formation of pri-mordial stone cells(PSCs).These PSCs exhibited a random distribution and showed significantly larger diameter and area compared to normal parenchyma cells.Subsequently,PSCs developed pit canals and initiated lignifi-cation process in their neighboring cells at 15 DAFB.A cascading effect in the formation of stone cell aggregations was visualized by tracing of the lignification trajectory.This expansion process exhibited a domino effect,whereby lignification progressively spread from one cell to the next,creating a cascading pattern of stone cell formation.Finally,a cellular developmental model was proposed for stone cell formation.This study presented a procedure for applying the cutting-edge technology,click chemistry imaging,to get insights into practical sci-entific questions.The findings elucidated the spatiotemporal dynamics of active lignification sites in pear fruit at the cellular level,thereby enhancing our understanding of the initiation and aggregation processes in stone cell formation.展开更多
Electrocatalytic reduction of nitrate(NO_(3)^(−))is a promising approach to achieving sustainable and green ammonia synthesis and environmental denitrification.Here,click chemistry is extended to fabricate dynamic sin...Electrocatalytic reduction of nitrate(NO_(3)^(−))is a promising approach to achieving sustainable and green ammonia synthesis and environmental denitrification.Here,click chemistry is extended to fabricate dynamic singlesite metal catalysts for NO3−electroreduction.Specifically,Co^(2+)-coordinated molecular units are covalently clicked into a stable Th-metal–organic framework,confining and dispersing single-site metals that exhibit the asymmetrical Co–N2Cl2 coordination configuration.The obtained CoN2Cl2@Th-BPDC electrocatalyst achieves an outstanding ammonia production rate of 770.3μmol h^(−1) cm^(−2)(5135.3 mmol gcat^(−1) h^(−1))at−0.4 V versus RHE,which is approximately 25.7 times higher than that of the Haber–Bosch process(<200 mmol gcat^(−1) h^(−1))and outperforms the most recently reported electrocatalysts.Theoretical calculations reveal that single-site Co2+exhibits strong bidentate adsorption toward NO_(3)^(−)due to the suitable geometric space provided by the rotation of Co-coordinated Cl atoms(a dynamic feature),which promotes NO_(3)^(−)activation and decreases the reaction barrier,resulting in excellent catalytic activity.This study describes an innovative strategy for fabricating dynamic asymmetrical single-site metal electrocatalysts and may inspire new methodologies for the precise synthesis of advanced catalytic materials.展开更多
基金financially supported by the National Natural Science Foundation of China (No.50773038,and No.20974093)National Basic Research Program of China (973 Program) (No.2007CB936000)+2 种基金Qianjiang Talent Foundation of Zhejiang Province (2010R10021)the Fundamental Research Funds for the Central Universities (2009QNA4040)the Foundation for the Author of National Excellent Doctoral Dissertation of China (No.200527)
文摘A facile "click chemistry" approach to functionalize 2D macromolecules of graphene oxide nanosheets with poly(ethylene glycol) of different molecular weights,polystyrene,palmitic acid and various amino acids was presented.FTIR,TGA,Raman spectroscopy,XPS,XRD,TEM,AFM and SEM were utilized to characterize the products.High degree of functionalization was achieved on the flat surfaces of graphene oxide,affording polymer-grafted 2D brushes and amino acids-immobilized nanosheets,which show improved solubility in organic solvents.The click chemistry strategy reported herein provides a facile and general method for functionalization of graphene oxide with macromolecules and desired biomolecules.
基金financially supported by the National Natural Science Foundation of China(Nos.51373168,51390484,51233004 and 51321062)
文摘In this study, a novel approach by combining base-catalyzed epoxide ring-opening and thiol-ene click chemistry is presented for the side-chain modification of dextran. The vinyl-modified dextran is prepared by a basic epoxide ring opening reaction of allyl glycidyl ether in 0.1 mol/L NaOH, followed by thiol-addition click reaction of three model sulfhydryl compounds using water-soluble Irgacure 2959 as the photoinitiator, leading to side-chain functionalized dextran modified with carboxyl, bidentate dicarboxyl or amino groups. This is the first example of combining epoxide ring-opening and thiol- ene click chemistry for side-chain modification of dextran in aqueous media. Importantly, it may also be extended as a convenient and efficient method for the side-chain modification of other polysaccharides.
基金financially supported by the National Natural Science Foundation of China(Nos.21502240,81972824)Guangdong Basic and Applied Basic Research Foundation(Nos.2020A1515010684,2020A1515011513)Guangdong Provincial Key Laboratory of Chiral Molecule and Drug Discovery(No.2019B030301005)。
文摘Since the sulfur(Ⅵ)fluoride exchange reaction(SuFEx)was introduced by Sharpless and co-workers in 2014,this new-generation click chemistry has emerged as an efficient and reliable tool for creating modular intermolecular connections.Sulfonyl fluorides,one of the most important sulfur(Ⅵ)fluoride species,have attracted enormous attention in diverse fields,ranging from organic synthesis and material science,to chemical biology and drug discovery.This review aims to introduce seminal and recent progresses on the synthetic methods of sulfonyl fluorides,which include aromatic,aliphatic,alkenyl,and alkynyl sulfonyl fluorides.While not meant to be exhaustive,the purpose is to give a timely overview and insight in this field,and stimulate the development of more efficient synthetic methods of sulfonyl fluorides.
文摘Click chemistry was applied to immobilize L-proline derivative onto azide-modified silica gel to give a novel chiral stationary phase （denoted as click-CSP） for ligand exchange chromatography. The developed protocol combines the benefits of operational simplicity, exceptionally mild conditions and high surface loadings. The enantioselectivity α of some DL-arnino acids on the click- CSP were found to be in the range from 1.13 to 3.46. The chromatographic resolutions of some DL-amino acids and the stability study firmly illustrate the potential of click chemistry for preparation chiral stationary phase for ligand exchange chromatography.
文摘This research work discloses the preparation of polyurethane coatings from cardanol modified using thiolene chemistry,wherein unsaturated long alkyl chain of cardanol was successfully utilized via thiol-ene click reaction to synthesize polyol.For this purpose,cardanol and thioglycerol was reacted in the presence of Irgacure 184(photoinitiator)and 1,8-Diazabicyclo[5.4.0]undec-7-ene(catalyst)and exposed to UV light for 12 h at 80℃.One mole of thioglycerol was successfully added across the double bond of fatty chain of cardanol and confirmed by chemical and spectroscopic analysis.Further,the polyol thus prepared was cured with various polyisocyanates,viz.,N-75(HDI based),L-67/BA(TDI based),Z-4470(IPDI based)and corresponding polyurethane coatings were developed.The coatings were then analyzed for mechanical,chemical,optical,thermal and anticorrosive properties.It was observed that cardanol-based PU coatings exhibited excellent mechanical,chemical and thermal and anticorrosive properties as compared to that of commercial acrylic-PU coatings.
基金supported by the National Basic Research Program of China(National 973 program,No.2011CB606206)National Science Foundation of China(NSFC,Nos.31170921,51133004)+1 种基金the National Science Foundation for Excellent Young Scholars(No.51222304)Program for Changjiang Scholars and Innovative Research Team in University(No.IRT1163)
文摘Inorganic polyhedral oligomeric silsesquioxane （POSS） was used as the core for the synthesis of poly（t- lysine） peptide dendrimer via copper-catalyzed azide-alkyne click chemistry. The inorganic/organic composite dendrimer was characterized by MS, 1H NMR, FTIR, GPC and DLS.
文摘Novel hybrid molecules 8a-8o were designed and synthesized by connecting indole ring with N- hydroxyarylamide through alkyl substituted triazole, and their in vitro biological activities were evaluated. It was discovered that most of target compounds showed promising anticancer activities, particularly for 8n, which had a significant HDACs inhibitory and antiproliferative activities comparable to or slightly stronger than SAHA against human carcinoma cells. Furthermore, compound 8n exhibited much better selectivity for HDAC1 over HDAC6 and HDAC8 than SAHA. In addition, compound 8n also could dose-dependently induce cancer cell cycling arrest at G0/G1 phase and promote the expression of the acetylation for histone H3 and tubulin in vitro. Therefore, our novel findings may provide a new framework for the design of new selective HDAC inhibitor for the treatment of cancer.
基金supported by the National Natural Science Foundation of China(Nos.51073031, 51003013,20971021 and 20974018)Doctoral Dissertation Innovation Project(No.BC200901)
文摘A novel octazido substituted nanobuilding precursor, octakis[dimethy（p-azidomethylene）siloxyl]octasilsesquioxane （ODA）, was prepared by the conventional diazo-transfer reaction of octalds[dimethy（p-chloromethylene）silyl]octasilsesquioxane （ODC） with NAN3, and its structure was characterized by FT-IR, 1H, a3C, 29Si NMR and MALDI-TOF MS, respectively. The structural rearrangement of POSS core in the synthesis strategy of ODA developed in this work was effectively prohibited in comparison with traditionary azidization process. The resultant ODA was not only soluble in common solvents such as CHC13, THF, toluene, DMF and DMSO, but also could effectively serve as a versatile nanobuilding precursor for the architecture of well-defined organic- inorganic hybrids via click chemistry.
文摘Although the concept of click chemistry was proposed more than twenty years ago,the research progress of click chemistry has emerged with great vitality,and this year's Nobel Prize in chemistry has once again highlighted the importance of the field of click chemistry.Click chemistry is a reaction in which a variety of molecules are quickly and reliably synthesized by piecing together small units.In particular,it emphasizes the development of new combinatorial chemistry methods based on the synthesis of carbon-heteroatomic bonds and the simple and efficient acquisition of molecular diversity through these reactions.Based on the superior reaction characteristics of click chemistry,click chemistry methods for production are advancing toward precision,simplicity,and high returns,especially in producing polymer materials and some bright biomedical applications.Here,we describe the development logic of typical click reactions with different substrates and catalysts.The latest technologies of click chemistry in the structure control and functional properties of polymers,as well as in the field of biomedicine and its expanding applications,are discussed.Finally,we identify the challenges of click chemistry in reaction mechanisms and engineering applications,and suggest potential future development directions in the future.
基金supported by the National Natural Science Foundation of China (Nos.20634020 and 50703033)the Ministry of Science & Technology (No.2009CB623605)+2 种基金the Research Grants Council of Hong Kong (Nos.603008,602707 and 602706)A.J.Q.acknowledges the support from the China Postdoctoral Science Foundation (No.20070420228)B.Z.T.thanks the support from the Cao Guangbiao Foundation of Zhejiang University.
文摘A new bis(aroylacetylene) containing tfiazole and fluorene moieties is synthesized by click chemistry. Polycyclotrimerization of the monomer is catalyzed by piperidine in refluxed dioxane,furnishing a regioregular poly(aroylarylene) in a satisfactory yield.The hyperbranched structure of the polymer is characterized spectroscopically with satisfactory results.The polymer enjoys no metal detriment and is soluble in common organic solvents such as tetrahydrofuran (THF),chloroform,dichloromethane (DCM),and N,N-...
基金supported by the National 863 Program(No2006AA02Z227)the Natural Science Fondation of Shaanxi Province(No2011JZ002)the National Fund for Fostering Talents in Basic Science(NoJ0830417)
文摘Click chemistry was applied to immobilize three kinds of alkyne-carboxylic acids onto azide-modified silica gel to prepare three novel stationary phases for weak cation exchange chromatography（WCX）.The developed protocol combines the benefits of operational simplicity,exceptionally mild conditions and high surface loadings.Six kinds of standard proteins were separated completely on the novel packings.Compared with commercial WCX columns,the three kinds of novel WCX packings prepared by click chemistry approach have better resolution and selectivity.Lysozyme was purified successfully from egg white with the novel WCX column by one step.The purity was more than 97%and a high specific activity was achieved to be 81,435 U/mg.The results illustrate the potential of click chemistry for preparation of stationary phase for IEC.
基金supported by the Research Funds of Happiness Flower ECNU (No. 2019ECNU-XFZH006)the National Social Science Fund of China (No. 19BZX041)+1 种基金the National Natural Science Foundation of China (Nos. 22125103 and 21971065)the Science Technology Commission Shanghai Municipality (Nos. 22JC1401000, 20JC1416800 and 20XD1421500)。
文摘The issue about how outstanding scientists obtained innovative findings has drawn the interest of researchers in science, policy and scientometrics. Here, we attempt to address this question by using computational methods to measure the cognitive content and concepts of K. Barry Sharpless’ research and estimate the knowledge flow of his click chemistry to other fields. First, we traced Sharpless’ conceptual journey over time through topic modeling approach, mapping and clustering of the epistemic network from distant reading his publications. We find that connectivity and functions, the core features of click chemistry, are embodied in his constant search for simplicity. What makes simplicity possible is his continuous work with collaborators on reactivity and reaction mechanisms. Moreover, citation and link analysis show that click chemistry had a much richer impact on other research fields than what is generally acknowledged, and drew solutions to significant and practical questions back to chemistry from biology.Together with these findings, we propose that the click chemistry philosophy follows the way that values nature’s principle. Chemistry has a clear-cut epistemic domain in modeling Nature. Thus, click chemistry as a concept on doing science beyond a connective technology goes across the boundaries between disciplines and impacts many other fields.
基金supported by the Natural Science Foundation of Xinjiang Uygur Autonomous Region(No.2022D01D38)the National Natural Science Foundation of China(Nos.82173681,21977116,82104004,81973223)+1 种基金the Open Project of State Key Laboratory of Natural Medicines(No.SKLNMZZ202213)the State Key Laboratory of Pathogenesis,Prevention and Treatment of High Incidence Diseases in Central Asia Fund(No.SKL-HIDCA-2021-1).
文摘The 2022 Nobel Prize in Chemistry was awarded to American scientists Carolyn Bertozzi,K.Barry Sharpless,and Danish scientist Morten P.Merdahl for their contributions to the development of click chemistry and bioorthogonal chemistry.
基金financially supported by the National Natural Science Foundation of China(No.51273029)
文摘Functionalized poly（phthalazinone ether sulfone ketone） was synthesized by successive chloromethylation and azidation, followed by curing reaction with the propargyl end-groups of various molecular weight crosslinking agents in the presence of Cu（I） catalyst via the azide-alkyne click reaction. The influences of the chain length of crosslinking agents on the poly（phthalazinone ether sulfone ketone） system were studied. FTIR and DSC tests demonstrated certain crosslinking by azide-alkyne reaction with the formation of triazole ring. DSC results showed that curing temperature shifted to lower temperatures considerably in the presence of Cu（I） catalyst. TGA showed cured polymers were of much higher thermal stability, including higher thermal decomposition temperatures and higher char-yielding properties. After being cured, the polymers became insoluble in organic solvents and the gel fraction of the cured polymers exceeded 71%. Wide-angle X-ray diffraction results indicated there was a short distance order in the poly（ether sulfone） （PES） main chain except for the azido methyl poly（phthalazinone ether sulfone ketone） and 4,4＇-bis（2-propynyloxy） biphenyl （AMPPESK-BP） system.
基金National Natural Science Foundation of China (No.31771039)Scientific Research Fund of National Innovation Center of Advanced Dyeing and Finishing Technology,China (No.ZJ2021B03)。
文摘To improve shrink-proofing performance and hydrophilicity of wool fabrics, the wool fibers were modified by poly(ethylene glycol) dimethacrylate(PEGDMA) through thiol-ene click chemistry reaction. Firstly, wool fabrics were reduced at room temperature with a high-efficiency disulfide bond reducing agent, tris(2-carbonxyethyl) phosphine hydrochloride(TCEP). Then the thiol-ene click chemistry reaction was initiated by dimethyl 2, 2’-azobis(2-methylpropionate)(AIBME) through the heating method. Fourier transform infrared(FTIR) spectroscopy, Raman spectroscopy, and scanning electron microscopy test results all showed that PEGDMA was successfully grafted onto wool fabric surface. Physical properties, hydrophilicity, and shrink-proofing performance were assessed. The wetting time of PEGDMA grafted wool fabrics decreased to about 3 s. After being grafted with PEGDMA, the felting shrinkage of wool fabrics rapidly decreased to about 8%. The anti-pilling properties of wool fabrics were also greatly improved to 5 class after 2 000 times of friction. Meanwhile, the load retention rate of fabrics could reach 90%. It provides a method of wool modification to improve hydrophilicity and anti-felting performance.
文摘Poly[（mercaptopropyl）methylsiloxane] （PMMS）-based antibacterial polymer coatings have been prepared through a two-step sequential thiol-ene click chemistry utilizing 1-allyl-3-decylimidazolium bromide （ADIm） as antibacterial monomer and triallyl cyanurate （TAC） as the crosslinker. These films with different content of ADIm were characterized by thermogravimetric analysis （TGA）, dynamic mechanical analysis （DMA） and pencil hardness. It was found that the mechanical and thermal properties of these films were largely influenced by the content of ADIm in the films. Films with imidazolium bromide groups displayed excellent antimicrobial activity against Staphylococcus aureus with 100% killing efficiency.
基金supported by the National Natural Science Foundation of China(52463013 and 52073133)the Major Science and Technology Project of Gansu Province(22ZD6GA008)the Incubation Program of Excelent Doctoral Dissertation-Lanzhou Univer-sity of Technology.
文摘Click chemistry is a rapid,reliable,and powerful function and a highly selective organic reaction that facilitates the efficient synthesis of various molecules by joining small units.This approach has found widespread applications in fields such as drug development,chemical synthesis,and molecular biology.In recent years,the reaction of alkali-catalyzed polymerization of thiol and sulfur has been employed to prepare various sulfur-containing polymers,which are applied as electrochemical active electrode materials in the pursuit of good performance.In this study,it is surprising to find that the reaction mechanism exhibits characteristics of both the alkali-catalyzed sulfhydryl Micheal addition reaction and thiol-epoxy click chemistry;for the first time,thiol-sulfur click chemistry is defined in detail,providing a comprehensive description of its underlying scientific principles.The introduction of this new reaction pathway holds significant potential for advancing research and the development of sulfur-containing polymers.Based on this novel click chemistry,a new sulfur-containing polymer,polydivinylthioether hexasulfide,has been designed and successfully applied as a cathode material in lithium-organosulfide batteries.This material demonstrates excellent electrochemical performance,achieving an initial capacity that reaches 790.5 mAh g−1(82.6%of theoretical capacity),and in a long-term cycle test,the capacity decay rate is only 0.063%after 1,000 cycles.
基金support from the National Natural Science Foundation of China(22271132,22350004)Q.L.thanks financial support from Guangdong Basic and Applied Basic Research Foundation(2023A1515110261).
文摘Comprehensive Summary:The reactions of potassium diazaphospholidinyl diazomethylide with phenylacetylene,acetonitrile,adamantyl phosphaalkyne,and styrene promptly form pyrazolide,triazolide,diazaphospholide,and pyrazolinide,respectively.The reaction mechanisms have been studied using DFT calculations.While the reactions with phenylacetylene and styrene proceed via stepwise pathways,those with acetonitrile and adamantyl phosphaalkyne follow concerted pathways.Additionally,the pyrazolide product readily undergoes N-functionalization,yielding methyl pyrazole,germanyl pyrazole,and copper pyrazolide complexes.
基金funded by the National Natural Science Foundation of China(32202454)the Natural Science Foundation of Jiangsu Province(BK20210396)+7 种基金the Fundamental Research Funds for the Central Universities(KYQN2023033)the Seed Industry Promotion Project of Jiangsu(JBGS(2021)022)the China Postdoctoral Science Foundation funded project(2020M681638)the Jiangsu Planned Projects for Postdoctoral Research Funds(2021K138B)Jiangsu Agricultural Science and Technology Innovation Fund(CX(24)1024)Major Scientific and Technological Project of Xinjiang(2024A02006)the Priority Academic Program Development of Jiangsu Higher Education Institutionsthe Earmarked Fund for Agriculture Research System of China(CARS-28).
文摘Pear fruit typically contains abundant highly lignified cells,known as stone cells,which have a negative impact on the fruit's edibility and processing quality.Despite extensive physiological and molecular research,there remains a limited understanding of the precise spatiotemporal aspects of lignification in flesh cells during pear devel-opment,particularly regarding the initiation of lignification and expansion of stone cell clusters.Here,an emerging bioorthogonal chemistry-based imaging technique was employed to in vivo visualize cell lignification dynamics in developing pear fruit.Specific identification of active sites undergoing lignification revealed that initial lignification of flesh cells occurred at 10 days after full bloom(DAFB),resulting in the formation of pri-mordial stone cells(PSCs).These PSCs exhibited a random distribution and showed significantly larger diameter and area compared to normal parenchyma cells.Subsequently,PSCs developed pit canals and initiated lignifi-cation process in their neighboring cells at 15 DAFB.A cascading effect in the formation of stone cell aggregations was visualized by tracing of the lignification trajectory.This expansion process exhibited a domino effect,whereby lignification progressively spread from one cell to the next,creating a cascading pattern of stone cell formation.Finally,a cellular developmental model was proposed for stone cell formation.This study presented a procedure for applying the cutting-edge technology,click chemistry imaging,to get insights into practical sci-entific questions.The findings elucidated the spatiotemporal dynamics of active lignification sites in pear fruit at the cellular level,thereby enhancing our understanding of the initiation and aggregation processes in stone cell formation.
基金support from NationalNatural Science Foundation of China (grant nos.22368002 and 52300195)Young Elite Scientists SponsorshipProgram by Jiangxi Association for Science andTechnology (JXAST) (grant no.2023QT10)+5 种基金JiangxiProvincial Natural Science Foundation (grant nos.20224BAB203003 and 20232BAB203021)OpeningProject of Project of National Key Laboratory of UraniumResources Exploration-Mining and Nuclear RemoteSensing (grant no.2024QZ-KF-06)Jiangxi ProvinceKey Laboratory of Polymer Micro/Nano Manufacturingand Devices (grant no.PMND202204)Japan Scienceand Technology Agency (JST)- Exploratory Research forAdvanced Technology (ERATO) Yamauchi Materials Space-Tectonics Project (grant no.JPMJER2003)theAustralian Research Council (ARC) Laureate Fellowship(grant no.FL230100095)Science and TechnologyResearch Program of Chongqing Municipal EducationCommission (grant no.KJQN202201308)。
文摘Electrocatalytic reduction of nitrate(NO_(3)^(−))is a promising approach to achieving sustainable and green ammonia synthesis and environmental denitrification.Here,click chemistry is extended to fabricate dynamic singlesite metal catalysts for NO3−electroreduction.Specifically,Co^(2+)-coordinated molecular units are covalently clicked into a stable Th-metal–organic framework,confining and dispersing single-site metals that exhibit the asymmetrical Co–N2Cl2 coordination configuration.The obtained CoN2Cl2@Th-BPDC electrocatalyst achieves an outstanding ammonia production rate of 770.3μmol h^(−1) cm^(−2)(5135.3 mmol gcat^(−1) h^(−1))at−0.4 V versus RHE,which is approximately 25.7 times higher than that of the Haber–Bosch process(<200 mmol gcat^(−1) h^(−1))and outperforms the most recently reported electrocatalysts.Theoretical calculations reveal that single-site Co2+exhibits strong bidentate adsorption toward NO_(3)^(−)due to the suitable geometric space provided by the rotation of Co-coordinated Cl atoms(a dynamic feature),which promotes NO_(3)^(−)activation and decreases the reaction barrier,resulting in excellent catalytic activity.This study describes an innovative strategy for fabricating dynamic asymmetrical single-site metal electrocatalysts and may inspire new methodologies for the precise synthesis of advanced catalytic materials.
