Click Chemistry合成1,2,3-三唑氨基酸衍生物

通过W ong叠氮转化和亲核取代反应,分别合成了叠氮苯丙氨酸、叠氮丙氨酸、苄基叠氮,采用上述叠氮化物与L-炔丙基甘氨酸进行C lick反应,合成了3个1,4-取代1,2,3-三唑氨基酸衍生物:2-氨基-3-[1-(1-羧基-2-苯乙基)-1H-1,2,3-三唑-4-基]丙酸、3,3-′(1H-1,2,3-三唑-1,4-基)双(2-氨基丙酸)和2-氨基-3-(1H-1,2,3-三唑-1-苄基-4-基)丙酸,收率分别是76%、62%和68%,产物结构经核磁共振波谱、质谱、红外光谱进行了表征。1,2,3-三唑氨基酸衍生物含双功能螯合基团,是很有潜力的fac-[188Re(CO)3(H2O)3]+放射性标记配体。

Click chemistry approach to functionalize two-dimensional macromolecules of graphene oxide nanosheets

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.

Development of Cardanol-Based Polyol via Click Chemistry and Crosslinking with Melamine Formaldehyde Resin for Coating Applications

The research work presented in this article deals with the synthesis of cardanol-based polyol and its curing with hexabutoxymethyl melamine(HBMM)for application in coatings.Cardanol-based polyol was prepared via thiol-ene click reaction using thioglycerol.Unsaturation present in the long chain of cardanol was successfully utilized to synthesize polyol via thiol-ene coupling.The reaction was carried out between cardanol and thioglycerol in the presence of Irgacure 184(photoinitiator)and 1,8-Diazabicyclo[5.4.0]undec-7-ene(catalyst)under UV light for 12 h at 80°C.After completion of the reaction,one mole of thioglycerol was successfully added across the double bond of a fatty chain of cardanol and confirmed by Fourier transform infrared spectroscopy(FTIR)and proton nuclear magnetic resonance spectroscopy and hydroxyl and iodine values were determined.Furthermore,the polyol thus prepared was cured with commercial HBMM in various proportions,such as 1:0.6,1:0.8 and 1:1,on an equivalent basis.The coatings were then characterized for mechanical,chemical,optical,thermal and anticorrosive properties.It was observed that coatings exhibited excellent performance properties as compared to that of its acrylic counterpart.

Preparation of novel chiral stationary phase based on click chemistry for ligand exchange chromatography

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.

SYNTHESIS OF A HYPERBRANCHED POLY(AROYLARYLENE) CONTAINING TRIAZOLE AND FLUORENE FUNCTIONALITIES BY CLICK CHEMISTRY AND METAL-FREE,REGIOSELECTIVE POLYCYCLOTRIMERIZATION

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-...

Cardanol-Based Polyurethane Coatings via Click Chemistry:An Eco-friendly Approach

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.

基于SCIE的有关“Click chemistry”研究论文分析

依据Web of Science平台下的SCIE数据库中2001-2014年间有关"Click chemistry"的论文数据和文献计量方法,从发表年份、国家、机构、期刊和研究方向等进行聚类分析,研究"Click chemistry"自首次提出后的研究发展情况。结果表明,美国发表相关论文的数量和质量均位居世界第一。中国的发文量排名第二,但是论文质量和世界先进水平仍有一定差距。

Study on technetium-99m labeling of graphene oxide nanosheets through click chemistry–^(99m)Tc labeling of graphene oxide nanosheets

Graphene oxide(GO)nanosheets possess several advantages,such as a large surface,outstanding biocompatibility,and straightforward chemical modification capability.They also have great potential as a drugcarrier.In this article,we radiolabeled GO nanosheets with99mTc,which satisfies the potential needs of microSPECT imaging probes in pre-clinical and clinical research.GO nanosheets were synthesized through the modified Hummers’method,then GO nanosheets with azide group covalently functionalized in two steps were conjugated to DOTA(1,4,7,10-tetraazacyclododecane-N,N,N,N-tetraacetic acid)and functionalized with an alkynyl group by means of click chemistry.Then through the addition and reduction of technetium-99m,the99mTc-DOTA-GO were attained.DOTA-conjugated GOs with lateral dimensions of 500–600 nm were synthesized.Both atomic force microscopy(AFM)and FT-IR were performed to characterize the GO-DOTA.Labeling efficiency of GO-DOTA with99mTc was>90%and radiochemical purities were>96%with purification.We successfully synthesized graphene oxide derivatives,DOTA-conjugated GOs,via Click Chemistry,and it was labeled with99mTc for SPECT imaging.High radiolabeling efficiency makes GO nanosheets suitable platforms for future molecular imaging research.

Preparation of Hydrophilic and Shrink-Proofing Wool Fabrics Through Thiol-Ene Click Chemistry Reaction

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.

Study on radiolabeling of 1,2,3-triazole analogs with fac-[^(188)Re(CO)_3 (H_2O)_3 ]^+ via click chemistry

Click chemistry was used to study on radiolabeling of 1,2,3-triazole analogs with fac-[188 Re(CO) 3 (H 2 O) 3]+ . CuSO 4 /L-sodium ascorbate was chosen as the catalyst system, three terminal alkynes were conjugated with two different azides respectively, and then the new prepared fac-[188 Re(CO) 3 (H 2 O) 3]+ was coordinated to the six triazoles. The results showed that the radiochemical yields (RCY) of the conjugation of fac-[188 Re(CO) 3]+ with six triazoles were over 90%, and the triazoles showed high stability in phosphate-buffered saline and new-born calf serum. The preliminary biological evaluation results showed that the new 188 Re-labeling method via click chemistry could have general application in labeling bioactive molecules in high radiochemical yield and high specific activity for further SPECT research.

建议将click chemistry译作“配搭化学”

学界通常将click chemistry翻译成"点击化学",有望文生义之嫌。笔者分析此术语提出者的原意--一是具有高度的双向选择性,二是如同搭扣"咔嗒"扣起来一样简单,再结合自己对此化学反应的深刻理解,建议将其译为形神兼备的"配搭化学"。

化学术语click chemistry和one-pot synthesis 的中文译法刍议

当前中文化学术语中存在粗疏翻译的现象,对click chemistry和one-pot synthesis的翻译即为两例。文章根据术语翻译信达雅的原则,建议将这两个英文化学术语分别译为"迅接化学"和"烩法合成",以取代在中文文献中常见的不甚合理的译法。

“Click”化学在药物发现中的应用

“click”化学是最近几年发展起来的一种新技术,它在药物发现的许多方面均有着广泛的应用:快速合成小分子化合物库并从中筛选先导化合物、进行靶标导向的活性小分子合成以及在生物耦联技术等方面的应用。

Click反应和多氮化合物手性催化剂

Click化学涉及一系列能够在温和条件下高产率进行的有机反应,已经被用来构建一些手性有机催化剂.一些多氮化合物作为手性有机催化剂,在反应过程中形成多重氢键使反应过渡态得以稳定,显示出非常好的立体选择性.

利用分子内Click反应合成哌嗪并三唑和哌嗪并四唑化合物

利用分子内的"点击化学"反应合成了三唑和四唑类化合物。在直接加热或金属铜粉催化下加热的条件下,不饱和炔键和氰基与叠氮基发生分子内的成环反应,以较高的收率分别生成哌嗪并三唑化合物和哌嗪并四唑化合物,其结构经NMR,IR和MS表征。

“Click”反应制备含芴单元共轭聚合物

通过"Click"反应合成了几种含芴单元的共轭聚合物。以芴为起始原料,合成了N3-Ar-N3和C≡C-Ar-C≡C类单体,分别以N,N-二甲基甲酰胺(DMF)和四氢呋喃(THF)为反应溶剂,通过Cu+催化得到聚合物。芴单元具有良好的溶解性和发光效率。"Click"反应合成的含芴单元共轭聚合物在溶液中发射蓝光,在薄膜中也有一定的荧光发射。文中以不同浓度的聚合物和聚苯乙烯(PS)共混甩膜,研究聚集对发光性能的影响。新合成的聚合物具有良好的热稳定性,热分解温度在300℃以上;差示扫描量热分析(DSC)结果显示,线性聚合物在300℃以内没有明显的相转变,保持一种稳定的无定型态,对于提高材料的发光效率是有利的。

纳米二氧化硅改性“Click”型侧链含氟聚氨酯的制备及在织物整理剂上的应用

以4,4′-二羟甲基-1,4-庚二炔为扩链剂制备了含有端炔功能基团的聚氨酯(PU),然后基于铜催化的炔基和叠氮基的1,3-偶极环加成点击化学(Click chemistry)反应将2-叠氮全氟辛基乙基醇酯(R f-N 3)接枝到PU侧链,制备了“Click”型侧链含氟PU。进一步将疏水改性的纳米二氧化硅(SiO 2)添加到“Click”型侧链含氟PU基体中,制备了“Click”型侧链含氟PU/纳米SiO 2复合材料(SiFPU)。采用红外光谱(FT-IR)、核磁氢谱(1H NMR)和能谱分析(EDS)表征了SiFPU的结构,研究了纳米SiO 2含量对SiFPU膜热稳定性和疏水性的影响,并考察了SiFPU在织物整理剂上的应用。结果表明,当R f-N 3占PU树脂的44%(质量分数,下同)时,随着纳米SiO 2含量从0%增大到2%,SiFPU的水接触角从104°增大到120°,最大失重时温度(T max)从323℃增大到348℃。当纳米SiO 2含量为1%时,用20 g/L SiFPU溶液处理后的织物的拒水性能即可达到最高级5级,此时被处理织物的吸水率从72.7%降低到6.6%。

Functionalization of carbon nanotubes and other nanocarbons by azide chemistry

Following the conventional carbon allotropes of diamond and graphite,fullerene,carbon nanotubes(CNTs) and graphene as 0D,1D and 2D graphitic macromolecules have been discovered recently in succession,declaring the unlimited potential of carbon-based nanomaterials and nanotechnology.Although CNTs exhibit significant potential applications in advanced materials and other fields due to their extraordinary mechanical strength and electrical/thermal conductivity properties,their low solubility,poor wettability and bad dispersibility in common solvents and solid matrices have limited their processing and applications.Thus,the attempt to achieve wettable/processable CNTs by functionalization has attracted increasing attention in both scientific and industrial communities.In recent years,azide chemistry has been demonstrated as a powerful means to covalently modify CNTs.It consists of two major approaches:click chemistry and nitrene chemistry,which both involve the usage of various azide compounds.The former one is based on highly reactive and stereospecifical Cu(I) catalyzed azide-alkyne cycloaddition reaction;the latter one is based on the electrophilic attack to unsaturated bonds of CNTs with nitrenes as reactive intermediates formed from thermolysis or photolysis of azides.In this mini-review paper,the azide chemistry to functionalize CNTs is highlighted and the corresponding functionalization routes to build CNT-based complex structures are also discussed.Besides,covalent functionalizations of other graphitic nanomaterials such as fullerence and graphene,via azide chemistry,are commented briefly.

Preparation of polymer brushes on attapulgite surfaces via a combination of CROP and click reaction

In this work,by a combination of controlled ring-opening polymerization(CROP) and click reaction,we reported a facile and useful method to synthesize linear poly(ε-caprolactone) at attapulgite nanocomposites with well-defined structures.For this,first, the chlorine terminated attapulgite was prepared by the self-assembly of 3-chloropropyltrimethoxysiIane from the surfaces of attapulgite.And then,the terminal chlorines of modified attapulgite were substituted with azido groups.As the second step,linear propa...