无气味、实用的缩硫醛/酮化反应试剂：2-（1，3-二噻-2-亚基）-3-羰基丁酸甲酯

a-Oxo ketene dithioacetals, methyl 2-（1,3-dithian/dithiolan-2-ylidene）-3-oxobutanoate （2a/2b） prepared in nearly quantitative yields simply from methyl acetylacetate, carbon disulfide and 1,3-dibromopropane/1,2-dibromoethane in the presence of potassium carbonate, were investigated in the thioacetalization with various carbonyl compounds 3. It has been demonstrated that methyl 2-（1,3-dithian-2-ylidene）-3-oxobutanoate （2a） could act as a nonthiolic, odorless and practical thioacetalization reagent. A range of aldehydes and ketones 3 were converted into the corresponding dithioacetals 4 in high yields （up to 91%） in the presence of 2a. Moreover, 2a showed high chemoselectivity between aldehyde and ketone in thioacetalization.     

Electrochemical Reduction of Ellman's Reagent: A Novel Selective Detection Protocol for Thiol Compounds

Herein we detail a novel approach to the detection of total sulfhydryl thiol species based on an electrochemical adaptation of the classical Ellman's reaction. The ability to electrochemically reduce the nitro moieties of both the parent 5,5‐dithiobis(2‐nitrobenzoic acid) (DTNB) and the resulting 5‐thio‐2‐nitrobenzoic acid (TNBA) species provides a selective means of detecting thiol compounds. The use of the reductive sweep means that electrode passivation as a result of oxidative electrochemical procedures can be avoided and the selectivity improved through positioning the analytical signal within a region where few interferences reside. The electrochemical protocol enables the detection of the thiols in both acidic and basic media, which the colorimetric method is unable to do.     

Bioanalytical considerations for compounds containing free sulfhydryl groups

Thiol-containing compounds pose bioanalytical challenge in several dimensions due to extreme reactivity of the sulfhydryl group. The development of robust bioanalytical methodology for thiol groups should address the aspects of adequate stabilization in the biological matrix and selectivity considerations. In this context, availability of plethora of thiol reagents provides ample opportunity to achieve the above goals. However, several considerations need to be factored into the decision-making of a suitable scheme for the thiol drugs under investigation. This review provides some critical insights to many such considerations that may be vital for development and validation of methods for thiol-containing drugs.     

Synthesis and properties of fluorinated telechelic macromolecular diols prepared by radical grafting of fluorinated thiols onto hydroxyl-terminated polybutadienes

The radical grafting of C_nF_{2n +1} CH₂CH₂SH (n = 6,8) onto the double bonds of hydroxyl-terminated liquid polybutadienes (HTPBD) was studied. Various methods for investigating the amount of grafting (titration of residual thiol and fluorine analysis) were used and compared. The nature and the amount of the initiator, the quantity of thiol, the temperature and the time of the reaction. the solvent, and the microstructure of HTPBD were optimized. The kinetic aspect showed that the thiol disappeared according to a first-norder law. A method using up to 100% of grafting fluorinated mercaptan was described and standards were set up with fluorine contents of 5–59% to evaluate the physicochemical properties of these thioether group-containing polymers: solubility, refractive index, intrinsic and dynamic viscosities, and thermal characteristics (glass transition and decomposition temperatures). Finally, the surface properties of these standards showed improvements of surface energy as low as 9 mN m^?1 for a totally saturated fluorinated HTPBD. © 1993 John Wiley & Sons, Inc.     

用于检测单硫醇和二硫醇化合物：芘-马来酰亚胺二元化合物

本文设计、合成了芘-马来酰亚胺二元化合物1。化合物1可以选择性的检测溶液体系中的半胱氨酸，而且还可以与二硫醇类化合物反应，并发现与二硫醇反应产生特征的芘的激基复合物的发射峰。因此，应用化合物1通过荧光信号的不同可以区分单硫醇和二硫醇化合物。     

An emerging post‐polymerization modification technique: The promise of thiol‐para‐fluoro click reaction

Post‐polymerization modification (PPM) of polymers is extremely beneficial in terms of designing brand new synthetic pathways toward functional complex polymers. Fortunately, the new developments in the field of organic chemistry along with controlled/living radical polymerization (CLRP) techniques have enabled scientists to readily design and synthesize the functionalized‐polymers for wide range of applications via the PPM. In this regard, the reactivity of para‐fluorine atom in the fluorinated aromatic structures toward the nucleophilic substitution reactions has made the polymers possessing this group to become a very strong candidate that can undergo efficient PPM. Besides, it has been proven that the thiol‐functionalized compounds react with the para‐fluorine atom of the pentafluorophenyl group more rapidly and efficiently than the amine‐ and the hydroxyl‐functionalized compounds. Furthermore, the milder experimental conditions to achieve quantitative conversions have led to the reaction between the thiol and the structures possessing pentafluorophenyl groups to be referred to as a click‐type reaction. Given this information, this review article aims to present the scientific developments regarding the thiol‐para‐fluoro “click” (TPF‐click) chemistry, and its impact on PPM to construct novel polymeric structures. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1181–1198     

Thiol‐ene click derived structurally well‐defined per(3,5‐dimethyl)phenylcarbamoylated cationic cyclodextrin separation material for achiral and chiral chromatography

In this work, a novel single sulfoether‐bridged cationic per(3,5‐dimethyl)phenylcarbamoylated‐β‐cyclodextrin separation material was prepared by thiol‐ene click chemistry and characterized by using FTIR spectroscopy, solid‐state ¹³C NMR spectroscopy and elemental analysis, which confirmed the correct structure. The separation material exhibited a good achiral separation performance for benzene homologues and phenylamine analogs, especially o‐xylene and m‐xylene, and m‐phenylenediamine and o‐phenylenediamine can be discriminated by the (3,5‐dimethyl)phenylcarbamoyl cyclodextrins. The chiral resolving ability of the separation material was evaluated by discriminating various isoxazolines, flavonoids, and β‐blockers in reversed‐phase high‐performance liquid chromatography. For isoxazolines, the material showed the best chiral discrimination toward 3‐aryl‐5‐(2‐oxopyrrolidin‐1‐yl)‐isoxazolines, where the resolution for 3ClPh‐OPr  reached 6.03. For flavonoids, it exhibited more efficient separation to the ones with more hydrophobic substituents, with a resolution of 5.93 for 6‐hydroxyflavanone. β‐Blockers were also enantioseparated satisfactorily on the material. The as‐prepared separation material is a good member of the thiol‐ene click derived cyclodextrin stationary phase family.     

巯基功能化聚倍半硅氧烷微球对银离子的吸附性能

以甲基三甲氧基硅烷(MTMS)和巯丙基三甲氧基硅烷(MPTMS)为前驱体、氨水为催化剂,通过共聚合法制备了单分散性良好的巯基功能化聚倍半硅氧烷(PSQ-SH)微球。利用扫描电镜(SEM)和红外光谱(FT-IR)对PSQ-SH微球进行了表征,并系统地研究了其对银离子的吸附性能。结果表明:25℃下、银离子初始浓度为0.025mol/L时,PSQ-SH微球对银离子的最大吸附容量为750.21mg/g。PSQ-SH微球对银离子的吸附符合Langmuir等温吸附模型,吸附动力学更适合准二级动力学吸附模型。热力学参数表明该吸附过程为吸热反应,并且是自发进行的。     

The Preparation and Cyclopolymerization of cis- and trans-l,3,5-Triisocyanatocyclohexane

The preparation of cis- and trans-1,3,5-triisocyanatocyclohexane is described. The coupling constants ^JAB, ^JAX> and ^JBX were obtained from the NMR spectrum of the cis-isomer. Both isomers were polymerized using sodium cyanide in N,N-dimethylformamide as initiator. The evidence indicated that cyclopolymerization had occurred and, in both cases, predominantly bicyclic structures obtained.     

Effect of surface modification with various thiol compounds on colloidal stability of gold nanoparticles

Gold nanoparticles (AuNPs) are attractive materials due to their special optical and electronic properties. However, they tend to aggregate particularly in the presence of thiol‐containing compounds. In this study, to investigate the effect of surface conjugation with thiol‐containing compounds on colloidal stability, thiol compounds with various structures as modifying agents were used. To this end, AuNPs were synthesized and stabilized by trisodium citrate in aqueous solution, and then modified with thiol‐containing compounds, namely cysteamine hydrochloride (MEA, containing primary amine groups), 2‐mercaptoethanol (BME, containing hydroxyl groups), 1‐dodecanthiol (LCA, containing long‐chain alkyl groups) and thioglycolic acid (TGA, containing carboxylic acid groups). We studied the effect of thiol ligands on solution stability of colloidal AuNPs and on the formation of aggregates originating from the modification process using UV–visible spectroscopy, dynamic light scattering, field emission scanning electron microscopy and transmission electron microscopy. Results showed that surface modification with MEA, BME and LCA led to the formation of aggregates. However, conjugation with TGA showed a concentration‐dependent behaviour: surface modification with low concentration resulted in the formation of aggregates whereas that with high concentration of TGA did not disturb the colloidal stability of AuNPs. Finally, the effect of surface modification on temperature increase of solutions originating from infrared light irradiation was studied, where the temperature increase depends on the surface‐modifying compound.