Sulfonyl halide synthesis by thiol oxyhalogenation using NBS/NCS – iPrOH

A rapid and facile method provides a general route to sulfonyl bromides/chlorides by the oxidation of thiols using NXS – ROH (X = Br,Cl, R = iPr) as an oxyhalogenation reagent. Control experiments suggest that the alcohol component is the source of oxygen. The proposed method enable the access to structurally diverse sulfonyl bromides and chlorides including challenging examples, inaccessible by other synthetic methods.     

Esr and endor studies of partially deuterated and chlorinated phenalenyls : New synthetic pathways

A variety of partially chlorinated and deuterated phenalenyl radicals has been produced by the reaction of the respective acenaphthylenes with chloroform as a carbenoid precursor and via thermal decomposition of some mercury carboxylates. By ESR and ENDOR-in-solution measurements the effectiveness of the different reaction paths to specifically substituted compounds has been investigated.     

Partial oxidation and oxidative polymerization of metallothionein

One mechanism for regulation of metal binding to metallothionein (MT) involves the non-enzymatic or enzymatic oxidation of its thiols to disulfides. Formation and speciation of oxidized MT have not been investigated in detail despite the biological significance of this redox biochemistry. While metal ion-bound thiols in MT are rather resistant towards oxidation, free thiols are readily oxidized. MT can be partially oxidized to a state in which some of its thiols remain reduced and bound to metal ions. Analysis of the oxidation products with SDS-PAGE and a thiol-specific labeling technique, employing eosin-5-iodoacetamide, demonstrates higher-order aggregates of MT with intermolecular disulfide linkages. The polymerization follows either non-enzymatic or enzymatic oxidation, indicating that it is a general property of oxidized MT. Supramolecular assemblies of MT add new perspectives to the complex redox and metal equilibria of this protein.     

Electrochemical and Electrocatalytic Properties of Imidazole Analogues of the Redox Cofactor Pyrroloquinoline Quinone

The electrochemical and electrocatalytic properties of two synthetic imidazole analogues of the redox cofactor pyrroloquinoline quinone (PQQ) were evaluated. Cyclic voltammetry measurements as a function of pH indicated that both 4,5‐dihydro‐4,5‐dioxo‐1H‐imidazolo[5,4‐f]quinoline‐7,9‐dicarboxylic acid ( 1 ) and 4,5‐dihydro‐4,5‐dioxo‐2‐methyl‐1H‐imidazolo[5,4‐f]quinoline‐7,9‐dicarboxylic acid ( 2 ) undergo a reversible reduction of the o‐quinone moiety below pH 8 with potentials slightly more positive than those observed for PQQ. Upon incorporation into a polypyrrole membrane on the tip of a glassy carbon electrode, 1 and 2 exhibited electrocatalytic properties sufficient for the indirect amperometric detection of cysteine. The response for cysteine was linear up to 1 mM over a wide pH range. Detection limits (S/N=3) were in the μM range and dependent on the solution pH. Interference from redox active species such as dopamine and uric acid were minimized by the pH‐dependent redox potentials of 1 and 2 and thus the ability to tune the detection potential.     

Sc(Ⅲ)催化硫醇对邻亚甲基苯醌的亲核加成反应合成邻羟基苄硫醚衍生物

以2-[羟基(苯基)甲基]苯酚类化合物和简单的硫醇为原料, 1,2-二氯乙烷为溶剂, 在Sc(Ⅲ)促进下原位生成邻亚甲基苯醌, 并发生亲核加成反应构建邻羟基苄硫醚. 该反应在50 ℃下搅拌2 h即可完成, 目标产物产率82%95%. 反应可放大至克级规模.     

Fluoroalkene chemistry: Part 1. Highly-toxic fluorobutenes and their mode of toxicity: reactions of perfluoroisobutene and polyfluorinated cyclobutenes with thiols

The reactions of four highly-toxic fluorobutenes - perfluoroisobutene (PFIB), 1-hydropentafluorocyclobutene (1-H), hexafluorocyclobutene (HFCB) and 3-chloropentafluorocyclobutene (3-Cl)—with propanethiol, 2,6-dimethoxybenzenethiol and N-acetylcysteine isopropyl ester were studied. PFIB and HFCB reacted with two molar equivalents of the aliphatic thiols, but with only one molar equivalent of the aromatic thiol (presumably due to steric hindrance) and resembled phosgene in their reactivity. The fluorocyclobutenes 1-H and 3-Cl reacted with one and up to three molar equivalents of the aliphatic thiols, respectively, but with only one molar equivalent of the aromatic thiol. The products of allyl and vinyl substitution were isolated and characterised as fully as possible. The inhalation toxicities of the fluorocyclobutenes to rodents correlated with the number of easily-displaceable fluorine substituents, supporting the contention that toxicity is due to reaction with biological thiols in the lung.     

AP1000屏蔽厂房在接触爆炸荷载作用下的非线性动力分析

屏蔽厂房是AP1000核岛厂房的第一层外部防线,确保屏蔽厂房在服役期间遭受爆炸冲击荷载作用下的安全性和完整性,十分重要。本文中,采用欧拉-拉格朗日算法(coupled Euler-Lagrange, CEL),对炸药在屏蔽厂房20种不同起爆部位作用下的动态破坏特征进行了研究,以结构贯穿破坏的损伤质量作为损伤程度的判别依据,着重探讨在不同起爆位置作用下结构的压力和损伤演化特性。研究表明：在接触爆炸荷载作用下,厂房在起爆点附近发生局部破坏;在相同高度下,环向不同角度起爆所引起的损伤程度差异较小,不同高度起爆的损伤程度差异较大。通过压力和损伤的演化分析,确定了屏蔽厂房最不利抗爆部位,对厂房不同部位的配筋策略提出建议。结论可为制定屏蔽厂房在爆炸冲击荷载作用下的安全防护措施提供参考依据。

     

超支化烯丙基聚硅氮烷-巯基化合物体系紫外光固化研究

采用等温差示光量热扫描技术(DPC)研究了超支化烯丙基聚硅氮烷-巯基化合物体系的紫外光固化.对比了超支化聚合物-巯基化合物体系、二官能烯丙基硅氮烷-巯基化合物体系和超支化自聚体系的紫外光固化特性,结果表明超支化-巯基化合物体系可在引发剂浓度低(0.1wt%)、辐照强度低(5mW/cm2)的情况下迅速发生光固化反应;与超支化自聚反应相比固化速率高、双键转化率高;而与低官能-巯基化合物体系相比,由于超支化分子结构的独特性,导致固化速率快,双键转化率偏低.对引发剂浓度、辐照强度和反应温度对固化行为的影响表明,在引发剂浓度不超过0.5wt%和辐照强度不大于30.50mW/cm2时,反应速率分别与引发剂浓度和辐照强度的1/2次方成线性关系.运用带扩散因子的自催化固化动力学模型研究了不同温度下的固化行为,计算出特定条件下的光固化动力学参数,表观总反应级数约为8.76,表观活化能为13.97kJ/mol.     

A novel and highly selective conversion of alcohols, thiols, and silyl ethers to azides using the triphenylphosphine/2,3-dichloro-5,6-dicyanobenzoquinone(DDQ)/n-Bu4NN3 system

Alcohols, thiols, and silyl ethers are converted into alkyl azides in good to excellent yields by treatment with PPh₃/DDQ/n-Bu₄NN₃ in CH₂Cl₂ at room temperature. The method is highly selective for 1° alcohols in the presence of 2° and 3° ones, and also thiols and silyl ethers.     

Construction of a new asymmetric reaction site: asymmetric 1,4-addition of thiol using pentagonal bipyramidal Hf(salen) complex as catalyst

Pentagonal bipyramidal Hf(salen) complex 1 was found to serve as a catalyst for 1,4-addition reaction of thiol to N-(2-alkenoyl)-2-oxazolidinones.