Synthesis and Free-Radical Thiilation (Addition of Thiophenols) of Unsaturated Cyclic Acetals

The synthesis of a series of unsaturated 4-methylene-1,3-dioxolanes has been realized and the addition of thiophenol to the synthesized compounds in the presence of radical initiators has been carried out. It has been established the behavior of the addition reaction both with opening of dioxolane cycle and without it. The influence of nature of substituents of С2-carbon atom of dioxolane cycle, ratio of the initial reagents and temperature on direction of the addition reaction has been studied. The adducts obtained as a result of the addition reaction have a linear and cyclic structure, which have been established by data of the chemical and spectral analyses. It has been found that the ratio dioxolane compound: thiophenol, reaction temperature and nature of the functional substituent influences on quantity of these adducts.

QSRR Study on the Relationship between the Chromatographic Capacity Factor and Lipophilicity and Structure Parameters of Halogenated Thiophenols

The capacity factors (k') of fourteen types of halogenated thiophenols in different phases of methanol-water eluent were determined by reversed phased high-performance liquid chromatography (RP-HPLC) and the relationships between the logarithm of capacity factor lgK' and methanol ratio ψ were analyzed. A fair linear relationship is found between lgK' and ψ, and the correlation coefficients R2 of the constructed linear equations are all greater than 0.990. Relationship between the chromatographic data lgKw' when extrapolated to pure water and n-octanol/water partition coefficient lgKow obtained by the group contribution method has shown a good linear correlation with R2 = 0.956. The structure parameters of fourteen halogenated thiophenols were calculated by using DFT, and the correlation equation of lgKw' and structure parameters was obtained by using SPSS, lgKw' = -0.409 + 0.039α and R2 = 0.981, meaning that lgKw' is mainly determined by the polarizability α.

A NIR fluorescent probe for imaging thiophenol in the living system and revealing thiophenol-induced oxidative stress

Thiophenol(PhSH)is an important raw material for organic synthesis,while its high toxicity to organisms makes it an environmental pollutant.Therefore,it is crucial to accurately detect PhSH and explore its metabolic process in the living system.Herein,a near-infrared(NIR)fluorescent probe TEM-FB was developed for sensing PhSH with a turn-on fluorescent signal at 719nm and a large Stokes shift(198 nm)based on generating the intramolecular charge transfer(ICT)process.TEM-FB shows high specificity and significant sensitivity towards PhSH(detection limit:10 nmol/L)via the aromatic nucleophilic substitution mechanism.Furthermore,it was successfully applied to image PhSH in multiple cell lines and in zebrafish.Notably,we revealed the oxidative stress process caused by PhSH and demonstrated that the hydrogen peroxide(H_(2)O_(2))in cells would alleviate the poisonousness from exogenous PhSH for the first time.This work provides a promising bioimaging tool for monitoring PhSH in living systems and visualizing the process of oxidative stress induced by PhSH.

Fast Response Fluorescent Probe with a Large Stokes Shift for Thiophenol Detection in Water Samples and Cell Imaging

Herein,the 2,4-dinitrophenyl functional group acting as the thiophenol reactive site was introduced into a carbazole-chalcone fluorophore to synthesize probe-CCF2,which could result in a remarkable increase in fluorescence when reacting with thiophenols.The selectivity and accuracy of probe-CCF2 were investigated with thiophenols,hydrosulphide salt,aliphatic thiols,glutathione,cysteine,anions and metal cations.Probe-CCF2 exhibited a detection limit of 37 nmol/L(R^(2)=0.9951),a remarkable Stokes shift of approximately 130 nm,and a brief response time of 9 min with a remarkable increase in fluorescence of 90-fold.Probe-CCF2 was applied for thiophenol detection in water samples and imaging in living cells successfully,with high sensitivity and excellent selectivity.

Controllable cross-coupling of thiophenols with dichloromethane mediated by consecutively paired electrolysis

Chloroalkanes are important building blocks in the synthesis,but their use in redox chemistry is limited by their negative reduction potentials.Electrosynthesis can precisely control the reaction energy just by adjusting the current or voltage to achieve the selectivity of regulation.In this study,the consecutively paired electrolyticmediated controllable radical cross-coupling of thiophenols with dichloromethane was developed to deliver the dithioacetals,sulfides,and sulfoxides in the absence of electrochemical mediator conditions.It features broad substrate scope,simple operation,gram-scale synthesis,and is eco-friendly.Mechanistic studies reveal that this electrochemical reaction is radical-induced cross-coupling of thiophenols with dichloromethane.

基于双金属高核钛氧簇基电极的高性能超级电容器的制备

制备了一系列专为超级电容器设计的新型钛氧簇(TOCs,包括Zn-Ti11和Cd-Ti11),扩大了TOCs材料的潜在应用范围。此类材料具有的优异赝电容性能充分展示了钛基材料的优点。所制备的TOCs基超级电容器的最大功率密度为9.5 W·kg^(-1),能量密度为463 Wh·kg^(-1)。

硫酚在有机染料催化的光化学反应中的应用

有机硫化物是重要的一类有机化合物,它们广泛存在于天然产物、农用化学品和医药化合物中。近年来,由于有机光催化合成技术的快速发展,有机染料作为光催化剂具有廉价易得、环境友好、反应类型丰富且催化效率高等诸多优点,它们催化促进的可见光诱导反应研究越来越受到人们重视。归纳和总结了近几年来以有机染料作为光催化剂、可见光诱导的硫酚参与有机反应的相关文献。

卤盐离子液体/氧气催化芳硫酚与异色满反应

以1-羧乙基-3-甲基咪唑氯盐([COOH-Et MIm][Cl])/O_(2)体系催化异色满与取代苯硫酚发生脱氢偶联反应,合成了1-(取代苯硫基)异色满。通过单因素实验对反应影响因素进行了筛选,得到适宜反应条件为:4-甲基苯硫酚(62 mg,0.5 mmol)、异色满(134 mg,1.0 mmol)、[COOH-EtMIm][Cl](95 mg,0.5 mmol)、O_(2)(0.10 MPa)、反应温度120℃、反应时间12 h。在该条件下,催化剂可使用4次,实现了1-(4-甲基苯硫基)异色满克级合成,底物拓展后得到12种1-(取代苯硫基)异色满,产率为52%~96%。提出了[COOH-Et MIm][Cl]阴阳离子通过氢键分别活化苯硫酚与异色满,经O_(2)氧化,脱氢得到1-(取代苯硫基)异色满的反应机理。

Electrochemical characteristics and application of thiophenol self-assembling monolayer modified gold electrode

The modification of electrode involves the attachment of chemical substances to the surfaces by physical adsorption, chemical bonding or polymer coating. The modified electrodes can thereby exhibit properties related to those of the modifying substances. It is quite clear that in order to perform increasingly complicated and demanded tasks using chemically modified electrodes, complex molecular structure must be constructed with a high degree of Control over the design and structure of the systems. The merits of

Fluorescent Turn-on Probe Based on Napthalimide Fused Triphenylamine Unit for Quickly Detecting Thiophenol in Aqueous Solution

A novel molecular probe system(NapTpa-dnbs)was prepared based on the chromophore napthalimide fused triphenylamine unit.NapTpa-dnbs was tuned to absorb a large fraction of UV and near-infrared radiation.The turn-on fluorescent response of NapTpa-dnbs to thiophenol caused an increased fluorescent emission by a factor of 11.5 at 597 nm in a PBS buffer solution.The photoinduced electron transform(PET)process of the probe became less feasible with the addition of thiophenol than that of the free probe.NapTpa-dnbs demonstrated high selective and sensitive detection toward thiophenol with respect to other competitive amine acids.The detection limit was determined to be 2.03×10^?7 mol/L thiophenol.The sensing process is rapid(3 min).NapTpa-dnbs can accurately detect the thiophenol with a qualified recovery in real water samples.NapTpa-dnbs on test strips can detect the thiophenol vapour in the atmosphere.

检测苯硫酚荧光探针的研究进展

苯硫酚(PhSH)是一类高活性和毒性的芳香族硫醇,在化学工业中广泛应用于制备农药、聚合物和药物。就近年来用于PhSH检测和成像的荧光探针的研究进展进行综述。这些探针根据识别部分进行了分类,并根据其结构和传感性能进行了详细介绍。此外,还讨论了未来的研究前景。

云南沧源某氧化铅锌矿浮选工艺研究

以云南省沧源县某深度氧化,且锌主要以异极矿形式存在的难选铅锌矿石为研究对象,进行了丁黄药直接浮选方铅矿、硫化—丁黄药浮选白铅矿、硫化—苯硫酚浮选异极矿的工艺技术条件研究。采用试验确定的先浮铅后浮锌、先选硫化矿后选氧化矿的闭路浮选工艺处理该矿石,获得了铅品位为53.93%、含锌13.13%、银品位为1 751.90 g/t的铅精矿,锌品位为31.82%、含铅2.75%的锌精矿,以及铅品位为33.38%、锌品位为19.10%、银品位为694.85 g/t的铅锌混合精矿,铅锌银的综合回收率均超过98%。

Au-Ag合金纳米粒子制备及其表面增强拉曼光谱研究

首先采用柠檬酸钠法制得Au-Ag合金纳米种子,然后采用盐酸羟胺生长法得到不同组成的Au-Ag合金纳米粒子.在其UV-V is光谱中只观察到一个位于单金属银和金之间的等离子体共振峰,表明Au-Ag合金纳米粒子已经形成.TEM结果表明,合金纳米粒子的粒径约为60 nm,且颜色均一,没有明显的核壳结构.用苯硫酚(TP)作为探针分子研究了合金纳米粒子的表面增强拉曼光谱(SERS).结果表明,SERS强度与合金纳米粒子的组成和尺寸有关.当纳米粒子粒径一定时,除Au25Ag75外,随着金的增加SERS强度增强.Au25Ag75的粒径比Ag小,导致SERS强度比Ag低.Au50Ag50和Au75Ag25加入TP分子后,其聚集方式与Au相似,等离子体共振峰逐渐靠近1 064 nm,金含量较高时,TP的SERS归于聚集体的等离子体共振增强的贡献.

焦化汽柴油中苯酚、苯硫酚类化合物对比分析及其来源探讨

采用NaOH质量分数20%的液碱对不同产地(或来源)的焦化汽油和焦化柴油进行抽提,得到可提取酸性物,采用气相色谱-质谱联用(GC-MS)技术对可提取酸性物进行分析,结果表明:焦化汽油中可提取酸性物除苯酚类化合物外,还含有苯硫酚类化合物以及少量小分子硫醚;与焦化汽油不同的是,焦化柴油中的可提取酸性物几乎全部是苯酚类化合物。不同产地的焦化汽油中苯硫酚质量分数(y)与对应的减压渣油硫质量分数(x)呈线性关系y=0.04x-0.005 06(R^2=0.999);焦化汽油的苯硫酚类化合物含量越高,其室温储存安定性越差;碱洗后的焦化汽油其室温储存安定性大幅提高;酚类化合物的来源可能与延迟焦化过程中芳基醚中醚键的断裂以及芳香酸的氧化脱羧等化学反应有关,而苯硫酚类化合物可能来自于苯酚类化合物与H_2S的高温反应。

苯硫酚各种形态在金上的拉曼光谱研究

用Gaussian 98程序在B3LYP/6-311+G**(C,H,S)水平上计算得到苯硫酚(TP)的一套校正因子,对苯硫酚各频率进行了势能分布(PEDs)分析,并对各振动模式进行了详细的指认.同时,在B3LYP/6-311+G**(C,H,S)/LANL2DZ(Au)水平上优化得到苯硫酚的各种形态与金结合,即C6H5SH-Au,C6H5SAu,C6H5S--Au的平衡构型,且在此基础上得到了C6H5SH-Au,C6H5SAu,C6H5S--Au三种形态的计算拉曼谱图.其中苯硫酚金盐(C6H5SAu)的拉曼谱图与实验得到的苯硫酚在金溶胶中的谱图是一致的,由此很好地证明了TP与金形成苯硫酚金盐.

囊泡双层膜中4,44"4-四(正丙氧基羰基)酞菁钴(Ⅱ)催化分子氧氧化巯基苯的反应

The oxidation of thiophenol（RSH） to phenyl disulfide catalyzed by Co（Ⅱ） tetrakis（propyl-oxycarbonyl）phthalocyanine[CoPc（COOC3H7）4] in the presence of molecular oxygen was studied in synthetic bilayer membrane of vesicle, which is composed of hexadecyl 2-hydroxy-3-chloropropyl phosphate, SDS micelle, ethanol and benzene respectively. The catalytic activities followed the order of \{CoPc（COOC\}3H7）4 in the bilayer membrane>ethanol>benzene, and in the bilayer membraneSDS micelle. UV-Vis spectroscopic studies reveal that the catalytic oxidation proceeds through RS--CoPc-O2 intermediate. The catalytic activity of CoPc（COOC3H7）4 in the bilayer membrane of vesicle higher than that in the other media is considered to be attributable to the disaggregation of CoPc（COOC3H7）4 incorporated into the bilayer membrane and the easier H+ dissociation of RSH on the polar surface of the bilayer membrane bordered by bulk aqueous phase.

苯硫酚及其衍生物在银电极表面的吸附取向

采用表面增强拉曼光谱技术研究了苯硫酚及其功能衍生物 ,对巯基苯胺和对苯硫酚在粗糙银电极上的吸附取向特征。结果表明 :虽然 3种分子的结构类似 ,但对位取代基直接影响各分子在电极上的吸附取向。 3种分子都通过硫原子与银电极形成S Ag键吸附在电极表面。苯硫酚采用倾斜的方式吸附 ,使得苯环与基底间表现一定程度的相互作用 ;吸附的对巯基苯胺则因质子化氨基间的静电相互作用而完全垂直于电极表面 ;而对苯硫酚则采用平躺于电极表面的方式吸附 。

煤中苯硫酚型有机硫与O_2反应机理

为研究煤中含硫活性基团在煤炭自燃过程中的影响，利用Gaussian03程序，采用密度泛函（DFT）方法，在B3LYP／6-311G水平下研究煤中苯硫酚型有机硫与02的反应机理。结果表明，此反应主要有6条反应路径：Path1～3生成产物S02，Path2的速控步骤反应能垒分别比Path1和Path3的反应能垒低85．79kJ／mol和135．94kJ／mol；Path4～5生成产物SO，Path4的速控步骤反应能垒比Path5低142．46kJ／tool，比Path2的反应能垒低6．52kJ／tool；Path6的生成产物HSO的反应势垒为316。60kJ／tool。因此，Path4为主要反应路径，产物P2（C6H5OH＋SO）为主要产物，SO2为次要产物，HSO为最难生成的产物。

巯基苯类为标记分子免疫检测的FT-SERS光谱研究

以对巯基苯甲酸、苯硫酚为标记分子 ,与金纳米粒子生成具有SERS信号的标记金溶胶 .在一定条件下 ,标记金溶胶与抗体羊抗小鼠IgG形成SERS标记免疫金溶胶 .用组装金纳米粒子的玻璃表面吸附抗体 ,通过对相应抗原小鼠IgG的识别 ,形成固相抗体 /抗原对 ,再将SERS标记免疫金溶胶组装到固相抗体 /抗原对上 ,形成“固相抗体 -待测抗原 -标记抗体(即标记免疫金溶胶 )”夹心复合物 。