对甲基苯磺酸在Ti/PbO2电极上的电氧化反应信息

采用原位红外光谱法系统地研究了对甲基苯磺酸（p-TSA）在钛基二氧化铅（Ti/PbO₂）电极上的电氧化反应信息。循环伏安曲线显示,Ti/PbO₂对p-TSA有良好的电氧化活性,直接氧化电位区间为0.55~0.9 V。多步电位阶跃FTIRS（MSFTIRS）和时间分辨FTIRS（TRFTIRS）分析显示,电压小于1000 mV时,p-TSA主要发生了磺酸基的脱落和苯环侧链甲基的氧化;电压大于1000 mV时,p-TSA的苯环骨架被破坏,同时生成了酸、醇、酮。反应动力学研究结果表明,p-TSA电氧化表观速率常数K与电流密度j呈线性关系,化学需氧量（COD）去除量随比电荷增大而增加,平均电流效率则呈下降趋势。     

Ag掺杂V2O5/TiO2催化氧化3-甲基吡啶 脱甲基效应

浸渍法制备了不同Ag掺杂的Ag-V/TiO2催化剂,考察其催化部分氧化3-甲基吡啶脱甲基性能。采用X射线衍射（XRD）,X射线光电子能谱（XPS）,H2程序升温还原（H2-TPR）对催化剂进行了表征。表征表明,Ag的掺杂提高催化剂中表面氧和 4价态的钒物种的含量,有效的加快了催化剂的还原过程,提高了氧化活性。3-甲基吡啶氧化反应表明,Ag掺杂使反应选择性发生根本性变化,主产物由烟酸变成吡啶,选择性84.7%,烟酸几乎不产生。该脱甲基氧化反应的过程是V4 /V5 （O2-）在攻击侧链的C-H键的同时Ag在O2的作用下形成了含有亲电子型氧（O-和O2-）的Agp O活性物种,攻击侧链和苯环相连的C-C键,Ag和V共同作用将侧链的甲基以氧化形成COx的形式脱除。     

吐哈稠油氧化-乳化降黏技术研究

以过氧化氢异丙苯为氧化剂、表面活性剂与醇为复合乳化剂,对吐哈稠油的氧化-乳化降黏技术进行了研究,通过族组分分析、红外光谱分析、元素分析等手段对氧化反应前后稠油的物化性质进行了分析,提出了可能的氧化-乳化降黏机理.结果 表明,稠油发生了氧化加氧、苯环侧链脱支或断裂、杂原子脱除、芳香环缩合等反应,其中沥青质为主要作用对象,...     

Ag掺杂V_2O_5/TiO_2催化氧化3-甲基吡啶脱甲基反应

采用浸渍法制备了不同Ag掺杂的Ag-V/TiO_2催化剂,考察其催化部分氧化3-甲基吡啶脱甲基性能。采用X射线衍射(XRD)、X射线光电子能谱(XPS)、H_2程序升温还原(H_2-TPR)对催化剂进行了表征。结果表明,Ag的掺杂提高了催化剂中表面氧和+4价态的钒物种的含量,加快了催化剂的还原过程,提高了氧化活性,Ag主要以单质的形态存在。3-甲基吡啶氧化反应表明,Ag的掺杂使反应选择性发生变化,主产物由烟酸变成吡啶,当Ag的掺杂量为2%(Ag相对于V_2O_5的摩尔分数)时,甲基的脱除率最好,摩尔产率为80.1%,选择性84.7%,烟酸几乎不产生。该脱甲基氧化反应的过程是V~(4+)/V~(5+)(O_2~-)在攻击侧链的C—H键的同时,Ag在O_2的作用下形成了含有亲电子型氧(O~-和O_2~-)的Agp+O活性物种,攻击侧链和苯环相连的C—C键,共同作用将侧链的甲基以氧化形成CO_x的形式脱除。     

用循环伏安法研究醌亚胺的脱氨反应

用循环伏安法研究了N,N-二乙基对苯二胺,N,N,N′,N′-四乙基对苯二胺,N,N-二乙基氨基酚三类化合物的电化学氧化及其氧化产物的后继化学反应,求算了脱氨反应速率常数,揭示了苯环上甲基取代基和氮原子上不同取代基对脱氨反应的影响。 脱氨反应为OH~-或水进攻醌亚胺的亲核反应。由于甲基的斥电子效应,当苯环上引进甲基取代基时,环上负电荷增大,带正电荷的醌亚胺趋于稳定,水解反应速度减慢。 苯环上引进二个甲基取代基,其相应的苯胺化合物的半波电位下降大约120mV。二乙基对苯二胺的苯环上每引进一个甲基取代基,其氧化产物与彩色成色剂偶合生成的染料的吸收峰向长波方向移动20—30nm。     

生漆中漆酚单体分离、化学结构修饰及生物活性研究进展

漆酚化合物是具有C₁₅或C₁₇烃基侧链的邻苯二酚结构,侧链不饱和度为0~3。漆酚良好的抗肿瘤、抑菌和抗氧化活性使其受到越来越多的关注。对不同不饱和度烃基漆酚单体的分离方法进行了叙述,介绍了通过对漆酚的苯环或侧链烃基进行化学结构修饰这2种途径以获得结构相对稳定的漆酚衍生物,并阐述了漆酚单体及其衍生物的抗肿瘤、抗氧化、抑菌和抗病毒等生物活性。     

金属卟啉催化烯烃不对称环氧化反应的研究

合成了5种简单金属卟啉锰配合物，并以这5种金属卟啉作为催化剂，以手性季铵盐为手性相转移催化剂，研究催化烯烃不对称环氧化反应。结果表明：金属卟啉锰中苯环上的不同取代基对烯烃环氧化速度有较大的影响；手性相转移催化剂的加入，不仅提高了反应速度，而且对烯烃的环氧化起到了一定的不对称诱导作用；不同底物的烯烃，不对称环氧化反应对映选择性不同。     

苯甲醛系列化合物的电合成进展

本文介绍了苯甲醛系列化合物的三种电合成方法：苯环上丙烯基、羟基和甲基的阳极氧化,苯环上羧基的阴极还原,苯环上甲基的阳极取代。着重对甲基的阳极氧化过程中运用的新技术及发展趋势作了评述。     

电合成芳香醛反应机理的研究

利用红外光谱（IR）研究了槽外合成对甲氧基苯甲醛和对溴苯甲醛的反应机理，结果证明：在Ce^4＋与对取代甲苯的氧化反应中，苯环上甲基被Ce^4＋氧化的难易受苯环上对位取代基的影响。对甲基苯甲醚先氧化成对甲氧基苯甲醇，再氧化成对甲氧基苯甲醛并最终氧化成对甲氧基苯甲酸，第一个电子传递步骤为控制步骤：对溴甲苯先氧化成对溴苯甲醇，再氧化成对溴苯甲醛，后者为控制步骤。     

煤自燃生成水的反应机理研究

应用傅立叶变换红外光谱仪研究了煤在氧化自燃过程中不同温度下生成的气体产物.在30℃～100 ℃左右有水和二氧化碳气体析出,温度升至105℃～150℃左右时,有一氧化碳生成.采用密度泛函B3LYP方法,在6-311G基组水平上研究了煤与氧发生自燃反应生成水和一氧化碳的反应体系,对反应势能面上各驻点的几何构型进行了全优化,用频率分析方法和内禀反应坐标(IRC)方法对过渡态进行了验证.计算结果表明,煤氧化自燃生成水的反应是氧分子攻击苯环侧链上的伯胺基团-C(29)H2-N(22)H2中间的N(22)原子,使煤分子苯环侧链上的伯胺基团生成了-CH2-N=O基团和水.由反应活化能可知,生成水的反应是一个自发式反应.     

Effect of substituents in the aromatic nucleus on the biodegradation behavior of alkylaryl sulfonates

Taking the results of methylene blue analysis as a yardstick for biodegradability, substituents in the benzene ring of linear alkylaryl sulfonates (CH₃, C₂H₅, OH) greatly deteriorate the aerobic biodegradation characteristics of these products: adaptation time, amount of hard residue, and, to a lesser extent, rate of biodegradation. Replacement of one long alkyl chain by two short ones of the same total length also retards biodegradation. When the benzene ring is replaced by a thiophene ring, adaptation is improved.     

Molecular Self-Aggregation of Tetradecylbenzene Sodium Sulfonate Isomers

This paper deals with the effect of the surfactant isomeric structure on self-aggregation in aqueous solution. The relationship between the molecular structure of a series of tetradecylbenzene sulfonate isomers (with the benzene ring located at different positions along the alkyl chain) and surface tension was made clear. It is found that the critical micelle concentration increases and the surface tension at critical micellar concentration decreases as the benzene group moves toward the center of the alkyl chain. The structure of micelles was studied by ¹H-NMR relaxation, which indicates that the density of methylene protons in the surface layer of the micellar core decreases as the branching of the hydrophobic group increases. The spontaneous vesicle formation in aqueous solution was investigated by transmission electron microscopy. The results reveal that, as the benzene group moves toward the center of alkyl chain, the assembly structure changes from micelle to vesicle, then to lamellar bilayers, while the critical packing parameter increases.     

Combined Use of Ozonation and Biodegradation of Anionic and Non-ionic Surfactants

This study investigated the extent of primary and final biodegradation of anionic and non-ionic surfactants to evaluate the combined use of ozonation and biodegradation in surfactant removal. The surfactants used were alkylpolyglucosides and linear alkyl benzene sulfonates. The anionic surfactant containing a benzene ring on its structure was oxidized faster than was the non-ionic surfactant. Both surfactants showed poor mineralization due to ozonation indicating an ozone attack primarily on carbon bonds. The results indicate that the removal of surfactants and of the total organic carbon is increased by the consecutive use of ozonation and biodegradation.     

烷基苯制润滑油

对合成洗涤剂烷基苯和其副产重烷基苯的润滑特性 ,以及烷基苯制取五类 (电器用油、冷冻机油、液压油、汽轮机油和导热油 ) 10种润滑油的生产应用进行了综述 ,对拓展烷基苯类产品在润滑方面的应用有指导意义     

重烷基苯的合成与应用

文章综述了重烷基苯的性能、合成、生产及在工业领域的多种应用。     

稳态荧光探针研究支链烷基苯磺酸钠的聚集行为

以芘为荧光探针、二苯酮为猝灭剂，用稳态荧光探针法测定了合成的4种带干扰基(磺酸基邻位的短链烷基)的支链烷基苯磺酸钠的临界胶团浓度、合适猝灭剂浓度下的胶团聚集数以及在不同浓度氯化钠水溶液中的胶团聚集数．结果表明，支链烷基苯磺酸钠分子中长链烷基碳数增加，临界胶团浓度大幅度降低，胶团聚集数减小；分子中短链烷基碳数增加，临界胶团浓度降低幅度小，胶团聚集数增大；胶团聚集数随氯化钠浓度增大而增大．     

Self-assembly of organogels via new luminol imide derivatives: diverse nanostructures and substituent chain effect

Luminol is considered as an efficient sycpstem in electrochemiluminescence (ECL) measurements for the detection of hydrogen peroxide. In this paper, new luminol imide derivatives with different alkyl substituent chains were designed and synthesized. Their gelation behaviors in 26 solvents were tested as novel low molecular mass organic gelators. It was shown that the length and number of alkyl substituent chains linked to a benzene ring in gelators played a crucial role in the gelation behavior of all compounds in various organic solvents. Longer alkyl chains in molecular skeletons in present gelators are favorable for the gelation of organic solvents. Scanning electron microscope and atomic force microscope observations revealed that the gelator molecules self-assemble into different micro/nanoscale aggregates from a dot, flower, belt, rod, and lamella to wrinkle with change of solvents. Spectral studies indicated that there existed different H-bond formations and hydrophobic forces, depending on the alkyl substituent chains in molecular skeletons. The present work may give some insight to the design and characteristic of new versatile soft materials and potential ECL biosensors with special molecular structures.     

不同平均分子量及其分布烷基芳基磺酸盐的制备与性能

以直链α烯烃、苯、甲苯、混和二甲苯等为原料,采用原位离子液体催化烷基化反应分别合成出不同碳数的直链烷基苯、烷基甲苯和烷基二甲苯,经降膜式磺化、中和反应、提纯等方法制得不同相对分子质量的烷基芳基磺酸盐,其纯度均大于97.0%,仪器分析证明了其结构与设计相符。不同平均分子量、不同分布形式的磺酸盐体系降低油水界面张力能力不同;平均分子量为432、递增分布和反正态分布体系与碱、聚合物组成的三元复合体系在人造岩心上,室内模拟驱油可在水驱基础上提高采收率22%以上。     

Production of lower alkenes and light fuels by gas phase oxidative cracking of heavy hydrocarbons

The gas phase oxidative cracking (GOC) and non-oxidative pyrolysis of heavy hydrocarbons were investigated, with decalin (decahydronaphthalene) and tetralin (tetrahydronaphthalene) as the model compounds for naphthenic hydrocarbon and aromatic hydrocarbon, respectively. Unlike pyrolysis, the ring rupture of decalin or tetralin molecule and the decoking ability of system were significantly enhanced due to the introduction of O₂ in GOC. For GOC of decalin, both the lower alkenes and the light fuels were obtained. At lower temperatures the light fuels mainly contained alkyl benzene, alkyl cyclohexane and isoparaffins, while it was rich in BTX (benzene, toluene and xylenes) at higher temperatures. A 38.9% yield of lower alkenes and 48.0% yield of light fuels (BTX mass content: 59.9%) at 100% decalin conversion were obtained under the conditions of 800 °C and decalin / O₂ = 0.5. For GOC of tetralin, both the dehydrogenation and the cracking reactions dominated the reaction routes, resulting in a high mass content of alkyl naphthalene and alkyl benzene in the light fuels. The estimation of O₂ distribution in the products demonstrated that O₂ participated primarily in the oxydehydrogenation reactions at low temperatures, while mainly in the partial oxidation reactions at high temperatures to produce CO_x (x = 1, 2).