傅里叶变换离子回旋共振质谱测定复杂表面活性剂组分

利用傅里叶变换离子回旋共振质谱(FT-ICR-MS)，分析了两类复杂的离子型表面活性剂样品。实验结果表明：高分辨FT-ICR-MS，可以简单、快速、准确地获得两类化合物的结构信息，利用其高准确度的质量测定数据，计算出复杂样品中各组分的元素组成，鉴定出具体化合物，显示了FT-ICR-MS在分子结构分析和未知物鉴定中的强大能力。     

电喷雾质谱对洗发水中多种表面活性剂的快速分析

利用电喷雾离子化质谱技术（ESIMS）快速鉴定了洗发水中的常用表面活性剂。在流动注射进样方式下,鉴定出所测试洗发水中含有2种主要表面活性剂：烷基单乙醇酰胺（CMEA）和脂肪醇聚氧乙烯十二烷基醚硫酸钠（SLES·nEO）。进一步通过高效液相色谱与质谱联用（HPLC—MS）利用ESI^＋和ESI^-之间的切换完成对不同类型表面活性剂的定量检测,测定出该洗发水中CMEA的使用量为1．198％（质量分数）,与实际添加量1．2％非常吻合。运用HPLC—MS对SLES·nEO在洗发水中的种类结构进行了鉴定。     

质谱法分析季铵盐型阳离子表面活性剂

以电子轰击质谱法(EI/MS)与电喷雾质谱法(ESI/MS)相结合,分析季铵盐型表面活性剂。由于阳离子表面活性剂在水溶液中离解成正离子,可用电喷雾质谱的正离子模式(ESI /MS)对其结构及组成进行鉴定,同时可判别季铵盐所含的Cl-、Br-、NO3-等阴离子。     

~(19)FNMR鉴定复杂体系中的含氟表面活性剂

建立了有机氟化物的核磁共振谱图集,通过系统地研究各类有机氟化物,根据典型例子分类总结各标准氟谱图中信号峰化学位移与耦合常数的变化规律,针对含氟表面活性剂建立19F NMR分析方法。采用该方法鉴定5种企业复杂体系样品中含氟表面活性剂的成分,确认了各含氟表面活性剂19F NMR谱峰的归属。结果表明,19F NMR测试适用于复杂体系中含氟表面活性剂的快速鉴定。     

气相色谱-质谱方法检测磺酸类阴离子表面活性剂

使用K I/DMF/(CF3CO)2O还原衍生方法,结合气相色谱-质谱(GC/MS)联用技术对磺酸类化合物进行了结构鉴定和成分分析。实验结果表明,这种新的还原衍生方法不仅方便快速、条件易控,而且产物稳定,具有良好的气相色谱-质谱行为,可以很好地解决磺酸类阴离子表面活性剂有效成分分析鉴定的难题。     

非离子型表面活性剂质谱的计算机模式识别

测定主要类型非离子型表面活性剂的电子轰击质谱(EI)和电喷雾质谱(ESI),并对其质谱行为进行归纳和总结,得到相应的质谱数据分布表。采用C 语言编制计算机识别软件并将这些数据集成在这个程序中,通过EI和ESI两种检索方式相结合可以快速确定非离子型表面活性剂的类别和化学结构。     

固体进样法气相色谱质谱分析表面活性剂

采用气相色谱质谱电子轰击技术以固体直接进样方法成功地对表面活性剂进行了分离定性，测定了表面活性剂中各个成分的加成环氧乙烷数，定出了各个组分的分子量。     

现代仪器分析方法在表面活性剂检测中的应用

表面活性剂是一种重要的精细化学品,需要对其进行表征和分析,以确定它的种类、含量和结构。本文重点综述了近年来表面活性剂分析检测中的现代仪器分析方法,包括色谱法、光谱法、质谱法、毛细管电泳法、电化学法和色谱-质谱联用法等。最后展望了表面活性剂分析检测的发展方向。     

普鲁洛尼克型非离子表面活性剂的结构分析及其同系物分子量分布的测定

以ＦＡＢＭＳ、ＥＩＭＳ、ＦＴＩＲ等手段鉴定了从工业产品中分离得到的一种未知表面活性剂的化学结构为聚氧丙烯／聚氧乙烯共聚物，其商品名称为普鲁洛尼克（Ｐｌｕｒｏｎｉｃ）型非离子表面活性剂．用ＦＡＢＭＳ谱观察到该表面活性剂同系物的各种准分子离子峰呈近似的高斯分布，根据各种准分子离子峰的相对强度得出该表面活性剂同系物的分子量分布及平均分子量．     

普鲁洛尼克型非离子表面活性剂的结构分檄及其同系物分子量分布…

以ＦＡＢＭＳ、ＥＩＭＳ、ＦＴＩＲ等手段鉴定了从工业产品中分离得到的一种未知表面活性剂的化学结构为聚氧丙烯／聚氧乙烯共聚物，其商品名称为普鲁洛尼克型非离子表面活性剂。用ＦＡＢＭＳ谱观察到该表面活性剂系物的各种准分子离子峰呈近似的高斯分布，根据各种准分子离子峰的相对强度得出该表面活剂同系物的分子量分布及平均分子量。     

Effects of surfactants on complex formation of CuII with 2-dimethylaminomethylphenol

The effect of cationic (cetyltrimethylammonium bromide) and nonionic (Triton X-100) surfactants on the complex formation of Cu^II with a bifunctional ligand, 2-dimethyl-aminomethylphenol, in water was studied by spectrophotometry, pH-metry, and mathematical modeling of equilibria in solutions. The character of complex formation depends on the nature and concentration of surfactants. The dependence of complex formation constants on the concentration of surfactants is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 999–2002, August, 1996.     

Comparative study on the interaction of DNA with three different kinds of surfactants and the formation of multilayer films

The interactions between double-stranded DNA (dsDNA) and three different kinds of surfactants, i.e., cationic, anionic, and nonionic surfactants, were investigated by cyclic voltammetry, electrochemical impedance spectroscopy and UV-vis spectroscopy. Multilayer films composed of DNA and surfactants were prepared at gold electrode by electrostatic or hydrophobic interactions. It was found that the cationic surfactant, CTAB, can bind to DNA by electrostatic interaction, and the electron transfer resistance of CTAB-DNA complex film increases first and then decreases with CTAB concentration. The anionic surfactant, LAS, can bind to DNA but by hydrophobic interaction, and the electron transfer resistance of the complex film keeps decreasing with LAS concentration. Nonionic surfactants can also directly bind to DNA by hydrophobic interaction. All the three different kinds of surfactants can form multilayer films with DNA on the electrode surface. The chemical structure of DNA keeps unchanged during interacting with these surfactants. The binding modes of DNA with these three different kinds of surfactants were also deduced.     

Organization of amphiphiles: XII. Evidence in favor of formation of hydrophobic complexes in aqueous solution

The effects of nonionic surfactants OP-10 and OP-30 (polyoxyethylated octyl phenols with 10 and 30 oxyethylene groups, respectively) in surfactant mixtures with ionic surfactants hexadecyltrimethylammonium bromide (CTAB) and sodium dodecyl sulphate (SDS) have been investigated by a conductometric method in conjunction with fluorescence, surface tension, zeta potential, and DLS measurements. The interactions are found to be antagonistic in nature for each of the systems; i.e., micellization of CTAB as well as SDS is hindered on addition of the nonionic surfactants. The antagonism is found to be more prominent in the presence of OP-10 compared to that of OP-30. Two types of mechanistic paths, path A operating below the critical micellar concentration and path B operating beyond the critical micellar concentration of nonionic surfactants, have been suggested. In path A, the retardation in micellization has been attributed to a decrease in monomeric concentration of the ionic surfactants from solution as a result of the formation of a hydrophobic complex between nonionic and ionic surfactants. In path B, the decrease in monomer concentration is due to the solubilization of the ionic surfactant in micelles of the nonionic surfactants in a 1:1 stoichiometric ratio. A theoretical treatment to the interaction in each ionic-nonionic pair yields a positive value of the interaction parameter supporting the concept of antagonism. The formation of the hydrophobic complex is supported by fluorescence and surface tension measurements. A schematic representation of the stabilization of these hydrophobic complexes has been suggested. The association of ionic surfactants by nonionic micelles is suggested by zeta potential and DLS studies.     

表面活性剂对Me-5-Br-DEPAP及Me-5-Cl-PADAB显色反应作用的研究

我们曾研究了离子型-非离子型混合表面活性剂对Ag²⁺-5-Cl-PADAB和Cu²⁺-5-Cl-PADAB等显色反应的作用。本文研究了阴离子、阳离子、非离子及阴-非混合表面活性剂对一系列Me-5-Br-DEPAP及Me-5-Cl-PADAB显色反应的作用,试图寻求表面活性剂对显色体系增敏作用及协同增敏作用的原因,并对其作用机理作一初步探讨。     

镉的高灵敏显色体系研究及表面活性剂作用机理

本文以2-氯-4-硝基苯重氮氨基偶氮苯(CNDAA)为显色剂, 研究了镉的高灵敏显色体系及表面活性剂的作用机理。研究结果表明: 对于Cd(II)-CNDAA配合物, 非离子型、阴离子型及阴-非混合型表面活性剂对此有显著的增溶增敏作用, 并以Cd(II)-CNDAA-SF显色体系建立了光度法测定微量镉的高灵敏新方法, 并对几种测定方法进行了比较, 筛选出显色条件宽容、选择性好的体系。该体系用于铝合金样品中镉的测定, 结果满意。另外, 还提出了Cd(II)-CNDAA配合物的结构, 对表面活生剂对体系的作用作了描述, 并阐明了试剂的酸性离解常数(pK~a)与显色酸度以及方法的选择性三者之间的关系。     

Cd(II) determination in the presence of aqueous micellar solutions

The equilibrium constants and molar absorptivities for the fast formation of a 1:3 complex between cadmium(II) (Cd(II)) and dithizonate anion, in the presence of cationic and non-ionic surfactants, allowed a simple and fast spectrophotometric determination of total cadmium. Indeed, the molar absorptivities of the Cd(II)-dithizone (Dz) complex formed in the presence of the neutral Triton X-100 and cationic cetyltrimethylammonium bromide (CTAB) surfactants are almost twice the value observed in the standard method and the maxima of absorption are shifted by about 40 nm when compared with the standard method. Clearly, the use of neutral and cationic surfactants promotes a higher value of the molar absorptivities of the complex, resulting in an increase in the sensitivity of the method. Application of the method to the desorption of Cd(II) ions from clays is illustrated.     

Self-assembly of ionogenic surfactants during their interaction with poly(propylenimine) dendrimers

The structure of complexes formed by poly(propylenimine) dendrimers of five generations and anionic micelle-forming surfactants is studied by X-ray diffraction. It is shown that, in complexes of lower generation dendrimers, the lamellar packing of surfactants is dominant. In complexes formed by dendrimers of the fourth and fifth generations, packing typical of compact dendrimer molecules prevails. This packing can be attributed to the distorted dense packing of ball-like complex species. Structural models of complexes that allow for penetration of surfactants into the dendrimer molecule and the size ratio of the aliphatic radical of a surfactant and a dendrimer are advanced.     

多元体系油水界面上常见表面活性剂行为的分子动力学模拟

采用分子动力学模拟研究了以十二烷基苯磺酸钠(SDBS)为代表的阴离子型表面活性剂,以十二烷基三甲基溴化铵(DTAB)为代表的阳离子型表面活性剂,以壬基酚聚氧乙烯醚(NPE)为代表的非离子型表面活性剂,以十二烷基二甲基甜菜碱(Betaine)为代表的两性表面活性剂及空白实验.模拟了表面活性剂在油水界面上的行为,考察了表面活性剂分子与石油分子之间的径向分布函数(RDF)、石油分子在竖直方向的均方位移(MSD)、油水界面张力(IFT)、石油层与岩石层之间的相互作用能、石油层的相对浓度在竖直方向的分布及石油分子质心位置随模拟时间的变化关系等,讨论了不同表面活性剂的洗油性能.结果表明:(1)SDBS,NPE和Betaine分子初始状态下呈近似的规律排列,非极性端部分插入油相中,极性端延伸进入水相中;随后表面活性剂的极性端表现出聚集趋势,逐渐形成一个外部亲油内部亲水的一个胶束状粒子,粒子随模拟的进行逐渐融入到油层当中;DTAB从开始的近似规则排列逐渐变为无规排列,但是始终保持亲油端插入到油相中,亲水端位于油水界面上.(2)表面活性剂分子与石油分子之间的相互作用强弱顺序为Betaine≈DTABSDBSNPE.(3)由质心高度和动力过程中的图像截图分析,表面活性剂洗油效果的顺序为BetaineSDBSNPEDTABNone.模拟结果与实际的驱油结果一致,从分子层面上解释了不同表面活性剂洗油的规律.     

Interaction of nonylphenyl and tributylphenyl ethylene oxide ionic surfactants with highly soluble cyclodextrin derivatives

The modification of the hydrophobicity of some ethoxylated nonylphenol and tributylphenol surfactants with various soluble -cyclodextrin polymers has been studied by reversed-phase chromatography. Stepwise regression analysis proved that the complex forming capacity of surfactants decreases with increasing diameter of the hydrophobic moiety of surfactants, the properties of the crosslinking agent used for preparation of the polymers has no significant effect on the host-guest interaction, the presence of carboxyl groups in the polymer considerably improved the complex stability.     

共聚物/表面活性剂体系微观与宏观粘度

高分子与表面活性剂的相互作用，无论从基础研究还是应用研究均很有意义＊．表面活性剂和高分子相互作用往往可以使高分子链的的象变化，例如通过生成分子缔合复合作问（associatedcomPleX），改变高分子链的静电相互作用，可引起高分子链的舒展和卷曲．另一方面，高分子也影响表面活性剂的物理化学性质．例如，溶液表面张力、粘度、电导、表现临界胶束浓度（＊＊C）和聚集数（＊叫等物理参数。‘］．在实用方面，在高分子和表面活性剂相互作用的复合体中，表面活性剂分子排列接近生物膜结构，可作为模拟生物酶催化的模型体系问．由超高分…