~(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。     

Gemini阳离子表面活性剂的合成及其胶束生成

传统的单头基单烷烃链表面活性剂由于离子头基间的电荷斥力或水化引起的分离倾向使得它们在界面或分子聚集体中难以紧密排列,造成表面活性偏低 .为克服这一缺陷进行了大量尝试,例如添加无机电解质屏蔽离子头基的电荷斥力、升高温度以降低头基的水化,甚至采用合适的二元表面活性剂复配等等 .当前一种从根本上克服头基间分离倾向的化学方法正受到关注 [1],这种方法通过化学键将二个单头基单烷烃链表面活性剂在离子头基处用联接基团（ spacer）使其联接起来,从而获得称之为 Gemini的新型表面活性剂 [2]. Gemini表面活性剂大大促进了其 "…     

核磁共振波谱技术应用在表面活性剂混合胶束体系中的研究进展

由于表面活性剂混合体系具有协同效应,又称协同作用或增效作用,使得混合体系通常较单一体系在性能上更具优势.当前,核磁共振技术(NMR)在表面活性剂混合体系研究中应用十分活跃,扩散、弛豫、二维等多种现代核磁共振技术被成功用于表面活性剂混合体系的胶束形成动力学过程、胶束表征以及胶束物理/化学特性等研究工作中.该文对近年来国内外有关工作进行分析和归纳,展望了核磁共振在表面活性剂混合体系研究中的潜力.     

核磁共振法研究三苯甲烷类酸性染料与非离子表面活性剂的相互作用

研究显色螯合剂和表面活性剂之间的相互作用,对于探讨胶束增溶分光光度法的反应机理是很重要的。等曾用核磁共振和分光光度两种方法研究了非离子表面活性剂OS-20与铬天青S(记作CAS)和磺酸铬青的相互作用,并对作用机理提出了他们的看法。本文用NMR研究了非离子表面活性剂TX-100和乳化剂OP与CAS和漂蓝6B(记作ECAB)的相互     

混合表面活性剂在非极性溶剂中的聚集行为

表面活性剂在非极性溶剂中的聚集行为比在水溶液中复杂得多. 水溶液中表面活性剂有一明确的临界胶束浓度(CMC),而在非极性溶剂中至今对CM C概念仍有怀疑^[1], 但已有多种手段如染料增溶法、水增溶法、光散射法、荧光偏振、紫外和核磁共振谱等证实并测定了非极性溶剂中 CMC 的存在^[1～5]. 表面活性剂在非极性溶剂中以非离子化状态存在, 其缔合主要靠两亲分子之间的偶极-偶极以及离子对相互作用, 那么在一种表面活性剂溶液中加入另一种表面活性剂, 即表面活性剂的复配, 必然对其聚集行为产生重大影响, 但迄今为止, 尚未见关于混合表面活性剂在非极性溶剂中聚集行为的报道. 本文采用碘光谱法和水增溶法测定了阴离子表面活性剂AOT 和非离子表面活性剂 Brij30 混合后在正庚烷中形成反胶束的 CMC, 以期考察表面活性剂的复配对其聚集行为的影响。     

苄泽类非离子表面活性剂与离子型表面活性剂复配性质研究

通过测定苄泽类非离子型表面活性剂Brij58、Brij76、Brij78与阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)、阴离子表面活性剂十二烷基硫酸钠(SDS)复配体系的表面张力,研究了复配体系的形成胶束能力、降低表面张力效率、降低表面张力能力3种增效作用,并结合复配体系中表面活性剂分子间的相互作用参数进行了深入的讨论。研究结果表明,与阳离子表面活性剂复配时,Brij76/CTAB体系增效作用最强;与阴离子表面活性剂复配时,Brij58/SDS复配体系增效作用最强,而且苄泽类非离子型表面活性剂与阴离子表面活性剂复配增效作用更加显著。     

一种金属洗涤剂的NMR分析

由于精细化工行业的迅速发展,作为“工业味精”的表面活性剂,已广泛进入日化、轻工、纺织、建筑、石化、金属加工等生产领域,对其的分析也显得日益重要。表面活性剂的分析历来是比较困难的课题之一,而通过核磁共振(NMR)进行定性和定量的文献则更少[1]。本文利用NMR为多种表面活     

邻苯二甲酸二甲酯胶束增溶过程的NMR研究

胶束的增溶作用，可通过X射线，紫外光谱以及核磁共振潜等进行研究.Eriksson等［‘］用NMR法研究了芳香烃在CTAB表面活性剂胶束溶液中的增溶作用.李干佐等问用NMR法研究了件二甲苯和末甲醇在SDS表面活性剂胶束溶液中的增溶作用.然而，关于既非亲油也非亲水的某些小的极性分子的     

无机盐存在下双水相体系萃取分离碘-乙基紫-镉(Ⅱ)缔合物

研究了在丙醇-水体系中加入表面活性剂乙基紫(EV)后,影响Cd2 分离的酸度、无机盐、卤离子种类等条件。实验表明,(NH4)2SO4存在下,无表面活性剂EV,一定量的I-,在酸性条件下,Cd2 的萃取率为68%,而同样条件下,加入mg级表面活性剂EV后,Cd2 与EV、г形成三元缔合物,被均相萃取、异相分离;缔合物进入丙醇相,Cd2 被完全萃取分离;在pH 1.0时,试验了Cd2 加入量为5μg/mL时与Fe3 、Co2 、Ni2 、Zn2 、Mn2 、Zn2 、Cr3 的二元或多元离子混合液的分离试验,分离完全。     

Triton X-100/甲苯/水三元体系界面张力的耗散颗粒动力学模拟

采用耗散颗粒动力学方法在介观层次上模拟了非离子表面活性剂Triton X-100 在油/水界面上的分布行为, 并把用于油/水二元体系界面张力的计算方法拓展到含表面活性剂的三元体系. 利用该方法可以得到与实验数值吻合的界面张力数据. 另外, 模拟结果直观展示了表面活性剂界面张力与界面密度的关系, 为表面活性剂复配增效理论提供了依据. 该模拟方法给出的微观信息可以为驱油体系配方筛选和表面活性剂有效应用提供指导.     

含表面活性剂多元配合物体系中化学平衡的研究

提出以光谱法与电导法研究含表面活性剂多元配合物体系的化学平衡,从定量方程式可知,三元配合物转化率最高时,相应的表面活性剂最佳浓度与有关组分间缔合数和稳定常数密切相关。     

An efficient contemporary multicomponent synthesis for the facile access to coumarin-fused new thiazolyl chromeno[4,3-b]quinolones in aqueous micellar medium

Coumarin-fused polycyclic chromenoquinolone derivatives were synthesized in CTAB/water system with high yields. This protocol is competent, feasible, and sequential one-pot multicomponent path for the building of titled products. In this projected route solvents, catalysts and surfactants are optimized, and the excellent results were achieved by CTAB in water. CTAB/water has efficiently catalyzed the synthesis of new thiazolyl chromenoquinolone heterocycles and avoids the use of hazardous conventional organic solvents. The synthesized compounds were confirmed by IR, mass, ¹H NMR spectral, and elemental analysis. This report represents the first case in which surfactant CTAB has been explored in the synthesis of fused chromenoquinolones in water. A probable reaction mechanism has been established to know the role of CTAB.     

Investigation on the locus of solubilization of polycyclic aromatic hydrocarbons in non-ionic surfactant micelles with H NMR spectroscopy

This research investigates the locus of solubilization of two significant compounds, the polycyclic aromatic hydrocarbons (PAHs) naphthalene and phenanthrene from a synthesized organic liquid phase comprised of the two PAHs and hexadecane in micelles of five polyoxyethylene non-ionic surfactants. The locus was inferred by the examination of the nuclear magnetic resonance (NMR) spectra. In this method, the ring current shifts on the ¹H resonance of the surfactant chain protons are monitored. ¹H NMR spectra were recorded for the five surfactant solutions in absence and presence of PAHs. The presence of the PAH induced the ¹H to shift along the surfactant chain. The proton shift changes were obtained by comparing the NMR spectra for the pure surfactant solutions with those for surfactant solution contacted with various non-aqueous phase liquids. It was demonstrated that the distribution of PAHs between the shell and the core of the micelles changed with the concentration of PAHs in the micelles and in the NAPL phase. The ¹H NMR analysis identified the presence of both PAHs in the shell region of the non-ionic micelles. This is an important observation because it is commonly assumed that in multi-component systems the solutes with relatively greater hydrophobicity are partitioned only in core of the non-ionic micelles. The results demonstrated the potential of the ¹H NMR analysis for the identification of the locus of solubilization of PAHs in micelles of non-ionic surfactant.     

First anionic micelle with unusually long lifetime: self-assembly of fluorocarbon-hydrocarbon hybrid surfactant

The exchange of a fluorocarbon-hydrocarbon hybrid surfactant between monomer and micelle states in deuterium oxide has been investigated through 19F NMR and 1H NMR experiments. The CF3 group in the surfactant gives two kinds of 19F NMR signals corresponding to the monomer and micelle states, indicating slow surfactant exchange on NMR time scale. The lifetime (taumic) of micelle, estimated by line shape analysis of the signals, is 2.0 ms at cmc, 102 to 103 times longer than that of general surfactant micelles. Pulsed-gradient spin-echo (PGSE) experiments show that the hybrid surfactant forms considerably small micelles with a hydrodynamic radius of 0.6 nm. In contrast, at a higher concentration where no slow surfactant exchange is observed, the micelle radius increases to 1.1 nm. The interdigitation between the surfactant molecules in the micelle will contribute to the unusually long lifetime, in other words, slow surfactant exchange on the NMR time scale.     

Separate detection of homologous surfactants by means of solid-contact unmodified and modified with molecular sieves potentiometric sensors

To improve the selectivity of surfactant sensors, the surface of their membranes was modified with molecular sieves with predetermined pore sizes. Water-soluble anionic, cationic and non-ionic surfactants were used as pore generators in the molecular sieves and introduced into the source membrane at the stage of its formation. The modified sensors enable detection of alkylsulfates homologues and alkylpyridinium with different lengths of the hydrocarbon chain (C₁₀-C₁₈); homologous poly(oxyethylated nonylphenols) differing in the number of oxyethyl groups (m = 10-100).A novel approach to separate detection of surfactant homologues implies the usage of inselective sensors as a multisensor system. The software-supported multisensor approach allows information of both mixture composition and concentrations of separate components in multicomponent systems to be obtained with a certain accuracy. Inselective non-modified sensors with the highest cross-sensitivity were used to design multisensor systems like an “electronic tongue”.The cross-sensitivity parameters of both source and modified sensors were estimated and the possibility of their usage in multisensor systems like an “electronic tongue” for analysis of multicomponent solutions of homologous surfactant is shown. Analytical signals were processed by artificial neural networks.     

Green chemistry multicomponent protocol for formylation and Knoevenagel condensation for synthesis of (Z)-5-arylaminomethylene pyrimidine 2, 4, 6-trione derivatives in water

A green, efficient, and novel one-pot multicomponent protocol was developed to achieve stereoselective (Z)-5-(arylpropenylidine)-2,4,6-pyrimidinetrione derivatives using a three-component reaction involving appropriate aromatic amines, formic acid, and barbituric acid using water as green solvent by conventional thermal heating process. In this way, N-formylation of various amines takes place. The resulted different formamides undergo Knoevenagel condensation with active methylene group containing compound, that is, barbituric acid. The newly synthesized compounds were characterized by spectral analysis (Fourier Transform Infrared [FT-IR], 1H nuclear magnetic resonance [NMR], 13C NMR, Heteronuclear Multiple-Bond Correlation [HMBC], Mass, UV spectroscopy) and elemental analysis. The multicomponent reactions (MCRs) showed good stereoselectivity.     

A facile approach toward multicomponent supramolecular structures: selective self-assembly via charge separation

A novel approach toward the construction of multicomponent two-dimensional (2-D) and three-dimensional (3-D) metallosupramolecules is reported. Simply by mixing carboxylate and pyridyl ligands with cis-Pt(PEt(3))(2)(OTf)(2) in a proper ratio, coordination-driven self-assembly occurs, allowing for the selective generation of discrete multicomponent structures via charge separation on the metal centers. Using this method, a variety of 2-D rectangles and 3-D prisms were prepared under mild conditions. Moreover, multicomponent self-assembly can also be achieved by supramolecule-to-supramolecule transformations. The products were characterized by (31)P and (1)H multinuclear NMR spectroscopy, electrospray ionization mass spectrometry, and pulsed-field-gradient spin echo NMR techniques together with computational simulations.     

Some selected problems of nonaqueous microemulsions — phase diagrams and variation of the composition in the quaternary and ternary systems

A variety of quaternary and ternary systems of the type of dodecane/aliphatic alcohols/Na-dodecyl sulphate/water or a water-replacing component (formamide, ethylene glycol, propylene glycol, propylene carbonate, dimethylsulfoxide, acetonitrile) were subjected to a comparative analysis of microemulsification. The compositions of the systems of the type of oil/surfactant/cosurfactant/water or nonaqueous liquid were changed with respect to surfactant (Na-dodecyl sulfate and triton X 114) concentration, cosurfactant (homologous aliphatic alcohols) concentration and mixing ratio of water and water-replacing component. The appertaining phase diagrams were plotted and compared with those of aqueous systems.The experimental results suggest that the phase regions, which are designated as nonaqueous microemulsions, probably represent, not only microemulsions in the usual sense, but a separate kind of mixed phase whose microstructure is examined by special studies. Analogously to aqueous microemulsion systems, transparency and spontaneous formation of homogeneous multicomponent systems cannot serve as the sole criteria for waterless microemulsion formation. But they are important guiding properties of microemulsion formation in multicomponent systems.The variety of components involved in the chemical composition and the current insufficient knowledge do not permit to generally decide whether nonaqueous systems can be assigned to microemulsions or to molecular solutions. For clarifying this problem a detailed examination of the miscibility behavior, especially that of binary systems as a function of temperature, and the role that surfactant and cosurfactant play in the formation of homogeneous systems will be necessary.     

Modulation of drug transport properties by multicomponent diffusion in surfactant aqueous solutions

Diffusion coefficients of drug compounds are crucial parameters used for modeling transport processes. Interestingly, diffusion of a solute can be generated not only by its own concentration gradient but also by concentration gradients of other solutes. This phenomenon is known as multicomponent diffusion. A multicomponent diffusion study on drug-surfactant-water ternary mixtures is reported here. Specifically, high-precision Rayleigh interferometry was used to determine multicomponent diffusion coefficients for the hydrocortisone-tyloxapol-water system at 25 degrees C. For comparison, diffusion measurements by dynamic light scattering were also performed. In addition, drug solubility was measured as a function of tyloxapol concentration, and drug-surfactant thermodynamic interactions using the two-phase partitioning model were characterized. The diffusion results are in agreement with a proposed coupled multicomponent diffusion model for ternary mixtures relevant to nonionic drug and surfactant molecules. Theoretical examination of diffusion-based drug transport in the presence of concentration gradients of micelles shows that drug fluxes and drug concentration profiles are significantly affected by coupled multicomponent diffusion. This work provides guidance for the development of accurate models of diffusion-based controlled release in multicomponent systems and for the applications of micelle concentration gradients to the modulation of diffusion-based drug transport.