The Viscous Properties of Anionic/Cationic and Cationic/Nonionic Mixed Surfactant Systems

The behavior of mixed cationic/anionic and cationic/nonionic surfactants solutions have been studied by viscosimetry. The systems studied were sodium dodecyl sulfate (SDS)/cetyltrimethylammonium bromide (CTAB) and CTAB/Brij (polyoxyethylene lauryl ether, n = 10 and 23) in aqueous and sodium chloride solutions. The relative viscosity of single nonionic surfactant solutions is larger than that of SDS or CTAB solutions. It increases with the number of ethylene oxide groups. In the mixed systems, viscosity deviates from ideal behavior. The deviation results from electrostatic interactions. The surfactant mixture composition affects the self-assembled microstructure and rheology. A new mixed system that forms clear micellar solution above CMC was detected. In CTAB/Brij systems, the experimental data also deviate from ideal behavior due to mixed micelle formation and electroviscous effect. This effect is less pronounced than that of SDS/CTAB system and could be suppressed by adding an electrolyte (NaCl).     

Ionic Mixed Interactions in Macromolecules

Purely ionic interactions in natural and synthetic macromolecules involve the mutual interaction of fixed charges and their interaction with mobile ions. Such charge‐dependent interactions lead to well‐documented effects, including chain expansion of polyelectrolytes, globularization of polyampholytes, distributions of mobile ions according to charge screening, or ion condensation models. A variety of structural features, functions, and applications of these systems is amplified by the superimposition of charge‐independent effects associated with the occurrence of less polar or hydrophobic groups, special salts, surfactants, or complementary protein assemblies. For instance, ionic and hydrophobic attractive interactions stabilize pearls (or rings)‐on‐a‐string conformations, possibly a model for the formation of the chromatin assembly. The attractive interactions due to hydrophobic fatty acid groups attached to polysaccharides promote the formation of vesicles that entrap and slowly release water‐soluble drugs. Intra‐ and intermolecular associations based on ion‐pairing mixed interactions also control the formation of host–guest compounds, protein conformation, and the assembly of layered polyelectrolytes. Metallo‐supramolecular polymers and networks are formed due to the coordination of multivalent cations with bi‐ and trifunctional organic ligands. The association of lithium salts to polymers in the absence of water allows the formation of highly efficient energy sources. It also allows the identification of the ionic species that control charge‐independent contributions to Hofmeister effects. This critical review presents a synthetic classification of systems displaying ionic mixed interactions, and a discussion of underlying molecular mechanisms.     

Interactions in Calcium Oxalate Hydrate/Surfactant Systems

Phase transformation of calcium oxalate dihydrate (COD) into the thermodynamically stable monohydrate (COM) in anionic (sodium dodecyl sulfate (SDS)) and cationic (dodecylammonium chloride) surfactant solutions has been studied. Both surfactants inhibit, but do not stop transformation from COD to COM due to their preferential adsorption at different crystal faces. SDS acts as a stronger transformation inhibitor. The general shape of adsorption isotherms of both surfactants at the solid/liquid interface is of two-plateau-type, but differences in the adsorption behavior exist. They originate from different ionic and molecular structures of crystal surfaces and interactions between surfactant headgroups and solid surface. Copyright 1999 Academic Press.     

Interaction of Nonionic Surfactant Triton-X-100 with Ionic Surfactants

The interaction in two mixtures of a nonionic surfactant Triton-X-100 (TX-100) and different ionic surfactants was investigated. The two mixtures were TX-100/sodium dodecyl sulfate (SDS) and TX-100/cetyltrimethylammonium bromide (CTAB) at molar fraction of TX-100, α_TX-100 = 0.6. The surface properties of the surfactants, critical micelle concentration (CMC), effectiveness of surface tension reduction (γ_CMC), maximum surface excess concentration (Γ_max), and minimum area per molecule at the air/solution interface (A _min) were determined for both individual surfactants and their mixtures. The significant deviations from ideal behavior (attractive interactions) of the nonionic/ionic surfactant mixtures were also determined. Mixtures of both TX-100/SDS and TX-100/CTAB exhibited synergism in surface tension reduction efficiency and mixed micelle formation, but neither exhibited synergism in surface tension reduction effectiveness.     

Micellar Aggregation Behavior and Electrochemically Reversible Solubilization of a Redox-Active Nonionic Surfactant

For the purpose of studying the potential of a novel nonionic switchable surfactant, 11-ferrocenylundecyl polyoxyethylene ether (FPEG), applied to surfactant-enhanced remediation (SER), the surface properties and micelle solubilization behavior of FPEG were investigated with different inorganic salts. With the addition of inorganic salts (NaCl and CaCl₂), the critical micelle concentration (CMC) of FPEG dropped from 15 to 12 and 8 mg·L^?1, respectively, due to the salting-out effect on the alkyl chain. Thermodynamic parameters based on the CMCs indicated that micelle formation was an entropy-driven process. Dynamic light scattering measurements verified that these inorganic salts can decrease the hydrodynamic diameters (D _h) of the micelles. Solubilization experiments with three typical polycyclic aromatic hydrocarbons (PAHs) demonstrated that the system of FPEG with NaCl shows the highest solubilization ability, and the molar solubilization ratio and micelle–water partition coefficient (K _m ) values follow the order pyrene > phenanthrene > acenaphthene. After oxidation, PAHs can be released from the micelles through breaking up of the micelles, and the cumulative release efficiency of pyrene, phenanthrene and acenaphthene are 31.2, 42.8 and 44.6 %; the order of release efficiency is opposite to that of the reduced form for solubilization abilities. All the results suggest that the ferrocene-containing, redox-active surfactant FPEG has the potential to be recycled in SER technology through electrochemistry approaches.     

尼罗红在离子表面活性剂水溶液中的荧光特性

尼罗红(NR)分子具有大的芳香环和基态时可与水分子形成氢键的吸电子基, 它对增溶在表面活性剂胶束栅栏层的环境尤其敏感, 在十二烷基三甲基溴化铵(C12TABr)胶束水溶液中表现为双重荧光, 最大发射波长分别位于578和630 nm. 十二烷基硫酸钠(SDS)胶束的反离子解离度大于C12TABr胶束, 这不仅增大了NR周边环境的极性, 也增多了溶剂化水, 导致与NR氢键作用增强, 荧光强度低于C12TABr, 但有效促进了分子内扭转电荷转移(TICT)激发态形成, 其布居甚至可达到98%以上, 表观上仅出现了在634 nm的单重荧光峰. NR对环境的敏感特性很好地反映了Gemini表面活性剂初始形成胶束的残缺结构信息, 是检测这类具有强烈相互作用两亲分子聚集行为的良好探针.     

表面活性离子液体溴化N-十二烷基异喹啉与非离子表面活性剂Triton X-100在水溶液中的混合胶束

用等温滴定微量热法测定表面活性离子液体溴化N-十二烷基异喹啉([C₁₂iQuin]Br)与非离子表面活性剂Triton X-100混合物在水溶液中的临界胶束浓度。并以¹H核磁共振(NMR)和二维核Overhauser效应增强谱(2D NOESY)研究[C₁₂iQuin]Br与Triton X-100在混合胶束中的作用机理。研究结果显示：混合胶束中,Triton X-100分子的苯环定位于混合胶束的内核,聚氧乙烯链卷曲在异喹啉环周围。本文还应用规则溶液理论和浊点法对比研究了十二烷基三甲基溴化铵(DTAB)-Triton X-100混合胶束体系的相关性质。     

Surface Property of Nonionic Surfactant Triton X-100 in an Ionic Liquid

A common nonionic surfactant Triton X-100 was dissolved in a commercial ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF₄). The surface tension of the bmimBF₄ solution was decreased with increasing the content of surfactant Triton X-100, a similar phenomenon with aqueous solution systems. Dynamic surface properties of Triton X-100 in bmimBF₄ were measured. It was found that pure IL solvents need rearrangement at the air-bmimBF₄ interface during the beginning stage of absorption. Moreover, the adsorption model was found to be in accord with the diffusion-controlled adsorption mechanism, and further, the dilute bmimBF₄ solutions are close to the diffusion-controlled adsorption.     

Fluorescence Spectroscopy Study of Polyoxyethylene Surfactant Micellar Systems

The systems investigated by fluorescence spectroscopy and atomic force microscopy were water/ethoxylated mono, di-glyceride/oil + ethanol. The oils were R (+)-limonene and isopropylmyristate. The mixing ratio (w/w) of ethanol/oil equals unity. The fluorescent probes auramine-O and 8-anilino-1-naphthalenesulfonic acid were used to determine the minimum ω′ value for the transition of reverse micelles to microemulsions in the systems based on the two oils, as well as at different surfactant contents. The fluorescence quenching of Safranine-T (3,6-diamino-2,7-dimethyl-5 phenyl phenazinium chloride) by the inorganic ions Fe²⁺, Fe³⁺ and Cu²⁺ was studied in reverse micelles and microemulsions. The Stern–Volmer quenching constants at different water/surfactant molar ratios (ω values) were calculated from the data of the quenching process. Atomic force microscopy was used to image the systems based on the two oils for different water to surfactant molar ratios below and above the minimum ω′ value.     

Pseudo Peak Phenomena in Micellar Electrokinetic Capillary Chromatography by Using Ionic Surfactant

The origin of pseudo peak was studied by means of micellar electrokinetic capillary chromatography with cetyltrimethylaminium bormide as the pseudo stationary phase.It has been pointed that two peaks may appear for one component under certain conditions.Experiments showed that the relative areas of the two peaks of analyte depended on the time and the temperature of reaction between analyte and surfactant,and the concentration of surfactant in the sample solution.It means that the interaction between the analyte and the surfactant is a slow process,and a stable substance can be produced from the interaction.It is the substance and the analyte that may lead to the formation of two peaks.The fast interaction mechanism between the solute and the micellar should be queried from the experiment result.     

Micellar Extraction of Carboxylic Acids with Phases of OP-10 Nonionic Surfactant on Heating

Extraction of carboxylic acids from aqueous solutions with phases of OP-10 nonionic surfactant on heating was studied in relation to the concentration and hydrophobicity of the acids. A multiple linear regression equation describing the process was suggested.     

Micellar Behavior of n-Alkyl Sulfates in Binary Mixed Systems

The micellar behavior of the binary mixed systems of sodium n-hexylsulfate with sodium n-decyl-, n-dodecyl-, and n-tetradecylsulfate has been studied. The critical micelle concentration of the mixtures was quantitatively estimated by conductance methods. The micellar composition in the micelles was determined by the Motomura model and the mutual interactions were estimated from Holland and Rubingh's theory. The surfactant mixtures were found to be nonideal. The influence of the alkyl chain length in these parameters was studied. Copyright 2000 Academic Press.     

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.     

Toward a Theory of Diffusion of a Nonionic Surfactant with Variable Aggregation Number in a Micellar System

Since the aggregation number of micelles always grows with concentration, and, in some cases this dependence is noticeable even for spherical micelles, there is a need to revise the theory of micellization, in which the aggregation number is assumed to be constant. This work reformulates the theory of diffusion of nonionic surfactants in micellar solutions with regard to the variability of the aggregation number. A new formula, which expresses the diffusion coefficient of a surfactant via the diffusion coefficients of monomers and micelles, contains an additional factor capable of increasing the diffusion coefficient with the surfactant concentration. However, this factor is not overly strong, and the “old” part of the formula acts in the opposite direction; as a result, the conventional decrease in the diffusion coefficient of a nonionic surfactant remains prevailing. The analytical consideration has been supplemented with numerical calculations, the results of which are presented in the tables.     

三聚阴离子表面活性剂/阳离子添加剂混合体系的流变行为

表面活性剂的分子结构对蠕虫胶束的形成与性质有着重要影响。本文以十四酸和间苯三酚为起始原料,合成了一种三聚阴离子表面活性剂（2, 2', 2"-（苯基-1, 3, 5-三（氧））-三-十四酸钠,简写为Ph-TrisC₁₄Na）,并通过稳态和动态流变测试,研究了单组分的Ph-TrisC₁₄Na和Ph-TrisC₁₄Na/阳离子添加剂体系的粘弹性质。阳离子添加剂分别为正丁基三甲基溴化铵（C₄TAB）,正己基三甲基溴化铵（C₆TAB）和正辛基三甲基溴化铵（C₈TAB）。结果表明,依赖于独特的分子构型,Ph-TrisC₁₄Na分子自身即可形成蠕虫胶束,使溶液表现出明显的粘弹性。阳离子添加剂的加入可进一步优化Ph-TrisC₁₄Na的分子几何结构,促进蠕虫胶束更为快速地生长。随着阳离子添加剂疏水链长的增加,溶液的粘弹性显著增强,体系微结构对添加剂的敏感性也增加。对于50 mmol·L^-1的Ph-TrisC₁₄Na溶液来说,在C₈TAB与Ph-TrisC₁₄Na的摩尔比为0.5时,体系的零剪切粘度可达1535 Pa·s,蠕虫胶束的长度则达到4.0-7.5 μm。该体系体现出低聚表面活性剂在构筑表面活性剂粘弹溶液方面的优势,可拓展高粘弹性阴离子蠕虫胶束体系的研究范围。     

新型阴离子Gemini表面活性剂与非离子表面活性剂C10E6混合溶液的胶团化的研究

研究了烷基苯磺酸盐Gemini表面活性剂Ia与非离子表面活性剂C10E6溶液混合胶团中分子间的相互作用. 通过表面张力法测定了Ia 和C10E6不同比例不同温度下的临界胶束浓度(cmc). 结果表明, 两种表面活性剂以任何比例复配的cmc比单一表面活性剂的cmc都低, 表现出良好的协同效应. 传统型非离子表面活性剂C10E6、Gemini表面活性剂Ia及混合物的cmc都随着温度升高而降低. 而且, 任何配比的混合胶团中两种表面活性剂分子间的相互作用参数β都是负值, 这说明两种表面活性剂在混合胶团中产生了相互吸引的作用. 混合表面活性剂体系的胶团聚集数比单一Ia的大, 但比单一C10E6的小. 向Gemini表面活性剂Ia胶束中加入非离子表面活性剂C10E6会使胶束的微观极性变小.     

Activity Coefficients of Aqueous Mixed Ionic Surfactant Solutions from Osmometry

Osmotic techniques for measuring thermodynamic activities, such as isopiestic equilibration, are well established for multicomponent solutions, especially mixed salt solutions. Surprisingly, these techniques have not yet been applied to mixed ionic surfactants, despite the numerous practical applications of these systems and the importance of the Gibbs free energy for micelle stability. In this study, mass-action equations are developed for the osmotic coefficients of solutions of ionic surfactant CA + ionic surfactant CB, with common counterion C. Extended Debye–Hückel equations are used for the ionic activity coefficients. The equilibrium constants for mixed micelle formation are evaluated by Gibbs–Duhem integration of critical micelle concentrations. Fitting the derived equations to the osmotic coefficients of aqueous sodium decanoate + sodium dodecylsulfate solutions measured by freezing-point osmometry is used to evaluate the activities of the total surfactant components. Very large departures from ideal solution behavior are indicated, including stoichiometric surfactant activity coefficients and micelle activity coefficients that drop below 0.05 and 10^?8, respectively, relative to unity for ideal solutions. Osmometry offers many interesting and unexplored possibilities for studies of mixed surfactant thermodynamics.     

Viscosity of Nonionic Polymer/Anionic Surfactant Complexes in Water

The polymer-micelle model, formerly established by Cabane, is revised to develop a new viscosity equation to describe the dependence of dilute solution viscosity on polymer concentration in PEG/SDS aqueous solutions. Two parameters inthe new equation were proposed to characterize the influence of the polymer solution viscosity on the added surfactant. The viscosity data of polyethylene glycol (PEG) solutions containing sodium dodecyl sulfate (SDS) were measured by the Ubbelohde dilution viscometer and the new equation proved to be in good agreement with the experimental data. Copyright 2000 Academic Press.     

Solubilization of (+)-α-Pinene by Cyclodextrin/Surfactant Mixed Systems

The mixing effects of 6-O-α-D-glucosyl-β-cyclodextrin (G-β-CD) and surfactants on the solubilization of (+)-α-pinene (αP, a fragrance) in aqueous solution were studied using a head-space gas chromatography technique. The findings show that the mixing of G-β-CD and surfactant result in negative synergistic effects on the solubility of αP.