阳、阴、非离子表面活性剂胶束对酯碱性水解的影响

应用紫外分光光度法和热动力学方法研究了芳香酸酯和正脂肪酸酯在表面活性剂ＤＴＡＢ、ＴＴＡＢ、ＣＴＡＢ、ＳＤＳ、Ｂｒｉｊ３５、ＴｒｉｔｏｎＸ－１００胶束中的碱性水解反应。阳、阴、非离子表面活性剂胶束对酯的碱性水解均有禁阻作用。讨论了胶束对酯碱性水解禁阻作用的原因。     

Percolative phenomena in lecithin reverse micelles: the role of water

 The role played by the solvation water molecules on the macroscopically observed sol–gel transition in lecithin/cyclohexane/water reverse micelles is investigated by quasielastic neutron scattering, dielectric relaxation and conductivity measurements. The experimental results are juxtaposed to those from spherical Aerosol OT reverse micelles. It is shown how the results from lecithin-based system can be interpreted only assuming that, in contrast to Aerosol OT systems, the water molecules are entrapped at the interfaces without coalescing into an inner water pool. It is suggested that, in the case of lecithin, the solvation water can induce a change in the surface curvature, in such a way promoting the formation of branch points. Such a hypothesis is supported by the temperature dependence of the conductivity which agrees with the hypothesis of an intermicellar bond percolation. The investigation of the structures imposed by an external electric field is also studied. The observed electrorheological behaviour seems to confirm the existence of a percolated transient network in the gel phase. Received: 21 March 2001 Accepted: 24 August 2001     

胶束增敏导数—可变角同步荧光法同时测定两种羟基联苯

本文建立了２，２’－二羟基联苯（ＤＨＰ）和４－羟基联苯（ＨＰ）的胶束增敏导数－可变角同步荧光同时分析方法，可变角同步扫描所得到的ＤＨＰ和ＨＰ的谱峰位置均对应于常规光谱中的最佳激发－发射位置，经二阶求导后，消除分析谱带干扰，所得的二阶导数－可变角同步光谱即可用于两物质的同时测定，方法快速灵敏，ＤＨＰ测定范围为０．０５～０．５ｍｇ／Ｌ，ＨＰ测定范围为０．０７～２ｍｇ／Ｌ。     

Effect of solution chemistry on the surface charge of polymeric reverse osmosis and nanofiltration membranes

A streaming potential analyzer has been used to investigate the effect of solution chemistry on the surface charge of four commercial reverse osmosis and nanofiltration membranes. Zeta potentials of these membranes were analyzed for aqueous solutions of various chemical compositions over a pH range of 2 to 9. In the presence of an indifferent electrolyte (NaCl), the isoelectric points of these membranes range from 3.0 to 5.2. The curves of zeta potential versus solution pH for all membranes display a shape characteristic of amphoteric surfaces with acidic and basic functional groups. Results with salts containing divalent ions (CaCl₂, Na₂SO₄, and MgSO₄) indicate that divalent cations more readily adsorb to the membrane surface than divalent anions, especially in the higher pH range. Three sources of humic acid, Suwannee River humic acid, peat humic acid, and Aldrich humic acid, were used to investigate the effect of dissolved natural organic matter on membrane surface charge. Other solution chemistries involved in this investigation include an anionic surfactant (sodium dodecyl sulfate) and a cationic surfactant (dodecyltrimethylammonium bromide). Results show that humic substances and surfactants readily adsorb to the membrane surface and markedly influence the membrane surface charge.     

Small angle X-ray scattering study of an extremely elongated micelle system of CTAB-p-toluidine solution

Whenp-toluidine is added to an aqueous solution of CTAB, a remarkable increase of viscosity is accompanied by a spectacular elasticity. We detected the existence of extremely elongated rod-like micelles in electron micrographs. SAXS measurements indicate a closely packed array of cylindrical rod-like micelles, brought about when solutions flow through a thin capillary. A scattering maximum ofd=160 Å almost corresponds to the distance between the nearest neighbours of the cylindrical rod-like micelles. This value agrees with the diameter measured on electron micrographs. The second broad peak (d=75 Å) is assigned to a subsidiary maximum of the shape function of the cylinder with infinite length.     

Micelle formation of ethoxylated nonyl-phenols in aqueous solutions

The micelle formation of nonyl-phenols with various numbers of ethoxy groups (n _EO=10–40) was investigated in aqueous solutions and the study was focussed on the effect of temperature (293–323 K), the chain length and the inorganic electrolyte (NaCl) on the critical micelle concentration (c.m.c).The c.m.c. was determined by surface tension and interfacial tension measurements in a water/n-octane system. On the basis of the actual c.m.c. and its temperature dependence the thermodynamic functions of micelle formation (H° _m,S°_m,G°_m) were also calculated. The latter study comprised the determination of the thermodynamic function for unity ethoxy groups ((Y° _m)) as a function ofn _EO.According to the experimental results the micellar solutions are the more stable, the smaller the number of ethoxy groups in the tenside molecule and the higher the temperature as well as the electrolyte content of the system.     

Mixed micelles of tetradecyltrimethylammonium bromide and chlorhexidine digluconate in aqueous solutions of isopropyl alcohol

The influence of isopropyl alcohol (IPA) on the size and composition of the mixed micelles in mixtures of tetradecyltrimethylammonium bromide (TTAB) and chlorhexidine digluconate (CG) has been determined as a function of the composition of the systems. The addition of 0.5 M and 1.0 M IPA had little significant effect on the composition of the mixed micelles as determined both by analysis of critical micelle concentration (CMC) data using a theoretical treatment based on excess thermodynamic quantities and by an empirical treatment of conductivity data. Static and quasielastic light scattering measurements showed a progressive decrease of the aggregation number and hydrodynamic radius of TTAB micelles on addition of IPA, but minimal changes in the properties of the small CG aggregates. The results show that the micellar weight in the TTAB/CG/IPA solutions is determined by the ratio of the surfactants in the system and for each TTAB/CG ratio decreases on addition of IPA.     

Volume and heat capacity of model non-aqueous self-assembly systems

Blends of immiscible polymers are often stabilized by block copolymers which can form non-aqueous micelles and microemulsions in the liquid polymers. The phase diagrans, apparent volumes and apparent heat capacities of model non-aqueous binary and ternary systems were studied in order to investigate the conditions under which such self-assembly systems could form. 1,2-Hexanediol, which can cosolubilize hexane and ethyleneglycol, forms inverse micelles in hexane and weak microaggregates in ethyleneglycol. Genapol X-060, a commercial alcoholic surfactant containing on the average an aliphatic chain of 13 carbons and 6 oxyethylenes (C₁₃E₆), forms microaggregates in poly(ethyleneglycol) 400. These self-assembly systems are strengthen in the presence of a third component which has an affinity for the inner phase.Presented at the Symposium, 76^th CSC Congress, Sherbrooke, Quebec, May 30–June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65^th birthday.     

反相流动注射化学发光法测定单宁

在碱性介质中 ,单宁对高碘酸钾氧化鲁米诺的化学发光反应有较强的增敏作用 ,据此建立了反相流动注射化学发光测定单宁的新方法 ,并研究了最佳反应条件。该方法快速、准确、线性范围宽 ,测定单宁的检出限为 1 .1 2× 1 0 - 9g/ m L,方法的线性范围为 2 .0× 1 0 - 8～ 6 .0× 1 0 - 6 g/ m L,对于 4.0× 1 0 - 6 g/ m L单宁 1 0次测定的相对标准偏差为 0 .79%。应用于中药五倍子、诃子中单宁的测定 ,结果满意     

All-trans-N-retinylidenetryptamine Schiff base in surfactant solubilized water pools in heptane—a fluorescence study

All-trns-N-retinylidenetryptamine Schiff base was incorporated into aerosol-OT (AOT, sodium bis(2-ethylhexyl)sulphosuccinate)/heptane reverse micelles. This micellar system was used as a model to study the retinal-tryptophan interactions in retinal proteins. The retinylidene Schiff base remains stable in the presence of reverse micelle-solubilized water pools. Partition coefficient and microviscosity measurements show that the Schiff base is located in the micellar interphase. The results are discussed in terms of the interaction between the retinylidene chromophore and the active site environment of rhodopsin and bacteriorhodopsin. In the present model, the quencher and emitting units are covalently attached, and are separated by two carbon spacer units. The fluorescence emission data obtained for the micelle-intercalated Schiff base chromophore are compared with the fluorescence of the native protein and intermediates in the photochemical cycle of bacteriofhodopsin. A comparison of the data obtained for tryptamine and the Schiff base with the results available for bacteriorhodopsin and bacterioopsin reveals that there is a large degree of quenching on intercalation of the retinylidene chromophore in the vicinity of the fluorophore. Evidence provided by this model suggests that energy transfer to retinal can occur from tryptophan residues located in the retinal pocket in the native protein. Thus the retinylidene unit can act as a quencher of the energy of tryptophan, the nature and extent of which may depend on the conformation and relative orientation of the protein-bound fluorophore.