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1.
We report light and small-angle neutron scattering measurements that characterize microstructures formed in aqueous surfactant solutions (up to 1.0 wt % surfactant) containing mixtures of sodium dodecyl sulfate (SDS) and the light-sensitive bolaform surfactant, bis(trimethylammoniumhexyloxy)azobenzene dibromide (BTHA) as a function of composition, equilibration time, and photostationary state (i.e., solutions rich in cis-BTHA or trans-BTHA). We observed formation of vesicles in both SDS-rich and trans-BTHA-rich regions of the microstructure diagram, with vesicles present over a particularly broad range of compositions for trans-BTHA-rich solutions. Illumination of mixtures of BTHA and SDS with a broadband UV light source leads to formation of photostationary states where the fraction of BTHA present as cis isomer (75-80% cis-BTHA) is largely independent of the mixing ratio of SDS and BTHA. For a relatively limited set of mixing ratios of SDS and BTHA, we observed UV illumination of SDS-rich vesicles to result in the reversible transformation of the vesicles to micellar aggregates and UV illumination of BTHA-rich vesicles to result in irreversible precipitation. Surprisingly, however, for many mixtures of trans-BTHA and SDS that formed solutions containing vesicles, illumination with UV light (which was confirmed to lead to photoisomerization of BTHA) resulted in only a small decrease in the number of vesicles in solution, relatively little change in the sizes of the remaining vesicles, and coexistance of the vesicles with micelles. These observations are consistent with a physical model in which the trans and cis isomers of BTHA present at the photostationary state tend to segregate between the different microstructures coexisting in solution (e.g., vesicles rich in trans-BTHA and SDS coexist with micelles rich in cis-BTHA and SDS). The results presented in this paper provide guidance for the design of light-tunable surfactants systems.  相似文献   

2.
The aggregation behavior of catanionics formed by the mixture of cationic geminis derived from dodecyltrimethylammonium chloride (DTAC) and anionic sodium dodecylsulfate (SDS) was studied by means of phase studies and comprehensive small-angle neutron scattering (SANS) experiments at 25 °C and 50 mM overall concentration. The results are compared to those for the previously studied SDS + DTAC system. Various gemini spacers of different natures and geometries were used, but all of them had similar lengths: an ethoxy bridge, a double bond, and an aromatic ring binding the two DTACs in three different substitutions (ortho, meta, and para). SANS and SAXS data analysis indicates that the spacer has no large effect on the spheroidal micelles of pure surfactants formed at low concentration in water; however, specific effects appear with the addition of electrolytes. Microstructures formed in the catanionic mixtures are rather strongly dependent on the nature of the spacer. The most important finding is that for the hydrophilic, flexible ethoxy bridge, monodisperse vesicles with a fixed anionic/cationic charge ratio (depending only on the surfactant in excess) are formed. Furthermore, the composition of these vesicles shows that strongly charged aggregates are formed. This study therefore provides new opportunities for developing tailor-made gemini surfactants that allow for the fine tuning of catanionic structures.  相似文献   

3.
Electron paramagnetic resonance, viscosity, and small-angle neutron scattering (SANS) measurements have been used to study the interaction of mixed anionic/nonionic surfactant micelles with the polyampholytic protein gelatin. Sodium dodecyl sulfate (SDS) and the nonionic surfactant dodecylmalono-bis-N-methylglucamide (C12BNMG) were chosen as "interacting" and "noninteracting" surfactants, respectively; SDS micelles bind strongly to gelatin but C12BNMG micelles do not. Further, the two surfactants interact synergistically in the absence of the gelatin. The effects of total surfactant concentration and surfactant mole fraction have been investigated. Previous work (Griffiths et al. Langmuir 2000, 16 (26), 9983-9990) has shown that above a critical solution mole fraction, mixed micelles bind to gelatin. This critical mole fraction corresponds to a micelle surface that has no displaceable water (Griffiths et al. J. Phys. Chem. B 2001, 105 (31), 7465). On binding of the mixed micelle, the bulk solution viscosity increases, with the viscosity-surfactant concentration behavior being strongly dependent on the solution surfactant mole fraction. The viscosity at a stoichiometry of approximately one micelle per gelatin molecule observed in SDS-rich mixtures scales with the surface area of the micelle occupied by the interacting surfactant, SDS. Below the critical solution mole fraction, there is no significant increase in viscosity with increasing surfactant concentration. Further, the SANS behavior of the gelatin/mixed surfactant systems below the critical micelle mole fraction can be described as a simple summation of those arising from the separate gelatin and binary mixed surfactant micelles. By contrast, for systems above the critical micelle mole fraction, the SANS data cannot be described by such a simple approach. No signature from any unperturbed gelatin could be detected in the gelatin/mixed surfactant system. The gelatin scattering is very similar in form to the surfactant scattering, confirming the widely accepted picture that the polymer "wraps" around the micelle surface. The gelatin scattering in the presence of deuterated surfactants is insensitive to the micelle composition provided the composition is above the critical value, suggesting that the viscosity enhancement observed arises from the number and strength of the micelle-polymer contact points rather than the gelatin conformation per se.  相似文献   

4.
Phase behavior of cationic/anionic surfactant mixtures of the same chain length (n=10, 12 or 14) strongly depends on the molar ratio and actual concentration of the surfactants. Precipitation of catanionic surfactant and mixed micelles formation are observed over the concentration range investigated. Coacervate and liquid crystals are found to coexist in the transition region from crystalline catanionic surfactant to mixed micelles.The addition of oppositely charged surfactant diminishes the surface charge density at the mixed micelle/solution interface and enhances the apparent degree of counterion dissociation from mixed micelles. Cationic surfactants have a greater tendency to be incorporated in mixed micelles than anionic ones.  相似文献   

5.
两性离子甜菜碱表面活性剂(SB3-12)胶束具有较好的生物相容性,由于相反电荷的极性头之间具有静电中和作用,胶束表面具有小的负电荷密度。当加入阴离子的十二烷基硫酸钠(SDS)以后,负离子SD-与SB3-12胶束极性区内层季铵正电荷的静电中和作用,能连续地调节胶束表面磺酸基的负电荷密度,这有利于对药物分子的选择性增溶和调节在生理条件下的药物的输送。等温滴定量热(ITC)研究发现SB3-12和SDS有强的协同效应,混合临界胶束浓度(CMC)和胶束化焓明显降低,并得到两者协同效应的弱静电作用机理。当模型药物分子芦丁(Rutin)与SB3-12/SDS混合胶束作用时,芦丁7位羟基的氢解离后的阴离子与SDS共同作用于SB3-12形成混合胶束。UV-Vis吸收光谱和~1H NMR谱研究发现,在SB3-12胶束中,芦丁分子的A环位于季铵阳离子附近,B环位于两个相反电荷之间的弱极性区域。在SDS胶束中,B环位于栅栏层,而A环和二糖暴露于水相侧。在混合胶束中,随着SDS摩尔分数增加,对A环的静电吸引变弱。离子表面活性剂对两性离子表面活性剂胶束表面电荷密度的调节作用,本质上是对胶束极性区域的物理及化学性质的微调,进而实现对药物的可控增溶。  相似文献   

6.
Ultrafast fluorescence resonance energy transfer (FRET) in a catanionic [sodium dodecyl sulfate (SDS)-dodecyltrimethyl ammonium bromide (DTAB)] vesicle is studied by femtosecond up-conversion. The vesicles (diameter ~400 nm for SDS-rich and ~250 nm for DTAB-rich vesicles) are much larger than the SDS and DTAB micelles (diameter ~4 nm). In both micelle and vesicles, FRET occurs in multiple time scales and the time scales of FRET correspond to a donor-acceptor distance varying between 12 and 36 A?.  相似文献   

7.
Aggregation behavior of a novel anionic amphiphilic molecule, sodium N-(2-(n-dodecylamino)ethanoyl)-L-alaninate (C(12)Ala), was studied in the presence of sodium dodecyl sulfate (SDS) surfactant at different [C(12)Ala]/[SDS] molar ratios and concentrations. The viscosity of aqueous SDS solution increased in the presence of C(12)Ala surfactant. The bulk viscosity of water was found to increase upon increase of both molar ratio and total surfactant concentration. The microenvironments of the self-assemblies were investigated using the fluorescence probe technique. Fluorescence anisotropy studies indicated formation of rodlike micelles. Both dynamic light scattering and small-angle neutron scattering measurements were performed to obtain the size and shape of the microstructures. The concentration and composition dependence of the hydrodynamic diameter of the aggregates were investigated. Transmission electron micrographs revealed the presence of a hexagonal liquid crystal phase in dilute solutions of the C(12)Ala-SDS mixture. The micrographs of moderately concentrated solution, however, showed cholesteric liquid-crystal structures with fingerprint-like texture. Temperature-dependent phase behavior of the self-assemblies was studied by use of the fluorescence probe technique.  相似文献   

8.
Salt-free 1:1 cationic/anionic (catanionic) surfactant mixture tetradecyltrimethylammonium laurate (TTAL) could be prepared by mixing equimolar tetradecyltrimethylammonium hydroxide (TTAOH) and lauric acid (LA) in water. Given the condition of suitable range of weight fraction of TTAL in total surfactant, rho=WTTAL/(WTTAL+WLA), and at existence of a small amount of water, it was found that the mixtures of so-obtained TTAL and LA could spontaneously form stable reverse vesicles in various organic solvents including toluene, tert-butylbenzene, and cyclohexane. The reverse vesicle phase shows a blue color against room light and exhibits strong birefringence under polarized microscope. The reverse vesicles are very sensitive to temperature change. Increasing temperature could make the rho values within which reverse vesicles were constructed move to higher values. In organic solvents of alkanes such as n-heptane, reverse vesicles could still form but become unstable upon time and centrifugation. Increasing temperature could accelerate phase separation, and finally a gel-like bottom phase was usually observed. Interestingly, the stable reverse vesicles formed by so-called salt-free catanionic surfactant mixtures still show some resistance against adding inorganic salts. They can trap inorganic ions such as Zn2+ and S2- into their hydrophilic layers. This opens the door for template applications of reverse vesicles to prepare inorganic nanoparticles.  相似文献   

9.

The electrochemical behavior of cationic tetradecyltrimethylammonium bromide (TTABr), anionic sodium dodecylsulfate (SDS), cationic‐anionic (catanionic) mixed surfactant and self‐assembled solutions at Pt wire electrode has been studied by cyclic voltammetry (CV). On the basis of the cyclic voltammograms and determining the self‐assembled structures by using freeze‐fracture transmission electron microscopy (FF‐TEM), the mechanisms of the electrochemical reactions near the electrode for the two surfactant self‐assembled solutions, i.e., micelles and vesicles, are presented. When mixing TTABr and SDS, at the right mixing ratio of TTABr:SDS, vesicles are established spontaneously. The redox behavior of two vesicle‐phase solutions at a constant total concentration of 25 mmol·L?1 with the ratios of TTABr:SDS 9.35:0.65 of positive charges of bilayer membranes and 1.25:8.75 of negative charges of bilayer membranes are investigated by cyclic voltammetry. These cyclic voltammograms of vesicles with different charges are compared with those of 100 mmol · L?1 TTABr and 100 mmol · L?1 SDS micelle solutions. This CV study on surfactant self‐assembled solutions should open up a new method of study in surfactant science.  相似文献   

10.
Dissipative particle dynamics (DPD) simulations are performed to study the factors that lead to the transition between micelle and vesicle in catanionic mixtures composed of sodium dodecyl sulfate (SDS) and dodecyltrimethylammonium bromide (DTAB), with the aim of understanding and controlling the structures of this system. The phase behavior, kinetics of vesicle formation, and micelle–vesicle transitions induced by salt, temperature, and selective solvents are investigated systematically. In this research, phase diagram of SDS/DTAB mixture is constructed by simulations at different concentrations and composition fractions. It is consistent with experimental results. The kinetic process of catanionic vesicle formation is illustrated. It is clarified that the transition between micelle and vesicle can be controlled by properly adjusting the external conditions. More interestingly, the evolution condition and transition mechanism between micelle and vesicle induced by various conditions are revealed. The membrane thickness differences between vesicles formed at different external conditions are compared. Here, the predicted phenomenon is compared with experimental results whenever possible, and we try to make a connection between the simulation model and the reality of the experiments. These studies help to shed light on the microscopic details of micelle–vesicle transition in catanionic mixtures.  相似文献   

11.
The interactions of alkylammonium chlorides (the number of carbon atom per chain was either 12, 14, or 16) with sodium cholate have been investigated by a combination of techniques including light and electron microscopy, surface tension, conductivity, light scattering, and microelectrophoretic measurements. The phase behavior has strongly depended on the molar ratio and actual concentration of oppositely charged surfactants. The change in the composition of the aggregates leads to a shape transformation from globular to elongated micelles to open and/or closed bilayers (vesicles) and precipitation. The length of micelles has been found to decrease dramatically with the concentration shift to the micellar regions of either surfactant. Upon a moderate excess of one surfactant, the mean hydrodynamic diameter of aggregates increases and wormlike micelles and/or open and closed bilayers are formed. Microscopic observations of alkylammonium cholates (novel catanionic surfactants precipitated in and/or close to equimolar region) have shown the presence of a variety of morphologies including twisted ribbons, tubules and bundles of tubules.  相似文献   

12.
The physicochemical properties, such as critical micelle concentration (cmc), surface tension at cmc (γ(cmc)), and surface activity parameters of the mixtures of a new amino acid-based zwitterionic surfactant, N-(n-dodecyl-2-aminoethanoyl)-glycine (C(12)Gly) and an anionic surfactant, sodium dodecyl sulfate (SDS) at different molar fractions, X(1) (= [C(12)Gly]/([C(12)Gly] + [SDS])) of C(12)Gly were studied. A synergistic interaction was observed between the surfactants in mixtures of different X(1). The self-organization of the mixtures at different molar fractions, concentrations, and pH was investigated. Fluorescence depolarization studies in combination with dynamic light scattering, and transmission electron microscopic and confocal fluorescence microscopic images suggested the formation of bilayer vesicles in dilute solutions of SDS rich mixtures with X(1) ≤ 0.17 in the pH range 7.0 to 9.0. However, the electronic micrographs showed structures with fingerprint-like texture in moderately dilute to concentrated C(12)Gly/SDS mixture at X(1) = 0.50. The vesicles were observed to transform into small micelles upon lowering the solution pH and upon increase of total surfactant concentration in mixtures with X(1) ≤ 0.17. However, decrease of SDS content transformed vesicles into wormlike micelles. The structural transitions were correlated with bulk viscosity of the binary mixtures.  相似文献   

13.
To study the influence of the chemical nature of headgroups and the type of counterion on the process of micellization in mixed surfactant systems, the cmc's of several binary mixtures of surfactants with the same length of hydrocarbon tail but with different headgroups have been determined as a function of the monomer composition using surface tension measurements. Based on these results, the interaction parameter between the surfactant species in mixed micelles has been determined using the pseudophase separation model. Experiments were carried out with (a) the nonionic/anionic C(12)E(6)/SDS ((hexa(ethyleneglycol) mono-n-dodecyl ether)/(sodium dodecyl sulfate)), (b) amphoteric/anionic DDAO/SDS ((dodecyldimethylamine oxide)/(sodium dodecyl sulfate)), and (c) amphoteric/nonionic C(12)E(6)/DDAO mixed surfactant systems. In the case of the mixed surfactant systems containing DDAO, experiments were carried out at pH 2 and pH 8 where the surfactant was in the cationic and nonionic form, respectively. It was shown that the mixtures of the nonionic surfactants with different kinds of headgroups exhibit almost ideal behavior, whereas for the nonionic/ionic surfactant mixtures, significant deviations from ideal behavior (attractive interactions) have been found, suggesting binding between the head groups. Molecular orbital calculations confirmed the existence of the strong specific interaction between (1) SDS and nonionic and cationic forms of DDAO and between (2) C(12)E(6) and the cationic form of DDAO. In the case for the C(12)E(6)/SDS system, an alternative mechanism for the stabilization of mixed micelles was suggested, which involved the lowering in the free energy of the hydration layer. Copyright 2000 Academic Press.  相似文献   

14.
The aqueous self-assembly of a novel lysine-derived surfactant with a gemini-like architecture, designated here as 12-Lys-12, has been experimentally investigated for the amphiphile alone in water and in a mixture with dodecyltrimethylammonium bromide (DTAB). The neat surfactant forms interesting micrometer-sized rigid tubules in the dilute region, resulting in very viscous solutions. For the catanionic mixture with DTAB, various single and multiphase regions were identified (up to a total surfactant concentration of 1.5 wt %) by means of combined polarizing light microscopy, cryo-TEM, and NMR. In the DTAB-rich side, for a mixing molar ratio in the range 2 < DTAB/12-Lys-12 < 4, a region of stable, unilamellar vesicles can be found. Furthermore, it was found that upon addition of 12-Lys-12 to pure DTAB solutions, the mixed micelles grow and beyond a given mixing ratio, vesicles assemble and coexist with small micelles. The transition is not continuous, since there is a narrow mixing range where phase separation occurs. Self-diffusion measurements and cryo-TEM imaging show that the average vesicle radius is on the order of 30-40 nm.  相似文献   

15.
The formation of mixed aggregates has been investigated in the mixture of oppositely charged surfactants vastly differing in molecular geometry and size. The systems considered is mixture of the cationic gemini surfactant, ethanediyl-1,2-bis(dodecyldimethylammonium bromide), and anionic surfactant, sodium dodecyl sulfate. Various mixed nano- and microaggregates (micelles, vesicles, thin lamellar sheets, and tubules) were formed depending on bulk composition and total surfactant concentration. Two types of aggregates were found in precipitate, the tubules as prevailing aggregates on the gemini-rich side, and vesicles as prevailing aggregates on the SDS-rich side. The tubules formation was ascribed to mutual influence of specific structure of cationic dimeric surfactant and electrostatic interactions at the bilayer/solution interface. The proposed mechanism involved the formation of lamellar sheets, which rolled-up into tubules.  相似文献   

16.
Interactions in an oppositely charged surfactant mixture composed of a gemini surfactant (bis(quaternary ammonium bromide)) and a bile salt (sodium cholate) in water were studied at 30°C. A combination of techniques was used including surface tension, conductometry, light scattering, light microscopy, and microelectrophoretic measurements. A strong dependence of the phase behavior on the molar ratio and actual concentration of surfactants was found. The interplay between electrostatic effects, geometry of molecules, and dissimilar separation of the hydrophobic and hydrophilic moieties in the surfactants dictate the interaction mode and the microstructures formed. Instead of precipitation, in the equivalent mixtures formation of complexes, mixed micelles, vesicles, coacervates, and solid crystalline phases have been observed. The extent of interacting forces in mixed micelles formed in equivalent mixtures was evaluated by regular solution theory. A relatively high negative value of interaction parameter indicated a strong attractive interaction between surfactants. The compositions of both mixed micelles and mixed monolayer are found to be almost equimolar.  相似文献   

17.
Mixed micelle formation and synergistic interactions of binary surfactant combinations of sodium nonylphenol polyoxyethylene ether sulfate (NPES) with typical surfactants such as sodium dodecyl sulfate (SDS), Triton X-100 (TX100), cetyl trimethyl ammonium bromide (CTAB), and sodium bis(2-ethylhexyl) sulfosuccinate (AOT) at 25 degrees C in the presence of NaCl have been investigated. The critical micelle concentration of the binary mixtures has been quantitatively estimated by steady-state fluorescence measurements. The micellar characteristics such as composition, activity coefficients, and mutual interaction parameters have been estimated following different theoretical treatments. Investigation on the micellization and synergistic interaction of NPES with four kinds of surfactants showed that the behavior of the binary mixture deviated from the ideal state. The analysis revealed that the interaction parameter values (beta) varied with variation of solvent composition. Besides the strong electrostatic attraction between the oppositely charged surfactant NPES-CTAB mixture, the interaction between NPES and SDS also showed far more deviation from ideal behavior than that of TX100 and AOT. The reason for the synergism is also discussed and the results show that an ionic and a nonionic surfactant character existed concurrently in NPES due to the combination of a sulfate group and polyoxyethylene as a hydrophilic moiety. Zeta potential and diffusion coefficient measurements of micelles confirmed the synergistic interaction between the binary surfactants.  相似文献   

18.
The phase equilibria of surfactant aqueous mixtures, hexadecyltrimethylammonium bromide and sodium dodecyl sulfate, have been studied by polarizing microscopy, quasielastic light scattering, conductivity, potentiometric, electrophoretic, and surface tension measurements. Adsorption at the air/solution interface, association and precipitation in bulk solution strongly depended on the molar ratio and the concentration of surfactants. Catanionic vesicles coexisted with crystalline catanionic salts in a broad concentration range. The relative proportions of crystallites and vesicles varied according to the concentration and the molar ratio of the surfactants. The solid crystalline phase was progressively converted to catanionic vesicles with increasing surfactant molar ratio. At the highest excess of one of the surfactants transition from catanionic vesicles to mixed micelles occurred. The formation and stability of different phases are discussed in terms of surfactant molecular packing constraints and electrostatic interactions in the headgroup region. Surfactant tail-length asymmetry and the change of electrostatic interactions in the headgroup region from attractive to repulsive are governing factors for the transition from planar to curved bilayers. Received: 9 June 1998 Accepted: 18 August 1998  相似文献   

19.
Upon the addition of a short EO chain nonionic surfactant, poly(oxyethylene) dodecyl ether (C12EOn), to dilute micellar solution of sodium dodecyl sulfate (SDS) above a particular concentration, a sharp increase in viscosity occurs and a highly viscoelastic micellar solution is formed. The oscillatory-shear rheological behavior of the viscoselastic solutions can be described by the Maxwell model at low shear frequency and combined Maxwell-Rouse model at high shear frequency. This property is typical of wormlike micelles entangled to form a transient network. It is found that when C12EO4 in the mixed system is replaced by C12EO3 the micellar growth occurs more effectively. However, with the further decrease in EO chain length, phase separation occurs before a viscoelastic solution is formed. As a result, the maximum zero-shear viscosity is observed at an appropriate mixing fraction of surfactant in the SDS-C12EO3 system. We also investigated the micellar growth in the mixed surfactant systems by means of small-angle X-ray scattering (SAXS). It was found from the SAXS data that the one-dimensional growth of micelles was obtained in all the SDS-C12EOn (n=0-4) aqueous solutions. In a short EO chain C12EOn system, the micelles grow faster at a low mixing fraction of nonionic surfactant.  相似文献   

20.
The size and shape of micelles formed in aqueous mixtures of the anionic surfactant sodium dodecyl sulfate (SDS) and the nonionic sugar-based surfactant n-decyl beta-D-glucopyranoside (C(10)G) at different concentrations of added salt have been investigated with small-angle neutron and static light scattering. Rather small prolate ellipsoidal micelles form in the absence of added salt and at [NaCl] = 10 mM in D(2)O. The micelles grow considerably in length to large rods as the electrolyte concentration is raised to [NaCl] = 0.1 M. In excess of nonionic surfactant ([SDS]/[C(10)G] = 1:3) at [NaCl] = 0.1 M in D(2)O, several thousands of Angstroms long wormlike micelles are observed. Most interestingly, a conspicuously large isotope solvent effect was observed from static light scattering data according to which micelles formed at [SDS]/[C(10)G] = 1:3 and [NaCl] = 0.1 M in H(2)O are at least five times smaller than micelles formed in the corresponding samples in D(2)O.  相似文献   

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