Spontaneous vesicle formation of single chain and double chain cationic surfactant mixtures

The concentration vs composition diagram of aggregate formation of the dodecyltrimethylammonium bromide (DTAB) and didodecyldimethylammonium bromide (DDAB) mixture in aqueous solution at rather dilute region was constructed by analyzing the surface tension, turbidity, and electrical conductivity data and inspected by cryo-TEM images and dynamic light scattering data. Although the aqueous solution of DTAB forms only micelles, the transition from monomer to small aggregates and then to vesicle was found at 0.1 < X2 相似文献   

Salt-induced vesicle formation from single anionic surfactant SDBS and its mixture with LSB in aqueous solution

Vesicles can be formed spontaneously in aqueous solution of a single anionic surfactant sodium dodecyl benzenesulfonate (SDBS) just under the inducement of salt, which makes the formation of vesicle much easier and simpler. The existence of vesicles was demonstrated by TEM image using the negative-staining method. The mechanism of the formation may be attributed to the compression of salt on the electric bilayer of the surfactant headgroups, which alters the packing parameter of the surfactant. The addition of the zwitterionic surfactant lauryl sulfonate betaine (LSB) makes the vesicles more stable, expands the range of formation and vesicle size, and reduces the polydispersity of the vesicles. The vesicle region was presented in a pseudoternary diagram of SDBS/LSB/brine. The variations of vesicle size with the salinity and mixing ratios, as well as the surfactant concentration, were determined using the dynamic light scattering method. It is found that the vesicle size is independent of the surfactant concentration but subject to the salinity and the mixing ratio of the two surfactants.     

Micelle-vesicle transitions in catanionic mixtures of SDS/DTAB induced by salt,temperature, and selective solvents: a dissipative particle dynamics simulation study

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.     

Surface tension and aggregation properties of novel cationic gemini surfactants with diethylammonium headgroups and a diamido spacer

A series of novel cationic gemini surfactants with diethylammonium headgroups and a diamido spacer were synthesized, and their surface and bulk properties were investigated by surface tension, electrical conductivity, fluorescence, viscosity, dynamic light scattering (DLS), and transmission electron microscopy (TEM) measurements. An interesting phenomenon, that is, the obvious decline in surface tension upon increasing concentration above the critical micelle concentration (cmc), was found in these gemini surfactant solutions, and two explanations were proposed. This surface tension behavior could be explained by the rapid increase in the counterion activity in the bulk phase or the continued filling of the interface with increasing surfactant concentration above the cmc. More interestingly, not only vesicles but also the surfactant-concentration-induced vesicle to larger aggregate (spongelike aggregate) transition and the salt-induced vesicle and spongelike aggregate to micelle transition were found in the aqueous solutions of these gemini surfactants. The spongelike aggregate that is first reported in the cationic gemini surfactant-water binary system is probably caused by the adhesion and fusion of vesicles at high surfactant concentration.     

Spontaneous vesicle formation of mixtures of double-chain cationic surfactants with a different counterion

Aggregate formation of a didodecyldimethylammonium bromide (DDAB) and didodecyldimethylammonium chloride (DDAC) mixture in aqueous solution was investigated. The concentration vs composition diagram of aggregate formation was constructed by analyzing the surface tension, turbidity, and electrical conductivity data. The cryogenic transmission electron microscopy was applied to several representative points in the diagram and provided information of the morphology of aggregates. The sequence of monomer (m) - m + small aggregate (A) - m + A + vesicle (V) - m + V was concluded with increasing total concentration of surfactants at all mixing ratios. The compositions of counterions in A and V were estimated on the basis of thermodynamic consideration and examined from the viewpoint of asymmetry of constituents and uneven distribution between outer and inner monolayers of a vesicle bilayer. Vesicle surfaces were suggested to abound in chloride ions compared to bulk solution, which is opposite to spherical micelle surfaces.     

Micellization of Cetylpyridinium Chloride Using Conductometric Technique

Abstract

Conductometric technique has been used to investigate the equilibrium properties of cetylpyridinium chloride (CPC) in the presence of a series of aliphatic alcohols. The dependence of conductivity of surfactant solution in the presence of particular amount of alcohol has been studied. According to the experimental results, ethanol cause to decrease the dielectric constant and conductivity of micellar solution. Alcohols with longer chain may change the conductivity of solution depend on concentration of surfactant. At low concentration of CPC near critical micelle concentration (cmc) region, the minimum value of conductivity can be observed. This minimum value can be controiled by decreasing of free monomer concentration and also increasing degree of dissociation of micelle because of penetration of alcohols in micellar core. Using Conductometric technique cmc and α (degree of dissociation of counterion) of CPC were evaluated. The micelle formation of CPC has been considered in ethylene glycol (E.G)/ water and glycerol/water mixtures. It has been shown, the logarithm of cmc is directly depended on the ratio of E.G/water or glycerol/water.     

Salinity Controlled Vesicle Formation and Growth in Aqueous Mixture of Aerosol OT/Triton X‐100

Mixed vesicles can be formed spontaneously from aqueous mixture of the double‐tailed anionic surfactant sodium bis(2‐ethylhexyl) sulfosuccinate (AOT) and the nonionic surfactant octylphenoxypolyethoxyethanol (Triton X‐100) under the inducement of salt, the formation mechanism of which should be attributed to the compression of salt on the electric bilayers of the head groups. The stability and the polydispersity of the vesicles are superior to single‐component AOT vesicles, which can be proved by the TEM image and visual observation. The vesicle region was presented in a pseudo‐ternary diagram of AOT/TX‐100/brine. The size of the vesicle was measured using dynamic light scattering. It is found that the vesicle size increases with the salinity but decreases with the content of TX‐100 in the mixture at the same salinity. Especially, the vesicle size is independent of the surfactant concentration at fixed salinity.     

Vesicles Formation Induced by Layered Double Hydroxides in Mixture of Lauryl Sulfonate Betaine and Sodium Dodecyl Benzenesulfonate

This paper reports that structurally positively charged layered double hydroxides (LDHs) nanoparticles induce the vesicle formation in a mixture of a zwitterionic surfactant, lauryl sulfonate betaine (LSB), and an anionic surfactant, sodium dodecyl benzenesulfonate (SDBS). The existence of vesicles was demonstrated by negative‐staining (NS‐TEM) and freeze‐fracture (FF‐TEM) transmission electron microscopy and confocal laser scanning microscopy (CLSM). The size of vesicles increased with the increase of volume ratio (Q) of Mg₃Al‐LDHs sol to the SDBS/LSB solution. A new composite of LDHs nanoparticles encapsulated in vesicles was formed. A possible mechanism of LDHs‐induced vesicle formation was suggested. The positive charged LDHs surface attracted negatively charged micelles or free amphiphilic molecules, which facilitated their aggregation into a bilayer membrane. The bilayer membranes could be closed to form vesicles that have LDHs particles encapsulated. It was also found that an adsorbed compound layer of LSB and SDBS micelles or molecules on the LDHs surface played a key role in the vesicle formation.     

Structural and morphological transition of long-chain phospholipid vesicles induced by mixing with short-chain phospholipid

Effects of a short-chain phospholipid, dihexanoylphosphatidylcholine (DHPC), on the structure and morphology of membrane assemblies of a long-chain phospholipid, dimyristoylphosphatidylcholine (DMPC), were examined by fluorescence spectroscopy, differential scanning calorimetry (DSC), and cryogenic transmission electron microscopy (cryo-TEM). It was found by fluorescence measurements that DHPC affects on the gel and liquid crystalline state of DMPC vesicle membranes in different ways. Further, the result of DSC suggested that, along the transition process from DMPC vesicle to DMPC–DHPC mixed micelle, there are at least three different concentration regions which are characterized by the individual variation pattern of the transition temperature and enthalpy change. The cryo-TEM micrographs demonstrated the formation of thread-like assemblies in the second region and the coexistence of the assemblies and spherical micelles in the third region. Thus, it was concluded that the structural transition from DMPC vesicle to DMPC–DHPC mixed micelle could occur in a stepwise manner through the formation of the thread-like assembly, which cannot be described by the three-stage model of vesicle to micelle transition.     

Micelle‐to‐vesicle transition induced by oligonucleotide in SDS/DEAB mixed system with a net negative charge

Sodium dodecyl sulfate (SDS)/dodecyl triethyl ammonium bromide (DEAB) mixed micelles (with SDS in excess) can transform to vesicles only when the temperature is higher than a critical value. In this study, we report for the first time that oligonucleotide can decrease the critical temperature to a much lower value and, hence, induce micelle‐to‐vesicle transition. The facilitation efficiency of oligonucleotide on vesicle formation is closely dependent on its size and base composition. Moreover, the SDS/DEAB/oligonucleotide vesicles are negatively charged and the hydrophobic interaction between oligonucleotide and SDS/DEAB mixed micelles is the driving force. As, so far, the report about the facilitation effect of oligonucleotide and DNA on vesicle formation is very limited, this study may provide some helpful information for the application of DNA/amphiphile system. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7491–7504, 2008     

Aggregation phenomena on the ternary ionic-nonionic surfactant system: didodecyldimethylammonium bromide/octyl-beta-D-glucopyranoside/water. Mixed microaggregates, vesicles, and micelles

The formation of a variety of mixed colloidal aggregates has been investigated on a ternary ionic-nonionic system constituted by (i) a double-chain cationic surfactant with a 12-carbon atom hydrophobic tail, didodecyldimethylammonium bromide (di-C(12)DMAB), (ii) a nonionic single-chain surfactant, octyl-beta-D-glucopyranoside (OBG), and (iii) water. The study has been carried out by means of conductivity, zeta-potential, transmission electron microscopy (TEM), and cryogenic transmission electron microscopy (cryo-TEM) experiments on the highly diluted, very diluted, and moderately diluted regions. The formation of mixed microaggregates, prior to the appearance of mixed vesicles, has been undoubtly confirmed by conductivity, TEM, and zeta-potential results. The concentrations at which these mixed colloidal aggregates form, i.e., the mixed critical microaggregate concentration (CAC), the mixed critical vesicle concentration (CVC), and the mixed critical micelle concentration (CMC), have been determined from conductivity data, while the zeta-potential experiments allow for the characterization of the aggregate/solution interface. The shape and size of the microaggregates and vesicles have been evaluated from TEM and cryo-TEM micrographs, respectively. All of the experimental evidence has been also analyzed in terms of the theoretical packing parameter, P.     

盐引发阴离子/非离子表面活性剂复配体系中囊泡自发形成

在无盐时, 阴离子表面活性剂十二烷基苯磺酸钠(SDBS)与非离子表面活性剂壬基酚聚氧乙烯(10)醚(TX-100)的复配体系中只有混合胶束存在, 而盐的加入即可以引发体系中囊泡的自发形成, 这使得囊泡的形成变得更加简单. 引发机理可以归因于盐对离子表面活性剂的极性头双电层的压缩作用, 减少了极性头的面积, 加上非离子表面活性剂的参与使得堆积参数P增加, 导致了半径更大的聚集体的形成. 制作了SDBS/TX-100/盐水拟三元相图, 通过目测和表面张力的变化确定了囊泡形成的带状区域, 并用负染色电镜(TEM)对囊泡进行了表征, 同时测定了盐度以及相同盐度下表面活性剂浓度对囊泡粒径的影响, 发现囊泡的粒径随着盐度的增加而增加, 而在同一盐度下, 囊泡的粒径基本不受表面活性剂浓度的影响.     

Influence of the preparation route on the supramolecular organization of lipids in a vesicular system

A confocal fluorescence microscopy-based assay was used for studying the influence of the preparation route on the supramolecular organization of lipids in a vesicular system. In this work, vesicles composed of cholesterol and CTAB (1/1 mol %) or cholesterol and DOPC (2/8 mol %) and incorporating two membrane dyes were prepared by either a compressed fluid (CF)-based method (DELOS-susp) or a conventional film hydration procedure. They were subsequently immobilized and imaged individually using a confocal fluorescence microscope. Two integrated fluorescence intensities, I(dye1) and I(dye2), were assigned to each tracked vesicle, and their ratio, I(dye1)/I(dye2), was used for quantifying the degree of membrane inhomogeneity between individual vesicles within each sample. A distribution of I(dye1)/I(dye2) values was obtained for all the studied vesicular systems, indicating intrasample heterogeneity. The degree of inhomogeneity (DI) was similar for Chol/DOPC vesicles prepared by both procedures. In contrast, DI was more than double for the hydration method compared to the CF-based method in the case of Chol/CTAB vesicles, which can suffer from lipid demixing during film formation. These findings reveal a more homogeneous vesicle formation path by CFs, which warranted good homogeneity of the vesicular system, independently of the lipid mixture used.     

Phase Behavior, Structure, and Physical Properties of the Quaternary System Tetradecyldimethylamine Oxide, HCl, 1-Hexanol, and Water

The phase diagram of the ternary surfactant system tetradecyldimethylamine oxide (TDMAO)/HCl/1-hexanol/water shows with increasing cosurfactant concentration an L(1) phase, two L(alpha) phases (a vesicle phase L(alpha1) and a stacked bilayer phase L(alphah)), and an L(3) phase, which are separated by the corresponding two-phase regions L(1)/L(alpha) and L(alpha)/L(3). In this investigation, the system was studied where some of the TDMAO was substituted by the protonated TDMAO. Under these conditions, one finds for constant surfactant concentration of 100 mM TDMAO a micellar L(1) phase, an L(alpha1) phase (consisting of multilamellar vesicles), and an interesting isotropic L(1)(*) phase in the middle of the L(1)/L(alpha) two-phase region. The L(1)(*) phase exists at intermediate degrees of charging of 30-60% and for 40-120 mM TDMAO and 70-140 mM hexanol concentration. At surfactant concentrations less than 80 mM the L(1)(*)-phase borders directly on the L(1) phase. The phase transition between the L(1) phase and the L(1)(*) phase was detected by electric conductivity and rheological measurements. The conductivity values show a sharp drop at the L(1)/L(1)(*) transition, and the zero shear viscosity of the L(1)(*) phase is much lower than in L(1) phase. The form and size of the aggregates in L(1)(*) were detected with FF-TEM and SANS. This phase contains small unilamellar vesicles (SUV) of about 10 nm and some large multilamellar vesicles with diameters up to 500 nm. The system exhibits another peculiarity. For 100 mM surfactant, the clear L(alpha1)-phase exists only at chargings below 30%. With oscillating rheological measurements a parallel development of the storage modulus G' and the loss modulus G" was observed. Both moduli are frequency independent and the system possesses a yield stress. The storage modulus is a magnitude larger than the loss modulus. Copyright 2000 Academic Press.     

温度调控表面活性剂溶液有序结构转变研究新进展

总结了近年来在温度调控表面活性剂有序结构转变研究方面的新进展. 主要介绍了囊泡的相转变, 温度诱导的胶束/囊泡转化, 离子表面活性剂胶束体系中的浊点现象, 温度控制的囊泡聚集以及温度诱导液晶相的形成与转化等五个方面的相关工作.     

Unique incorporation behavior of amino acid-type surfactant into phospholipid vesicle membrane

The incorporation behavior of some anionic surfactants, including amino acid-type surfactants, on phospholipid vesicles was investigated. This was done by measuring the release of a vesicle-entrapped fluorescence probe and the scattered light intensities of vesicle particles in the surfactant solution as a function of surfactant concentration and time. Sodium dodecyl sulfate, sodium dodecanesulfonate, sodium dodecanoyl sarcosinate, and sodium dodecanoyl glutamate were employed in this study. All surfactants ruptured the phospholipid vesicle at around each critical micelle concentration by mixed micelle formation with phospholipid. While leakage of the fluorescence probe took place at a very low concentration in the sulfate- or sulfonate-type surfactant systems, it occurred at the concentration just below the CMC in the amino acid-type surfactant systems. Kinetic analysis of the release of the probe from the vesicles showed that the former surfactants adsorbed independently and homogeneously onto the phospholipid vesicles, while the latter surfactants were cooperatively incorporated.     

Vesicle-micelle transition in aqueous mixtures of the cationic dioctadecyldimethylammonium and octadecyltrimethylammonium bromide surfactants

The vesicle-micelle transition in aqueous mixtures of dioctadecyldimethylammonium and octadecyltrimethylammonium bromide (DODAB and C(18)TAB) cationic surfactants, having respectively double and single chain, was investigated by differential scanning calorimetry (DSC), steady-state fluorescence, dynamic light scattering (DLS) and surface tension. The experiments performed at constant total surfactant concentration, up to 1.0 mM, reveal that these homologous surfactants mix together to form mixed vesicles and/or micelles, depending on the relative amount of the surfactants. The melting temperature T(m) of the mixed DODAB-C(18)TAB vesicles is larger than that for the neat DODAB in water owing to the incorporation of C(18)TAB in the vesicle bilayer. The surface tension decreases sigmoidally with C(18)TAB concentration and the inflection point lies around x(DODAB) approximately 0.4, indicating the onset of micelle formation owing to saturation of DODAB vesicles by C(18)TAB molecules. When x(DODAB)>0.5 C(18)TAB molecules are mainly solubilised by the vesicles, but when x(DODAB)<0.25 micelles are dominant. Fluorescence data of the Nile Red probe incorporated in the system at different surfactant molar fractions indicate the formation of micelle and vesicle structures. These structures have apparent hydrodynamic radius R(H) of about 180 and 500-800 nm, respectively, as obtained by DLS measurements.     

Adsorption, association and precipitation in hexadecyltrimethylammonium bromide/sodium dodecyl sulfate mixtures

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     

Self-assembly of mixtures of block copolymers of poly(styrene-b-acrylic acid) with random copolymers of poly(styrene-co-methacrylic acid)

The effects of the addition of random copolymers of poly(styrene-co-methacrylic acid) [P(S-co-MAA)] on the self-assembly of block copolymers of poly(styrene-b-acrylic acid) (PS-b-PAA) are described. The effects of variation of five factors, including the MAA content, the weight fraction and molar mass of the P(S-co-MAA), the initial concentration of the mixture, and the length of the PAA segment in the block copolymer, were investigated. With increasing MAA content, the localization of the random copolymer in the aggregate changed from the core to the interface, which led to a morphological transition from spheres to vesicles. Vesicles, mixtures of vesicles and large spheres, and large spheres alone were formed with increasing weight fraction of the random copolymer. When the molar mass of the random copolymer was high, both rods and vesicles were observed at low water contents; otherwise, only vesicles were observed. The vesicle size increased (from 100 to 140 nm) with increasing initial polymer concentration, whereas the vesicle membrane thickness remained constant. The size of the vesicles prepared from the mixtures increased with water content but decreased with the length of PAA in the diblock.     

Temperature-induced reversible morphological changes of polystyrene-block-poly(ethylene oxide) micelles in solution

Temperature-induced reversible morphological changes of polystyrene-block-poly(ethylene oxide) micelles with degrees of polymerization of 962 for the PS and 227 for the PEO blocks (PS962-b-PEO227) in N,N-dimethylformamide (DMF)/water, in which water is a selective solvent for the PEO block, were observed. For a system with 0.2 wt % copolymer concentration and 4.5 wt % water concentration in DMF/water, the micelle morphology observed in transmission electron microscopy changed from vesicles at room temperature to worm-like cylinders and then to spheres with increasing temperature. Mixed morphologies were also formed in the intermediate temperature regions. Cooling the system back to room temperature regenerated the vesicle morphology, indicating that the morphological changes were reversible. No hysteresis was observed in the morphological changes during heating and cooling. Dynamic light scattering revealed that the hydrodynamic radius of the micelles decreased with increasing temperature. Combined static and dynamic light scattering results supported the change in morphology with temperature. The critical micellization temperatures and critical morphological transition temperatures were determined by turbidity measurements and were found to be dependent on the copolymer and water concentrations in the DMF/water system. The morphological changes were only possible if the water concentration in the DMF/water system was low, or else the mobility of the PS blocks would be severely restricted. The driving force for these morphological changes was understood to be mainly a reduction in the free energy of the corona and a minor reduction in the free energy of the interface. Morphological observations at different time periods of isothermal experiments indicated that in the pathway from one equilibrium morphology to another, large compound micelles formed as an intermediate or metastable stage.