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1.
The solubility of a water-insoluble dye, Sudan Red B, in aqueous sodium halide solutions of tetradecyl-, cetyl-, and stearyltrimethylammonium halides has been measured at different surfactant and salt concentrations, and the dependence of solubilization properties on alkyl chain length has been discussed with reference to the micelle size and shape. At low ionic strengths where only spherical micelles exist, the solubilization power of micellar surfactant slightly increases with increasing the ionic strength, but it sharply increases at high ionic strengths above the threshold value of sphere-rod transition. However, the solubilization power becomes independent of the ionic strength, if their rodlike micelles are sufficiently long. The solubilization capacity increases linearly with increasing the molecular weight, almost independent of counterion species, but the rod-like micelle has a higher solubilization capacity than the spherical micelle. The solubilization capacity is larger for a surfactant with longer alkyl chain, indicating that the dye is solubilized more readily in a larger hydrophobic core. The solubilized dye is situated in a rodlike micelle of alkyltrimethylammonium halides, on average, 4.5–7.5 nm apart from each other.  相似文献   

2.
We report measurements of self aggregation in aqueous solution of an ionic liquid (IL), didecyl-dimethylammonium nitrate ([DDA][NO(3)]) and a surfactant hexadecyl-trimethylammonium bromide (CTAB) and of mixtures of these two salts. The electrical conductivity and dynamic light scattering (DLS) measurements were used for the characterization of the aggregation process. The conductivity measurements were performed at three temperatures. The critical micelle concentration (CMC) was determined at different temperatures and at different ratio of two salts. The effect of IL on the micellization of CTAB has been discussed. Our results suggest that organized structures formed by CTAB and [DDA][NO(3)] self assembly in domains of several hundred nanometers size. The micellar solubility of the salicylic acid in mixed salt aqueous solutions was determined to probe the physical properties of these assemblies. We have observed, that the micellar solubility enhancement was only slightly influenced by the nature of micelles present in aqueous solution. This proves that salicylic acid solubilization is enthalpy driven.  相似文献   

3.
The interaction of bile salts with model membranes composed of soybean phosphatidylcholine (SPC) and synthetic 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) was investigated using high sensitivity isothermal titration calorimetry (ITC). The partitioning and incorporation of the bile salts sodium cholate (NaC) and sodium deoxycholate (NaDC) from an aqueous phase (pure water or 0.1 M NaCl) into fluid bilayer vesicles was studied as a function of temperature and ionic strength. The thermodynamic parameters of partitioning were determined with a model taking electrostatic interactions into account. In addition, the solubilization of SPC and POPC vesicles with NaC and NaDC as a function of temperature was also studied by ITC and the phase diagrams for the vesicle to micelle transition at two different temperatures were established. Unsaturated phospholipids require higher amounts of detergent to be transformed into micelles compared to saturated phospholipids. In addition, the width of the coexistence region of mixed micelles and mixed vesicles is larger for phosphatidylcholines with unsaturated chains. A comparison of NaDC with NaC shows the higher solubilization effectiveness of NaDC in agreement with its lower cmc. Furthermore, increasing the ionic strength decreases the amount of bile salt necessary for the formation of mixed micelles, which is also expected from the decrease of the cmc with ionic strength due to the shielding of the charges of the bile salts.  相似文献   

4.
Herein we describe a new strategy for producing micelles with mixed coronal chains. This method involves attachment of an atom transfer radical polymerization (ATRP) initiator at the interface of a micelle and preparation of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes at the interface by a "grafting from" method. Poly(ethylene glycol)- block-polystyrene (PEG- b-PS) diblock copolymer was achieved by ATRP. After the sulfonation reaction PS blocks were partly sulfonated. In aqueous solution at low pH the sulfonated block copolymer self-assembled into micelles with PS cores and PEG coronae and sodium 4-styrenesulfonate groups were distributed at the interfaces of the micelles. An ATRP initiator consisting of a quaternary ammonium salt moiety and a 2-bromo-2-methyl propionate moiety was ion exchanged onto the interface of the micelle. ATRP of DMAEMA was initiated at the interface, and micelles with PEG/PDMAEMA mixed coronal chains were prepared by ATRP. The structures of the micelles were characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM), and zeta potential measurements. The size and morphology of the micelles were controlled by pH in aqueous solution. At high pH, PDMAEMA brushes collapse, forming nanodomains on the surface of the micelles. PDMAEMA brushes in the coronae of the micelles could be used as a template for preparation of gold nanoparticles.  相似文献   

5.
应用动力学方法研究了二苯甲酮/三乙胺引发MMA在胶束水溶液中的光敏聚合反应,结果表明表面活性剂的胶束对聚合反应具有催化作用,以离子型胶束的效果显著,可使反应的量子收率提高4—5倍。聚合速度和产物分子量随胶速浓度而增加,用紫外光谱和~1H—NMR测定了BP/TEA/MMA在离子型胶束中增溶位置,结果表明反应发生在胶束-水界面层。由于增溶于离子胶束中的单体分子具有一定取向性,提高了PMMA的立构有序性。  相似文献   

6.
The association of many classes of surface active molecules into micellar aggregates is a well-known phenomenon. Micelles are often drawn as static structures of spherical aggregates of oriented molecules. However, micelles are in dynamic equilibrium with surfactant monomers in the bulk solution constantly being exchanged with the surfactant molecules in the micelles. Additionally, the micelles themselves are continuously disintegrating and reforming. The first process is a fast relaxation process typically referred to as τ1. The latter is a slow relaxation process with relaxation time τ2. Thus, τ2 represents the entire process of the formation or disintegration of a micelle. The slow relaxation time is directly correlated with the average lifetime of a micelle, and hence the molecular packing in the micelle, which in turn relates to the stability of a micelle. It was shown earlier by Shah and coworkers that the stability of sodium dodecyl sulfate (SDS) micelles plays an important role in various technological processes involving an increase in interfacial area, such as foaming, wetting, emulsification, solubilization and detergency. The slow relaxation time of SDS micelles, as measured by pressure-jump and temperature-jump techniques was in the range of 10−4–101 s depending on the surfactant concentration. A maximum relaxation time and thus a maximum micellar stability was found at 200 mM SDS, corresponding to the least foaming, largest bubble size, longest wetting time of textile, largest emulsion droplet size and the most rapid solubilization of oil. These results are explained in terms of the flux of surfactant monomers from the bulk to the interface, which determines the dynamic surface tension. The more stable micelles lead to less monomer flux and hence to a higher dynamic surface tension. As the SDS concentration increases, the micelles become more rigid and stable as a result of the decrease in intermicellar distance. The smaller the intermicellar distance, the larger the Coulombic repulsive forces between the micelles leading to enhanced stability of micelles (presumably by increased counterion binding to the micelles). The Center for Surface Science & Engineering at the University of Florida has developed methods using stopped-flow and pressure-jump with optical detection to determine the slow relaxation time of micelles of nonionic surfactants. The results show relaxation times τ2 in the range of seconds for Triton X-100 to minutes for polyoxyethylene alkyl ethers. The slow relaxation times are much longer for nonionic surfactants than for ionic surfactants, because of the absence of ionic repulsion between the head groups. The observed relaxation time τ2 was related to dynamic surface tension and foaming experiments. A slow break-up of micelles, (i.e. a long relaxation time τ2) corresponds to a high dynamic surface tension and low foamability, whereas a fast break-up of micelles, leads to a lower dynamic surface tension and higher foamability. In conclusion, micellar stability and thus the micellar break-up time is a key factor in controlling technological processes involving a rapid increase in interfacial area, such as foaming, wetting, emulsification and oil solubilization. First, the available monomers adsorb onto the freshly created interface. Then, additional monomers must be provided by the break-up of micelles. Especially when the free monomer concentration is low, as indicated by a low CMC, the micellar break-up time is a rate limiting step in the supply of monomers, which is the case for many nonionic surfactant solutions. Therefore, relaxation time data of surfactant solutions enables us to predict the performance of a given surfactant solution. Moreover, the results suggest that one can design appropriate micelles with specific stability or τ2 by controlling the surfactant structure, concentration and physico-chemical conditions, as well as by mixing anionic/cationic or ionic/nonionic surfactants for a desired technological application.  相似文献   

7.
It is often proposed that oil solubilization in anionic and nonionic micelles proceeds by different mechanisms, with diffusion of the oil molecule thought to control the former, and the latter interfacially controlled. In order to investigate this hypothesis, the effect of aqueous phase viscosity, salt, and surfactant concentration during the solubilization process was studied. The progressive decrease in average droplet size of nearly monodisperse emulsions during solubilization in SDS or Tween 20 micellar solutions was monitored by light scattering, and the change in turbidity was measured by UV-vis spectrophotometer. The solubilization rates were analyzed using a population balance approach to calculate the mass transfer coefficients. Increasing the aqueous viscosity by adding sucrose reduced the mass transfer coefficients of n-tetradecane and n-dodecane but had a smaller effect on n-hexadecane. The strong dependence of the solubilization rate for the shorter chain length alkanes on aqueous viscosity supported a mechanism in which the oil undergoes molecular diffusion before being taken up by micelles. The dependence of the solubilization kinetics on surfactant concentration appeared consistent with this mechanism but yielded a slower micellar uptake rate than previously predicted theoretically. As the solute chain length increased in nonionic surfactant solutions, an interfacial mechanism mediated by micelles appeared to contribute substantially to the overall rate. Addition of salt only slightly increased the solubilization rate of n-hexadecane in SDS solutions and, thus, indicated a weak role of electrostatic interactions for ionic surfactants on the overall mechanism.  相似文献   

8.
 The aqueous catanionic system dodecyltrimethylammonium bromide (DTAB)–disodiumdodecanephosphonate (DSDP) was studied by potentiometry, conductivity, surface tension, spectrometry and dye solubilization. No precipitation of neutral salts was found in the entire range of compositions studied. Up to four transitions were detected. The first transition, at about 0.001 mol dm−3, was probably related to a state change in the adsorption monolayer at the air/water interface. The second, at about 0.0065 mol dm−3, was probably related to the formation of ion pairs. The third transition was the critical micelle concentration which was analyzed with the pseudophase separation model and regular solution theory. The interaction between DTAB and DSDP molecules in micelles was weaker than in other cationic–anionic surfactant mixed micelles. Large, probably rodlike, micelles formed at the fourth transition at higher surfactant concentration. No vesicles or lamellar liquid crystals were detected. The adsorbed monolayer at the air/water interface was also studied by means of regular solution theory. It was much richer in DTAB than the micelles and the intermicellar solution. The interaction between DTAB and DSDP molecules at the air/water interface was very low. The results were explained on the basis of steric factors. Received: 6 January 1999 Accepted in revised form: 13 April 1999  相似文献   

9.
Conductivity and static fluorescence measurements have been carried out at 25 degrees C to study the monomeric and micellar phases of aqueous solutions of mixed micelles constituted by a conventional cationic surfactant, dodecyltrimethylammonium bromide (D(12)TAB), and a tricyclic antidepressant drug, amitriptyline hydrochloride (AMYTP), with aggregation properties. From conductivity data, the total mixed critical micelle concentration and the dissociation degree of the mixed micelle have been obtained, while fluorescence experiments allow for the determination of the total aggregation number, and the micropolarity of micellar inside. Furthermore, the partial contribution of each surfactant to the mixed micellization process, through their critical micelle concentrations and their aggregation numbers have been determined, as well. The solubilization of the drug in the mixed micelles has been also studied through the mass action model, by determining the association constant between the micelles and the drug. From these results, the use of the micelles studied in this work as potential models for vectors of antidepressant drugs of the amitriptyline family has been discussed. The theoretical aspects of the mixed micellization process have been also analyzed.  相似文献   

10.
Dimeric and oligomeric surfactants are novel surfactants that are presently attracting considerable interest in the academic and industrial communities working on surfactants. This paper first presents a number of chemical structures that have been reported for ionic, amphoteric and nonionic dimeric and oligomeric surfactants. The following aspects of these surfactants are then successively reviewed the state of dimeric and oligomeric surfactants in aqueous solutions at concentration below the critical micellization concentration (cmc); their behavior at the air/solution and solid/solution interfaces; their solubility in water, cmc and thermodynamics of micellization; the properties of the aqueous micelles of dimeric and oligomeric surfactants (ionization degree, size, shape, micropolarity and microviscosity, solution microstructure, solution rheology, micelle dynamics, micellar solubilization, interaction between dimeric surfactants and water-soluble polymers); the mixed micellization of dimeric surfactants with various conventional surfactants; the phase behavior of dimeric surfactants and the applications of these novel surfactants.  相似文献   

11.
The solubility of n-pentane gas in aqueous solution of sodium dodecyl sulfate (SDS), SDS-0.1 wt% polyethylene oxide (PEG), SDS-0.1 wt% PEG+NaCl (0.1 mol/l), and SDS-0.1 wt% PEG+NaOH (0.1 mol/l) has been determined at 318.15 K. The concentration of SDS (m(SDS)) is up to 50 mmol/kg. The solubility increases linearly with the concentration of SDS above its critical micelle concentration (CMC) or critical aggregation concentration (CAC), indicating that micelles in the solutions solubilize the gas molecules and the solubility of n-pentane gas in the micelles is independent of the SDS concentration. It was found that the solubilization ability of micelles bound to PEG and free micelles to n-pentane gas is almost the same. The solubility of n-pentane gas in micelle phase is three magnitudes higher than that in the bulk solution. The solubilization property of SDS is changed by the addition of PEG, although the solubilizing effect of the polymer alone is not considerable. NaCl and NaOH affect the solubilization noticeably and increase the interaction strength between SDS and PEG. The standard Gibbs energies for the transfer of n-pentane gas from bulk phase to micelle phase are large negative values, indicating that the hydrocarbon gas prefers to exist in the hydrophobic interior of the micelles.  相似文献   

12.
Degradation of kinetically-stable o/w emulsions   总被引:3,自引:0,他引:3  
This article summarizes the studies on the degradation of the thermodynamically unstable o/w (nano)emulsion--a dispersion of one liquid in another, where each liquid is immiscible, or poorly miscible in the other. Emulsions are unstable exhibiting flocculation, coalescence, creaming and degradation. The physical degradation of emulsions is due to the spontaneous trend toward a minimal interfacial area between the dispersed phase and the dispersion medium. Minimizing the interfacial area is mainly achieved by two mechanisms: first coagulation possibly followed by coalescence and second by Ostwald ripening. Coalescence is often considered as the most important destabilization mechanism leading to coursing of dispersions and can be prevented by a careful choice of stabilizers. The molecular diffusion of solubilizate (Ostwald ripening), however, will continuously occur as soon as curved interfaces are present. Mass transfers in emulsion may be driven not only by differences in droplet curvatures, but also by differences in their compositions. This is observed when two or more chemically different oils are emulsified separately and the resulting emulsions are mixed. Compositional ripening involves the exchange of oil molecules between emulsion droplets with different compositions. The stability of the electrostatically- and sterically-stabilized dispersions can be controlled by the charge of the electrical double layer and the thickness of the droplet surface layer formed by non-ionic emulsifier. In spite of the similarities between electrostatically- and sterically-stabilized emulsions, there are large differences in the partitioning of molecules of ionic and non-ionic emulsifiers between the oil and water phases and the thickness of the interfacial layers at the droplet surface. The thin interfacial layer (the electrical double layer) at the surface of electrostatically stabilized droplets does not create any steric barrier for mass transfer. This may not be true for the thick interfacial layer formed by non-ionic emulsifier. The interactive sterically-stabilized oil droplets, however, can favor the transfer of materials within the intermediate agglomerates. The stability of electrosterically-stabilized emulsion is controlled by the ratio of the thickness of the non-ionic emulsifier adsorption layer (delta) to the thickness of the electrical double layer (kappa(-1)) around the oil droplets (delta/(kappa(-1))) = (deltakappa). The monomer droplet degradation can be somewhat depressed by transformation of coarse emulsions to nano-emulsion (miniemulsion) by intensive homogenization and by the addition of a surface active agent (coemulsifier) or/and a water-insoluble compound (hydrophobe). The addition of hydrophobe (hexadecane) to the dispersed phase significantly retards the rate of ripening. A long chain alcohol (coemulsifier) resulted in a marked improvement in stability, as well, which was attributed to a specific interaction between alcohol and emulsifier and to the alcohols tendency to concentrate at the o/w interface to form stronger interfacial film. The rate of ripening, according to the Lifshitz-Slyozov-Wagner (LSW) model, is directly proportional to the solubility of the dispersed phase in the dispersion medium. The increased polarity of the dispersed phase (oil) decreases the stability of the emulsion. The molar volume of solubilizate is a further parameter, which influences the stability of emulsion or the transfer of materials through the aqueous phase. The interparticle interaction is expected to favor the transfer of solubilizate located at the interfacial layer. The kinetics of solubilization of non-polar oils by ionic micelles is strongly related to the aqueous solubility of the oil phase (the diffusion approach), whilst their solubilization into non-ionic micelles can be contributed by interparticle collisions.  相似文献   

13.
A modified rotating disk apparatus was used to investigate the mass transfer of two polycyclic aromatic hydrocarbon (PAH) compounds, naphthalene and phenanthrene from a synthesized non-aqueous phase liquid (NAPL) comprised of hexadecane and the 2 PAHs into different non-ionic surfactant solutions. Major factors influencing the rate of solubilization of PAHs from a NAPL in micelles of different non-ionic surfactants were determined. As the surfactant concentration increased, the mass transfer coefficients for both PAHs from the NAPL decreased. The maximum rates of solubilization of the PAHs however increase with surfactant dose. The rate of solubilization was found to be limited by rates of desorption of mixed micelles from the NAPL and their rate of diffusion into the bulk solution phase. The influence of the surfactant molecular structure on the kinetics of the solubilization process was investigated. The results suggested that the length of the alkyl portion of the non-ionic surfactant and the micelle volume influenced the solubilization kinetics. The results of the investigation improve our ability to provide a rational basis for selecting the optimum surfactant and dose to enhance the solubilization of PAHs from NAPLs.  相似文献   

14.
Four poly((1,2-butadiene)- block-ethylene oxide) (PB-PEO) diblock copolymers were shown to self-assemble into micelles with PB cores and PEO coronas (including spheres, cylinders, and vesicles) in the ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]). All four systems exhibited the "micelle shuttle" (He, Y.; Lodge, T. P. J. Am. Chem. Soc. 2006, 128, 12666-12667), whereby PB-PEO micelles transferred, reversibly and with preservation of micelle structure, from an aqueous phase at room temperature to a hydrophobic ionic liquid at high temperature. The micelle size (both mean and distribution) depends on whether it was initially dissolved in water or in the ionic liquid, but the initial micelle structures in the ionic liquid were shown by dynamic light scattering to be preserved during the transfer and persist essentially unchanged for months in both the ionic liquid and water. The transfer was shown to be driven by the deteriorating solvent quality of water for PEO at high temperature, while the ionic liquid remains a good solvent. The transfer temperature could be tuned by adding ionic or nonionic additives to the aqueous phase to change the solvent quality of water for PEO, and by using ionic liquids with different polarity.  相似文献   

15.
The mixed electrolyte model of Shanks and Franses has been applied to estimate the critical micelle concentration, aggregation number, and counterion binding constant of sodium dodecyl sulfate in a water + 1-butanol medium from its measured conductivity data at 25 degrees C. The surface potential of the ionic micelle in this mixed solvent medium was computed by solving the nonlinear Poisson-Boltzmann equation. The standard free energy terms of micellization were also calculated. The present study confirms further the observation made in the previous studies that ionic micelles do not contribute to the ionic strength of a surfactant solution, an inference originally made by McBain and coworkers.  相似文献   

16.
The aqueous mixed system decyltrimethylammonium bromide (C(10)TAB)-hexadecyltrimethylammonium bromide (C(16)TAB) was studied by conductivity, ion-selective electrodes, surface tension, and fluorescence spectroscopy techniques. The mixture critical micelle concentration, cmc(*), aggregation number, N( *), and micelle molar conductivity, Lambda(M)(cmc), showed that the system aggregation is strongly nonideal. Both cmc(*) and N( *) results were analyzed with two different procedures: (i) the regular solution theory on mixed micelles or Rubingh's theory, and (ii) by the determination of the partial critical micelle concentration of the amphiphile component i in the presence of a constant concentration of the other amphiphile component, cmc(i)( *). The Rubingh procedure gives micelles richer in C(16)TAB than the overall mixtures, while procedure (ii) gives micelles having the same composition as in the complete surfactant mixture (alpha(C(10)TAB). Mixed micelles are larger than pure surfactant ones, with nonspherical shape. Using a literature model, the cause of the synergistic effect seems to be a reduction of the hydrocarbon/water contact at the micelle surface when mixed micelles form. Conductivity and ion-selective electrodes indicate that highly ionized premicelles form immediately before the cmc(*). The air/solution interface is strongly nonideal and much richer in C(16)TAB than the composition in the bulk. When micelles form there is a strong desorption from the air/solution interface because micelles are energetically favored when compared with the monolayer.  相似文献   

17.
18.
The micellar solubilization mechanism of curcumin by mixed surfactants of SDS and Brij35 was investigated at the molecular scale by NMR spectroscopy. Through the investigation of the micelle formation process, types and structures of mixed micelles and solubilization sites, the intrinsic factors influencing the solubilization capacity were revealed. For systems with αSDS = 0.5 and 0.2, the obtained molar solubilization ratios (MSRs) are consistent with the MSRideal values. However, for αSDS = 0.8, the solubilization capacity of curcumin is weakened compared to the MSRideal. Furthermore, only one single mixed SDS/Brij35 micelles are formed for αSDS = 0.5 and 0.2. However, for αSDS = 0.8, there are separate SDS-rich and Brij35-rich mixed micelles formed. In addition, NOESY spectra show that the interaction patterns of SDS and Brij35 in mixed micelles are similar for three systems, as are the solubilization sites of curcumin. Therefore, for αSDS = 0.5 and 0.2 with single mixed micelles formed, the solubility of curcumin depends only on the mixed micelle composition, which is almost equal to the surfactant molar ratio. Although curcumin is solubilized in both separate micelles at αSDS = 0.8, a less stable micelle structure may be responsible for the low solubility. This study provides new insights into the investigation and application of mixed micelle solubilization.  相似文献   

19.
Measurements of counterion binding in mixtures of surfactant aqueous solutions have been performed to study the structure of the anionic/cationic mixed micelle/solution interface. The mixtures studied were SDS/DDAC and STS/TDPC. The binding of chloride and sodium ions to mixed anionic/cationic micelles was measured using ion-specific electrodes. Counterion binding was found to be strongly dependent on the molar ratio of surfactants present. The mixed micelle/solution interface includes the headgroups of both surfactants and counterions of surfactant in excess. The addition of oppositely charged surfactant caused an increasing dissociation of counterions.  相似文献   

20.
Electron spin resonance spectroscopy (ESR) of the nitroxide labelled fatty acid probes (5-, 16-doxyl stearic acid) was used to monitor the micelle microviscosity of three surfactants at various concentrations in aqueous solution: sodium dodecyl sulphate (SDS), dodecyltrimethylammonium bromide (DTAB) and cetyltrimethylammonium bromide (CTAB). At low surfactant concentration, there is no micelle, the ESR probe is dissolved in water/surfactant homogeneous phase and gives his microviscosity. At higher surfactant concentration, an abrupt increase in microviscosity indicates the apparition of micelles and, the solubilization of the probes in micelles. The microviscosity of the three surfactants, in a large surfactant range, was obtained as well as the critical micelle concentration (CMC). The microviscosity increased slightly with the increase in surfactant concentration. Phosphate buffer lowered the CMC value and generally increased the microviscosity.  相似文献   

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