Small-angle neutron scattering of ionic perfluoropolyether micellar solutions: role of counterions and temperature

This paper reports a small-angle neutron scattering (SANS) characterization of perfluoropolyether (PFPE) aqueous micellar solutions with lithium, sodium, cesium and diethanol ammonium salts obtained from a chlorine terminated carboxylic acid and with two perfluoroisopropoxy units in the tail (n(2)). The counterion and temperature effects on the micelle formation and micellar growth extend our previous work on ammonium and potassium salts n(2) micellar solutions. Lithium, sodium, cesium and diethanol ammonium salts are studied at 0.1 and 0.2 M surfactant concentration in the temperature interval 28-67 degrees C. SANS spectra have been analyzed by a two-shell model for the micellar form factor and a screened Coulombic plus steric repulsion potential for the structure factor in the frame of the mean spherical approximation of a multicomponent system reduced to a generalized one component macroions system (GOCM). At 28 degrees C, for all the salts, the micelles are ellipsoidal with an axial ratio that increases from 1.6 to 4.2 as the counterion volume increases. The micellar core short axis is 13 A and the shell thickness 4.0 A for the alkali micelles, and 14 and 5.1 A for the diethanol ammonium micelles. Therefore, the core short axis mainly depends on the surfactant tail length and the shell thickness on the carboxylate polar head. The bulky diethanol ammonium counterion solely influences the shell thickness. Micellar charge and average aggregation number depend on concentration, temperature and counterion. At 28 degrees C, the fractional ionization decreases vs the counterion volume (or molecular weight) increase at constant concentration for both C = 0.1 M and C = 0.2 M. The increase of the counterion volume leads also to more ellipsoidal shapes. At C = 0.2 M, at 67 degrees C, for sodium and cesium micelles the axial ratio changes significantly, leading to spherical micelles with a core radius of 15 A, lower average aggregation number, and larger fractional ionization.     

SDS对SB3-12胶束表面电荷密度的调控作用及对药物增溶的影响

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。     

Comparison of oleyl and elaidyl isomer surfactant-counterion systems in drag reduction, rheological properties and nanostructure

Compared with quaternary ammonium cationic surfactants with saturated alkyl chains, quaternary ammonium cationic surfactants with one double-bond in their alkyl chains, when mixed with appropriate counterions (in certain molar concentration ratios, ξ), can reach much lower effective drag-reduction temperatures, while maintaining the upper drag-reduction temperature limit of the corresponding saturated drag reducing surfactant solutions. No previous study has compared the effects of cis- vs. trans-unsaturated alkyl hydrocarbon tail configurations (oleyl vs. elaidyl) trimethyl ammonium chloride cationic surfactants at different counterion/surfactant concentration ratios on micellar nanostructures, (1)H NMR spectra and on rheological and drag-reduction behavior of their solutions. Since neither pure oleyl (cis-) nor elaidyl (trans-) trimethyl ammonium chloride surfactants are commercially available, they were synthesized and their 5mM solutions with NaSal counterion at concentrations of 5mM, 7.5mM and 12.5mM were studied.     

Micellar medium effects on the hydrolysis of phenyl chloroformate in ionic,zwitterionic, nonionic,and mixed micellar solutions

The spontaneous hydrolysis of phenyl chloroformate was studied in various anionic, nonionic, zwitterionic, and cationic aqueous micellar solutions, as well as in mixed anionic–nonionic micellar solutions. In all cases, an increase in the surfactant concentration results in a decrease in the reaction rate and micellar effects were quantitatively explained in terms of distribution of the substrate between water and micelles and the first‐order rate constants in the aqueous and micellar pseudophases. A comparison of the kinetic data in nonionic micellar solutions to those in anionic and zwiterionic micellar solutions makes clear that charge effects of micelles is not the only factor responsible for the variations in the reaction rate. Depletion of water in the interfacial region and its different characteristics as compared to bulk water, the presence of high ionic concentration in the Stern layer of ionic micelles, and differences in the stabilization of the initial state and the transition state by hydrophobic interactions with surfactant tails can also influence reactivity. The different deceleration of the reaction observed in the various micellar solutions studied was discussed by considering these factors. Synergism in mixed‐micellar solutions is shown through the kinetic data obtained in these media. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 445–451, 2002     

SOLUBILIZATION IN MIXED REVERSE MICELLAR SYSTEMS OF AOT/NONIONIC SURFACTANTS/n-HEPTANE

Solubilization of water and aqueous NaCl solutions in mixed reverse micellar systems of anionic surfactant AOT and nonionic surfactants in n-heptane was studied. It was found that the maximum solubilization capacity of water was higher in the presence of certain concentrations of NaCl electrolyte, and these concentrations increased with the increase of nonionic surfactant content and their EO chain length. Soluibilization capacity was enhanced by mixing AOT with nonionic surfactants. The observed phenomena were interpreted in terms of the stability of the interfacial film of reverse micellar microdroplet and the packing parameter of the surfactant that formed mixed reverse micelles.     

Mixed spherical and wormlike micelles: a contrast-matching study by small-angle neutron scattering

Small-angle neutron scattering studies were used to investigate the effect of adding an alcohol ethoxylate nonionic surfactant (d-C12E20) to aqueous solutions of a cationic surfactant, erucyl bis(hydroxyethyl) methylammonium chloride (EHAC), with and without salt (KCl). The systematic use of contrast-matching, by alternately highlighting or hiding one of the surfactants, confirms that mixed micelles are formed. In salt-free solutions, mixed spherical micelles are formed and a core-shell model combined with a Hayter-Penfold potential was used to describe the data. The core radius is dominated by the EHAC tails and the outer radius determined by the ethoxylate headgroups of the nonionic surfactant. Addition of KCl promotes micellar growth; however, results of varying the solvent contrast revealed that when the nonionic surfactant is incorporated into the wormlike structure micellar breaking is promoted. Thus, mixed wormlike micelles with shorter contour lengths compared to the pure EHAC worms are formed.     

CORRELATION BETWEEN INTERFACIAL TENSIONS AND MICELLAR STRUCTURES

It is shown that results of surface and interfacial tension measurements can be used to predict the type of micelles and of liquid crystalline phases which are formed in binary and ternary surfactant solutions. In particular it is possible to predict the position of l.c. cubic phases in ternary systems consisting of surfactant, hydrocarbon and water. Data to demonstrate the conclusions were obtained on the surfactants Alkyltrimethylammoniumbromides, Alkyldimethylaminoxides and Alkyldimethylphosphinoxides. It was found that the interfacial tension of a dilute micellar solution against a reference hydrocarbon is a most sensitive and indicative parameter for the prediction of the different structures. Large changes of the interfacial tension were observed for the three systems having the same hydrocarbon chainlength. The value of the interfacial tension directly reflects also the amount of hydrocarbon which can be solubilized in the micellar solution. Interfacial tensions larger than 1mN/m are indicative of globular micelles while interfacial tensions between 0.1 and 1 mN/m indicate the formation of rods. Values below 0.1 mN/m indicate disclike micelles or lamellar phases.

The interfacial tension depends somewhat on the kind of hydrocarbon which is used for the measurements. It is observed that for several surfactant solutions the interfacial tension passes through a shallow minimum when the chainlength of the hydrocarbon is increased from six to sixteen.     

Counterion binding on mixed anionic/cationic micelles

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.     

Selective transport of amino acids into the gas phase: driving forces for amino acid solubilization in gas-phase reverse micelles

We report a study on encapsulation of various amino acids into gas-phase sodium bis(2-ethylhexyl) sulfosuccinate (NaAOT) reverse micelles, using electrospray ionization guided-ion-beam tandem mass spectrometry. Collision-induced dissociation of mass-selected reverse micellar ions with Xe was performed to probe structures of gas-phase micellar assemblies, identify solute-surfactant interactions, and determine preferential incorporation sites of amino acids. Integration into gas-phase reverse micelles depends upon amino acid hydrophobicity and charge state. For examples, glycine and protonated amino acids (such as protonated tryptophan) are encapsulated within the micellar core via electrostatic interactions; while neutral tryptophan is adsorbed in the surfactant layer. As verified using model polar hydrophobic compounds, the hydrophobic effect and solute-interface hydrogen-bonding do not provide sufficient driving force needed for interfacial solubilization of neutral tryptophan. Neutral tryptophan, with a zwitterionic structure, is intercalated at the micellar interface between surfactant molecules through complementary effects of electrostatic interactions between tryptophan backbone and AOT polar heads, and hydrophobic interactions between tryptophan side chain and AOT alkyl tails. Protonation of tryptophan could significantly improve its incorporation capacity into gas-phase reverse micelles, and displace its incorporation site from the micellar interfacial zone to the core; protonation of glycine, on the other hand, has little effect on its encapsulation capacity. Another interesting observation is that amino acids of different isoelectric points could be selectively encapsulated into, and transported by, reverse micelles from solution to the gas phase, based upon their competition for protonation and subsequent encapsulation within the micellar core.     

Effects of ethylene glycol addition on the aggregation and micellar growth of gemini surfactants

Micellization of three didodecyl dicationic dibromide gemini surfactants with different methylene spacer lengths, 12-s-12,2Br- where s = 3-5 methylene groups, has been investigated in water-ethylene glycol, EG, mixtures with weight percentages of EG up to 50%. Subsequently, effects of the addition of the organic solvent on the micellar growth of these surfactants and on the surfactant concentration range where sphere-to-rod transitions occur were studied by means of steady-state and time-resolved fluorescence quenching and spectroscopic measurements. Results show that an increase in the weight percentage of ethylene glycol added to aqueous 12-s-12,2Br- (s = 3-5) micellar solutions causes the sphere-to-rod transition to occur at higher surfactant concentrations than in pure water. The diminution in the average aggregation number, N(agg), when wt % EG increases, provoked by the decrease in the interfacial Gibbs energy contribution to DeltaG degrees M, is the main factor responsible for this observation. The decrease in N(agg) is accompanied by a decrease in the ionic interactions and the extra packing contribution to the deformation of the surfactants tails, making formation of cylindrical micelles less favorable. Besides, an increase in the solvent content and polarity of the interfacial region does not favor formation of direct ion pairs, decreasing the tendency of micelles to grow.     

Mixed micelles of polyethylene glycol (23) lauryl ether with ionic surfactants studied by proton 1D and 2D NMR

(1)H NMR chemical shift, spin-lattice relaxation time, spin-spin relaxation time, self-diffusion coefficient, and two-dimensional nuclear Overhauser enhancement (2D NOESY) measurements have been used to study the nonionic-ionic surfactant mixed micelles. Cetyl trimethyl ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) were used as the ionic surfactants and polyethylene glycol (23) lauryl ether (Brij-35) as the nonionic surfactant. The two systems are both with varying molar ratios of CTAB/Brij-35 (C/B) and SDS/Brij-35 (S/B) ranging from 0.5 to 2, respectively, at a constant concentration of 6 mM for Brij-35 in aqueous solutions. Results give information about the relative arrangement of the surfactant molecules in the mixed micelles. In the former system, the trimethyl groups attached to the polar heads of the CTAB molecules are located between the first oxy-ethylene groups next to the hydrophobic chains of Brij-35 molecules. These oxy-ethylene groups gradually move outward from the hydrophobic core of the mixed micelle with an increase in C/B in the mixed solution. In contrast to the case of the CTAB/Triton X-100 system, the long flexible hydrophilic poly oxy-ethylene chains, which are in the exterior part of the mixed micelles, remain coiled, but looser, surrounding the hydrophobic core. There is almost no variation in conformation of the hydrophilic chains of Brij-35 molecules in the mixed micelles of the SDS/Brij-35 system as the S/B increases. The hydrophobic chains of both CTAB and SDS are co-aggregated with Brij-35, respectively, in their mixed micellar cores.     

Controlling the melting of kinetically frozen poly(butyl acrylate-b-acrylic acid) micelles via addition of surfactant

We have studied the melting of polymeric amphiphilic micelles induced by small-molecule surfactant and explained the results by experimental determination of the interfacial tension between the core of the micelles and the surfactant solutions. Poly(n-butyl acrylate-b-acrylic acid) (PBA-b-PAA) amphiphilic diblock copolymers form kinetically frozen micelles in aqueous solutions. Strong interactions with surfactants, either neutral or anionic [C12E6, C6E4, sodium dodecyl sulfate (SDS)], were revealed by critical micelle concentration (cmc) shifts in specific electrode and surface tension measurements. Since both polymer and surfactant are either neutral or bear negative charges, the attractive interactions are not due to electrostatic interactions. Light scattering, neutron scattering, and capillary electrophoresis experiments showed important structural changes in mixed PBA-b-PAA/surfactant systems. Kinetically frozen micelles of PBA-b-PAA, that are hardly perturbed by concentration, ionization, ionic strength, and temperature stresses, can be disintegrated by addition of small-molecule surfactants. The interfacial energy of the PBA in surfactant solutions was measured by drop shape analysis with h-PBA homopolymer drops immersed in small-molecule surfactant solutions. The PBA/water interfacial energy gammaPBA/H2O of 20 mN/m induces a high energy cost for the extraction of unimers from micelles so that PBA-b-PAA micelles are kinetically frozen. Small-molecule surfactants can reduce the interfacial energy gammaPBA/solution to 5 mN/m. This induces a shift of the micelle-unimer equilibrium toward unimers and leads, in some cases, to the apparent disintegration of PBA-b-PAA micelles. Before total disintegration, polymer/surfactant mixtures are dispersions of polydisperse mixed micelles. Based on core interfacial energy arguments, the disintegration of kinetically frozen polymeric micelles was interpreted by gradual fractionation of objects (polydisperse dispersion mechanism), whereas the disintegration of polymeric micelles in a thermodynamically stable state was interpreted by an exchange between a population of large polymer-rich micelles and a population of small surfactant-rich micelles (bidisperse dispersion mechanism). Finally, in our system and other systems from the literature, interfacial energy arguments could explain why the disintegration of polymer micelles is either partial or total as a function of the surfactant type and concentration and the hydrophobic block molar mass of the polymer.     

Appearance of pure fluorocarbon micelles surveyed by fluorescence quenching of amphiphilic quinoline derivatives in fluorocarbon and hydrocarbon surfactant mixtures

A halide-sensitive fluorescence probe was utilized to evaluate the miscibility of fluorocarbon and hydrocarbon surfactants in aqueous micellar systems. The fluorescence of 6-methoxy-N-1,1,2,2-tetrahydroheptadecafluorodecylquinolinium chloride, FC10MQ, was quenched by halide ions dissociated from the surfactant. The fluorescence in micellar solutions showed an initially rapid decay. This suggests that halide ions effectively quench FC10MQ fluorescence at the micellar surface. The subsequent slow decay corresponds to the quenching of FC10MQ fluorescence in the aqueous bulk phase by the free counterions. The Stern-Volmer plots for fluorescence quenching gave a distinct break at the critical micelle concentration of the cationic surfactants. The abrupt increase in fluorescence quenching is attributed to the solubilization of the probe in the micelles. The fluorescence quenching behavior provides direct information about the immiscibility of fluorocarbon and hydrocarbon species in micelles, and the results indicate that almost pure fluorocarbon micelles appear in surfactants mixtures.     

Interfacial properties of branch-tailed fluorinated surfactants yielding a water/supercritical CO2 microemulsion

We have examined the interfacial properties of several fluorinated surfactants in a water/CO2 mixture with a pendant drop tensiometer and revealed the relationships between the interfacial properties, the surfactant structure, and the microemulsifying power. We employed the following Aerosol-OT analogue surfactants that have two fluorinated tails: bis(1H,1H,5H-octafluoropentyl)-2-sulfosuccinate (di-HCF4), sodium bis(1H,1H,9H-hexadecafluorononyl)-2-sulfosuccinate (di-HCF8), sodium bis(1H,1H,2H,2H-heptadecafluorodecyl)-2-sulfosuccinate (8FS(EO)2), and sodium bis((1H,1H,2H,2H-heptadecafluorodecyl)-oxyethylene)-2-sulfosuccinate (8FS(EO)4). To discuss the effect of the fluorocarbon/hydrocarbon ratio in single surfactant molecules, water/CO2 interfacial tension (IFT) of a hybrid surfactant with one fluorocarbon and one hydrocarbon tail, that of a surfactant with a single fluorinated tail, and that of a hydrocarbon surfactant, Aerosol-OT (AOT), were examined. The hybrid surfactant employed was sodium 1-oxo-1-[4-(tridecafluorohexyl)phenyl]-2-hexanesulfonate (FC6-HC4), and the single-tailed surfactant was perfluoropolyether ammonium carboxylate (PFPECOONH4, CF3CF2(CF2OCF(CF3))4COONH4). All of the fluorinated AOT analogue surfactants exhibited an excellent level of activity at the water/CO2 interface compared with other fluorinated surfactants and AOT. With a larger hydrocarbon chain number in the CO2-philic tails (i.e., from 0 to 2), the IFT of the AOT analogue surfactants was increased. The area occupied by one surfactant molecule at the water/CO2 interface, A, and the critical microemulsion concentration, cmicroc, were determined and used to examine the water-to-surfactant molar ratio within a reversed micelle, W0c, of the surfactants. The surfactants that form W/scCO2 microemulsions with a large W0c were found to lower the interfacial tension efficiently irrespective of increases in temperature. To achieve the most desirable W0C, the surfactant needs not only a high CO2-philicity of the tails but also a high Krafft point, properties which induce a low hydrophilic/CO2-philic balance.     

Nature of cationic poly(propylenimine) dendrimers in aqueous solutions as studied using versatile indicator dyes

Aqueous solutions of four cationic poly(propylenimine) low-generation dendrimers of different architecture and hydrophobicity have been examined as media for acid-base reactions of indicator dyes. The cationic dendrimers in solution can be considered as oligomers of cationic polyelectrolytes, or surfactant-like species, able to form micelles through self-association or sometimes even as unimolecular micelles. The dendrimers influence the ionization constants, tautomeric equilibria, and absorption/emission/excitation spectra of indicator dyes. The p K a values of the majority of the indicator dyes decrease in dendrimer solutions, often by 1-2 p K a units, similar to effects registered in micellar solutions of cationic surfactants. Analogously, the shifts of absorption band maxima indicate that the microenvironments of the dyes bound to the dendrimers are less polar than in water. However, some spectral effects denote the specificity of the dendrimers. The greatest difference between the dendrimers and spherical surfactant micelles is revealed by kinetic processes, especially of bromophenol blue alkaline fading in a dendrimer solution but not in a micellar surfactant solution. Within the dendrimer series, the most significant differences were observed for substances possessing n-dodecyl tails on the one hand and those without such hydrophobic portions on the other. For the last-named, the decrease in p K a's of indicators, band shifts of their anions, and in particular displacement of tautomeric equilibria compared with aqueous solutions are much smaller than for more hydrophobic dendrimers.     

Prediction of conformational characteristics and micellar solution properties of fluorocarbon surfactants

A molecular-thermodynamic theory is developed to model the micellization of fluorocarbon surfactants in aqueous solutions, by combining a molecular model that evaluates the free energy of micellization of fluorocarbon surfactant micelles with a previously developed thermodynamic framework describing the free energy of the micellar solution. In the molecular model of micellization developed, a single-chain mean-field theory is combined with an appropriate rotational isomeric state model of fluorocarbon chains to describe the packing of the fluorocarbon surfactant tails inside the micelle core. Utilizing this single-chain mean-field theory, the packing free energies of fluorocarbon surfactants are evaluated and compared with those of their hydrocarbon analogues. We find that the greater rigidity of the fluorocarbon chain promotes its packing in micellar aggregates of low curvatures, such as bilayers. In addition, the mean-field approach is utilized to predict the average conformational characteristics (specifically, the bond order parameters) of fluorocarbon and hydrocarbon surfactant tails within the micelle core, and the predictions are found to agree well with the available experimental results. The electrostatic effects in fluorocarbon ionic surfactant micelles are modeled by allowing for counterion binding onto the charged micelle surface, which accounts explicitly for the effect of the counterion type on the micellar solution properties. In addition, a theoretical formulation is developed to evaluate the free energy of micellization and the size distribution of finite disklike micelles, which often form in the case of fluorocarbon surfactants. We find that, compared to their hydrocarbon analogues, fluorocarbon surfactants exhibit a greater tendency to form cylindrical or disklike micelles, as a result of their larger molecular volume as well as due to the greater conformational rigidity of the fluorocarbon tails. The molecular-thermodynamic theory developed is then applied to several ionic fluorocarbon surfactant-electrolyte systems, including perfluoroalkanoates and perfluorosulfonates with added LiCl or NH(4)Cl, and various micellar solution properties, including critical micelle concentrations (cmc's), optimal micelle shapes, and average micelle aggregation numbers, are predicted. The predicted micellar solution properties agree reasonably well with the available experimental results.     

Importance of micellar kinetics in relation to technological processes

The association of many classes of surface-active molecules into micellar aggregates is a well-known phenomenon. Micelles are in dynamic equilibrium, constantly disintegrating and reforming. This relaxation process is characterized by the slow micellar relaxation time constant, tau(2), which is directly related to the micellar stability. Theories of the kinetics of micelle formation and disintegration have been discussed to identify the gaps in our complete understanding of this kinetic process. The micellar stability of sodium dodecyl sulfate micelles has been shown to significantly influence technological processes involving a rapid increase in interfacial area, such as foaming, wetting, emulsification, solubilization, and detergency. First, the available monomers adsorb onto the freshly created interface. Then, additional monomers must be provided by the breakup of micelles. Especially when the free monomer concentration is low, which is the case for many nonionic surfactant solutions, the micellar breakup time is a rate-limiting step in the supply of monomers. 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 showed that the ionic surfactants such as SDS exhibit slow relaxation times in the range from milliseconds to seconds, whereas nonionic surfactants exhibit slow relaxation times in the range from 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 times showed a direct correlation with dynamic surface tension and foaming experiments. In conclusion, relaxation time data of surfactant solutions correlate with the dynamic properties of the micellar solutions. Moreover, the results suggest that appropriate micelles with specific stability or tau(2) can be designed by controlling the surfactant structure, concentration, and physicochemical conditions (e.g., salt concentration, temperature, and pressure). One can also tailor micelles by mixing anionic/cationic or ionic/nonionic surfactants for a desired stability to control various technological processes.     

Atomistic structure of a micelle in solution determined by wide Q-range neutron diffraction

The accepted picture of the structure of a micelle in solution arises from the idea that the surfactant molecules self-assemble into a spherical aggregate, driven by the conflicting affinity of their head and tail groups with the solvent. It is also assumed that the micelle's size and shape can be explained by simple arguments involving volumetric packing parameters and electrostatic interactions. By using wide Q-range neutron diffraction measurements of H/D isotopically substituted solutions of decyltrimethylammonimum bromide (C(10)TAB) surfactants, we are able to determine the complete, atomistic structure of a micelle and its surroundings in solution. The properties of the micelle we extract are in agreement with previous experimental studies. We find that ~45 surfactant molecules aggregate to form a spherical micelle with a radius of gyration of 14.2 ? and that the larger micelles are more ellipsoidal. The surfactant tail groups are hidden away from the solvent to form a central dry hydrophobic core. This is surrounded by a disordered corona containing the surfactant headgroups, counterions, water, and some alkyl groups from the hydrophobic tails. We find a Stern layer of 0.7 bromide counterion per surfactant molecule, in which the bromide counterions maintain their hydration shells. The atomistic resolution of this technique provides us with unprecedented detail of the physicochemical properties of the micelle in its solvent.     

The microstructure of di-alkyl chain cationic/nonionic surfactant mixtures: observation of coexisting lamellar and micellar phases and depletion induced phase separation

The evolution of the microstructure and composition occurring in the aqueous solutions of di-alkyl chain cationic/nonionic surfactant mixtures has been studied in detail using small angle neutron scattering, SANS. For all the systems studied we observe an evolution from a predominantly lamellar phase, for solutions rich in di-alkyl chain cationic surfactant, to mixed cationic/nonionic micelles, for solutions rich in the nonionic surfactant. At intermediate solution compositions there is a region of coexistence of lamellar and micellar phases, where the relative amounts change with solution composition. A number of different di-alkyl chain cationic surfactants, DHDAB, 2HT, DHTAC, DHTA methyl sulfate, and DISDA methyl sulfate, and nonionic surfactants, C12E12 and C12E23, are investigated. For these systems the differences in phase behavior is discussed, and for the mixture DHDAB/C12E12 a direct comparison with theoretical predictions of phase behavior is made. It is shown that the phase separation that can occur in these mixed systems is induced by a depletion force arising from the micellar component, and that the size and volume fraction of the micelles are critical factors.