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The physical, electrophoretic and chromatographic properties (mean diameter, electroosmotic flow, electrophoretic mobility, elution range, efficiency, retention, and hydrophobic, shape, and chemical selectivity) of three surfactant vesicles and one phospholipid vesicle were investigated and compared to a conventional micellar pseudostationary phase comprised of sodium dodecyl sulfate (SDS). Chemical selectivity (solute-pseudostationary phase interactions) was discussed from the perspective of linear solvation energy relationship (LSER) analysis. Two of the surfactant vesicles were formulated from nonstoichiometric aqueous mixtures of oppositely charged, single-tailed surfactants, either cetyltrimethylammonium bromide (CTAB) and sodium octyl sulfate (SOS) in a 3:7 mole ratio or octyltrimethylammonium bromide (OTAB) and SDS in a 7:3 mole ratio. The remaining surfactant vesicle was comprised solely of bis(2-ethylhexyl)sodium sulfosuccinate (AOT) in 10% v/v methanol, and the phospholipid vesicle consisted of 1-palmitoyl-2-oleyl-sn-glycero-3-phosphocholine (POPC) and phosphatidyl serine (PS) in 8:2 mole ratio. The mean diameters of the vesicles were 76.3 nm (AOT), 86.9 nm (CTAB/SOS), 90.1 nm (OTAB/SDS), and 108 nm (POPC/PS). Whereas the coefficient of electroosmotic flow (10(-4) cm2 V(-1) s(-1)) varied considerably (1.72 (OTAB/SDS), 3.77 (CTAB/SOS), 4.05 (AOT), 5.26 (POPC/PS), 5.31 (SDS)), the electrophoretic mobility was fairly consistent (-3.33 to -3.87 x 10(-4) cm2 V(-1) s(-1)), except for the OTAB/SDS vesicles (-1.68). This resulted in elution ranges that were slightly to significantly larger than that observed for SDS (3.12): 3.85 (POPC/PS), 8.6 (CTAB/SOS), 10.1 (AOT), 15.2 (OTAB/SDS). Significant differences were also noted in the efficiency (using propiophenone) and hydrophobic selectivity; the plate counts were lower with the OTAB/SDS and POPC/PS vesicles than the other pseudostationary phases (< or = 75,000/m vs. > 105,000/m), and the methylene selectivity was considerably higher with the CTAB/SOS and OTAB/SDS vesicles compared to the others (ca. 3.10 vs. < or = 2.6). In terms of shape selectivity, only the CTAB/SOS vesicles were able to separate all three positional isomers of nitrotoluene with near-baseline resolution. Finally, through LSER analysis, it was determined that the cohesiveness and hydrogen bond acidity of these pseudostationary phases have the greatest effect on solute retention and selectivity.
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PMID:Characterization of surfactant and phospholipid vesicles for use as pseudostationary phases in electrokinetic chromatography. 1467 70

Titration calorimetry has been used to study the effect of the addition of two primary alcohols, 1-butanol and 1-heptanol, to the aqueous phase on the thermal effects of micellization of benzyldimethyldodecylammonium bromide (BDDAB) as well as its adsorption onto nonporous Spherosil XO15M and onto porous aluminosilicate SiAl32d22 possessing uniformly sized mesopores. A linear decrease of the critical micelle concentration (CMC) of the cationic surfactant with the additive content was inferred from the specific conductivity measurements. All adsorption and calorimetry experiments were carried out at 298 K and at a fixed alcohol content (0.01 mol kg(-1)) either in deionized water or in a 0.01 mol kg(-1) NaBr solution. Dilution calorimetry measurements allowed determination of the cumulative molar enthalpy changes and a new analysis of these data was proposed to calculate easily the enthalpy of micellization per mole of BDDAB, Delta(mic)h, and the CMC value. The alcohol addition was shown to render the micellization phenomenon more exothermic, the effect being larger as the chain length of alcohol increased. These effects were attributed to the location of alcohol molecules between the surfactant units, their hydroxyl groups close to the surfactant head-groups, in competition with the surfactant counterions. The individual isotherms of alcohol and surfactant adsorption onto XO15M and SiAl32d22 were determined. The plots of the pseudo-differential molar enthalpy of displacement, Delta(dpl)h, against the surface coverage by the surfactant cation, Theta(BDDA+), were derived from the titration calorimetry data. The formation of surface-bound aggregates was thought to be a prerequisite for alcohol coadsorption at the solid-solution interface. At least two different types of adsolubilization sites were postulated, one of the sites being the same as in micelles and the other related to the contact area between the hydrophobic surfactant tails and the equilibrium bulk solution. Coadsorption (adsolubilization) of alcohol molecules at such sites was found to increase the exothermic contribution to the enthalpy of displacement per mole of the BDDA+ adsorbed.
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PMID:Effect of alcohol addition to the aqueous phase on the thermal effects of micellization of cationic benzyldimethyldodecylammonium bromide and its adsorption onto porous and nonporous silicas. 1502 84

Silver bromide precipitate of nanoparticles was prepared by addition of silver nitrate aqueous solution to a single microemulsion system consisting of dioctyldimethylammonium bromide, n-decanol, and water in isooctane. The silver ion reacted readily with the surfactant counterion, bromide, to form the precipitate of nanoparticles, which was stabilized in the water pools. The use of the surfactant counterion as a reactant is a new approach to nanoparticle preparation in microemulsions. It is characterized by high reactivity and less dependency on the intermicellar exchange of solubilizate. The effects of the surfactant and the cosurfactant concentrations, the amount of silver nitrate, and the water to surfactant mole ratio, R, were evaluated. Increasing the surfactant concentration at fixed R and amount of silver nitrate enhanced the role of intermicellar nucleation and resulted in the formation of larger particles, while increasing the amount of silver nitrate at fixed values of all the other variables enhanced the direct nucleation and resulted in the formation of smaller particles. Particle aggregation and flocculation took place when the concentration of n-decanol or the value of R was increased. Particle aggregation and flocculation were attributed to the decrease in the interaction between the surfactant protective layer and the nanoparticles in the water pools.
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PMID:Formation of silver bromide precipitate of nanoparticles in a single microemulsion utilizing the surfactant counterion. 1508 77

NMR self-diffusion coefficient measurements have been used to study the properties of polyethylene glycol (23) lauryl ether (Brij-35) with cetyltrimethylammonium bromide (CTAB) in the mixed aqueous solutions with different mole fractions of CTAB. By fitting the self-diffusion coefficients to the two-state exchange model, the critical micelle concentrations of the two solutes in the mixed solutions (cmc*1 and cmc*2) were obtained. The critical mixed micelle concentrations (cmc*) were then evaluated by the sum of cmc*1 and cmc*2, which are in good agreement with the results measured by the surface tension method. The cmc* values are lower than those of the ideal case of mixing, which indicates that the behavior of the CTAB/Brij-35 system is nonideal. Moderate interactions between CTAB and Brij-35 in their mixtures can be deduced from the interaction parameters (betaM) based on the cmc* obtained by the NMR self-diffusion method. The compositions (x1) of the mixed micelles at different total surfactant concentrations were also evaluated. By using these results, a possible mechanism of mixed micellar formation and a picture of the formation of nonsimultaneous CTAB/Brij-35 binary mixed micelle were proposed. In contrast to the case of CTAB/TX-100 system, Brij-35 molecules have a tendency to form micelles first at any mole fraction of CTAB. The mixed micellar self-diffusion coefficients (Dm) increase slightly at lower CTAB molar ratios, and then speed up with increasing CTAB mole fraction.
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PMID:Properties of polyethylene glycol (23) lauryl ether with cetyltrimethylammonium bromide in mixed aqueous solutions studied by self-diffusion coefficient NMR. 1508 2

Long-chain alkanes exhibit surface freezing at the alkane-air but not the alkane-water interface. Ellipsometry and surface tensiometry are used to show that a simple cationic surfactant, hexadecyltrimethylammonium bromide (CTAB), can induce surface freezing at the tetradecane-water interface even when present in mole fractions as low as 0.1. The surface-freezing temperature T(s) is a linear function of the interfacial excess of CTAB. The excess surface entropy below T(s), S(sigma)=-0.76+/-0.02 mJ K-1 m(-2), is consistent with a rotator phase. Ellipsometry provides strong evidence for a frozen monolayer in which the chains are oriented near the surface normal.
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PMID:Surfactant-induced surface freezing at the alkane-water interface. 1516 72

Mixtures of alkyltrimethylammonium bromide (CnTAB, n=12, 14, 16, 18) and Triton X-100 were studied at a range of mole fractions of ionic surfactant per nonionic surfactant. For each mixture, the cmc obtained from surface tension measurements differed from that obtained using potentiometry. The behavior of these mixed-surfactant systems showed three different regions with increasing total surfactant concentration. From the surface tension and potentiometry data, we obtained the free monomer concentration of ionic surfactant (mi), the micellar mole fraction of surfactant (xi), and the degree of dissociation (alpha) of ionic surfactant. We also obtained the free monomer concentration of Triton X-100 (m2) using PFG-NMR technique. A new equation was introduced to evaluate the activity coefficient in the micellar phase. The excess free energy (GE) and the synergetic parameters of mixtures were determined at various mole fractions of CnTAB/Triton X-100. Finally, the complexity of the synergism parameters was investigated.
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PMID:Thermodynamic studies of mixed ionic/nonionic surfactant systems. 1521 49

Four different quaternary ammonium chloride-modified poly(propylenimine) (PPI) dendrimers were synthesized by alkylation of a PPI dendrimer having eight dimethylamino end groups with 1-bromooctane or 1-bromododecane. By varying the mole ratio of alkyl bromide to dendrimer, averages of 4-10 quaternary ammonium groups were formed. The new amphiphilic dendrimers are surface active and are micellar catalysts in water. The dendrimers have critical aggregation concentrations between 8.5 x 10(-4) and 9.0 x 10(-5) M. Decarboxylation of 6-nitrobenzisoxazole-3-carboxylate at 25 degrees C was 650 times faster than in water alone in the presence of a dendrimer quaternized with eight dodecyl chains at a concentration of 2.45 mM in quaternary ammonium groups. The order of the catalytic efficiency of the new dendrimers decreased with the length and number of hydrophobic alkyl groups in the order (C(12))(8) > (C(12))(4) > (C(8))(10) > (C(8))(5). The pseudo-first-order rate constants for basic hydrolysis of p-nitrophenyl hexanoate in pH 9.4 buffer at 30 degrees C using the (C(12))(8) and (C(12))(4) dendrimers were 26 and 13 times higher than those for hydrolysis with no dendrimer. The kinetic data were fit to a single-site binding model to evaluate the contributions of binding constants of reactants to the dendrimers and catalytic rate constants of the bound species to the overall catalytic activity.
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PMID:Catalysis by hydrophobically modified poly(propylenimine) dendrimers having quaternary ammonium and tertiary amine functionality. 1535 Jan 7

Surfactants of practical interest are invariably mixtures of different types. In this study, mixtures of sugar-based n-dodecyl-beta-D-maltoside with cationic dodecyltrimethylammonium bromide, anionic sodium dodecylsulfate, and nonionic pentaethyleneglycol monododecyl ether in solution, with and without supporting electrolyte, have been studied using surface tension and fluorescence spectroscopic techniques. Interaction parameters and mole fraction of components in mixed micelles were calculated using regular solution theory. The magnitude of interactions between n-dodecyl-beta-D-maltoside and other surfactants followed the order anionic/nonionic > cationic/nonionic > nonionic/nonionic mixtures. Since all surfactants have the same hydrophobic groups, strengths of interactions are attributed to the structures of hydrophilic headgroups. Electrolyte reduced synergism between n-dodecyl-beta-D-maltoside and ionic surfactant due to charge neutralization. Industrial sugar-based surfactant, dodecyl polyglucoside, yielded results similar to that with dodecyl maltoside, implying that tested commercial alkyl polyglucosides are similar to the pure laboratory samples in synergistic interactions with other surfactants. Fluorescence study not only supported the cmc results using tensiometry, but showed that interfaces of all the above mixed micelle/solution interfaces are mildly hydrophobic. Based on these results, an attempt is made to discover the nature of interactions to be a combination of intermolecular potential energies and free energy due to packing of surfactant molecules in micelles.
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PMID:Study of mixtures of n-dodecyl-beta-D-maltoside with anionic, cationic, and nonionic surfactant in aqueous solutions using surface tension and fluorescence techniques. 1545 Apr 66

Salt effect on the interaction of anionic polyelectrolyte sodium carboxymethylcellulose (NaCMC) with cationic gemini surfactant hexamethylene-1,6-bis(dodecyldimethylammonium bromide) [C12H25(CH3)2N(CH2)6N(CH3)2C12H25]Br2 (C12C6C12Br2) has been investigated using turbidimetric titration, steady-state fluorescence, and mobility measurement. It is found that the critical aggregation concentration(cac) for C12C6C12Br2/NaCMC complexes depends little on addition of sodium bromide (NaBr). However, in the presence of nonionic surfactant Triton X-100 (TX100), the critical ionic surfactant mole fraction for the onset of complex formation (Yc) increases markedly with increasing NaBr concentration. These salt effects are supposed as the overall result from competition between the increase of interaction and the screening of interaction. The increase of interaction is referred to as the effect that the larger micelle with higher surface charge density induced by salt has a stronger interaction with oppositely charged polyelectrolyte. The screening of interaction is referred to as the salt screening of electrostatic attraction between the polymer chain and the surfactant. For complex formation between C12C6C12Br2 and NaCMC, the increase of interaction probably compensates the screening of interaction, leading to constant cac values at different salt concentrations. For complex formation between the C12C6C12Br2/TX100 mixed micelle and NaCMC, the screening of interaction probably plays a dominant role, leading to higher suppression of electrostatic binding of micelles to polyelectrolyte.
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PMID:Salt effect on the complex formation between cationic gemini surfactant and anionic polyelectrolyte in aqueous solution. 1546 81

In the presence of mixed surfactant cetyl trimethyl ammonium bromide(CTMAB) and Tween80, the photometric analysis properties of color reaction of 3,5-dibronosalicyl fluorone (DBSAF) with tungsten(VI) were studied. The experimental result showed that tungsten(VI) reacted with DBSAF to form a micelle complex with a maximum absorption at 527 nm in a 0.60 mol x L(-1) hydrochloric acid medium. The mixed surfactant remarkably improved the sensitivity of the method and the dissolubility of the complex. The apparent molar absorptivity of the complex is 2.64 x 10(5) L x mol(-1) x cm(-1) at 527 nm. Tungsten (VI) reacted with DBSAF to form a complex with a stoichiometric ratio of 1:2, which was determined by mole ratio method and continual method of transformation, respectively. Beer's law was obeyed in the range of 0-400 microg tungsten (VI) per L. The proposed method has been applied to the determination of trace amount of tungsten in alloy steel samples.
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PMID:[Spectrophotometric study on the color reaction of multicomponent complex of tungsten-3,5-dibromosalicyl fluorone-CTMAB-Tween80]. 1576 29


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