Mixed aquo-organic solvents are used in chemical, industrial, and pharmaceutical processes along with amphiphilic materials. Their fundamental studies with reference to bulk and interfacial phenomena are thus considered to be important, but such detailed studies are limited. In this work, the interfacial adsorption of sodium dodecylsulfate (SDS, C12H25SO4(-)Na(+)) in dioxane-water (Dn-W) and methanol-water (Ml-W) media in extensive mixing ratios along with its bulk behavior have been investigated. The solvent-composition-dependent properties have been identified, and their quantifications have been attempted. The SDS micellization has been assessed in terms of different solvent parameters, and the possible formation of an ion pair and triple ion of the colloidal electrolyte, C12H25SO4(-)Na(+) in the Dn-W medium has been correlated and quantified. In the Ml-W medium at a high volume percent of Ml, the SDS amphiphile formed special associated species instead of ion association. The formation of self-assembly and the energetics of SDS in the mixed solvent media have been determined and assessed using conductometry, calorimetry, tensiometry, viscometry, NMR, and DLS methods. The detailed study undertaken herein with respect to the behavior of SDS in the mixed aquo-organic solvent media (Dn-W and Ml-W) is a new kind of endeavor.
The self-aggregation of Tween 40, Tween 60, and Tween 80 in ethylene glycol-water mixture was investigated using surface tension, density, and fluorescence measurements. The mixtures were observed to appreciably affect the critical micelle concentration (cmc) of the surfactants and their aggregation numbers. In order to evaluate the influence of the solvent mixture, the difference in the Gibbs energy of micellization of Tween 40, Tween 60, and Tween 80 between water and binary mixtures were determined. The ability of ethylene glycol acting as a structure breaker and its interaction with the surfactant hydrophilic group are the controlling factors for the micellization of the surfactants in the mixture. The surface activity of the surfactants decreases with increasing concentration of ethylene glycol in the mixture. Micellar micropolarity was determined using the fluorescence method. The results indicate the participation by ethylene glycol in the micellar solvation layer.
The micellization behavior of cetylammonium bromide and its mono-, di-, and trihydroxyethylated head group analogues and water/oil (w/o) microemulsion formation with them have been studied with detailed thermodynamic and structural considerations. The critical micellar concentration, micellar aggregation number, and behavior of the surfactants at the air/solution interface have been studied in detail. The results have been analyzed and discussed. The formation of the w/o microemulsion stabilized by the aforesaid surfactants in conjunction with the cosurfactant n-hexanol in isooctane has been investigated by the dilution method. The energetics of the transfer of cosurfactant from oil to the interface has been estimated. The structural parameters, namely, droplet dimension, droplet number, and population of surfactant and cosurfactant on the droplet surface, have also been estimated. The efficacy of the surfactants in respect to water dispersion in oil and cosurfactant concentration level at the oil/water interface has been worked out. Such microemulsions are prospective compartmentalized systems to assist enzyme activities. In this respect, the trihydroxyethylated head group analogue in the above series has been found to be a better performer for the preparation and stabilization of microemulsions that has correlated well with its performance than the others in the hydrolysis of p-nitrophenyl-n-hexanoate by the enzyme Chromobacterium viscosum lipase.
The present strategy proposes a simple and single step aqueous route for synthesizing stable, fluorescent ZnTe/dendrimer nanocomposites with varying dendrimer terminal groups. In these hybrid materials, the fluorescence of the semiconductor combines with the biomimetic properties of the dendrimer making them suitable for various biomedical applications. The ZnTe nanocomposites thus obtained demonstrate bactericidal activity against enteropathogenic bacteria without having toxic effects on the human erythrocytes. The average size of the ZnTe nanoparticles within the dendrimer matrix was in the range of 2.9-6.0 nm, and they have a good degree of crystallinity with a hexagonal crystal phase. The antibacterial activities of the ZnTe/dendrimer nanocomposites (ZnTe DNCs) as well other semiconductor nanocomposites were evaluated against enteropathogenic bacteria including multi-drug resistant Vibrio cholerae serogroup O1 and enterotoxigenic Escherichia coli (ETEC). ZnTe DNCs had significant antibacterial activity against strains of V. cholerae and ETEC with minimum inhibitory concentrations ranging from 64 to 512 μg ml(-1) and minimum bactericidal concentrations ranging from 128 to 1000 μg ml(-1). Thus, the observed results suggest that these water-soluble active nanocomposites have potential for the treatment of enteric diseases like diarrhoea and cholera.
Selective quenching of luminescence of quantum dots (QDs) by Cu2+ ions vis-à-vis other physiologically relevant cations has been reexamined. In view of the contradiction regarding the mechanism, we have attempted to show why Cu2+ ions quench QD-luminescence by taking CdS and CdTe QDs with varying surface groups. A detailed study of the solvent effect and also size dependence on the observed luminescence has been carried out. For a 13% decrease in particle diameter (4.3 nm -->3.7 nm), the quenching constant increased by a factor of 20. It is established that instead of surface ligands of QDs, conduction band potential of the core facilitates the photo-induced reduction of Cu (II) to Cu (I) thereby quenching the photoluminescence. Taking the advantage of biocompatibility of dendrimer and its high affinity towards Cu2+ ions, we have followed interaction of Cu2+-PAMAM and also dendrimer with the CdTe QDs. Nanomolar concentration of PAMAM dendrimer was found to quench the luminescence of CdTe QDs. In contrast, Cu2+-PAMAM enhanced the fluorescence of CdTe QDs and the effect has been attributed to the binding of Cu2+-PAMAM complex to the CdTe particle surface. The linear portion of the enhancement plot due to Cu2+-PAMAM can be used for determination of Cu2+ ions with detection limit of 70 nM.
Bulk and interfacial properties of ion-pair amphiphiles (IPA), formed between sodium dodecylsulfate (SDS) and n-alkyltrimethylammonium bromide homologues (C n TAB; n = 10, 12, 14, 16, and 18), have been investigated. Different phases and aggregated states, formed in the ternary combinations of C n TAB/SDS/H 2 O, have been identified and described. Equimolar mixture of IPAs in water yielded precipitates, in the form of coacervates. Aqueous solubility of isolated coacervates in presence and absence of additives like cholesterol and bile salts have been examined. The isolated coacervates have been characterized by 1 H NMR, FTIR, X-ray diffraction (XRD), differential scanning calorimetry (DSC) and polarization microscopic measurements. The coacervates have appeared in the shape of needle and complex flower-like aggregates. Surface pressure (π)-area (A) isotherm of the coacervates at the air/water interface have been constructed and compared with the lipid 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC). Morphologies of the IPA monolayers at different surface pressures have been also examined by epifluorescence microscopy. The compressed interfacial monolayers have produced spherical (both regular and irregular) and fern-leaf like domains.
Interfacial behavior, structural and thermodynamic parameters of a water/(surfactant?n-butanol)/ n-heptane water-in-oil (w/o) microemulsion have been investigated using the dilution technique at different temperatures, and [water]/[surfactant] mole ratios. The cationic surfactants used were alkyltrimethyl ammonium bromides (CnTAB, n = 10, 14 and 16) while the nonionic surfactants were polyoxyethylene (20) sorbitan monoalkanoates (polysorbate), viz., palmitate (PS 40), stearate (PS 60) and oleate (PS 80). The distribution of cosurfactant between the oil-water interface and the bulk oil at the threshold level of stability, and the thermodynamics of transfer of the cosurfactant from the bulk oil to the interface were evaluated. Structural parameters such as the dimensions, population density and effective water pool radius of the dispersed water droplets in the oil phase and the interfacial population of the surfactant and cosurfactant have been evaluated in terms of the surfactant chain length.
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