Small-angle neutron-scattering study of concentrated nonionic-amphiphile solutions

The structure of aqueous solutions of two polyoxyethylene non-ionic amphiphiles, C₁₀E₅ and C₈E₄, is studied by small-angle neutron-scattering along isothermal paths crossing the isotropic single-phase region from 0% to 100% amphiphile volume fractions. The scattered intensityI(k) shows a peak at a valuek _m , which grows monotonically as the amphiphile volume fraction increases. The interpretation of the scattering data lead to the following conclusion: as increases the micellar structure becomes less and less sharp, but some orientational correlations between neighboring amphiphile molecules are preserved even in the pure amphiphile phase.     

Thermodynamic and Dynamic Properties of Micellar Aggregates of Nonionic Surfactants with Short Hydrophobic Tails

The densities and viscosities of binary aqueous mixtures of poly(ethylenoxide)hexanols [C₆H₁₃(OCH₂CH₂)_mOH, C₆E_m] (m= 3, 4, and 5) have been studied in the micellar composition range. For the same surfactants the self-diffusion coefficients in mixtures with heavy water have been determined by the spin-echo pulsed field gradient method. The volumetric data are interpreted by means of the phase separation model, and values of the CMC, volume change, and standard free energy change of micellization are obtained. From the viscosity data the hydration numbers of the surfactant hydrophilic head in the micellar state are computed; they are in agreement with those obtained from HDO self-diffusion data. The surfactant self-diffusion data are used to calculate the apparent micelle radius and the aggregation number. The micellization parameters obtained for the different surfactants are compared and discussed.     

Unusual volumetric and hydration behavior of the catanionic system sodium undecenoate: sodecyltrimethylammonium bromide

Following the studies on the effect of double bonds in the surfactant hydrophobic tail on the formation of mixed surfactant aggregates, we studied the viscosity and density of the system Sodium 10-undecenoate (SUD)–decyltrimethylammonium bromide (DTAB)–water. We found that the partial molar volume (pmv) and intrinsic viscosity of both, micellised and unmicellised mixtures, are non-ideal, dependent on the mixture composition and related to structural changes in micelles. These phenomena are caused by the presence of the double bond at the distal extreme of the SUD molecule, which has some affinity with water by formation of hydrogen bonds. In particular, as far as we know, this is the first report on non-ideal behavior of the pmv in mixed micelles.     

Dendrimers as potential drug carriers; encapsulation of acidic hydrophobes within water soluble PAMAM derivatives

This paper describes the synthesis of three neutral water soluble poly(amidoamine) (PAMAM) dendrimer derivatives. The ability of the two larger dendrimers to bind small acidic hydrophobic molecules is reported. Spectroscopic data and pH behaviour suggested that the acidic hydrophobes were forming stable ion pairs with the dendrimer's internal, basic tertiary nitrogens. With respect to forming 1:1 and 2:1 substrate/dendrimer complexes, both of the larger dendrimers were equally efficient at binding. All dendrimer/substrate complexes were completely miscible with water in all proportions (i.e. infinitely water soluble). When the bound substrates are drug moieties, then the resulting complexes could be considered as potential drug delivery systems. Flow calorimetry demonstrated that the dendrimers were able to release their hydrophobic guests when in contact with a biological cell.     

Hydrolysis of phosphorus acid esters in the sodium bis(2-ethylhexyl)sulfosuccinate—<Emphasis Type="Italic">n</Emphasis>-nonane—polyethylene glycol—water supramolecular system before and after the percolation threshold

The kinetics of alkaline hydrolysis of O-ethyl O-p-nitrophenyl chloromethylphosphonate in a sodium bis(2-ethylhexyl)sulfosuccinate—n-nonane—polyethylene glycol—water reverse micellar system was studied in a wide range of concentrations of the surfactant and water. The sign of the catalytic effect of micelles is inverted in the presence of the polymer. A sharp change in the apparent rate constant of hydrolysis of the phosphonate was found in a region of the temperature percolation threshold. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 60–67, January, 2007.     

Enzymes Hosted in Reverse Micelles in Hydrocarbon Solution

Reverse micelles are spheroidal aggregates formed by certain surfactants in apolar media. In contrast to normal micelles in water, the polar head groups of the surfactant molecules are directed towards the interior of the aggregate and form a polar core which can solubilize water (the “water pool”); the lipophilic chains are exposed to the solvent. The water of the water pool exhibits properties that (depending on the mole ratio of water to surfactant) differ from those of bulk water. Surprisingly, these reverse micelles are able to solubilize in hydrocarbon solvents hydrophilic molecules, e.g., enzymes and even plasmids, that are much larger than the original water-pool diameter. These biopolymer-containing reverse micelles can be viewed as novel microreactors, whose physical properties can be controlled through the water content. Remarkable is the ability of enzyme-containing micelles to react with water-insoluble, hydrocarbon-soluble substrates, as in the example of lipoxygenase with linoleic acid.     

Percolative phenomena in lecithin reverse micelles: the role of water

 The role played by the solvation water molecules on the macroscopically observed sol–gel transition in lecithin/cyclohexane/water reverse micelles is investigated by quasielastic neutron scattering, dielectric relaxation and conductivity measurements. The experimental results are juxtaposed to those from spherical Aerosol OT reverse micelles. It is shown how the results from lecithin-based system can be interpreted only assuming that, in contrast to Aerosol OT systems, the water molecules are entrapped at the interfaces without coalescing into an inner water pool. It is suggested that, in the case of lecithin, the solvation water can induce a change in the surface curvature, in such a way promoting the formation of branch points. Such a hypothesis is supported by the temperature dependence of the conductivity which agrees with the hypothesis of an intermicellar bond percolation. The investigation of the structures imposed by an external electric field is also studied. The observed electrorheological behaviour seems to confirm the existence of a percolated transient network in the gel phase. Received: 21 March 2001 Accepted: 24 August 2001     

Conductometric study of cationic and anionic complexes in propylene carbonate

Conductivity data are used to determine thermodynamic complex formation constants for cases in which both the initial electrolyte and the complexed electrolyte form ion pairs. Using the method described in the text, the complex formation constants of Li⁺, Na⁺ and K⁺ with the crown ether 18-crown-6 and of Li⁺ with the ligand triphenylphosphine oxide in propylene carbonate have been evaluated from conductance data. The complexation of AgBr in propylene carbonate solutions of n-etrabutylammonium bromide has also been studied by the measurement of molar conductivities. The results of these studies indicate that ion pairing should not be neglected, even in high permittivity solvents such as propylene carbonate, and that the ion pair association constants correlate well with structural studies on cation-crown ether molecular conformations.     

Synthesis and cationic photopolymerization of electroactive monomers containing functional groups

The synthesis and cationic photopolymerization of different cationically polymerizable monomers containing electroactive groups are reviewed with 98 references. The preparation of various compounds containing electron‐donor or electron‐acceptor moieties and photopolymerizable functional groups is described. After a short discussion of basic principles of cationic polymerization, photoinduced cationic polymerizations of various cationically polymerizable monomers containing both electron‐donor or electron‐acceptor chromophores and the functional groups such as epoxy, vinyl, thiiranyl, oxetanyl and others are reviewed. Copyright © 2005 John Wiley & Sons, Ltd.     

Novel polycationic biocides: Synthesis and antibacterial activity of polymeric phosphonium salts

Various polymeric phosphonium salts and the corresponding low-molecular-weight model compounds were prepared and their antibacterial activities against Staphylococcus aureus and Escherichia coli were explored by the viable cell counting method in sterile distilled water. Antibacterial activity of the polymers was found to be higher than that of the corresponding model compounds, particularly against S. aureus. Furthermore, the polymeric phosphonium salt exhibited a higher activity by 2 orders of magnitude than the polymeric quaternary ammonium salt with the same structure except the cationic part. Compounds with the longest alkyl chain (octyl) studied were found to exhibit particularly high activity, and this finding may be ascribed to the contribution of the increased hydrophobicity of the compounds to the cidal activity. © 1993 John Wiley & Sons, Inc.