Hydrolysis driven surface activity of esterquat surfactants.

HYPOTHESIS: Surface activity of selected cleavable esterquat cationic surfactants is determined by the synergistic effect of surface active products of their hydrolysis. EXPERIMENTS: Interfacial behavior of two classes of esterquat surfactants, quaternary alkylammmoniumesters and amino acid betaine (trimethylglycine) esters of fatty acids were examined both experimentally and theoretically. The surface tension measurements at air/water interface were performed by the pendant drop shape analysis method, then the obtained isotherms were theoretically described by the model of adsorption of ionic/non-ionic surfactants mixtures taking into account the presence of surface active products of surfactant hydrolysis. FINDINGS: We found that surface activity of the mixture of surface active compounds resulting from the esterquat basic hydrolysis increases with time and it is higher when the ester carbonyl group is connected with the quaternary amine by bridging oxygen than in the inverted (betaine ester type) arrangement. That is, in the first case, the consequence of strong synergistic effect between the cationic esterquat surfactant and the anionic product of its hydrolysis - dodecanoate ion, while in the second case, the non-ionic hydrolysis product - dodecanol exhibits much weaker synergy. The addition of side CH3 group into the esterquat head-group slows down the hydrolysis that leads to the lower surface activity of the resulting mixture.

Experimental and theoretical approach to nonequivalent adsorption of novel dicephalic ammonium surfactants at the air/solution interface.

The interfacial behavior of novel dicephalic cationic surfactants, N,N-bis[3,3'-(trimethylammonio)propyl]alkylamide dibromides and N,N-bis[3,3'-(trimethylammonio)propyl]alkylamide dimethylsulfates, was analyzed both experimentally and theoretically in comparison to their linear standards, 3-[(trimethylammonio)propyl]dodecanamide bromide and 3-[(trimethylammonio)propyl]dodecanamide methylsulfate. Adsorption of the studied double head-single tail surfactants depends strongly upon their structure, making them less surface active in comparison to the single head-single tail structures having the same alkyl chain length. Surface tension isotherms of aqueous solutions of the studied dicephalic derivatives were measured using the pendant drop shape analysis method and interpreted with the so-called surface quasi-two-dimensional electrolyte (STDE) model of ionic surfactant adsorption. The model is based on the assumption that the surfactant ions and counterions (bromide and methylsulfate ions in the studied case) undergo nonequivalent adsorption within the Stern layer, and it allows for accounting for the formation of surfactant ion-counterion associates in the case of multivalent surfactant headgroup ions. As a result, good agreement between theory and experiment was obtained. Additionally, the presence of surfactant-counterion complexes was successfully confirmed by both measurements of the concentration of free bromide ions in solution and molecular modeling simulations. The results of the present study may prove useful in the potential application of the investigated dicephalic cationic surfactants.

Encapsulation of liquid cores by layer-by-layer adsorption of polyelectrolytes.

The aim of this work was to develop the method of preparation of loaded, submicron nanocapsules based on the liquid core encapsulation by polyelectrolyte (PE) multilayer adsorption. The procedure of PE adsorption on the emulsion droplets requires a specific selection of surfactants, which have good properties as emulsifiers and provide a stable surface charge for sequential adsorption of PE without losing stability of emulsion. Using AOT as emulsifier this study obtained droplets, stabilized by AOT/PDADMAC surface complexes. These positively charged liquid cores were then modified by sequential adsorption of polyelectrolytes to obtain nanocapsules with the average size of 200 nm, with various combinations of polyelectrolytes (PDADMAC, CHIT, PAH, PSS, ALG). This study demonstrated the formation of consecutive layers of PE shells by measuring zeta potential of capsules after adsorption of each layer. It visualized the cores by dissolving fluorescent dye Coumarine6 in oil phase and multilayer shells by using FITC labelled polycation.

Adsorption of multiple ammonium salts at the air/solution interface.

The interfacial behavior of aqueous solutions of newly synthesized bis- and tris-ammonium salts (i.e., bis[2-hydroxy-3-(dodecyldimethylammonio)propyl]alkylamine dichlorides and bis[2-hydroxy-3-(dodecyldimethylammonio)propyl]dialkylammmonium trichlorides, respectively) was analyzed, both experimentally and theoretically. The dynamic and equilibrium surface tension of multiple ammonium salt solutions was measured by using a pendant drop shape analysis method. The determined surface tension isotherms indicated the lack of significant differences in surface activity between bis- and tris-ammonium salts, contrary to the expectations for divalent and trivalent surfactant ions. That effect was explained by assuming the formation of multiple surfactant ion-counterion associates. Taking into account the association process, a good correlation between experimental data and theoretical predictions was obtained by means of the "surface quasi two-dimensional electrolyte" (STDE) model of ionic surfactant adsorption. The degree of association necessary to explain the lack of difference in surface activity between bis- and tris-ammonium salts was in quantitative agreement with the results of measurements of the concentration of free chloride anions in the surfactant solution.