Mixed Langmuir and Langmuir-Blodgett films of a proton sponge and a fatty acid: influence of the subphase nature on the interactions between the two components.

Abstract

The H+ acceptor activity of a proton sponge, namely, diphenyl bis(octadecylamino)phosphonium bromide, has been studied at the air-liquid interface using several subphases. Mixed Langmuir and Langmuir-Blodgett (LB) films containing the proton sponge and a fatty acid (behenic acid) in the whole composition range have been prepared. Surface pressure versus area per molecule isotherms were recorded and excess Gibbs energies of mixing calculated. The existence of strong interactions between the proton sponge and the fatty acid is observed when the subphase is either pure water or a NaOH aqueous solution. A stoichiometric 1:1 reaction between both molecules takes place at the air-water interface. This reaction has an efficiency close to 100% at high surface pressures, provided the majority anion present in the subphase is OH-. However, when the majority anion is another one, this complex is hardly formed. From the experimental results, we conclude that the acid-base reaction is highly dependent on the protonation state of the proton sponge at the air-liquid interface that is a function of the present counterion in the subphase. The floating films were also transferred onto solid substrates and characterized by means of IR spectroscopy, atomic force microscopy (AFM), and X-ray diffraction to investigate in more detail the complex formation. The interactions between the complex (when formed) and the excess component have been studied in terms of the subphase nature. It was found that the complex is immiscible with the proton sponge, yielding films made of different domains. Nevertheless, the complex is miscible with the fatty acid when the subphase used is an alkaline solution, presumably due to electrostatic interactions between the carboxylate group of the acid and the complex.