Structures of the water-insoluble complexes of poly( l -lysine) with octyl and octadedecyl sulfates, and with the mixtures of these surfactants, were examined via X-ray diffraction, infrared spectroscopy, and differential scanning calorimetry. The solid-state structures of the complexes were shown to be governed by their compositions. In the stoichiometric poly( l -lysine) complex with octadecyl sulfate, surfactant chains crystallize on a hexagonal lattice. In the poly( l -lysine)−octyl sulfate complex of nearly stoichiometric composition, the surfactants are arranged on an alkane-type two-dimensional lattice. In the complex with 20 mol % octadecyl sulfate and about 75 mol % octyl sulfate, the longer surfactant chains form hexagonal crystalline blocks, and the shorter chains are arranged on an alkane-type two-dimensional lattice. In the poly( l -lysine) complex with 10 mol % octadecyl sulfate and about 85 mol % octyl sulfate, all surfactant chains are arranged on a two-dimensional alkane-type lattice. All complexes are organized in lamellar structures consisting of layers of poly( l -lysine) chains in β-sheet conformations, separated by layers of surfactants. Complexes with crystalline and partially crystalline surfactants adopt lamellar structures with identical long periods and with interdigitated octadecyl chains. Complexes with two-dimensional order in the surfactant arrangement also adopt lamellar structures with identical long periods and with octyl chains packed tail to tail.
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Ponomarenko et al. (1998) studied this question.