Environmentally responsive adsorption and assembly behaviors from N-alkyl-1,2-ethylenediamines

Abstract

A series of pH sensitive single-tailed surfactants, N-alkyl-1,2-ethylenediamine (CmN2N, where m = 8, 10, 12, 14, 16), were synthesized and characterized. The adsorption and aggregation properties of them were determined by equilibrium surface tension, static and dynamic light scattering (SLS and DLS), rheology, and cryogenic transmission electron microscopy (cryo-TEM) techniques in detail. It was found that both the surface activity and self-assembly behavior of CmN2N were strongly dependent on the solution pH, owing to the protonation state of amino groups in CmN2N. When at least one of the amino groups of CmN2N was protonated the logarithm of the critical micelle concentration (cmc) followed the well-known Klevens equation, i.e. cmc decreased linearly with the increase of hydrocarbon chain length. Simultaneously, the surface adsorption area per molecule (A_min) was decreased for each CmN2N when the solution pH varied from acidic to basic conditions. The pH-dependent micelle to vesicle transition was universally observed in the bulk phase of CmN2N. More interestingly, the rodlike micelles formed in C10N2N, C12N2N and C14N2N could transform into vesicles reversibly upon heating or cooling, which indicated the thermal sensitivityof organized assemblies, whereas not in C8N2N and C16N2N.