Complementary amphiphilic ribonucleotides confined into nanostructured environments

Abstract

This article focuses on the physico-chemical investigation of the time evolution of self-assembled structures composed by oppositely charged surfactant monomers. The cationic components were represented by the well known cetyl-trimethyl-ammonium-bromide (CTAB) while the anionic monomers consisted of amphiphilic ribonucleotide derivatives, also called nucleo-lipids (NL). The latter were generated in situ by direct reaction between a hydrophobic precursor, dodecyl epoxide (DE), and a pair of complementary ribonucleotide mono-phosphates: adenosine mono-phosphate (AMP) and uridine mono-phosphate (UMP). Analysis of reaction mixtures by liquid chromatography-electrospray ionization-single, tandem and sequential mass spectrometry (LC-ESI-MS, MS/MS and MS³) confirmed that the generated NL corresponded to ribonucleotides linked to one, two and even three hydroxy-dodecyl tails on their molecular structures and whose amounts had peculiar time dependences. In the solutions incubated with an equimolar mixture of both types of ribonucleotides, a remarkable positive feedback effect on the reaction products was ascribed to the contemporary presence of AMP and UMP. The variation of aggregate sizes, due to the incorporation process of NL monomers into starting CTAB micelles, was monitored through time-resolved measurements of both dynamic light-scattering (DLS) and electrophoretic mobilities, together with calculated zeta-(ζ)-potential. Finally, a kinetic model based on auto-catalytic mechanisms was outlined to analyze the process of the catanionic vesicles growth observed during the whole reaction time-course. The model was also in good agreement with MS data. The proposed colloidal system may be considered a simplified model whereby to study the potential role of complementary nucleic bases in triggering primitive chemical selections.