Quantum Chemical Investigations on C14C10-Branched-Chain Glucoside Isomers Towards Understanding Self-Assembly

Density Functional Theory (DFT) calculations have been carried out using a Polarizable Continuum Model (PCM) in an attempt to investigate the electro-molecular properties of branched-chain glucoside (C14C10-D-glucoside) isomers. The results showed that αconfiguration of pyranoside form is thermodynamically the most stable, while the solution should contain much more β than α, according to the calculated Boltzmann distribution. Additionally, C14C10-β-D-xylopyranoside is studied for comparison with its glucoside analog in order to investigate the electronic effect of the hydroxymethyl (−CH2-OH) group at position 5-C. The topological parameters of intramolecular X-H∙∙∙Y hydrogen bonds were analyzed and the nature of these interactions were considered using the Atoms in Molecules (AIM) approach. Moreover, natural bond orbital analysis (NBO) was performed to define bond orders, charge, and lone pair electrons on each atom and effective non-bonding interactions. HOMO/LUMO analysis allowed the description of investigated isomers and led to a further understanding of their behaviors. The computational results, especially intramolecular hydrogen bonding and molecular electronic potential analysis are directly relevant to liquid crystal self-assembly and membrane biophysics.