Conformational behavior of stereo regular substituted polyglycolides is side chain dependent

Fateh S. Nandel, Roobee Garla
2011 Journal of Biophysical Chemistry  
Substituted polyglycolides having two asymmetric centers are attractive alternatives to materials derived from petroleum because of their biocompatibility and biodegradability. The conformational behavior of various substituted polyglycolides has been investigated by both quantum mechanical and molecular dynamics approaches. Polymethylglycolide (polylactide) and polyphenylmethylglycolide in RS or SR forms are predicted to adopt 2 7 ribbon type structures with φ, ψ values of ±30, ±50 or ∓30 or
more » ... 30, ±50 or ∓30 or ∓50 respectively stabilised by carbonyl-carbonyl interactions. Isopropylglycolide and isobutylglycolide having branching at β & γ positions respectively in their side chains can be realized in all SS form with φ, ψ values lying in right handed helical region. In addition to carbonylcarbonyl interactions, the hydrophobic interactions between the side chains in isopropylglycolide the C-H-O interactions also contributes to the stability. With cyclic side chains directly attached to C α of backbone, polyphenylglycolide (polymandelide) and polycyclohexylglycolide are found to adopt left handed helical structure without hydrogen bonds in RR form, stabilised by stacking interactions and hydrophobic interactions respectively. In all the forms of polyphenylglycolide & polycyclohexylglycolide, the cyclic side chains are found to be locked into unfavourable gauche plus conformation. The stability of substituted polyglycolides has been analyzed in terms of various interactions. The carbonyl-carbonyl interactions in all the conformations of all forms of substituted polyglycolides are found to be of highly shielded parallel motif with only one short carbon-oxygen interaction. Simulation studies of substituted polyglycolides in water give a good insight of the approach of water molecules to the backbone.
doi:10.4236/jbpc.2011.23033 fatcat:hjlfip7s2jchtipjl3tweuanhy