Computer simulation and quantum chemistry analysis ware applied for a prediction of molecular architecture of biopolymer-inorganic systems for preparation of new nanoscale hybrid supramolecular materials. Polyaminoacid (PAA) fragments attached to cyclotriphosphazene (CTP) through spacer groups form organic/inorganic hybrids. Further modification of these compounds by photosensitive, biologically active species results in systems possessing multifunctional properties.

PAA/CTP fragments structure optimization done by methods of non-empirical, semiempirical quantum chemistry and methods of molecular mechanics. Quantum-topological analysis of electronic density revealed secondary non-valent interactions between C and Н atoms in neighboring phenoxy-groups connected to phosphazene cycle. These interactions reflect mutual influence of spacer groups, providing their spatial orientation and stabilizing molecular structure.

We simulated the architecture of poly(g-methyl L-glutamate) (PMG) and poly(g-benzyl L-glutamate) (PBG) (total degree of polymerization n= 60) derivatives of cyclotriphosphazene and confirmed the structure experimentally. PAA/CTP hybrids include six a-helices in trans-position to CTP core. a- helices in turn organized into bundles. Further self-assembling leads to formation of aggregates comprising 5 molecules for PBG/CTP and 6 molecules for PMG/CTP, where helices are organized into two-dimensional hexagonal packing structure that was proved by SWAXS. Formation of this highly ordered supramolecular systems becomes possible owing to hydrogen bonding and non-covalent interactions, that is illustrated by IR and CD data.

Quantum chemical prediction and structural properties study permits to elaborate an approach for creation of multi-functional materials with defined properties.

The authors are grateful for financial support to Russian Ministry of Education and Science (Projects 5051 and 5118).

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1. QTAIM Analysis of Weak Interactions in Bio-Inspired Substances: Derivatives of the L-α-Glutamic Acid and Cyclotriphosphazene
2. Quantum Chemistry Analysis of Electron Density in Cyclophosphazenes and in their Supramolecular Complexes