Cholesteric Liquid Crystal Polyesteramides: Non-Viral Vectors

Polyesteramides PNOBDME (C34H38N2O6)n, Poly[oxy(1,2-dodecane)-oxy-carbonyl-1,4-phenylene-amine-carbonyl-1,4-phenylene-carbonyl-amine-1,4-phenylene-carbonyl], and PNOBEE (C26H22N2O6)n, Poly[oxy(1,2-butylene)-oxy-carbonyl-1,4-phenylene-amine-carbonyl-1,4-phenylene-carbonyl-amine-1,4-phenylene-carbonyl], have been designed and synthesized as cholesteric liquid crystals (LCs)—through a condensation reaction between 4- 4′-(terephthaloyl-diaminedibenzoic chloride) (NOBC) and racemic glycol, DL-1,2-dodecanediol or DL-1,2-butanediol, respectively—as chemical modifications of multifunctional cholesteric LC polyesters, involving new properties but holding the precursor helical macromolecular structures. The new compounds have been characterized by 1H and 13C-NMR, COSY and HSQC, exhibiting two 1H-independent sets of signals observed for each enantiomer, attributed to two diastereomeric conformers, gg and gt, of the torsion containing the asymmetric carbon atom in the spacer. They have also been characterized by x-ray diffraction with synchrotron radiation source. Thermal behaviour of the new compounds is studied by thermogravimetric (TG) and differential scanning calorimetry (DSC) analysis. The substitution of the ester groups in the mesogen by amide groups causes an increase of thermal stability with respect to the precursors. Optical rotatory dispersion (ORD) is evaluated. Morphology of powdered PNOBDME exhibits spherical clusters of about 5 μm in diameter homogeneously dispersed. Molecular models show helical polymeric chains with stereoregular head-tail, isotactic structure, explained as due to the higher reactivity of the primary hydroxyl with respect to the secondary one in the glycol through the polycondensation reaction. Besides being biocompatible, these synthetic polyesteramides have proved to act as non-viral vectors in gene therapy and be able to transfect DNA to the nucleus cell. Similar new cationic cholesteric liquid crystal polyesters have also been synthesized in our laboratory

Molecular Simulation of Cholesteric Liquid-Crystal Polyesteramides: Conformational and Structure Analysis by Rietveld Refinement

Molecular modeling techniques are applied to polyesteramides designed as PNOBDME (C34H38N2O6)n and PNOBEE (C26H22N2O6)n, synthesized and characterized as cholesteric liquid crystals -through the condensation reaction between 4 and 4′-(terephthaloyl- diaminedibenzoic chloride (NOBC) and racemic glycol: DL-1,2 dodecanediol, or DL-1,2-butanediol, respectively, being chemical modifications of precursor multifunctional cholesteric LC polyesters, adding new properties but holding their helical macromolecular structures. Although the starting raw materials were racemic, these cholesteric LC polymers exhibit unexpected optical activity and chiral morphology. For that reason, conformational analysis is studied on the monomer models of PNOBDME and PNOBEE. Four helical conformers models, experimentally observed by NMR, are proposed for each cholesteric polyesteramide: Rgg, Rgt, Sgg, Sgt. Polymerization of the monomeric conformers, with minima energies, have been simulated and used to reproduce the crystalline fraction observed by x-ray diffraction. Three orders of chirality are observed in the structure of the polymer chains: One due to the asymmetric carbon atoms, a second chirality due to the two successive rotations of the benzene groups, along the main chain, within the monomer which implies the formation of helical molecules, for both R and S chirality and still, a third chirality corresponding to the twisting of the rigid/semirigid cholesteric LC polymer chains. All these factors contributing to the net optical activity observed in these materials. Crystal packing is simulated in triclinic primitive P1cells, with molecular chains oriented parallel to the z-axis (c lattice parameter equal to the pitch length of each simulated polymer helix) and parameters a, b, α, β and γ, obtained by Pawley refinement from the known structures of precursor polyesters. The simulated x-ray diffraction patterns of the proposed crystal models fit, after successive Pawley and Rietveld refinement cycles, the experimental WAXS. Powder Quantitative Phase Analysis applied to an ideal mixture with the four possible helical conformers, for each degree of polymerization, allows to refine their relative weight and determine the major phase relative amount. These results would confirm the theory of a preferable recrystallization, among the four possible helical diastereoisomers, depending on the synthetic conditions