Orientational properties of poly-gamma-benzyl-L-glutamate: influence of molecular weight and solvent on order parameters of the solute.
Residual dipolar couplings (RDCs) have recently become increasingly important in organic structure determination due to their unique information content. One main limitation for the use of RDCs in organic compounds, however, is that the compound in question needs to be oriented with respect to the magnetic field in order to measure RDCs. So far, there are very few possibilities for modulating the induced degree of orientation. The situation is even worse when chiral orienting media are considered, which could allow absolute configuration determination in the future. We have conducted a systematic investigation into modulating the orientation induced by one chiral orienting medium, namely organic solutions of PBLG (poly-gamma-benzyl-L-glutamate), as a function of its molecular weight and the organic co-solvent used, and have obtained significant insights into factors that influence the order induced. With increasing molecular weight of the polypeptide the orientation of the solutes decreases, leading to well-resolved spectra with improved line shapes. This can be attributed exclusively to the fact that the critical concentration of the liquid-crystalline phase decreases with increasing molecular weight (pure dilution effect). Any influence of increasing flexibility on the orientation can be ruled out.
Marx
Andreas
A
Technische Universität Darmstadt, Clemens Schöpf Institut für Organische Chemie und Biochemie, Petersenstr. 22, 64287 Darmstadt, Germany.
Thiele
Christina
C