13C CP/MAS of LDLL mixtures of amino acids

A unit cell in which three isomers are in an L configuration and one is in a D configuration is inherently asymmetrical. For LDLL mixtures of amino acids with identical chemical structures (apart from chirality), the inter- and intramolecular interactions observed from the 13C CP/MAS NMR spectra are even larger than those which have been observed with mixtures of diastereoisomers in the solid state. This occurs even though the chemical composition of these molecular clusters consists only of nearest neighbor enantiomers. Because D and L isomers have identical chemical shifts, changes in chemical shift and peak intensities of these asymmetrical solid mixtures cannot be unambiguously assigned to either the D or one of the L isomers. In LLDL mixtures of amino acids in which half is L isomers and the other half is DL isomers, the NMR spectra clearly depend upon which amino acid contains the D isomer. Any further structural interpretation of these molecular clusters is equivocal without assigning chemical shifts to the D isomer (or alternatively designated the R, [-] or [+] isomer). Both more rigorous mathematical analysis and new NMR experiments are required which link interactions at chiral centers with NMR spectra of LLDL mixtures in the solid state.