We demonstrate the analyti-cal potential of 2H-{1H} NMR spectros-copy in weakly ordering, chiral lyotrop-ic liquid crystals made of poly(gamma-benzyl-l-glutamate) (PBLG) dissolved in chloroform or dichloromethane for in-vestigating the intramolecular dynamic processes of four deuterated diAaryls (derivatives of 1-(4’-methylphenyl)-naphthalene). When the rotation of the aryl groups about the sp2-sp2 bond is sufficiently slow relative to the NMR timescale, the method allows the spec-tral discrimination of enantiomeric atropisomers or enantiotopic directions in the prochiral derivatives. The effect of the position of substituents on the phenyl group on the conformational dynamics of these compounds has been examined as well as the nature of the organic co-solvent. When coalescence phenomena are observed, simulation of the experimental 2H-{1H} lineshapes using a formalism tailored for two deu-terons undergoing mutual exchange allows the rate constants and the acti-vation parameters for the internal rota-tion processes to be calculated. Experi-mental values of DHhave been com-pared with data evaluated by molecular modelling calculations and the activa-tion parameters are discussed for the various compounds. It is shown that these polypeptide mesophases have no significant impact on the interconver-sion dynamics of these compounds. In contrast with the nematic thermotropic phases, Hallers equation cannot be used to predict the evolution of the quadrupolar splittings (DnQ values), and hence the order parameters, versus T in the PBLG mesophases. For these particular lyotropic systems, it is shown that an exponential function of the form DnQ[Hz] = exp (E/RT[K]) provides excellent agreement between the experimental and expected DnQ values. Analysis of the results reported in this work suggests that orientation and chiral discrimination phenomena in these lyotropic solvents could be treated separately because they would involve different interaction mecha-nisms.