Characterization of chemical exchange using residual dipolar coupling. Academic Article uri icon

abstract

  • NMR lineshape analysis and relaxation dispersion measurements for N,N-dimethyltrichloroacetamide (DMTCA) weakly aligned using poly--benzyl-L-glutamate, which forms a lyotropic nematic phase when dissolved in chloroform, were used to characterize chemical exchange kinetics for the rotation around the C-N amide bond. At low temperatures (<312 K), slow-exchange 1H-coupled 13C NMR spectra show two resolved 13C methyl quartets with different residual dipolar coupling constants (RDCs). At high temperatures (>312 K), a single population-averaged 13C methyl quartet is observed; in this regime, the differences in RDCs contribute to differential linebroadening of the quartet components. Self-consistent measurements of the difference in RDCs are obtained both from lineshape and relaxation dispersion techniques. The results show that NMR spectroscopy of weakly aligned molecules allow complete characterization of chemical exchange processes using RDCs, even if exchange broadening is absent in isotropic samples.

published proceedings

  • J Am Chem Soc

author list (cited authors)

  • Igumenova, T. I., Brath, U., Akke, M., & Palmer, A. G.

citation count

  • 57

complete list of authors

  • Igumenova, Tatyana I||Brath, Ulrika||Akke, Mikael||Palmer, Arthur G

publication date

  • November 2007