J. Chem. Phys.

Internal symmetry of basic elements in symmetry-based recoupling sequences under magic-angle spinning

from Journal of Chemical Physics: All Topics

Fang-Chieh Chou, Hsin-Kuan Lee, and Jerry C. C. Chan

In solid-state NMR, many powerful pulse sequences under the condition of magic-angle spinning can be analyzed on the basis of the C- and R-sequences developed by Levitt and co-workers. It has been speculated for some years that the basic elements commonly used in symmetry-based recoupling pulse sequences have certain kind of internal symmetries. We show by a detailed analysis that a set of internal selection rules does exist for many basic elements. These internal selection rules may allow a more versatile design of CNnν or RNnν sequences when n is an integer or half-integer multiple of N. As an illustration, we have derived the symmetry arguments to rationalize the observation that the C-REDOR pulse sequence can suppress homonuclear dipole-dipole interaction, leading to the design of new windowed basic elements usable for heteronuclear dipolar recoupling with active suppression of homonuclear dipole-dipole interaction. Numerical simulations and experiments measured for [U–¹³C,¹⁵N]-L-alanine have been used to validate our approach. On a more general note, the symmetry rules discussed in this work can also be applied for the design of supercycles.

Puckering free energy of pyranoses: A NMR and metadynamics-umbrella sampling investigation

from Journal of Chemical Physics: All Topics

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E. Autieri, M. Sega, F. Pederiva, and G. Guella

We present the results of a combined metadynamics-umbrella sampling investigation of the puckered conformers of pyranoses described using the GROMOS 45a4 force field. The free energy landscape of Cremer–Pople puckering coordinates has been calculated for the whole series of α and β aldohexoses, showing that the current force field parameters fail in reproducing proper puckering free energy differences between chair conformers. We suggest a modification to the GROMOS 45a4 parameter set which improves considerably the agreement of simulation results with theoretical and experimental estimates of puckering free energies. We also report on the experimental measurement of altrose conformer populations by means of NMR spectroscopy, which show good agreement with the predictions of current theoretical models.