Sergey V. Dvinskikh

Heteronuclear dipolar recoupling in liquid crystals and solids by PISEMA-type pulse sequences

A pulse sequence is described for the recoupling of heteronuclear dipolar interactions under MAS. The method is similar to the PISEMA experiment, but employs a well-defined amplitude modulation of one of the two radio-frequency fields. The technique is used for measurements of 1H-13C dipolar couplings in unoriented solid and liquid-crystalline samples.

Heteronuclear isotropic mixing separated local field NMR spectroscopy

This paper presents a theoretical, numerical, and experimental study of a new class of separated local field (SLF) techniques. These techniques are based on the heteronuclear isotropic mixing leading to spin exchange via the local field (HIMSELF). It is shown that highly efficient and robust SLF experiments can be designed based on double channel windowless homonuclear decoupling sequences. Compared to rotating frame techniques based on Hartmann-Hahn cross polarization, the new approach is less susceptible to the frequency offset and chemical shift interaction and can be applied in the structural studies of macromolecules that are uniformly labeled with isotopes such as (13)C and (15)N. Furthermore, isotropic mixing sequences allow for transfer of any magnetization component of one nucleus to the corresponding component of its dipolar coupled partner. The performance of HIMSELF is studied by analysis of the average Hamiltonian and numerical simulation and is experimentally demonstrated on a single crystalline sample of a dipeptide and a liquid crystalline sample exhibiting motionally averaged dipolar couplings.

Efficient solid-state NMR methods for measuring heteronuclear dipolar couplings in unoriented lipid membrane systems

Recently (Dvinskikh et al., J. Magn. Reson., 2003, 164, 165 and Dvinskikh et al., J. Magn. Reson., 2004, 168, 194), some of us introduced two efficient solid-state NMR techniques for the determination of heteronuclear dipolar couplings under magic-angle spinning (MAS). These two-dimensional (2D) recoupling methods have been applied previously to simple amino acids, and to columnar systems with high positional and orientational order. In this work, we show that the 2D MAS sequences produce unparalleled 1H-13C dipolar resolution in unoriented lipid membranes. The recoupling experiments were applied to hydrated dimyristoylphosphatidylcholine (DMPC) in the liquid-crystalline Lalpha phase, and the results agreed well with previous NMR investigations using specifically deuterated phospholipids.

Heteronuclear dipolar recoupling in solid-state nuclear magnetic resonance by amplitude-, phase-, and frequency-modulated Lee-Goldburg cross-polarization.

This paper presents a theoretical, numerical, and experimental study of phase- and frequency-switched Lee-Goldburg cross-polarization (FSLG-CP) under magic-angle spinning conditions. It is shown that a well-defined amplitude modulation of one of the two radio-frequency (rf) fields in the FSLG-CP sequence results in highly efficient heteronuclear dipolar recoupling. The recoupled dipolar interaction is gamma-encoded and, under ideal conditions, the effective spin Hamiltonian is equivalent to that in continuous-wave Lee-Goldburg CP. In practice, however, FSLG-CP is less susceptible to rf field mismatch and inhomogeneity, and provides better suppression of (1)H spin diffusion. The performance of FSLG-CP is experimentally demonstrated on liquid-crystalline samples exhibiting motionally averaged dipolar couplings.

Anisotropic self-diffusion in the nematic phase of a thermotropic liquid crystal by 1H-spin-echo nuclear magnetic resonance

The orientation-dependent molecular diffusion in the nematic liquid crystal 4-pentyl-4′-cyanobiphenyl is measured to high accuracy. The applied nuclear magnetic resonance method combines multiple-pulse homonuclear dipolar decoupling with pulsed-field-gradient stimulated echo and slice selection. The obtained temperature dependencies of the principal diffusion coefficients are not described by a simple Arrhenius relationship but reflect the decrease of the molecular orientational order close to the nematic-to-isotropic phase transition. The geometric average of the principal diffusion coefficients is continuous with the diffusion coefficient in the isotropic phase. The results are best described in terms of the affine transformation model of diffusion in hard-ellipsoid nematics.The orientation-dependent molecular diffusion in the nematic liquid crystal 4-pentyl-4′-cyanobiphenyl is measured to high accuracy. The applied nuclear magnetic resonance method combines multiple-pulse homonuclear dipolar decoupling with pulsed-field-gradient stimulated echo and slice selection. The obtained temperature dependencies of the principal diffusion coefficients are not described by a simple Arrhenius relationship but reflect the decrease of the molecular orientational order close to the nematic-to-isotropic phase transition. The geometric average of the principal diffusion coefficients is continuous with the diffusion coefficient in the isotropic phase. The results are best described in terms of the affine transformation model of diffusion in hard-ellipsoid nematics.

Separated local field spectroscopy of columnar and nematic liquid crystals.

We are in this work comparing the efficiencies of various 1H-13C separated local field (SLF) experiments when applied to columnar and nematic liquid crystals. In particular, the performances of the conventional SLF, proton-detected local field (PDLF), and polarization inversion spin exchange at the magic angle (PISEMA) methods in terms of spectral resolution, robustness, and ability to measure long-range couplings are investigated. The PDLF sequence provides in most cases the best dipolar resolution. This is especially obvious for weakly coupled 1H-13C spin pairs.

NMR investigations of interactions between anesthetics and lipid bilayers

Interactions between anesthetics (lidocaine and short chain alcohols) and lipid membranes formed by dimyristoylphosphatidylcholine (DMPC) were studied using NMR spectroscopy. The orientational order of lidocaine was investigated using deuterium NMR on a selectively labelled compound whereas segmental ordering in the lipids was probed by two-dimensional 1H-13C separated local field experiments under magic-angle spinning conditions. In addition, trajectories generated in molecular dynamics (MD) computer simulations were used for interpretation of the experimental results. Separate simulations were carried out with charged and uncharged lidocaine molecules. Reasonable agreement between experimental dipolar interactions and the calculated counterparts was observed. Our results clearly show that charged lidocaine affects significantly the lipid headgroup. In particular the ordering of the lipids is increased accompanied by drastic changes in the orientation of the P-N vector in the choline group.

Ion conductive behaviour in a confined nanostructure: NMR observation of self-diffusion in a liquid-crystalline bicontinuous cubic phase

The diffusion of ions in an ionic liquid crystal exhibiting a bicontinuous cubic liquid-crystalline phase has been investigated by NMR spectroscopy in order to examine the behaviour of ions in an ordered nanostructure.

Probing segmental order in lipid bilayers at variable hydration levels by amplitude- and phase-modulated cross-polarization NMR

The conformational response of dimyristoylphosphatidylcholine bilayers in the liquid crystalline phase to hydration is investigated by a novel magic-angle spinning cross-polarization NMR technique.

Experimental Detection of Trinitramide, N(NO2)3

Propeller propellant: The largest nitrogen oxide to date, trinitramide (TNA), has been prepared following extensive quantum chemical studies in which its kinetic stability and several physical properties were estimated. TNA was detected using IR and NMR spectroscopy. The compound is highly energetic and shows promise for cryogenic propulsion and as a reagent in high-energy-density material research.