Nuclear magnetic resonance molecular reorientation

Nuclear magnetic resonance provides means to study molecular dynamics in every state of matter. When going from solid state over liquids to gases, besides mole- cular reorientations, translational diffusion occurs as well. CD4 molecule inserted into a zeolite supercage provides a new specific model system for studies of rotational and translational dynamics by deuteron NMR. 

Vittadini, E., Dickinson, L.C., and Chinachoti, P. 2002. NMR water mobility in xanthan and locust bean gum mixtures Possible explanation of microbial response. Carbohydr. Polym. 49, 261-269. Wachner, A.M. and Jeffrey, K.R. 1999. A two-dimensional deuterium nuclear magnetic resonance study of molecular reorientation in sugar/water glasses. J. Chem. Phys. Ill, 10611-10616. Wagner, W. and Pruss, A. 1993. International equations for the saturation properties of ordinary water substance Revised according to the international temperature scale of 1990. J. Phys. Chem. Ref. Data 22, 783-787. 

At room temperature, these molecules occupy well-defined locations in their respective crystal lattices. However, they tumble freely and isotropically (equally in all directions) in place at their lattice positions. As a result, their solid phase NMR spectra show features highly reminiscent of liquids. We will see an illustration of this point shortly. Other molecules may reorient anisotropically (as in solid benzene). Polymer segmental motions in the melt may cause rapid reorientation about the chain axis but only relatively slow reorientation of the chain axes themselves. Large molecular aggregates in solution (such as surfactant micelles or protein complexes or nucleic acids) may appear to have solidlike spectra if their tumbling rates are sufficiently slow. There are numerous other instances in which our macroscopic motions of solid and liquid may be at odds with the molecular dynamics. Nuclear magnetic resonance is one of the foremost ways of investigating these situations. 

Wachner, A.M. and Jeffrey, K.R. A two-dimensional deuterium nuclear magnetic resonance study of molecular reorientation in sugar/water glasses, /. Chem. Phys., Ill, 10611,1999. 

Nuclear magnetic resonance (NMR), in particular, deuterium NMR, has proven to be a valuable technique for determining the nature of molecular organization in liquid crystals. The utility of the NMR technique derives from the fact that the relevant NMR interactions are entirely intramolecular, i.e. the dominant interaction is that between the nuclear quadrupole moment of the deuteron and the local electric-field gradient (EFG) at the deuterium nucleus. The EFG tensor is a traceless, axially symmetric, second-rank tensor with its principal component along the C—D bond. In a nematic fluid rapid anisotropic reorientation incompletely averages the quadrupolar interaction tensor q, resulting in a nonzero projection similar to the result in Eq. (5.6) ... 

The parameters characterizing the nuclear magnetic resonance in a solid, in particular the linewidth, second moment, and the spin-spin and spin-lattice relaxation times, are strongly affected by molecular reorientations and atomic diffusive motions. Application of NMR methods to the study of hydrogen (and deuterium) diffusion in the non-magnetic rare-earth hydrides has been extensive. 

Quasielectric Light Scattering and Order Fluctuations in the Isotropic Phase 174 Nuclear Magnetic Resonance and Order Fluctuations in the Isotropic Phase. 175 Quasielastic Light Scattering and Orientational Fluctuations below Tc. . . 177 Nuclear Magnetic Resonance and Orientational Fluctuations below Tc.. .. 177 Optical Kerr Effect and Transient Laser-Induced Molecular Reorientation.. 181... 

Nuclear magnetic resonance (NMR) provides a powerful method for the study of molecular motion. The techniques can distinguish molecular reorientation and translation and have proved particularly valuable for the study of self-diffusion in bulk liquids. The molecular motion of liquids in the confined geometry provided by their containment in porous materials has been of considerable interest for many years. It is of importance both as a fundamental scientific problem and because of its technological importance in such diverse systems as oil recovery from rocks and catalytic agents. The purpose of this paper is to question the reliability of many previous investigations and the validity of their interpretation. Potential sources of error are demonstrated by measurements on mobile liquids adsorbed into porous silicas with different geometrical characteristics. The principles illustrated are equally valid for other porous systems. Preliminary measurements of the diffusion coefficient of n-butane in silica as a fimction of temperature and the effect of pore dimensions are presented. 

A nuclear magnetic relaxation study85 of lactose (17), which is a basic constituent disaccharide unit of all gangliosides, demonstrates that this molecule reorients anisotropically. The favored axis of molecular reorientation appears to lie along the axis of the molecule and therefore is reflected in the shorter T, value at C-4 of the galactose residue. The apparent differences between the relaxation times observed for the C-l resonances of the a (17a) and /3 (17b) isomers may also be reflected in their differing C—H orientations relative to the anisotropic axis. Similar anisotropic motion was observed for methyl /3-lactoside,85 methyl /3-cellobioside,84 and other disaccharide derivatives in solution. 

As already mentioned, in some molecular crystals, a hindered or nearly free rotation of entire molecules is observed, e.g. of benzene molecules in crystals of benzene, or of molecular groups, e.g. of CH3 groups in crystals of methyl naphthalene. These motions are stochastic and are termed pseudorotations or reorientations. These two terms denote the two limiting approximations, that of free rotation and that of a fixed orientation of the molecules or molecular groups. Experimental methods which have proved useful for the investigation of these stochastic motions are nuclear-spin magnetic resonance (NMR) [24] and quasielastic neutron scattering [35, 36]. 

There are a large number of studies concerned with nuclear spin relaxation [7.45] in liquid crystals. The majority of these involve observation of the total proton magnetization arising from all protons in a mesogen. The experiments usually yield only one relaxation time, which is difficult, if not impossible, to relate to details of motion in the liquid crystalline phase. Deuteron and carbon-13 NMR may be used to study nuclear spin relaxation at several sites in a mesogen. In particular, direct measurement of spectral densities using deuterium resonant lines has made testing of motional models possible in liquid crystals. As yet, there is no report on systematic comparison between the different models of molecular reorientation. 

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