Nuclear magnetic resonance relaxation rate

There are other physical measurements which reflect molecular mobility and can be related to relaxation times and friction coefficients similar to those which characterize the rates of viscoelastic relaxations. Although such phenomena are outside the scope of this book, they are mentioned here because in some cases their dependence on temperature and other variables can be described by reduced variables and, by means of equation 49 or modifications of it, free volume parameters can be deduced which are closely related to those obtained from viscoelastic data. These include measurements of dispersion of the dielectric constant, nuclear magnetic resonance relaxation, diffusion of small molecules through polymers, and diffusion-controlled aspects of crystallization and polymerization. 

In the previous section was given the experimental demonstration of two sites. Here the steady state scheme and equations necessary to calculate the single channel currents are given. The elemental rate constants are thereby defined and related to experimentally determinable rate constants. Eyring rate theory is then used to introduce the voltage dependence to these rate constants. Having identified the experimentally required quantities, these are then derived from nuclear magnetic resonance and dielectric relaxation studies on channel incorporated into lipid bilayers. 

Dawson, M.J., Gadian, D.G., Wilkie, D.R. (1980). Mechanical relaxation rate and metabolism studied in fatiguing muscle by phosphorus nuclear magnetic resonance. J. Physiol. 299,465-484. 

The proton spin-lattice relaxation-rate (R,) is a well established, nuclear magnetic resonance (n.m.r.) parameter for structural, configurational, and conformational analysis of organic molecules in solution. " As yet, however, its utility has received little attention in the field of carbohydrate chemistry,... 

Richardson, S.J. 1989. Contribution of proton exchange to the oxygen-17 nuclear magnetic resonance transverse relaxation rate in water and starch-water systems. Cereal Chem. 66, 244-246. Richardson, M.J. and Saville, N.G. 1975. Derivation of accurate glass transition temperatures by differential scanning calorimetry. Polymer 16, 753-757. 

In the standard mathematical expressions for the contribution of quadrupolar relaxation to the relaxation rates of the quadrupolar nucleus (in nuclear magnetic resonance), rapid isotropic motion is assumed to occur. This behavior, in most cases, will not be true in the solid or liquid crystalline state ". ... 

Nuclear magnetic resonance (NMR) spectroscopy is a most effective and significant method for observing the structure and dynamics of polymer chains both in solution and in the solid state [1]. Undoubtedly the widest application of NMR spectroscopy is in the field of structure determination. The identification of certain atoms or groups in a molecule as well as their position relative to each other can be obtained by one-, two-, and three-dimensional NMR. Of importance to polymerization of vinyl monomers is the orientation of each vinyl monomer unit to the growing chain tacticity. The time scale involved in NMR measurements makes it possible to study certain rate processes, including chemical reaction rates. Other applications are isomerism, internal relaxation, conformational analysis, and tautomerism. 

A second steady-state method involves the analysis of the broadening of the nuclear magnetic resonance spectra of phospholipids in bilayers containing low concentrations of spin-labeled phospholipids. A theoretical analysis of the relation between this line broadening and diffusion rates has been given by Brulet and McConnell.3 [In this paper (6) is not correct the subsequent equations are nonetheless correct. For an alternative derivation, see Brulet.2] In this paper it is shown that a number of measurements of nuclear relaxation rates T71 of nuclei in phospholipids are consistent with lateral diffusion constants in the range 10 7 to 10 R cm2/s. 

Figure 15.16. H Relaxation of 1-naphthol protons with increasing humic acid concentration at pH 7. All protons are observed to relax at a similar rate, suggesting a nonselective interaction between the protons of 1-naphthol and humic acid. Reprinted from Simpson, M. I, Simpson, A. J., and Hatcher, R G. (2004). Noncovalent interactions between aromatic compounds and dissolved humic acid examined by nuclear magnetic resonance spectroscopy. Environ. Toxi. Chem. 23, 355-362, with permission from the Society of Environmental Toxicology and Chemistry.

Methods such as nuclear magnetic resonance (NMR), electron spectroscopy for chemical analysis (ESCA), electron spin resonance (ESR), infrared (IR), and laser raman spectroscopy could be used in conjunction with rate studies to define mechanisms. Another alternative would be to use fast kinetic techniques such as pressure-jump relaxation, electric field pulse, or stopped flow (Chapter 4), where chemical kinetics are measured and mechanisms can be definitively established. 

Abstract We use Nuclear Magnetic Resonance relaxometry (i.e. the frequency variation of the NMR relaxation rates) of quadrupolar nucleus ( Na) and H Pulsed Gradient Spin Echo NMR to determine the mobility of the counterions and the water molecules within aqueous dispersions of clays. The local ordering of isotropic dilute clay dispersions is investigated by NMR relaxometry. In contrast, the NMR spectra of the quadrupolar nucleus and the anisotropy of the water self-diffusion tensor clearly exhibit the occurrence of nematic ordering in dense aqueous dispersions. Multi-scale numerical models exploiting molecular orbital quantum calculations, Grand Canonical Monte Carlo simulations, Molecular and Brownian Dynamics are used to interpret the measured water mobility and the ionic quadrupolar relaxation measurements. 

Water Associated with the External Contour of Tactoids. The existence of tactoids can be evidenced by studying th longitudinal relaxation time of the nuclear magnetic resonance of H or H in aqueous slurries (7-8). In simple terms, the relaxation rate, e.g. the inverse of the relaxation time, is the sum of three terms... 

Peters, J.A., Huskens, J., and Raber, D.J. (1996) Lanthanide induced shifts and relaxation rate enhancements. Progress in Nuclear Magnetic Resonance Spectroscopy, 28, 283-350. 

The dilatometric method is time-consuming and subject to the bias introduced by the convention described. More recently pulsed Nuclear Magnetic Resonance (pNMR) has been used to measure the relative amounts of liquid and solid fat in a sample, based upon the difference in rates of relaxation of protons in the two phases after the sample has been pulsed (AOCS Method Cd 16-81). With proper calibration this gives a direct determination of the percentage of solid fat, and the results are termed sohd fat content (SFC). The analysis takes less time than dilato-metry, but the equipment is more expensive. 

The results of nuclear magnetic resonance (NMR) measurements on alkali fullerides K cC o reported. The NMR spectra demonstrate that material with 0 < X < 3 is in fact a two-phase system at equilibrium, with x = 0 and x = 3. NMR lineshapes indicate that C o Ions rotate rapidly in the KsC q phase at 300 K, while 50 ions in the insulating KaC o phase are static on the time scale of the lineshape measurement. The temperature dependence of the spin-lattice relaxation rate in the normal state of is found to be characteristic of a metal, indicating the... 

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