Relaxation studies

Linewidth effects and relaxation time studies have been very extensive in this field. These are, of course, primarily studies of rates, which are not my present 

Although well over 3000 trigonal and tetrahedral boron compounds have been examined by B NMR spectroscopy, liquid-state relaxation behavior appears to be essentially unexamined, even though the potential usefulness of work in this area was demonstrated some two decades ago (for example. Ref. 66). Even linewidths, which are readily obtained by straightforward spectroscopy and can vary substantially with compound and solvent, have only been reported for a handful of species. It would be useful if these could be reported routinely. There would seem to be much scope for systematic study within this general area, which can in principle yield much information about electronic environment, geometry, molecular motion, states of aggregation, etc. (see Chapter 4). 

NMR is a crucial tool in polyhedral boron chemistry the literature is extensive and detailed excellent comprehensive compilations of the data published to mid-1981 are in Refs. 3, 6, and 7, but unfortunately no recent critical and comparative comprehensive account is available. Citations given should themselves be considered as sources of further references. 

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Besides measuring and T2 for nuclei such as C or N, relaxation studies for these nuclei also include measurements of the NOE factor, cf equation B 1.13.6. Knowing the (pj) and the steady-state NOE... 

In this section, I present a few illustrative examples of applications of NMR relaxation studies within different branches of chemistry. The three subsections cover one story each, in order of increasing molecular size and complexity of the questions asked. 

Champmartin D and Rubini P 1996 Determination of the 0-17 quadrupolar coupling constant and of the C-13 chemical shielding tensor anisotropy of the CO groups of pentane-2,4-dione and beta-diketonate complexes in solution. NMR relaxation study/norg. Chem. 35 179-83... 

In electron spin echo relaxation studies, the two-pulse echo amplitude, as a fiinction of tire pulse separation time T, gives a measure of the phase memory relaxation time from which can be extracted if Jj-effects are taken into consideration. Problems may arise from spectral diflfrision due to incomplete excitation of the EPR spectrum. In this case some of the transverse magnetization may leak into adjacent parts of the spectrum that have not been excited by the MW pulses. Spectral diflfrision effects can be suppressed by using the Carr-Purcell-Meiboom-Gill pulse sequence, which is also well known in NMR. The experiment involves using a sequence of n-pulses separated by 2r and can be denoted as [7i/2-(x-7i-T-echo) J. A series of echoes separated by lx is generated and the decay in their amplitudes is characterized by Ty. ... 

Stress relaxation studies were conducted on samples of nylon yarn at a constant strain of 2% and the following results were obtained ... 

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. 

K = 63 M 1, Kb = 1.4M-1)47 lithium-7 (K = 14 M 1 K" = 0.5 M 1) 49) and for cesium-133 (K, st 50 M-1, K = 4M 1)S0). In the case of sodium-23, transverse relaxation times could also be utilized to determine off-rate constants k ff = 3 x 105/sec k"ff = 2x 107/sec47,51). Therefore for sodium ion four of the five rate constants have been independently determined. What has not been obtained for sodium ion is the rate constant for the central barrier, kcb. By means of dielectric relaxation studies a rate constant considered to be for passage over the central barrier, i.e. for jumping between sites, has been determined for Tl+ to be approximately 4 x 106/sec 52). If we make the assumption that the binding process functions as a normalization of free energies, recognize that the contribution of the lipid to the central barrier is independent of the ion and note that the channel is quite uniform, then it is reasonable to utilize the value of 4x 106/sec for the sodium ion. 

Despite the results from various experiments such as transference number measurements, polarographic studies, spectroscopic measurements, and dielectric relaxation studies in addition to conductivity measurements, unilateral triple-ions remain a matter of debate. For experimental examples and other hypotheses for the interpretation of conductance minima the reader is referred to Ref. [15] and the literature cited there. 

Up to now it has been tacitly assumed that each molecular motion can be described by a single correlation time. On the other hand, it is well-known, e.g., from dielectric and mechanical relaxation studies as well as from photon correlation spectroscopy and NMR relaxation times that in polymers one often deals with a distribution of correlation times60 65), in particular in glassy systems. Although the phenomenon as such is well established, little is known about the nature of this distribution. In particular, most techniques employed in this area do not allow a distinction of a heterogeneous distribution, where spatially separed groups move with different time constants and a homogeneous distribution, where each monomer unit shows essentially the same non-exponential relaxation. Even worse, relaxation... 

Gillen K. T., Douglas D. S., Malmberg M. S., Maryott A. A. NMR relaxation study of liquid CCI3F. Reorientational and angular momentum correlation times and rotational diffusion, J. Chem. Phys. 57, 5170-9 (1972). 

Jameson C. J., Jameson A. K., Smith N. C. 15N spin-relaxation studies of N2 in buffer gases. Cross-sections for molecular reorientation and rotational energy transfer, J. Chem. Phys. 86, 6833-8 (1987). 

Courtney J. A., Armstrong R. L. A nuclear spin relaxation study of the spin-rotation interaction in spherical top molecules. Can. J. Phys. 50, 1252-61 (1972). 

Bohidar et al. 1998, realized studies of Sol and Gel state properties of aqueous gelatin solutions of concentrations 4%, 6%, 8% and 10% (w/v) were investigated through dielectric relaxation studies done at various temperatures in the range from 20 to 60°C carried out over a frequency range 20Hz-10MHz and no relaxation of any nature was observed. 

Urry DW, Trapane TL, McMichens RB et al (1986) N-15 nmr relaxation study of inverse temperature transitions in elastin pol)q)entapeptide and its cross-linked elastomer. Biopolymers 25 5209-5228... 

Qualitative relaxation-studies have also been reported for an extensive series of derivatives of inositols, pentopyranoses, l,6-anhydro-/3-D-hexopyranoses, furanoses, and septanoses. In all instances, the experimentally determined Ri(ns) values reflect the anticipated geometry. For the furanose derivatives especially, they provide a better means for distinguishing between epimeric pairs than the relatively ambiguous interpretation of coupling-constant data. 

Dielectric relaxation studies of phosphorylated polyethers from — 180° to 200 °C have been used to study their structures. The magnitude of the dielectric constants of high-phosphonic-acid-content polymers is much larger than predicted, which suggests a microphase-separated structure. Conductance studies on some aryl- and alkyl-phosphonium salts showed a higher conductance for the halides than for the nitrate. ... 

Paddon, J. M. Wilson, A. D. (1976). Stress relaxation studies on dental materials. 1. Dental cements. Journal of Dentistry, 4, 183-9. 

IL Claeys, FH Arnold. Nuclear magnetic relaxation study of hindered rotational diffusion in gels. AIChE J 35 335-338, 1990. 

Brady C, McGarvey JJ, McCusker JK, Toftlund H, Hendrickson DN (2004) Time-Resolved Relaxation Studies of Spin Crossover Systems in Solution. 235 1-22 Brand SC, see Haley MM (1999) 201 81-129 Bravic G,see Guionneau P (2004) 234 97-128... 

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