Spin-lattice relaxation parameters

A similar continuity in the Tj s through the melting temperature was previously reported for linear polyethylene. (17) We have now investigated the temperature dependence of this quantity, for this polymer, in more detail and have also studied a low density (branched) polyethylene. The results for the poly-ethylenes are summarized in Fig. 8. The new data reported here substantiate the conclusion previously reached for linear polyethylene. A similar conclusion can now be reached for the baclc-bone carbons of low density (branched) polyethylene. The melting temperature for this particular sample, under the crystallization conditions studied, is less than 110°C. (33) Thus, the spin-lattice relaxation parameters for the bac)cbone carbons are the same for both the linear and branched polymers over the temperature range studied here. Changes that occur in Tq as the temperature is reduced below 0°C involve other considerations and will be discussed in detail elsewhere. (22)... 

Proton NMR relaxation parameters have also been determined for polyethylene ( ) and polyethylene oxide (39) in the melting region. The apparent contradiction between the proton spin-lattice relaxation parameter for a high molecular weight linear polyethylene sample at its melting point, with the relaxation measurements, has previously been pointed out. (17) This discrepancy is still maintained with the more detailed results reported here for both types of polyethylene. For the proton relaxation a small, but distinct, discontinuity is reported at the melting teirperature. (38)... 

In contrast to the spin-lattice relaxation parameters, which remain invariant, a sijbstantial broadening of the resonant lines occurs upon crystallization. The effect is relatively modest for cis polyisoprene at 0°C and 57.9 MHz, where comparison can be made at the same temperature. Here there is about a 50% increase in the linewidths upon the development of 30% crystallinity. Schaefer (13) reports approximately 3- to 5-fold broader lines (but they are still relatively narrow) for the crystalline trans polyisoprene relative to the completely amorphous cis polyisoprene at 40°C and 22.5 MHz. It is interesting to note in this connection that for carbon black filled cis polyisoprene the line-widths are greater by factors of 5-10 relative to the unfilled polymer. 

The results discussed above indicate that the further study of the spin relaxation parameters possess the potential to develop our understanding of the structure of the non-crystalline regions of semicrystalline polymers. Significant progress has already been made in relating the spin-lattice relaxation parameters with that of the pure melt. The linewidths, or spin-spin relaxation parameters, of semicrystalline polymers have been... 

Relaxation, CIDNP, and N.Q.R.—Relaxation. Phosphorus-31 and carbon-13 relaxation times are reported for dimethyl methylphosphonate. The mobility of phosphazene polymers has been studied using P spin-lattice relaxation parameters. The structure and mobility of polycrystalline nitrilotrimethylphos-phonic acid was estimated by line shape analysis. Molecular interactions of guanosine monophosphate and ATP have been studied through their relaxation properties. ... 

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,... 

The process of spin-lattice relaxation involves the transfer of magnetization between the magnetic nuclei (spins) and their environment (the lattice). The rate at which this transfer of energy occurs is the spin-lattice relaxation-rate (/ , in s ). The inverse of this quantity is the spin-lattice relaxation-time (Ti, in s), which is the experimentally determinable parameter. In principle, this energy interchange can be mediated by several different mechanisms, including dipole-dipole interactions, chemical-shift anisotropy, and spin-rotation interactions. For protons, as will be seen later, the dominant relaxation-mechanism for energy transfer is usually the intramolecular dipole-dipole interaction. 

The most popular, and also a very accurate, experimental method for measuring nonselective spin-lattice relaxation-rates is the inversion recovery (180°-r-90°-AT-PD)NT pulse sequence. Here, t is the variable parameter, the little t between pulses, AT is the acquisition time, PD is the pulse delay, set such that AT-I- PD s 5 x T, and NT is the total number of transients required for an acceptable signal-to-noise ratio. Sequential application of a series of two-pulse sequences, each using a different pulsespacing, t, gives a series of partially relaxed spectra. Values of Rj can... 

The significance of n.m.r. spectroscopy for structural elucidation of carbohydrates can scarcely be underestimated, and the field has become vast with ramifications of specialized techniques. Although chemical shifts and spin couplings of individual nuclei constitute the primary data for most n.m.r.-spectral analyses, other n.m.r. parameters may provide important additional data. P. Dais and A. S. Perlin (Montreal) here discuss the measurement of proton spin-lattice relaxation rates. The authors present the basic theory concerning spin-lattice relaxation, explain how reliable data may be determined, and demonstrate how these rates can be correlated with stereospecific dependencies, especially regarding the estimation of interproton distances and the implications of these values in the interpretation of sugar conformations. 

Kusumi, A., W. K. Subczynski, and J. S. Hyde. 1982b. Oxygen transport parameter in membranes as deduced by saturation recovery measurements of spin-lattice relaxation times of spin labels. Proc. Natl. Acad. Sci. USA 79 1854-1858. 

Since the magnetic moments are smaller, now we have a smaller susceptibility and therefore much smaller signal, requiring more sensitive detection systems. These are resonance or SQUID (see Section 14.5) techniques. Thermal response time are shorter, since pure metals can be used with good thermal conductivity and fast spin-lattice relaxation. The parameter to be measured is the nuclear susceptibility ... 

Fig. 20. Square-law functional dependence of spin-lattice relaxation rates R z on segmental order parameters for a homologous series of disaturated phosphat-...

Fig. 18. The proton spin-lattice relaxation rate recorded as a function of the magnetic field strength plotted as the proton Larmor frequency for lysozyme samples. Dry ( ), hydrated to 8.9% ( ), 15.7% (O). 23.1% (A), and cross-linked in a gel ( ). The solid lines were computed from the theory. The solid lines are fits to the data using Eq. (4) with Rs given by Eq. (6). The two parameters adjusted are Rsl and b (97). The small peaks most apparent in the dry samples are caused by cross-relaxation to the peptide nitrogen spin (90,122).

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