Structure spin-lattice relaxation

Figure Bl.13.4. The inversion-recovery detennination of the carbon-13 spin-lattice relaxation rates in melezitose. (Reproduced by pemiission of Elsevier from Kowalewski J and Maler L 1997 Methods for Structure Elucidation by High-Resolution N R ed Gy Batta, K E Kover and Cs Szantay (Amsterdam Elsevier) pp 325-47.)...

In this section, the characteristics of the spectra displayed by the different types of iron—sulfur centers are presented, with special emphasis on how they depend on the geometrical and electronic structure of the centers. The electronic structure is only briefly recalled here, however, and interested readers are referred to the excellent standard texts published on this topic (3, 4). Likewise, the relaxation properties of the centers are described, but the nature of the underlying spin-lattice relaxation processes is not analyzed in detail. However, a short outline of these processes is given in the Appendix. The aim of this introductory section is therefore mainly to describe the tools used in the practical applications presented in Sections III and IV. It ends in a discussion about some of the issues that may arise when EPR spectroscopy is used to identify iron-sulfur centers. 

PROTON SPIN-LATTICE RELAXATION RATES IN THE STRUCTURAL ANALYSIS OF CARBOHYDRATE MOLECULES... 

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,... 

Proton Spin—Lattice Relaxation Rates in the Structural Analysis of Carbohydrate Molecules in Solution... 

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. 

The saturation behavior of a spectrum - the variation of integrated intensity with microwave power - is related to the spin-lattice relaxation time, a measure of the rate of energy transfer between the electron spin and its surroundings. Saturation often depends on the same structural and dynamic properties as line widths. 

Crystals of (TTF)[Au(C6F5)C1] have been grown by electrocrystallization [53] however, their crystal structure has not been determined. The room temperature conductivity, as measured on compacted pellets, is quite low (10-6 S cm-1). At room temperature, the EPR line width of these salts is about 10 G. This line width decreases with temperature as a result of increased spin-lattice relaxation times and a lower electrical conductivity. 

Recently, Lipton et al. [25] have used zinc-67 NMR to investigate [Zn(HB(3,5-(CH3)2pz)3)2] complexes which have been doped with traces of paramagnetic [Fe(HB(3,4,5-(CH3)3pz)3)2]. The low-temperature Boltzmann enhanced cross polarization between XH and 67Zn has shown that the paramagnetic iron(II) dopant reduces the proton spin-lattice relaxation time, Tj, of the zinc complexes without changing the proton spin-lattice relaxation time in the Tip rotating time frame. This approach and the resulting structural information has proven very useful in the study of various four-coordinate and six-coordinate zinc(II) poly(pyrazolyl)borate complexes that are useful as enzymatic models. 

Another possible solution to the problem of analyzing multiple-layered membrane composites is a newly developed method using NMR spin-lattice relaxation measurements (Glaves 1989). In this method, which allows a wide range of pore sizes to be studied (from less than 1 nm to greater than 10 microns), the moisture content of the composite membrane is controlled so that the fine pores in the membrane film of a two-layered composite are saturated with water, but only a small quantity of adsorbed water is present in the large pores of the support. It has been found that the spin-lattice relaxation decay time of a fluid (such as water) in a pore is shorter than that for the same fluid in the bulk. From the relaxation data the pore volume distribution can be calculated. Thus, the NMR spin-lattice relaxation data of a properly prepared membrane composite sample can be used to derive the pore size distribution that conventional pore structure analysis techniques... 

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