Deuterium water relaxation

Richardson and co-workers87,88 have reported oxygen-17 and deuterium water transverse relaxation rates in corn starch suspensions over a wide... 

Investigation of water motion in AOT reverse micelles determining the solvent correlation function, C i), was first reported by Sarkar et al. [29]. They obtained time-resolved fluorescence measurements of C480 in an AOT reverse micellar solution with time resolution of > 50 ps and observed solvent relaxation rates with time constants ranging from 1.7 to 12 ns. They also attributed these dynamical changes to relaxation processes of water molecules in various environments of the water pool. In a similar study investigating the deuterium isotope effect on solvent motion in AOT reverse micelles. Das et al. [37] reported that the solvation dynamics of D2O is 1.5 times slower than H2O motion. 

The T2 relaxation of protons and deuterium in muscle water is much faster than T2 relaxation of pure water. 

Several other nmr procedures have been used for the determination of fractionation factors. These have advantages in some systems. Instead of determining the effect of the concentration of an exchanging site on the averaged chemical shift, the effect on the averaged relaxation rate of water protons can be used in a very similar way (Silverman, 1981 Kassebaum and Silverman, 1989), For example, addition of the enzyme Co(ii)-carbonic anhydrase to an aqueous solution increases the observed value of XjT because the proton-relaxation rate is the average of that for the bulk solvent (cfl. 0.3 s ) and that for water bound to the cobalt ca. 6x 10 s ). The average is different in an H2O/D2O mixture if the bulk solvent and the Cobound solvent have different deuterium contents, and it has been used to determine a value for the fractionation factor of Co-bound water molecules in the enzyme. 

This study is similar to those previously done by Derbyshire and Duff (20) and Nystrom et al. (21) who studied water swellable gels. However, in the first of these, the use of proton NMR complicated the relaxation data because of proton-proton coupling. Furthermore, their study focused on the freezing (or non-freezing) of water which also complicated matters. In the present study, we are always well above the freezing point of toluene so that one need not worry about the freezing of the solvent. The study by Nystrom et al. (21) used deuterium NMR of D2O, but an unusual temperature dependence was observed, possibly due to the exchange of the protons or deuterons. Our present data are not complicated... 

The rotational correlation time can be directly obtained from 13C or deuterium relaxation measurements on a diamagnetic analogue (Y(III), La(III) or Lu(III)) of the Gd(III) complex [38,70-72]. One disadvantage is low sensitivity of 13C or 2D at natural abundance. Moreover, these methods do not measure the rotation of the metal - coordinated water vector, important from the practical point of view, and this may cause problems mainly in the case of large molecules. 

For the self-same clay samples, we have measured longitudinal relaxation rates for deuterium nuclei in heavy water. The relaxation rate is enhanced in proportion to the amount of suspended clay, according to ... 

Deuterium nuclei in water molecules have negligible asymmetry parameters and residual anisotropies. After correcting for the paramagnetic impurities present, that affect relaxation rates somewhat (35), one obtains from the experimental data a value of the longitudinal relaxation rate for the water deuterons in the bound state of 650 s 1. This value incorporates the quadrupolar coupling constant (above determined) and the correlation time for bound waters. Using the standard expression for quadrupolar relaxation (29,35) yields a value for t 1.6 ns. 

Cu isotopes both with nuclear spin I-3/2. The nucle r g-factors of these two isotopes are sufficiently close that no resolution of the two isotopes is typically seen in zeolite matrices. No Jahn-Teller effects have been observed for Cu2+ in zeolites. The spin-lattice relaxation time of cupric ion is sufficiently long that it can be easily observed by GSR at room temperature and below. Thus cupric ion exchanged zeolites have been extensively studied (5,17-26) by ESR, but ESR alone has not typically given unambiguous information about the water coordination of cupric ion or the specific location of cupric ion in the zeolite lattice. This situation can be substantially improved by using electron spin echo modulation spectrometry. The modulation analysis is carried out as described in the previous sections. The number of coordinated deuterated water molecules is determined from deuterium modulation in three pulse electron spin echo spectra. The location in the zeolite lattice is determined partly from aluminum modulation and more quantitatively from cesium modulation. The symmetry of the various copper species is determined from the water coordination number and the characteristics of the ESR spectra. 

Mobility of water in cellulose has been studied by solid-state and high-resolution NMR as a function of moisture content within the unfreezable moisture range (0-19% dry basis).Measurements of relative mobilities were based on relative intensities, transverse and longitudinal relaxation times and line shape analysis. At 2-16% moisture content (dry basis), water molecules reoriented anisotropically, suggesting an interaction with cellulose fibers. At moisture content below the monolayer value (2.8%, dry basis), 90% of the protons were immobile and no liquid deuterium signal was detected. A sharp increase in liquid or mobile intensity (accompanied by a decreased LW) and increases in NMR Ti and T2 relaxation times were observed as moisture increased above 9% (dry basis). 

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