Neutron scattering, hydration

Figure 10 Elastic incoherent structure factors for lipid H atoms obtained from an MD simulation of a fully hydrated DPPC bilayer, and quasielastic neutron scattering experiments on DPPC bilayers at two hydration levels for (a) motion in the plane of the bilayer and (b) motion m the direction of the bilayer normal.

Neutron scattering has been used for studying the state of solvation of ions in aqueous solution (Enderby et al., 1987 Salmon, Neilson Enderby, 1988). These studies have shown that a distinct shell of water molecules of characteristic size surrounds each ion in solution. This immediate hydration shell was called zone A by Frank Wen (1957) they also postulated the existence of a zone B, an outer sphere of molecules, less firmly attached, but forming part of the hydration layer around a given ion. The evidence for the existence of zone B lies in the thermodynamics of... 

Fig. 4. A schematic two-dimensional illustration of the idea for an information theory model of hydrophobic hydration. Direct insertion of a solute of substantial size (the larger circle) will be impractical. For smaller solutes (the smaller circles) the situation is tractable a successful insertion is found, for example, in the upper panel on the right. For either the small or the large solute, statistical information can be collected that leads to reasonable but approximate models of the hydration free energy, Eq. (7). An important issue is that the solvent configurations (here, the point sets) are supplied by simulation or X-ray or neutron scattering experiments. Therefore, solvent structural assumptions can be avoided to some degree. The point set for the upper panel is obtained by pseudo-random-number generation so the correct inference would be of a Poisson distribution of points and = kTpv where v is the van der Waals volume of the solute. Quasi-random series were used for the bottom panel so those inferences should be different. See Pratt et al. (1999).

Keywords Polymer interactions, Raman spectra, hydration, rheology, neutron scattering. 

The average DNA helix diameter used in modeling applications such as the ones described here includes the diameter of the atomic-scale B-DNA structure and— approximately—the thickness of the hydration shell and ion layer closest to the double helix [18]. Both for the calculation of the electrostatic potential and the hydrodynamic properties of DNA (i.e., the friction coefficient of the helix for viscous drag) a helix diameter of 2.4 nm describes the chain best [19-22]. The choice of this parameter was supported by the results of chain knotting [23] or catenation [24], as well as light scattering [25] and neutron scattering [26] experiments. 

The hydration number of the Ln " " ions has been extensively addressed by various techniques like neutron scattering (121,122), X-ray scattering... 

A primary hydration number of 6 for Fe + in aqueous (or D2O) solution has been indicated by neutron diffraction with isotopic substitution (NDIS), XRD, 16,1017 EXAFS, and for Fe " " by NDIS and EXAFS. Fe—O bond distances in aqueous solution have been determined, since 1984, for Fe(H20)/+ by EXAFS and neutron diffraction, for ternary Fe " "-aqua-anion species by XRD (in sulfate and in chloride media, and in bromide media ), for Fe(H20)g by neutron diffraction, and for ternary Fe -aqua-anion species. The NDIS studies hint at the second solvation shell in D2O solution high energy-resolution incoherent quasi-elastic neutron scattering (IQENS) can give some idea of the half-lives of water-protons in the secondary hydration shell of ions such as Fe aq. This is believed to be less than 5 X I0 s, whereas t>5x10 s for the binding time of protons in the primary hydration shell. X-Ray absorption spectroscopy (XAS—EXAFS and XANES) has been used... 

The above molecular dynamics results have been confirmed by incoherent inelastic neutron scattering (IINS) measurements on xenon hydrate (Tse et al., 2001 Gutt et al., 2002). In earlier measurements on methane hydrate, the dominant... 

Persistent hydrate crystallites (long-range ordered structure), which were shown from neutron scattering to remain in solution for several hours after increasing the temperature above the hydrate dissociation temperature (Buchanan et al 2005). 

Table 6.3 provides a summary of the different microscopic techniques that have been applied to hydrate studies and the type of information that can be obtained from these tools. The following discussion provides a brief overview of the application of diffraction and spectroscopy to study hydrate structure and dynamics, and formation/decomposition kinetics. For information on the principles and theory of these techniques, the reader is referred to the following texts on x-ray diffraction (Hammond, 2001), neutron scattering (Higgins and Benoit, 1996), NMR spectroscopy (Abragam, 1961 Schmidt-Rohr and Spiess, 1994), and Raman spectroscopy (Lewis and Edwards, 2001). 

Small angle neutron scattering instruments are specifically designed to examine disordered materials, such as to determine hydration structures during hydrate formation (Koh et al., 2000 Buchanan et al., 2005 Thompson et al., 2006), or to study kinetic inhibitor adsorption onto a hydrate surface (Hutter et al., 2000 King et al., 2000). 

Neutron spectroscopy (also referred to as inelastic neutron scattering) has been used to measure the extent of guest-host interactions in a hydrate lattice, which help to explain the anomalous thermal behavior of hydrates (e.g., low thermal... 

Fig. 2. Number of observed deviations of the H-bond angle zero in solid hydrates (Data are of the neutron scattering values taken from the review of Falk and Knop )...

Fig. 3. Number of hydrates with O. .. O distances with a most probable O. . distance of about 2.8 A (Data are neutron scattering values collected by Falk and Knop32))...

For an example of structure analysis by X-ray scattering, see D. I. Svergun, S. Richard, M. H. Koch, Z. Sayers, S. Kuprin, and G. Zaccai, Protein hydration in solution experimental observation by X-ray and neutron scattering, Proc. Natl Acad. 3d. USA 95,2267-2272, 1998. 

Neutron-scattering and dielectric relaxation studies [23] both indicate that the water molecules solvating monovalent exchangeable cations on montmorillonite are a little less mobile, in respect to translational and reorientational motion, than are water molecules in the bulk liquid. For example, as with vermiculite, neutron-scattering data show that no water molecule is stationary on the neutron-scattering time scale. In the one-layer hydrate of Li-montmorillonite, the residence time of a water molecules is about six times longer than in the bulk liquid, with a diffusive jump distance of about 0.35 nm, and a water molecules reorients its dipole axis about half... 

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