Water dynamics in physical hydrogels based on partially hydrophobized hyaluronic acid.

The dynamics of hyaluronate-based hydrogels has been investigated by quasielastic neutron scattering (QENS). Hyaluronate (HYA) has been compared, in the same conditions of temperature and polymer concentration, to a chemically modified form, HYADD, in which the backbone has been grafted with a hexadecyl (C(16)) side-chain with a degree of substitution of about 2% (mol/mol). This modification increases the hydrophobicity of the polysaccharide and leads to a stable gel already at polymer concentration of 0.3% (w/v), yielding a viscosupplementation with less quantity of polysaccharide. The time-scale covered by our measurements probes both water and segmental biopolymer motions. In both systems, the local dynamics of the network in the ps time-scale is mostly due to local reorientational motions of side groups. Such motions are not significantly affected by the small amount of aliphatic chains forming the hydrophobic junctions in HYADD. The diffusivity of water in both HYA and HYADD coincides with that of pure water within the experimental uncertainty. This result confirms previous ones on the dynamics of water in HYA solutions and it is of relevance for biomedical applications of hyaluronate-based systems because it affects the diffusive processes of metabolites and their interaction with tissues.

Alcohol induced structural and dynamic changes in ß-lactoglobulin in aqueous solution: a neutron scattering study.

Structural and dynamic properties of ß-lactoglobulin (ß-LG) were revealed as a function of alcohol concentration in ethanol- and trifluoroethanol(TFE)-water mixtures with circular dichroism (CD), small-angle neutron scattering (SANS) and quasi-elastic neutron scattering (QENS). The CD spectra showed that an increase in TFE concentration promotes the formation of the ß-sheet structure of ß-LG. The SANS-intensities were fitted using form factors for two attached spheres for the native and native-like states of the protein. At higher alcohol concentrations, where aggregation takes place, a form factor modelling diffusion limited colloidal aggregation (DLCA) was employed. The QENS-data were analyzed in terms of internal motions for all alcohol concentrations. While low concentrations of TFE (10% (v/v)) lead to an increase of the mean square amplitudes of vibrations and a retention of a native-like structure - but not to an increase of the characteristic radius of proton diffusion processes a. Addition of 20% (v/v) of TFE induces aggregation, going along with a further increase of . Further increase of TFE concentration to 30% (v/v) changes the nanoscale structure of the oligomeric nucleate, but induces no further significant changes in . The present study underlines the necessity of methods sensitive to the dynamics of a system to obtain a complete picture of a molecular process.

Structure determination of two modulated gamma-brass structures in the Zn-Pd System through a (3 + 1)-dimensional space description.

The structure determination of two composite compounds in the Zn-Pd system with close relationships to the cubic gamma-brass structure Zn(11-delta)Pd(2+delta) is reported. Their structures have been solved from single crystal X-ray diffraction data within a (3 + 1)-dimensional [(3 + 1)D] formalism. Zn(75.7(7))Pd(24.3) and Zn(78.8(7))Pd(21.2) crystallize with orthorhombic symmetry, superspace group Xmmm(00gamma)0s0 (X = [(1/2,1/2,0,0); (0,1/2,1/2,1/2); (1/2,0,1/2,1/2)]), with the following lattice parameters, respectively: a(s) = 12.929(3) A, b(s) = 9.112(4) A, c(s) = 2.5631(7) A, q = 8/13 c* and V(s) = 302.1(3) A(3) and a(s) = 12.909(3) A, b(s) = 9.115(3) A, c(s) = 2.6052(6) A, q = 11/18 c* and V(s) = 306.4(2) A(3). Their structures may be considered as commensurate because they can be refined in the conventional 3D space groups (Cmce and Cmcm, respectively) using supercells, but they also refined within the (3 + 1)D formalism to residual factors R = 3.14% for 139 parameters and 1184 independent reflections for Zn(75.7(7))Pd(24.3) and R = 3.16% for 175 parameters and 1804 independent reflections for Zn(78.8(7))Pd(21.2). The use of the (3 + 1)D formalism improves the results of the refinement and leads to a better understanding of the complexity of the atomic arrangement through the various modulations (occupation waves and displacive waves). Our refinements emphasize a unique Pd/Zn occupancy modulation at the center of distorted icosahedra, a modulation which correlates with the distortion of these polyhedra.

Revision of pyrrhotite structures within a common superspace model.

The structure of pyrrhotite (Fe(1 - x)S with 0.05 < or = x < or = 0.125) has been reinvestigated in the framework of the superspace formalism. A common model with a centrosymmetric superspace group is proposed for the whole family. The atomic domains in the internal space representing the Fe atoms are parametrized as crenel functions that fulfil the closeness condition. The proposed model explains the x-dependent space groups observed and the basic features of the structures reported up to now. Our model yields for any x value a well defined ordered distribution of Fe vacancies in contrast to some of the structural models proposed in the literature. A new (3 + 1)-dimensional refinement of Fe(0.91)S using the deposited dataset [Yamamoto & Nakazawa (1982). Acta Cryst. A38, 79-86] has been performed as a benchmark of the model. The consistency of the proposed superspace symmetry and its validity for other compositions has been further checked by means of ab initio calculations of both atomic forces and equilibrium atomic positions in non-relaxed and relaxed structures, respectively.

Apparently complex high-pressure phase of gallium as a simple modulated structure.

The phase of gallium GaII, with symmetry C222(1) and 104 atoms per unit cell, has been recently reported as an example of structural complexity under high pressure. It is shown here that this phase is a simple modulated distortion of an average structure of Fddd symmetry with all atoms structurally equivalent. The modulation can be described with only 4 parameters and satisfies symmetry properties described by a centrosymmetric superspace group. The structural distortion is dominated by a frozen transversal mode associated with a single irreducible representation of Fddd, with a wave vector on the line Q, at an edge of the Brillouin zone. The average structure can be related with an hcp configuration through simple sliding of hcp layers, reminiscent of the hcp-bcc Bürgers mechanism.