7Li magic angle spinning solid-state nuclear magnetic resonance is applied to investigate the lithium local environment and lithium ion mobility in tetragonal anatase TiO(2) and orthorhombic lithium titanate Li(0.6)TiO(2). Upon lithium insertion, an increasing fraction of the material changes its crystallographic structure from anatase TiO(2) to lithium titanate Li(0.6)TiO(2). Phase separation occurs, and as a result, the Li-rich lithium titanate phase is coexisting with the Li-poor TiO(2) phase containing only small Li amounts approximately equal to 0.01. In both the anatase and the lithium titanate lattice, Li is found to be hopping over the available sites with activation energies of 0.2 and 0.09 eV, respectively. This leads to rapid microscopic diffusion rates at room temperature (D(micr) = 4.7 x 10(-12) cm(2)s(-1) in anatase and D(micr) = 1.3 x 10(-11) cm(2)s(-1) in lithium titanate). However, macroscopic intercalation data show activation energies of approximately 0.5 eV and smaller diffusion coefficients. We suggest that the diffusion through the phase boundary is determining the activation energy of the overall diffusion and the overall diffusion rate itself. The chemical shift of lithium in anatase is independent of temperature up to approximately 250 K but decreases at higher temperatures, reflecting a change in the 3d conduction electron densities. The Li mobility becomes prominent from this same temperature showing that such electronic effects possibly facilitate the mobility.
Intercalation of Li in TiO2 anatase results in a phase separation in a Li-poor and a Li-rich phase. The local lithium configuration in the coexisting crystallographic phases is resolved by detailed analysis of neutron diffraction data. In each of the phases, two distinct positions within the octahedral interstices are found, with a temperature-dependent occupancy. A combination of quasi-elastic neutron scattering and force field molecular dynamics simulations shows that Li is hopping on a picosecond time scale between the two sites in the octahedral interstices. The results also suggest a specific Li arrangement along the crystallographic a direction, albeit without long range order. It is likely that multiple discrete Li sites within a distorted oxygen octahedron occur not only in intercalated TiO2 anatase but also in other (transition metal) oxides.
In several experimental techniques D2O rather then H2O is often used as a solvent for proteins. Concerning the influence of the solvent on the stability of the proteins, contradicting results have been reported in literature. In this paper the influence of H2O-D2O solvent substitution on the stability of globular protein structure is determined in a systematic way. The differential scanning calorimetry technique is applied to allow for a thermodynamic analysis of two types of globular proteins: hen's egg lysozyme (LSZ) with relatively strong internal cohesion ("hard" globular protein) and bovine serum albumin (BSA), which is known for its conformational adaptability ("soft" globular protein). Both proteins tend to be more stable in D2O compared to H2O. We explain the increase of protein stability in D2O by the observation that D2O is a poorer solvent for nonpolar amino acids than H2O, implying that the hydrophobic effect is larger in D2O. In case of BSA the transitions between different isomeric forms, at low pH values the Nm and F forms, and at higher pH values Nm and B, were observed by the presence of a supplementary peak in the DSC thermogram. It appears that the pH-range for which the Nm form is the preferred one is wider in D2O than in H2O.
We investigate the microscopic structure and density fluctuations of complex coacervates of flexible polyelectrolytes using scattering of neutrons, X-rays, and light. Poly(acrylic acid) and poly(N,N-dimethylaminoethyl methacrylate) offer a well-defined model system that allows for selective labeling and systematic variation of the strength of the attractive electrostatic interactions. Two neutron scattering experiments have been carried out: (i) we use deuterated polymeric tracers in a complex coacervate with an overall neutron scattering length density that is matched to that of the solvent, to probe the conformation of single polymer chains in the complex coacervates, and (ii) we measure complex coacervates in which all polymer chains of one type are deuterated, to probe their overall structure. The single chain static structure factors reveal that both polycations and polyanions have an ideal Gaussian chain conformation in the complex coacervates. At the same time, the overall structure is similar to that of a semidilute polymer solution, with polycations and polyanions strongly overlapping to form a network with a mesh size that is much smaller than the radius of gyration of the polymers. The mesh size decreases with decreasing salt concentration, following a scaling that is in good agreement with predictions from the corresponding salt–polymer phase diagram. These findings are confirmed by complementary X-ray scattering experiments. Finally, in all scattering experiments with light, X-rays, and neutrons, and for all polymer chain lengths and salt concentrations, we find a remarkable low-q excess scattering, following a power law with a slope close to −2. This points to the presence of equilibrium, large-scale density fluctuations in the complex coacervates. Dynamic light scattering experiments reveal two complementary diffusive modes in the complex coacervates, corresponding to fluctuations of the polymer mesh and diffusion of domains of varying density, respectively.
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