Fast Na+ ion conductivity in glass,intermediate and crystalline phases of Na4UO2(SO4)3

The ac electrical conductivity, DSC calorimetry and density data for pure Na₄UO₂(SO₄)₃ and for compound incorporating guest ions Rb⁺, Cd²⁺, Gd³⁺, SiO ₄ ^4– in the glass, quasi-crystalline intermediate and crystalline phases are reported. The glass phase conductivity data show an increase in Na⁺ conductivity by a factor 10³ relative to pure crystalline Na₂SO₄ in the low temperature (LT) region, i.e. 180°C. There is no onset of phase transition up to 260°C. The distinct conductivity regimes prior to devitrification in the glass suggest that higher energy or excited structural states/configurations can exist in the glass phase. The apparent activation energy Q _c value 76±5 kJ/mole for the glass state of all compositions is in excellent agreement with the Na₂SO₄ III Q _c value. The conductivity regime immediately after devitrification with Q _c of 40±3 kJ/mole represents the stable intermediate phase. The conductivity of the final product of devitrification on cooling resembles crystalline behavior except for (Na_3.5Rb_0.5)UO₂(SO₄)₃. A gradual jump in conductivity accompanies the transition in the crystalline sample. The Q _c value is 75±5 kJ/mole for the (HT) phase conductivity in the heating mode but remains constant at 66±5 kJ/mole for the (LT) phase in the heating mode and for both and phases in the cooling mode.The excellent conductivity-volume, i.e. /V correlation is consistent with the free volume contribution to conductivity enhancement and the percolation-type mechanism of transport.This study received partial support from the Natural Sciences and Engineering Research Council of Canada     

Solid-state NMR and calorimetry of structural waters in helical peptides

The peptide hydrates Gly-Gly-Val x 2H(2)O (GGV) and Gly-Ala-Leu x 3H(2)O (GAL) are known to adopt alpha-helical configurations containing waters of hydration in which each water is H-bonded to three or four peptide groups. Herein we report a thermodynamic and solid-state NMR ((2)H and (17)O) study of these peptides. From TGA and DSC, the average enthalpy per H-bond is 15 kJ/mol. The dynamics and average orientation of the hydrate are studied by powder and single-crystal (2)H NMR. Whereas waters that are shown by the X-ray structure to be coordinated by four hydrogen bonds do not yield observable (2)H NMR signals at room temperature, two of the three triply coordinated waters yield residual (2)H quadrupole coupling tensors characteristic of rapid 180 degrees flip motions and the orientation of the residual tensor is that expected from the X-ray structure-derived H-bonding pattern. At -65 degrees C, the flip motions of triply coordinated water in GGV slow into the (2)H NMR intermediate exchange regime whereas the tetrahedrally coordinated water approaches the slow-exchange limit and yields an observable NMR signal. Extensive isotope exchange between water vapor and crystalline GGV establishes the presence of additional hydrate dynamics and solid-state proton transfer along a chain of water-bridged protonated alpha-amino groups.