Solid state {sup 31}P/{sup 27}Al and {sup 31}P/{sup 23}Na MAS NMR dipolar dephasing experiments have been used to investigate the spatial distribution of aluminum and sodium cations with respect to the phosphate backbone for a series of sodium aluminophosphate glasses, xAl{sub 2}O{sub 3}{center_dot}50Na{sub 2}O{center_dot}(50{minus}x)P{sub 2}O{sub 5} (0{le} x {le} 17.5). From the {sup 31}P/{sup 27}Al and {sup 31}P/{sup 23}Na connectivity data gathered, information about the medium range order in these glasses is obtained. The expanded connectivity data allows for better identification and interpretation of the new resonances observed in the {sup 31}P MAS NMR spectra with the addition of alumina. The results of the dipolar dephasing experiments show that the sodium-phosphate distribution remains relatively unchanged for the glass series, and that the addition of aluminum occurs primarily through the depolymerization of the phosphate tetrahedral backbone.
The author's laboratory continues to use NMR to investigate the structure and dynamics in amorphous materials, including the local structure of ultraphosphate glasses. Changes in the alkali environment in these phosphate glasses as a function of modifier concentration has recently been probed using {sup 6}Li and {sup 23}Na solid state NMR. Molecular dynamic (MD) simulations have also been performed in an attempt to gain additional insight into the variations of the local structure. Interestingly, although there are distinct variations in the Li coordination number as well as the Li-O bond lengths in the MD simulations (with a minimum or maximum in these parameters near the 20% Li{sub 2}O concentration), a linear change in the {sup 6}Li NMR chemical shift is observed between 5 and 50% Li{sub 2}O mole fraction. One would expect that such variations should be observable in the NMR chemical shift. In an attempt to understand this behavior the author has performed empirical calculation of the {sup 6}Li NMR chemical shift directly from the structures obtained in the MD simulations. It has been argued that the NMR chemical shift of alkali species can be related to a chemical shift parameter A, where A is defined as the summation of the shift contributions for all the oxygens located within the first (and possibly the second) coordination sphere around the cation. For the present case of Li phosphate glasses, the chemical shift correlates directly to the bond valence of the coordinating oxygen.
Phosphonate binding sites in guanidine and ammonium surface-functionalized silica xerogels were prepared via the molecular imprinting technique and characterized using solid state {sup 31}P MAS NMR. One-point, two-point, and non-specific host-guest interactions between phenylphosphonic acid (PPA) and the functionalized gels were distinguished by characteristic chemical shifts of the observed absorption peaks. Using solid state as well as solution phase NMR analyses, absorptions observed at 15.5 ppm and 6.5 ppm were identified as resulting from the 1:1 (one-point) and 2:1 (two-point) guanidine to phosphonate interactions, respectively. Similar absorptions were observed with the ammonium functionalized gels. By examining the host-guest interactions within the gels, the efficiency of the molecular imprinting procedure with regard to the functional monomer-to-template interaction could be readily assessed. Template removal followed by substrate adsorption studies conducted on the guanidine functionalized gels provided a method to evaluate the binding characteristics of the receptor sites to a phosphonate substrate. During these experiments, {sup 29}Si and {sup 31}P MAS NMR acted as diagnostic monitors to identify structural changes occurring in the gel matrix and at the receptor site from solvent mediated processes.
Monte Carlo (MC) simulations of phosphate tetrahedron connectivity distributions in alkali and alkaline earth phosphate glasses are reported. By utilizing a discrete bond model, the distribution of next-nearest neighbor connectivities between phosphate polyhedron for random, alternating and clustering bonding scenarios was evaluated as a function of the relative bond energy difference. The simulated distributions are compared to experimentally observed connectivities reported for solid-state two-dimensional (2D) exchange and double-quantum (2Q) nuclear magnetic resonance (NMR) experiments of phosphate glasses. These MC simulations demonstrate that the polyhedron connectivity is best described by a random distribution in lithium phosphate and calcium phosphate glasses.