Dy. Sasaki et Tm. Alam, Solid-state P-31 NMR study of phosphonate binding sites in guanidine-functionalized, molecular imprinted silica xerogels, CHEM MATER, 12(5), 2000, pp. 1400-1407
Phosphonate binding sites in guanidine and ammonium surface-functionalized
silica xerogels were prepared via the molecular imprinting technique and ch
aracterized using solid-state P-31 MAS NMR. One-point, two-point, and nonsp
ecific 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 and 6.5 ppm were identified as
resulting from the 1:1 (one-point) and 2:1 (two-point) guanidine to phospho
nate interactions, respectively. Similar absorptions were observed with the
ammonium functionalized gels. By examining the host-guest interactions wit
hin the gels, the efficiency of the molecular imprinting procedure with reg
ard to the functional monomer-to-template interaction could be readily asse
ssed. Template removal followed by substrate adsorption studies conducted o
n the guanidine-functionalized gels provided a method to evaluate the bindi
ng characteristics of the receptor sites to a phosphonate substrate. During
these experiments, Si-29 and P-31 MAS NMR acted as diagnostic monitors to
identify structural changes occurring in the gel matrix and at the receptor
site from solvent-mediated processes.