Electron spin resonance studies on tooth phosphoproteins using manganese ions as probes.
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Biomedical subjects
Publications and source records attributed to I Pullman.
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Free radicals generated in synthetic apatitic calcium phosphates by X-ray radiation were investigated by electron spin resonance (ESR) spectroscopy. Among the species stable enough at -188 degrees C to be identified were hydrogen atoms, phosphate radicals, and oxygen anion radicals. The ESR spectra were markedly dependent on the specific surface of the mineral. Oxygen radicals dominated the spectra of low specific surface samples while phosphate radicals were the predominant species at higher specific surfaces. Our studies suggest that the oxygen radicals are more stable in the bulk of the crystal while the hydrogen atoms and the phosphate radicals are stabilized at or near the crystal surface. It was concluded that the surface species are potentially capable of serving as probes of biologically relevant mineral-organic interfaces.
Exposure of bone mineral to X-rays generates free radicals. These are usually very labile, but can be stabilized at liquid nitrogen temperatures for study by electron spin resonance spectroscopy. The free radicals thus detected in the present study included one with resonances arising from an electron excess center and 2 species with electron-deficit centers: a phosphate anion radical and a radical associated with carbonate. Each of these radicals seemed to be located chiefly at the mineral surface and was sensitive to the surface environment. Presence of an organic phase, as in whole bone, modified free radical production in a manner that suggests interference with the formation of electron deficit centers. Comparison with other synthetic minerals suggests that precipitated carbonate-apatites are good models for bone mineral.
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Fluor-hydroxyapatites of varying fluoride and hydroxide contents were irradiated by soft x-rays at -188 degrees C and examined by means of electron spin resonance spectroscopy. Variation in fluoride-hydroxide contents affected radical yield and resulted in the observation of two kinds of oxygen anion resonances: a doublet due to hydrogen hyperfine splitting and a singlet. At higher temperatures a spin transfer process became operative which enhanced the oxygen anion radical population. Increasing fluoride content was paralleled by decreasing g-values for the oxygen anion resonances, possibly attributable to increased delocalization of the unpaired spin.
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