Fourier Transform and Multi Dimensional EPR Spectroscopy for the Characterization of Sol-Gel Derived Hydroxyapatite

Abstract

Calcium hydroxyapatite powder was prepared by sol-gel method using calcium acetate and PO(OC₂H₅)₃ as initial compounds, and alcohol (methyl, ethyl, and propyl-alcohol) as solvent. Homogeneous solution and gels were prepared using a molar ratio of Ca/P = 1.67. The evolution of the structure was detected by X-ray diffraction, IR, and FT-n(=1,2,3)D-EPR spectroscopy. The dried gels exhibit a signal characterized by a central line and two satellites. The 2D spectrum (ESEEM vs. field sweep) showed the same modulation for the central line. The FT-EPR spectrum vs. field sweep 2D-spectrum indicated that the satellites are due to an hfs splitting with water. The central region of this 2D spectrum is influenced by P and H in a concentration ratio of [H]/[P]=2.5. The ESEEM spectrum was simulated assuming the equation $V_{\bmod } = V_{\bmod } (P)^m V_{\bmod } (H)^n$ for two spin systems S = 1/2 and I = 1/2. This simulation gave for m and n the values of 2 and 5, respectively. This finding suggests the structure:$\begin{gathered} {\text{ O = P}}---{\text{O}}---{\text{CH}}_{\text{2}} ---{\text{CH}}_{\text{3}} \hfill \\ {\text{ |}} \hfill \\ {\text{ O}} \hfill \\ {\text{O}}---*{\text{P}}---{\text{O}}---{\text{CH}}_{\text{2}} ---{\text{CH}}_{\text{3}} \hfill \\ {\text{ |}} \hfill \\ {\text{ O}} \hfill \\ {\text{ O = P}}---{\text{O}}---{\text{CH}}_{\text{2}} ---{\text{CH}}_{\text{3}} \hfill \\ \end{gathered}$ for the unpaired state. It appears that one ethyl group does not hydrolyse in the gelation process. The ESEEM spectra of hydroxyapatite exhibit a modulation generated by P, H and Ca atoms.