Dataset Information

Electron Paramagnetic Resonance Characterization of Sodium- and Carbonate-Containing Hydroxyapatite Cement.

ABSTRACT: Ionizing radiation-induced paramagnetic defects in calcified tissues like tooth enamel are indicators of irradiation dose. Hydroxyapatite (HA), the principal constituent in these materials, incorporates a variety of anions (CO₃^2-, F^-, Cl^-, and SiO₄^4-) and cations (Mn²⁺, Li⁺, Cu²⁺, Fe³⁺, Mg²⁺, and Na⁺) that directly or indirectly contribute to the formation of stable paramagnetic centers upon irradiation. Here, we used an underexploited synthesis method based on the ambient temperature setting reaction of a self-hardening calcium phosphate cement (CPC) to create carbonate-containing hydroxyapatite (CHA) and investigate its paramagnetic properties following γ-irradiation. Powder X-ray diffraction and IR spectroscopic characterization of the hardened CHA samples indicate the formation of pure B-type CHA cement. CHA samples exposed to γ-radiation doses ranging from 1 Gy to 150 kGy exhibited an electron paramagnetic resonance (EPR) signal from an orthorhombic CO₂^•- free radical. At γ-radiation doses from 30 to 150 kGy, a second signal emerged that is assigned to the CO₃^•- free radical. We observed that the formation of this second species is dose-dependent, which provided a means to extend the useful dynamic range of irradiated CHA to doses >30 kGy. These results indicate that CHA synthesized via a CPC cement is a promising substrate for EPR-based dosimetry. Further studies on the CHA cement are underway to determine the suitability of these materials for a range of biological and industrial dosimetry applications.

SUBMITTER: Karim ET

PROVIDER: S-EPMC9400659 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Electron Paramagnetic Resonance Characterization of Sodium- and Carbonate-Containing Hydroxyapatite Cement.

Karim Eaman T ET Szalai Veronika V Cumberland Lonnie L Myers Alline F AF Takagi Shozo S Frukhtbeyn Stanislav A SA Pazos Ileana I Chow Laurence C LC

Inorganic chemistry 20220805 33

Ionizing radiation-induced paramagnetic defects in calcified tissues like tooth enamel are indicators of irradiation dose. Hydroxyapatite (HA), the principal constituent in these materials, incorporates a variety of anions (CO32-, F-, Cl-, and SiO44-) and cations (Mn2+, Li+, Cu2+, Fe3+, Mg2+, and Na+) that directly or indirectly contribute to the formation of stable ...[more]

PMID: 35930806

Similar Datasets

Project description:The fleeting ferric peroxo and hydroperoxo intermediates of dioxygen activation by hemoproteins can be readily trapped and characterized during cryoradiolytic reduction of ferrous hemoprotein-O2 complexes at 77 K. Previous cryoannealing studies suggested that the relaxation of cryogenerated hydroperoxoferric intermediates of myoglobin (Mb), hemoglobin, and horseradish peroxidase (HRP), either trapped directly at 77 K or generated by cryoannealing of a trapped peroxo-ferric state, proceeds through dissociation of bound H2O2 and formation of the ferric heme without formation of the ferryl porphyrin π-cation radical intermediate, compound I (Cpd I). Herein we have reinvestigated the mechanism of decays of the cryogenerated hydroperoxyferric intermediates of α- and β-chains of human hemoglobin, HRP, and chloroperoxidase (CPO). The latter two proteins are well-known to form spectroscopically detectable quasistable Cpds I. Peroxoferric intermediates are trapped during 77 K cryoreduction of oxy Mb, α-chains, and β-chains of human hemoglobin and CPO. They convert into hydroperoxoferric intermediates during annealing at temperatures above 160 K. The hydroperoxoferric intermediate of HRP is trapped directly at 77 K. All studied hydroperoxoferric intermediates decay with measurable rates at temperatures above 170 K with appreciable solvent kinetic isotope effects. The hydroperoxoferric intermediate of β-chains converts to the S = 3/2 Cpd I, which in turn decays to an electron paramagnetic resonance (EPR)-silent product at temperature above 220 K. For all the other hemoproteins studied, cryoannealing of the hydroperoxo intermediate directly yields an EPR-silent majority product. In each case, a second follow-up 77 K γ-irradiation of the annealed samples yields low-spin EPR signals characteristic of cryoreduced ferrylheme (compound II, Cpd II). This indicates that in general the hydroperoxoferric intermediates relax to Cpd I during cryoanealing at low temperatures, but when this state is not captured by reaction with a bound substrate, it is reduced to Cpd II by redox-active products of radiolysis.

Dataset Information

Electron Paramagnetic Resonance Characterization of Sodium- and Carbonate-Containing Hydroxyapatite Cement.

Publications

Electron Paramagnetic Resonance Characterization of Sodium- and Carbonate-Containing Hydroxyapatite Cement.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets