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A solid-state NMR study of lead and vanadium substitution into hydroxyapatite
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Pizzala, Helene, Caldarelli, Stefano, Eon, Jean-Guillaume, Rossi, Alexandre Malta, Laurencin, Danielle and Smith, Mark E. (2009) A solid-state NMR study of lead and vanadium substitution into hydroxyapatite. Journal of the American Chemical Society, Vol.131 (No.14). pp. 5145-5152. doi:10.1021/ja808270v ISSN 0002-7863.
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Official URL: http://dx.doi.org/10.1021/ja808270v
Abstract
A systematic study on cationic and anionic substitution in hydroxyapatite structures was carried out, with the aim of understanding the impact of ion exchange on the crystalline structure and properties of these materials. Lead and vanadium were chosen for the exchange, due to their known effects on the redox and catalytic properties of hydroxypatites. Hydroxyapatites with variable Pb and V contents, Pb-x- Ca10-x(VO4)y(PO4)(6-y)(OH)(2) (x = 0, 2, 4, 6, 8 and 10 for y = 1; y = 0, 0.5, 1, 2, 3 and 6 for x = 10) were synthesized and characterized by NMR spectroscopy. Solid-state NMR allowed an analysis of the chemical environment of every ion after substitution into the hydroxyapatite network. Ca-43 and 207 Pb NMR spectra at different lead concentrations provided clear evidence of the preferential substitution of lead into the Ca(II) site, the replacement of the Ca(I) site starting at x = 4 for y = 1. Two NMR distinguishable Pb(I) sites were observed in Pb-10(PO4)(6)(OH)(2), which is compatible with the absence of a local mirror plane pi rpendicular to the c direction. In contrast with P-31 NMR, for which only small variations related to the incorporation of Pb are observed, the strong change in the V-51 NMR spectrum indicates that lead perturbs the vanadium environment more than the phosphorus one. The existence of a wide variety of environments for OH in substituted apatites, is revealed by H-1 NMR, and the mobility of the water molecules appears to vary upon introduction of lead into the structure.
Item Type: | Journal Article | ||||
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Subjects: | Q Science > QC Physics Q Science > QD Chemistry |
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Divisions: | Administration > University Executive Office Faculty of Science, Engineering and Medicine > Science > Physics |
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Library of Congress Subject Headings (LCSH): | Magnetic resonance imaging, Magnetic resonance microscopy, Hydroxyapatite, Phosphates, Lead, Vanadium, Substitution reactions | ||||
Journal or Publication Title: | Journal of the American Chemical Society | ||||
Publisher: | American Chemical Society | ||||
ISSN: | 0002-7863 | ||||
Official Date: | 15 April 2009 | ||||
Dates: |
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Volume: | Vol.131 | ||||
Number: | No.14 | ||||
Number of Pages: | 8 | ||||
Page Range: | pp. 5145-5152 | ||||
DOI: | 10.1021/ja808270v | ||||
Status: | Peer Reviewed | ||||
Publication Status: | Published | ||||
Access rights to Published version: | Restricted or Subscription Access | ||||
Funder: | Programa CAPES/Cofecub, France. Ministère des affaires Ă©trangères et europĂ©ennes (MAEE), Provence-Alpes-CĂ´te d'Azur (France) (PACA), Conselho Nacional de Desenvolvimento CientĂfico e TecnolĂłgico [ National Council for Scientific and Technological Development (Brazil)] (CNPq), Engineering and Physical Sciences Research Council (EPSRC), University of Warwick, CAPES (Organization : Brazil) | ||||
Grant number: | 436/03 (CAPES/Cofecub) |
Data sourced from Thomson Reuters' Web of Knowledge
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