Interfacial Ca2+ environments in nanocrystalline apatites revealed by dynamic nuclear polarization enhanced 43Ca NMR spectroscopy

Daniel Lee, César Leroy, Charlène Crevant, Laure Bonhomme-Coury, Florence Babonneau, Danielle Laurencin, Christian Bonhomme and Gaël De Paëpe ()
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Daniel Lee: Univ. Grenoble Alpes, INAC
César Leroy: Sorbonne Universités, UPMC Univ Paris 06, Collège de France, UMR CNRS 7574, Laboratoire de Chimie de la Matière Condensée de Paris
Charlène Crevant: Sorbonne Universités, UPMC Univ Paris 06, Collège de France, UMR CNRS 7574, Laboratoire de Chimie de la Matière Condensée de Paris
Laure Bonhomme-Coury: Sorbonne Universités, UPMC Univ Paris 06, Collège de France, UMR CNRS 7574, Laboratoire de Chimie de la Matière Condensée de Paris
Florence Babonneau: Sorbonne Universités, UPMC Univ Paris 06, Collège de France, UMR CNRS 7574, Laboratoire de Chimie de la Matière Condensée de Paris
Danielle Laurencin: Institut Charles Gerhardt de Montpellier, UMR5253, CNRS UM ENSCM, CC1701
Christian Bonhomme: Sorbonne Universités, UPMC Univ Paris 06, Collège de France, UMR CNRS 7574, Laboratoire de Chimie de la Matière Condensée de Paris
Gaël De Paëpe: Univ. Grenoble Alpes, INAC

Nature Communications, 2017, vol. 8, issue 1, 1-7

Abstract: Abstract The interfaces within bones, teeth and other hybrid biomaterials are of paramount importance but remain particularly difficult to characterize at the molecular level because both sensitive and selective techniques are mandatory. Here, it is demonstrated that unprecedented insights into calcium environments, for example the differentiation of surface and core species of hydroxyapatite nanoparticles, can be obtained using solid-state NMR, when combined with dynamic nuclear polarization. Although calcium represents an ideal NMR target here (and de facto for a large variety of calcium-derived materials), its stable NMR-active isotope, calcium-43, is a highly unreceptive probe. Using the sensitivity gains from dynamic nuclear polarization, not only could calcium-43 NMR spectra be obtained easily, but natural isotopic abundance 2D correlation experiments could be recorded for calcium-43 in short experimental time. This opens perspectives for the detailed study of interfaces in nanostructured materials of the highest biological interest as well as calcium-based nanosystems in general.

Date: 2017
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DOI: 10.1038/ncomms14104

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