First Direct Insight into the Local Environment and Dynamics of Water Molecules in the Whewellite Mineral Phase: Mechanochemical Isotopic Enrichment and High-Resolution 17 O and 2 H NMR Analyses
In: ISSN: 1932-7447, 2022
Online
academicJournal
Zugriff:
International audience ; Calcium oxalate minerals of the general formula CaC2O4.xH2O are widely present in nature and usually associated with pathological calcifications, constituting up to 70−80% of the mineral component of renal calculi. The monohydrate phase (CaC2O4.H2O, COM) is the most stable form, accounting for the majority of the hydrated calcium oxalates found. These mineral phases have been studied extensively via X-ray diffraction and IRspectroscopy and, to a lesser extent, using 1H, 13C, and 43Ca solidstate NMR spectroscopy. However, several aspects of their structure and reactivity are still unclear, such as the evolution from low- to high-temperature COM structures (LT-COM and HT-COM, respectively) and the involvement of water molecules in this phase transition. Here, we report for the first time a 17O and 2H solid-state NMR investigation of the local structure and dynamics of water in the COM phase. A new procedure for the selective 17O- and 2H-isotopic enrichment of water molecules within the COM mineral is presented using mechanochemistry, which employsonly microliter quantities of enriched water and leads to exchange yields up to ∼30%. 17O NMR allows both crystallographically inequivalent water molecules in the LT-COM structure to be resolved, while 2H NMR studies provide unambiguous evidence that these water molecules are undergoing different types of motions at high temperatures without exchanging with one another. Dynamics appear to be essential for water molecules in these structures, which have not been accounted for in previous structuralstudies on the HT-COM structure due to lack of available tools, highlighting the importance of such NMR investigations for refining the overall knowledge on biologically relevant minerals like calcium oxalates.
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First Direct Insight into the Local Environment and Dynamics of Water Molecules in the Whewellite Mineral Phase: Mechanochemical Isotopic Enrichment and High-Resolution 17 O and 2 H NMR Analyses
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Autor/in / Beteiligte Person: | Goldberga, Ieva ; Patris, Nicolas ; Chen, Chia-Hsin ; Thomassot, Emilie ; Trébosc, Julien ; Hung, Ivan ; Gan, Zhehong ; Berthomieu, Dorothée ; Métro, Thomas-Xavier ; Bonhomme, Christian ; Gervais, Christel ; Laurencin, Danielle ; Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM) ; Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM) ; Université de Montpellier (UM) ; Hydrosciences Montpellier (HSM) ; Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM) ; Centre de Recherches Pétrographiques et Géochimiques (CRPG) ; Institut national des sciences de l'Univers (INSU - CNRS)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS) ; Institut Michel Eugène Chevreul - FR 2638 (IMEC) ; Université d'Artois (UA)-Centrale Lille-Institut de Chimie - CNRS Chimie (INC-CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE) ; National High Magnetic Field Laboratory (NHMFL) ; Florida State University Tallahassee (FSU) ; Institut des Biomolécules Max Mousseron Pôle Chimie Balard (IBMM) ; Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP) ; Institut de Chimie - CNRS Chimie (INC-CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS) ; GENCI-IDRIS ; IR-RMN-THC FR 3050, CNRS ; European Project: 772204,MISOTOP |
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Zeitschrift: | ISSN: 1932-7447, 2022 |
Veröffentlichung: | HAL CCSD ; American Chemical Society, 2022 |
Medientyp: | academicJournal |
DOI: | 10.1021/acs.jpcc.2c02070 |
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