17O solid state NMR as a valuable tool for deciphering reaction mechanisms in mechanochemistry: the case study on the 17O-enrichment of hydrated Ca-pyrophosphate biominerals

Abstract

The possibility of enriching in ¹⁷O the water molecules within hydrated biominerals belonging to the Ca-pyrophosphate family was investigated, using liquid assisted grinding (LAG) in the presence of ¹⁷O-labelled water. Two phases with different hydration levels, namely triclinic calcium pyrophosphate dihydrate (Ca₂P₂O₇·2H₂O, denoted t-CPPD) and monoclinic calcium pyrophosphate tetrahydrate (Ca₂P₂O₇·4H₂O, denoted m-CPPT β) were enriched in ¹⁷O using a “post-enrichment” strategy, in which the non-labelled precursors were ground under gentle milling conditions in the presence of stoichiometric quantities of ¹⁷O-enriched water (introduced here in very small volumes ∼10 μL). Using high-resolution ¹⁷O solid-state NMR (ssNMR) analyses at multiple magnetic fields, and dynamic nuclear polarisation (DNP)-enhanced ¹⁷O NMR, it was possible to show that the labelled water molecules are mainly located at the core of the crystal structures, but that they can enter the lattice in different ways, namely by dissolution/recrystallisation or by diffusion. Overall, this work sheds light on the importance of high-resolution ¹⁷O NMR to help decipher the different roles that water can play as a liquid-assisted grinding agent and as a reagent for ¹⁷O-isotopic enrichment.