First direct insight into the local environment and dynamics of water molecules in the whewellite mineral phase: mechanochemical isotopic enrichment and high-resolution 17O and 2H NMR analyses



Calcium oxalate minerals of 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, IR spectroscopy and, to a lesser extent, using 1H, 13C and 43Ca solid-state 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 employs only 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 structural studies on the HT-COM structure due to lack of available tools — highlighting the importance of such NMR investigations for studying the crystallographic structure of biologically relevant minerals like calcium oxalates.

Version notes

Improved comparison to previous studies on LT to HT transitions in COM. Minor typos edited.


Supplementary material

Details on exchange yield estimation using IR-MS and LG-SIMS analysis. IR and pXRD results of various COM and COD samples described in this manuscript. NMR acquisition parameters used for all NMR experiments. Fitted static and MAS NMR data for oxygen-17 and static 2H NMR data. Experimental and calculated quadrupolar and CSA parameters of oxygen-17. Details on GIPAW DFT calculations for 17O and 2H nuclei. 2H NMR line-shapes calculated for C2 symmetry jumps of the water molecules. Plots showing the effects of the motional averaging caused by a twisting motion on the apparent quadrupolar parameters of the water molecules.