Resilient Intracrystalline Occlusions: A Solid-State NMR View of Local Structure as It Tunes Bulk Lattice Properties

Journal of the American Chemical Society
Ira Ben ShirAsher Schmidt

Abstract

In many marine organisms, biomineralization-the crystallization of calcium-based ionic lattices-demonstrates how regulated processes optimize for diverse functions, often via incorporation of agents from the precipitation medium. We study a model system consisting of l-aspartic acid (Asp) which when added to the precipitation solution of calcium carbonate crystallizes the thermodynamically disfavored polymorph vaterite. Though vaterite is at best only kinetically stable, that stability is tunable, as vaterite grown with Asp at high concentration is both thermally and temporally stable, while vaterite grown at 10-fold lower Asp concentration, yet 2-fold less in the crystal, spontaneously transforms to calcite. Solid-state NMR shows that Asp is sparsely occluded within vaterite and calcite. CP-REDOR NMR reveals that each Asp is embedded in a perturbed occlusion shell of ∼8 disordered carbonates which bridge to the bulk. In both the as-deposited vaterites and the evolved calcite, the perturbed shell contains two sets of carbonate species distinguished by their proximity to the amine and identifiable based on 13C chemical shifts. The embedding shell and the occluded Asp act as an integral until which minimally rearranges even as th...Continue Reading

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Citations

Feb 26, 2021·Acta Biomaterialia·J M Walker, G Langer

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Methods Mentioned

BETA
X-ray
NMR

Software Mentioned

CP
REDOR

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