Abstract
Water is a fundamental solvent sustaining life, key to the conformations and equilibria associated with solute species. Emerging studies on nucleation and crystallization phenomena reveal that the dynamics of hydration associated with mineral precursors are critical in determining material formation and growth. With certain small molecules affecting the hydration and conformational stability of co-solutes, this study systematically explores the effects of these chaotropes and kosmotropes as well as certain sugar enantiomers on the early stages of calcium carbonate formation. These small molecules appear to modulate mineral nucleation in a class-dependent manner. The observed effects are finite in comparison to the established, strong interactions between charged polymers and intermediate mineral forms. Thus, perturbations to hydration dynamics of ion clusters by co-solute species can affect nucleation phenomena in a discernable manner.
Highlights
Water is one of the most abundant molecules in the universe [1]
This study identifies the distinct trends of the early stages of precipitation of calcium carbonate in the presence of small molecules, classified on their chao/kosmotropic nature and stereochemistry
Since ion association of CaCO3 pre-nucleation clusters (PNCs) is driven by the release of hydration waters [29], stabilized hydration shells would have adverse effects
Summary
Water is one of the most abundant molecules in the universe [1]. It affects global processes such as erosion and climate as well as phenomena at atomic length scales such as molecular configurations and interactions. Certain salts have been linked with an ability to influence water structure, and thereby the conformational states of co-solute macromolecules. This gradually led to the nomenclature of solute additives as either structure-breakers or structure-makers, corresponding to their respective stabilizing or disruptive effect on the short-range order i.e., hydrogen bonding networks in the liquid [2,4]. Convincing evidence for a significant perturbation of bulk water structure by solutes still remains lacking
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