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Molecular Dynamics of Cation Hydration in the Presence ofCarboxylated Molecules: Implications for Calcification

Published online by Cambridge University Press:  09 February 2011

Laura M. Hamm ,
Adam F. Wallace  and
Patricia M. Dove
Laura M. Hamm
Affiliation:
Department of Geosciences, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061
Adam F. Wallace
Affiliation:
Earth Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720
Patricia M. Dove
Affiliation:
Department of Geosciences, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061
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Abstract

Biomolecules rich in aspartic acid (Asp) are known to play a role inbiomineral morphology and polymorph selection, and have been shown togreatly enhance the growth kinetics of calcite. The mechanism by which thesecompounds favor calcification may be related to their effects upon cationsolvation. Using molecular dynamics, we investigated the influence of smallcarboxylated molecules on the hydration states and water exchange rates ofdivalent cations. We show that the carboxylate moieties of Asp promotedehydration of Ca2+ and Sr2+ and that contact ion pair(CIP) formation is not required to disrupt the hydration of these cations. Ca2+- Asp and Sr2+ - Asp CIP formation decreasesthe total inner sphere coordination from an average of 8.0 and 8.4 in bulkwater to 7.5 and 8.0, respectively. Water residence times estimated for Mg2+, Ca2+and Sr2+ follow the expectedtrend of decreasing residence time with increasing ionic radius. In thepresence of Asp, both solvent-separated ion pair (SSIP) and CIP formationdecrease the residence times of Ca2+and Sr2+ innersphere water molecules. Comparable impacts on Mg2+ hydration arenot observed. Mg2+ - Asp CIP formation is energeticallyunfavorable and Asp does not affect Mg2+ inner sphere waterresidence times.

Keywords

biomimetic (assembly)Cacrystal growth

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