Adsorption of Aspartate Derivatives to Calcite Surfaces in Aqueous Environment

Stepic R, Jurković L, Klementyeva K, Ukrainczyk M, Gredičak M, Smith DM, Kralj D, Smith AS (2020)

Publication Type: Journal article

Publication year: 2020

Journal

Crystal Growth and Design American Chemical Society

Book Volume: 20

Pages Range: 2853-2859

Journal Issue: 5

DOI: 10.1021/acs.cgd.0c00061

Abstract

In many living organisms, biomolecules interact favorably with various surfaces of calcium carbonate. In this work, we considered the interactions of aspartate (Asp) derivatives, as models of complex biomolecules, with calcite. Using kinetic growth experiments, we investigated the inhibition of calcite growth by Asp, Asp2, and Asp3.This entailed the determination of a step-pinning growth regime as well as the evaluation of the adsorption constants and binding free energies for the three species to calcite crystals. These latter values are compared to free energy profiles obtained from fully atomistic molecular dynamics simulations. When a flat (104) calcite surface is used in the models, the measured trend of binding energies is poorly reproduced. However, a more realistic model comprised of a surface with an island containing edges and corners yields binding energies that compare very well with experiments. Surprisingly, we find that most binding modes involve the positively charged ammonium group. Moreover, while attachment of the negatively charged carboxylate groups is also frequently observed, it is always balanced by the aqueous solvation of an equal or greater number of carboxylates. These effects are observed on all calcite features including edges and corners, the latter being associated with dominant affinities to Asp derivatives. As these features are also precisely the active sites for crystal growth, the experimental and theoretical results point strongly to a growth inhibition mechanism, whereby these sites become blocked, preventing further attachment of dissolved ions and halting further growth.

Authors with CRIS profile

Robert Stepic Physics Underlying Life Science Ksenia Klementyeva Physics Underlying Life Science Ana-Suncana Smith Physics Underlying Life Science

Related research project(s)

Molecular modelling of surface and particle interactions (SFB 1411 - D01) Design of particulate products (SFB 1411) Jan. 1, 2020 - Dec. 31, 2023

Involved external institutions

Rudjer Boskovic Institute (RBI) / Institut Ruđer Bošković (IRB) HR Croatia (HR)

How to cite

APA:

Stepic, R., Jurković, L., Klementyeva, K., Ukrainczyk, M., Gredičak, M., Smith, D.M.,... Smith, A.-S. (2020). Adsorption of Aspartate Derivatives to Calcite Surfaces in Aqueous Environment. Crystal Growth and Design, 20(5), 2853-2859. https://dx.doi.org/10.1021/acs.cgd.0c00061

MLA:

Stepic, Robert, et al. "Adsorption of Aspartate Derivatives to Calcite Surfaces in Aqueous Environment." Crystal Growth and Design 20.5 (2020): 2853-2859.

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