Cited by 167Calcium Carbonate Crystallization and InhibitionCrystallization and Solubility StudiesMicrobial Applications in Construction Materials

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Peptide Controls on Calcite Mineralization: Polyaspartate Chain Length Affects Growth Kinetics and Acts as a Stereochemical Switch on Morphology

Elhadj, S., Salter, E. A., Wierzbicki, A., De Yoreo, J. J., Han, N., Dove, P. M.·2006·Crystal Growth & Design

DOI 10.1021/cg050288+

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Abstract

Polyaspartate domains are a prominent feature of proteins associated with biogenic carbonates and have been implicated in modifying crystal morphology through specific interactions with step edges. Here, we show that the morphology and growth kinetics of calcite are modified in a systematic way when a series of poly- l -aspartates, Asp 1 - 6, are introduced into solution. In-situ measurements of step propagation rates by atomic force microscopy reveal these effects are strongly chain-length dependent and specific to the crystallographically distinct, obtuse and acute step types. Direct observations of differential roughening and rounding of the step edges demonstrate that, while Asp 1 and Asp 2 have stronger effects on acute step edges, a crossover occurs for the longer Asp 4,5,6 peptides that preferentially affect obtuse steps. Independent analysis of Asp n −step edge interactions by semiempirical quantum mechanical modeling gives estimates of aspartate−step edge binding energies and predicts that the crossover should occur at n = 2. The switch occurs because, upon Asp n binding, the energy required to dehydrate acute steps is greater than that at the obtuse steps when n = 3−6. Step velocity measurements show that the concentration of Asp n needed to stop growth scales exponentially and inversely with the calculated binding energies. A simple model of Asp n adsorption to the steps is derived from these results. These findings suggest a process by which small fluctuations in primary structure in proteins can control calcite shape.

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Authors: Elhadj, S., Salter, E. A., Wierzbicki, A., De Yoreo, J. J., Han, N., & Dove, P. M.
Affiliations: Lawrence Livermore National Laboratory (US)
Department of Geosciences, Virginia Tech, Derring Hall, Blacksburg, Virginia 24061, Department of Chemistry, University of South Alabama, Mobile, Alabama 36688, and Department of Chemistry and Materials Science, Lawrence Livermore National Laboratory, P.O. Box 808, Livermore, California 94551
Corresponding author: Elhadj, S.
ORCID: Elhadj, S.
Dove, P. M.
Venue: Crystal Growth & Design
Publisher: American Chemical Society (ACS)
Published: 2005-09-21
Volume: 6
Issue: 1
Pages: 197-201
ISSN: 1528-7483 (ISSN-L)
1528-7505
DOI: 10.1021/cg050288+
OpenAlex: W2150295685
Cited by: 165
References: 24
Citations by year: 2026: 2 · 2025: 2 · 2024: 6 · 2023: 4 · 2022: 9 · 2021: 5 · 2020: 9 · 2019: 4 · 2018: 8 · 2017: 7 · 2016: 4 · 2015: 8 · 2014: 8 · 2013: 15 · 2012: 19
FWCI: 3.23
Type: journal article
Language: en
Open access: closed
Locations: Crystal Growth & Design (publishedVersion)
Topics: Physical Sciences › Materials Science › Biomaterials › Calcium Carbonate Crystallization and Inhibition
Physical Sciences › Materials Science › Materials Chemistry › Crystallization and Solubility Studies
Physical Sciences › Environmental Science › Environmental Engineering › Microbial Applications in Construction Materials
Keywords: polyaspartate, calcite crystal growth, crystal morphology, step propagation, chain length dependence, peptide adsorption, biomineralization, crystal growth kinetics, binding energy

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Peptide Controls on Calcite Mineralization: Polyaspartate Chain Length Affects Growth Kinetics and Acts as a Stereochemical Switch on Morphology

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