Peptide controls on calcite mineralization: polyaspartate chain length affects growth kinetics and acts as a stereochemical switch on morphology
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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Greater negative charge density associated with longer peptides is more efficient at promoting Ca ion dehydration kinetics.
“while the greater negative charge density associated with longer peptides is more efficient at promoting Ca ion dehydration kinetics (Elhadj et al., 2006).”
From Inorganic synthesis of Fe–Ca–Mg carbonates at low temperature (2009) · cites this paper as Elhadj et al., 2006
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“…work, polyaspartate peptide with a negative charge has been found to promote the incorporation of Mg into calcite (Stephenson et al., 2008), while the greater negative charge density associated with longer peptides is more efficient at promoting Ca ion dehydration kinetics (Elhadj et al., 2006).”
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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.
- 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
- 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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