Thermodynamic and Kinetic Parameters for Calcite Nucleation on Peptoid and Model Scaffolds: A Step toward Nacre Mimicry
Abstract
The production of novel composite materials, assembled using biomimetic polymers known as peptoids (N-substituted glycines) to nucleate CaCO3, can open new pathways for advanced material design. However, a better understanding of the heterogeneous CaCO3 nucleation process is a necessary first step. We determined the thermodynamic and kinetic parameters for calcite nucleation on self-assembled monolayers (SAMs) of nanosheet-forming peptoid polymers and simpler, alkanethiol analogues. We used nucleation rate studies to determine the net interfacial free energy (γnet) for the peptoid-calcite interface and for SAMs terminated with carboxyl headgroups, amine headgroups, or a mix of the two. We compared the results with γnet determined from dynamic force spectroscopy (DFS) and from density functional theory (DFT), using COSMO-RS simulations. Calcite nucleation has a lower thermodynamic barrier on the peptoid surface than on carboxyl and amine SAMs. From the relationship between nucleation rate (J0) and saturation state, we found that under low-saturation conditions, i.e. <3.3 (pH 9.0), nucleation on the peptoid substrate was faster than that on all of the model surfaces, indicating a thermodynamic drive toward heterogeneous nucleation. When they are taken together, our results indicate that nanosheet-forming peptoid monolayers can serve as an organic template for CaCO3 polymorph growth.
- Authors:
-
[1];
[2];
[1];
[2];
[3]
- Nano-Science Center, Department of Chemistry, University of Copenhagen, Copenhagen, Denmark
- Biological Nanostructures Facility, The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California, United States
- Department of Geography & Earth Sciences, Aberystwyth University, Aberystwyth, United Kingdom
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); European Research Council (ERC)
- OSTI Identifier:
- 1698055
- Alternate Identifier(s):
- OSTI ID: 1760251
- Grant/Contract Number:
- AC02-05CH11231; 3517; 663830
- Resource Type:
- Published Article
- Journal Name:
- Crystal Growth and Design
- Additional Journal Information:
- Journal Name: Crystal Growth and Design Journal Volume: 20 Journal Issue: 6; Journal ID: ISSN 1528-7483
- Publisher:
- American Chemical Society
- Country of Publication:
- France
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Nielsen, Anne R., Jelavić, Stanislav, Murray, Daniel, Rad, Behzad, Andersson, Martin P., Ceccato, Marcel, Mitchell, Andrew C., Stipp, Susan L. S., Zuckermann, Ronald N., and Sand, Karina K. Thermodynamic and Kinetic Parameters for Calcite Nucleation on Peptoid and Model Scaffolds: A Step toward Nacre Mimicry. France: N. p., 2020.
Web. doi:10.1021/acs.cgd.0c00029.
Nielsen, Anne R., Jelavić, Stanislav, Murray, Daniel, Rad, Behzad, Andersson, Martin P., Ceccato, Marcel, Mitchell, Andrew C., Stipp, Susan L. S., Zuckermann, Ronald N., & Sand, Karina K. Thermodynamic and Kinetic Parameters for Calcite Nucleation on Peptoid and Model Scaffolds: A Step toward Nacre Mimicry. France. https://doi.org/10.1021/acs.cgd.0c00029
Nielsen, Anne R., Jelavić, Stanislav, Murray, Daniel, Rad, Behzad, Andersson, Martin P., Ceccato, Marcel, Mitchell, Andrew C., Stipp, Susan L. S., Zuckermann, Ronald N., and Sand, Karina K. Fri .
"Thermodynamic and Kinetic Parameters for Calcite Nucleation on Peptoid and Model Scaffolds: A Step toward Nacre Mimicry". France. https://doi.org/10.1021/acs.cgd.0c00029.
@article{osti_1698055,
title = {Thermodynamic and Kinetic Parameters for Calcite Nucleation on Peptoid and Model Scaffolds: A Step toward Nacre Mimicry},
author = {Nielsen, Anne R. and Jelavić, Stanislav and Murray, Daniel and Rad, Behzad and Andersson, Martin P. and Ceccato, Marcel and Mitchell, Andrew C. and Stipp, Susan L. S. and Zuckermann, Ronald N. and Sand, Karina K.},
abstractNote = {The production of novel composite materials, assembled using biomimetic polymers known as peptoids (N-substituted glycines) to nucleate CaCO3, can open new pathways for advanced material design. However, a better understanding of the heterogeneous CaCO3 nucleation process is a necessary first step. We determined the thermodynamic and kinetic parameters for calcite nucleation on self-assembled monolayers (SAMs) of nanosheet-forming peptoid polymers and simpler, alkanethiol analogues. We used nucleation rate studies to determine the net interfacial free energy (γnet) for the peptoid-calcite interface and for SAMs terminated with carboxyl headgroups, amine headgroups, or a mix of the two. We compared the results with γnet determined from dynamic force spectroscopy (DFS) and from density functional theory (DFT), using COSMO-RS simulations. Calcite nucleation has a lower thermodynamic barrier on the peptoid surface than on carboxyl and amine SAMs. From the relationship between nucleation rate (J0) and saturation state, we found that under low-saturation conditions, i.e. <3.3 (pH 9.0), nucleation on the peptoid substrate was faster than that on all of the model surfaces, indicating a thermodynamic drive toward heterogeneous nucleation. When they are taken together, our results indicate that nanosheet-forming peptoid monolayers can serve as an organic template for CaCO3 polymorph growth.},
doi = {10.1021/acs.cgd.0c00029},
journal = {Crystal Growth and Design},
number = 6,
volume = 20,
place = {France},
year = {Fri Apr 24 00:00:00 EDT 2020},
month = {Fri Apr 24 00:00:00 EDT 2020}
}
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