Thermodynamic and Kinetic Parameters for Calcite Nucleation on Peptoid and Model Scaffolds: A Step toward Nacre Mimicry

Anne R. Nielsen, Stanislav Jelavić, Daniel Murray, Behzad Rad, Martin P. Andersson, Marcel Ceccato, Andrew C. Mitchell, Susan L.S. Stipp, Ronald N. Zuckermann, Karina K. Sand*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

5 Citations (SciVal)
226 Downloads (Pure)


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.

Original languageEnglish
Pages (from-to)3762-3771
Number of pages10
JournalCrystal Growth and Design
Issue number6
Early online date24 Apr 2020
Publication statusPublished - 03 Jun 2020


Dive into the research topics of 'Thermodynamic and Kinetic Parameters for Calcite Nucleation on Peptoid and Model Scaffolds: A Step toward Nacre Mimicry'. Together they form a unique fingerprint.

Cite this