Thermodynamic and Kinetic Parameters for Calcite Nucleation on Peptoid and Model Scaffolds: A Step toward Nacre Mimicry
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Thermodynamic and Kinetic Parameters for Calcite Nucleation on Peptoid and Model Scaffolds: A Step toward Nacre Mimicry. / Nielsen, Anne Rath; Jelavic, Stanislav; Murray, Daniel; Rad, Behzad ; Andersson, Martin Peter; Ceccato, Marcel; Mitchell, Andrew C.; Stipp, Susan Louise Svane; Zuckermann, Ronald N.; Sand, Karina Krarup.
In: Crystal Growth and Design, Vol. 20, No. 6, 2020, p. 3762-3771.Research output: Contribution to journal › Journal article › peer-review
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TY - JOUR
T1 - Thermodynamic and Kinetic Parameters for Calcite Nucleation on Peptoid and Model Scaffolds: A Step toward Nacre Mimicry
AU - Nielsen, Anne Rath
AU - Jelavic, Stanislav
AU - Murray, Daniel
AU - Rad, Behzad
AU - Andersson, Martin Peter
AU - Ceccato, Marcel
AU - Mitchell, Andrew C.
AU - Stipp, Susan Louise Svane
AU - Zuckermann, Ronald N.
AU - Sand, Karina Krarup
PY - 2020
Y1 - 2020
N2 - 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.
AB - 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.
U2 - 10.1021/acs.cgd.0c00029
DO - 10.1021/acs.cgd.0c00029
M3 - Journal article
C2 - 33192182
VL - 20
SP - 3762
EP - 3771
JO - Crystal Growth & Design
JF - Crystal Growth & Design
SN - 1528-7483
IS - 6
ER -
ID: 241644650