title: Tuning calcite morphology and growth acceleration by a rational design of highly stable protein-mimetics.
abstract: In nature, proteins play a significant role in biomineral formation. One of the ultimate goals of bioinspired materials science is to develop highly stable synthetic molecules that mimic the function of these natural proteins by controlling crystal formation. Here, we demonstrate that both the morphology and the degree of acceleration or inhibition observed during growth of calcite in the presence of peptoids can be rationally tuned by balancing the electrostatic and hydrophobic interactions, with hydrophobic interactions playing the dominant role. While either strong electrostatic or hydrophobic interactions inhibit growth and reduces expression of the {104} faces, correlations between peptoid-crystal binding energies and observed changes in calcite growth indicate moderate electrostatic interactions allow peptoids to weakly adsorb while moderate hydrophobic interactions cause disruption of surface-adsorbed water layers, leading to growth acceleration with retained expression of the {104} faces. This study provides fundamental principles for designing peptoids as crystallization promoters, and offers a straightforward screening method based on macroscopic crystal morphology. Because peptoids are sequence-specific, highly stable, and easily synthesized, peptoid-enhanced crystallization offers a broad range of potential applications.
authors.affiliation: 1] Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 [2] Pacific Northwest National Laboratory, PO Box 999, MS K2-01, Richland, WA 99352.
authors.forename: Chun-Long
authors.initials: CL
authors.lastname: Chen
authors.affiliation: 1] Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 [2] Department of Materials, Imperial College London, London, SW7 2AZ.
authors.forename: Jiahui
authors.initials: J
authors.lastname: Qi
authors.affiliation: 1] Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 [2] Pacific Northwest National Laboratory, PO Box 999, MS K2-01, Richland, WA 99352.
authors.forename: Jinhui
authors.initials: J
authors.lastname: Tao
authors.affiliation: Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA 94720.
authors.forename: Ronald N
authors.initials: RN
authors.lastname: Zuckermann
authors.affiliation: 1] Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 [2] Pacific Northwest National Laboratory, PO Box 999, MS K2-01, Richland, WA 99352 [3] Department of Materials Science and Engineering, University of Washington, Seattle, WA 98195.
authors.forename: James J
authors.initials: JJ
authors.lastname: DeYoreo
mesh_terms: D002119:Calcium Carbonate / Q000737:chemistry*; D002264:Carboxylic Acids; D003460:Crystallization; D057927:Hydrophobic and Hydrophilic Interactions; D018716:Molecular Mimicry; D034444:Peptoids / Q000737:chemistry*
chemical_list: D002264:Carboxylic Acids; D034444:Peptoids; D002119:Calcium Carbonate