title: Chiral acidic amino acids induce chiral hierarchical structure in calcium carbonate.
abstract: Chirality is ubiquitous in biology, including in biomineralization, where it is found in many hardened structures of invertebrate marine and terrestrial organisms (for example, spiralling gastropod shells). Here we show that chiral, hierarchically organized architectures for calcium carbonate (vaterite) can be controlled simply by adding chiral acidic amino acids (Asp and Glu). Chiral, vaterite toroidal suprastructure having a 'right-handed' (counterclockwise) spiralling morphology is induced by L-enantiomers of Asp and Glu, whereas 'left-handed' (clockwise) morphology is induced by D-enantiomers, and sequentially switching between amino-acid enantiomers causes a switch in chirality. Nanoparticle tilting after binding of chiral amino acids is proposed as a chiral growth mechanism, where a 'mother' subunit nanoparticle spawns a slightly tilted, consequential 'daughter' nanoparticle, which by amplification over various length scales creates oriented mineral platelets and chiral vaterite suprastructures. These findings suggest a molecular mechanism for how biomineralization-related enantiomers might exert hierarchical control to form extended chiral suprastructures.
authors.affiliation: Faculty of Dentistry, McGill University, Montreal, Quebec, Canada H3A 0C7.
authors.forename: Wenge
authors.initials: W
authors.lastname: Jiang
authors.affiliation: Department of Biomedical Engineering, Johns Hopkins University, Baltimore, Maryland 21218, USA.
authors.forename: Michael S
authors.initials: MS
authors.lastname: Pacella
authors.affiliation: Faculty of Dentistry, McGill University, Montreal, Quebec, Canada H3A 0C7.
authors.forename: Dimitra
authors.initials: D
authors.lastname: Athanasiadou
authors.affiliation: Faculty of Dentistry, McGill University, Montreal, Quebec, Canada H3A 0C7.
authors.forename: Valentin
authors.initials: V
authors.lastname: Nelea
authors.affiliation: Department of Anatomy and Cell Biology, Faculty of Medicine, McGill University, Montreal, Quebec, Canada H3A 0C7.
authors.forename: Hojatollah
authors.initials: H
authors.lastname: Vali
authors.affiliation: Geophysical Laboratory, Carnegie Institution of Washington, 5251 Broad Branch Road NW, Washington, District of Columbia 20015, USA.
authors.forename: Robert M
authors.initials: RM
authors.lastname: Hazen
authors.affiliation: Department of Chemical and Biomolecular Engineering, Johns Hopkins University, Baltimore, Maryland 21218, USA.
authors.forename: Jeffrey J
authors.identifier: 0000-0001-6380-2324
authors.initials: JJ
authors.lastname: Gray
authors.affiliation: Faculty of Dentistry, McGill University, Montreal, Quebec, Canada H3A 0C7.|Department of Anatomy and Cell Biology, Faculty of Medicine, McGill University, Montreal, Quebec, Canada H3A 0C7.
authors.forename: Marc D
authors.initials: MD
authors.lastname: McKee
mesh_terms: D024342:Amino Acids, Acidic / Q000737:chemistry*; D001224:Aspartic Acid / Q000737:chemistry*; D002119:Calcium Carbonate / Q000737:chemistry*; D018698:Glutamic Acid / Q000737:chemistry*; D008854:Microscopy, Electron; D049329:Nanostructures / Q000737:chemistry / Q000648:ultrastructure; D013237:Stereoisomerism; D014961:X-Ray Diffraction
chemical_list: D024342:Amino Acids, Acidic; D001224:Aspartic Acid; D018698:Glutamic Acid; D002119:Calcium Carbonate