title: Stable prenucleation mineral clusters are liquid-like ionic polymers.
abstract: Calcium carbonate is an abundant substance that can be created in several mineral forms by the reaction of dissolved carbon dioxide in water with calcium ions. Through biomineralization, organisms can harness and control this process to form various functional materials that can act as anything from shells through to lenses. The early stages of calcium carbonate formation have recently attracted attention as stable prenucleation clusters have been observed, contrary to classical models. Here we show, using computer simulations combined with the analysis of experimental data, that these mineral clusters are made of an ionic polymer, composed of alternating calcium and carbonate ions, with a dynamic topology consisting of chains, branches and rings. The existence of a disordered, flexible and strongly hydrated precursor provides a basis for explaining the formation of other liquid-like amorphous states of calcium carbonate, in addition to the non-classical behaviour during growth of amorphous calcium carbonate.
authors.affiliation: Department of Chemistry, Nanochemistry Research Institute, Curtin University, PO Box U1987, Perth, Western Australia 6845, Australia.
authors.forename: Raffaella
authors.initials: R
authors.lastname: Demichelis
authors.forename: Paolo
authors.initials: P
authors.lastname: Raiteri
authors.forename: Julian D
authors.initials: JD
authors.lastname: Gale
authors.forename: David
authors.initials: D
authors.lastname: Quigley
authors.forename: Denis
authors.initials: D
authors.lastname: Gebauer
mesh_terms: D002119:Calcium Carbonate / Q000032:analysis / Q000737:chemistry*; D002245:Carbon Dioxide / Q000737:chemistry; D002627:Chemistry, Physical; D003198:Computer Simulation; D003460:Crystallization; D007477:Ions / Q000737:chemistry; D015233:Models, Statistical; D015394:Molecular Structure; D011108:Polymers / Q000737:chemistry*; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
chemical_list: D007477:Ions; D011108:Polymers; D014867:Water; D002245:Carbon Dioxide; D002119:Calcium Carbonate