title: Two competitive nucleation mechanisms of calcium carbonate biomineralization in response to surface functionality in low calcium ion concentration solution.
abstract: Four self-assembled monolayer surfaces terminated with -COOH, -OH, -NH2 and -CH3 functional groups are used to direct the biomineralization processes of calcium carbonate (CaCO3) in low Ca(2+) concentration, and the mechanism of nucleation and initial crystallization within 12 h was further explored. On -COOH surface, nucleation occurs mainly via ion aggregation mechanism while prenucleation ions clusters may be also involved. On -OH and -NH2 surfaces, however, nucleation forms via calcium carbonate clusters, which aggregate in solution and then are adsorbed onto surfaces following with nucleation of amorphous calcium carbonate (ACC). Furthermore, strongly negative-charged -COOH surface facilitates the direct formation of calcites, and the -OH and -NH2 surfaces determine the formation of vaterites with preferred crystalline orientations. Neither ACC nor crystalline CaCO3 is observed on -CH3 surface. Our findings present a valuable model to understand the CaCO3 biomineralization pathway in natural system where functional groups composition plays a determining role during calcium carbonate crystallization.
authors.affiliation: State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China;; Department of Chemistry and Biochemistry, Jackson State University, Jackson, MS 39203, USA;
authors.forename: Hua
authors.initials: H
authors.lastname: Deng
authors.affiliation: State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China;
authors.forename: Shuo
authors.initials: S
authors.lastname: Wang
authors.affiliation: State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China;
authors.forename: Xiumei
authors.initials: X
authors.lastname: Wang
authors.affiliation: School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641, China and.
authors.forename: Chang
authors.initials: C
authors.lastname: Du
authors.affiliation: Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Chemical Engineering, Guangxi Normal University, Guilin 541004, China.
authors.forename: Xingcan
authors.initials: X
authors.lastname: Shen
authors.affiliation: School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641, China and.
authors.forename: Yingjun
authors.initials: Y
authors.lastname: Wang
authors.affiliation: State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China;
authors.forename: Fuzhai
authors.initials: F
authors.lastname: Cui
keywords: biomineralization; calcium carbonate; ions adsorption; prenucleation clusters; self-assembled monolayer
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