Origin of the biphase nature and surface roughness of biogenic calcite secreted by the giant barnacle Austromegabalanus psittacus – ScienceOpen
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      Origin of the biphase nature and surface roughness of biogenic calcite secreted by the giant barnacle Austromegabalanus psittacus

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          Abstract

          The calcite grains forming the wall plates of the giant barnacle Austramegabalanus psittacus have a distinctive surface roughness made of variously sized crystalline nanoprotrusions covered by extremely thin amorphous pellicles. This biphase (crystalline-amorphous) structure also penetrates through the crystal’s interiors, forming a web-like structure. Nanoprotrusions very frequently elongate following directions related to the crystallographic structure of calcite, in particular, the <− 441> directions, which are the strongest periodic bond chains (PBCs) in calcite. We propose that the formation of elongated nanoprotrusions happens during the crystallization of calcite from a precursor amorphous calcium carbonate (ACC). This is because biomolecules integrated within the ACC are expelled from such PBCs due to the force of crystallization, with the consequent formation of uninterrupted crystalline nanorods. Expelled biomolecules accumulate in adjacent regions, thereby stabilizing small pellicle-like volumes of ACC. With growth, such pellicles become occluded within the crystal. In summary, the surface roughness of the biomineral surface reflects the complex shape of the crystallization front, and the biphase structure provides evidence for crystallization from an amorphous precursor. The surface roughness is generally explained as resulting from the attachment of ACC particles to the crystal surface, which later crystallised in concordance with the crystal lattice. If this was the case, the nanoprotrusions do not reflect the size and shape of any precursor particle. Accordingly, the particle attachment model for biomineral formation should seek new evidence.

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          CRYSTAL GROWTH. Crystallization by particle attachment in synthetic, biogenic, and geologic environments.

          Field and laboratory observations show that crystals commonly form by the addition and attachment of particles that range from multi-ion complexes to fully formed nanoparticles. The particles involved in these nonclassical pathways to crystallization are diverse, in contrast to classical models that consider only the addition of monomeric chemical species. We review progress toward understanding crystal growth by particle-attachment processes and show that multiple pathways result from the interplay of free-energy landscapes and reaction dynamics. Much remains unknown about the fundamental aspects, particularly the relationships between solution structure, interfacial forces, and particle motion. Developing a predictive description that connects molecular details to ensemble behavior will require revisiting long-standing interpretations of crystal formation in synthetic systems, biominerals, and patterns of mineralization in natural environments.
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            Taking Advantage of Disorder: Amorphous Calcium Carbonate and Its Roles in Biomineralization

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              Biomimetic model systems for investigating the amorphous precursor pathway and its role in biomineralization.

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                Author and article information

                Contributors
                acheca@ugr.es
                Journal
                Sci Rep
                Sci Rep
                Scientific Reports
                Nature Publishing Group UK (London )
                2045-2322
                8 October 2020
                8 October 2020
                2020
                : 10
                : 16784
                Affiliations
                [1 ]GRID grid.4489.1, ISNI 0000000121678994, Departamento de Estratigrafía y Paleontología, , Universidad de Granada, ; 18071 Granada, Spain
                [2 ]GRID grid.4489.1, ISNI 0000000121678994, Instituto Andaluz de Ciencias de la Tierra, , CSIC-Universidad de Granada, ; 18100 Armilla, Spain
                [3 ]GRID grid.461760.2, Radboud University Medical Center, , Radboud Institute for Molecular Life Sciences, ; 6500 HB Nijmegen, The Netherlands
                [4 ]GRID grid.419564.b, Max Planck Institute of Colloids and Interfaces, ; 14476 Potsdam, Germany
                [5 ]GRID grid.4489.1, ISNI 0000000121678994, Departamento de Mineralogía y Petrología, , Universidad de Granada, ; 18071 Granada, Spain
                [6 ]GRID grid.441783.d, ISNI 0000 0004 0487 9411, Centro de Investigación e Innovación para el Cambio Climático, Facultad de Ciencias, , Universidad Santo Tomás, ; Santiago, Chile
                Article
                73804
                10.1038/s41598-020-73804-8
                7544902
                33033294
                672270c2-34ee-4b3a-be71-debcf56da02a
                © The Author(s) 2020

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 6 July 2020
                : 23 September 2020
                Funding
                Funded by: FundRef http://dx.doi.org/10.13039/501100006393, Universidad de Granada;
                Award ID: UCE-PP2016-05
                Award ID: UCE-PP2016-05
                Award Recipient :
                Funded by: FundRef http://dx.doi.org/10.13039/501100002878, Consejería de Economía, Innovación, Ciencia y Empleo, Junta de Andalucía;
                Award ID: RNM363
                Award Recipient :
                Funded by: FundRef http://dx.doi.org/10.13039/501100004837, Ministerio de Ciencia e Innovación;
                Award ID: CGL2017-85118-P
                Award ID: CGL2015-64683-P
                Award Recipient :
                Funded by: FundRef http://dx.doi.org/10.13039/501100002848, Comisión Nacional de Investigación Científica y Tecnológica;
                Award ID: FONDECYT 1140938, PCI REDES 170106, PIA ANILLOS ACT172037
                Award Recipient :
                Categories
                Article
                Custom metadata
                © The Author(s) 2020

                Uncategorized
                mineralogy,biomaterials,structural materials,nanoscale biophysics
                Uncategorized
                mineralogy, biomaterials, structural materials, nanoscale biophysics

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