碳酸钙矿物的生物矿化研究及生物启发下碳酸钙的可控晶化、组装及应用

Under the funding support of NSFC, the applicant realized the synthesis of high Mg calcite (Crystal Growth Des. 2011) and one dimensional calcite single crystals in large yield via bio-inspired methods under mild conditions. We characterized systematically synthetic and biogenic Mg-containing calcium carbonate samples (especially sea urchin teeth) in detail by using two FTIR microspectroscopy instruments and compare these samples with KBr pellet FTIR measurements (Phys. Chem. Chem. Phys. 2012). As an exploratory study, the relationship of the structure and the mechanical properties of calcium carbonate mineral shells of sea butterfly were studies in details (Angew. Chem. Int. Ed., 2011). All the novel characters of the ultrathin shells of sea butterfly, such as the helical nanofibers, the interlocking properties, and the crystallographic orientations, may strengthen the ultrathin armor in pteropods. The present funding support for young investigator has been proceeded successfully and quite a lot important results were obtained. As a corresponding author, the applicant has published five papers on important international journals in less than 3 years. To have a thorough, continuous and broadening study based on the present youth program funding support, the applicant is applying a youth- continuous general program for deep investigations within the related field. The content of the main research project will be focused on the biomineralization of calcium carbonate minerals and the bioinspired synthesis of calcium carbonate hierarchical nanostructures. Firstly, we would focus on the structural properties, the mineralization mechanism and the relationship of the structures and the mechanical properties of biogenic calcium carbonate minerals such as high Mg calcite and aragonite. Secondly, the nucleation, crystallization process and ordered assembly of calcium carbonate would be studied via bioinspired methods. The synthesis and potential applications of nacre-like layered aragonite and oriented patterns of one dimensional calcite single crystals with hierarchical micro- and nanostructures will be studied in details.

在青年基金的支持下，申请人利用生物矿化原理实现了高Mg含量方解石（Crystal Growth Des. 2011) 及一维方解石单晶的仿生矿化合成，利用显微红外光谱对生物体内的及人工合成的高Mg方解石进行了系统研究。作为生物碳酸钙矿化的探索性研究，研究了海蝴蝶超薄矿化外壳的特殊微观结构与其机械性能之间的关系（Angew. Chem. Int. Ed., 2011）。以通讯作者身份发表研究论文5篇，总起来青年科学基金项目的研究工作顺利完成。本人申请青年基金-面上顺延项目，以拓展并深化原青年基金项目的研究内容。一方面研究具有优异机械性能的碳酸钙生物矿物即高镁方解石及文石的结构特点、矿化机理、结构与性能的关系，探讨生物矿物形成多级有序结构的矿化机理；另一方面，受生物矿化机理的启发，在实验室内实现碳酸钙成核及生长的有效调控及组装，实现片状文石的层层排列和一维方解石的有序组装，并应用到实际生产中。

在过去4年里，本项目的主要研究进展包含以下几方面，一是高镁方解石的生物矿化及其仿生合成研究，利用溶解法研究了高镁方解石生物矿物海胆骨针的微纳结构特点及其矿化机理(CrystEngComm, 2016, 18, 9374)，提取了高镁方解石生物矿物珊瑚藻中的有机组分，并研究该有机组分对碳酸钙的晶型调控的影响，通过水热合成法可控合成出镁含量在10-63 mol%之间的纯的高镁方解石(CrystEngComm, 2016, 18, 157, J. Struct. Biol., 2014, 185, 1)。二是基于碳酸钙的一维阵列结构及层状多级有序结构的可控合成及其应用，通过外延生长法(Crystal Growth Des., 2013, 13, 3856)和溶解法(CrystEngComm, 2013, 15, 8867, Chem. Eur. J., 2014, 20, 4264)分别获得了方解石的微针阵列结构并将其用于经皮肤的药物输运，结合取向溶解法和外延生长法，进一步扩展到其他碳酸盐（碳酸锶、碳酸钡）的微针阵列结构的控制合成(Crystal Growth Des. 2015, 15, 2156, 物理化学学报, 2015, 31, 189)。通过基于反应中间体的气相扩散法合成出碳酸钙的片状结构，以该片状结构为组装基元，用于层层多级有序结构薄膜的合成。在过去的4年里，在本面上项目的支持下，负责人以通讯作者身份在国际重要学术期刊已发表12篇学术论文，其中影响因子在3.8以上的论文有9篇。另外，在该面上项目的支持下，我们积极参与国内外学术交流活动，做过2次邀请报告，多次口头报告，负责人还作为分会主席参与组织了2016年MRS Spring meeting.