Department of Materials Science and Technology, Faculty of Industrial Science and Technology, Tokyo University of Science , 6-3-1 Niijuku, Katsushika-ku, Tokyo 125-8585, Japan.
Nagoya Institute of Technology , Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan.
Langmuir. 2016 Sep 13;32(36):9351-9. doi: 10.1021/acs.langmuir.6b02439. Epub 2016 Aug 31.
Crystal phase and morphology of biominerals may be precisely regulated by controlled nucleation and selective crystal growth through biomineralization on organic templates such as a protein. We herein propose new control factors of selective crystal growth by the biomineralization process. In this study, a designed β-sheet Ac-VHVEVS-CONH2 peptide was used as a multifunctional template that acted as mineral source supplier and having crystal phase control ability of calcium carbonate (CaCO3) during a self-supplied mineralization. The peptides formed three-dimensional nanofiber networks composed of assembled bilayer β-sheets. The assembly hydrolyzed urea molecules to one carbonate anion and two ammonium cations owing to a charge relay effect between His and Ser residues under mild conditions. CaCO3 was selectively mineralized on the peptide assembly using the generated carbonate anions on the template. Morphology of the obtained CaCO3 was fiber-like structure, similar to that of the peptide template. The mineralized CaCO3 on the peptide template had aragonite phase. This implies that CaCO3 nuclei, generated using the carbonate anions produced by the hydrolysis of urea on the surface of the peptide assembly, preferentially grew into aragonite phase, the growth axis of which aligned parallel to the direction of the β-sheet fiber axis.
生物矿化可以通过在有机模板(如蛋白质)上进行控制成核和选择性晶体生长,从而精确调控生物矿中矿物质的晶体相和形态。本文提出了生物矿化过程中控制选择性晶体生长的新因素。在这项研究中,设计的β-折叠 Ac-VHVEVS-CONH2 肽被用作多功能模板,在自供应矿化过程中充当碳酸钙(CaCO3)的矿物源供应者和具有晶体相控制能力。这些肽形成了由组装双层β-折叠组成的三维纳米纤维网络。在温和条件下,由于 His 和 Ser 残基之间的电荷传递效应,组装体水解尿素分子生成一个碳酸根阴离子和两个铵阳离子。使用模板上生成的碳酸根阴离子,在肽组装体上选择性地矿化 CaCO3。所得 CaCO3 的形态为纤维状结构,与肽模板相似。在肽模板上矿化的 CaCO3 为文石相。这表明,在肽组装体表面上尿素水解生成的碳酸根阴离子所产生的 CaCO3 核优先生长为文石相,其生长轴与β-折叠纤维轴的方向平行。