Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061, United States.
Department of Geosciences, Virginia Tech, Blacksburg, Virginia 24061, United States.
Biomacromolecules. 2023 Mar 13;24(3):1078-1102. doi: 10.1021/acs.biomac.2c01394. Epub 2023 Feb 28.
A mechanistic understanding of how macromolecules, typically as an organic matrix, nucleate and grow crystals to produce functional biomineral structures remains elusive. Advances in structural biology indicate that polysaccharides (e.g., chitin) and negatively charged proteoglycans (due to carboxyl, sulfate, and phosphate groups) are ubiquitous in biocrystallization settings and play greater roles than currently recognized. This review highlights studies of CaCO crystallization onto chitinous materials and demonstrates that a broader understanding of macromolecular controls on mineralization has not emerged. With recent advances in biopolymer chemistry, it is now possible to prepare chitosan-based hydrogels with tailored functional group compositions. By deploying these characterized compounds in hypothesis-based studies of nucleation rate, quantitative relationships between energy barrier to crystallization, macromolecule composition, and solvent structuring can be determined. This foundational knowledge will help researchers understand composition-structure-function controls on mineralization in living systems and tune the designs of new materials for advanced applications.
对于生物矿化过程中，大分子（通常为有机基质）如何成核和生长晶体以产生功能性生物矿物结构，其机制仍难以捉摸。结构生物学的进展表明，多糖（例如几丁质）和带负电荷的蛋白聚糖（由于羧基、硫酸基和磷酸基）在生物结晶环境中无处不在，其作用比目前所认识到的更为重要。本综述重点介绍了几丁质材料上 CaCO3 结晶的研究，并表明对矿化过程中大分子控制的理解尚未取得进展。随着生物聚合物化学的最新进展，现在可以制备具有定制官能团组成的壳聚糖基水凝胶。通过在基于假设的成核速率研究中使用这些经过表征的化合物，可以确定结晶能垒、大分子组成和溶剂结构之间的定量关系。这些基础知识将帮助研究人员了解生物体系中矿化的组成-结构-功能控制，并调整新材料的设计以用于先进应用。
