Biominerals and Biomineralization on Nanoscale: From Perspective of Mesocrystals
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摘要: 纳米地质学的兴起和发展，促使地质工作者从纳米尺度重新认识固体地球物质，将对地球科学的各个领域产生广泛而深刻的影响.作为纳米地质学的重要分支，纳米矿物学也将走出传统矿物学只把矿物看成理想晶体点阵的局限，从纳米尺度深入探究矿物包括生物矿物在内的矿物结构与性质，突破口之一是介晶.介晶是一种特殊的结晶纳米结构，近年来得到了物理学家和化学家尤其是材料化学家越来越多的关注.介晶是非经典结晶过程产物，以纳米颗粒为基本构筑单元，具备纳米颗粒的性质和宏观尺寸.现已发现，许多生物矿物如脊椎动物骨骼和牙齿、贝壳珍珠层、蛋壳、海胆骨针、有孔虫和珊瑚等都具有介晶结构.因此，从纳米尺度和介晶角度重新理解生物矿化，有助于揭示生物矿物中纳米多级结构的成因机制，拓展纳米矿物学的科学内涵.首先介绍生物矿化和生物矿物的基本概念，之后对介晶的概念和结构特征进行阐述，最后介绍生物矿物中的介晶结构及介晶形成的典型机制，涉及有机基质辅助、物理场驱动、矿物桥或有机桥连接、空间限域、取向附集和晶面选择性分子作用等多种物理化学过程，有望进一步推动纳米矿物学的发展.Abstract: The rise and development of nanogeology lead to exploration of the solid earth materials at the nanoscale, exerting extensive and profound impact on various fields of earth science. As an important branch of nanogeology, nanomineralogy also explores the structure and properties of the minerals including biominerals at the nanoscale, eliminating the limitations of traditional mineralogy which only regards the mineral as ideal crystal lattice, of which mesocrystal is one breakthrough. Mesocrystals represent a class of crystalline nanostructured materials drawing increasing attention from physicists and chemists especially material chemists in recent years. Mesocrystals are the products of non-classical crystallization process with nanoparticles as the basic subunits, sharing the properties of nanoparticles with order on the macroscopic length scale. It has been found that a number of biominerals including vertebrate bones and teeth, nacre, egg shells, sea urchin spines, foraminifera, and corals have the mesocrystals structure. Therefore, re-understanding the biomineralization at the nanoscale and the perspective of mesocrystals will undoubtedly help to reveal the formation mechanisms of hierarchical nanostructures in biominerals and expand the scientific connotation of nanomineralogy. Firstly, the basic concepts of biomineralization and biominerals are introduced. Then, the concept and structural feature of mesocrystals are expounded. Finally, the mesocrystal structure in biominerals and the mechanisms of mesocrystal formation are clarified in detail, referring to several physical and chemical processes such as alignment by the organic matrix, alignment by physical forces, connection by mineral bridges or organic bridges, alignment by spatial constraints, alignment by oriented attachment and alignment by face selective molecules. It is expected that this study may promote the further development of nanomineralogy.
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Key words:
- nanogeology /
- nanomineralogy /
- biomineral /
- biomineralization /
- mesocrystal
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图 1 方解石单晶对比
据Weiner and Dove(2003).棘皮动物硬组织(a)和人工合成的菱面体方解石(b)
Fig. 1. Comparison of calcite single crystals
图 2 六方柱状球霰石的FESEM照片(a, b)、TEM照片(c, e)和SAED花样(d, f)
Fig. 2. FESEM images (a, b), TEM images (c, e) and SAED patterns (d, f) of hexagonal prismatic vaterite
图 3 介晶形成机制
据Sturm and Cölfen(2016).a.有机基质辅助；b.物理场驱动；c.矿物桥或有机桥连接；d.空间限域；e.取向附集；f.晶面选择性分子作用
Fig. 3. Formation mechanisms of mesocrystals
图 4 红鲍鱼Haliotis rufescens贝壳纵断面
Fig. 4. Schematic of a vertical section of the shell of a red abalone (Haliotis rufescens)
图 5 软体动物贝壳微观结构
文石层断裂面(a)和横截面(b)；文石层晶体堆积示意图(c)(Addadi et al., 2006).文石片的FETEM图像及SAED花样(d)；文石片亚单元的FETEM图像(e)(Oaki and Imai, 2005)；珍珠质层中局部共取向的文石柱(f)及其示意图(g)
Fig. 5. Molluscs shell microstructure
图 6 介晶结构文石棒的典型FESEM照片
a.低放大倍数；b.高放大倍数；c.具有假六方柱形表面的文石介晶.文石介晶的TEM照片(d, f)和SAED花样(e, g).文石晶体聚形结构示意图(h)和沿着不同结晶学方向的结构投影(i, j)(Zhou et al., 2009)
Fig. 6. Typical FESEM images of aragonite mesocrystal rods
图 7 趋磁细菌磁小体晶体形貌特征
a.立方八面体；b.子弹头形；c, d.假六方棱柱状(Bäuerlein, 2003)
Fig. 7. Crystal morphologies of magnetosomes from magnetotactic bacteria
图 8 PASP存在下鸟粪石的形貌演化过程
Fig. 8. Schematic illustration of the morphology evolution process of struvite in the presence of PASP
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