生物矿化

生物矿化（Biomineralization）是生物经细胞代谢产生矿物的过程，常用于制造硬组织（矿化组织（英语：Mineralized tissues））。各类群生物均能进行生物矿化，目前已知超过60种矿物可经由生物矿化生成，包括矽藻的矽酸盐、软体动物与甲壳动物的碳酸钙、以及脊椎动物的磷酸钙等^[9][10][11]。这些矿化组织具结构支持^[12]、捕食^[13]、防御^[14][15]与调节胞内环境等多种功能^[16][17][18]。

各类群真核生物生物矿化形成的矿物种类^[1]，演化树为基于Adl et al. (2012)绘制^[2]，类群旁的字母表示该类群可形成此矿物，圆圈中的字母表示该矿物在该类群生物中被广泛、大量合成。S：矽酸盐；C：碳酸钙；P：磷酸钙；I：铁矿物；X：草酸钙；SO₄：硫酸盐^{[3][4][5][6][7][8]}。

最常见的生物矿化产物为磷酸钙与碳酸钙，可与胶原蛋白和几丁质等有机聚合物一起组成坚硬的壳、骨骼及牙齿等矿化组织，其结构受多层次的精密调控而有复杂功能^[19]。在生物学领域外，生物矿化也是材料工程等领域感兴趣的议题^[20][21]。

功能

动物

动物的生物矿化产物有碳酸钙、磷酸钙与二氧化矽（海绵动物的骨针^[22]）等，有包括支撑组织、防御与捕食等多种功能^[23]。

软体动物

多种软体动物的壳

软体动物经生物矿化形成的壳（英语：Mollusc shell）有95%至99%成分为碳酸钙（霰石与方解石等），剩下的1%至5%为有机物，其断裂韧性为纯碳酸钙的3000倍，因而为材料科学界所关注^[24]。壳形成的过程中有些蛋白为促进结晶的结晶核，其他蛋白则负责导引壳的成长。珍珠母即为著名的软体动物壳，其结构复杂，各层结构与组成的晶体、有机物种类均不同，并可能因物种而异^[11]。

真菌

真菌也会进行生物矿化，在多种地质作用中扮演重要角色，“地质真菌学”（geomycology）即为研究真菌生物矿化、生物降解以及与金属作用等过程的学门^[25]。许多真菌可分泌蛋白质至胞外，作为结晶核以合成碳酸盐等无机矿物，在金属离子存在时可形成金属碳酸盐，例如粉色面包霉菌与一些拟盘多毛孢属和漆斑菌属的真菌可矿化产生碱式碳酸铜与碳酸铵的混合物^[26]。除碳酸盐外，有些真菌可将基质中的铀矿化形成铀的磷酸盐，累积于其菌丝体中，放射性的铀虽对生物体有害，但这些真菌一般耐受一定含量^[27]。

许多真菌也可分解矿物，特别是可分泌草酸的真菌（包括黑曲霉、扇索状干腐菌（英语：Serpula himantioides）与云芝等可分解尿素的真菌），可分解磷灰石与方铅矿等矿物^[28]。

细菌

有些细菌可进行生物矿化，但许多功能尚不明，有假说认为其作用可能是避免代谢产生的副产物抑制自身生长，也有学者认为其形成氧化铁等矿物可能有助于促进自身代谢反应^[29]。

趋磁细菌可矿化生成磁铁矿，组成名为磁小体的膜状结构，可感应地磁而影响其排列、分布形式^[30]。

• 
  钙板金藻（定鞭藻门）具矿化的外壳（颗石粒，其成分为碳酸钙^[31]）
• 
  有孔虫的外壳一般为碳酸钙
• 
  许多无脊椎动物经生物矿化产生坚硬的碳酸钙外骨骼
• 
  脊椎动物内骨骼的成分为磷酸钙结合产生的羟磷灰石^[32]
• 
  趋磁细菌与其胞内排列的磁小体

成分

大多数生物矿化的产物可分为矽酸盐、碳酸盐与磷酸盐三大类^[5]：

矽酸盐

具矽壳的有壳变形虫（英语：testate amoeba）

矽酸盐为许多海洋生物矿化的产物，如矽藻与放射虫的矽壳^[33]，以及海绵动物的骨针^[22]，陆地上可合成矽酸盐的主要生物则为陆生植物^[1]。矽酸盐为三种生物矿物中在生物分类上分布最广的，各大类群的真核生物都可合成^[6]。不同生物组织矽化（英语：Silicification）的程度也有区别，从仅与其他矿物共同组成结构（如笠螺（英语：limpet）的牙齿^[34]）、自行组成微小的结构^[35]至组成个体的主要结构者皆有^[36]。

碳酸盐

生物矿化产生最常见的碳酸盐为碳酸钙，其中又以方解石（有孔虫的壳与钙板金藻的颗石粒等）与霰石（珊瑚礁）的形态为大宗，也有少数为六方方解石或非晶质碳酸钙（英语：Amorphous calcium carbonate）（可能有结构功能^[37][38]，或作为生物矿化的中间产物^[39][40]）。有些生物矿化的产物为上述数种矿物以有组织分层的方式混合而成（如双壳贝（英语：Bivalve shell））。碳酸盐在海生动物的生物矿化中相当常见，但也见于陆生动物与淡水动物^[41]。

磷酸盐

蝉形齿指虾蛄以坚硬的掠肢攻击猎物^[42]

生物矿化产生最常见的磷酸盐为羟磷灰石（HA），为一种天然的磷灰石，是脊椎动物骨骼、牙齿与鱼鳞的主要成分^[43]。骨骼有65%至70%为羟磷灰石组成，其馀则为胶原蛋白交织而成的网络；牙齿的象牙质与珐琅质也有70%至80%为羟磷灰石，其中后者的蛋白网络为釉原蛋白（英语：amelogenin）与釉蛋白（英语：Enamelin）组成，而非胶原蛋白^[44]。牙齿再矿化（英语：Remineralisation）即为新的钙与磷酸离子沉积形成羟磷灰石的过程，可修补酸化造成的牙齿损伤^[45]。

蝉形齿指虾蛄可形成非常坚硬的掠肢（dactyl club），其结构极为致密，抗冲击能力极高^[46]，可分为冲击层（表层）、周期层与横纹层等三层，其中冲击层等主要成分为羟磷灰石，其馀两层为磷酸钙与碳酸钙的混合物，其钙离子与磷酸离子的含量从外至内递减，大大降低其模量，可抑制裂痕的延伸，迫使新形成的裂痕转换方向，且内外两层的模量差异巨大也有助于减少跨层的能量传导^[46]。

多毛纲缨鳃虫科的Glomerula piloseta所形成的柱状霰石结构

成分	生物
碳酸钙 （方解石或霰石）	有孔虫门 钙板金藻 钙质海绵纲（海绵骨针） 珊瑚 古杯动物门 外肛动物门 腕足动物门与软体动物门的壳 棘皮动物 龙介虫科
二氧化硅 （矽酸盐）	放射虫 矽藻 多数海绵的骨针
磷灰石 （磷酸盐矿物）	牙釉质（脊椎动物的牙齿） 脊椎动物的骨骼 牙形石 舌形贝型亚门的壳

其他矿物

石鳖的牙齿具磁铁矿

帽贝的牙齿具针铁矿

等辐骨亚纲的放射虫外壳成分为天青石

除上述三大类矿物外，还有若干种矿物能经生物矿化形成，其中许多为生存在特殊环境的生物产生，用以形成具特定物理性质的结构。有些动物因取食坚硬的基质而加强牙齿的结构，如石鳖的牙齿覆有磁铁矿^[47]，笠螺（英语：Limpet）的牙齿具针铁矿^[48]；居于海底热泉周边的腹足纲动物外壳除碳酸钙外还有黄铁矿与硫复铁矿（英语：Greigite）以加固结构^[49]。

天青石为硫酸锶组成的矿物^[50]，等辐骨亚纲的放射虫外壳成分即为天青石，质地致密，因其密度较大，可使放射虫快速沉淀至半深海带，而有矿物压载（mineral ballast）的功能^[50][51][52]。

演化

一些钙质海绵

最早的生物矿化可能为距今20亿年前生成磁铁矿的趋磁细菌，两侧动物的共祖应已有此途径，在寒武纪时因基因扩增而产生另一套平行的矿化系统，用以合成含钙的矿物^[53]。真核生物的生物矿化痕迹可追溯至距今7亿5000万年前^[54][55]，类似海绵的生物可能在距今6亿3000万年前即出现方解石的外骨骼^[56]，但多数动物类群的生物矿化应是起源自寒武纪或奥陶纪^[57]。动物矿化的碳酸钙结晶形式可能取决该类群祖先在矿化演化出现当下的环境因子，其衍生的类群随后即沿用该形式的矿物^[58][59][60]，水层中钙与镁离子的比例与大气中的二氧化碳（英语：Carbon dioxide in Earth's atmosphere）浓度皆会影响矿化演化出现时各类矿物的稳定度^[58]。

生物矿化在各类群生物中多次演化出现^[61]，许多演化上无关的生物类群都使用类似的矿化途径（讯息传递因子、抑制物与转录因子等^[62]，如碳酸酐酶在各类群动物的矿化中均有类似功能，可能在动物的共祖中即已出现^[63]。），显示这些同源的反应途径与蛋白可能在生物矿化出现前（前寒武纪）即存在生物中，并具矿化以外的功能^[5]，在生物矿化出现后它们多负责调控矿化中较根本的步骤（如决定哪些细胞将被用来合成矿物），而后续微调矿化反应的步骤（如结晶的具体形状与排列方式）在演化上则一般较晚出现，为在各类群生物中各自独立演化产生^[23][64]。有假说认为前者由非矿化功能演化出矿化反应的动力是避免在离子近饱和的海水中发生不受控制的自发矿化^[62]，许多参与矿化反应的黏液可能最初即有此类抑制自发矿化的功能^[65]。此外各类群动物中，控制细胞内钙离子浓度的蛋白高度同源，在各类群分化后各自演化产生矿化功能^[66]，如石珊瑚的galaxin蛋白原本具其他功能，在三叠纪左右演化出矿化的新功能^[67]。

有研究将软体动物壳的珠母层移植到人类牙齿上，发现此移植并未触发免疫排斥反应，移植的矿物可被人类牙齿吸收；也有研究发现腕足动物门与软体动物门动物生物矿化的反应途径高度类似，皆使用若干演化上保守的基因，显示生物矿化可能是冠轮动物的祖征（英语：Primitive (phylogenetics)）^[68]。与生物矿化有关的基因演化迅速，至今仍有许多基因座具有很大的变异^[64]。

一般来说若产生矿化组织所需的能量小于产生等量有机组织所需的能量，进行生物矿化便是演化上有利的^[69][70][71]，例如产生矽酸盐所需的能量仅为制造等量木质素的约5%，即制造等量多糖（如纤维素）的10%^[72]。

应用

工程上许多制造奈米材料的传统方法相当耗能，需高温高压等严苛条件，并可能生成有毒的副产物，产量有限且经常难以重复^[73][74]。相较之下许多生物矿化所形成的材料物理性质超越人工的材料，且在温和环境条件下即可在溶液中使用大分子与离子合成，可重复可靠地生成材料。无机矿物与有机物（蛋白质等）相结合而成的生物组织结构经常比纯矿物更为坚固，例如矽藻的矽壳是已知每单位密度强度最强的生物材料^[75][76]，海绵的骨针弹性也比纯矽酸盐高得多^[77][78]。有仿生学研究即以模仿生物矿化作用合成所需材料为宗旨^[73][74]。

有研究利用可生成碳酸钙的细菌（巨大芽孢杆菌（英语：Bacillus megaterium））来制造可“自我愈合”的混凝土，即在混凝土中加入细菌的内孢子与有机分子等材料，当建筑出现裂缝时，渗水可将有机分子溶解，使孢子萌发，细菌即可矿化生成新的碳酸钙以修补裂缝^[79][80]。除被动修补外，未来生物矿化可能在建筑中扮演更多角色，如随环境变化而精密控制材料生成的时间、位点或物理性质，使建筑得以随时感测环境因子并作出反应^[81][82][83]。

移除污染物

钙铀云母结晶

生物矿化可被用于移除被铀污染的水层。有些细菌与真菌细胞表面配体上带负电的磷酸离子可与水中带正电的UO₂²⁺离子结合，当浓度够高时可作为结晶核，和UO₂²⁺矿化生成钙铀云母（Ca(UO₂)₂(PO₄)₂·10–12H₂O）等含铀的结晶矿物，将铀自水中矿化移除。与直接往水中加入磷酸根以生成沉淀相较，生物矿化移除铀的特异性较高，较不易与水中其他金属离子结合，因而移除铀的效率较高^[84][85]。

天体生物学

生物矿化产生的矿物以及与其关联的生命印迹是搜索地外生命时可以使用的线索^[86]。

参见

• 生物结晶（英语：Biocrystallization）
• 生物薄膜
• 生物介面（英语：Biointerface）
• 生物矿化多毛虫（英语：Biomineralising polychaete）：能行生物矿化产生碳酸钙的多毛纲动物
• 微生物诱导碳酸钙沉淀（英语：Microbiologically induced calcite precipitation）（MICP）
• 骨矿物质（英语：Bone mineral）
• 矿化组织（英语：Mineralized tissues）

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