摘要
生物体中的矿物(如骨骼、牙齿、软体动物的壳、植物维管束等)无论在结构还是功能上都具有很强的应用价值,吸引了人们越来越多的兴趣。碳酸钙作为-个生物矿化领域研究的标准模型体系广泛地存在于自然界及生物体中。在模拟生物矿化过程中,碳酸钙的物相控制起了关键性的作用。在本论文中主要讨论了碳酸钙几种相(方解石、霰石、文石和无定形)的调控以及研究无定形碳酸钙如何受限结晶,主要研究成果如下:
1、在没有添加任何有机或者无机添加剂的前提下利用双注射方法完美地实现碳酸钙的三个无水结晶相的相选择。在这个单一的体系中,仅仅通过改变反应温度,观察到了一个完整的相转变过程,即从纯的文石相,转变到纯的霰石相,继而得到霰石和方解石的混合相。这种一元的溶液体系可以通过控制反应温度来调节其动力学和热力学因素,从而成功地控制了碳酸钙的物相及形貌。该研究结果为碳酸钙晶相的选择合成提供了一个简单、温和、可控,廉价和绿色的方法,可望在工业上扩大规模生产不同物相的碳酸钙,并且对于深刻理解自然界中生物矿化的过程有参考价值。另外,这个无模板参与的相选择合成系统对于其它的无机材料也具有一定的借鉴作用。
2、首次研究了不同反应温度下聚乙二醇-聚(N-异丙基丙烯酰胺)-聚(2-丙烯酰胺-2-甲基丙磺酸)(PEG-PNIPAM-PAMPS)这个三嵌段温敏共聚物在模拟生物矿化中的作用,同时在50℃反应条件下得到了表面结构可控的均一花状文石。基于温敏三嵌段聚合物有趣的温敏特性,提出了PNIPAM调控下碳酸钙矿化机制。同时,我们能在该体系中通过控制反应温度来很好的获得三种无水结晶相(如方解石、文石和球霰石)。另外,关于PNIPAM的碳酸钙矿化机制可能给其他无机材料体系可控结晶过程的研究带来新的曙光。
3、发展了一种快速合成大规模、低成本、高稳定性的含镁无定形碳酸钙纳米颗粒的简单化学合成方法。Mg-ACC的结构被定义为Mg0.15Ca0.85CO3·H2O0.85。Mg2+: Ca2+:CO32-的摩尔比以及反应物(CaCl2、Na2CO3和MgCl2)的浓度对制得的Mg-ACC纳米粒子的镁钙摩尔比起着关键作用。另外,如果将含镁无定形碳酸钙干燥粉末保存在-5℃或者将其置于乙醇溶液中保存在5℃条件下,则可以使含镁无定形碳酸钙纳米粒子保存超过一年而不结晶。这两种有效的保存方法可以用于长期保存含镁无定形碳酸钙,以便其作为前驱体在实际生产生活中发挥更广泛的应用。由于Mg-ACC具有良好的可塑性,它可以经过一些诱导结晶而得到令人满意形貌及相态的结晶相。因此,大规模地成功合成含镁无定形碳酸钙纳米粒子对于生物矿化研究及工业应用来说具有重要意义。
4、利用一种简易的压片受限结晶方法在没有使用任何有机添加剂的情况下以含镁无定形碳酸钙(Mg-ACC)为前驱体成功制备了多晶高镁方解石。这是一种在方解石晶格结构中插入镁的简单合成方法。利用这种方法,我们首次指出受限结晶能够有效阻止镁离子的逃逸并在方解石晶格结构中插入镁,这也表明自然界中高镁方解石的生成可能是由于受限结晶的环境导致。例如,在生物矿化过程中人们经常可以观察到有机框架形成的限域结构。此外,在这个镁碳酸钙压缩片状物的结晶过程中,一些结晶的过渡态能被我们捕捉到,这对于我们研究无定形的结晶是非常有利的。
Recently, material synthesis that simulates biomineralization in organic systems such as calcium carbonate, magnetic iron oxide, and amorphous silica of exquisite morphology, has attracted increasing interest because of their structural and functional value. CaCO3is one of the standard model systems for studying biomineralization because of its abundance in nature and important industrial application. Interestingly, polymorph selection of CaCO3mineral is a key step for studying biomineralization process of CaCO3mineral. Therefore, polymorph control of CaCO3has been a hot research field. The mail results can be summarized as follows:
1. We have demonstrated for the first time a facile double-jet method for polymorph discrimination of CaCO3in aqueous solution under mild conditions without using any organic additives. It has been demonstrated that the thermodynamic and kinetic regimes, which contribute to the polymorph control, can be manipulated in solution by simply tuning the temperature of the reaction system. The present study may further provide clues for a deeper understanding of the biomineralization process of CaCO3as it occurs in nature. Furthermore, this template-free polymorph discrimination method in aqueous solution system may shed new light on the controlled crystallization of other inorganic materials.
2. The role of the temperature sensitive polymers in mineralization of calcium carbonate at different temperature using the so-called double-jet method has been reported. Employing the poly (ethylene glycol)-poly (N-isopropyl acrylamid)-poly (acrylamido methyl propane sulfonate)(PEG-PNIPAM-PAMPS), the unusual homogeneous aragonite flowers with controlled surface structures can be prepared at50℃. Herein, a new mineralization of CaCO3mechanism about PNIPAM is firstly introduced due to the interesting property of the temperature-sensitive triblock copolymer. In addition, three anhydrous crystalline phases, i.e. calcite, aragonite and vaterite, can be nicely captured simply by this choice of the reaction temperature in the present system. Furthermore, this new mineralization of calcium carbonate mechanism about PNIPAM may provide a new route for the controlled crystallization of other inorganic materials.
3. The gram-scale, low cost, rapid synthesis of highly stable Mg-ACC nanoparticles has been systhesized. The possible structure of Mg-ACC can be defined as Mg0.15Ca0.85CO3H2O0.85.The molar ratio of Mg2+:Ca2+:CO32-and the concentration (CaCl2, Na2CO3, and MgCl2) play important role in the Mg/Ca molar ratio of the obtained Mg-ACC. As-prepared Mg-ACC nanoparticles can be preserved for over one year without crystallization by storing either its dry powder at-5℃or storing it in ethanol at5℃. The successful access of Mg-ACC nanoparticles in large scale would be useful for further biomineralization study and industry applications.
4. Finally, a facile confined crystallization method has been developed to incorporate high content Mg in calcite by crystallization of compact tablet of Mg-ACC in water without using any organic additives. It has been demonstrated that the confined crystallization plays a key role in preventing the escape of Mg2+and incorporation of magnesium in the calcite lattice, which may suggest that similar roles of confined environment in the formation of biological magnesian calcite. In addition, some intermediate states can be captured in this special confined crystallization process of the compact tablet of magnesian amorphous calcium carbonate nanoparticles.
引文
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