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作 者:周宇彤 李沁娱 郑丹婷 徐圣波 晏培清 张兆鸿 蒋久信[1,2] ZHOU Yutong;LI Qinyu;ZHENG Danting;XU Shengbo;YAN Peiqing;ZHANG Zhaohong;JIANG Jiuxin(Hubei Provincial Key Laboratory of Green Materials for Light Industry,Hubei University of Technology,Wuhan 430068,Hubei,China;New Materials and Green Manufacturing Talent Introduction and Innovation Demonstration Base,Hubei University of Technology,Wuhan 430068,Hubei,China)
机构地区:[1]湖北工业大学绿色轻工材料湖北省重点实验室,湖北武汉430068 [2]湖北工业大学新材料与绿色制造湖北省引智创新示范基地,湖北武汉430068
出 处:《陶瓷学报》2025年第1期43-59,共17页Journal of Ceramics
基 金:国家自然科学基金(51802087);湖北省大学生创新创业训练计划项目(S202010500027,S202210500067)。
摘 要:无定形CaCO_(3)(amorphous calcium carbonate,ACC)作为晶态CaCO_(3)的重要前驱体,在生物矿化中起着重要作用。因其良好的生物相容性,ACC广泛应用于补钙、骨再生、生物医药、药物载体和蛋白质吸附等方面。虽然已有多种通过模拟计算得到的结构模型,但ACC的真实结构尚存在争议。由于ACC极低的热力学稳定性,特别是水的存在能够促进其向球霰石、文石或方解石的结晶,因此ACC在合成和储存均面临诸多挑战。通过系统性地综述近年来ACC的合成方法以及反应因素对ACC稳定和结晶的影响,总结了各合成体系的优缺点,指出了无水体系对ACC的合成与储存具有的独特优势。最后,提出了ACC的制备和存储所面临的挑战,并对未来ACC相关材料的发展进行了展望。[Significance]Amorphous calcium carbonate(amorphous CaCO_(3),ACC)is the amorphism of CaCO_(3) with molecular formula of CaCO_(3)·nH_(2)O.It is termed as anhydrous ACC for n=0,which is unstable,and as hydrous ACC for n>0,which is stable to a certain extent.The value of n in hydrous ACC is also variable,leading to a series of amorphous CaCO_(3) with different water contents,which is referred to as polyamorphism.ACC has been identified in diverse biological structures and synthesized in laboratory under certain conditions.Due to its thermodynamic instability,ACC serves as a crucial precursor for both geologic CaCO_(3)(calcite)and biologic CaCO_(3)(vaterite and aragonite).Particularly,it plays very important roles in biomineralization.ACC has been widely applied in the fields of calcium supplement,bone regeneration,biological medicine,drug carrier and protein adsorption.Despite decades of study,challenges persist regarding the preparation and conservation of ACC.Furthermore,comprehensive reviews on ACC remain insufficient,especially for the development in recent years.This paper is aimed to provide a comprehensive review on ACC,covering structural model,preparation routes and stability.[Progress]Several structural models of ACC were derived from simulations with different methods,such as Reverse Monte Carlo(RMC),Classical Molecular Dynamics(CMD)and Ab initio molecular dynamics(AIMD).However,it is still debatable on the real structure of ACC.ACC can be synthesized with two basic systems,Ca^(2+)-H_(2)O-CO_(3)^(2−)and Ca^(2+)-H_(2)O-CO_(2),referred as to double decomposition reaction and carbonation reaction,respectively.The reaction between calcium salt and carbonate in aqueous solution is the most commonly used to synthesize ACC,in which high pH,high concentration and additive,e.g.Mg^(2+),PO_(4)^(3−),amino acid and protein,are the key factors to obtain ACC with desirable stability.In Ca^(2+)-H_(2)O-CO_(2) reaction system,the sources of CO_(3)^(2−)are diverse,including pure CO_(2),CO_(2) in air,CO_(2) released f
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