Leamy P, Brown P W, TenHuisen K, Randall C
Department of Materials Science and Engineering, Penn State University, University Park, Pennsylvania 16802, USA.
J Biomed Mater Res. 1998 Dec 5;42(3):458-64. doi: 10.1002/(sici)1097-4636(19981205)42:3<458::aid-jbm16>3.0.co;2-c.
Although there is interest in forming synthetic analogs of hard tissues at physiologic temperature, significant gaps in knowledge exist with respect to the mechanisms by which precursor solids convert to apatites and also with respect to the apatite compositions that may be formed. In this study calcium-deficient HAp [Ca9(HPO4)(PO4)5OH] was prepared by hydrolysis of tricalcium phosphate (TCP), alpha-Ca3(PO4)2. The kinetics of HAp formation were studied as a function of temperature by isothermal calorimetry. TCP hydrolyzed completely within about 12 h, and the hydrolysis reaction evolved 133 kJ/mol of HAp formed. Although the kinetics of hydrolysis exhibited a strong temperature dependence, the mechanistic path taken appeared independent of temperature. The fluoridation of hydroxyapatite compositions having Ca/P ratios higher than 1.59 previously has been investigated. However, little work has been done on the fluoridation of more calcium-deficient hydroxyapatite. Ca9(HPO4)(PO4)5OH was formed at temperatures between 37.4 degrees and 55 degrees C to vary its morphology. These preparations then were reacted in NaF solution and the kinetics of fluoride incorporation studied. Solution chemical analyses were used to determine the amounts of fluoride incorporated. The extent of hydroxyl replacement by fluoride ranged from 17 to 72% and correlated with the surface area of the parent HAp.
尽管人们对在生理温度下形成硬组织的合成类似物感兴趣,但在前驱体固体转化为磷灰石的机制以及可能形成的磷灰石组成方面,仍存在重大的知识空白。在本研究中,通过磷酸三钙(TCP),即α-Ca3(PO4)2的水解制备了缺钙羟基磷灰石[Ca9(HPO4)(PO4)5OH]。通过等温量热法研究了羟基磷灰石形成的动力学与温度的关系。TCP在约12小时内完全水解,水解反应每生成1摩尔羟基磷灰石释放133千焦热量。尽管水解动力学表现出强烈的温度依赖性,但所采取的反应路径似乎与温度无关。此前已对钙磷比高于1.59的羟基磷灰石组合物的氟化进行了研究。然而,对于钙含量更低的羟基磷灰石的氟化研究较少。在37.4℃至55℃之间形成Ca9(HPO4)(PO4)5OH以改变其形态。然后将这些制剂在NaF溶液中反应,并研究氟掺入的动力学。使用溶液化学分析来确定掺入的氟量。氟取代羟基的程度在17%至72%之间,并且与母体羟基磷灰石的表面积相关。