Bertoni E, Bigi A, Cojazzi G, Gandolfi M, Panzavolta S, Roveri N
Dipartimento di Chimica G. Ciamician, Università delgi studi di Bologna, Italy.
J Inorg Biochem. 1998 Oct;72(1-2):29-35. doi: 10.1016/s0162-0134(98)10058-2.
Hydroxyapatite nanocrystals synthetized in the presence of different concentrations of magnesium and fluoride ions in solutions--1, 5 and 10 at.% have been submitted to a structural and chemical characterization. The syntheses were carried out in the presence of low molecular weight polyacrylic acid, which has been verified to inhibit hydroxyapatite crystallization. The polyelectrolyte is adsorbed into the crystals during the synthesis and provokes a reduction of the mean crystal sizes. The reduction is greater along the direction orthogonal to the c-axis, suggesting a preferential adsorption of the polyelectrolyte on the crystalline faces parallel to the c-axis. Both magnesium and fluoride can be incorporated into the hydroxyapatite structure. On the basis of the values of the lattice constants and of the magnesium relative content of the solid phase, it can be suggested that probably just a part of magnesium is substituted for calcium, the remainder being adsorbed on the crystal surface. However, magnesium destabilizes the apatitic structure favouring its thermal conversion into beta-tricalcium phosphate, and displays an inhibiting effect on the crystallization of hydroxyapatite. This last effect is enhanced by the simultaneous presence of polyacrylic acid. Fluoride substitution for hydroxyl ions into hydroxyapatite structure induces a slight increase of the crystal sizes along the c-axis direction. The data indicate that the experimental approach can be successfully used to prepare nanoapatite with crystallinity, crystal dimensions, composition, structure and stability very close to those characteristics of biological apatites.
在含有不同浓度(1、5和10原子百分比)镁离子和氟离子的溶液中合成的羟基磷灰石纳米晶体,已进行了结构和化学表征。合成过程是在低分子量聚丙烯酸存在下进行的,已证实该聚丙烯酸可抑制羟基磷灰石结晶。在合成过程中,聚电解质吸附到晶体中,导致平均晶体尺寸减小。沿与c轴正交的方向尺寸减小更大,这表明聚电解质优先吸附在与c轴平行的晶面上。镁和氟都可以掺入羟基磷灰石结构中。根据晶格常数和固相镁相对含量的值,可以推测可能只有一部分镁替代了钙,其余部分吸附在晶体表面。然而,镁会使磷灰石结构不稳定,有利于其热转化为β-磷酸三钙,并且对羟基磷灰石的结晶有抑制作用。聚丙烯酸的同时存在会增强这种抑制作用。氟取代羟基磷灰石结构中的氢氧根离子会导致晶体尺寸沿c轴方向略有增加。数据表明,该实验方法可成功用于制备结晶度、晶体尺寸、组成、结构和稳定性与生物磷灰石的那些特征非常接近的纳米磷灰石。