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在模拟体液中对生物活性钛金属上类骨磷灰石形成机制的透射电子显微镜-能量色散X射线研究

TEM-EDX study of mechanism of bonelike apatite formation on bioactive titanium metal in simulated body fluid.

作者信息

Takadama H, Kim H M, Kokubo T, Nakamura T

机构信息

Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan.

出版信息

J Biomed Mater Res. 2001 Dec 5;57(3):441-8. doi: 10.1002/1097-4636(20011205)57:3<441::aid-jbm1187>3.0.co;2-b.

Abstract

Bioactive titanium metal, which forms a bonelike apatite layer on its surface in the body and bonds to the bone through the apatite layer, can be prepared by NaOH and heat treatments to form an amorphous sodium titanate layer on the metal. In the present study, the mechanism of apatite formation on the bioactive titanium metal has been investigated in vitro. The metal surface was examined using transmission electron microscopy and energy dispersive X-ray spectrometry as a function of the soaking time in a simulated body fluid (SBF) and complemented with atomic emission spectroscopy analysis of the fluid. It was found that, immediately after immersion in the SBF, the metal exchanged Na(+) ions from the surface sodium titanate with H(3)O(+) ions in the fluid to form Ti-OH groups on its surface. The Ti-OH groups, immediately after they were formed, incorporated the calcium ions in the fluid to form an amorphous calcium titanate. After a long soaking time, the amorphous calcium titanate incorporated the phosphate ions in the fluid to form an amorphous calcium phosphate with a low Ca/P atomic ratio of 1.40. The amorphous calcium phosphate thereafter converted into bonelike crystalline apatite with a Ca/P ratio of 1.65, which is equal to the value of bone mineral. The initial formation of the amorphous calcium titanate is proposed to be a consequence of the electrostatic interaction of negatively charged units of titania, which are dissociated from the Ti-OH groups, with the positively charged calcium ions in the fluid. The amorphous calcium titanate is speculated to gain a positive charge and to interact with the negatively charged phosphate ions in the fluid to form the amorphous calcium phosphate, which eventually stabilizes into bonelike crystalline apatite.

摘要

生物活性钛金属在体内其表面会形成类骨磷灰石层,并通过该磷灰石层与骨结合,可通过氢氧化钠和热处理制备,从而在金属表面形成非晶态钛酸钠层。在本研究中,已对生物活性钛金属上磷灰石形成的机制进行了体外研究。使用透射电子显微镜和能量色散X射线光谱仪对金属表面进行了检测,检测结果作为在模拟体液(SBF)中浸泡时间的函数,并辅以对该液体的原子发射光谱分析。结果发现,将金属浸入SBF后,其表面钛酸钠中的Na(+)离子立即与液体中的H(3)O(+)离子发生交换,在其表面形成Ti-OH基团。Ti-OH基团形成后,立即结合液体中的钙离子形成非晶态钛酸钙。经过长时间浸泡,非晶态钛酸钙结合液体中的磷酸根离子形成Ca/P原子比为1.40的低钙磷比非晶态磷酸钙。此后,非晶态磷酸钙转化为Ca/P比为1.65的类骨结晶磷灰石,该比例与骨矿物质的值相等。非晶态钛酸钙的初始形成被认为是二氧化钛带负电单元(从Ti-OH基团解离)与液体中带正电钙离子静电相互作用的结果。推测非晶态钛酸钙带正电荷,并与液体中带负电的磷酸根离子相互作用形成非晶态磷酸钙,最终稳定为类骨结晶磷灰石。

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