John M. Hughes, Daniel Harlov, John F. Rakovan, Jamshid Ahmadi, Melanie J. Sieber
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引用次数: 0
摘要
氟是世界上消耗量最大的药物之一,它在预防龋齿方面的作用被公认为是 20 世纪十大公共卫生成就之一。虽然羟基磷灰石经常被用作牙釉质的类似物,但人们对磷灰石阴离子柱中 F 取代 OH 的细节并不十分了解。本研究利用新的合成技术,沿着 F-OH 磷灰石连接的中间部分,将 P63/m 磷灰石的结构工作扩展到接近氟化人类牙齿成分的组成。羟基磷灰石中的第一个 F 取代基接近氟化牙釉质成分,在羟基磷灰石基质中与周围 Ca2 原子的结合力明显不足(0.72 vu)。然而,羟基氢能够提供 0.20 或 0.10 vu 的氢键,这取决于取代是否会在阴离子柱中产生一个反向位点;这种氢键减轻了取代基 F 的键合要求。随着连接处 F 浓度的增加,平均羟基对 F 柱阴离子的氢键作用越来越大;为了减轻氢键作用的损失,羟基氧向包含键合 Ca2 原子的相邻镜面迁移,键合 Ca2 离子的三角形同时收缩。这两种机制增加了邻近 Ca2 原子对柱羟基氧的键合,以平衡稳定取代基 F 柱阴离子的氢键损失和键合不足的 F 浓度的增加。
REVISION 1: Structural variations along the apatite F-OH join: II. The role of hydrogen bonding in fluoridated teeth
Fluoride is one of the most consumed pharmaceuticals in the world, and its facility in preventing dental caries is recognized as one of the top 10 public health achievements of the 20th century. Although hydroxylapatite is often used as an analog of dental enamel, the details of the substitution of F for OH in the apatite anion column are not well known. Using new synthesis techniques, this study extends the structure work on P63/m apatites along the middle portion of the F-OH apatite join to compositions near the composition of fluoridated human teeth. The first F substituent in hydroxylapatite, near fluoridated dental enamel compositions, is dramatically underbonded by the surrounding Ca2 atoms (0.72 vu) in a hydroxylapatite matrix. However, the hydroxyl hydrogen is able to contribute 0.20 or 0.10 vu in hydrogen bonding, depending on whether the substitution creates a reversal site in the anion column; this hydrogen bonding alleviates the bonding requirements of the substituent F. As F concentrations increase along the join, the average hydroxyl contributes increasing amounts of hydrogen bonding to the F column anions; to mitigate the loss of its hydrogen bonding, the hydroxyl oxygen migrates toward the adjacent mirror plane that contains the bonded Ca2 atoms, and the triangle of bonded Ca2 ions concomitantly contracts. These two mechanisms increase bonding to the column hydroxyl oxygen from the adjoining Ca2 atoms to balance the loss of hydrogen bonding that stabilizes the substituent F column anion and the increasing concentration of underbonded F.
期刊介绍:
American Mineralogist: Journal of Earth and Planetary Materials (Am Min), is the flagship journal of the Mineralogical Society of America (MSA), continuously published since 1916. Am Min is home to some of the most important advances in the Earth Sciences. Our mission is a continuance of this heritage: to provide readers with reports on original scientific research, both fundamental and applied, with far reaching implications and far ranging appeal. Topics of interest cover all aspects of planetary evolution, and biological and atmospheric processes mediated by solid-state phenomena. These include, but are not limited to, mineralogy and crystallography, high- and low-temperature geochemistry, petrology, geofluids, bio-geochemistry, bio-mineralogy, synthetic materials of relevance to the Earth and planetary sciences, and breakthroughs in analytical methods of any of the aforementioned.