Modification of Hydroxyapatite with Ion-Selective Complexants: 1-Hydroxyethane-1,1-diphosphonic Acid.
Modification of Hydroxyapatite with Ion-Selective Complexants: 1-Hydroxyethane-1,1-diphosphonic Acid.
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用离子选择复合物修饰羟基磷灰石：1-羟基乙烷-1,1-二磷酸。
DOI：
10.1021/ie504181z
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发表时间：
2015-01-21
影响因子：
4.2
通讯作者：
Alexandratos, Spiro D.
中科院分区：
文献类型：
--
作者：
Daniels, Yasmine;Lyczko, Nathalie;Nzihou, Ange;Alexandratos, Spiro D.
用1-羟基乙烷-1，1-二膦酸（HEDP）对羟基磷灰石（HAP）进行表面改性，研究了其对二价金属离子结合的影响。以氢氧化钙和磷酸为原料合成了羟基磷灰石。煅烧后，用HEDP对其进行改性，考察了改性时间和温度对改性效果的影响。HEDP掺入随着其初始溶液浓度从0.01增加到0.50 M而增加。采用傅里叶变换红外光谱、X射线衍射、扫描电子显微镜、能量色散X射线光谱和比表面积分析对未改性和改性的HAP进行了表征。Ca/P比，酸容量，和磷元素分析给出了组合物和表面特性的改性效果。高反应温度在993、1082和1144 cm-1处产生新的膦酸酯谱带，表明存在HEDP。HAP改性在高温长时间的反应具有最高的HEDP负载量，并给出了最尖锐的XRD峰。在处理样品的SEM图像中观察到新的HAP-HEDP链的出现，而EDS显示这些链中的高磷含量。改性的HAP具有高的酸容量，来自HEDP中额外的P-OH基团。P（O）OH基团保持其在HAP基质内结合金属离子的能力：将改性的HAP与5种过渡金属离子的10-4 N硝酸盐溶液接触，得到Pb（II）> Cd（II）> Zn（II）> Ni（II）> Cu（II）的亲和顺序。这一结果与市售的二（2-乙基己基）磷酸（一种常见的溶剂萃取剂）的结果相当，并且该趋势与金属离子极化率的Misono软参数一致。
Hydroxyapatite (HAP) was modified with 1-hydroxyethane-1,1-diphosphonic acid (HEDP), and its effect on divalent metal ion binding was determined. HAP was synthesized from calcium hydroxide and phosphoric acid. After calcination, it was modified with HEDP, and the influence of time and temperature on the modification was investigated. HEDP incorporation increased as its initial solution concentration increased from 0.01 to 0.50 M. Unmodified and modified HAP were characterized using Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, and specific surface area analysis. Ca/P ratios, acid capacities, and phosphorus elemental analyses gave the effect of modification on composition and surface characteristics. A high reaction temperature produced new phosphonate bands at 993, 1082, and 1144 cm–1 that indicated the presence of HEDP. HAP modification at a high temperature–long reaction time had the highest HEDP loading and gave the sharpest XRD peaks. The emergence of new HAP–HEDP strands was observed in SEM images for treated samples while EDS showed high phosphorus contents in these strands. Modified HAP had a high acid capacity from the additional P–OH groups in HEDP. The P(O)OH groups maintain their ability to bind metal ions within the HAP matrix: contacting the modified HAP with 10–4 N nitrate solutions of five transition metal ions gives an affinity sequence of Pb(II) > Cd(II) > Zn(II) > Ni(II) > Cu(II). This result is comparable to that of commercially available di(2-ethylhexyl)phosphoric acid, a common solvent extractant, and the trend is consistent with the Misono softness parameter of metal ion polarizabilities.
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