Elucidation of adsorption mechanism of bone-staining agent alizarin red S on hydroxyapatite by FT-IR microspectroscopy
Elucidation of adsorption mechanism of bone-staining agent alizarin red S on hydroxyapatite by FT-IR microspectroscopy
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DOI：
10.1016/s0021-9797(02)00157-1
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发表时间：
2003-04-01
影响因子：
9.9
通讯作者：
Kaji, E
中科院分区：
文献类型：
--
作者：
Moriguchi, T;Yano, K;Kaji, E
为了阐明骨组织染色常用的茜素红S （ARS）的吸附机理，采用批量法研究了ARS对羟基磷灰石Ca-10(PO4)(6)(OH)(2) （HAP）的吸附，并与茜素、酚类和苯磺酸盐进行了比较。我们发现ARS的离子化1-，2-OH基团（1-,2-O-）可以与HAP上的Ca2+静电结合，但ARS的3-SO3-基团几乎不参与HAP上的吸附。制备了深紫红色ARS吸附HAP (ARS-HAP)，并用FT-IR微光谱分析了ARS与HAP之间的键合结构信息。在1627 cm（-1）处有一个v（C=O）的单波段，在1345 cm（-1）处有is (C-O) + v（C=C）和vs (CO) + 8（O-C=C）在1272 cm（-1）处有两种对称的C-O拉伸带。这些谱带通过ARS的1-，2-OH基团暗示ARS- hap中存在盐形式。由于ARS- hap通过ARS的1-OH和9-C=O基团存在螯合形式，在1572 cm（-1）处还观察到v(C=C) + v（C=O）和v(C=O) + v（C=C）在1537 cm（-1）处的两个波段。此外，用中性磷酸盐缓冲液在50°c下将ARS从着色的ARS-HAP中几乎解吸，得到略淡粉色的HAP或De-ARS-HAP。解吸的ARS属于先前通过盐形成吸附在HAP上的ARS，而De-ARS-HAP上的剩余颜色表明ARS仍然通过螯合形成吸附在HAP上。因此，我们阐明了ARS在HAP上的两种吸附机制：主要吸附是ARS和Ca2+在HAP上的1-、2-O-组成的盐，次要吸附是ARS和Ca2+在HAP上的1-O-和9-C=O组成的螯合物。(C) 2003 Elsevier Science（美国）版权所有。
To elucidate adsorption mechanism of alizarin red S (ARS), which is often used for staining bones in histology, adsorption of ARS on hydroxyapatite, Ca-10(PO4)(6)(OH)(2) (HAP), was investigated by a batch method, compared with alizarin, phenols, and benzenesulfonates. We found that ionized 1-, 2-OH groups (1-, 2-O-) of ARS can be electrostatically bound to Ca2+ on HAP, but that the 3-SO3- group of ARS hardly participates in adsorption on HAP. ARS-adsorbed HAP (ARS-HAP) in dark reddish violet was also prepared and analyzed by FT-IR microspectroscopy to gain structural information on bonding between ARS and HAP. The obtained spectrum, which was converted to difference spectra, indicated a single band of v(C=O) at 1627 cm(-1) and two types of symmetric C-O stretching bands of is (C-O) + v(C=C) at 1345 cm(-1) and vs (CO) + 8(O-C=C) at 1272 cm(-1). These bands imply the existence of a salt form in ARS-HAP via 1-, 2-OH groups of ARS. As a result of the existence of a chelate form in ARS-HAP via 1-OH and 9-C=O groups of ARS, two bands of v(C=C) + v(C=O) at 1572 cm(-1) and v(C=O) + v(C=C) at 1537 cm(-1) were also observed. In addition, ARS was almost desorbed from colored ARS-HAP at 50 degreesC by using neutral phosphate buffer to recover slightly pale pinkish HAP, or De-ARS-HAP. The desorbed ARS belongs to ARS previously adsorbed on HAP by salt formation, while the remaining color on De-ARS-HAP indicates ARS still adsorbed on HAP by chelate formation. Consequently, we elucidated two adsorption mechanisms of ARS on HAP: The major adsorption is salt formation made up with 1-, 2-O- of ARS and Ca2+ on HAP, and the minor adsorption is chelate formation made up with 1-O- and 9-C=O of ARS and Ca2+ on HAP. (C) 2003 Elsevier Science (USA). All rights reserved.