含菲罗啉配体的铁(III)配合离子的合成、表征和稳定性。

Shawnt Tosonian, Charles J Ruiz, Andrew Rios, Elma Frias, Jack F Eichler
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引用次数: 15

摘要

先前已经证明,用于制造金金属治疗剂的以菲罗啉为基础的配体在不与金属中心协调时具有表现细胞毒性的能力。为了帮助评估这些配体可能导致肿瘤细胞死亡的机制,人们考虑了铁结合和去除实验。细胞增殖与细胞内铁浓度之间的密切联系表明,铁剥夺策略可能是抑制肿瘤细胞生长的一种机制。随着铁(III)菲配合物的产生,三种多吡啶配体[1,10-菲罗啉(phen), 2,9-二甲基- 1,10-菲罗啉(methylphen)和2,9-二-仲丁基- 1,10-菲罗啉(仲丁基)]的铁结合能力可以通过与已知铁螯合剂的竞争反应来测试。因此,合成了具有这三种配体的铁(III)配合物。初始质谱和红外吸收数据表明,四氯化铁(III)与质子化苯配体(RphenH+)形成了配合离子:[phenH][FeCl4],[甲基phenH][FeCl4], [secs - butylphenh][FeCl4]。采用紫外可见光谱法对配合物离子的稳定性进行了监测,发现仲丁基苯铁配合物比苯和甲基苯类似物更稳定。这是基于EDTA加入到[phenH][FeCl4]和[甲基phenH][FeCl4]络合物离子后立即观察到自由配体。
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Synthesis, characterization, and stability of iron (III) complex ions possessing phenanthroline-based ligands.

It has previously been demonstrated that phenanthroline-based ligands used to make gold metallotherapuetics have the ability to exhibit cytotoxicity when not coordinated to the metal center. In an effort to help assess the mechanism by which these ligands may cause tumor cell death, iron binding and removal experiments have been considered. The close linkage between cell proliferation and intracellular iron concentrations suggest that iron deprivation strategies may be a mechanism involved in inhibiting tumor cell growth. With the creation of iron (III) phen complexes, the iron binding abilities of three polypyridal ligands [1,10-phenanthroline (phen), 2,9-dimethyl-1, 10-phenanthroline (methylphen), and 2,9-di-sec-butyl-1, 10-phenanthroline ( sec-butylphen)] can be tested via a competition reaction with a known iron chelator. Therefore, iron (III) complexes possessing all three ligands were synthesized. Initial mass spectrometric and infrared absorption data indicate that iron (III) tetrachloride complex ions with protonated phen ligands (RphenH+) were formed: [phenH][FeCl4], [methylphenH][FeCl4], [ sec-butylphenH][FeCl4]. UV-Vis spectroscopy was used to monitor the stability of the complex ions, and it was found that the sec-butylpheniron complex was more stable than the phen and methylphen analogues. This was based on the observation that free ligand was observed immediately upon the addition of EDTA to the [phenH][FeCl4] and [methylphenH] [FeCl4] complex ions.

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