Berlett B S, Levine R L, Chock P B, Chevion M, Stadtman E R
Laboratory of Biochemistry, National Heart, Lung, and Blood Institute, National Institutes of Health, Building 3, Room 222, Bethesda, MD 20892, USA.
Proc Natl Acad Sci U S A. 2001 Jan 16;98(2):451-6. doi: 10.1073/pnas.98.2.451. Epub 2001 Jan 9.
Amino acid-Fe(II)-chelator complexes exhibit strong antioxidant activity. Taking advantage of the unique spectral characteristics of the complexes formed when Ferrozine (Fz) is used as the chelator, we now show that the primary blue complex (epsilon(max) at 632 nm) decomposes by two independent pathways: (i) a nonoxidative pathway involving dissociation of the amino acid component and formation of a purple complex (epsilon(max) at 562 nm) and (ii) an oxidative pathway leading to Fe(III) and colorless products. Quantitative conversion of the blue to purple complex yields an isosbestic point (i.p.) at 601 nm, whereas no i.p. is formed during quantitative oxidation of the blue complex. However, under some experimental conditions, decomposition of the blue product occurs by both pathways, leading to occurrence of a clean i.p. at wavelengths varying from 601 to 574 nm. Results of simulation experiments, confirmed by direct analysis, demonstrate that shifts in the i.p. reflect differences in the fractions of blue compound that decompose by the oxidative and nonoxidative pathways. Indeed, the fraction of blue that is converted to the purple complex is readily deduced from the wavelength of the i.p. These results suggest that identification of a physiological chelator that can replace Ferrozine in amino acid-iron complexes might have important physiological and pharmacological applications.
氨基酸 - 亚铁(II) - 螯合剂复合物具有很强的抗氧化活性。利用以菲咯嗪(Fz)作为螯合剂时形成的复合物独特的光谱特性,我们现在表明,主要的蓝色复合物(在632 nm处的最大吸收波长)通过两条独立途径分解:(i)一条非氧化途径,涉及氨基酸成分的解离并形成紫色复合物(在562 nm处的最大吸收波长),以及(ii)一条氧化途径,导致生成铁(III)和无色产物。蓝色复合物向紫色复合物的定量转化在601 nm处产生一个等吸收点(i.p.),而蓝色复合物的定量氧化过程中不形成等吸收点。然而,在某些实验条件下,蓝色产物通过两条途径分解,导致在601至574 nm不同波长处出现清晰的等吸收点。经直接分析证实的模拟实验结果表明,等吸收点的移动反映了通过氧化和非氧化途径分解的蓝色化合物部分的差异。实际上,从等吸收点的波长很容易推断出转化为紫色复合物的蓝色部分的比例。这些结果表明,鉴定一种能够在氨基酸 - 铁复合物中替代菲咯嗪的生理性螯合剂可能具有重要的生理和药理应用。