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氧化还原活性过渡金属离子使黑色素易受有机过氧化物诱导的化学降解影响。

Redox Active Transition Metal ions Make Melanin Susceptible to Chemical Degradation Induced by Organic Peroxide.

作者信息

Zadlo Andrzej, Pilat Anna, Sarna Michal, Pawlak Anna, Sarna Tadeusz

机构信息

Department of Biophysics, Faculty of Biochemistry, Biophysics and Biotechnology, Jagiellonian University, Krakow, Poland.

出版信息

Cell Biochem Biophys. 2017 Dec;75(3-4):319-333. doi: 10.1007/s12013-017-0793-6. Epub 2017 Apr 11.

DOI:10.1007/s12013-017-0793-6
PMID:28401421
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5691108/
Abstract

With aging, retinal pigment epithelium melanosomes, by fusion with the age pigment lipofuscin, form complex granules called melanolipofuscin. Lipofuscin granules may contain oxidized proteins and lipid hydroperoxides, which in melanolipofuscin could chemically modify melanin polymer, while transition metal ions present in melanin can accelerate such oxidative modifications. The aim of this research was to examine the effect of selected transition metal ions on melanin susceptibility to chemical modification induced by the water-soluble tert-butyl hydroperoxide used as an oxidizing agent. Synthetic melanin obtained by DOPA autooxidation and melanosomes isolated from bovine retinal pigment epithelium were analyzed. To monitor tert-butyl hydroperoxide-induced oxidative changes of DMa and BMs, electron paramagnetic resonance spectroscopy, UV-vis absorption spectroscopy, dynamic light scattering, atomic force microscopy and electron paramagnetic resonance oximetry were employed. These measurements revealed that both copper and iron ions accelerated chemical degradation induced by tert-butyl hydroperoxide, while zinc ions had no effect. Strong prooxidant action was detected only in the case of melanosomes and melanin degraded in the presence of iron. It can be postulated that similar chemical processes, if they occur in situ in melanolipofuscin granules of the human retinal pigment epithelium, would modify antioxidant properties of melanin and its reactivity.

摘要

随着年龄增长，视网膜色素上皮黑素体通过与老年色素脂褐质融合，形成称为黑素脂褐质的复合颗粒。脂褐质颗粒可能含有氧化蛋白质和脂质氢过氧化物，在黑素脂褐质中，它们可对黑色素聚合物进行化学修饰，而黑色素中存在的过渡金属离子可加速这种氧化修饰。本研究的目的是研究选定的过渡金属离子对黑色素对作为氧化剂的水溶性叔丁基过氧化氢诱导的化学修饰的敏感性的影响。分析了通过多巴自氧化获得的合成黑色素和从牛视网膜色素上皮分离的黑素体。为了监测叔丁基过氧化氢诱导的合成黑色素（DMa）和牛黑素体（BMs）的氧化变化，采用了电子顺磁共振光谱、紫外可见吸收光谱、动态光散射、原子力显微镜和电子顺磁共振血氧测定法。这些测量结果表明，铜离子和铁离子均加速了叔丁基过氧化氢诱导的化学降解，而锌离子则无影响。仅在铁存在下降解的黑素体和黑色素的情况下检测到强烈的促氧化作用。可以推测，如果在人类视网膜色素上皮的黑素脂褐质颗粒中原位发生类似的化学过程，将会改变黑色素的抗氧化特性及其反应性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/25c64714be68/12013_2017_793_Fig10_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/8b354b2e85bf/12013_2017_793_Fig1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/e59cf9249dd9/12013_2017_793_Fig2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/0973afabc307/12013_2017_793_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/52d1877ae6d5/12013_2017_793_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/64b9b9ed8156/12013_2017_793_Fig5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/1ae0a11a34a3/12013_2017_793_Fig6_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/9170aa303e60/12013_2017_793_Fig7_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/33d4cdcff5a8/12013_2017_793_Fig8_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/f25b25a0932f/12013_2017_793_Fig9_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/25c64714be68/12013_2017_793_Fig10_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/8b354b2e85bf/12013_2017_793_Fig1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/e59cf9249dd9/12013_2017_793_Fig2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/0973afabc307/12013_2017_793_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/52d1877ae6d5/12013_2017_793_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/64b9b9ed8156/12013_2017_793_Fig5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/1ae0a11a34a3/12013_2017_793_Fig6_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/9170aa303e60/12013_2017_793_Fig7_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/33d4cdcff5a8/12013_2017_793_Fig8_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/f25b25a0932f/12013_2017_793_Fig9_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9637/5691108/25c64714be68/12013_2017_793_Fig10_HTML.jpg

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