Blessing Holger, Kraus Silke, Heindl Philipp, Bal Wojciech, Hartwig Andrea
Institute of Food Chemistry and Toxicology, University of Karlsruhe, Germany.
Eur J Biochem. 2004 Aug;271(15):3190-9. doi: 10.1111/j.1432-1033.2004.04251.x.
As an essential element, selenium is present in enzymes from several families, including glutathione peroxidases, and is thought to exert anticarcinogenic properties. A remarkable feature of selenium consists of its ability to oxidize thiols under reducing conditions. Thus, one mode of action recently suggested is the oxidation of thiol groups of metallothionein, thereby providing zinc for essential reactions. However, tetrahedral zinc ion complexation to four thiolates, similar to that found in metallothionein, is present in one of the major classes of transcription factors and other so-called zinc finger proteins. Within this study we investigated the effect of selenium compounds on the activity of the formamidopyrimidine-DNA glycosylase (Fpg), a zinc finger protein involved in base excision repair, and on the DNA-binding capacity and integrity of xeroderma pigmentosum group A protein (XPA), a zinc finger protein essential for nucleotide excision repair. The reducible selenium compounds phenylseleninic acid, phenylselenyl chloride, selenocystine, ebselen, and 2-nitrophenylselenocyanate caused a concentration-dependent decrease of Fpg activity, while no inhibition was detected with fully reduced selenomethionine, methylselenocysteine or some sulfur-containing analogs. Furthermore, reducible selenium compounds interfered with XPA-DNA binding and released zinc from the zinc finger motif, XPAzf. Zinc release was even evident at high glutathione/oxidised glutathine ratios prevailing under cellular conditions. Finally, comparative studies with metallothionein and XPAzf revealed similar or even accelerated zinc release from XPAzf. Altogether, the results indicate that zinc finger motifs are highly reactive towards oxidizing selenium compounds. This could affect gene expression, DNA repair and, thus, genomic stability.
作为一种必需元素,硒存在于包括谷胱甘肽过氧化物酶在内的多个家族的酶中,被认为具有抗癌特性。硒的一个显著特征是其在还原条件下氧化硫醇的能力。因此,最近提出的一种作用模式是氧化金属硫蛋白的硫醇基团,从而为关键反应提供锌。然而,在一类主要的转录因子和其他所谓的锌指蛋白中,存在与金属硫蛋白中相似的四面体锌离子与四个硫醇盐的络合。在本研究中,我们研究了硒化合物对甲酰胺嘧啶 - DNA 糖基化酶(Fpg)活性的影响,Fpg 是一种参与碱基切除修复的锌指蛋白,以及对着色性干皮病 A 组蛋白(XPA)的 DNA 结合能力和完整性的影响,XPA 是核苷酸切除修复所必需的锌指蛋白。可还原的硒化合物苯亚硒酸、苯硒基氯、硒代胱氨酸、依布硒仑和 2 - 硝基苯硒氰酸盐导致 Fpg 活性呈浓度依赖性下降,而完全还原的硒代蛋氨酸、甲基硒代半胱氨酸或一些含硫类似物未检测到抑制作用。此外,可还原的硒化合物干扰 XPA 与 DNA 的结合,并从锌指基序 XPAzf 中释放锌。在细胞条件下普遍存在的高谷胱甘肽/氧化型谷胱甘肽比率下,锌的释放甚至很明显。最后,与金属硫蛋白和 XPAzf 的比较研究表明,XPAzf 中锌的释放相似甚至加速。总之,结果表明锌指基序对氧化型硒化合物具有高度反应性。这可能影响基因表达、DNA 修复,进而影响基因组稳定性。