Federal Research and Clinical Center of Physical-Chemical Medicine, Department of Biophysics, Malaya Pirogovskaya, 1a, Moscow 119435, Russia.
Institute for Regenerative Medicine, Laboratory of Navigational Redox Lipidomics, Sechenov University, 8-2 Trubetskaya St., Moscow 119991, Russia.
Molecules. 2018 Oct 8;23(10):2561. doi: 10.3390/molecules23102561.
The heme in the active center of peroxidases reacts with hydrogen peroxide to form highly reactive intermediates, which then oxidize simple substances called peroxidase substrates. Human peroxidases can be divided into two groups: (1) True peroxidases are enzymes whose main function is to generate free radicals in the peroxidase cycle and (pseudo)hypohalous acids in the halogenation cycle. The major true peroxidases are myeloperoxidase, eosinophil peroxidase and lactoperoxidase. (2) Pseudo-peroxidases perform various important functions in the body, but under the influence of external conditions they can display peroxidase-like activity. As oxidative intermediates, these peroxidases produce not only active heme compounds, but also protein-based tyrosyl radicals. Hemoglobin, myoglobin, cytochrome /cardiolipin complexes and cytoglobin are considered as pseudo-peroxidases. Рeroxidases play an important role in innate immunity and in a number of physiologically important processes like apoptosis and cell signaling. Unfavorable excessive peroxidase activity is implicated in oxidative damage of cells and tissues, thereby initiating the variety of human diseases. Hence, regulation of peroxidase activity is of considerable importance. Since peroxidases differ in structure, properties and location, the mechanisms controlling peroxidase activity and the biological effects of peroxidase products are specific for each hemoprotein. This review summarizes the knowledge about the properties, activities, regulations and biological effects of true and pseudo-peroxidases in order to better understand the mechanisms underlying beneficial and adverse effects of this class of enzymes.
过氧化物酶活性中心的血红素与过氧化氢反应,形成高反应性中间体,然后氧化称为过氧化物酶底物的简单物质。人类过氧化物酶可以分为两类:(1) 真正的过氧化物酶是其主要功能是在过氧化物酶循环中产生自由基和卤化循环中的(伪)次卤酸的酶。主要的真正过氧化物酶是髓过氧化物酶、嗜酸性粒细胞过氧化物酶和乳过氧化物酶。(2) 伪过氧化物酶在体内发挥各种重要功能,但在外部条件的影响下,它们可以表现出过氧化物酶样活性。作为氧化中间体,这些过氧化物酶不仅产生活性血红素化合物,还产生基于蛋白质的酪氨酸自由基。血红蛋白、肌红蛋白、细胞色素/心磷脂复合物和细胞球蛋白被认为是伪过氧化物酶。过氧化物酶在先天免疫和许多生理重要过程中发挥重要作用,如细胞凋亡和细胞信号转导。不利的过氧化物酶活性过度与细胞和组织的氧化损伤有关,从而引发多种人类疾病。因此,过氧化物酶活性的调节具有重要意义。由于过氧化物酶在结构、性质和位置上存在差异,控制过氧化物酶活性的机制和过氧化物酶产物的生物学效应是针对每种血红素蛋白特异性的。本综述总结了真正和伪过氧化物酶的性质、活性、调节和生物学效应的知识,以便更好地理解这类酶的有益和有害作用的机制。