DuBois Jennifer L, Ojha Sunil
Department of Chemistry and Biochemistry, Montana State University, Bozeman, MT, 59717, USA,
Met Ions Life Sci. 2015;15:45-87. doi: 10.1007/978-3-319-12415-5_3.
O₂-generating reactions are exceedingly rare in biology and difficult to mimic synthetically. Perchlorate-respiring bacteria enzymatically detoxify chlorite (ClO₂(-) ), the end product of the perchlorate (ClO(4)(-) ) respiratory pathway, by rapidly converting it to dioxygen (O₂) and chloride (Cl(-)). This reaction is catalyzed by a heme-containing protein, called chlorite dismutase (Cld), which bears no structural or sequence relationships with known peroxidases or other heme proteins and is part of a large family of proteins with more than one biochemical function. The original assumptions from the 1990s that perchlorate is not a natural product and that perchlorate respiration might be confined to a taxonomically narrow group of species have been called into question, as have the roles of perchlorate respiration and Cld-mediated reactions in the global biogeochemical cycle of chlorine. In this chapter, the chemistry and biochemistry of Cld-mediated O₂generation, as well as the biological and geochemical context of this extraordinary reaction, are described.
在生物学中,产生氧气的反应极为罕见,且难以通过合成来模拟。利用高氯酸盐呼吸的细菌会通过酶将亚氯酸盐(ClO₂⁻)——高氯酸盐(ClO₄⁻)呼吸途径的终产物——快速转化为氧气(O₂)和氯离子(Cl⁻),从而对其进行解毒。该反应由一种含血红素的蛋白质催化,这种蛋白质称为亚氯酸盐歧化酶(Cld),它与已知的过氧化物酶或其他血红素蛋白在结构或序列上均无关联,并且是一个具有多种生化功能的蛋白质大家族的一部分。20世纪90年代的最初假设认为高氯酸盐不是天然产物,且高氯酸盐呼吸可能仅限于分类学上范围狭窄的一组物种,如今这些假设已受到质疑,高氯酸盐呼吸和Cld介导的反应在全球氯生物地球化学循环中的作用也受到了质疑。在本章中,将描述Cld介导的氧气生成的化学和生物化学,以及这一非凡反应的生物学和地球化学背景。