Cobalt: B12 Enzymes and Coenzymes

Cobalt: B12 Enzymes and Coenzymes
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钴:B12 酶和辅酶

DOI:
10.1002/9781119951438.eibc0043.pub2
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发表时间:
2013
影响因子:
4.3
通讯作者:
B. Kräutler
B. Kräutler
中科院分区:
生物学2区
文献类型:
--
作者:
B. Kräutler

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钴作为维生素 B12 及其辅助因子变体的金属中心,具有重要的生物学作用。天然 B12 衍生物是非常复杂的钴-咕啉,属于较大类别的四吡咯天然产物。维生素 B12 的辅助因子形式(抗恶性贫血因子)是人类和动物健康所必需的。除(高等)植物外,大多数生命形式似乎都依赖于维生素 B12 及其天然衍生物。类咕啉在古细菌和细菌的碳代谢中发挥着特别重要的作用,而古细菌和细菌是 B12 衍生物的唯一天然来源。这些微生物已经开发出用于 B12 衍生物的生物合成及其调节的非凡方法,以应对钴咕啉的结构和功能复杂性。其他依赖 B12 的生命形式已经进化出复杂的策略,以经济且有效地摄取和运输类咕啉。钴-类咕啉的已知辅助因子功能归因于其非凡的有机金属化学性质,加上其在生理条件下的氧化还原化学:腺苷类咕啉、甲基类咕啉和还原类咕啉是各种重要且独特的有机金属酶的辅助因子,其复杂的结构和机械特性一直是广泛研究活动的焦点。类咕啉在厌氧微生物的碳固定和进一步碳代谢的有机金属途径中的重要作用引起了特别关注。事实上,类咕啉的主要化学反应性及其重要的生物学作用可能反映了它们对地球生命早期阶段的可能贡献。因此,维生素 B12 及其衍生物在生命科学中占有重要地位,并且是医学、生物学、化学和物理学跨学科兴趣的中心。 关键词: 生物有机金属化学; 生物合成; 钴; 科林; 电子转移; 甲基化; 甲基转移; 有机金属化学; 自由基反应; 重排反应; 合成; 维生素B12
Cobalt has its important biological role as metal center of vitamin B12 and of its cofactor variants. The natural B12 derivatives are remarkably complex cobalt-corrins and belong to the larger class of the tetrapyrrolic natural products. The cofactor forms of vitamin B12, the antipernicious anemia factor, are required for human and animal health. With the exception of the (higher) plants, most forms of life appear to depend on vitamin B12 and its natural derivatives. The corrinoids play a particularly basic role in carbon metabolism in archaea and bacteria, which are the only natural sources of the B12 derivatives. These microorganisms have developed extraordinary means for the biosynthesis of the B12 derivatives and for its regulation, in order to cope with the structural and functional complexity of the cobalt-corrinoids. The other B12-dependent forms of life have evolved intricate strategies for the economic and efficient uptake and transport of the corrinoids. The known cofactor functions of the cobalt-corrinoids are due to their extraordinary organometallic chemistry, coupled with their redox chemistry under physiological conditions: adenosylcorrinoids, methylcorrinoids, and reduced corrinoids are the cofactors in various important and unique organometallic enzymes, whose intricate structural and mechanistic properties have been the focus of extensive research activities. The essential role of the corrinoids in organometallic paths of carbon fixation and further carbon metabolism in anerobic microorganisms has attracted particular attention. Indeed, the main chemical reactivity of the corrinoids and their essential biological roles may reflect their possible contributions to the early stages of life on earth. Vitamin B12 and its derivatives thus hold an important position in the life sciences and are at the center of interdisciplinary interests from medicine, biology, chemistry, and physics. Keywords: bioorganometallic chemistry; biosynthesis; cobalt; corrin; electron transfer; methylation; methyl transfer; organometallic chemistry; radical reactions; rearrangement reactions; synthesis; vitamin B12
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发表时间: 2008
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