钴(II)离子 | 22541-53-3

• 分子结构分类: 无机化合物 - 均相金属化合物 - 均相过渡金属化合物
• 中文名称: 钴(II)离子
• 英文名称: Cobaltous Cation
• 英文别名: cobalt(2+)
• CAS: 22541-53-3
• 化学式: Co+2
• 分子量: 58.93319
• InChiKey: XLJKHNWPARRRJB-UHFFFAOYSA-N

物化性质

• 物理描述：
  Solid
• 熔点：
  1495°C

计算性质

• 辛醇/水分配系数(LogP)：
  -0.0
• 重原子数：
  1
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

ADMET

代谢

钴通过肺部、胃肠系统和皮肤被吸收。由于它是维生素B12（氰钴胺）的一个组成部分，因此它被分布到身体的大多数组织中。它在血液中运输，通常与白蛋白结合，肝脏和肾脏中的含量最高。钴主要通过尿液和粪便排出。

Cobalt is absorbed though the lungs, gastrointestinal tract, and skin. Since it is a component of the vitamin B12 (cyanocobalamin), it is distributed to most tissues of the body. It is transported in the blood, often bound to albumin, with the highest levels being found in the liver and kidney. Cobalt is excreted mainly in the urine and faeces. (L29)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 毒性总结

钴被认为通过氧化剂和自由基反应过程表现出其毒性。它能产生氧自由基，并且可能被氧化成离子态的钴，导致脂质过氧化增加、DNA损伤，并诱导某些酶，从而导致细胞凋亡。�alt还被证明能阻断无机钙通道，可能影响神经递质的传递。钴还能与硫辛酸螯合，影响丙酮酸或脂肪酸的氧化。此外，钴可能通过干扰锌指DNA修复蛋白来抑制DNA修复，还显示出能抑制血红素合成和葡萄糖代谢。钴可能激活特定的辅助T淋巴细胞，并直接与免疫蛋白相互作用，如抗体（IgA和IgE）或Fc受体，导致免疫致敏。

Cobalt is believed to exhibit its toxicity through a oxidant-based and free radical-based processes. It produces oxygen radicals and may be oxidized to ionic cobalt, causing increased lipid peroxidation, DNA damage, and inducing certain enzymes that lead to cell apoptosis. Cobalt has also been shown to block inorganic calcium channels, possibly impairing neurotransmission. Cobalt can also chelate lipoic acids, impairing oxidation of pyruvate or fatty acids. In addition, cobalt may inhibit DNA repair by interacting with zinc finger DNA repair proteins, and has also been shown to inhibit heme synthesis and glucose metabolism. Cobalt may activate specific helper T-lymphocyte cells and interact directly with immunologic proteins, such as antibodies (IgA and IgE) or Fc receptors, resulting in immunosensitization. (L29)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 致癌物分类

钴金属与碳化钨：2A，可能对人类有致癌性。不含碳化钨的钴金属：2B，可能对人类有致癌性。（L135）

Cobalt metal with tungsten carbide: 2A, probably carcinogenic to humans. Cobalt metal without tungsten carbide: 2B, posiibly carcinogenic to humans. (L135)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 健康影响

接触高量的钴可能会导致心脏、肺、肾脏和肝脏损伤。皮肤接触已知会导致接触性皮炎。钴还可能具有致突变和致癌作用。

Exposure to high amount of cobalt can cause heart, lung, kidney, and liver damage. Skin contact is known to result in contact dermatitis. Cobalt may also have mutagenic and carcinogenic effects. (L29, L30)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 暴露途径

吸入（L29）；口服（L29）；皮肤（L29）

Inhalation (L29) ; oral (L29) ; dermal (L29)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 症状

钴吸入可能导致类似哮喘的呼吸问题。皮肤接触会导致接触性皮炎，其特征是刺激和皮疹。摄入大量钴可能会导致恶心和呕吐。

Cobalt inhalation can cause asthma-like breathing problems. Skin contact is known to result in contact dermatitis, which is characterized by irritation and rashes. Ingesting large amounts of cobalt may cause nausea and vomiting. (L2090)

来源:Toxin and Toxin Target Database (T3DB)

反应信息

• 作为反应物：
  描述：

  adenosine 5'-triphosphate 、 钴(II)离子 、 水 、 hydrogenobyrinate a,c-diamide 生成 adenosine 5'-diphosphate 、 3-[(1R,2S,3S,5Z,7S,8S,10Z,13S,15Z,17R,18R,19R)-2,7-bis(2-amino-2-oxoethyl)-3,13,17-tris(2-carboxylatoethyl)-18-(carboxylatomethyl)-1,2,5,7,12,12,15,17-octamethyl-8,13,18,19-tetrahydro-3H-corrin-24-id-8-yl]propanoate;cobalt(2+) 、 氢(+1)阳离子 、 H3PO4
  参考文献：
  名称：

  腺苷钴胺素（维生素B12）的生物合成。

  摘要：

  维生素B12或钴胺素是自然界中结构最复杂的小分子之一。在过去的十年中，在理解如何完成这种合成方面取得了重大进展。这篇综述涵盖了一些最重要的发现，并为读者提供了将尿卟啉原原III转化为腺苷钴胺素（AdoCbl）的完整说明。引用了183篇参考文献。

  DOI：

  10.1039/b108967f
• 作为产物：
  描述：

  Cobalt-sirohydrochlorin(8-) 、 氢(+1)阳离子 生成 钴(II)离子 、 sirohydrochlorin
  参考文献：
  名称：

  腺苷钴胺素（维生素B12）的生物合成。

  摘要：

  维生素B12或钴胺素是自然界中结构最复杂的小分子之一。在过去的十年中，在理解如何完成这种合成方面取得了重大进展。这篇综述涵盖了一些最重要的发现，并为读者提供了将尿卟啉原原III转化为腺苷钴胺素（AdoCbl）的完整说明。引用了183篇参考文献。

  DOI：

  10.1039/b108967f
• 作为试剂：
  描述：

  、 5-(3-chloropropyl)-1-methyl-1,4,5,6,7,8-hexahydro-pyrrolo[3,2-c]azepine-4,8-dione 、 在 钴(II)离子 、 saturated saline solution 、 水 、 magnesium sulfate 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以to give 6.16 g (optical purity: 83.5% e.e.) of (S)-5-(3-chloropropyl)-8-hydroxy-1-methyl-1,4,5,6,7,8-hexahydropyrrolo[3,2-c]azepin-4-one as pale brown crystalline的产率得到(S)-5-(3-chloropropyl)-8-hydroxy-1-methyl-1,4,5,6,7,8-hexahydropyrrolo[3,2-c]azepin-4-one
  参考文献：
  名称：

  Process for production of optically active pyrroloazepine derivatives

  摘要：

  本发明提供了一种制备吡咯并氮杂环衍生物的方法，特别是制备对手性有用的药物，该方法低廉简单且适用于工业规模，所述衍生物由下式（I）表示：其中Z代表可选取代的苯基；该方法包括：利用手性钴配合物催化剂，在金属氢化物化合物和醇化合物的存在下进行酮化合物的不对称还原，以及纯化所得化合物的过程。

  公开号：

  US06632943B2

文献信息

• Assay, purification, and characterization of cobaltochelatase, a unique complex enzyme catalyzing cobalt insertion in hydrogenobyrinic acid a,c-diamide during coenzyme B12 biosynthesis in Pseudomonas denitrificans
  作者：L Debussche、M Couder、D Thibaut、B Cameron、J Crouzet、F Blanche

  DOI：10.1128/jb.174.22.7445-7451.1992

  日期：1992.11

  Hydrogenobyrinic acid a,c-diamide was shown to be the substrate of cobaltochelatase, an enzyme that catalyzes cobalt insertion in the corrin ring during the biosynthesis of coenzyme B12 in Pseudomonas denitrificans. Cobaltochelatase was demonstrated to be a complex enzyme composed of two different components of M(r) 140,000 and 450,000, which were purified to homogeneity. The 140,000-M(r) component was shown to be coded by cobN, whereas the 450,000-M(r) component was composed of two polypeptides specified by cobS and cobT. Each component was inactive by itself, but cobaltochelatase activity was reconstituted upon mixing CobN and CobST. The reaction was ATP dependent, and the Km values for hydrogenobyrinic acid a,c-diamide, Co2+, and ATP were 0.085 +/- 0.015, 4.2 +/- 0.2, and 220 +/- 36 microM, respectively. Spectroscopic data revealed that the reaction product was cob(II)yrinic acid a,c-diamide, and experiments with a coupled-enzyme incubation system containing both cobaltochelatase and cob(II)yrinic acid a,c-diamide reductase (F. Blanche, L. Maton, L. Debussche, and D. Thibaut, J. Bacteriol. 174:7452-7454, 1992) confirmed this result. This report not only provides the first evidence that hydrogenobyrinic acid and its a,c-diamide derivative are indeed precursors of adenosylcobalamin but also demonstrates that precorrin-6x, precorrin-6y, and precorrin-8x, three established precursors of hydrogenobyrinic acid (D. Thibaut, M. Couder, A. Famechon, L. Debussche, B. Cameron, J. Crouzet, and F. Blanche, J. Bacteriol. 174:1043-1049, 1992), are also on the pathway to cobalamin.

  氢代卟啉酸a，c-二酰胺被证明是假单胞菌中辅酶B12生物合成过程中催化卟环中钴插入的酰胺酶的底物。已经证实，卟环酰化酶是一个复合酶，由两种不同的分子量为140,000和450,000的组分组成，这些组分被纯化到了同质性。140,000-M(r)组分被证明是由cobN编码的，而450,000-M(r)组分由cobS和cobT指定的两个多肽组成。每个组分本身都是不活性的，但是混合CobN和CobST可以重新组装出卟环酰化酶活性。反应是ATP依赖性的，氢代卟啉酸a，c-二酰胺，Co2+和ATP的Km值分别为0.085+/-0.015，4.2+/-0.2和220+/-36微米。光谱数据显示，反应产物是cob(II)yrinic acid a，c-二酰胺，使用同时含有卟环酰化酶和cob(II)yrinic acid a，c-二酰胺还原酶的耦合酶反应体系的实验证实了这一结果。这份报告不仅提供了第一份证据，证明氢代卟啉酸及其a，c-二酰胺衍生物确实是腺苷基钴胺的前体，而且还证明了已经确定的氢代卟啉酸的前体precorn-6x，precorn-6y和precorn-8x（D. Thibaut，M. Couder，A. Famechon，L. Debussche，B. Cameron，J. Crouzet和F. Blanche，J. Bacteriol. 174：1043-1049，1992）也在通向钴胺的途径上。
• A role for Salmonella typhimurium cbiK in cobalamin (vitamin B12) and siroheme biosynthesis
  作者：E Raux、C Thermes、P Heathcote、A Rambach、M J Warren

  DOI：10.1128/jb.179.10.3202-3212.1997

  日期：1997.5

  Collectively these results suggest that CbiK can function in fashion analogous to that of the N-terminal domain of CysG (CysG(B)), which catalyzes the final two steps in siroheme synthesis, i.e., NAD-dependent dehydrogenation of precorrin-2 to sirohydrochlorin and ferrochelation. Thus, phenotypically CysG(B) and CbiK have very similar properties in vivo, although the two proteins do not have any sequence

  通过研究其在大肠杆菌中的体内功能，研究了cbiK（一种在鼠伤寒沙门氏菌芯子操纵子中编码的基因）的作用。首先，发现在基因组cysG基因（编码西罗血红素合酶）背景下，钴胺素的生物合成不需要cbiK。其次，在缺乏基因组cysG基因的情况下，发现大肠杆菌中钴胺素的生物合成取决于cobA（P。denitrificans）（编码来自Pseudomonas denitrificans的尿卟啉原III甲基转移酶）和cbiK的存在。第三，大肠杆菌cysG缺失菌株302δa的半胱氨酸营养缺陷型的互补可以通过cobA（P。denitrificans）和鼠伤寒沙门氏菌cbiK基因的组合存在而获得。这些结果共同表明，CbiK可以以类似于CysG（CysG（B））N端结构域的方式发挥功能，该催化作用催化了Siroheme合成的最后两个步骤，即将NAD依赖的precorrin-2脱氢为Sirohydrochlorin。
• Redox potential changes during ATP‐dependent corrinoid reduction determined by redox titrations with europium(II)–DTPA
  作者：Hendrike Dürichen、Gabriele Diekert、Sandra Studenik

  DOI：10.1002/pro.3699

  日期：2019.10

  Corrinoids are essential cofactors of enzymes involved in the C1 metabolism of anaerobes. The active, super‐reduced [CoI] state of the corrinoid cofactor is highly sensitive to autoxidation. In O‐demethylases, the oxidation to inactive [CoII] is reversed by an ATP‐dependent electron transfer catalyzed by the activating enzyme (AE). The redox potential changes of the corrinoid cofactor, which occur

  类皮质激素是参与厌氧菌C 1代谢的酶的必需辅因子。类皮质激素辅因子的活性，超还原[Co I ]状态对自氧化高度敏感。在O-脱甲基酶中，由活化酶（AE）催化的ATP依赖性电子转移逆转了氧化为无活性的[Co II ]。通过电位滴定与紫外/可见光谱法研究了在该反应过程中发生的类皮质激素辅因子的氧化还原电位变化。通过使用euro（II）-二亚乙基三胺五乙酸（DTPA）作为还原剂，我们能够确定[Co II ] / [Co I]在缺乏和/或存在AE和/或ATP的情况下，结合蛋白的类固醇类辅因子对。数据显示，通过将类固醇辅助因子的电势从-530±15 mV增大到-250±10 mV，可以实现将电子从生理供体转移到作为电子接受部位的类海藻素上（E SHE，pH 7.5）。氧化还原电位的前50到100 mV似乎是核苷酸结合的AE与类rinrin蛋白或其辅因子的相互作用引起的。其余的150–200 mV必须通
• Common Chelatase Design in the Branched Tetrapyrrole Pathways of Heme and Anaerobic Cobalamin Synthesis
  作者：Heidi L. Schubert、Evelyne Raux、Keith S. Wilson、Martin J. Warren

  DOI：10.1021/bi9906773

  日期：1999.8.1

  Prosthetic groups such as heme, chlorophyll, and cobalamin (vitamin B(12)) are characterized by their branched biosynthetic pathway and unique metal insertion steps. The metal ion chelatases can be broadly classed either as single-subunit ATP-independent enzymes, such as the anaerobic cobalt chelatase and the protoporphyrin IX (PPIX) ferrochelatase, or as heterotrimeric, ATP-dependent enzymes, such as the Mg chelatase involved in chlorophyll biosynthesis. The X-ray structure of the anaerobic cobalt chelatase from Salmonella typhimurium, CbiK, has been solved to 2.4 A resolution. Despite a lack of significant amino acid sequence similarity, the protein structure is homologous to that of Bacillus subtilis PPIX ferrochelatase. Both enzymes contain a histidine residue previously identified as the metal ion ligand, but CbiK contains a second histidine in place of the glutamic acid residue identified as a general base in PPIX ferrochelatase. Site-directed mutagenesis has confirmed a role for this histidine and a nearby glutamic acid in cobalt binding, modulating metal ion specificity as well as catalytic efficiency. Contrary to the predicted protoporphyrin binding site in PPIX ferrochelatase, the precorrin-2 binding site in CbiK is clearly defined within a large horizontal cleft between the N- and C-terminal domains. The structural similarity has implications for the understanding of the evolution of this branched biosynthetic pathway.
• RamA, a Protein Required for Reductive Activation of Corrinoid-dependent Methylamine Methyltransferase Reactions in Methanogenic Archaea
  作者：Tsuneo Ferguson、Jitesh A. Soares、Tanja Lienard、Gerhard Gottschalk、Joseph A. Krzycki

  DOI：10.1074/jbc.m807392200

  日期：2009.1

  Archaeal methane formation from methylamines is initiated by distinct methyltransferases with specificity for monomethylamine, dimethylamine, or trimethylamine. Each methylamine methyltransferase methylates a cognate corrinoid protein, which is subsequently demethylated by a second methyltransferase to form methyl-coenzyme M, the direct methane precursor. Methylation of the corrinoid protein requires reduction of the central cobalt to the highly reducing and nucleophilic Co(I) state. RamA, a 60-kDa monomeric iron-sulfur protein, was isolated from Methanosarcina barkeri and is required for in vitro ATP-dependent reductive activation of methylamine: CoM methyl transfer from all three methylamines. In the absence of the methyltransferases, highly purified RamA was shown to mediate the ATP-dependent reductive activation of Co(II) corrinoid to the Co(I) state for the monomethylamine corrinoid protein, MtmC. The ramA gene is located near a cluster of genes required for monomethylamine methyltransferase activity, including MtbA, the methylamine-specific CoM methylase and the pyl operon required for co-translational insertion of pyrrolysine into the active site of methylamine methyltransferases. RamA possesses a C-terminal ferredoxinlike domain capable of binding two tetranuclear iron-sulfur proteins. Mutliple ramA homologs were identified in genomes of methanogenic Archaea, often encoded near methyltrophic methyltransferase genes. RamA homologs are also encoded in a diverse selection of bacterial genomes, often located near genes for corrinoid-dependent methyltransferases. These results suggest that RamA mediates reductive activation of corrinoid proteins and that it is the first functional archetype of COG3894, a family of redox proteins of unknown function.