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首页> 外文期刊>Journal of Inorganic Biochemistry: An Interdisciplinary Journal >Synthesis and characterization of isolable thiolatocobalamin complexes relevant to coenzyme B_(12)-dependent ribonucleoside triphosphate reductase
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Synthesis and characterization of isolable thiolatocobalamin complexes relevant to coenzyme B_(12)-dependent ribonucleoside triphosphate reductase

机译：与辅酶B_（12）依赖的核糖核苷三磷酸还原酶有关的可分离的硫代latocobalamin复合物的合成和表征

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摘要

The syntheses, isolation and characterization of cyclohexylthiolatocobalamin (C_6H_(11)SCbl), glutathionylcobalamin (GluSCbl), and cysteinylcobalamin (CysSCbl) are reported in 75, 55, and 65% yield, respectively. Characterization was achieved using elemental analyses, L-SIMS (liquid secondary ion mass spectrometry), UV-visible spectroscopy and, for the more stable C_6H_(11)SCbl and GluSCbl, our recently established ~1H NMR method (which emphasizes the readily interpreted aromatic region of the cobalamin's ~1H NMR spectrum). Preliminary evidence is presented for clean homolysis of the RS-Co bond in C_6H_(11)SCbl, GluSCbl, and CysSCbl to give RS~center dot and ~center dotCo(II)Cbl radical pairs analogous to those that are intermediates in ribonucleoside triphosphate reductase (RTPR). A summary is provided which emphasizes the seven variables identified to date, underlying the successful syntheses and isolation of thiolatocobalamins, variables which make the one-step syntheses of RSCbls considerably more complex than they initially appear. Also briefly discussed are the analogous protein-S-Cbl complexes that are seen as side-products in RTPR, and the probability that such side-products are formed when HOCbl center dot HX is used as a possible 'activesite inhibitor' complex with B_(12)-dependent enzymes.
机译：据报道，环己基硫代latolabaobalamin（C_6H_（11）SCbl），谷胱甘肽钴胺素（GluSCbl）和半胱氨酰钴胺素（CysSCbl）的合成，分离和表征分别产率为75、55和65％。使用元素分析，L-SIMS（液体二次离子质谱），UV-可见光谱法进行表征，对于更稳定的C_6H_（11）SCbl和GluSCbl，我们最近建立的〜1H NMR方法（强调了易于理解的芳族化合物）钴胺素〜1H NMR光谱的区域）。初步证据表明C_6H_（11）SCbl，GluSCbl和CysSCbl中的RS-Co键完全均质化，得到的RS_中心点和〜中心点Co（II）Cbl自由基对类似于核糖核苷三磷酸还原酶的中间体（RTPR）。提供了一个摘要，强调了迄今已成功鉴定和分离出硫代latocobalamins的七个变量，这些变量使RSCbls的一步合成比最初显示的要复杂得多。还简要讨论了在RTPR中被视为副产物的类似蛋白质-S-Cbl复合物，以及将HOCbl中心点HX用作可能的B_（活性位点抑制剂）复合物时形成此类副产物的可能性。 12）依赖性酶。

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