SYNTHESIS OF 13C & 2H LABELED GLYCEROL & DIHYDROXY ACETONE

SIR提供了K77 SeCN（硒氰酸钾）; 117 mg A 在氢化酶中发现的双核活性中心的模型已经被 制备和表征。 该模型由两个Ni中心组成 由两个硫醇盐配体桥接并具有一个末端硫醇盐， 一个叔胺配位到每个Ni中心（Choudhury等人，Inorg. Chem. 1994，33，4831-4839）。 为了研究 在某些酶中，我们用硒代半胱氨酸取代 模型中的硫醇盐的硒酸盐（同上）。我们希望应用核磁共振 和ENDOR光谱学来预测这些模型， 酶也一样。 这些技术可以让我们直接探测 硒代半胱氨酸镍配体在酶催化中的作用。 的 提出的模型研究将使我们能够发展ENDOR技术 并提供用于解释酶数据的数据库。 这些研究需要通过77 Se富集硒核， Se的同位素，具有核磁矩（I = 1/2）。 我们将 通过公开的方法合成模型化合物， K（77 SeCN）由LANL的稳定同位素资源生产。 后 成功完成模型研究后，酶样品将 通过补充所涉及的细菌的生长培养基来制备 (e.g.,脱硫微生物菌（Desulfomicrobium baculaturn）或甲烷球菌（Methanococcus baculaturn）， 77 Se.

The SIR provided K 77 SeCN (Potassium Selenocyanate); 117mg A model of the dinuclear active site found in hydrogenases has been prepared and characterized. This model consists of two Ni centers bridged by two thiolate ligands and having one terminal thiolate and one tertiary amine liganded to each Ni center (Choudhury et al. Inorg. Chem. 1994, 33, 4831-4839). In order to examine the role of selenocysteine substitution in some enzymes, we have substituted selenolates for thiolates in the model (ibid.). We wish to apply NMR and ENDOR spectroscopy to these models in anticipation of doing the same for the enzyme. These techniques will allow us to directly probe the role of the Ni selenocysteine ligand in enzyme catalysis. The proposed model studies will allow us to develop the ENDOR technique and to provide a data base with which to interpret the enzyme data. These studies require enrichment of the selenium nucleus by 77Se, the isotope of Se with a nuclear magnetic moment (I = 1/2). We will synthesize the model compound by the published procedure employing K(77SeCN) produced by the Stable Isotope Resource at LANL. Upon successful completion of the model studies, enzyme samples will be prepared by supplementing the growth medium of the bacteria involved (e.g., Desulfomicrobiurn baculaturn or Methanococcus voltae) with 77Se.