Optimized Biocatalytic Synthesis of 2-Selenopyrimidine Nucleosides by Transglycosylation**

Selenium-modified nucleosides are powerful tools to study the structure and function of nucleic acids and their protein interactions. The widespread application of 2-selenopyrimidine nucleosides is currently limited by low yields in established synthetic routes. Herein, we describe the optimization of the synthesis of 2-Se-uridine and 2-Se-thymidine derivatives by thermostable nucleoside phosphorylases in transglycosylation reactions using natural uridine or thymidine as sugar donors. Reactions were performed at 60 or 80 °C and at pH 9 under hypoxic conditions to improve the solubility and stability of the 2-Se-nucleobases in aqueous media. To optimize the conversion, the reaction equilibria in analytical transglycosylation reactions were studied. The equilibrium constants of phosphorolysis of the 2-Se-pyrimidines were between 5 and 10, and therefore differ by an order of magnitude from the equilibrium constants of any other known case. Hence, the thermodynamic properties of the target nucleosides are inherently unfavorable, and this complicates their synthesis significantly. A tenfold excess of sugar donor was needed to achieve 40−48 % conversion to the target nucleoside. Scale-up of the optimized conditions provided four Se-containing nucleosides in 6–40 % isolated yield, which compares favorably to established chemical routes.     

Biofortification with selenium and lithium improves nutraceutical properties of major winery grapes in the Midwestern United States

Enriching the micronutrients, selenium (Se) and lithium (Li), in grapes to improve their nutraceutical properties were implemented by foliar application of organic fertiliser rich in Se and Li onto five grape cultivars. The effects of this biofortification on vine vigour, fruit quality, overall micronutrients and phenolic compounds also were investigated. Agronomic biofortification was found greatly increased the Se and Li content in the whole grape by multiple times, meanwhile it did not significantly affect the vine vigour and fruit quality of grapes. However, the biofortification did impact the Ionome (including all the mineral nutrients and trace elements) and phenolic compounds in grapes and this varied among cultivars. This study demonstrated foliar spray of organic Se/Li fertiliser was a very effective strategy to biofortify these micronutrients in grape berries, particularly in the skin, and therefore might be a promising strategy to increase the consumption and awareness of these grapes.     

正交设计法优选麻叶千里光碱溶态中硒提取工艺的研究

利用正交设计法优选麻叶千里光碱溶态中硒提取工艺。首先,选用不同溶剂提取麻叶千里光,用石墨炉原子吸收法测定各种形态中硒元素的含量,然后,用超声波—微波协同提取麻叶千里光碱溶态中硒,正交实验确定麻叶千里光碱溶态中硒的最佳提取条件.结果不同溶剂提取麻叶千里光时得:碱溶态(23.10μg/g)>盐溶态(17.20μg/g)>水溶态(14.60μg/g)>醇溶态(13.83μg/g)>醚溶态(10.60μg/g)>四氯化碳溶态(6.03μg/g);相对标准偏差在0.29%—1.96%间;加标回收率在98.24%—105.1%间.根据正交实验,通过极差分析:A>D>B>C;优方案为A_2D_3B_4C_2,即麻叶千里光中的硒在碱浓度为0.25 mol/L,料液比为1:20,提取功率为200 W,提取时间为180s时提取效果最好.     

硒催化水合肼还原芳香族硝基化合物制芳胺

在温和条件下,研究了硒对水合肼还原芳香族硝基化合物制芳胺的催化性能。邻位或对位有取代基的芳香族硝基化合物被还原为相应芳胺的收率较低;硝基苯或间位有取代基的芳香族硝基化合物被还原为相应芳胺的收率较高。以硝基苯为底物,考察了溶剂、硒粉用量和NaOH用量等因素对反应的影响。得到的适宜条件为:以5 mL乙醇和1 mL水为溶剂,2 mmol芳香族硝基化合物,4 mmol水合肼,O.04 g NaOH和0.02 g硒粉,反应温度为75℃,反应时间为2～5 h,硝基苯或间位有取代基的芳香族硝基化合物被还原为芳胺的收率为87%～99%。催化剂重复使用4次活性没有降低。     

氢化物原子荧光光谱法测定党参中的硒含量

为建立一种操作简便,快速,高灵敏度的氢化物原子荧光光谱法测定党参中硒的分析方法。方法 采用原子荧光光谱法对测定党参中硒元素进行含量的定量分析方法。结果 硒含量在0~40 μg/L质量范围内与其荧光强度呈现良好的线性关系（R²=0.9999）,检出限为Q=0.065 ng/mL;加样回收率为113.33%,相对标准偏差（RSD）为4.97%;精密度RSD为1.65%;准确度RSD为4.58%;稳定性RSD为6.52 %。11个不同品种党参之间的硒含量稍有不同,但都在0.1 mg/kg以下。结论 在富硒党参质量控制检测中,用原子荧光光谱法测定硒含量,其操作快速、简便,能准确测定党参硒含量。     

The Pharmacology and Therapeutic Utility of Sodium Hydroselenide

Metabolically active gasotransmitters (nitric oxide, carbon monoxide and hydrogen sulfide) are important signalling molecules that show therapeutic utility in oxidative pathologies. The reduced form of selenium, hydrogen selenide (HSe⁻/H₂Se), shares some characteristics with these molecules. The simple selenide salt, sodium hydroselenide (NaHSe) showed significant metabolic activity, dose-dependently decreasing ex vivo O₂ consumption (rat soleus muscle, liver) and transiently inhibiting mitochondrial cytochrome C oxidase (liver, heart). Pharmacological manipulation of selenoprotein expression in HepG2 human hepatocytes revealed that the oxidation status of selenium impacts on protein expression; reduced selenide (NaHSe) increased, whereas (oxidized) sodium selenite decreased the abundance of two ubiquitous selenoproteins. An inhibitor of endogenous sulfide production (DL-propargylglycine; PAG) also reduced selenoprotein expression; this was reversed by exogenous NaHSe, but not sodium hydrosulfide (NaHS). NaHSe also conferred cytoprotection against an oxidative challenge (H₂O₂), and this was associated with an increase in mitochondrial membrane potential. Anesthetized Wistar rats receiving intravenous NaHSe exhibited significant bradycardia, metabolic acidosis and hyperlactataemia. In summary, NaHSe modulates metabolism by inhibition of cytochrome C oxidase. Modification of selenoprotein expression revealed the importance of oxidation status of selenium therapies, with implications for current clinical practice. The utility of NaHSe as a research tool and putative therapeutic is discussed.     

纳米晶体Se的微观结构特征

本文采用Ｘ射线衍射和透射电子显微镜研究了纳米晶体Ｓｅ的微观结构特征．通过测定不同晶粒尺寸的纳米晶体Ｓｅ的点阵参数ａ和ｃ，发现纳米晶体Ｓｅ中存在晶格畸变，畸变量与晶粒尺寸有关．得到了纳米晶体Ｓｅ中晶胞体积变化与晶粒尺寸的关系．并由点阵参数计算出纳米晶体Ｓｅ的键长．用非晶态Ｓｅ中的无规链折叠的晶化机制解释了纳米晶体Ｓｅ中晶格畸变现象．     

2-苯基-1,2-苯并异硒唑-3-(2H)-酮的合成研究

在N2保护下,采用水合肼的碱性水溶液还原硒粉制备了K2Se2,不经分离直接与邻氨基苯甲酸的重氮盐反应得到了中间体2,2'-二硒化苯甲酸;在环合反应合成2-苯基-1,2-苯并异硒唑-3-(2H)-酮(Ebselen)时改用了乙醚-水为反应体系,K2CO3水溶液作为副产物HCl的吸收剂,促使胺解关环反应顺利进行,产物易分离、纯化得2-苯基-1,2-苯并异硒唑-3-(2H)-酮。     

茶多酚硒配合物合成与结构表征

在水溶液中,以n(茶多酚)∶n(Se4+)=4∶1,pH=3-4,反应温度60℃,反应时间20 m in条件下合成了标题化合物茶多酚硒。配合物的FTIR为3 411.58,1 699.43,1 617.71,1 450.17,1 364,1 233.6,1 037.46cm-1,1HNMR,:δ2.18,2.35,3.18-3.8,5.15-5.35,6.55-8.38,10.34,XRD,λ/nm为1.634,2.002,2.668,2.836,3.281,最后确定Se4+离子为四配位和五配位构型晶体。     

一种合成二烃基硒醚的新方法

在固体氢氧化钠存在下，卤代烃及硼氢化钠与硒粉作用，在乙醇溶液中制得二烃基硒醚。