用离子抑制色谱法分析二（2,2,6,6—四甲基—4—哌啶基）马来酸酯合？…

建立了用离子抑制色谱法分析二（２,２,６,６－四甲基－４－哌啶基）马来酸酯合成反应液的方法。平均回收率为９８．８％,相对标准偏差为０．５６％,测量的平均相对偏差不大于５．０％,方法简单,快速,可用于工艺条件的选择和质量检测。     

硒酵母中有机硒及硒代氨基酸含量的测定方法

报道了人工培养硒酵母中有机硒及硒代胱氨酸（ＳｅＣｙｓ）和硒代蛋氨酸（ＳｅＭｅｔ）含量的测定方法。采用透析处理法使硒酵母中的无机硒和有机硒得以分离,并采用催化分光光度法测定了硒酵母中有机硒的含量;采用氨基酸自动分析仪测定了硒酵母中ＳｅＣｙｓ和ＳｅＭｅｔ的含量。     

硒酵母中硒含量测定方法的研究

报道了人工培养硒酵母中总硒、无机硒和有机硒的测定方法,建立了无机硒和有机硒的鉴别方法,并采用透析处理法使硒酵母中的无机硒和有机硒得以分离;还报道了不同培养条件下得到的5种硒酵母中总硒、无机硒和有机硒的定量分析数据,为硒酵母在医药和添加剂领域的应用提供了可靠的数据。     

Selenium speciation in animal tissues after enzymatic digestion by high-performance liquid chromatography coupled to inductively coupled plasma mass spectrometry

A procedure is described for the enzymatic digestion of tuna and mussel samples that allows the determination of selenium species by high-performance liquid chromatography in conjunction with inductively coupled plasma mass spectrometry. The species were extracted by two-step enzymatic hydrolysis with a non-specific protease (subtilisin). The selenium species were separated on a Spherisorb 5 ODS/AMINO column using two different chromatographic conditions, namely phosphate buffers at pH 2.8 and pH 6.0 as mobile phases. The method determines organic (trimethylselenonium, selenocystine, selenomethionine and selenoethionine) and inorganic selenium species (selenite and selenate), but only organic selenium species were found in the samples. The sum of identified selenium species in the sample was about 30% of the total selenium present in the enzymatic extract despite the fact that recoveries of total hydrolysed selenium were 93-102%. Trimethylselenonium ion and selenomethionine were found in both tuna and mussel samples and an unknown selenium species was also found in tuna samples.     

Determination of selenium in atmospheric particulate material of Ankara and its possible sources

The monthly variation of selenium concentration in atmospheric particulate material of Ankara was investigated. The selenium concentrations in possible pollution source materials like coal, fuel oil and their bottom and fly ashes were determined to obtain the percent transference of selenium into the atmosphere. Instrumental thermal neutron activation analysis and atomic absorption spectroscopy were applied for the analysis of selenium in the samples. Selenium enrichment factors with respect to the fuels, soil of Ankara and crustal material were also calculated. Atmospheric selenium concentration is found to increase during winter months and the main cause of this increase is the emission of selenium into the atmosphere due to fuel combustion.     

Electrothermal atomization of palladium stabilized selenium in the presence of phosphate

The interference caused by phosphate (as Na₂HPO₄) in the electrothermal atomic absorption determination of selenium was investigated for reduced and unreduced palladium nitrate modifiers. An increase of the amount of phosphate in the sample was accompanied with increasing losses of selenium. Kinetic parameters of the selenium atomization were calculated for various amounts of phosphate interference. These results were compared with previous findings for palladium stabilized selenium and the sulfate interference observed for this system. The increasing chemical interference is due to phosphorous replacing the selenium bound by palladium. The phosphorus thus makes the palladium surface unavailable for the stabilization of selenium.     

54例白血病患者血清硒含量分析

以催化极谱法测定了５４例白血病患者血清硒含量。结果表明，急淋、急粒患者血清硒含量均低于正常对照组，慢粒及急、慢粒经治疗缓解者血清硒含量与正常对照组间均无显著性差异，提示低硒状态只存在于急性患者，且随病情缓解后血硒水平趋于正常，慢粒与血硒含量没有明显的相关关系。     

Speciation of Selenium in Supplements by High Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometry

Anion and cation exchange high-performance liquid chromatography (HPLC) combined with inductively coupled plasma-mass spectrometry (ICP-MS) were used for speciation of selenium in supplements. All the parameters in the extraction, separation, and determination procedures were optimized. Recovery studies for the selenium species from the anion and cation exchange columns were performed and there were no analyte losses. Limits of detection for selenium(IV), selenium(VI), Se in selenomethionine, and Se in selenocystine were 0.85, 0.68, 0.84, and 0.99 nanogram per milliliter, respectively. Six brands were analyzed to identify and quantify the selenium species present, and the results found were compared with the values given on the labels. The selenium species matched the labeled species for four brands, whereas two brands were found to contain inorganic Se(VI) in contrast with the labeled claim of selenomethionine.     

Determination of elemental selenium and pyrite-selenium in sediments

A method is described for the selective determination of concentrations of elemental selenium and pyrite-selenium in sediments. A 1 M sodium sulfite solution is used to solubilize elemental selenium and a Cr(II) solution releases selenium in pyrite. The accuracy of the methods was evaluated by using various selenium compounds. The detection limits for the elemental and pyrite-selenium procedures are 0.001 and 0.025 μg Se per gram of sediment, respectively. The relative standard deviationis < 10% for elemental selenium and < 16% for pyrite-selenium. These and other procedures were used for selenium speciation in marine and freshwater sediments.     

Separation and speciation of selenium in food and water samples by the combination of magnesium hydroxide coprecipitation-graphite furnace atomic absorption spectrometric determination

A simple and economic separation and speciation procedure for selenium in food and water samples have been presented prior to its graphite furnace atomic absorption spectrometry (GFAAS). Magnesium hydroxide coprecipitation system for selenium(IV) was applied to the separation and speciation of selenium ions. The influences of the various analytical parameters for the quantitative recoveries of selenium ions like pH, amounts of magnesium ions as carrier elements, etc. on were examined. The effects of the alkaline and earth alkaline metals, some transition metals and some anions on the recoveries of selenium(IV) were also investigated. The recoveries of analytes were found greater than 95%. No appreciable matrix effects were observed. The detection limit, defined as three times the blank standard deviation (3σ), was 0.030 μg l⁻¹. The preconcentration factor for the presented system was 25. The proposed method was applied to the speciation of selenium(IV), selenium(VI) and determination of total selenium in natural waters and microwave digested various food samples with satisfactory results. The procedure was validated with certified reference materials. The relative errors and relative standard deviations were below 6% and 10%, respectively.     

蛋氨酸硒络合反应条件的响应曲面法优化

以蛋氨酸和亚硒酸钠为原料合成了蛋氨酸硒;采用基于3因素5水平的中心组合设计实验的响应曲面法,分析了温度(30℃~80℃)、酸度(pH 4~9)、时间以及它们之间的交互作用对蛋氨酸硒产率的影响,确定了合成蛋氨酸硒的最佳工艺条件.通过典型分析确定优化的络合反应条件为:温度50℃,pH 6.93,时间90 min;相应的蛋氨酸硒的产率为51.58%.相关研究结果表明,采用响应曲面法优化确定的蛋氨酸硒合成工艺合理有效、切实可行.     

富硒香菇规模化栽培实验及其富硒规律研究

为了了解规模化栽培后富硒香菇的产量（生物学效率）及富硒规律，本实验通过香菇栽培基质添加模式，采取规模化生产进行富硒香菇栽培试验，选取不同浓度硒营养强化剂对香菇品种“向阳二号”和“9608”进行添加，测定相对应的香菇生物学效率以及第一潮次和第二潮次的总硒及硒代氨基酸的含量。实验发现向阳二号香菇，在硒添加量较低（0-6mg/kg）时香菇的生物转化率基本不随硒添加量的增加而改变，当硒添加量继续增加（10-60mg/kg）时，香菇的生物转化率整体低于低添加量；9608香菇，随着硒添加量的增加（0～60mg/kg），香菇的生物转化率表现出微弱的增加趋势，但差异性不显著；而两种不同品种、潮次香菇的总硒及硒代氨基酸含量均随着硒添加量的增加而提高，但硒代氨基酸占总硒的比例变化趋势却有所不同，在66.7-85.4%范围内。此外，对于不同品种的香菇，其第一潮次总硒含量在硒的添加量在0～20 mg/kg的范围内呈现良好的规律性，总硒是基质（风干）中硒含量的约4-5倍。可见，按照该规模化栽培模式进行生产栽培，可以得到总硒含量稳定、硒代氨基酸占总硒比＞65%的富硒香菇产品，对富硒香菇产业的发展有一定的指导意义。     

Selenium distribution in tissues and monitor materials after long-term selenium supplementation investigated by neutron activation analysis

The effects of long-term selenium supplementation on the selenium body status were investigated in humans and rats. Selenium was determined in human muscle biopsies and monitor materials and in rat tissues by neutron activation analysis. The results showed that the body selenium load is raised by additional supply of selenomethionine or selenomethionine-containing yeast but not proportionally to the intake. The surplus selenium can serve as an endogenous source to maintain the selenoprotein levels during insufficient supply. Highly significant correlations between the muscle selenium concentrations and those in blood, blood fractions, hair and nails indicate that the selenium status can be assessed by analysis of these monitor materials.     

低硒克山病病区和非病区居民红细胞免疫功能的对比测定

对比测定了低硒克山病病区和非病区居民的红细胞免疫功能、血清红细胞免疫粘附调节因子和血硒含量。结果表明，低硒病区和非病区居民红细胞Ｃ３ｂＲ花环率和血硒水平显著低于对照非病区，而血清红细胞免疫粘附花环抑制率显著高于对照非病区；３组居民的红细胞免疫复合物花环率和血清红细胞免疫粘附花环促进率无明显差异；低硒病区和非病区居民上述各参数值均相似。研究说明，克山病病区居民红细胞免疫功能低下和血清红细胞免疫粘附抑     

The determination of selenium in urine

The selenium excreted in urine can be measured to assess the dietary status of selenium, an essential trace element in human nutrition. The objectives of this work were: 1) to develop a procedure, capable of high sample throughout, by which the major interferences can be reduced such that selenium concentrations can be measured in urine by Neutron Activation Analysis (NAA) using^77mSe (17.4 s; and 2) to apply the method to a human dietary selenium study in which several selenium monitors were compared. The method involves a pre-irradiation arsenic-coprecipitation separation of the selenium from urine in the presence of a high specific-activity⁷⁵Se tracer. The processed urine samples are analyzed using NAA. The procedure was applied to 58 urine specimens longitudinally collected from 12 subjects consuming three different levels of selenium. A dose-response relationship was observed in urine as well as a high correlations with both serum and whole blood selenium concentrations.     

高硒情况下维生素E对幼龄大鼠抗氧化作用的研究

研究了高Se或高维生系E下,幼龄大鼠体内抗氧化活性的变化以及高Se下,维生素E对其体内抗氧化水平的影响。将三月龄Wistar大鼠32只随机分成4组：正常饲料组、高Se高维生素E饲料组、高Se饲料组和高维生素E饲料组。饲至十周末,处死大鼠,按试剂盒要求分别取其血液、心、肝、肾制成标本测SOD、CAT活性及MDA、GSH含量。结果表明,高Se或高维生素E下饲养下的大鼠与对照组比较,血液中SOD活性明显下降;维生素E能明显抑制高Se大鼠血液中SOD活性的下降。结论：单独高Se或高维生素E会降低幼龄大鼠的抗氧化活性,而维生素E能明显提高高Se下幼龄大鼠体内抗氧化活性。     

Preconcentration and separation of inorganic selenium on Dowex 1X8 prior to hydride generation-atomic absorption spectrometry

Exchange reactions between inorganic selenium species and chloride were studied on Dowex 1X8. The concentration exchange constants were determined with the batch technique at room temperature and used to predict the chromatographic enrichment and separation of tetra- and hexavalent selenium. A procedure for the determination of total selenium after digestion with permanganate and anion exchange preconcentration was also developed. The enrichment techniques were applied to the determination of Se(IV) and total dissolved selenium in drinking water and fresh water using flow injection hydride generation-atomic absorption spectrometry (HG-AAS). Results agreed with those obtained in a HG-AAS system where selenium was preconcentrated as hydrogen selenide in a trap at liquid nitrogen temperature.     

Effect of selenium on uranium biosorption

The effects of selenium on uranium biosorption were examined using 67 microorganisms (17 bacteria, 19 actinomycetes, 18 fungi, and 13 yeasts). The growth suppression by selenium in the medium was observed in most of the microorganisms tested. The amounts of selenium taken up in microbial cells differ with different species and groups of microorganisms. The marked enhancement of uranium adsorbing ability by Se-loading was only found in yeasts, such as Candida utilis. The amounts of uranium adsorbed by the cells were increased with increasing selenium in the cells. Thus, it is assumed that the selenium in the cells will play an important role in uranium binding.     

Uptake and speciation of selenium in garlic cultivated in soil amended with symbiotic fungi (mycorrhiza) and selenate

The scope of the work was to investigate the influence of selenate fertilisation and the addition of symbiotic fungi (mycorrhiza) to soil on selenium and selenium species concentrations in garlic. The selenium species were extracted from garlic cultivated in experimental plots by proteolytic enzymes, which ensured liberation of selenium species contained in peptides or proteins. Separate extractions using an aqueous solution of enzyme-deactivating hydroxylamine hydrochloride counteracted the possible degradation of labile selenium species by enzymes (such as alliinase) that occur naturally in garlic. The selenium content in garlic, which was analysed by ICP–MS, showed that addition of mycorrhiza to the natural soil increased the selenium uptake by garlic tenfold to 15 μg g⁻¹ (dry mass). Fertilisation with selenate and addition of mycorrhiza strongly increased the selenium content in garlic to around one part per thousand. The parallel analysis of the sample extracts by cation exchange and reversed-phase HPLC with ICP–MS detection showed that γ-glutamyl-Se-methyl-selenocysteine amounted to 2/3, whereas methylselenocysteine, selenomethionine and selenate each amounted to a few percent of the total chromatographed selenium in all garlic samples. Se-allyl-selenocysteine and Se-propyl-selenocysteine, which are selenium analogues of biologically active sulfur-containing amino acids known to occur in garlic, were searched for but not detected in any of the extracts. The amendment of soil by mycorrhiza and/or by selenate increased the content of selenium but not the distribution of detected selenium species in garlic. Finally, the use of two-dimensional HPLC (size exclusion followed by reversed-phase) allowed the structural characterisation of γ-glutamyl-Se-methyl-selenocysteine and γ-glutamyl-Se-methyl-selenomethionine in isolated chromatographic fractions by quadrupole time-of-flight mass spectrometry.     

硒的土壤化学及其生物有效性

硒是重要的生命元素。高硒和低硒均会引起动物发生各种疾病，硒由土壤进入植物体，通过食物链控制着动物的硒营养状况，因此研究硒的土壤化学及其对生物的有效性对维护人类健康和牲畜生产是十分有意义的，本文拟就土壤中硒的含量、形态、有效性影响因素，硒的保健作用和调节措施等方面作一综述。