Radiochemical separation of7 5Se with o-phenylenediamine for instrumental neutron activation analysis of selenium in biological materials

A new method of radiochemical separation for determination of selenium in biological materials has been developed. The method is based on the reaction of tetravalent selenium with the amino groups of aromatic ortho-diamines resulting in selenodiazoles, which can be easily extracted with organic solvents. The biological samples were irradiated in a reactor, mineralized with nitric and perchloric acids and MgCl₂. Selenium was transformed to teravalent form with hydrochloric acid and the resulting bezoselenodiazole formed in the reaction with o-phenylenediamine was extracted with toluene. The radioactivity of selenium^{7 5}Se was measured with a well-type NaI(Tl) scientillation detector. The accuracy of the method was verified by determining selenium levels in SRM NBS. The detection limit of the method was found to be 0.5 ng Se. The comparison of selenium levels in human blood determined by HG-AAS. non-destructive NAA and the described method is presented.     

阴极溶出催化极谱法测定微量硒

本文提出将溶出伏安法和极谱催化法结合起来,用溶出催化波来测定微量硒;考察了各种试验条件及其它离子对分析结果的影响,并对实样进行了分析测定。用国产883型笔录式极谱仪,配用旋转玻碳电极测定硒,电解富集3-5分钟,可定量测定浓度在4×10^-9-1×10^-7M 范围内的硒;富集20-30分钟,硒的检出下限为7×10^-10M。测定时不必除氧。在测定硒的基础上,用玻碳电极和大汞电极相配合,对硒的溶出催化电极过程进行了研究,探讨了此过程中各步反应的机理。     

Kinetic-spectrophotometric determination of selenium in natural water after preconcentration of elemental selenium on activated carbon

A simple, accurate, sensitive and selective method is described for rapid determination of ultra-trace quantities of selenium. Selenium (IV) was collected on activated carbon after reduction to elemental Se by l-ascorbic acid. The collected selenium was then determined based on its accelerating effect on the oxidation reaction of methyl orange with bromate in acidic media. Total amount of Se(IV) and Se(VI) were collected on AC after their reduction by hydrazine. Se(IV), Se(VI) and total selenium could be determined by the method. Selenium in the range 10-10 000 ng could be determined by the method. The method was used to the determination of Se(IV), Se(VI) and total selenium in natural water with satisfactory results.     

Differential pulse polarographic determination of arsenic, selenium and tellurium at mug levels

An analytical method, based on differential pulse polarography, for determination of arsenic, selenium and tellurium in solid matrices, is described. The method involves decomposition of the matrix with a mixture of nitric, perchloric and hydrofluoric acid, isolation of tellurium from the other analytes by liquid-liquid extraction (from 4M hydrochloric acid with methyl isobutyl ketone), and determination of the analytes. Tellurium is determined separately, and arsenic is determined in the same solution as selenium after determination and oxidation of the selenium and addition of catechol. Graphitized carbon black and chelating resin were used to eliminate the organic solvent in the aqueous solution and avoid interferences due to the other metals of the matrix. The decomposition, the influence of each analyte on the determination of the others, and the extraction process were given particular attention. The method is characterized by>96% recovery, with a relative standard deviation ranging from 2 to 10% at ppm levels.     

Etude de la Fragmentation du Benzisothiazole et de Quelques Benzoselenazoles et Benzisoselenazoles

The mass spectra of benzisothiazole, three benzoselenazoles and three benzisoselenazoles have been determined and compared with those of the corresponding benzothiazoles. The elimination of CS known to occur from these latter substances is confirmed in the case of benzisothiazole, but a different mechanism is proposed. The fragmentation of the selenium analogues led to ions of the same type as the benzothiazoles and benzisothiazole, through extrusion of molecules of the type CN—R, but loss of the heteroatom was not accompanied by loss of carbon. Furthermore, the isoselenazole structure seems to be more sensitive to electronolysis than its isomer. All six selenium heterocyclics investigated gave rise to two ions (130 and 132) resulting from a recombination of various fragments, suggesting that this is a characteristic feature of the electron-impact fragmentation of compounds of this type.     

Differential determination of selenium(IV) and selenium(VI) with sodium diethyldithiocarbamate, ammonium pyrrolidinedithiocarbamate and dithizone by atomic-absorption spectrophotometry with a carbon-tube atomizer

The extraction behaviour of selenium(IV) and selenium(VI) with sodium diethyldithiocarbamate, ammonium pyrrolidinedithiocarbamate and dithizone in organic solvents has been investigated by means of flameless atomic-absorption spectrophotometry with a carbon-tube atomizer. The selective extraction of selenium(IV) and differential determination of selenium(IV) and selenium(VI) have been developed. With sodium diethyldithiocarbamate and carbon tetrachloride, when the aqueous phase/organic solvent volume ratio is 5 and the injection volume in the carbon tube is 20 microl, the sensitivity for selenium is 0.4 ng/ml for 1% absorption. The relative standard deviations are ca. 3%. Interference by many metal ions can he prevented by masking with EDTA. The proposed methods have been applied satisfactorily to determination of Se(IV) and Se(VI) in various types of water.     

Selenium speciation by HPLC with tandem mass spectrometric detection

An HPLC/MS-MS method was developed for the analysis of selenium species. Tandem mass spectrometry (MS-MS) was chosen as a detector to provide structural and molecular information allowing the identification of species, which are not commercially available as standards. A new separation method for selenium species was developed, based on porous graphitic carbon (PGC) as the stationary phase. The applicability of the optimized HPLC/MS-MS system was demonstrated by the analysis of a mixture containing Se-methyl-selenocysteine, selenomethionine, selenocystine, selenoethionine and selenocystamine. All peaks were baseline-resolved and eluted within 16 min. Positive ionization led to higher intensities than negative ionization. Signal suppression tests showed that electrospray ionization (ESI) is a more effective ionization method than atmospheric pressure chemical ionization (APCI) for selenium species in a matrix containing pentafluoropropionic acid, heptafluorobutyric acid or ammonium formate. Comparative experiments with a triple quadrupole mass spectrometer (Quattro LC) and a time-of-flight instrument (Q-Tof-2) showed a 20 fold higher mass resolution of the latter mass spectrometer (m/Am= 5000) and significantly lower intensities for analyte signals as well as background noise compared to the triple quadrupole instrument. MS-MS spectra of the investigated selenium species including characteristic fragmentation patterns are presented.     

Stereo- and Site-Selectivity in the Reaction of Chiral Episelenonium Ion with Carbon Nucleophile

Abstract

There are two important aspects in the reaction of chiral episelenonium ion (episelenonium ion bearing chiral carbon in the three-membered ring) with carbon nucleophile; namely, (1) whether the chiral carbon racemizes during the reaction or not, and (2) the carbon nucleophile attacks the carbon atom (carbophilic attack) or selenium atom (selenophilic attack) in the three-membered ring. When carbon nucleophile such as alkenyl silyl ethers, trimethylsilyl cyanide, and allyltrimethyl-silane are employed, steric protection of the selenium atom by the attachment of tri-tert-butylphenyl (TTBP) group to the selenium atom is inevitable to avoid both of the racemization of the chiral carbon atom and selenophilic attack of the carbon nucleophile. When aromatic compounds are employed as carbon nucleophile, on the other hand, selenophilic attack is rarely observed irrespective of the nature of the aryl group on the selenium atom and introduction of electron withdrawing group into the aryl group on the selenium atom is effective to retard the racemization of the chiral carbon atom.     

Photometric determination of selenium with ferrocene

A sensitive spectrophotometric method for the determination of selenium has been developed. The method depends on a redox reaction between selenious acid in 8M hydrochloric acid and a chloroform solution of ferrocene. One mole of selenious acid produces 4 moles of ferricenium ions, which are then oxidized by bromine water. The resulting iron(III) is reduced to iron(II) and determined with 1,10-phenanthroline. The relative standard deviation for 20 mug of selenium was 1.1%. The apparent molar absorptivity of the final solution, referred to selenious acid, is 4.23 x 10(4) 1. mole(-1). cm(-1) at 512 nm. This method has been used to determine selenium in copper metal.     

空心碳球负载二硫化硒复合材料作为锂离子电池正极材料

制备了一种空心碳球负载二硫化硒(SeS₂@HCS)复合材料作为锂离子电池正极材料。通过扫描电子显微镜(SEM),X射线衍射(XRD)以及氮气吸脱附测试(BET)等对产物形貌、组成和结构进行了表征。实验结果显示,采用模板法结合化学聚合法可以合成形貌均一、单分散的空心碳球;其直径约为500 nm,壁厚约为30 nm。进一步采用熔融灌入法可以得到空心碳球负载二硫化硒复合材料。将所制备复合材料组装成电池进行电化学性能测试,与原始二硫化硒块体材料相比,SeS₂@HCS复合材料具有更高的初始容量(100 mA·g^-1电流密度下,初始放电容量为956 mAh·g^-1)和更长的循环寿命(100 mA·g^-1电流密度下,循环200圈),同时显示出更优异的倍率性能。研究结果表明该复合材料是一种具有应用前景的新型锂离子电池正极材料。     

Cathodic stripping voltammetric determination of selenium(IV) at a thin-film mercury electrode in a thiocyanate-containing electrolyte

The well-known method for the determination of selenium(IV), which is based on the cathodic stripping voltammetry of copper(I) selenide, has been adapted for application at the thin-film mercury electrode on glassy carbon (TFME). Insufficient reproducibility and sensitivity have been overcome by using a 0.1 mol/L HClO₄ electrolyte solution containing 0.02 mol/L thiocyanate ions. Thiocyanate ions have been found to increase the peak height of the selenium response and shift it to more positive potentials. This behaviour is explained by an adsorption of SCN^– at the interface glassy carbon/Cu₂Se and its action as an electron transfer catalyst between glassy carbon and copper(I) selenide. A 3σ-detection limit of 75 ng/L Se^(IV) has been achieved. The relative standard deviation is 5.2% at 5 μg/L selenium(IV). The influence of cadmium(II), arsenic(III), zinc(II), iron(III) and lead(II) ions on the selenium response has been studied. In case of lead ions, a new signal occurred at more negative potentials than the reduction of Cu₂Se. This signal, which is probably due to the reduction of PbSe, can also be used for the determination of selenium(IV).     

Extraction and preconcentration of selenium from aqueous solutions and its determination in water and hair samples by atomic-absorption spectrophotometry

Several organic solvents, including benzene, xylene, toluene, nitrobenzene, chloroform, carbon tetrachloride, chlorobenzene and high molecular-weight pyridines such as 4-(5-nonyl)pyridine, 2-hexyl-pyridine and benzylpyridine have been investigated as components of systems for the extraction and preconcentration of selenium from nitric acid solutions containing iodide. The results are discussed in terms of choice of reagents and the acid and iodide concentrations, and of several other parameters affecting the extraction. The utility of the method for separation of selenium from aqueous solution has been evaluated. The method has been used for preconcentration of trace levels of selenium from water and hair samples for determination by atomic-absorption spectrophotometry.     

Study of the bioavailability of selenium in cows’ milk after a supplementation of cow feed with different forms of selenium

The purpose of the work described in this paper was to develop an easy and quick in-vitro method for comparing the bioavailability of selenium in cows’ milk after different cow feed. The study focuses on bioavailability differences resulting from the use of different selenium species (organic selenium as selenised yeast and sodium selenite) for supplementation of forage. A procedure for determination of selenium in cows’ milk and dialysates, by hydride-generation atomic-fluorescence spectrometry (HG-AFS) after microwave-assisted acid digestion, was optimised. The results show it is possible to obtain cows’ milk enriched with selenium at different concentration without altering the original composition of the milk. The bioavailability was statistically greater for cows’ milk obtained after supplementation of forage with organic selenium at levels of 0.4 and 0.5 μg Se g⁻¹ than for that obtained after supplementation with inorganic and organic selenium at levels of 0.2 and 0.3 μg Se g⁻¹.     

The determination of selenium in water samples from the environment

A method for the determination of selenium by preconcentration and thermal neutron activation is presented. Selenium is adsorbed on active charcoal after reduction to the elemental state. By varying the conditions of the reduction, it is possible to measure the total selenium content and tetravalent selenium separately. The contribution of hexavalent selenium is obtained by substraction. The lower limit of determination is 5 ng°1⁻¹. About 40 samples per day can be handled by one analyst. The preconcentration can be performed at the sampling site resulting in samples, which can be stored easily for later analyses by neutron activation.     

Cathodic stripping voltammetric determination of selenium(IV) at a thin-film mercury electrode in a thiocyanate-containing electrolyte

The well-known method for the determination of selenium(IV), which is based on the cathodic stripping voltammetry of copper(I) selenide, has been adapted for application at the thin-film mercury electrode on glassy carbon (TFME). Insufficient reproducibility and sensitivity have been overcome by using a 0.1 mol/L HClO₄ electrolyte solution containing 0.02 mol/L thiocyanate ions. Thiocyanate ions have been found to increase the peak height of the selenium response and shift it to more positive potentials. This behaviour is explained by an adsorption of SCN^– at the interface glassy carbon/Cu₂Se and its action as an electron transfer catalyst between glassy carbon and copper(I) selenide. A 3σ-detection limit of 75 ng/L Se^(IV) has been achieved. The relative standard deviation is 5.2% at 5 μg/L selenium(IV). The influence of cadmium(II), arsenic(III), zinc(II), iron(III) and lead(II) ions on the selenium response has been studied. In case of lead ions, a new signal occurred at more negative potentials than the reduction of Cu₂Se. This signal, which is probably due to the reduction of PbSe, can also be used for the determination of selenium(IV). Received: 13 November 1996 / Revised: 19 December 1996 / Accepted: 24 December 1996     

Activation analysis of selenium in cancer research

The method described in a previous work to separate trace amounts of selenium in organic samples without using a carrier, based on the adsorption on active carbon filters of the complex formed with ammonium pyrrolidindithiocarbamate (APDC) at pH 1.5–2, has been applied to urine samples from 15 females patients suffering from cervical uterine cancer. With this type of sample the method reaches a maximum sensitivity (few ppb) with a good statistical variation (±12%). Since the highest concentration of selenium in human tissues is found in the kidney, and the elimination of this element is mainly by the urine, the method seems to be a powerful tool in the research about the human metabolism of selenium. This paper shows a possible relation of selenium concentration in human urine and the evolution time of cervical uterine cancer, in spite of limits imposed by the statistical error plus the inhomogeneity of the sample.     

Separation and determination of selenium in rocks, marine sediments and plankton by direct evolution with the bromide-condensed phosphoric acid reagent

A new method is presented for the quantitative separation and determination of selenium by direct evolution with the bromide-condensed phosphoric acid reagent (Br(-)-CPA) from rocks, marine sediments and plankton. In the reaction with the Br(-1)-CPA, selenium(IV) and (VI) in the solid samples are evolved as selenium tetrabromide, and can be collected in an absorbing solution of 0.3M hydrochloric acid and 06M perchloric add (1:1), and then determined spectrophotometrically with 4-substituted o-phenylenediamines followed by the extraction of the resulting 5-substituted piazselenol into toluene. Elemental selenium and selenide do not react with the Br(-)-CPA, but can be determined after oxidation to selenite with potassium iodate. Therefore, successive distillations, the first with Br(-)-CPA and the second with IO(3)(-)-Br(-)-CPA, give a satisfactory means of diflerential determination of selenium(IV) and (VI), and elemental selenium and selenide. This method can be successfully applied for the separation of selenium in the neutron-activation analysis of standard rock samples, marine sediments and plankton, giving good and reliable results.     

Materials and biological applications of 1,2,3-selenadiazoles: a review

In recent years, chemistry of metal-nitrogen–bonded compounds have attracted tremendous attention mainly because of unusual properties resulting from such a bond involving carbon and other heteroatoms. M?N–bonded compounds, when containing group VI elements, especially selenium, has attracted great attention in materials chemistry. In addition, the increased interest in synthesis of N-containing bioactive compounds with other heteroatoms such as selenium, sulfur, etc is mainly because of their tremendous potential as antioxidants, additives, dyes for polymers, and as insecticides, in solvent extraction, and in nanotechnology. Thus, the synthesis and applications of 1,2,3-selenadiazoles have attracted recent interest of materials scientists, including nanotechnologists, pharmaceutical chemists, and organic chemists. The chemistry of 1,2,3-selenadiazoles is highly rich and has been practiced ever since its first report in 1972. Such N-containing Se-heterocycles form several types of selenadiazoles that are a rich source of selenium for semiconductor nanoparticles of metal selenides. The materials chemistry of such molecules has been documented for over three decades, and their great scope in semiconductors has emerged. This review article is an attempt to bring a variety of materials and biological application of 1,2,3-selenadiazoles for better understanding of the researchers.     

Relationship between the cervical uterine cancer evolution and selenium concentration in urine determied by NAA

Neutron activation analysis of Se in urine reaches an optimum sensitivity (few ppb) and precision (±12%) when the traces are complexed without using a carrier by ammonium pryrrolidindithiocarbamate (APDC) at pH 1.5–2 and adsorbed on activated carbon filters. In this way the selenium traces analysis have been carried out through^77mSe in 45 urine samples on a pre-separation basis by cyclic activation ofthe carbon filters. The selenium concentration in our blanks is virtually zero, because APDC proved to be selnium free and selenium mass in 50 mg of activated carbon used as a filter is 20 times below our qualitative detection limit and 144 times below our quantitative detection limit. The samples were first of day urine from healthy and ill women suffering cervical uterine cancer, at different evolution stages: incipient, intemediate and advanced, with no treatment, and surgery, radiotherapy, chemotherapy, or a combined treatment. The results show a consistent tred to increase the selenium trace concentration during the intemediate stage, whereas it is the same than nomal for incipient cases, and it decreases to the lowest concentrations for advanced cases.     

活性炭吸附-火焰原子吸收光谱法测定粗硒中的金

建立了活性炭吸附-火焰原子吸收光谱法测定粗硒中金量的分析方法。讨论了称样量、溶样条件和活性炭的灰化程度对金量测定的影响,并且对火焰原子吸收光谱法与火试金法测定粗硒中的金量做了比较。火焰原子吸收光谱法和火试金法测定的相对标准偏差分别为1.3%~5.9%和0.91%~7.8%;加标回收率分别为93.1%~100.7%和94.8%~102.2%。结果表明,方法有较好的精密度和准确度,并且具有较强的实用性。