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Seleno-polysaccharides have become a major topic for research owing to their high anti-oxidative capacity and immune-enhancing activities. In this study, galactomannan (GM) was isolated from Sesbania cannabina, and next modified using HNO 3 -Na 2 SeO 3 method to obtain six varieties of seleno-galactomannans (SeGMs). FT-IR and GPC results showed the changes in chemical structure of SeGMs, indicating successful combination of selenium and GM. By measuring superoxide dismutase and malondialdehyde, the SeGMs showed a stronger protective effect against H 2 O 2 -induced oxidative damage in vitro than unmodified GM using macrophage RAW264.7 cell as a model, and the effect of SeGMs-14 was prominent. However, the selenylation modification did not show any obvious effect on the immunomodulatory activity of GM, as determined by the index of tumor necrosis factor-α, interleukin-6, and interleukin-1β. Overall, the prepared SeGMs from galactomannan could potentially serve as a dietary supplement of Se or an organic antioxidant., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Background: Gracilaria has been shown to be an important source of marine bioactive natural biomaterials and compounds. Although there are no enough patents used Gracilaria worldwide, the current study tries to put the Gracilaria on the spot for further important patents in the future., Objective: The current study investigates the pharmaceuticals and biochemical activity of Gracilaria because no previous studies have been carried out to examine the biochemical and pharmaceutical activates of Gracilaria from the Suez Canal of Egypt as an excellent source for bioactive compounds., Methods: Different advanced experimental models and analytical techniques, such as cytotoxicity, total antioxidant capacity, anticancer, and anti-inflammatory profiling were applied. The phytochemical analysis of different constituents was also carried out., Results: The mineral analysis revealed the presence of copper (188.3 ppm) and iron (10.07 ppm) in addition to a remarkable wealth of selenium and sulfur contents giving up to 36% of its dry mass. The elemental analysis showed high contents of sulfur and nitrogen compounds. The GCMS profiling showed varieties of different bioactive compounds, such as fatty acids, different types of carotenoids in addition to pigments, alkaloids, steroids. Many other compounds, such as carbohydrates and amino acids having antioxidant, anti-inflammatory, and antiviral activities, etc. were identified. The cytotoxicity activity of Gracilaria marine extract was very effective against cancerous cell lines and showed high ability as a potent antitumor due to their bioactive constituents. Specialized screening assays using two anticancer experimental models, i.e., PTK and SKH1 revealed 77.88% and 84.50% inhibition anticancer activity; respectively. The anti-inflammatory activities investigated using four different experimental models, i.e., COX1, COX2, IL6, and TNF resulted in 68%, 81.76%, 56.02% and 78.43% inhibition; respectively. Moreover, Gracilaria extracts showed potent anti-Alzheimer with all concentrations., Conclusion: Gracilaria proved to be a multi-product source of marine natural products for different biotechnological applications. Our recommendation is to investigate the Gracilaria bioactive secondary metabolites in order to create and innovate in more patents from current important seaweeds (Gracilaria)., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.net.)

The fungi Aureobasidium pullulans, Mortierella humilis, Trichoderma harzianum and Phoma glomerata were used to investigate the formation of selenium- and tellurium-containing nanoparticles during growth on selenium- and tellurium-containing media. Most organisms were able to grow on both selenium- and tellurium-containing media at concentrations of 1 mM resulting in extensive precipitation of elemental selenium and tellurium on fungal surfaces as observed by the red and black colour changes. Red or black deposits were confirmed as elemental selenium and tellurium, respectively. Selenium oxide and tellurium oxide were also found after growth of Trichoderma harzianum with 1 mM selenite and tellurite as well as the formation of elemental selenium and tellurium. The hyphal matrix provided nucleation sites for metalloid deposition with extracellular protein and extracellular polymeric substances localizing the resultant Se or Te nanoparticles. These findings are relevant to remedial treatments for selenium and tellurium and to novel approaches for selenium and tellurium biorecovery.

Cadmium zinc telluride selenide (Cd 1-x Zn x Te 1-y Se y or CZTS) is one of the emerging CdTe-based semiconductor materials for detecting X- and gamma-ray radiation at or near room temperature (i.e., without cryogenic cooling). Potential applications of CZTS sensors include medical imaging, X-ray detection, and gamma-ray spectroscopy. Chemical passivation of CZTS is needed to reduce the conductivity of Te-rich surfaces, which reduces the noise and improves the device performance. In this study, we focus on the effect of surface passivation of CZTS using a 10% aqueous solution of ammonium fluoride. The effects of the chemical treatment were studied on the leakage current, charge transport measured as the electron mobility-lifetime (µτ) product, and the spectral resolution measured as the full-width at half-maximum (FWHM) of specific peaks. After passivation, the leakage current increased and began to decrease towards pre-passivation levels. The energy resolutions were recorded for eight applied voltages between -35 V and -200 V. The results showed an average of 25% improvement in the detector's energy resolution for the 59.6 keV gamma peak of Am-241. The electron µτ product was unchanged at 2 × 10 -3 cm 2 /V. These results show that ammonium fluoride is effective for chemical passivation of CZTS detectors.

An electrochemical biosensor was developed based on a steric hindrance hybridization assay to allow the highly sensitive detection of streptavidin. In the steric hindrance hybridization assay, the signaling strand DNA (sig-DNA) was labeled at the 3' end with CdSe quantum dots (QDs) and at the 5' end with biotin, and capturing strand DNA (the complementary strand of sig-DNA) was labeled at the 5' end with thiol. The steric hindrance effect generated by streptavidin which was bound with the signaling DNA strand. The streptavidin limited the ability of the sig-DNA to hybridize with the cap-DNA, which were linked on the surface of a gold electrode. Therefore, the concentration of streptavidin was detected indirectly based on the concentration of CdSe QDs on the electrode surface. The concentration of CdSe QDs on the electrode surface was detected by differential pulse anodic stripping voltammetry. Under optimal conditions, the streptavidin detection range using the as-prepared biosensor was 1.96pg/mL to 1.96µg/mL and the detection limit was 0.65pg/mL. The experimental results showed that the electrochemical biosensor could detect streptavidin rapidly and accurately., (Copyright © 2017. Published by Elsevier B.V.)

Selenate and selenite are considered emerging contaminants and pose a risk to living organisms. Since selenium anion species are at low concentration in aquatic environments, materials for its retention are required to enable monitoring. Herein, hydrotalcite was calcined and characterised to investigate sorption and desorption of selenite and selenate in competition with nitrate, sulfate and phosphate. Sorption experiments were carried out in batch system and desorption by sequential dilution. Selenite and selenate concentration remaining after N desorption steps was determined by mass balance. The isotherms were adjusted to the dual-mode Langmuir-Freundlich model (R 2  > 0.99). Maximum sorption capacity ranged from 494 to 563 meq kg -1 for selenite and from 609 to 659 meq kg -1 for selenate. Sulfate and phosphate ions showed greater competitive effect on the sorption of selenate and selenite, respectively. Low mobilization factors and high sorption efficiency (MF<3%; SE ≈ 100%) indicated that calcined hydrotalcite has the wanted characteristics for retention of relevant selenium anion species in aqueous media., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Selenium (Se) exposure poses potential risks to wildlife at the Salton Sea. Our previous research suggests Chlorella sp. be highly efficient at absorbing and volatilizing Se. In developing an algal treatment system for Se removal, this study further evaluated the performance under the conditions to be encountered in the field using Chlorella pyrenoidosa and Chlorella vulgaris. The results show the algal Se removal efficiency was little affected by photoperiod, yet volatilization became relatively greater in dark/light cycles over a longer term. The rates of Se absorption and volatilization by C. vulgaris were 88% and 77% more, respectively, in the DI water, while C. pyrenoidosa acted oppositely, indicating C. vulgaris will perform better in Se removal if nutrient levels are reduced in advance. The presence of sulfate reduced biomass Se, especially through volatilization, by 8% for C. vulgaris, lessening potential ecotoxicity. Finally, C. vulgaris released biomass Se back to the water column under hypersaline conditions, leading to a 6% increase in water Se concentrations. These results suggest C. vulgaris be the best alga for the treatment of Se laden river water in the Salton Sea area, yet a filtering system is required to prevent Se containing algae from entering food chains., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

This work reports the selenium (Se(IV)) detection and removal from water by ligand functionalized organic-inorganic based novel composite adsorbent. The composite adsorbent was prepared by direct immobilization of N,N'-di(3-carboxysalicylidene)-3,4-diamino-5-hydroxypyrazole onto the mesoporous silica monolith. The adsorbent exhibited distinct color change in the presence of various concentrations of Se(IV). This was characterized by UV-vis spectroscopy, and the color change was observed by naked-eye observation. The detection limit was determined to be 1.14 μg/L. The effect of solution pH, interferential metal ions, contact time, initial Se(IV) concentration, and adsorbent regeneration were evaluated. The maximum sorption capacity was determined based on the initial concentration. The data fitted well to the Langmuir isotherm model, and the maximum Se(IV) sorption capacity was 111.12 mg/g. The presence of diverse competing ions did not affect the Se(IV) sorption capacity, and the adsorbent had almost no sorption capacity for these coexisting ions, which suggests the high selectivity to Se(IV) ions. The adsorbed Se(IV) was eluted with suitable eluent (0.10 M NaOH) and simultaneously regenerated into the initial form for the next operation. The excellent reusability of the adsorbent was justified after eight consecutive sorption-elution-regeneration cycles. The proposed adsorbent is cost-effective and environmentally friendly and a potential candidate for treatment of water containing Se(IV)., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A preconcentration system has been developed to determine inorganic selenium species. Selenium was retained by a column filled with polyvinyl chloride (PVC) with lanthanum hydroxide co-precipitation. Speciation was achieved by selective photoreduction previous Se preconcentration. The retention pH was optimized at 10.0. Two multivariate calibrations and a central composite design were employed for optimization of the system. Sample, reagents and acid flow rates are significant variables affecting the system. Employing HG-ICP-OES as detection, the optimized system reached a detection limit of 0.03μg/L, and an enhancement factor of 14875 (25 for preconcentration system, 595 for hydride generation). To verify the method' accuracy, two certified reference materials, BCR® 414 Plankton & IRMM-804 Rice Flour, were analysed. The system was applied to inorganic selenium speciation in several Argentinean beverages to estimate their selenium contribution to diet., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Solidified floating organic drop microextraction was combined with electrothermal vapourisation inductively coupled plasma mass spectrometry for Se species in Se-rich tea leaves and tea infusion, including total, suspended, soluble, organic and inorganic Se as well as Se(IV) and Se(VI). Ammonium pyrrolidinedithiocarbamate was used as both chelating reagent and chemical modifier in this study. Se(IV) and Se(VI) were separated at pH range of 2.0-5.0. An enrichment factor of 500 was obtained for Se(IV) from this method. Under the optimum conditions, the detection limits for Se(IV) and Se(VI) were 0.19 and 0.26pgmL(-1), respectively. The relative standard deviations were less than 5.5% (c=0.1ngmL(-1), n=9). This method was applied for Se species, its content and distribution in Se-rich tea leaves and tea infusion with satisfactory results. The recoveries of spike experiments are in the range of 92.2-106%. A certified reference material of tea leaves was analyzed by this method, and the results were in agreement with certified values., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The determination of hormone-binding sites in plants is essential in understanding the mechanisms behind hormone function. Salicylic acid (SA) is an important plant hormone that regulates responses to biotic and abiotic stresses. In order to label SA-binding sites in plant tissues, a quantum dots (QDs) probe functionalized with a SA moiety was successfully synthesized by coupling CdSe QDs capped with 3-mercaptopropionic acid (MPA) to 4-amino-2-hydroxybenzoic acid (PAS), using 1-ethyl-3-(3-dimethyllaminopropyl) carbodiimide (EDC) as the coupling agent. The probe was then characterized by dynamic light scattering and transmission electron microscopy, as well as UV/vis and fluorescence spectrophotometry. The results confirmed the successful conjugation of PAS to CdSe QDs and revealed that the conjugates maintained the properties of the original QDs, with small core diameters and adequate dispersal in solution. The PAS-CdSe QDs were used to detect SA-binding sites in mung bean and Arabidopsis thaliana seedlings in vitro and in vivo. The PAS-CdSe QDs were effectively transported into plant tissues and specifically bound to SA receptors in vivo. In addition, the effects of the PAS-CdSe QDs on cytosolic Ca(2+) levels in the tips of A. thaliana seedlings were investigated. Both SA and PAS-CdSe QDs had similar effects on the trend in cytosolic-free Ca(2+) concentrations, suggesting that the PAS-CdSe QDs maintained the bioactivity of SA. To summarize, PAS-CdSe QDs have high potential as a fluorescent probe for the in vitro/in vivo labeling and imaging of SA receptors in plants., (Copyright © 2014 John Wiley & Sons, Ltd.)

A model small-scale field experiment was set up to investigate selenium (Se) uptake by four different varieties of broccoli plants, as well as the effect of Se foliar application on the uptake of essential elements for plants calcium (Ca), copper (Cu), iron (Fe), potassium (K), magnesium (Mg), manganese (Mn), phosphorus (P), sulfur (S), and zinc (Zn). Foliar application of sodium selenate (Na2SeO4) was carried out at two rates (25 and 50 g Se/ha), and an untreated control variant was included. Analyses of individual parts of broccoli were performed, whereby it was found that Se in the plant accumulates mainly in the flower heads and slightly less in the leaves, stems, and roots, regardless of the Se rate and broccoli variety. In most cases, there was a statistically significant increase of Se content in all parts of the plant, while there was no confirmed systematic influence of the addition of Se on the changing intake of other monitored elements. Selenization of broccoli leads to an effective increase in the Se content at a rate of 25 g/ha, whereas the higher rate did not result in a substantial increase of Se content compared to the lower rate in all varieties. Therefore, the rate of 25 g/ha can be recommended as effective to produce broccoli with an increased Se content suitable for consumption. Moreover, Se application resulted in an adequate increase of the main organic compounds of Se, such as selenocystine (SeCys2), selenomethionine (SeMet), and Se-methylselenocysteine (Se-MeSeCys).

Cadmium sulfide (CdS) nanoparticles (NPs) were synthesized by using banana peel extract as a convenient, non-toxic, eco-friendly 'green' capping agent. Cadmium nitrate and sodium sulfide are main reagents. A variety of CdS NPs are prepared through changing reaction conditions (banana extracts, the amount of banana peel extract, solution pH, concentration and reactive temperature). The prepared CdS colloid displays strong fluorescence spectrum. X-ray diffraction analysis demonstrates the successful formation of CdS NPs. Fourier transform infra-red (FTIR) spectrogram indicates the involvement of carboxyl, amine and hydroxyl groups in the formation of CdS NPs. Transmission electron microscope (TEM) result reveals that the average size of the NPs is around 1.48 nm.

HPLC-ICP-MS based on ion-paired reversed phase chromatography for the selenium speciation using the mixture of 1-butanesulfonic acid (BA) and trifluoroacetic acid (TFA) as the mixed ion-pairing reagents was developed and applied to selenium-enriched pakchoi (Brassica chinensis Jusl var parachinensis (Bailey) Tsen & Lee). Several conditions of ion-paired reversed phase HPLC-ICP-MS, such as pH of the mobile phase, concentration of ion pairing reagents, types and length of analytical column, and flow rate of the mobile phase, were optimised for five selenium species; selenate (Se(VI)), Selenite (se(IV)), selenocysteine (SeC), Se-methylselenocysteine (SeMC) and selenomethionine (SeM). The results showed that the optimum conditions for pH, BA and TFA condition, type of separating column and flow rate, were 4.5, 8mM, 4mM, C18 (250 mm length × 4.6mm I.D) and 1.2 mL min(-1), respectively. These conditions archived separation of the organic selenium species. The limits of detection (LOD) and quantitation (LOQ) of each selenium species were lower than 5 and 16 ng Se mL(-1), respectively. Furthermore, the recoveries of most selenium species were good, except for SeC. In this research, selenium-enriched pakchoi was cultivated by supplementing inorganic selenium from selenate into sand. The result showed that inorganic selenium, SeMC, SeM and several unknown species were found in selenium-enriched pakchoi sprouts by using the proposed method. Thereby, the biotransformation of selenate in pakchoi was similar to other Brassicaceae plants such as kale and broccoli., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Background: Selenium (Se) is an essential dietary mineral and Radix puerariae (RP) (the dried root of Pueraria lobata Willd.) is a botanical supplement widely used as a nutraceutical. Food enriched with Se provides a feasible and economic approach for production of organic Se compounds. However, little is known about Se-enriched RP and the structure of Se-containing polysaccharides and proteins derived from Se-enriched RP., Results: The organic form of Se accounted for 82.42% of total content. Purification by DEAE-52 and Sephadex G-100 column chromatography yielded three single fractions--RP-SeP-11, RP-SeP-22 and RP-SeP-33--with Se contents of 0.9562 × 10⁻³, 0.6113 × 10⁻³ and 0.3827 × 10⁻³ g kg⁻¹, respectively. RP-SeP-11 (3.5 kDa) was made of glucose, RP-SeP-22 (19.6 kDa) was composed of xylose and glucose, and RP-SeP-33 (97.9 kDa) was made up galactose, mannose and glucose. Two Se-containing proteins were obtained with Se content of 3.175 × 10⁻³ and 4.328 × 10⁻³ g kg⁻¹, respectively. One appeared as three subunits with molecular masses of 43.0, 29.0 and 17.8 kDa while the other appeared as two subunits with molecular masses of 43.0 and 26.3 kDa., Conclusion: The results provide a basis for promoting the utilisation of RP resources enriched with Se as a promising tool for the food industry and are significant for its contribution to Se biochemistry in plants., (© 2013 Society of Chemical Industry.)

Selenium (Se) species, Se-methyl-seleno-cysteine (MeSeCys), seleno-cystine (SeCys2), seleno-methionine (SeMet), selenite (SeO3(2-)) and selenate (SeO4(2-)), in the three main anatomical tissues of bay scallops (Argopecten irradians), the adductor muscle, the mantle and the visceral mass, were completely released by enzymatic hydrolysis and detected by high performance liquid chromatography (HPLC) in combination with inductively coupled plasma mass spectrometry (ICP-MS). For the thorough hydrolysis of the proteins to free the Se species, bay scallop tissues were pre-treated (pre-hydrolyzed) with papain in a 1molL(-1) sodium bicarbonate solution containing 5mmolL(-1) sodium thiosulfate at 30-40°C for 24h, then hydrolyzed by the combination of Flavourzyme(®) 500 L, carboxypeptidase Y and trypsin (3+1+1) at 45°C, at a constant pH of 8.00 for 6h. Under the optimized conditions, the quantification limits of MeSeCys, SeCys2, SeMet, SeO3(2-) and SeO4(2-) were 0.69, 0.48, 0.93 0.53 and 1.22μgL(-1), respectively (equivalent to 0.14, 0.097, 0.19, 0.11 and 0.24μgg(-1) for real samples). The working curves in the concentration ranges of 2 to 500μgL(-1) were linear with all the RSD (n=5) smaller than 15% and regression coefficients greater than 0.999. The recoveries of the species for spiked samples at 4μgg(-1) (equivalent to 20μgL(-1) in the final hydrolyzates) levels all exceeded 90%. The developed method was validated by the determination of SeMet in SELM-1, a Se enriched yeast certified reference material (CRM). Selenate was the only absent species, whereas the other four species did exist in bay scallops., (Copyright © 2013 Elsevier B.V. All rights reserved.)

A novel method based on dispersive liquid liquid microextraction (DLLME) followed by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) determination was proposed for the speciation of inorganic selenium by using 5-mercapto-3-phenyl-1,3,4-thiadiazole-2-thione potassium salt (Bismuthiol II) as both chelating reagent and chemical modifier. In this method, 500 μL ethanol (as disperser solvent) containing 70 μL chloroform (as extraction solvent) and 0.2 g L(-1) Bismuthiol II (as chelating reagent) was rapidly injected into a sample solution to form cloudy solution. The complex of Se(IV) with Bismuthiol II was rapidly extracted into the extraction solvent at pH 2.0, while Se(VI) was remained in the aqueous solutions. Thus, the separation of Se(IV) and Se(VI) could be realized. After centrifugation, the complex of Se(IV) and Bismuthiol II concentrated in the extraction solvent was introduced into the ETV-ICP-MS for determination of Se(IV). Se(VI) was reduced to Se(IV) prior to determination of total selenium, and its assay was based on subtracting Se(IV) from total selenium. The main factors influencing the DLLME and the vaporization behavior of selenium in ETV were investigated systematically. Under the optimal conditions, the limit of detection (LOD) for Se(IV) was 0.047 ng mL(-1). The relative standard deviation (RSD) was 7.2% (CSe(IV)=1.0 ng mL(-1), n=8) with an enhancement factor of 64.8-fold from only 5 mL of water sample. The proposed method was successfully applied to the speciation of inorganic selenium in different environmental water samples with recoveries ranging from 94.8 to 108% for the spiking samples. In order to validate the proposed method, a Certified Reference Material of Environment Water (GBW(E)080395) was analyzed, and the determined value obtained was in good agreement with the certified value., (Copyright © 2013 Elsevier B.V. All rights reserved.)

A new PEGylation reagent enabling selective modification of free thiol groups is described in this article. The reagent was synthesized by attaching linear polyethylene glycol (PEG) N-hydroxysuccinimide to selenocystamine. The reaction was very fast, resulting in over 95% conversion yield. The active group of this new PEG-Se reagent is a diselenide, reacting with thiols via thiol/diselenide exchange reaction. Recombinant human granulocyte colony-stimulating factor (rhG-CSF) with an unpaired cysteine at the position 18 (Cys18) was used as a model protein. It was comparatively PEGylated with the new PEG-Se reagent, as well as with commercially available maleimide (PEG-Mal) and ortho-pyridyl disulfide (PEG-OPSS) PEG reagents. The highest PEGylation yield was obtained with PEG-Mal, followed by PEG-OPSS and PEG-Se. The reaction rates of PEG-Mal and PEG-Se were comparable, while the reaction rate of PEG-OPSS was lower. Purified monoPEGylated rhG-CSF conjugates were characterized and compared. Differences in activity, stability, and in vivo performance were observed, although all conjugates contained a 20 kDa PEG attached to the Cys18. Minor conformational changes were observed in the conjugate prepared with PEG-Mal. These changes were also reflected in low in vitro biological activity and aggregate formation of the maleimide conjugate. The conjugate prepared with PEG-Se had the highest in vitro biological activity, while the conjugate prepared with PEG-OPSS had the best in vivo performance.

The removal of aqueous Se(VI) from a simulated groundwater by granular iron (GI), organic carbon (OC), and a mixture of these reactive materials (GI-OC) was evaluated in laboratory batch experiments. The experiments were performed under anoxic conditions to simulate subsurface treatment. A total reaction time of 120 h (5 d) was chosen to investigate the rapid changes in speciation occurring over reaction times that are reasonable for permeable reactive barrier (PRB) systems. After 120 h, concentrations of Se decreased by >90% in the GI system, 15% in the OC system and 35% in the GI-OC mixture. Analysis of the materials after contact with Se using synchrotron-radiation based X-ray absorption spectroscopy (XAS) indicated the presence of Se(IV) and Se(0) on the margins of GI grains after 6h with evidence of SeO and SeSe bonding, whereas Se(VI) was not observed. After 72 h, Se(0) was the only form of Se present in the GI experiments. In the OC batches, the XAS analysis indicated binding consistent with sorption of aqueous Se(VI) onto the OC with only minor reduction to Se(IV) and Se(0) after 120 h. Selenium XAS spectra collected for the GI-OC mixture were consistent with spectra for Se(IV) and Se(0) on both the margins of GI grains and OC particles, suggesting that the presence of dissolved Fe may have mediated the reduction of sorbed Se(VI). The results suggest that the application of granular Fe is effective at inducing aqueous Se removal in anoxic conditions through reductive precipitation processes., (Copyright © 2012 Elsevier B.V. All rights reserved.)

The isotope (79)Se may be of great concern with regard to the safe disposal of nuclear wastes in deep geological repositories due to its long half-life and potential mobility in the geosphere. The Se mobility is controlled by the oxidation state: the oxidized species (Se(IV)) and (Se(VI)) are highly mobile, whereas the reduced species (Se(0) and Se(-II)) form low soluble solids. The mobility of this trace pollutant can be greatly reduced by interacting with the various barriers of the repository. Numerous studies report on the oxidized species retention by mineral phases, but only very scarce studies report on the selenide (Se(-II)) retention. In the present study, the selenide retention by coprecipitation with and by adsorption on mackinawite (FeS) was investigated. XRD and SEM analyses of the samples reveal no significant influence of Se on the mackinawite precipitate morphology and structure. Samples from coprecipitation and from adsorption are characterized at the molecular scale by a multi-edge X-ray absorption spectroscopy (XAS) investigation. In the coprecipitation experiment, all elements (S, Fe, and Se) are in a low ionic oxidation state and the EXAFS data strongly point to selenium located in a mackinawite-like sulfide environment. By contacting selenide ions with FeS in suspension, part of Se is located in an environment similar to that found in the coprecipitation experiment. The explanation is a dynamical dissolution-recrystallization mechanism of the highly reactive mackinawite. This is the first experimental study to report on selenide incorporation in iron monosulfide by a multi-edge XAS approach.

Fish are selenium rich foodstuffs and a major selenium source for the Japanese population. Niboshi is processed from Japanese anchovy (Engraulis japonicus) and commonly used to prepare soup stock for Japanese dishes. In this study, we characterized selenium species in the Niboshi extract by ultrafiltration, ion-exchange chromatography and mass spectrometry. Selenium species in the Niboshi were more extractable by polar solvents (water and ethanol) than an apolar one (hexane) along with amino acids and proteinous species. Selenium in the water-extract from the Niboshi was mostly ascribed to organoselenium compounds with a molecular mass less than 5 kDa. Although selenoamino acids and selenoproteins and their fragments were involved in the extract, a large portion of the selenium species appeared to be low-molecular-mass organoselenium compounds other than selenoamino acids and their derivatives. Ion-exchange chromatographic separations revealed that most of the selenium species in the extract possess anionic and/or amphoteric characteristics. One of these selenium species from the Niboshi extract was detected at m/z 577 for 80Se by mass spectrometry subsequent to ion-pair extraction.

A non-chromatographic separation and preconcentration method for Se species determination based on the use of an on-line ionic liquid (IL) dispersive microextraction system coupled to electrothermal atomic absorption spectrometry (ETAAS) is proposed. Retention and separation of the IL phase was achieved with a Florisil(®)-packed microcolumn after dispersive liquid-liquid microextraction (DLLME) with tetradecyl(trihexyl)phosphonium chloride IL (CYPHOS(®) IL 101). Selenite [Se(IV)] species was selectively separated by forming Se-ammonium pyrrolidine dithiocarbamate (Se-APDC) complex followed by extraction with CYPHOS(®) IL 101. The methodology was highly selective towards Se(IV), while selenate [Se(VI)] was reduced and then indirectly determined. Several factors influencing the efficiency of the preconcentration technique, such as APDC concentration, sample volume, extractant phase volume, type of eluent, elution flow rate, etc., have been investigated in detail. The limit of detection (LOD) was 15 ng L(-1) and the relative standard deviation (RSD) for 10 replicates at 0.5 μg L(-1) Se concentration was 5.1%, calculated with peak heights. The calibration graph was linear and a correlation coefficient of 0.9993 was achieved. The method was successfully employed for Se speciation studies in garlic extracts and water samples., (Copyright © 2011 Elsevier B.V. All rights reserved.)

The H(2)-based membrane biofilm reactor (MBfR) was shown to consistently remove nitrate, nitrite, and selenate at high efficiencies from flue-gas desulfurization brine. Selenate was removed to <50 ppb which is the National Pollutant Discharge Elimination System (NPDES) criteria for the brine to be released into the environment. When selenate was removed to <50 ppb, nitrate and nitrite were still present in the mg/L range which suggests that selenate is able to be secondarily reduced to low levels when nitrate and nitrite serve as the main electron acceptors for bacterial growth. SO(4)(2-) was not removed and therefore did not compete with nitrate and selenate reduction for the available H(2)., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

This paper describes a novel application of tetrabutylammonium hydroxide-modified activated carbon (AC-TBAH) to the speciation of ultra-trace Se(IV) and Se(VI) using LC-ICP-DRC-MS. The anion exchange functionality was immobilized onto the AC surface enables selective preconcentration of inorganic Se anions in a wide range of working pHs. Simultaneous retention and elution of both analytes, followed by subsequent analysis with LC-ICP-DRC-MS, allows to accomplish speciation analysis in natural samples without complicated redox pre-treatment. The laboratory-made column of immobilized AC (0.4 g of sorbent packed in a 6 mL syringe barrel) has achieved analyte enrichment factors of 76 and 93, respectively, for Se(IV) and Se(VI), thus proving its superior preconcentration efficiency and selectivity over common AC. The considerable enhancement in sensitivity achieved by using the preconcentration column has improved the method's detection limits to 1.9-2.2 ng L(-1), which is a 100-fold improvement compared with direct injection. The analyte recoveries from heavily polluted river matrix were between 95.3 and 107.7% with less than 5.0% RSD. The robustness of the preconcentration and speciation method was validated by analysis of natural waters collected from rivers and reservoirs in Hong Kong. The modified AC material is hence presented as a low-cost yet robust substitute for conventional anion exchange resins for routine applications., (Copyright © 2011 Elsevier B.V. All rights reserved.)

An analytical method for selenium species of selenate (SeVI), selenite (SeIV), selenomethionine (SeMet), selenocystine (SeCys2 ) and selenoethionine (SeEt) was established using high performance liquid chromatography with inductively coupled plasma mass spectrometry (HPLC-ICP-MS). A Hamilton PRP X-100 reversed-phase anion exchange column (250 mm x 4.6 mm, 5 microm) with a 5 mmol/L citric acid buffer solution (pH 4.5, adjusted with 20% (v/ v) ammonia) as mobile phase was used for separation, and ICP-MS was used for detection. The five species were completely separated within 21 min. All the linear correlation coefficients of the five selenium species were greater than 0.999 5, and the detection limits of SeVI, SeIV, SeMet, SeCys2, SeEt were 0.4, 0.4, 5.6, 0.9 and 1.2 microg/L, respectively. The extraction procedure was studied for fresh mushroom and pork samples. For water-soluble selenium compounds, citric acid was a good extraction solution, and the recoveries were around 100% for inorganic selenium and in the range of 85.0% - 95.3% for SeMet; but worse for SeCys2 and SeEt. As for the proteinase K, the recoveries of SeCys2 and SeEt were raised to the range of 79.9% -91.5%. The method has the advantages of simple operation and good accuracy, and can be used for the quantitative determination of the five selenium species in food.

Room-temperature ionic liquids (RTILs) improved reversed-phase high performance liquid chromatography (RP-HPLC) on-line combined with inductively coupled plasma mass spectrometry (ICP-MS) was developed for selenium speciation. The different parameters affecting the retention behaviors of six target selenium species especially the effect of RTILs as mobile phase additives have been studied, it was found that the mobile phase consisting of 0.4% (v/v) 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), 0.4% (v/v) 1-butyl-2,3-dimethylimidazolium tetrafluroborate ([BMMIM]BF(4)) and 99.2% (v/v) water has effectively improved the peak profile and six target selenium species including Na(2)SeO(3) (Se(IV)), Na(2)SeO(4) (Se(VI)), L-selenocystine (SeCys(2)), D,L-selenomethionine (SeMet), Se-methylseleno-l-cysteine (MeSeCys), seleno-D,L-ethionine (SeEt) were separated in 8 min. In order to validate the accuracy of the method, a Certified Reference Material of SELM-1 yeast sample was analyzed and the results obtained were in good agreement with the certified values. The developed method was also successfully applied to the speciation of selenium in Se-enriched yeasts and clover. For fresh Se-enriched yeast cells, it was found that the spiked SeCys(2) in living yeast cells could be transformed into SeMet. Compared with other ion-pair RP-HPLC-ICP-MS approaches for selenium speciation, the proposed method possessed the advantages including ability to regulate the retention time of the target selenium species by selecting the suitable RTILs and their concentration, simplicity, rapidness and low injection volume, thus providing wide potential applications for elemental speciation in biological systems., (Copyright © 2010 Elsevier B.V. All rights reserved.)

Increased tightening of air regulations is leading more electric utilities to install flue gas desulfurization (FGD) systems. These systems produce brine containing high concentrations of nitrate, nitrite, and selenate which must be removed before discharge. The H2-based membrane biofilm reactor (MBfR) was shown to consistently remove nitrate, nitrite, and selenate at high efficiencies. The maximum selenate removal flux reached 362 mgSe m(-2)d(-1) and was higher than that observed in earlier research, which shows continual improvement of the biofilm for selenate reduction. A low pH of 6.8 inhibited precipitation when treating actual FGD brine, yet did not inhibit removal. SO4(2-) was not removed and therefore did not compete with nitrate, nitrite, and selenate reduction for the available H2.

This research has demonstrated that the Friedel phase, e.g. a chloride-containing hydrocalumite (Ca(2)Al(OH)(6)Cl(H(2)O)(2) x mH(2)O), can rapidly adsorb large amounts of SeO(4)(2-) (up to 1.37 mmol/g). SeO(4)(2-) is removed via anionic exchange, as evidenced by the expansion of the d-spacing from 0.78 nm of Cl-hydrocalumite to 0.97-0.98 nm of SeO(4)-hydrocalumite. The newly formed SeO(4)-adsorbed hydrocalumite is stable in water at pH 4-13, indicating the strong fixation of selenate within the phase. In contrast, intercalated selenate in the Freidel phase can be recovered by desorbing in the NaCl solution, which can also regenerate and recycle the used adsorbent. The findings in this research strongly suggest that the Friedel phase is a new, environmentally friendly and cost-effective adsorbent to adsorb selenate from wastewater streams and dilute solutions., (2009 Elsevier B.V. All rights reserved.)

Replacement of the native (as-synthesized) ligands of colloidal CdSe QDs with varying concentrations of a series of para-substituted anilines (R-An), where R ranges from strongly electron-withdrawing to strongly electron-donating, decreases the PL of the QDs. The molar ratio of R-An to QD ([R-An]:[QD]) at which the PL decreases by 50% shifts by 4 orders of magnitude over the series R-An. The model employed to describe the data combines a Freundlich binding isotherm (which reflects the dependence of the binding affinity of the amine headgroups of R-An on the substituent R) with a function that describes the response of the PL to R-An ligands once they are bound at their equilibrium surface coverage. The latter function includes as a parameter the rate constant, k(nr), for nonradiative decay of the exciton at a site to which an R-An ligand is coordinated. The value of this parameter reveals that the predominant mechanism of QD-ligand interaction is passivation of Cd(2+) surface sites through sigma-donation for R-An ligands with R = H, Br, OCF(3), and reductive quenching through photoinduced hole transfer for R = MeO, (Me)(2)N.

This work investigates for the first time the potential of mixed-mode (anion-exchange with reversed-phase) high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (ICP-MS) for the simultaneous retention and selective separation of a range of inorganic and organically-bound selenium (Se) species. Baseline separation and detection of selenocystine (SeCys(2)), Se-methyl-selenocysteine (SeMC), selenomethionine (SeMet), methylseleninic acid (MSA), selenite, gamma-glutamyl-methyl-selenocysteine (gamma-glutamyl-SeMC), and selenate in a Se standard mixture by mixed-mode HPLC-ICP-MS was achieved by switching between two citrate mobile phases of different pH and ionic strength within a single chromatographic run of 20 min. Limits of detection obtained for these Se species ranged from 80 ng kg(-1) (for SeMC) to 123 ng kg(-1) (for selenate). Using this approach as developed for selenium speciation, an adequate separation of inorganic and organic As compounds was also achieved. These include arsenite, arsenate, arsenobetaine (AsB) and dimethylarsenic acid (DMA), which may coexist with Se species in biological samples. Application of the newly proposed methodology to the investigation of the elemental species distribution in watercress (used as the model sample) after enzymatic hydrolysis or leaching in water by accelerated solvent extraction (ASE) was addressed. Only SeMet, SeMC and selenate could be tentatively identified in watercress extracts by mixed-mode HPLC-ICP-MS and retention time matching with standards. Recoveries (n=3) of these Se species from samples spiked with standards averaged 102% (for SeMC), 94.9% (for SeMet) and 98.3% (for selenate). Verification of the presence of SeMet and SeMC in an enzymatic watercress extract was achieved by on-line HPLC-ESI MS/MS in selected reaction monitoring (SRM) mode.

Pollution caused by boric acid and toxic anions such as As(V), Cr(VI) and Se(VI) is hazardous to human health and environment. The sorption characteristics of these environmentally significant ionic species on allophane-like nanoparticles were investigated in order to determine whether allophane can reduce their mobility in the subsurface environment at circum-neutral pH condition. Solutions containing 100 or 150 mmol of AlCl(3)x6H(2)O were mixed to 100 mmol of Na(4)SiO(4) and the pH were adjusted to 6.4+/-0.3. The mineral suspensions were shaken for 1h and incubated at 80 degrees C for 5 days. Appropriate amounts of As, B, Cr and Se solutions were added separately during and after allophane precipitation. The results showed that As(V) and boric acid can be irreversibly fixed during co-precipitation in addition to surface adsorption. However, Cr(VI) and Se(VI) retention during and after allophane precipitation is mainly controlled by surface adsorption. The structurally fixed As(V) and boric acid were more resistant to release than those bound on the surface. The sorption characteristics of oxyanions and boric acid were also influenced by the final Si/Al molar ratio of allophane in which Al-rich allophane tend to have higher uptake capacity. The overall results of this study have demonstrated the role of allophane-like nanoparticles and the effect of its Si/Al ratio on As, B, Cr and Se transport processes in the subsurface environment.

Removal of selenate ion from the liquid phase by hydroxysulfate green rust (GR(SO4)) was investigated in the pH range from 7.5 to 10.0. Batch tests showed that the total selenium concentration decreased more rapidly with increasing pH. However, the amount of selenium removed from the liquid phase increased as the pH decreased. X-ray absorption spectrometric analysis demonstrated that the Se(VI) in the selenate ion was reduced to elemental selenium Se(0) at pH 9.0, whereas the existence of small amount of intermediate Se(IV) was detected at pH 7.5. Comparing the mass balance of the amount of consumed ferrous iron in GR(SO4), [DeltaFe(II)], and the amount of Se(VI) removed from the liquid phase, [DeltaSe(VI)], [DeltaFe(II)] is approximately six times larger than [DeltaSe(VI)] in mol units. This is also indirect but convincing evidence that the oxidation of Fe(II) in GR(SO4) leads to the simultaneous reduction of Se(VI) to Se(0). Powder X-ray diffraction analysis showed that the end product of GR(SO4) depends on the pH: magnetite for pH>9.0, goethite for pH<8.0, and their mixture at pH 8.5. These results indicate that the solution pH has a significant effect on the reaction path of selenate removal by GR(SO4).

Bioremediation of toxic nonmetal and metalloid oxyanions is of great interest. In this study, among 148 bacterial isolates from two types of polluted water, strain STG-83 showed maximum oxyanion reduction and resistance ability. Sequencing of the 16S rDNA gene of STG-83 showed that the strain is closely related to Bacillus pumilus and morphological and biochemical tests confirmed the result. The strain was nitrate negative, but it could reduce half of tellurite in solution containing 1-mM concentration and completely reduced selenite and selenate in solutions containing 1-mM concentrations. Both reduction to elemental form and volatilization occurred in case of all oxyanions tested, according to hydride generation atomic absorption spectroscopy and proton induced X-ray emission analytical methods. The strain was able to tolerate remarkably high concentrations of selenite (640 mM), selenate (320 mM), and tellurite (1250 microM); and tolerance to tellurite increased in presence of selenite and selenate. Biochemical tests and zymogram of extracted culture solutions on gel electrophoresis showed that the strain was nitrate negative and therefore nitrate did not interfere with reduction of other oxyanions. Thus, the strain opens up good opportunities for the bioremediation of polluted waters in natural environment, since nitrate usually inhibits or decelerates reduction of the mentioned toxic oxyanions.

A microwave-assisted enzymatic extraction (MAEE) method was developed for the simultaneous extraction of arsenic (As) and selenium (Se) species in rice products. The total arsenic and selenium content in the enzymatic extracts were determined by inductively coupled plasma mass spectrometry (ICP-MS), while the speciation analysis was performed by ion chromatography coupled to inductively coupled plasma-mass spectrometry (IC-ICP-MS). The main factors affecting the enzymatic extraction process were evaluated in NIST SRM-1568a rice flour. The optimum extraction conditions were 500 mg of sample, 50 mg of protease XIV, and 25 mg of alpha-amylase in aqueous medium during 40 min at 37 degrees C. The extraction recoveries of total As and Se reached 100 +/- 3 and 80 +/- 4%, respectively. The species stability study during the MAEE process did not show transformation of the target species in rice products. The results of As speciation obtained for SRM-1568a were in agreement with previous studies of As speciation performed on the same reference material. The proposed method was applied to the determination of As and Se species in rice and rice-based cereals. Arsenite [As(III)], arsenate [As(V)], dimethylarsinic acid (DMA), and selenomethionine (SeMet) were the predominant species identified in rice products.

The aim of this work was to study selenium (Se) speciation in the potato ( Solanum tuberosum L.) cultivar Desiree, enriched in Se by foliar spraying with a water solution containing 10 mg of Se/L in the form of sodium selenate. Four combinations of treatments were used: well-watered plants with and without Se foliar spraying and drought-exposed plants with and without Se foliar spraying. Water-soluble Se compounds were extracted from potato tubers by water or enzymatic hydrolysis with the enzyme protease XIV, amylase, or a combination of protease XIV and amylase. Extraction was performed using incubation at a constant temperature and stirring (37 degrees C at 200 rpm) or by ultrasound-assisted extraction (300 W), using different extraction times. Separation of soluble Se species (SeCys2, SeMet, SeMeSeCys, selenite, and selenate) was achieved by ion-exchange chromatography, and detection was performed by inductively coupled plasma-mass spectrometry (ICP-MS). Results showed that the concentration of selenate extracted was independent of the enzymatic extraction technique (approximately 98 ng/g for drought-exposed and 308 ng/g for well-watered potato tubers), whereas the extraction yield of SeMet changed with the protocol used (10-36%). Selenate and SeMet were the main soluble Se species (representing 51-68% of total Se) in potato tubers, regardless of the growth conditions.

This paper evaluates the use of upflow anaerobic sludge bed (UASB) bioreactors (30 degrees C, pH=7.0) to remove selenium oxyanions from contaminated waters (790 microg Se L(-1)) under methanogenic and sulfate-reducing conditions using lactate as electron donor. One UASB reactor received sulfate at different sulfate to selenate ratios, while another UASB was operated under methanogenic conditions for 132 days without sulfate in the influent. The selenate effluent concentrations in the sulfate-reducing and methanogenic reactor were 24 and 8 microg Se L(-1), corresponding to removal efficiencies of 97% and 99%, respectively. X-ray diffraction (XRD) analysis and sequential extractions showed that selenium was mainly retained as elemental selenium in the biomass. However, the total dissolved selenium effluent concentrations amounted to 73 and 80 microg Se L(-1), respectively, suggesting that selenate was partly converted to another selenium compound, most likely colloidally dispersed Se(0) nanoparticles. Possible intermediates of selenium reduction (selenite, dimethylselenide, dimethyldiselenide, H(2)Se) could not be detected. Sulfate reducers removed selenate at molar excess of sulfate to selenate (up to a factor of 2600) and elevated dissolved sulfide concentrations (up to 168 mg L(-1)), but selenium removal efficiencies were limited by the applied sulfate-loading rate. In the methanogenic bioreactor, selenate and dissolved selenium removal were independent of the sulfate load, but inhibited by sulfide (101 mg L(-1)). The selenium removal efficiency of the methanogenic UASB abruptly improved after 58 days of operation, suggesting that a specialized selenium-converting population developed in the reactor. This paper demonstrates that both sulfate-reducing and methanogenic UASB reactors can be applied to remove selenate from contaminated natural waters and anthropogenic waste streams, e.g. agricultural drainage waters, acid mine drainage and flue gas desulfurization bleeds.

To study the role of trace elements for the quality and nutritional value of bovine milk, the distribution of selenium, zinc, and copper in whey was investigated using a method linking size exclusion chromatography to inductively coupled plasma mass spectrometry (SEC-ICP-MS). Three major peaks were detected for selenium, two peaks for zinc, and five peaks for copper. More than 65% of the selenium was found in protein fractions, mainly in fractions coinciding with the major whey proteins beta-lactoglobulin and alpha-lactalbumin. All zinc was associated with low molecular weight compounds (<5 kDa) and one of these compounds was probably citrate. More than 60% of the copper eluted in protein fractions and two of the five major peaks probably contained metallothionein and citrate. This method was used to compare milk and whey produced by organic and conventional feeding procedures. The selenium content in whey and desalted milk produced using organic regimens was significantly lower than that in conventional samples. Moreover, the proportion of selenium in protein fractions of organic whey was significantly smaller than that in conventional whey, but the distributions of zinc and copper did not differ. This study showed that with the SEC-ICP-MS technique the distribution profiles of several trace elements in whey could be studied in the same run and that the selenium profile differed in whey produced by organic and conventional procedures.

Size exclusion and anion-exchange chromatographies coupled with inductively coupled plasma-mass spectrometry (ICP-MS) were used for the speciation of selenium (Se) in a dietary supplement. A sequential extraction method resulted in 85% recovery of Se and 78% of the Se extracted could be identified. The results obtained show that selenomethionine and its oxide are the predominant compounds, while selenite and selenomethylcysteine are present at low concentrations. Methane seleninic acid, probably arising from the oxidation of selenomethylcysteine, accounted for 22% of total Se. High-molecular-weight compounds, probably proteins, were detected in sodium dodecyl sulfate (SDS) and driselase extracts by size exclusion chromatography.

Sulfur dioxide (SO2) and trace elements are all pollutants derived from coal combustion. This study relates to the simultaneous removal of SO2 and trace selenium dioxide (SeO2) from flue gas by calcium oxide (CaO) adsorption in the moderate temperature range, especially the effect of SO2 presence on selenium capture. Experiments performed on a thermogravimetric analyzer (TGA) can reach the following conclusions. When the CaO conversion is relatively low and the reaction rate is controlled by chemical kinetics, the SO2 presence does not affect the selenium capture. When the CaO conversion is very high and the reaction rate is controlled by product layer diffusion, the SO2 presence and the product layer diffusion resistance jointly reduce the selenium capture. On the basis of the kinetics study, a method to estimate the trace selenium removal efficiency using kinetic parameters and the sulfur removal efficiency is developed.

In the environment and living organisms, limited concentrations and complexity of selenium compounds constitute challenges to the analytical techniques. Since their biological activities are dependent on their chemical states and structure, the key issue lies in the selective determination of the particular species of selenium, which is beneficial to clearly understanding its biochemical roles in metabolism, physiology, toxicology, nutrition, and clinical chemistry. For these purposes, the advanced analytical techniques are greatly indispensable. In the present paper, the current status and development trends in the speciation analysis of selenium by hyphenated techniques is selectively reviewed with the emphasis on the coupling of electrophoretic or chromatographic separation with atomic spectroscopy and mass spectrometry, which render element-selective detection and identification of selenium compounds.

We introduce a T-type interface and a crossflow nebulizer to find ways to combine CEC with inductively coupled plasma MS (ICP-MS) detection for selenium speciation. For CEC separation, we employed a macrocyclic polyamine-bonded phase capillary as the separation column and a bare fused-silica capillary filled with the make-up liquid (0.05 M HNO3). The effect of nebulizer gas flow rate, make-up liquid flow, type, concentration and pH of the mobile phase on the separation have been studied. Tris buffer of 50 mM at pH 8.50 gave the best performance for selenium speciation. The reproducibility of the retention time indicated that sample injection by electrokinetic and nebulizer gas flow was better than that by self-aspiration alone. The detection limits for selenate, selenite, selenocystine and selenomethionine were found to be 2.40, 3.53, 12.86 and 11.25 ng/mL, respectively. Due to the high sensitivity and element-specific detection, as well as the high selectivity of the bonded phase, quantitative analysis of selenium speciation in urine was also achieved.

A review of the recent developments in selenium speciation analysis was presented, focusing on the techniques of separation, interface, elemental specific detection and identification of selenium species; the methods of sample storage and pretreatment storage for selenium speciation were also introduced.

Garlic (Allium sativum) and onion (Allium cepa) are widely known for their biological properties but are far from having revealed all of their secrets even if the compounds involved in the biological mechanisms, flavenols, sulphur and seleno compounds have been identified. The beneficial effect of garlic on health including protection against cardiovascular diseases and cancers results from all of these compounds although their individual involvement is complex. Garlic and onion, broccoli, wild leek, have the ability to accumulate the selenium (Se) from soil. These Se-enriched plants present a greater protection against carcinogenesis than the common plants and two Se-compounds possessing anti-cancer activity have been identified: Se-methyl selenocysteine and gamma-glutamyl-Se-methyl selenocysteine. However, several Se-compounds from Se-enriched garlic or onion remain unidentified. The techniques for the detection of Se-species are numerous but few methods are able to identify the detected compounds. The very small quantities of Se-compounds present and the clear lack of standards do not make their analysis straightforward, particularly for non-enriched samples. Over the last 10 or so years development of the synthesis of Se-compounds and the use of GC-AED or EC/HPLC-ICP-MS have shown considerable possibilities. These techniques have allowed advances in the identification of Se-compounds, some of which are analogues of S-compounds in plants and yeasts. When these techniques are coupled to EC/HPLC-APCI-MS-MS, they provide a lot of information about the Se-biosynthesis in garlic. This has allowed the preferential formation of methylated compounds in Se-biochemistry to be identified, in contrast to the sulphur biochemistry of the Allium spp. in which compounds containing propenylic groups predominate. This review focuses on the recent advances in the analytical methods of Se-compounds in garlic and onion and particular attention is given to the biological properties of Se-species identified in Se-enriched plants.

We show how simple mechanical agitation of precipitated CdSe quantum dot aggregates causes partially reversible color changes (clearly visible to the eye) in the absorption spectrum of the CdSe (about 4 nm size). The color changes, which are due to changes in size quantization, are not accompanied by change in quantum dot size. This phenomenon is explained by partial deaggregation of the precipitates, leading to reduced charge overlap between neighboring dots. Shaking was shown to result in a looser aggregate structure. It is suggested that CdSO3 particles (an initial product of the CdSe formation reaction) act as weak bridges between CdSe quantum dots, mediating the interparticle interactions and allowing the deaggregation to occur on shaking.

Zero-valent iron (ZVI) is an inexpensive agent that can remove many common environmental contaminants. We investigated the effects of arsenate [As(V)] and molybdate [Mo(VI)] on the removal of selenate [Se(VI)] (1000 microg/L) in a 5 mM Cl- and SO4(2-) solution by ZVI. Analysis of selenium (Se) species in a control experiment revealed that there was no detectable selenite [Se(IV)] in the solution and Se(IV) was the only dominant form of Se in the PO(4)3- extract, revealing that the removal of Se(VI) by ZVI appeared to be partly attributed to the reduction of Se(VI) to Se(IV) by Fe(II) oxidized from ZVI, followed by rapid adsorption of Se(IV) to Fe oxyhydroxes (Fe(OH)). Addition of As(V) in a range of 5 to 25 mg/L in the solution did not affect Se(VI) removal. As(V) was removed at much faster rates than Se(VI). It took 16 h for ZVI to completely remove As(V) from the solutions, whereas it needed 31 h to remove 99% of the added Se(VI). Addition of Mo(VI) to the solution significantly affects the removal of Se. After 16 h, 99%, 98%, and 73% of the added Mo(VI) was removed from the solutions with 10, 50, and 200 mg/L Mo(VI) added, respectively. Whereas about 18%, 38%, and 78% of the added Se(VI) still remained in the solutions, respectively. This study suggests that a sequence for rapid element removal by ZVI is As(V)>Mo(VI)>Se(VI) and that ZVI can be used to effectively remove a high concentration level of As(V), Mo(VI), and Se(VI) from water.

Identify and quantify of diversity of selenocompounds in environment and organism is necessary to further understand and fairly evaluate the effects of selenium in clinical chemistry, nutrition, toxicity, environment and ecology. For the purpose, many state-of-the-art of analytical techniques are applied with the particular emphasis on the effective isolation, high-sensitively element-selective detection and the identification of the detected selenocompounds. Some practical and recently-developed methods, especially Se speciation by the combination of chromatography with mass spectrography, are here reviewed, which is of benefit to the deep researches on the selenium species in environmental samples and biomaterials.

Zerovalent iron (ZVI) has been widely used in the removal of environmental contaminants from water. In this study, ZVI was used to remove selenate [Se(VI)] at a level of 1000 microg L(-1) in the presence of varying concentrations of Cl-, SO(2-)4, NO(-)3, HCO(-)3, and PO(3-)4. Results showed that Se(VI) was rapidly removed during the corrosion of ZVI to iron oxyhydroxides (Fe(OH)). During the 16 h of the experiments, 100 and 56% of the added Se(VI) was removed in 10 mM Cl- and SO(2-)4 solutions under a closed contained system, respectively. Under an open condition, 100 and 93% of the added Se(VI) were removed in the Cl- and SO(2-)4 solutions, respectively. Analysis of Se species in ZVI-Fe(OH) revealed that selenite [Se(IV)] and nonextractable Se increased during the first 2 to 4 h of reaction, with a decrease of Se(VI) in the Cl- experiment and no detection of Se(VI) in the SO(2-)4 experiment. Two mechanisms can be attributed to the rapid removal of Se(VI) from the solutions. One is the reduction of Se(VI) to Se(IV), followed by rapid adsorption of Se(IV) to Fe(OH). The other is the adsorption of Se(VI) directly to Fe(OH), followed by its reduction to Se(IV). The results also show that there was little effect on Se(VI) removal in the presence of Cl- (5, 50, and 100 mM), NO(-)3 (1, 5, and 10 mM), SO(2-)4 (5 mM), HCO(-)3 (1 and 5 mM), or PO(3-)4 (1 mM) and only a slight effect in the presence of SO(2-)4 (50 and 100 mM), HCO(-)3 (10 mM), and PO(3-)4 (5 mM) during a 2-d experiment, whereas 10 mM PO(3-)4 significantly inhibited Se(VI) removal. This work suggests that ZVI may be an effective agent to remove Se from Se-contaminated agricultural drainage water.

Selenium-accumulating plants such as Brassica juncea (Indian mustard) concentrate the element in plant shoots and roots. Such behavior may provide a cost-effective technology to clean up contaminated soils and waters that pose major environmental and human health problems (phytoremediation). Such ability to transform selenium into bioactive compounds has important implications for human nutrition and health. Element selective characterization of B. juncea grown in the presence of inorganic selenium under hydroponic conditions provides valuable information to better understand selenium metabolism in plants. The present work determines both previously observed organoselenium species such as selenomethionine and Se-methylselenocysteine and for the first time detects the newly characterized S-(methylseleno)cysteine in plant shoots and roots when grown in the presence of selenate or selenite as the only selenium source. A key feature of this study is the complementary role of selenium and sulfur specific chromatographic detection by HPLC with interfaced inductively coupled plasma mass spectrometry (ICP-MS) detection and by derivatization GC with interfaced atomic spectral emission. HPLC-ICP-MS limits of detection for such species were in the range 5-50 ng Se mL(-1) in the injected extracts. Speciation profiles are compared with those of selenium-enriched yeast by both HPLC-ICP-MS and GC-AED.

Nitric oxide (NO) is a messenger molecule implicated in a number of physiological processes. Nitrosation of selenoproteins has been suggested as playing an important role in NO-mediated cellular functions such as the inactivation of glutathione peroxidase (GPx), but no chemical information about Se-nitrosated species has been available to date. Here a stable Se-nitrososelenol (RSeNO), a new class of NO derivative, was synthesized and fully characterized by X-ray crystallography and spectroscopic methods. This Se-nitrososelenol can be formed by direct transnitrosation from an S-nitrosothiol to a selenol, as is the case in the proposed mechanism for the NO-mediated inactivation of GPx.

Volatile arsenic and selenium compounds present in coals may cause environmental problems during coal combustion and gasification. A possible way to avoid such problems may be the use of solid sorbents capable of retaining these elements from flue gases in gas cleaning systems. Lime and limestone are materials that are extensively employed for the capture of sulfur during coal processing. Moreover, they have also proven to have good retention characteristics for arsenic and selenium during combustion. The aim of this work was to ascertain whether this sorbent is also useful for retaining arsenic and selenium species in gases produced in coal gasification. The study was carried out in a laboratory-scale reactor in which the sorbent was employed as a fixed bed, using synthetic gas mixtures. In these conditions, retention capacities for arsenic may reach 17 mg g(-1) in a gasification atmosphere free of H2S, whereas the presence of H2S implies a significant decrease in arsenic retention. In the case of selenium, H2S does not influence retention which may reach 65 mg g(-1). Post-retention sorbent characterization, thermal stability, and water solubility tests have shown that chemical reaction is one of the mechanisms responsible for the capture of arsenic and selenium, with Ca(AsO2)2 and CaSe being the main compounds formed.