Selenite Species Research Articles

Isoselenazole Synthesis by Rh-Catalyzed Direct Annulation of Benzimidates with Sodium Selenite

Organoselenium compounds have attracted significant research interest because of their potent therapeutic activities and indispensable applications in the organic chemistry field. The selenation reactions conventionally rely on the use of sensitive Se reagents; thus, new synthetic methods with improved efficiency and operational simplicity have recently been of particular interest. In this manuscript, we report a Rh-catalyzed direct selenium annulation using tractable sodium selenite (Na2SeO3) as the limiting reagent. The selenite species was converted to highly electrophilic SeO(OBz)2 in situ upon treatment with Bz2O, thereby undergoing C–H/N–H double nucleophilic selenation. A series of benzimidates successfully underwent selenation under mild reaction conditions to afford isoselenazole derivatives.

Catalytic effect of tetrasulfonated cobalt phthalocyanine on selenite reduction by dithionite

This works reports that tetrasulfonated cobalt(II) phthalocyanine (Co(II)TSPc) catalyzes reduction of selenite (SeO32−), the one of the most toxic form of selenium, to slightly toxic Se(0) by dithionite (S2O42−) in neutral aqueous solutions. The overall reaction mechanism involves rapid reduction of Co(II)TSPc to Co(I)TSPc by dithionite followed by slower oxidation of Co(I)TSPc by selenite. Reaction of Co(I)TSPc with selenite proceeds via two consecutive steps, i.e. the formation of complex between reactants followed by electron transfer from Co(I)-ion to selenite and dissociation of reduced selenite species from Co(II)-ion.

Effect of phosphate and silicate on selenite uptake and phloem-mediated transport in tomato (Solanum lycopersicum L.).

The ambiguous mechanism that selenite seems to be absorbed by roots via phosphorus (P) and silicon (Si) transporters signifies P and Si may affect selenite uptake. However, the role of P and Si in phloem-mediated selenium (Se) transport within plant tissue is unknown. Therefore, in this work, tomato (Solanum lycopersicum L.) seedlings were exposed to selenite under different hydroponic conditions firstly. And then, split-root experiments were conducted. Results showed that Se uptake decreased as external pH increased. At pH 8, more selenite in the form of SeO32- was assimilated under P-deficient conditions than under P-normal conditions. Silicate inhibited Se uptake only at pH 3 (27.5% H2SeO3 +72.5% HSeO3-). The results of split-root experiments showed that Se concentrations in seedlings increased under heterogeneously high P or Si. Selenium transport from shoots to roots immersed in solution without selenite was also enhanced. This study illustrated that the affinity of tomato roots to assimilate selenite species followed the order of H2SeO3 >HSeO3- >SeO32-. H2SeO3 was absorbed into roots via Si transporters, whereas HSeO3- and a portion of SeO32- were absorbed via low- and high-affinity P transporters, respectively. In addition, heterogeneously high P or Si concentrations in environmental media could enhance phloem-mediated Se redistribution.

Bioaccessibility of selenium after human ingestion in relation to its chemical species and compartmentalization in maize.

Selenium is a micronutrient needed by all living organisms including humans, but often present in low concentration in food with possible deficiency. From another side, at higher concentrations in soils as observed in seleniferous regions of the world, and in function of its chemical species, Se can also induce (eco)toxicity. Root Se uptake was therefore studied in function of its initial form for maize (Zea mays L.), a plant widely cultivated for human and animal food over the world. Se phytotoxicity and compartmentalization were studied in different aerial plant tissues. For the first time, Se oral human bioaccessibility after ingestion was assessed for the main Se species (Se(IV) and Se(VI)) with the BARGE ex vivo test in maize seeds (consumed by humans), and in stems and leaves consumed by animals. Corn seedlings were cultivated in hydroponic conditions supplemented with 1mgL(-1) of selenium (Se(IV), Se(VI), Control) for 4months. Biomass, Se concentration, and bioaccessibility were measured on harvested plants. A reduction in plant biomass was observed under Se treatments compared to control, suggesting its phytotoxicity. This plant biomass reduction was higher for selenite species than selenate, and seed was the main affected compartment compared to control. Selenium compartmentalization study showed that for selenate species, a preferential accumulation was observed in leaves, whereas selenite translocation was very limited toward maize aerial parts, except in the seeds where selenite concentrations are generally high. Selenium oral bioaccessibility after ingestion fluctuated from 49 to 89% according to the considered plant tissue and Se species. Whatever the tissue, selenate appeared as the most human bioaccessible form. A potential Se toxicity was highlighted for people living in seleniferous regions, this risk being enhanced by the high Se bioaccessibility.

Photocatalytic removal of selenite and selenate species: effect of EDTA and other process variables

TiO2-assisted photocatalysis was employed for the removal of aqueous phase selenite and selenate species in conjunction with EDTA as a hole (h+) scavenger. Findings from the binary selenite/EDTA and selenate/EDTA systems showed high selenite and selenate removal at pH 4 and pH 6, with faster removal kinetics noted for the selenite species compared with the selenate species that showed a gradual change over the reaction course. The noted removal of selenite and selenate was attributed to their reduction by the conduction band electrons (e−). The effect of pH studies indicated high selenite, selenate, and EDTA removal in the acidic pH range, with the following specific trend: pH 4>pH 6>pH 12. Different from the EDTA studies, the use of thiocyanate alone did not initiate reduction of selenium oxyanions, and hence, its role as a hole scavenger in the present systems was not evident. However, the addition of EDTA to respective selenite/selenate/thiocyanate system at pH 4 did yield near complete removal of selenite and selenate species. The marginal role of thiocyanate as a hole scavenger was attributed to its negligible adsorption onto TiO2 surface. Furthermore, at pH 4 and within 3 h reaction time, enhanced selenate removal was noted with an increase in its initial concentration from 20 to 100 ppm, with near complete selenate removal noted for both cases. In general, findings from the present work indicate that both selenite and selenate can be successfully removed from the aqueous phase employing the TiO2-mediated photocatalysis and h+-scavenging agent EDTA.

Characterization of the Selenite Uptake Mechanism in the Coccolithophore Emiliania huxleyi (Haptophyta)

The marine coccolithophore Emiliania huxleyi (Haptophyta) requires selenium as an essential element for growth, and the active species absorbed is selenite, not selenate. This study characterized the selenite uptake mechanism using ⁷⁵Se as a tracer. Kinetic analysis of selenite uptake showed the involvement of both active and passive transport processes. The active transport was suppressed by 0.5 mM vanadate, a membrane-permeable inhibitor of H⁺-ATPase, at pH 8.3. When the pH was lowered from 8.3 to 5.3, the selenite uptake activity greatly increased, even in the presence of vanadate, suggesting that the H⁺ concentration gradient may be a motive force for selenite transport. [⁷⁵Se]Selenite uptake at selenite-limiting concentrations was hardly affected by selenate, sulfate and sulfite, even at 100 μM. In contrast, 3 μM orthophosphate increased the K(m) 5-fold. These data showed that HSeO₃⁻, a dominant selenite species at acidic pH, is the active species for transport through the plasma membrane and transport is driven by ΔpH energized by H⁺-ATPase. Kinetic analysis showed that the selenite uptake activity was competitively inhibited by orthophosphate. Furthermore, the active selenite transport mechanism was shown to be induced de novo under Se-deficient conditions and induction was suppressed by the addition of either sufficient selenite or cycloheximide, an inhibitor of de novo protein synthesis. These results indicate that E. huxleyi cells developed an active selenite uptake mechanism to overcome the disadvantages of Se limitation in ecosystems, maintaining selenium metabolism and selenoproteins for high viability.

Synchrotron-radiation-induced oxidation of selenite to selenate in coal-derived fly ash

Systematic changes observed in consecutive XANES spectra of selenium in samples of fly ash from a power plant in Alberta, Canada, burning subbituminous coal have been interpreted as arising from synchrotron-radiation-induced oxidation of a selenite species to selenate. It was estimated that about 15-20% of the selenite was oxidized to selenate during the 2 h exposure of the fly ash to the synchrotron beam. In contrast, the XANES spectra of arsenic (and other trace elements not documented herein) showed no variation. It is believed that this is the first time that radiation-induced changes have been observed for an element in coal-derived fly ash.

Selenite retention by nanocrystalline magnetite: Role of adsorption, reduction and dissolution/co-precipitation processes

We studied selenite ( SeO 3 2 - ) retention by magnetite ( Fe II Fe III 2 O 4 ) using both surface complexation modeling and X-ray absorption spectroscopy (XAS) to characterize the processes of adsorption, reduction, and dissolution/co-precipitation. The experimental sorption results for magnetite were compared to those of goethite (Fe IIIOOH) under similar conditions. Selenite sorption was investigated under both oxic and anoxic conditions and as a function of pH, ionic strength, solid-to-liquid ratio and Se concentration. Sorption onto both oxides was independent of ionic strength and decreased as pH increased, as expected for anion sorption; however, the shape of the sorption edges was different. The goethite sorption data could be modeled assuming the formation of an inner-sphere complex with iron oxide surface sites (SOH). In contrast, the magnetite sorption data at low pH could be modeled only when the dissolution of magnetite, the formation of aqueous iron–selenite species, and the subsequent surface complexation of these species were implemented. The precipitation of ferric selenite was the predominant retention process at higher selenite concentrations (>1 × 10 −4 M) and pH < 5, which was in agreement with the XAS results. Sorption behavior onto magnetite was similar under oxic and anoxic conditions. Under anoxic conditions, we did not observe the reduction of selenite. Possible reasons for the absence of reduction are discussed. In conclusion, we show that under acidic reaction conditions, selenite retention by magnetite is largely influenced by dissolution and co-precipitation processes.

DRC™ ICP-MS coupled with automated flow injection system with anion exchange minicolumns for determination of selenium compounds in water samples

A flow injection system with anion exchange resin minicolumns was coupled with dynamic reaction cell (DRC™) ICP-MS for the determination and speciation of selenite and selenate at sub μg L −1 levels. The charged selenate and uncharged selenite were separated on the first resin column in which only selenate was retained. The unretained selenite was then deprotonated with alkaline solution, and the resulting anionic selenite species was collected on the second column serially connected downstream. By setting a sample loop, total selenium can be determined together with selenite and selenate. The selenium species was eluted by nitric acid and carried to DRC™ ICP-MS for their detection. Using ammonia as reaction gas, the detection of 78Se was improved. The enrichment factor was 20 for 10 mL of sample. The standard deviations ( n = 5) of peak heights were 4.9%, 4.1%, and 7.0% for a 5.0 × 10 −2 μg L −1 selenite and selenate, and total Se, respectively. The calibration graphs were linear from 2.0 × 10 −2 to 1.0 μg L −1 selenite and selenate. And, the linearity for total selenium was good in the range of 10.0 × 10 −2 to 1.0 μg L −1. The proposed method has been demonstrated for the application to natural and bottled drinking water samples.

Interactions of selenate with copper(I) oxide particles.

The chemical mechanisms responsible for the immobilization of selenate (SeO4(2-) from aqueous solutions on cuprite (Cu2O) particles were determined from batch experiments. This was achieved by performing both solution-phase analyses and characterization of solid particles by X-ray photoelectron spectroscopy and transmission electron microscopy techniques, after equilibration of cuprite particles with selenate-containing solutions at various pH values, solid-to-solution ratios, and ionic strengths. Two distinct mechanisms have been pointed out. In the acidic medium, where the acid-catalyzed dissolution of cuprite into CuI species occurs, the immobilization of selenate implies a redox reaction with transient CuI leading to the precipitation of copper(II) selenite, CuSeO3. In the absence of protons added in the medium, Cu2O is chemically stable and immobilization of SeO4(2-) is essentially due to adsorption in the form of an outer-sphere surface complex. The uptake level of selenate by Cu2O is markedly lower than that observed for selenite species in the same conditions.

Chemical Mechanisms Responsible for the Immobilization of Selenite Species from an Aqueous Medium in the Presence of Copper(I) Oxide Particles

The ability of cuprite (Cu2O) to reduce the mobility of selenite species (SeO32- or HSeO3-), by means of chemical immobilization from an aqueous medium, was evaluated from batch experiments. The effect of pH was critically discussed as it was found to have a major influence on the nature of the mechanism involved in the uptake process of selenite by cuprite. Three pH-dependent mechanisms were evidenced by combining quantitative analysis of selenite solutions after equilibration with cuprite, solid-phase characterization, and surface analyses. In the presence of protons, the immobilization of selenite occurs via the formation of a copper selenite solid (i.e., chalcomenite, CuSeO3·2H2O). The driving force is the acid-catalyzed dissolution of cuprite into CuI species, followed by their fast disproportionation into Cu0 and CuII, this latter reacting with selenite to give the precipitation product. In an alkaline medium (pH > 7.5), selenite was mainly accumulated on the cuprite surface according to two distinc...

Selenate and Selenite Sorption on Iron Oxides An Infrared and Electrophoretic Study

We studied selenate and selenite sorption by amorphous Fe oxide [am‐Fe(OH)3] and goethite (α‐FeOOH) as a function of time (25 min–96 h), pH (3–12), ionic strength (0.01–1.0 M NaCl), and total Se concentration (0.0001–1.0 M). We examined sorbed selenate and selenite by in situ attenuated total reflectance Fourier transform infrared (ATR–FTIR) spectroscopy, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, and electrophoresis to deduce sorption mechanisms. Sorption of both selenate and selenite reached equilibrium in &lt;25 min and the sorption isotherm was not reversible. Increasing ionic strength decreased selenate sorption but did not affect selenite sorption. The presence of either selenate or selenite lowered the electrophoretic mobility (EM) and decreased the point of zero charge (PZC) of both sorbents, suggesting inner‐sphere complexation for both selenate and selenite species. Both in situ ATR–FTIR and DRIFT difference spectra showed bidentate complexes of selenate with am‐Fe(OH)3 The structure of selenite complexes in am‐Fe(OH)3 –solution interface was uncertain due to insensitivity of the in situ ATR–FTIR technique. The DRIFT spectra of selenite on am‐Fe(OH)3 showed ν3 splitting as evidence of complexation. The DRIFT spectra of selenite on goethite showed bridging bidentate complex of selenite. We conclude that the influence of ionic strength on Se sorption cannot be used as a criterion for distinguishing outer‐ vs. inner‐sphere complex formation.