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1.
Carbohydr Polym ; 261: 117833, 2021 Jun 01.
Article in English | MEDLINE | ID: mdl-33766336

ABSTRACT

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 HNO3-Na2SeO3 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 H2O2-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-1ß. Overall, the prepared SeGMs from galactomannan could potentially serve as a dietary supplement of Se or an organic antioxidant.


Subject(s)
Macrophages/drug effects , Mannans/pharmacology , Selenium Compounds/pharmacology , Sesbania/chemistry , Animals , Antioxidants/physiology , Galactose/analogs & derivatives , Hydrogen Peroxide/toxicity , Immunity/drug effects , Macrophages/immunology , Macrophages/physiology , Mannans/isolation & purification , Mice , Oxidation-Reduction/drug effects , Oxidative Stress/drug effects , RAW 264.7 Cells , Selenium Compounds/isolation & purification
2.
Appl Microbiol Biotechnol ; 103(17): 7241-7259, 2019 Sep.
Article in English | MEDLINE | ID: mdl-31324941

ABSTRACT

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.


Subject(s)
Fungi/metabolism , Nanoparticles/microbiology , Selenium/metabolism , Tellurium/metabolism , Biodegradation, Environmental , Fungi/classification , Fungi/growth & development , Nanoparticles/chemistry , Oxidation-Reduction , Selenium Compounds/isolation & purification , Selenium Compounds/metabolism , Tellurium/isolation & purification
3.
Sensors (Basel) ; 19(15)2019 Jul 25.
Article in English | MEDLINE | ID: mdl-31349605

ABSTRACT

Cadmium zinc telluride selenide (Cd1-xZnxTe1-ySey 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 cm2/V. These results show that ammonium fluoride is effective for chemical passivation of CZTS detectors.


Subject(s)
Ammonium Compounds/chemistry , Cadmium Compounds/isolation & purification , Fluorides/chemistry , Selenium Compounds/isolation & purification , Tellurium/isolation & purification , Zinc/isolation & purification , Cadmium Compounds/chemistry , Cadmium Compounds/therapeutic use , Humans , Monte Carlo Method , Positron-Emission Tomography/methods , Quantum Dots/chemistry , Radiography/methods , Selenium Compounds/chemistry , Selenium Compounds/therapeutic use , Tellurium/chemistry , Tellurium/therapeutic use , Zinc/chemistry
4.
Biosens Bioelectron ; 103: 99-103, 2018 Apr 30.
Article in English | MEDLINE | ID: mdl-29288884

ABSTRACT

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.


Subject(s)
Biosensing Techniques/methods , Cadmium Compounds/isolation & purification , DNA/chemistry , Electrochemical Techniques , Selenium Compounds/isolation & purification , Cadmium Compounds/toxicity , Gold/chemistry , Limit of Detection , Nucleic Acid Hybridization/genetics , Quantum Dots/chemistry , Selenium Compounds/toxicity , Streptavidin/chemistry
5.
Chemosphere ; 181: 627-634, 2017 Aug.
Article in English | MEDLINE | ID: mdl-28476002

ABSTRACT

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 (R2 > 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.


Subject(s)
Environmental Monitoring/methods , Hydroxides/chemistry , Selenic Acid/chemistry , Selenious Acid/chemistry , Absorption, Physicochemical , Aluminum Hydroxide/chemistry , Magnesium/chemistry , Magnesium Hydroxide/chemistry , Models, Theoretical , Nitrates/chemistry , Phosphates/chemistry , Selenic Acid/analysis , Selenic Acid/isolation & purification , Selenious Acid/analysis , Selenious Acid/isolation & purification , Selenium Compounds/chemistry , Selenium Compounds/isolation & purification , Sulfates/chemistry , Water Pollutants/chemistry , Water Pollutants/isolation & purification
6.
Chemosphere ; 164: 372-378, 2016 Dec.
Article in English | MEDLINE | ID: mdl-27596824

ABSTRACT

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.


Subject(s)
Chlorella vulgaris/metabolism , Food/adverse effects , Photoperiod , Salinity , Selenium Compounds/isolation & purification , Sulfates/pharmacology , Water Pollutants, Chemical/isolation & purification , Biodegradation, Environmental , Biomass , Chlorella vulgaris/drug effects , Chlorella vulgaris/growth & development , Humans , Selenium Compounds/metabolism , Volatilization , Water Pollutants, Chemical/metabolism , Water Purification/methods
7.
Article in English | MEDLINE | ID: mdl-26414440

ABSTRACT

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).


Subject(s)
Brassica/metabolism , Cystine/analogs & derivatives , Organoselenium Compounds/isolation & purification , Selenium Compounds/metabolism , Selenocysteine/analogs & derivatives , Selenomethionine/metabolism , Biological Transport , Brassica/drug effects , Cations, Divalent/metabolism , Cations, Monovalent/metabolism , Cystine/isolation & purification , Cystine/metabolism , Flowers/drug effects , Flowers/metabolism , Organoselenium Compounds/metabolism , Plant Leaves/drug effects , Plant Leaves/metabolism , Plant Roots/drug effects , Plant Roots/metabolism , Plant Stems/drug effects , Plant Stems/metabolism , Selenium Compounds/isolation & purification , Selenium Compounds/pharmacology , Selenocysteine/isolation & purification , Selenocysteine/metabolism , Selenomethionine/isolation & purification , Spectrophotometry, Atomic
8.
J Hazard Mater ; 291: 111-9, 2015 Jun 30.
Article in English | MEDLINE | ID: mdl-25771216

ABSTRACT

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).


Subject(s)
Environmental Monitoring/methods , Selenium Compounds/analysis , Water Pollutants, Chemical/isolation & purification , Adsorption , Hydrogen-Ion Concentration , Ligands , Organic Chemicals , Selenium Compounds/isolation & purification , Silicon Dioxide , Water Purification
9.
Luminescence ; 30(1): 18-25, 2015 Feb.
Article in English | MEDLINE | ID: mdl-24833131

ABSTRACT

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.


Subject(s)
Arabidopsis/chemistry , Cadmium Compounds/chemistry , Quantum Dots , Salicylic Acid/analysis , Seeds/chemistry , Selenium Compounds/chemistry , Binding Sites , Cadmium Compounds/chemical synthesis , Cadmium Compounds/isolation & purification , Particle Size , Selenium Compounds/chemical synthesis , Selenium Compounds/isolation & purification , Surface Properties
10.
Food Chem ; 169: 73-9, 2015 Feb 15.
Article in English | MEDLINE | ID: mdl-25236200

ABSTRACT

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.


Subject(s)
Beverages/analysis , Mass Spectrometry/methods , Selenium Compounds/analysis , Selenium Compounds/isolation & purification , Solid Phase Extraction/methods , Argentina , Calibration , Limit of Detection , Selenium/analysis
11.
Food Chem ; 169: 156-61, 2015 Feb 15.
Article in English | MEDLINE | ID: mdl-25236211

ABSTRACT

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.


Subject(s)
Camellia sinensis/chemistry , Mass Spectrometry/methods , Selenium Compounds/chemistry , Selenium Compounds/isolation & purification , Solid Phase Microextraction/methods , Tea/chemistry , Plant Leaves/chemistry , Volatilization
12.
J Nanosci Nanotechnol ; 14(6): 4437-42, 2014 Jun.
Article in English | MEDLINE | ID: mdl-24738409

ABSTRACT

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.


Subject(s)
Biological Products/chemistry , Cadmium Compounds/chemistry , Musa/metabolism , Nanostructures/chemistry , Nanostructures/ultrastructure , Plant Extracts/chemistry , Selenium Compounds/chemistry , Biological Products/isolation & purification , Cadmium Compounds/isolation & purification , Materials Testing , Particle Size , Plant Extracts/isolation & purification , Selenium Compounds/isolation & purification
13.
J Sci Food Agric ; 94(2): 349-58, 2014 Jan 30.
Article in English | MEDLINE | ID: mdl-24037994

ABSTRACT

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.


Subject(s)
Diet , Food, Fortified , Plant Proteins/chemistry , Polysaccharides/chemistry , Pueraria/chemistry , Selenium Compounds/chemistry , Selenium/analysis , Humans , Molecular Weight , Monosaccharides/analysis , Plant Proteins/isolation & purification , Plant Roots/chemistry , Polysaccharides/isolation & purification , Protein Subunits , Selenium Compounds/isolation & purification
14.
J Chromatogr A ; 1325: 83-91, 2014 Jan 17.
Article in English | MEDLINE | ID: mdl-24342533

ABSTRACT

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.


Subject(s)
Chromatography, High Pressure Liquid/methods , Mass Spectrometry/methods , Pectinidae/chemistry , Selenium Compounds/isolation & purification , Selenium/isolation & purification , Animals , Aspergillus oryzae/enzymology , Cysteine/analogs & derivatives , Cysteine/chemistry , Methionine/chemistry , Pectinidae/metabolism , Selenium/chemistry , Selenium/metabolism , Selenium Compounds/chemistry , Selenium Compounds/metabolism
15.
Food Chem ; 145: 736-42, 2014 Feb 15.
Article in English | MEDLINE | ID: mdl-24128538

ABSTRACT

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.


Subject(s)
Brassica/chemistry , Mass Spectrometry , Selenium Compounds/chemistry , Alkanesulfonic Acids/chemistry , Brassica/metabolism , Chromatography, High Pressure Liquid , Chromatography, Reverse-Phase , Hydrogen-Ion Concentration , Plant Extracts/chemistry , Selenic Acid/analysis , Selenic Acid/isolation & purification , Selenious Acid/analysis , Selenious Acid/isolation & purification , Selenium Compounds/analysis , Selenium Compounds/isolation & purification , Selenocysteine/analogs & derivatives , Selenocysteine/analysis , Selenocysteine/isolation & purification , Selenomethionine/analysis , Selenomethionine/isolation & purification
16.
Talanta ; 115: 730-6, 2013 Oct 15.
Article in English | MEDLINE | ID: mdl-24054655

ABSTRACT

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.


Subject(s)
Chelating Agents/chemistry , Liquid Phase Microextraction/methods , Selenium Compounds/isolation & purification , Thiadiazoles/chemistry , Water Pollutants, Chemical/isolation & purification , Chloroform , Electricity , Ethanol , Fresh Water/chemistry , Hot Temperature , Hydrogen-Ion Concentration , Limit of Detection , Oxidation-Reduction , Spectrophotometry, Atomic , Volatilization , Wastewater/chemistry
17.
Bioconjug Chem ; 24(6): 889-96, 2013 Jun 19.
Article in English | MEDLINE | ID: mdl-23600957

ABSTRACT

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.


Subject(s)
Cysteine/chemistry , Granulocyte Colony-Stimulating Factor/chemistry , Polyethylene Glycols/chemistry , Selenium Compounds/chemistry , Animals , Cell Line , Circular Dichroism , Granulocyte Colony-Stimulating Factor/isolation & purification , Humans , Mice , Models, Molecular , Molecular Structure , Polyethylene Glycols/isolation & purification , Polyethylene Glycols/pharmacokinetics , Rats , Recombinant Proteins/chemistry , Recombinant Proteins/isolation & purification , Recombinant Proteins/pharmacokinetics , Selenium Compounds/isolation & purification , Selenium Compounds/pharmacokinetics
18.
J Hazard Mater ; 241-242: 92-100, 2012 Nov 30.
Article in English | MEDLINE | ID: mdl-23040313

ABSTRACT

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.


Subject(s)
Environmental Restoration and Remediation/methods , Groundwater/analysis , Iron/chemistry , Selenium Compounds/isolation & purification , Soil/chemistry , Water Pollutants, Chemical/isolation & purification , Water Purification/methods , Adsorption , Chemical Precipitation , Groundwater/chemistry , Groundwater/standards , Oxygen/chemistry , Research Design , Selenium Compounds/chemistry , Solubility , Surface Properties , Water Pollutants, Chemical/chemistry , Wood/chemistry , X-Ray Absorption Spectroscopy
19.
Environ Sci Technol ; 46(18): 10004-11, 2012 Sep 18.
Article in English | MEDLINE | ID: mdl-22900520

ABSTRACT

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.


Subject(s)
Ferrous Compounds/chemistry , Selenium Compounds/isolation & purification , Selenium/isolation & purification , Adsorption , Chemical Precipitation , Models, Molecular , Selenium/chemistry , Selenium Compounds/chemistry , X-Ray Absorption Spectroscopy , X-Ray Diffraction
20.
Chem Pharm Bull (Tokyo) ; 60(3): 348-53, 2012.
Article in English | MEDLINE | ID: mdl-22382415

ABSTRACT

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.


Subject(s)
Organoselenium Compounds/chemistry , Selenium/chemistry , Animals , Chromatography, Ion Exchange/methods , Fishes , Mass Spectrometry/methods , Molecular Weight , Organoselenium Compounds/isolation & purification , Selenium/isolation & purification , Selenium Compounds/chemistry , Selenium Compounds/isolation & purification , Selenoproteins/chemistry , Solvents/chemistry , Ultrafiltration/methods
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