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PubMed1997

Speciation of selenium and arsenic compounds by capillary electrophoresis with hydrodynamically modified electroosmotic flow and on-line reduction of selenium(VI) to selenium(IV) with hydride generation inductively coupled plasma mass spectrometric detection.

Capillary electrophoresis (CE) with hydride generation inductively coupled plasma mass spectrometry was used to determine four arsenicals and two selenium species. Selenate (SeVI) was reduced on-line to selenite (SeIV) by mixing the CE effluent with concentrated HCl. A microporous PTFE tube was used as a gas-liquid separator to eliminate the 40Ar37Cl and 40Ar35Cl interference from 77Se and 75As, respectively. The direction of the electroosmotic flow during CE was reversed with hydrodynamic pressure, which allowed increased freedom of buffer choice. For conventional pressure injection, method detection limits for SeIV and SeVI based on seven replicate injections were 10 and 24 pg, respectively. Recoveries of SeIV and SeVI in drinking water were measured.

Arsenicals↗

PubMed2000

Thioredoxin reductase.

The mammalian thioredoxin reductases (TrxRs) are a family of selenium-containing pyridine nucleotide-disulphide oxidoreductases with mechanistic and sequence identity, including a conserved -Cys-Val-Asn-Val-Gly-Cys- redox catalytic site, to glutathione reductases. TrxRs catalyse the NADPH-dependent reduction of the redox protein thioredoxin (Trx), as well as of other endogenous and exogenous compounds. The broad substrate specificity of mammalian TrxRs is due to a second redox-active site, a C-terminal -Cys-SeCys- (where SeCys is selenocysteine), that is not found in glutathione reductase or Escherichia coli TrxR. There are currently two confirmed forms of mammalian TrxRs, TrxR1 and TrxR2, and it is possible that other forms will be identified. The availability of Se is a key factor determining TrxR activity both in cell culture and in vivo, and the mechanism(s) for the incorporation of Se into TrxRs, as well as the regulation of TrxR activity, have only recently begun to be investigated. The importance of Trx to many aspects of cell function make it likely that TrxRs also play a role in protection against oxidant injury, cell growth and transformation, and the recycling of ascorbate from its oxidized form. Since TrxRs are able to reduce a number of substrates other than Trx, it is likely that additional biological effects will be discovered for TrxR. Furthermore, inhibiting TrxR with drugs may lead to new treatments for human diseases such as cancer, AIDS and autoimmune diseases.

Animals↗

PubMed2003

Oxidative stress in end-stage renal disease: an emerging threat to patient outcome.

INTRODUCTION: Patients affected by end-stage renal disease (ESRD) experience an excess of morbidity and mortality due to cardiovascular disease (CVD), which cannot be fully explained by the classical CVD risk factors. Among emerging CVD risk factors, oxidative stress is currently being given emphasis. METHODS: We achieved a consensus on key points relating to oxidative stress in ESRD patients. RESULTS: ESRD patients are subjected to enhanced oxidative stress, as a result of reduced anti-oxidant systems (vitamin C and selenium deficiency, reduced intracellular levels of vitamin E, reduced activity of the glutathione system) and increased pro-oxidant activity (advanced age, high frequency of diabetes, chronic inflammatory state, uraemic syndrome, bio-incompatibility of dialysis membranes and solutions). Oxidative stress and inflammation are deeply inter-related, as different oxidant free radicals are generated by phagocytic cells in response to inflammatory stimuli: both are related to endothelial dysfunction, as the endothelium is a source and a target of oxidants and participates in the inflammatory response. There is growing evidence, from experimental and clinical studies, that oxidative stress may be implicated in the pathogenesis of atherosclerosis and other complications of ESRD, namely dialysis-related amyloidosis, malnutrition and anaemia. Given that free radicals have very short half-lives (seconds), the clinical assessment of oxidative stress is based on the measurement of different stable oxidized compounds (such as lipid peroxidation products, advanced glycation and oxidation lipid and protein products, nucleic acid oxidation derivatives) or antibodies directed against oxidized epitopes (such as anti-oxidized low-density lipoprotein antibodies). At the same time, both enzymatic anti-oxidants (superoxide dismutase, catalase, glutathione peroxidase) and non-enzymatic anti-oxidants (glutathione, vitamin C, vitamin E, negative inflammatory proteins) can be evaluated. However, many laboratory methods assessing various oxidative stress components still have to be standardized. Moreover, it is still uncertain whether it is better measuring plasma and/or intracellular concentrations or activities of these components. The possibility of improving patient outcome by therapeutic interventions aimed at reducing oxidative stress, e.g. by vitamin C or vitamin E supplementation, currently is to the fore, but results so far have remained inconclusive. CONCLUSIONS: It is important to consider oxidative stress as a potentially important source of patient morbidity and mortality, although this knowledge is not yet immediately applicable in the clinical arena. Further well-designed, randomized controlled clinical trials with anti-oxidants (e.g. vitamin E, vitamin C, N-acetyl cysteine, L-arginine) are required to establish evidence-based recommendations for clinical practice.

Cardiovascular Diseases↗

PubMed2002

Sublethal effects in avocet and stilt hatchlings from selenium-contaminated sites.

Excess selenium (Se) in the aquatic food chain is embryotoxic and teratogenic to avocets, stilts, and other waterbirds. American avocet (Recurvirostra americana) and black-necked stilt (Himantopus mexicanus) eggs were collected from three sites in the Tulare Lake Basin of California, USA, and hatched in the laboratory. These sites included the Tulare Lake Drainage District-north (TLDD-N, water 2.5 ppb Se), TLDD-south (TLDD-S, water 8.6 ppb Se), and Westfarmers (WF, water 190 ppb Se). Highest egg Se concentrations occurred at WF (geometric mean 31.4 ppm dry wt for avocets and 20.5 ppm dry wt for stilts). Mean egg Se concentrations were 6.7 ppm for avocets and 8.4 ppm for stilts at TLDD-S, and 3.3 ppm for avocets and 2.3 ppm for stilts at TLDD-N. Hatching success and incidence of malformations did not differ among sites, but yolk sac-free hatching weights and bone lengths were less for avocets at the WF site, whereas liver weights and liver to body weight ratios were greater at that site. With increasing Se concentration, oxidative stress was most apparent in avocet hatchlings from WF: hepatic glutathione (GSH) peroxidase activity increased, glucose-6-phosphate dehydrogenase activity decreased, and oxidized glutathione (GSSG) concentration as well as the ratio of GSSG to reduced GSH concentration increased. In stilts, hepatic GSH concentration was lower in WF hatchlings. In conclusion, our findings of Se-impaired embryo growth and hepatotoxicity in avocet hatchlings suggest that oxidative stress observed in hatchlings may be related to these biological effects and may serve as a potential bioindicator of subsequent impaired functions.

Agriculture↗

PubMed2000

The selenium-coxsackievirus connection: chronicle of a collaboration.

This review provides a historical account of a collaboration established between a nutritionist and a virologist to investigate the interrelationship of host nutritional status and viral virulence. The parties to this collaboration consider themselves specialists in the fields of antioxidant nutrition and viral immunology, respectively. The advantages of such talent pooling are discussed (rapid startup, well-focused experimentation, ability to visualize the "big picture"), as are some of the disadvantages (limited common scientific vocabulary, proper apportioning of credit, lack of institutional infrastructure to house such efforts). The common perception that some of the most exciting science occurs when the advancing edges of two disparate disciplines intersect is borne out by this project because host nutriture was shown for the first time to influence the genetic make-up of an invading viral pathogen. Encouragement of joint cooperative ventures should have a high priority as demanded by increasingly difficult scientific problems and as desired by scientists themselves who wish to see their research progress more quickly.

Animals↗

PubMed1982

[Activity of the glutathione redox system in human erythrocytes at various ages].

Human erythrocytes were separated into three groups according to their density and age by centrifugation in a continuous Percoll gradient. The specific activities of glucose-6-phosphate dehydrogenase, catalase, glutathione peroxidase, glutathione reductases as well as the glutathione and selenium content were highest in the youngest cell and uniformly decreased by about 20-30% in the eldest group. The age-dependence of superoxide dismutase was much more pronounced. The malondialdehyde content taken as an estimate for lipid peroxidation showed an inverse age dependence and increased by 35% in the eldest cell population. Red blood cells from 10 anemic patients exhibited less glutathione and also less malondialdehyde, while GSH-peroxidase and GSSG-reductase contents were higher. The parameters showed similar age profiles as in healthy subjects. The findings support the concept of lipid peroxidation as one of the causal events in red cell aging, but do not allow to deduce the involvement of a single enzyme related to the glutathione redox cycle in this process.

Adult↗

PubMed2006

Update on clinical micronutrient supplementation studies in the critically ill.

PURPOSE OF REVIEW: During the past 2 years a number of studies, meta-analyses and reviews have shown that micronutrient supplementation may be beneficial in critical illness. Selenium is emerging as a particularly important micronutrient. This paper reviews the evidence from trials in the critically ill, putting mechanisms, methods and shortcomings into perspective. RECENT FINDINGS: There is growing evidence that antioxidant supplements, particularly high-dose selenium, may reduce mortality, infectious complications, and improve wound healing. Deleterious effects may result from prolonged high doses, whereas short-term high dose supplements are probably safe in most critically ill populations. SUMMARY: Plasma micronutrient concentrations are low during critical illness, as a result of losses, low intakes and dilution, and redistribution from plasma to tissues. An assessment of status is difficult. Micronutrient supplements appear beneficial in conditions such as major burns, trauma and sepsis and stroke, and are most likely to benefit patients with previous or actual depletion. The intravenous route seems more efficient than the enteral. Although chronic high intakes may be harmful, short-term interventions appear to be free of deleterious effects. Further research is required to determine the optimal micronutrient combinations and the doses required according to the timing of intervention and severity of disease.

Antioxidants↗

PubMed2000

[Syntheses, reactions and spectroscopic properties of cluster compounds containing ME4 (M = Mo, W; E = S, Se) units].

The synthetic reactions and spectroscopic studied of molybdenum (tungsten) -copper (silver, iron) -sulphur (selenium) cluster compounds, which can be prepared by the stepwise or unit construction reactions through the successive addition ML (L = Cl, Br, Sr, R2 etc) across six edges or four faces of ME4 (M = Mo, W; E = S, Se) tetrahedra, are described. A series of Mo (W)-Cu-S cluster compounds, (Et4N)2 [MCu2E4 (S2CNR2)2], (Et4N)2 [MCu2E3O (S2CNR2)2], [MCu2E4 (dppe)2] (dppe = bis (diphenylphosphine) ethane), (Et4N)2 [MCu3E4 (S2CNR2)4] (M = Mo, E = Se, R = Et (1a), R2 = C4H8 (1b), R = PhCH2 (lc)), (Et4N)2 [MCu4E4 (S2CNR2)4] (M = Mo, E = Se, R = Me (2)) (Et4N)2 [M2Cu4S8 (S2CNEt2)2], (Et4N)2 [M2Cu4S6O2- (S2CNC4H8)2], [Mo2Cu4S8 (dppm)2], [Mo2Cu4S6O2 (dppm)2], (dppm = bis (diphenylphosphine) -methane), (Et4N)4 (ME4Cu10L12) (M = Mo, E = Se, L = PhCH2S (3)), MoFe3Se4 (mu-R2NCS2)2 (R2NCS2)4 have been prepared and characterized by UV, IR and X-ray diffraction analyses.

Copper↗

PubMed1995

Vitamin E, selenium, trolox C, ascorbic acid palmitate, acetylcysteine, coenzyme Q, beta-carotene, canthaxanthin, and (+)-catechin protect against oxidative damage to kidney, heart, lung and spleen.

Male Sprague-Dawley rats were fed diets that varied qualitatively and quantitatively in antioxidants. Kidney, heart, lung, and spleen homogenates were incubated at 37 degrees C with and without hydroperoxide or Fe+2. Protection of antioxidants against oxidative damage to tissue was determined by measurement of oxidized heme proteins. Tissues from rats supplemented with dietary vitamin E and selenium showed protection compared to tissues from rats on the basal diet. Tissues from rats with diets containing larger quantities of antioxidants and both fat soluble antioxidants: vitamin E, beta-carotene, coenzyme Q10, ascorbic acid 6-palmitate and water soluble antioxidants: selenium, trolox C, acetylcysteine, coenzyme Q0, (+)-catechin, showed the highest protection.

Acetylcysteine↗

PubMed1987

Analysis of the high-spin states of the 2[4Fe-4Se]+ ferredoxin from Clostridium pasteurianum by Mössbauer spectroscopy.

A Mössbauer study of the three spin states of the reduced selenium-substituted 2[4Fe-4Se]+ ferredoxin from Clostridium pasteurianum was carried out at T = 1.6 K, in perpendicular and parallel applied magnetic fields of up to 10 T. In low (0.1 T) applied fields, the spectra of the classical S = 1/2 state exhibit magnetic hyperfine patterns arising from two pairs of iron atoms with opposite hyperfine fields. The S = 7/2 state is in the slow relaxation limit at T less than or equal to 4 K in the absence of applied field. The corresponding Mössbauer spectrum can be understood in terms of anti-parallel coupling between one high-spin Fe3+ ion (Hhf = +21.2 T) and three high-spin Fe2+ ions (Hhf,xy = -25.5 T, Hhf,z = -28.5 T). For the S = 3/2 spin state, the use of high (8-10 T) applied fields was necessary to ensure the validity of the high-field approximation and overcome the intercluster spin-spin interaction. The spectral data obtained under such conditions allowed the determination of the hyperfine field (-4.2 T) and a tentative estimation of the zero-field splitting (D approximately less than 3 cm-1).

Clostridium↗

PubMed1996

Identification and metabolism of selenocysteine-glutathione selenenyl sulfide (CySeSG) in small intestine of mice orally exposed to selenocystine.

This investigation was carried out to elucidate the chemical form of selenium-containing metabolite in small intestine of ICR male mice orally administered selenocystine (CySeSeCy). The metabolite in intestinal cytosol of mice treated with CySeSeCy (50 mg/kg) was identified as selenocysteine-glutathione selenenyl sulfide (CySeSG) by high performance liquid chromatography using a gel filtration and reversed phase column. Hydrogen selenide formation was caused as a result of the anaerobic reaction between the CySeSG and liver cytosol containing selenocysteine beta-lyase, which specifically acts on selenocysteine (CySeH). Effects of GSH or glutathione reductase on hydrogen selenide formation from CyseSG reacted with the liver cytosol were examined. The CySeSG was nonenzymatically reduced to CySeH by excess GSH in the liver cytosol. It was also recognized that CySeSG was enzymatically reduced to CySeH by glutathione reductase in the presence of NADPH. These results indicate that the chemical form of this metabolite is CySeSG, which has a molecular weight of 473, the CySeSG is then reduced by excess GSH and/or glutathione reductase yielding CySeH, which is decomposed by selenocysteine beta-lyase to hydrogen selenide. CySeSG may be a stable precursor of hydrogen selenide in animals.

Administration, Oral↗

PubMed2004

Relationship among serum selenium levels, lipid peroxidation, and acute bronchiolitis in infancy.

Thirty-four infants with acute bronchiolitis and 25 age-matched healthy controls were enrolled to investigate the possible relationship between serum malondialdehyde (MDA) and selenium (Se) levels and the occurrence and severity of acute bronchiolitis in children. Serum samples were taken for serum Se and MDA measurements, and the clinical score was assessed at admission. Blood was taken again from the children with bronchiolitis at 2 mo after discharge from the hospital. Mean serum MDA levels were significantly higher in patients with acute bronchiolitis than at the postbronchiolitis stage and the controls (4.2+/-2.5 nmol/L, 1.4+/-0.8 nmol/L, and 0.7+/-0.2 nmol/L, respectively [p<0.001]). Infants with bronchiolitis had lower mean serum Se levels at the acute stage than after 2 mo (31.7+/-28.9 micro g/L versus 68.4+/-26.4 micro g/L, p<0.05, respectively); both of which were significantly lower than the control group measurements (145.0+/-21.9 micro g/L) (p<0.001). There was a negative correlation between serum MDA and Se levels in the patient group (r= -0.85, p<0.001). The age of the patient, child's immunization status, parental smoking habit, and family crowding index were not correlated with serum Se, MDA levels, or clinical score at admission. In conclusion, increased MDA levels and impaired Se status demonstrate the presence of possible relationship of these parameters with pathogenesis of acute bronchiolitis, and antioxidant supplementation with Se might be thought to supply a beneficial effect against bronchiolitis.

Age Factors↗

PubMed1996

Bioavailability of selenium accumulated by selenite-reducing bacteria.

The bioavailability of selenium (Se) was determined in bacterial strains that reduce selenite to red elemental Se (SeO). A laboratory strain of Bacillus subtilis and a bacterial rod isolated from soil in the vicinity of the Kesterson Reservoir, San Joaquin Valley, CA, (Microbacterium arborescens) were cultured in the presence of 1 mM sodium selenite (Na2SeO3). After harvest, the washed, lyophilized B. Subtilis and M. arborescens samples contained 2.62 and 4.23% total Se, respectively, which was shown to consist, within error, entirely of SeO. These preparations were fed to chicks as supplements to a low-Se, vitamin E-free diet. Three experiments showed that the Se in both bacteria had bioavailabilities of approx 2% that of selenite. A fourth experiment revealed that gray SeO had a bioavailability of 2% of selenite, but that the bioavailability of red SeO depended on the way it was prepared (by reduction of selenite). When glutathione was the reductant, bioavailability resembled that of gray SeO and bacterial Se; when ascorbate was the reductant, bioavailability was twice that level (3-4%). These findings suggest that aerobic bacteria such as B. subtilis and M. arborescens may be useful for the bioremediation of Se-contaminated sites, i.e., by converting selenite to a form of Se with very low bioavailability.

Animals↗

PubMedDate not supplied

Selenium as an anticancerogenic agent.

Selenium is an essential component of the intracellular antioxidant system, which defends the cell and the whole organism against oxidative damage and so from oxidative disease, especially from cancer. Selenium may be considered as an anticancerogenic agent, and a higher concentration of selenium in plasma may be a protective factor against human malignancies. It is also interesting to note that higher doses of selenium, applied to patients simultaneously with chemotherapy, may lower the toxicity of antineoplasm drugs without weakening the therapeutic effect.

Anticarcinogenic Agents↗

PubMed2006

Spatial distribution of natural enrichments of arsenic, selenium, and uranium in a minerotrophic peatland, Gola di Lago, Canton Ticino, Switzerland.

Gola di Lago is a small (ca. 3 ha), minerotrophic peatland in Canton Ticino, southern Switzerland. Chemical analyses of peat show remarkable concentrations of As, Se, and U. Coring at regular intervals (19 sites) revealed several zones of pronounced accumulation, with As concentrations up to 350 mg kg(-1) (2000 mg kg(-1) on a mineral matter basis). Both Fe and S are also enriched at this depth, suggesting that redox-related transformations have affected all three elements. High concentrations of Se (up to 28 mg kg(-1)) and U (up to 470 mg kg(-1)) were also detected, representing on a mineral matter basis 350 and 2900 mg kg(-1), respectively. An intermittent stream entering the peatland contained up to 400 microg of As L(-1), but the permanent stream leaving the mire contains <2 microg L(-1). A three-dimensional map of the spatial distribution of As shows that the main source of As is the intermittent stream and not the basal, mineral sediment underlying the peatland. Arsenic is highly enriched not only in shallow peat layers at the interface between the stream and peatland today but also in deeper peat layers in the center of the mire, at what must have been the stream-peat interface in the past. By sequential extraction of fresh peat samples, 100% of the As could be extracted from a shallow sample but only 19% from a sample taken from the deeper layers. In both cases, most of the As was associated with the organic matter fraction (73% and 57% respectively). Although this peatland is an effective geochemical trap for As in the stream waters, the mechanisms of removal remain unclear.

Arsenic↗

PubMed2007

Arsenic speciation and accumulation in evapoconcentrating waters of agricultural evaporation basins.

To sustain agricultural productivity, evaporation basins (or ponds) have been widely used for the disposal of agricultural drainage in areas requiring subsurface drainage in the San Joaquin Valley of California, USA. The drainage water contains elevated concentration of trace elements including selenium (Se) and arsenic (As). Unlike Se, little information is available about As, a potentially high risk element. The objective of this study was to characterize the chemical behavior of As and acquire data for better understanding of biogeochemical processes and conditions affecting As fate in evaporation ponds. The study site was a 726 ha evaporation basin facility (containing 10 cells with water flowing in series) in the hydrologically closed Tulare Basin of California. We examined water chemistry, As concentration and speciation along the water flow path between cells as well as within the cells. Arsenic concentrations in the water increased linearly with Cl(-), a conservative ion from evapoconcentration. Reduced As species as arsenite [As(III)] and organic arsenic (org-As) also increased with increases in Cl(-) and salinity. Water samples with elevated EC (i.e., towards the end of flow path) had high dissolved organic matter, low dissolved oxygen, and elevated sulfide concentrations, indicating the development of reducing conditions. We hypothesize that such changes could facilitate the reduction of arsenate [As(V)] to As(III) and org-As. Elevated As in sediment profiles indicate a solid phase sink mechanism, but not significant enough to remove and reduce As concentrations in the water columns. These findings help us better define the processes that affect As in drainage facilities and contribute to our understanding of how As behaves in other regions of the world that have similar climatic and hydrogeochemical conditions.

Agriculture↗

PubMed2006

Selenium speciation in kerogen from two Chinese selenium deposits: environmental implications.

Selenium is an essential trace element for humans, animals, and vegetation. Its occurrence in the environment is characterized by specific chemical and biochemical properties that control its elemental solubility, toxicity, and environmental behavior. The Laerma Se-Au deposit and Yutangba Se deposit are two important Se-bearing deposits found recently in China. In one of these areas (Yutangba), a serious environmental impact happened involving Se poisoning. Previous studies have shown that Se in both deposits is closely related to organic matter, especially kerogen fractions, but detailed relationships between Se and kerogen and Se chemical forms were not reported. In this study, the different speciation of Se is identified by transmission electron microscopy (TEM) and other geochemical techniques (infrared spectra (IS) and X-ray diffraction (XRD)) from kerogen samples extracted from ore rocks of both deposits. The occurrence of organically bound Se in the Laerma deposit and elemental Se nanograins in the Yutangba deposit is observed, indicating the diversity of formation mechanisms and possible chemical forms of Se in Se-rich rocks. The formation of elemental Se associated with organic matter is likely related to redox conditions, whereas organic species are related to the higher sulfur content of kerogen and possibly result from S-Se substitutions. This discovery provides new evidence with which to assess potential Se mobility during weathering of ore-bearing rocks. In an altered rock, the elemental Se in kerogen is more steadily mobilized and is potentially accumulated by vegetation, which may explain the sudden prevalence of Se poisoning in the Yutangba area. In contrast, organically bound Se seems more resistant to chemical alteration compared to other Se species so that its bioavailability may be very restricted.

Adsorption↗

PubMed2003

Evaluation of sulfur, selenium and tellurium catalysts with antioxidant potential.

Oxidative stress is implicated, either directly or indirectly, in the pathology of a range of human diseases. As a consequence, the development of efficient antioxidants for medical use has become increasingly important. We have synthesised a range of structurally related organo-sulfur, -selenium and -tellurium agents and demonstrated that a combination of electrochemical methodology, in vitro assays and cell culture tests can be used to rationalise the antioxidant activity of these catalytic agents. Based on its exceptionally low anodic oxidation potential (Epa) and high activity against the representative oxidative stressors tert-butyl hydroperoxide and peroxynitrite, 4,4'-dihydroxydiphenyltelluride is predicted to be a potent antioxidant. This compound exhibits a correspondingly high activity with a remarkably low IC50 value of 20 nM, when tested in PC12 cell culture using a bioassay indicative of the early stages of Alzheimer's disease.

Alzheimer Disease↗