Cancer Influences the Elemental Composition of the Myocardium More Strongly than Conjugated Linoleic Acids-Chemometric Approach to Cardio-Oncological Studies.

The aim of the study was to verify in a cardio-oncological model experiment if conjugated linoleic acids (CLA) fed to rats with mammary tumors affect the content of selected macro- and microelements in their myocardium. The diet of Sprague-Dawley females was supplemented either with CLA isomers or with safflower oil. In hearts of rats suffering from breast cancer, selected elements were analyzed with a quadrupole mass spectrometer with inductively coupled plasma ionization (ICP-MS). In order to better understand the data trends, cluster analysis, principal component analysis and linear discriminant analysis were applied. Mammary tumors influenced macro- and microelements content in the myocardium to a greater extent than applied diet supplementation. Significant influences of diet (p = 0.0192), mammary tumors (p = 0.0200) and interactions of both factors (p = 0.0151) were documented in terms of Fe content. CLA significantly decreased the contents of Cu and Mn (p = 0.0158 and p = 0.0265, respectively). The level of Ni was significantly higher (p = 0.0073), which was more pronounced in groups supplemented with CLA. The obtained results confirmed antioxidant properties of CLA and the relationship with Se deposition. Chemometric techniques distinctly showed that the coexisting pathological process induced differences to the greater extent than diet supplementation in the elemental content in the myocardium, which may impinge on cardiac tissue's susceptibility to injuries.

Analytical Problems in Separation of Selenomethionine and Its Oxidative Product in HILIC HPLC.

Selenomethionine (SeMet) is one of the main selenium forms in foods and supplements. Determining its presence in natural food samples creates difficulties due to possible oxidation processes. The objective of this study was to evaluate the possible degradation of SeMet in water extracts of green teas, one of the most consumed beverages worldwide. Such a medium has not been investigated at this time. The HILIC-HPLC MS/MS method with different stationary phases was used to achieve the satisfactory separation of SeMet and selenomethionine oxide (SeMetO). The addition of dithiothreitol and ß-mercaptoethanol, recommended to ensure that SeMet is kept in the reduced form, was also evaluated. The best separation was achieved using the zwitterionic HILIC stationary phase coupled to mass spectrometry and MeOH with water (85/15, v/v) as the eluent. Extraction was done with hot water with the addition of ß-mercaptoethanol. The infusions prepared from Lung-Ching teas (from the Zhejiang Province in China) contained the highest concentration of selenium in a typical cup of tea (12.5-17.3 µg L-1). For other tested teas it decreased in the following order: Yunnan > Dilmah > Lipton. For Lung-Ching teas, the sum of concentrations of SeMet and SeMetO corresponded to about 46-63% of the total selenium in their extracts.

Determination of trace levels of selenium in natural water, agriculture soil and food samples by vortex assisted liquid-liquid microextraction method: Multivariate techniques.

A green vortex assisted based liquid-liquid microextraction (VA-LLME) method was developed for preconcentration of selenium. Ammonium pyrrolidine dithiocarbamate (APDC) was used to form a hydrophobic complex with selenium in natural water, agricultural soil and food samples by GFAAS. Whereas Triton X-114, a nonionic surfactant and 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid were used for Se extraction as a dispersing medium. The conical flasks contents were shack on a vortex mixer to increase the extraction efficiency. Multivariate techniques were used to evaluate extraction parameters; pH, vortex time, APDC amount, volume of ionic liquid and Triton X-114 and centrifugation rate on the recovery of Se. The central composite design (CCD) was used for further optimization of the essential extraction parameters. The enhancement factor and limit of detection were obtained as 98.7 and 0.07 µg L-1. The certified reference materials was used for accuracy of method and the related standard deviation was found to be 3.51%. The resulted data indicated that concentrations of Se in all types of water samples were below the permissible limit recommended by WHO.

A water-soluble selenium-enriched polysaccharide produced by Pleurotus ostreatus: Purification, characterization, antioxidant and antitumor activities in vitro.

The development and application of new selenium-enriched polysaccharides has become a critical topic in recent years. In this study, a natural selenium-enriched polysaccharide fraction (Se-POP-21) produced by Pleurotus ostreatus was purified, characterized, and investigated the antioxidant and antitumor activities in vitro. The Se-POP-21 was mainly composed of mannose, glucose, galactose and arabinose, with a molar ratio of 18.01:2.40:26.15:7.34, of which molecular weight was 15,888 Da and the selenium content was 5.31 µg/g. Spectral analysis demonstrated that Se-POP-21 represented a non-triple helix pyranopolysaccharide and selenium occurred in the form of C-O-Se and SeO. Molecular size and morphology studies showed that Se-POP-21 exhibited a spherical shape with a particle size distribution between 100 and 200 nm, even though Se-POP-21 aggregates were also found with a size between 500 and 600 nm. In addition, Se-POP-21 showed strong scavenging capacity to DPPH and hydroxyl radical. More, cell experiments showed that Se-POP-21 could reduce viability of A549, SKOV3, HepG2 and MCF-7 cells, induce apoptosis and inhibit metastasis of A549 cells. A potential mechanism was that Se-POP-21 inhibited the epithelial-to-mesenchymal transition of cancer cells. Se-POP-21 featured no significant effect on normal cells. Se-POP-21 showed great potential to develop into a natural antioxidant or low-toxic antitumor drug.

Zirconium nanoparticles based dispersive solid phase extraction prior to slotted quartz tube-flame atomic absorption spectrophotometry for the determination of selenium in green tea samples.

In this study, a novel, easy, rapid and green zirconium nanoparticles (Zr-NPs) based dispersive solid phase extraction (DSPE) method is presented for the precise and sensitive determination of selenium by slotted quartz tube-flame atomic absorption spectrophotometry (SQT-FAAS). Influential parameters of the extraction procedure were optimized by altering one parameter while keeping the other parameters constant. The optimum conditions were selected as 10 mg of Zr-NPs, 75 s vortex period, and 200 µL of concentrated HCl for 30 mL of sample/standard solution. The linear range of the developed method was found to be between 25 and 100 µg/L, and the respective limits of detection and quantification were 5.3 and 18 µg/L. About 415 folds enhancement in detection power was achieved by the optimized method relative to the conventional FAAS. Green tea samples were spiked and used for recovery experiments and the results obtained were between 92 and 102%.

Gentamicin-Assisted Mycogenic Selenium Nanoparticles Synthesized Under Gamma Irradiation for Robust Reluctance of Resistant Urinary Tract Infection-Causing Pathogens.

The purpose of this research is to compare and enhance the antimicrobial and antibiofilm potentials of the biogenic selenium nanoparticles (Se NPs) produced by cost-effective and eco-friendly green methods. The synthesis of Se NPs is described in this manuscript by two different methods: a biogenic process using Penicillium chrysogenum filtrate and by utilizing gentamicin drug (CN) following the application of gamma irradiation. Se NPs were characterized by UV-Vis., HRTM, FTIR, XRD, DLS, SEM, and EDX mapping technique. Antimicrobial and antibiofilm activities of the synthesized Se NPs were investigated against multidrug-resistant (MDR) bacteria and yeast causing severe diseases such as urinary tract infection (UTI). The biogenic Se NPs exhibited an absorption peak at 435.0 nm while Se NPs-CN showed an absorption peak at 350.0 nm which is related to the surface plasmon resonance (SPR). Data obtained from HRTEM, SEM/mapping, and XRD analysis confirmed the mono-dispersion and crystalline nature of the prepared samples with an average diameter of 33.84 nm and 22.37 nm for the mycogenic Se NPs and Se NPs-CN, respectively. The synthesized Se NPs-CN possesses an encouraging antimicrobial potential with respect to the biogenic Se NPs against all examined UTI-causing microbes. Remarkably, Se NPs-CN showed antimicrobial potential toward Candida albicans with a zone of Inhibition (ZOI) recorded at 26.0 mm, 23.0 mm ZOI for Escherichia coli and 20.0 mm ZOI against Staphylococcus aureus. In addition, the incorporated Se NPs-CN displayed an enhanced percentage of biofilm inhibition of 88.67%, 87.93%, and 85.20% against S. aureus, P. aeruginosa, and E. coli, respectively. Accordingly, the novelty of the present research involves the green synthesis of mono-dispersed Se NPs and combining the synergistic potential of CN with Se NPs for potential biomedical, pharmaceutical, and therapeutic applications especially in the treatment of UTI. Graphical Abstract.

Medición del contenido de selenio en especímenes biológicos: aplicación en el laboratorio clínico / Measurement of selenium content in biological specimens: medicine laboratory application

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Selenium-containing polysaccharides from Lentinula edodes-Biological activity.

We hypothesized that selenium(Se)-enriched polysaccharides would possess superior biological activity when compared to those non-enriched. To verify this hypothesis, we obtained by biotechnological methods a Se-enriched analog of Japanese anticancer drug lentinan and, as a reference, the non-Se-enriched fraction. We tested the effects of the obtained fractions on the proliferation of human peripheral blood mononuclear cells. The results suggested a selective immunosuppressive activity, non-typical for mushroom derived polysaccharides. Both fractions caused significant inhibition of human T lymphocyte proliferation induced by mitogens, without significant effects on B lymphocytes. The inhibitory effect was not due to the toxicity of the examined polysaccharides. In normal (HUVEC) or malignant (HeLa) cells tested fractions significantly enhanced cell viability and protected the cells from oxidative stress conditions. However, we observed no effect of the polysaccharide fractions on the production of reactive oxygen species by granulocytes in vitro. The selenium content increased the biological activity of the tested polysaccharide fractions.

Electrochemical Evaluation of Selenium (IV) Removal from Its Aqueous Solutions by Unmodified and Modified Graphene Oxide.

The removal of selenium from superficial and waste water is a worldwide problem. The maximum limit according to the World Health Organization (WHO) for the selenium in the water is set at a concentration of 10 µg/L. Carbon based adsorbents have attracted much attention and recently demonstrated promising performance in removal of selenium. In this work, several materials (iron oxide based microparticles and graphene oxides materials) and their composites were prepared to remove Se(IV) from water. The graphene oxides were prepared according to the simplified Hummer's method. In addition, the effect of pH, contact time and initial Se(IV) concentration was tested. An electrochemical method such as the differential pulse cathodic stripping voltammetry was used to determine the residual selenium concentration. From the experimental data, Langmuir adsorption model was used to calculate the maximum adsorption capacity. Graphene oxide particles modified by iron oxide based microparticles was the most promising material for the removal of Se(IV) from its aqueous solution at pH 2.0. Its adsorption efficiency reached more than 90% for a solution with given Se(IV) concentration, meanwhile its maximal recorded adsorption capacity was 18.69 mg/g.

A newly synthesized graft copolymer for magnetic solid phase microextraction of total selenium and its electrothermal atomic absorption spectrometric determination in food and water samples.

A newly synthesized polystyrene-g-polyoleic acid-g-polyethylene glycol graft copolymer (PoleS-PEG) was used as adsorbent in the solid phase microextraction of selenium ions by using electrothermal atomic absorption spectrometry (ETAAS). Neodymium magnet was used for separation of analyte ions. Various analytical parameters such as pH, adsorbent amount, mixing time, eluent solution, sample volume, etc. were optimized. The matrix effects of some cations and anions were also studied. The capacity of the adsorbent was found 11.5 mg g-1. The preconcentration factor was found to be 50. The detection limit (LOD) and quantification limit (LOQ) were found 6.06 ng L-1 and 20 ng L-1, respectively. The calibration curve was linear in the range of 0.02-4.0 µg L-1. Relative standard deviation was found 3.2%. The accuracy of the method was provided by using standard reference materials. The optimized method was successfully applied to natural water and food samples.

Development of an algal treatment system for selenium removal: Effects of environmental factors and post-treatment processing of Se-laden algae.

In developing an algal treatment system, selenium (Se) removal efficiency by Chlorella vulgaris was evaluated under various conditions such as Se concentration, algal density, temperature and pH. A maximum removal efficiency plateau of ∼90% was observed between 1000-3000 µg Se/L while the tolerance of Se toxicity was found at 6000 µg Se/L. C. vulgaris of 0.75 g DW/L showed the highest removal efficiency (84%), and volatilization was dominant below 1.37 g DW/L. Se volatilization was two times higher at 25 °C than at 20 °C in the first 24 h. Moreover, the highest removal efficiency (77%) was obtained at pH 8.0, compared to 66.5% at pH 6.5 and 40% at pH 10.0. To prevent ecotoxicity, Se laden algae were further burned to ashes or filtered out by Anodonta woodiana. After burning, biomass Se was reduced by 99%, with organo-Se entirely converted into inorganic Se, lowering Se bioavailability. A. woodiana removed 54% of Se in 24 h, leading to Se bioaccumulation in soft tissues, which may serve as dietary Se supplements for human health. Our results suggest the cleanup of Se-contaminated water from either agricultural runoff or industrial discharge could be achieved using an algal treatment system with minimum potential ecotoxicity.

Use of Selenium-enriched olive leaves in the feed of growing rabbits: Effect on oxidative status, mineral profile and Selenium speciation of Longissimus dorsi meat.

In the present study the use of Selenium-fortified olive leaves as potential dietary source of Se in rabbit nutrition was evaluated. Sixty New Zealand White rabbits (35 days of age) were randomly assigned to the following dietary treatments: standard diet (C), and C supplemented with either 10% olive leaves (OL) or 10% Selenium-fortified olive leaves (SeOL; 100 mg/L of foliar spray sodium selenate solution). At 70 days of age, 10 rabbits per group were slaughtered and the oxidative status, mineral profile and Selenium speciation of Longissimus dorsi meat was analyzed. Meat of the SeOL group exhibited better oxidative status (lower TBARS, higher GPx and α-tocopherol values) and a 5-fold higher Se content compared to that of the other treatments. The main Se form was SeMet (7-fold higher in the SeOL group), followed by SeCys2. The present trial demonstrates the possibility of using agro-industrial by-products as ingredients in rabbit feeds, thereby enriching meat bioactive compound content.

Biosynthesis of Ag, Se, and ZnO nanoparticles with antimicrobial activities against resistant pathogens using waste isolate Streptomyces enissocaesilis.

Nanoparticles (NPs) are gaining special interest due to their recent applications as antimicrobial agents to defeat the massive threat of resistant pathogens. This study focused on the utilisation of Streptomyces isolate S12 purified from waste discharge soil in the biological synthesis of silver (Ag), selenium (Se), and zinc oxide (ZnO) NPs. The isolate S12 was related to Streptomyces enissocaesilis according to 16S rRNA sequence analysis, morphological characteristics, and biochemical reactions. The cell-free supernatant has been used for the synthesis of Ag, Se, and ZnO NPs. The synthesised NPs were characterised using ultraviolet-visible spectroscopy, dynamic light scattering (DLS), transmission electron microscopy, and Fourier transform infrared spectroscopy. The biogenic NPs were evaluated for antimicrobial effects against different Gram-positive and Gram-negative resistant isolates using the broth microdilution method. They showed antibacterial effect against standard and resistant isolates; Bacillus cereus, Staphylococcus aureus ATCC 29213, S. aureus S1.1, methicillin resistant S. aureus (MRSA 303, 402 and 807), Escherichia coli ATCC 12435, E. coli E7, Klebsiella pneumoniae ATCC 51503, K. pneumoniae K5, K112, Pseudomonas aeruginosa PAO1, and P. aeruginosa P8. This study showed the green synthesis of various NPs using Streptomyces isolate S12 which demonstrated diverse activities against multi-drug resistant isolates.

Preparation, structural characterization and bioactivities of Se-containing polysaccharide: A review.

Se-containing polysaccharide is known to Se-conjugated macromolecule, with potent bioactivities due to the synergistic effects of Se and native polysaccharide. It is not only explored as a novel Se source in dietary supplement, but also as the superb bioactive component owning various functions, including antioxidant, antitumor, immune-enhancement, hepatoprotective, antidiabetic, anti-inflammatory and neuroprotective activities. Se-containing polysaccharide can exert the efficacy of Se and polysaccharide, and its activities are much higher than those of Se or polysaccharide. In the last decades, numerous reports on Se-containing polysaccharide (including natural Se-containing polysaccharide and selenylated polysaccharide) appeared in literature. For the first time, this article systematically introduces recent advances on preparation, structural characterization and bioactivities of Se-containing polysaccharide in details, and discusses its future prospects and the weaknesses in the current study.

Selenium and selenium species in feeds and muscle tissue of Atlantic salmon.

Selenium (Se) is an essential element for animals, including fish. Due to changes in feed composition for Atlantic salmon (Salmo salar), it may be necessary to supplement feeds with Se. In the present work, the transfer of Se and Se species from feed to muscle of Atlantic salmon fed Se supplemented diets was studied. Salmon were fed basal fish feed (0.35 mg Se/kg and 0.89 mg Se/kg feed), or feed supplemented either with selenised yeast or sodium selenite, at low (1-2 mg Se/kg feed) and high (15 mg Se/kg feed) levels, for 12 weeks. For the extraction of Se species from fish muscle, enzymatic cleavage with protease type XIV was applied. The extraction methods for Se species from fish feed were optimised, and two separate extraction procedures were applied, 1) enzymatic cleavage for organic Se supplemented feeds and 2) weak alkaline solvent for inorganic Se supplemented feeds, respectively. For selenium speciation analysis in feed and muscle tissue anion-exchange HPLC-ICP-MS for analysis of inorganic Se species and cation-exchange HPLC-ICP-MS for analysis of organic Se species, were applied. In addition, reversed phase HPLC-ICP-MS was applied for analysis of selenocysteine (SeCys) in selected muscle samples. The results demonstrated that supplemented Se (organic and inorganic) accumulated in muscle of Atlantic salmon, and a higher retention of Se was seen in the muscle of salmon fed organic Se diets. Selenomethionine (SeMet) was the major Se species in salmon fed basal diets and diets supplemented with organic Se, accounting for 91-118% of the total Se. In contrast, for muscle of salmon fed high inorganic Se diet, SeMet accounted for 30% of the total Se peaks detected. Several unidentified Se peaks were detected, in the fish fed high inorganic diet, and analysis showed indicated SeCys is a minor Se species present in this fish muscle tissue.

Preparation and purification of organic samples for selenium isotope studies.

Selenium (Se) is an important micronutrient but also a strong toxin with a narrow tolerance range for many organisms. As such, a globally heterogeneous Se distribution in soils is responsible for various disease patterns (i.e. Se excess and deficiency) and environmental problems, whereby plants play a key role for the Se entrance into the biosphere. Selenium isotope variations were proved to be a powerful tracer for redox processes and are therefore promising for the exploration of the species dependent Se metabolism in plants and the Se cycling within the Critical Zone. Plant cultivation setups enable systematic controlled investigations, but samples derived from them-plant tissue and phytoagar-are particularly challenging and require specific preparation and purification steps to ensure precise and valid Se isotope analytics performed with HG-MC-ICP-MS. In this study, different methods for the entire process from solid tissue preparation to Se isotope measurements were tested, optimized and validated. A particular microwave digestion procedure for plant tissue and a vacuum filtration method for phytoagar led to full Se recoveries, whereby unfavorable organic residues were reduced to a minimum. Three purification methods predominantly described in the literature were systematically tested with pure Se solution, high concentrated multi-element standard solution as well as plant and phytoagar as target matrices. All these methods efficiently remove critical matrix elements, but differ in Se recovery and organic residues. Validation tests doping Se-free plant material and phytoagar with a reference material of known Se isotope composition revealed the high impact of organic residues on the accuracy of MC-ICP-MS measurements. Only the purification method with no detectable organic residues, hydride generation and trapping, results in valid mass bias correction for plant samples with an average deviation to true δ82/76Se values of 0.2 ‰ and a reproducibility (2 SD) of ± 0.2 ‰. For phytoagar this test yields a higher deviation of 1.1 ‰ from the true value and a 2 SD of ± 0.1 ‰. The application of the developed methods to cultivated plants shows sufficient accuracy and precision and is a promising approach to resolve plant internal Se isotope fractionations, for which respective δ82/76Se values of +2.3 to +3.5 ‰ for selenate and +1.2 to +1.9 ‰ for selenite were obtained.

Separation of selenium species and their sensitive determination in rice samples by ion-pairing reversed-phase liquid chromatography with inductively coupled plasma tandem mass spectrometry.

A highly sensitive method was developed for the simultaneous separation and determination of organic and inorganic selenium species in rice by ion-pairing reversed-phase chromatography combined with inductively coupled plasma tandem mass spectrometry. To achieve a good separation of these species, a comparison between anion-exchange chromatography and ion-pairing reversed-phase chromatography was performed. The results indicated that ion-pairing reversed-phase chromatography was more suitable due to better separation and higher sensitivity for all analytes. In this case, a StableBond C18 column proved to be more robust or to have a better resolution than other C18 columns, when 0.5 mM tetrabutylammonium hydroxide and 10 mM ammonium acetate at pH 5.5 were used as the mobile phase. Moreover, an excellent sensitivity was obtained in terms of interferences by means of tandem mass spectrometry in the hydrogen mode. The detection limits were 0.02-0.12 µg/L, and recoveries of five selenium species were 75-114%, with relative standard deviations ≤ 9.4%. This method was successfully applied to the analysis of rice samples. Compared with previous studies, the proposed method not only gave comparable results when used for measuring selenium-enriched rice, but it can provide greater sensitivity for the detection of low concentrations of selenium species in rice.

Selenite removal and reduction by growing Aspergillus sp. J2.

In this study, the removal and reduction of selenite [Se(IV)] by growing Aspergillus sp. J2 were investigated. The lag phase, growth rate and biomass of J2 was not significantly influenced by the presence of 100 mg/L Se(IV). A rapid Se(IV) removal process took place from the 3rd to the 4th day during the growth of J2. Scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction analyses showed that the Se(IV) did not cause any visible effects on cell morphology and the reduced amorphous elemental selenium [Se(0)] nanoparticles were mainly on the surface of the mycelial cell walls. The macromolecules containing amine groups also interact with Se(IV) and could play an important role in Se(IV) removal by J2.

Deproteinization assessment using isotopically enriched compounds to trace the coprecipitation of low-molecular-weight selenium species with proteins.

Studies have shown that information related to the presence of low-molecular-weight metabolites is frequently lost after deproteinization of complex matrices, such as blood and plasma, during sample preparation. Therefore, the effect of several deproteinization reagents on low-molecular-weight selenium species has been compared by species-specific isotope labeling. Two isotopically enriched selenium tracers were used to mimic models of small inorganic anionic (77Se-selenite) and organic zwitterionic (76Se-selenomethionine) species. The results presented here show that the use of a methanol-acetonitrile-acetone (1:1:1 v/v/v) mixture provided approximately two times less tracer loss from plasma samples in comparison with the classic procedure using acetonitrile, which may not be optimal as it leads to important losses of low-molecular-weight selenium species. In addition, the possible interactions between selenium tracers and proteins were investigated, revealing that both coprecipitation phenomena and association with proteins were potentially responsible for selenite tracer losses during protein precipitation in blood samples. However, coprecipitation phenomena were found to be fully responsible for losses of both tracers observed in plasma samples and of the selenomethionine tracer in blood samples. This successfully applied strategy is anticipated to be useful for more extensive future studies in selenometabolomics.