In vitro study on the competitive reactions between arsenite and selenite with glutathione.

Exposure to arsenic can cause various biological effects by increasing the production of reactive oxygen species (ROS). Selenium acts as a beneficial element by regulating ROS and limiting heavy metal uptake and translocation. There are studies on the interactive effects of As and Se in plants, but the antagonistic and synergistic effects of these elements based on their binding to glutathione (GSH) molecules have not been studied yet. In this study, we aimed to investigate the antagonistic or synergistic effects of As and Se on the binding mechanism of Se and As with GSH at pH 3.0, 5.0, or 6.5. The interaction of As and Se in Se(SG)2 + As(III) or As(SG)3 + Se(IV) binary systems and As(III) + Se(IV) + GSH ternary system were examined depending on their ratios via liquid chromatography diode array detector/electrospray mass spectrometry (LC-DAD/MS) and liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS). The results showed that the formation of As(GS)3 was not detected in the As(III) + Se(SG)2 binary system, indicating that As(III) did not affect the stability of Se(SG)2 complex antagonistically. However, in the Se(IV) + As(SG)3 binary system, the addition of Se(IV) to As(SG)3 affected the stability of As(SG)3 antagonistically. Se(IV) reacted with GSH, disrupting the As(SG)3 complex, and consequently, Se(SG)2 formation was measured using LC-MS/DAD. In the Se(IV) + GSH + As(III) ternary system, Se(SG)2 formation was detected upon mixing As(III), Se(IV), and GSH. The increase in the concentration of As(III) did not influence the stability of the Se(SG)2 complex. Additionally, Se(IV) has a higher affinity than As(III) to the GSH, regardless of the pH of the solution. In both binary and ternary systems, the formation of the by-product glutathione trisulfide (GSSSG) was detected using LC-ESI-MS/MS.

Evaluation of colloidal platinum on cytotoxicity, oxidative stress and barrier permeability across the gut epithelium.

Colloidal platinum (Pt) is widely consumed due to its health promoting benefits. However, the exact biological effects of these nanoparticles have not been studied in detail, particularly in the gut. In the present study we observed that colloidal Pt was not cytotoxic towards three different epithelial colon cancer cell lines. Co-treatment of the colon cancer cell line Caco-2 with the oxidative stress inducing agent hydrogen peroxide (H2O2) and colloidal Pt resulted in a significant decrease in H2O2 induced oxidative stress. Colloidal Pt by itself did not induce any oxidative stress. Additionally, both overnight pretreatment of Caco-2 cells with colloidal Pt followed by 1 h treatment with H2O2, or co-treatment of cells for 1 h with colloidal Pt and H2O2 resulted in a significant recovery of cell death. Of note, the same protective effects of colloidal Pt were not observed when the oxidative stress was induced in the presence of 2, 2-azobis (2-amidinopropane) dihydrochloride, indicating that the source of free radicals may define the outcome of anti-oxidant activity of colloidal Pt. Colloidal Pt was also able to cross a model intestinal barrier formed in vitro with differentiated Caco-2 cells easily. Overall, our data indicate that colloidal Pt was not toxic towards intestinal epithelial cells, reduced H2O2 induced oxidative stress, protected from oxidative stress related death of intestinal epithelial cells and could pass a model gut barrier easily. Colloidal Pt can therefore be consumed orally for its anti-oxidant and other health promoting benefits.

'Fairy Chimney'-shaped tandem metamaterials as double resonance SERS substrates.

A highly tunable design for obtaining double resonance substrates to be used in surface-enhanced Raman spectroscopy is proposed. Tandem truncated nanocones composed of Au-SiO(2)-Au layers are designed, simulated and fabricated to obtain resonances at laser excitation and Stokes frequencies. Surface-enhanced Raman scattering experiments are conducted to compare the enhancements obtained from double resonance substrates to those obtained from single resonance gold truncated nanocones. The best enhancement factor obtained using the new design is 3.86 × 10(7). The resultant tandem structures are named after "Fairy Chimneys" rock formation in Cappadocia, Turkey.

Tunable surface plasmon resonance on an elastomeric substrate.

In this study, we demonstrate that periods of metallic gratings on elastomeric substrates can be tuned with external strain and hence are found to control the resonance condition of surface plasmon polaritons. We have excited the plasmon resonance on the elastomeric grating coated with gold and silver. The grating period is increased up to 25% by applying an external mechanical strain. The tunability of the elastomeric substrate provides the opportunity to use such gratings as efficient surface enhanced Raman spectroscopy substrates. It's been demonstrated that the Raman signal can be maximized by applying an external mechanical strain to the elastomeric grating.

Plasmonic band gap structures for surface-enhanced Raman scattering.

Surface-enhanced Raman Scattering (SERS) of rhodamine 6G (R6G) adsorbed on biharmonic metallic grating structures was studied. Biharmonic metallic gratings include two different grating components, one acting as a coupler to excite surface plasmon polaritons (SPP), and the other forming a plasmonic band gap for the propagating SPPs. In the vicinity of the band edges, localized surface plasmons are formed. These localized plasmons strongly enhance the scattering efficiency of the Raman signal emitted on the metallic grating surfaces. It was shown that reproducible Raman scattering enhancement factors of over 10(5) can be achieved by fabricating biharmonic SERS templates using soft nano-imprint technique. We have shown that the SERS activities from these templates are tunable as a function of plasmonic resonance conditions. Similar enhancement factors were also measured for directional emission of photoluminescence. At the wavelengths of the plasmonic absorption peak, directional enhancement by a factor of 30 was deduced for photoluminescence measurements.

Effect of solvent refractive index on the surface plasmon resonance nanoparticle optical absorption.

Optical properties of plasmon coupled silver and gold nanoparticles were studied as a function of the refractive index of the surrounding medium. Our studies confirmed that the effect of changes in the refractive index of the surrounding medium was more difficult to demonstrate from an experimental point of view, because of the very high susceptibility of nanoparticles to aggregate in aqueous and organic solvents. Whereas the position of the absorption bands of triiodide in these solvents shows a clear dependence on medium's refractive index, the surface plasmon band position of silver and gold nanoparticles do not exhibit the same dependence. This is attributed to a non-negligible interaction of these solvents with nanoparticle surfaces.

Differentiation of domains in composite surface structures by charge-contrast X-ray photoelectron spectroscopy.

An external bias is applied to two samples containing composite surface structures, while recording an XPS spectrum. Altering the polarity of the bias affects the extent of differential charging in domains that are chemically or electronically different to create a charge contrast. By utilizing this charge contrast, we show that two distinct silicon nitride and silicon oxynitride domains are present in one of the composite samples. Similarly, we use this technique to show that titanium oxide and silicon oxide domains exist as separate chemical entities in another composite sample.

Interference effect of iron on the determination of gold in geological samples using the vapor generation technique and preconcentration in a graphite furnace.

A vapor generation procedure for the production of volatile species of Au was studied using electrothermal atomic absorption spectrometry (ETAAS). The interference effects of iron in solution and in the gas phase in a quartz T-tube were studied for the first time in detail. A dual vapor generation system was used for a single heated quartz tube atomizer, so that it was possible to study interferences and classify them regarding their origins. Results show that both gas-phase and liquid-phase interferences are present. It was also concluded that since the total interference effect causes the Au signal to be lower as compared to only the presence of gas-phase interactions in the experiment, the net liquid-phase interference from Fe should be suppressed. The method described in this study was used for the determination of gold in an ore reference material, Carlin Ore Mine, for the purpose of demonstrating the ability of the reported method to determine Au without any extraction procedure.

X-ray-induced production of gold nanoparticles on a SiO(2)/Si system and in a poly(methyl methacrylate) matrix.

Prolonged exposure to X-rays of HAuCl(4) deposited from an aqueous solution onto a SiO(2)/Si substrate or into a poly(methyl methacrylate) (PMMA) matrix induces reduction of the Au(3+) ions to Au(0) and subsequent nucleation to gold nanoclusters as recorded by X-ray photoelectron spectroscopy. The corresponding major oxidation product is determined as chlorine {HAuCl(4)(ads) + X-rays --> Au(ads) + (3/2)Cl(2)(ads) + HCl(ads)}, which is initially adsorbed onto the surface but eventually diffuses out of the system into the vacuum. The reduced gold atoms aggregate (three-dimensionally) into gold nanoclusters as evidenced by the variation in the binding energy during X-ray exposure, which starts as 1.3 eV but approaches a value that is 0.5 eV higher than that of the bulk gold. The disappearance of the oxidation product (Cl2p signal) and the growth of the nanoclusters (related to the measured binding energy difference between the Si2p of the oxide and Au4f of the reduced gold) exhibit first-order kinetics which is approximately 3 times slower than the reduction of Au(3+), indicating that both of the former processes are diffusion controlled. Similarly, gold ions incorporated into PMMA can also be reduced and aggregated to gold nanoclusters using 254 nm deep UV irradiation in air evidenced by UV-vis-NIR absorption spectrocopy.

Electrothermal atomic absorption spectrometric determination of gold by vapor formation and in situ trapping in graphite tubes.

Gold was determined in ore samples following generation, separation, collection on a graphite cuvette inner wall, and atomization of its volatile species formed by combining an acidified sample solution with an aqueous sodium tetrahydroborate solution at room temperature. A detection limit of 2.6 microg L(-1) (3sigma) was obtained with a 5.0 mL sample volume. Precision of replicate measurements was typically 10% RSD. The overall efficiency of the volatile species generation, transport, and trapping process was 0.4%. Atomization of gold from Pd, Ir, Cu, Ag, and W coated graphite cuvettes, following by trapping of the gaseous volatile gold species on these surfaces, has been investigated. Pd coating was found to decrease the sensitivity. Five microg of Ir, 20 microg of Cu, 20 microg of Ag, and 5 microg of W were chosen as optimum masses. W treatment was the best one for sensitivity enhancement, having an improvement factor of 2.4. Silanization of glass surfaces significantly decreased memory effects; improved peak shapes were thus obtained for flow injection vapor generation atomic absorption spectrometry (FI-VGAAS). The method described in this study was used for the determination of gold in an ore reference material, Gold Ore (MA-1b), Canadian Reference Materials Program.