Se Molar Ratio Research Articles

Thickness dependent correlation between structural and optical properties of textured CdSe thin film

Nano-crystalline CdSe thin films of different thicknesses under sub-micron range were deposited on glass substrate via thermal evaporation route. A gradual deterioration in film crystallinity confirmed by XRD line profile analysis has been accompanied by a reduction in Cd to Se molar ratio as the film thickness decreases. A coordinated microstructural and crystallographic orientation distribution analysis explicitly demonstrated that CdSe tends to grow in nano-sized columns with hexagonal c-axis parallel to its growth direction on glass substrate. A thickness dependence of structural evolution was discussed in terms of aspect ratio of the columnar structure and dispersion in orientation of hexagonal (002) basal plane. The variation in the spectra of optical constants [n(λ), k(λ)] obtained from Swanepoel envelop method was interpreted in terms of crystallographic defects arising from stoichiometric disorder which was also accounted for the observed thickness dependent shifts in band gap and valence band split energy. The bathochromic shifts in dielectric and energy loss functions, optical conductivity, skin depth and cut-off energy were discussed in detail along with the variations in their spectral shapes in connection with the dispersion in the real and imaginary parts of complex refractive index, which might shed a new light upon holistic comprehension of thickness dependent optical properties of other chalcogenide semiconducting thin films.

Controlling defect state emission in ultra-small sized tellurium doped CdSe nanocrystals via two-phase synthesis method

The utilization of semiconductor nanocrystals as white light emission source draws intense attention since semiconductor nanocrystals are promising candidates to fabricate new generation light emitting diodes. However, to synthesize high quality white light emitting semiconductor nanocrystals under mild reaction conditions at single step is a challenge. Here, we synthesized tellurium doped cadmium selenide (Te-doped CdSe) nanocrystals by using two phase synthesis method under mild reaction conditions at single step. Random localization of tellurium atoms in cadmium selenide nanocrystals caused emergence of defect state emission. The defect state emission was controlled by tuning initial Te:Se molar ratio in aqueous phase of the two phase system. Luminescence behaviour of Te-doped CdSe nanocrystals was affected by defect state emission and therefore, dual light emission (composition of blue-green light, whitish color) was observed. The Te-doped CdSe had cubic structure with Te composition at most 10% with size ranging around 1.8 nm. The CRI 1931 coordinates of the Te-doped CdSe nanocrystals revealed that Te-doped CdSe nanocrystals can be a powerful constituent for new generation light emitting diodes.

Efficient Solar-to-Hydrogen Conversion from Neutral Electrolytes using Morphology-Controlled Sb2Se3 Light Absorbers

We present a novel solution-based synthesis method enabling the morphology variation of Sb2Se3 light absorbers. The morphology of Sb2Se3 films varies from dense particulate planar films to one-dimensional nanowire-stacked films upon modulating the Sb and Se molar ratio in the precursor ink. The effect of morphology and crystallographic orientation on the electrical and consequently the PEC properties of Sb2Se3-based photocathodes is investigated. Sequential deposition of CdS as a buffer layer with TiO2 and Pt enables us to build a favorable band structure. An onset potential of 0.47 V versus a reversible hydrogen electrode (RHE) is observed with 13.5 mA cm–2 at 0 V versus a RHE under air mass 1.5 global illumination in a pH 1 electrolyte. In addition, the surface-modified photocathode stably produces hydrogen with a photocurrent of 11 mA cm–2 at 0 V versus RHE in a neutral electrolyte, thus demonstrating the promising potential of the proposed Sb2Se3 photocathodes as efficient PEC water-splitting devices.

Mercury and selenium levels, and Se:Hg molar ratios in freshwater fish from South Louisiana

Ample historical evidence has demonstrated the neurotoxicity of organic Hg. However, several studies have suggested that Se effectively sequesters MeHg. The affinity of Hg is up to ≈106 times higher for Se molecules than for comparable sulfur molecules, most of which are components of brain enzymes. The neurotoxicity of MeHg is associated with its binding to Se and the resultant interference with selenoenzymes (Ralston & Raymond, Global Advances in Selenium Research from Theory to Application, 2016). Therefore, having ample Se reserves is an effective way to mitigate MeHg’s toxicity. When the molar ratios of Se to Hg in fish exceed 1.0, ingestion of the fish is unlikely to deplete Se reserves. The goal of this study was to determine the Hg and Se levels, and the Se:Hg molar ratios in freshwater fish from south Louisiana and the implications of those ratios with respect to fish consumption and Hg advisories. Five waterbodies were surveyed (University lake, Calcasieu lake, Toledo Bend, the Atchafalaya River and Henderson Lake). The sampled species included black drum (Pogonias cromis), catfish sp., largemouth bass (Micropterus salmoides) and bluegill (Eupomotis macrochirus). All fish were assayed for total Hg and Se. The average Hg concentration was 0.001 µmol g−1 (0.21 ppm), and all concentrations were below the 1 ppm US FDA action level (from 3.1 × 10–5 to 0.003 µmol g−1). Se concentrations exceeded Hg concentrations in most cases. The average Se concentration was 0.003 µmol g−1 (0.27 ppm), all concentrations were around or less than 1.0 ppm (from 3.7 × 10–4 to 0.017 µmol g−1). Hence, the Se:Hg molar ratios were >1 in all fish except largemouth bass from Henderson Lake. In general, Se was detected in sufficient amounts to sequester Hg, but consumption of largemouth bass from Henderson Lake would pose no risk only if anglers followed the posted Hg advisory. For advisory purposes, perhaps, both Hg and Se levels and Se:Hg molar ratios should be considered. In general, the results indicated that risk assessment will require consideration of both the fish species and body of water, because both can influence Se and Hg concentrations and Se:Hg molar ratios.

Temporal and geographical variations of mercury and selenium in eggs of Larus michahellis and Larus audouinii from central Mediterranean islands

ABSTRACTIn this study, we determined mercury and selenium levels in abandoned unhatched eggs of the yellow-legged gull (Larus michahellis) and Audouin’s gull (Larus audouinii) collected during 2004–2005 from the Tuscan archipelago and Sardinia (Italy). The different feeding habits of the two species probably determine the different uptakes of trace elements, as the study shows highly significant differences for selenium and mercury levels as well as shell thickness and Hg:Se molar ratio values. Audouin’s gulls nesting on the coasts of the Tuscan archipelago showed significantly higher selenium levels than did gulls from colonies from the islands around Sardinia. Comparisons with a similar investigation previously conducted in the same area suggested that mercury and selenium concentrations, although in line with reports in the literature, were significantly lower than levels encountered in gulls in the early 1980s. Mercury (mg/kg d.w.) dropped from 8.631 to 5.030 in Audouin’s gulls and from 2.509 to 0.828 in yellow-legged gulls. The regional decline in mercury levels following reduced use of the metal in industry and the probable food depletion effects linked to the overfishing of fish prey of these two gull species are discussed as hypotheses that could explain the decrease in mercury levels found in eggs.

NIR-Emitting Alloyed CdTeSe QDs and Organic Dye Assemblies: A Nontoxic, Stable, and Efficient FRET System.

In the present work, we synthesize Near Infrared (NIR)-emitting alloyed mercaptopropionic acid (MPA)-capped CdTeSe quantum dots (QDs) in a single-step one-hour process, without the use of an inert atmosphere or any pyrophoric ligands. The quantum dots are water soluble, non-toxic, and highly photostable and have high quantum yields (QYs) up to 84%. The alloyed MPA-capped CdTeSe QDs exhibit a red-shifted emission, whose color can be tuned between visible and NIR regions (608–750 nm) by controlling the Te:Se molar ratio in the precursor mixtures and/or changing the time reaction. The MPA-capped QDs were characterized by UV-visible absorption spectroscopy, fluorescence spectroscopy, transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), and zeta potential measurements. Photostability studies were performed by irradiating the QDs with a high-power xenon lamp. The ternary MPA-CdTeSe QDs showed greater photostability than the corresponding binary MPA-CdTe QDs. We report the Förster resonance energy transfer (FRET) from the MPA-capped CdTeSe QDs as energy donors and Cyanine5 NHS-ester (Cy5) dye as an energy acceptor with efficiency (E) up to 95%. The distance between the QDs and dye (r), the Förster distance (R0), and the binding constant (K) are reported. Additionally, cytocompatibility and cell internalization experiments conducted on human cancer cells (HeLa) cells revealed that alloyed MPA-capped CdTeSe QDs are more cytocompatible than MPA-capped CdTe QDs and are capable of ordering homogeneously all over the cytoplasm, which allows their use as potential safe, green donors for biological FRET applications.

Biomarkers of the cholinergic and dopaminergic signaling pathways in Arctic beluga whales (Delphinapterus leucas): relationship to methylmercury and selenium

There are increasing concerns about potential neurotoxicity of chronic methylmercury (MeHg) exposure in Arctic wildlife and human populations. The relationships between mercury (Hg), MeHg, inorganic Hg (iHg), and selenium (Se) exposure, and neurochemical and molecular biomarkers in beluga whales (Delphinapterus leucas (Pallas, 1776)) were characterized. Samples were collected in 2008 (n = 20) and 2010 (n = 15) in the Canadian Arctic from hunter-harvested beluga whales. Total Hg concentrations in the temporal cortex and cerebellum were 21.0 ± 22.6 mg kg−1 dry weight (dw) and 14.9 ± 18.9 mg kg−1 dw, respectively. Monoamine oxidase (MAO) activity was predicted by MeHg and the molar ratio of total Hg to Se (Hg:Se, p < 0.05); MAO-A mRNA transcription levels were predicted by iHg and Se (p < 0.05). Muscarinic AChR binding was predicted by MeHg (p < 0.05) and Hg:Se molar ratio (p < 0.05), and mRNA transcription levels of mAChR m1 was predicted by the Hg:Se molar ratio (p < 0.05). These results suggest that the c...

Hepatic trace element concentrations of breeding female common eiders across a latitudinal gradient in the eastern Canadian Arctic

We examined hepatic concentrations of arsenic (As), cadmium (Cd), copper (Cu), lead (Pb), manganese (Mn), mercury (Hg), rubidium (Rb), selenium (Se) and zinc (Zn) in 10 breeding female common eiders (Somateria mollissima) from each of three colonies across 20° of latitude. Levels of many elements were elevated in eiders, although generally below levels of toxicological concern. We found significant differences in concentrations of As, Rb, Hg, Mn and Se among colonies, but not in a consistent pattern with latitude, and Hg:Se molar ratios did not vary among colonies. Furthermore, overlap in element concentrations from birds at different colonies meant that we could not reliably differentiate birds from different colonies based on a suite of their hepatic trace element concentrations. We encourage other researchers to assess baseline trace element levels on this important, harvested species, as a means of tracking contamination of nearshore benthic environments in the circumpolar Arctic.

Simple synthesis of PbSe nanocrystals and their self-assembly into 2D ‘flakes’ and 1D ‘ribbons’ structures

This work presents a simple and low-temperature method to prepare a variety of Lead selenide (PbSe) nanostructures, using aqueous solutions of Pb(NO3)2 and NaHSe. Nanostructures with different morphology were obtained by varying the Pb:Se molar ratio, as well as the mixing sequence of NH4OH with either Pb(NO3)2 or NaHSe. Nanoparticles with different shapes (spherical and octahedral), and self-assembled structures (flakes and ribbons) were observed by Transmission Electron Microscopy. X-ray results confirmed that the PbSe rock-salt crystalline structure was obtained for all of the prepared samples. The crystal size is in the order of 7.3 to 8.9nm for single nanocrystals. The absorption spectra of the samples show exciton absorption bands at 1395nm and 1660nm. This material could be used to develop more advanced structures for thermoelectric generators.

Aqueous synthesis of high bright Ag2Se[sbnd]ZnSe quantum dots with tunable near-infrared emission

Efficient aqueous synthetic methods for near-infrared quantum dots as bioimaging agents are urgently required. In this work, a simple and fast synthesis of highly luminescent, near-infrared Ag2Se quantum dots (QDs) in aqueous media is reported. The method avoids high temperature, pressure and organic solvents to directly generate water-dispersible Ag2Se QDs. The photoluminescence emission of Ag2Se QDs ranges from 835 to 940 nm by different Ag:Se molar ratio. Using the ZnSe as a shell, the quantum yield reaches up to 42%. The Ag2SeZnSe QDs with high quantum yield, near-infrared and low cytotoxic could be used as good cell labels, showing great potential applications in bio-imaging.

Mercury and selenium in tissues and stomach contents of the migratory sailfish, Istiophorus platypterus, from the Eastern Pacific: Concentration, biomagnification, and dietary intake

Mercury and selenium were assessed in the sailfish, Istiophorus platypterus, from the Eastern Pacific. Sixty-seven individuals were sampled, muscle, liver, kidney, gonads and the prey found in the stomach contents were isolated during fishing 2011–2013 tournaments. Hg exhibited the following pattern (μgg−1 wet weight): liver (0.57±0.07)>muscle (0.56±0.04)>kidney (0.44±0.08)>gonad (0.14±0.01). The maximum concentration of Se was found in kidneys (14.1±1.9μgg−1), and the minimum in muscles (0.67±0.03μgg−1). High Se:Hg ratios were found for muscle (4.1±0.3), kidney (132.4±12.1), liver (54.0±4.4) and gonads (88.2±7.9); Hg:Se molar ratios were several orders of magnitude lower (muscle<0.4 and liver, kidney and gonad<0.03). Sailfish feed mainly on fishes and cephalopods with low Hg levels (<0.13μgg−1), these results indicate biomagnification of Hg and Se. The muscle of I. platypterus should be consumed (according the provisional tolerable weekly intake) by people cautiously so as not to exceed the recommended intake of 215g per week.

Synthesis of Cu(In,Ga)Se2 crystals using a crank ball mill

AbstractCu(In,Ga)Se2 (CIGS) crystals were synthesized by a mechanochemical (MC) process using a crank ball mill. The molar ratios of starting materials were Cu:In:Ga:Se=1:1‐x:x:2 (0≤x≤1) and Cu:In:Ga:Se=1:0.7:0.3:y (2≤y≤3). The reaction time reduced with decreasing Se and Ga molar ratios. The collection rate decreased with longer reaction times. From XRD patterns, we confirmed that the CuInSe2 and/or CuGaSe2crystals were successfully grown when the powders reacted. Although the crystals grown with a selenium molar ration of 2 were Se‐poor, those grown at a molar ratio of 3 were Se‐rich. When Se increasing molar ratio, Cu, In, and Ga were away from the stoichiometric. With a molar ratio of Cu:In:Ga:Se=1:0.7:0.3:2.5∼2.7, their composition became stoichiometric. Crystal morphology was varied. CIGS crystals were thus successfully synthesized using a crank ball mill. (© 2015 WILEY‐VCH Verlag GmbH &amp; Co. KGaA, Weinheim)

RuSe Electrocatalysts and Single Wall Carbon Nanohorns Supports for the Oxygen Reduction Reaction

Selenium modified ruthenium electrocatalysts supported on carbon black were synthesized using NaBH4 reduction of the metal precursor. Prepared Ru/C electrocatalysts showed high dispersion and very small averaged particle size. These Ru/C electrocatalysts were subsequently modified with Se following two procedures: (a) preformed Ru/carbon catalyst was mixed with SeO2 in xylene and reduced in H2 and (b) Ru metal precursor was mixed with SeO2 followed by reduction with NaBH4. The XRD patterns indicate that a pyrite-type structure was obtained at higher annealing temperatures, regardless of the Ru:Se molar ratio used in the preparation step. A pyrite-type structure also emerged in samples that were not calcined; however, in this case, the pyrite-type structure was only prominent for samples with higher Ru:Se ratios. The characterization of the RuSe/C electrocatalysts suggested that the Se in noncalcined samples was present mainly as an amorphous skin. Preliminary study of activity toward oxygen reduction reaction (ORR) using electrocatalysts with a Ru:Se ratio of 1:0.7 indicated that annealing after modification with Se had a detrimental effect on their activity. This result could be related to the increased particle size of crystalline RuSe2 in heat-treated samples. Higher activity of not annealed RuSe/C catalysts could also be a result of the structure containing amorphous Se skin on the Ru crystal. The electrode obtained using not calcined RuSe showed a very promising performance with a slightly lower activity and higher overpotential in comparison with a commercial Pt/C electrode. Single wall carbon nanohorns (SWNH) were considered for application as ORR electrocatalysts' supports. The characterization of SWNH was carried out regarding their tolerance toward strong catalyzed corrosion conditions. Tests indicated that SWNH have a three times higher electrochemical surface area (ESA) loss than carbon black or Pt commercial electrodes.

Facile and Green Synthesis of CdSe Quantum Dots in Protein Matrix: Tuning of Morphology and Optical Properties

Herein, we have demonstrated a facile and green approach for the synthesis of Cadmium selenide (CdSe) quantum dots (QDs). The process was mediated by bovine serum albumin (BSA) and it was found that BSA plays the dual role of reducing agent as well as a stabilizing agent. The QDs exhibited sharp excitonic absorption features at ~500 nm and subsequently showed reasonably good photoluminescence (PL) at room temperature. The PL is seen to be strongly dependent on the concentration of the precursors and hence, the luminescence of these QDs could be conveniently tuned across the visible spectrum simply by varying molar ratio of the precursors. It can be envisaged from the fact that a red-shift of about 100 nm in the PL peak position was observed when the molar ratio of the precursors ([Cd2+]:[Se2-], in mM) was varied from 10:5 to 10:40. Subsequently, the charge carrier relaxation dynamics associated with the different molar ratio of precursors has been investigated and very interesting information regarding the energy level structures of these QDs were revealed. Most importantly, in conjunction with the optical tuning, the nanomorphology of these nanoparticles was found to vary with the change in molar ratios of Se and Cd precursors. This aspect can provide a new direction of controlling the shape of CdSe nanoparticles. The possible mechanism of the formation as well as for the shape variation of these nanoparticles with the molar ratios of precursors has been proposed, taking into account the role of amino acid residues (present in BSA). Moreover, the QDs were water soluble and possessed fairly good colloidal stability therefore, can have potential applications in catalysis and bio-labeling. On the whole, the present methodology of protein assisted synthesis is relatively new especially for semiconducting nanomaterials and may provide some unique and interesting aspects to control and fine tune the morphology vis-à-vis, their optical properties.

Preparation of highly luminescent CdSe quantum dots by reverse micelles

CdSe quantum dots (QDs) with relatively high photoluminescence (PL) quantum yield (QY) (about 30%) were prepared by a safe, low-cost, and simple synthesis method, utilizing a sodium bis(2-ethylhexyl) sulfosuccinate (AOT)/water/cyclohexane microemulsion system. Cadmium chloride (CdCl2) and selenium powder were used as the cadmium and selenium sources, respectively. Size-tunable CdSe nanoparticles were obtained at various water-to-surfactant ratios, W ([H2O]/[surfactant]). The size of the CdSe nanoparticles increased, and the UV–vis absorption and PL peaks shifted towards the red region as W increased. Interestingly, the redshift also occurred when the ratio of Cd to Se increased. The highest PL efficiency was obtained at W of 5 and a Cd/Se ratio of . In addition, the CdSe nanoparticles with higher Cd to Se molar ratio (3/1) showed a higher stability against photooxidation.

An assessment of contaminant concentrations in toothed whale species of the NW Iberian Peninsula: Part II. Trace element concentrations

Concentrations of Ag, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, V and Zn were investigated in the liver and kidney of the five most common toothed whales off the Northwest Iberian Peninsula (NWIP), specifically common dolphin, long-finned pilot whale, harbour porpoise, striped dolphin and bottlenose dolphin. Differences were observed in the bioaccumulation of the above elements between the five species. The differences are probably related to biological factors such as age and sex and/or to ecological factors specific to each species such as feeding habits or bioavailability of the various elements. However, no significant relationship was observed between element accumulation and sex. Pilot whale and striped dolphin showed the highest concentrations of renal Cd and the highest concentrations of hepatic Hg and Se, while bottlenose dolphin showed the highest concentrations of Hg in kidneys. An analysis of inter-elemental relationships showed strong positive correlations between Hg and Se in the five species, however most individuals have Hg:Se molar ratio less than 1:1 indicating an excess of Se compare to Hg. This result, probably reflect the high proportion of young animals in the sample available for this study and/or that these animals had a good health status. We also observed a positive correlation in striped dolphins between Cd and Cu and between Cd and Zn in kidneys. In addition, comparing with other studies world-wide, the element concentrations (Hg and Cd) found in Iberian toothed whales indicate that these populations are not specially threatened by Hg and Cd exposure in the area.

Preparation of Copper Selenide Platelets

Preparation of Copper Selenide Platelets Copper selenide (CuxSe) particles were prepared by heating copper carbonate and selenous acid in diethylene glycol in the presence of various dispersing agents. The impact of reaction conditions on the structural and morphological properties of the precipitated particles were assessed by X-ray diffraction (XRD) and electron microscopy. Although all additives promoted anisotropic growth, it was found that polyvinyl alcohol (PVA) was particularly effective in generating dispersed high aspect ratio CuxSe platelets. The optimum reaction conditions for the formation of hexagonal copper selenide were 190°C and a Cu: Se molar ratio of 1 to 1.2.

Elements of concern in fillets of bighead and silver carp from the Illinois River, Illinois

Efforts to control invasive bighead (Hypophthalmichthys nobilis) and silver carp (H. molitrix) may include harvest for human consumption. We measured concentrations of arsenic (As), mercury (Hg), and selenium (Se) in fillets from silver and bighead carp collected from the lower Illinois River, Illinois, USA, to determine whether concentrations were of health concern and differed by species, size, and location. Concentrations of total As were below detection limits in most bighead (92%) and silver (77%) carp fillets, whereas inorganic As was below detection limits in all samples. Mean Hg concentrations were greater in bighead (0.068mgkg−1) than in silver carp (0.035mgkg−1), and were smallest in carp from the confluence of the Illinois and Mississippi rivers. Mercury concentrations in fillets were positively correlated with body mass in both species. Concentrations of Hg were below the US Food and Drug Administration’s (USFDA) action level (1ppm as methyl-Hg); however, concentrations in some bighead (70%) and silver (12%) carp fell within the range that would invoke a recommendation to limit meals in sensitive cohorts. Mean Se concentrations were greater in silver (0.332mgkg−1) than in bighead (0.281mgkg−1) carp fillets, and were below the 1.5mgkg−1 limit for an unrestricted number of meals/month. The mean molar ratio of Se:Hg in fillets was lower in bighead (14.0) than in silver (29.1) carp and was negatively correlated with mass in both species Concentrations of Hg in bighead and silver carp fillets should be considered when assessing the risks associated with the use of these species as a protein source.

A facile approach to the synthesis of CdSe/P3HT nanocomposites

In this article, we report a facile, direct synthesis route to prepare CdSe/P3HT nanocomposites with CdO used as cadmium source, Se powder as selenium source, liquid paraffin and oleic acid as solvents, P3HT as a conjugated polymer template. The effect of the reaction temperature as well as the Cd:Se molar ratio on the morphology and photovoltaic property of CdSe/P3HT nanocomposites was studied. The results show that the shape and the degree of aggregation of CdSe nanocrystals are not only temperature-dependent, but also heavily influenced by the Cd:Se ratio, changing from dot-shaped to tetrapod-shaped, and from homo-dispersed to seriously aggregative. The UV–vis absorption spectra of CdSe-P3HT show a broader range and higher intensity of absorption than that of pure P3HT. The improved PL quenching in PL spectra of CdSe-P3HT indicates charge transfer between CdSe nanocrystals and P3HT.

Contrasting Food Web Factor and Body Size Relationships with Hg and Se Concentrations in Marine Biota

Marine fish and shellfish are primary sources of human exposure to mercury, a potentially toxic metal, and selenium, an essential element that may protect against mercury bioaccumulation and toxicity. Yet we lack a thorough understanding of Hg and Se patterns in common marine taxa, particularly those that are commercially important, and how food web and body size factors differ in their influence on Hg and Se patterns. We compared Hg and Se content among marine fish and invertebrate taxa collected from Long Island, NY, and examined associations between Hg, Se, body length, trophic level (measured by δ15N) and degree of pelagic feeding (measured by δ13C). Finfish, particularly shark, had high Hg content whereas bivalves generally had high Se content. Both taxonomic differences and variability were larger for Hg than Se, and Hg content explained most of the variation in Hg:Se molar ratios among taxa. Finally, Hg was more strongly associated with length and trophic level across taxa than Se, consistent with a greater degree of Hg bioaccumulation in the body over time, and biomagnification through the food web, respectively. Overall, our findings indicate distinct taxonomic and ecological Hg and Se patterns in commercially important marine biota, and these patterns have nutritional and toxicological implications for seafood-consuming wildlife and humans.