Narrow-Band Red-Emitting Phosphors with High Color Purity, Trifling Thermal and Concentration Quenching for Hybrid White LEDs and Li3Y3BaSr(MoO4)8:Sm3+, Eu3+-Based Deep-Red LEDs for Plant Growth Applications.

Trivalent europium-based monochromatic red light-emitting phosphors are an essential component to realize high-performance smart lighting devices; however, the concentration and thermal quenching restrict their usage. Here, we report a series of efficient Eu3+-substituted Li3Y3BaSr(MoO4)8 red-emitting phosphors based on a stratified scheelite structure with negligible concentration and thermal quenching. All of the host and phosphor compositions crystallize in monoclinic crystal structure (space group C2/c). All of the phosphor compositions produce narrow-band red emission (FWHM ∼6 nm), which is highly apparent to the human eyes, and lead to exceptional chromatic saturation of the red spectral window. Concurrently, detailed investigations were carried out to comprehend the concentration and thermal quenching mechanism. Absolute quantum yields as high as 88.5% were obtained for Li3Y0.3Eu2.7BaSr(MoO4)8 phosphor with virtuous thermal stability (at 400 K, retaining 87% of its emission intensity). The light-emitting diodes were constructed by coupling Li3BaSrY0.3Eu2.7(MoO4)8 red phosphor with a near-UV LED chip (395 nm) operated at 20 mA forward bias, and the hybrid white LED (an organic yellow dye + red Li3Y3BaSr(MoO4)8:Eu3+ phosphor integrated with an NUV LED chip) showed a low CCT (6645 K), high CRI (83) values, and CIE values of x = 0.303; y = 0.368, which indicated that the synthesized phosphors can be a suitable red component for white LEDs. In addition, we have systematically investigated the Sm3+ and Sm3+, Eu3+ activation in Li3Y3BaSr(MoO4)8 to display the latent use of the system in plant growth applications and establish that the phosphor exhibits orange red emission with an intense deep-red emission (645 nm (4G5/2 → 6H9/2)). The phytochrome (Pr) absorption spectrum well matched the fabricated deep-red LED (by integrating a NUV LED + Li3Y3BaSr(MoO4)8:Sm3+ and Eu3+ phosphor) spectral lines.

Leishmanicidal activities of biosynthesized BaCO3 (witherite) nanoparticles and their biocompatibility with macrophages.

The aim of this study was cost-effective and greener synthesis of barium carbonate (BaCO3 or witherite) nanoparticles with economic importance, and to evaluate their therapeutic potentials and biocompatibility with immune cells. Barium carbonate nanoparticles were biosynthesized using black elderberry extract in one step with non-toxic precursors and simple laboratory conditions; their morphologies and specific structures were analyzed using field emission scanning electron microscopy with energy dispersive X-ray spectroscopy (FESEM-EDX). The therapeutic capabilities of these nanoparticles on the immune cells of murine macrophages J774 and promastigotes Leishmania tropica were evaluated. BaCO3 nanoparticles with IC50 = 46.6 µg/mL were more effective than negative control and glucantium (positive control) in reducing promastigotes (P < 0.01). Additionally, these nanoparticles with a high value of cytotoxicity concentration 50% (CC50) were less toxic to macrophage cells than glucantime; however, they were significantly different at high concentrations compared to the negative control.

Geochemical conditions conducive for retention of trace elements and radionuclides during shale-fluid interactions.

Produced water generated during unconventional oil and gas extractions contains a complex milieu of natural and anthropogenic potentially toxic chemical constituents including arsenic (As), chromium (Cr), and cadmium (Cd), naturally occurring radioactive materials (NORMs) including U and Ra, and a myriad of organic compounds. The human-ecological health risks and challenges associated with the disposal of produced water may be alleviated by understanding geochemical controls on processes responsible for the solubilization of potentially hazardous natural shale constituents to produced water. Here, we investigated, through a series of batch treatments, the leaching behavior of As, Se, Cu, Fe, Ba, Cr, Cd, and radioactive nuclides U, Ra from shale to produced water. Specifically, the effect of four major controls on element mobility was studied: (1) solution pH, (2) ionic strength of the solution, (3) oxic-anoxic conditions, and (4) an additive used in fracking fluid. The mobilization of metals and metalloids from shale was greatest in treatments containing sodium persulfate, an oxidant and a commonly used additive in fracture fluid. In the high ionic strength treatments, dissolved Ba concentrations increased 5-fold compared to low ionic strength treatments. Overall, anoxic conditions superimposed with low pH resulted in the largest increase of dissolved metals and radionuclides such as Ra. Overall, our results suggest that (1) limiting pore water acidification by injection of alkaline fluid in carbonate-low shale and (2) minimizing strong oxidizing conditions in shale formations may result in cost-effective in situ retention of produced water contaminants.

High-Throughput Synthesis and Characterization of Eu Doped Ba xSr2- xSiO4 Thin Film Phosphors.

High-throughput techniques have been employed for the synthesis and characterization of thin film phosphors of Eu-doped Ba xSr2- xSiO4. Direct synthesis from evaporation of the constituent elements under a flux of atomic oxygen on a sapphire substrate at 850 °C was used to directly produce thin film libraries (415 nm thickness) of the crystalline orthosilicate phase with the desired compositional variation (0.24 > x > 1.86). The orthosilicate phase could be synthesized as a pure, or predominantly pure, phase. Annealing the as synthesized library in a reducing atmosphere resulted in the reduction of the Eu while retaining the orthosilicate phase, and resulted in a materials thin film library where fluorescence excited by blue light (450 nm) was observable by the naked eye. Parallel screening of the fluorescence from the combinatorial libraries of Eu doped Ba xSr2- xSiO4 has been implemented by imaging the fluorescent radiation over the library using a monochrome digital camera using a series of color filters. Informatics tools have been developed to allow the 1931 CIE color coordinates and the relative quantum efficiencies of the materials library to be rapidly assessed and mapped against composition, crystal structure and phase purity. The range of compositions gave values of CIE x between 0.17 and 0.52 and CIE y between 0.48 and 0.69 with relative efficiencies in the range 2.0 × 10-4-7.6 × 10-4. Good agreement was obtained between the thin film phosphors and the fluorescence characteristics of a number of corresponding bulk phosphor powders. The thermal quenching of fluorescence in the thin film libraries was also measured in the temperature range 25-130 °C: The phase purity of the thin film was found to significantly influence both the relative quantum efficiency and the thermal quenching of the fluorescence.

Spatial variability and solubility of barium in a petroleum well-drilling waste disposal area.

The petroleum industry generates a range of wastes which is often are disposed in soil close to the well location, negatively affecting soil and water quality. The objective of this study was to evaluate the solubility and map the spatial variability of barium in a potentially contaminated area. The study area consisted of a petroleum well-drilling waste disposal site located in the municipality of Mato Rico-PR. A large georeferenced sampling grid was organized. Soil samples were collected at depths of 30, 60, 90, and 120 cm for determination of the "pseudo-total" concentrations and geochemical fractionation of barium. The barium concentrations showed spatial dependence, which permitted the use of geostatistical interpolators. Regarding depth, the depth of 0-30 cm showed the largest contaminated area; however, higher concentrations of barium were found at the depth of 60-90 cm. The results of geochemical fractionation showed that the analyzed samples contained percentages higher than 99% in the non-labile fraction (residual). These results indicate clearly that the barium was in a condition of low solubility, even for samples that had the highest concentrations, presenting low-environmental risk.

Effect of brine salinity and guar gum on the transport of barium through dolomite rocks: Implications for unconventional oil and gas wastewater disposal.

This research aimed to elucidate the effect of brine salinity and guar gum on the sorption and transport of Ba in dolomite rocks collected from the Arbuckle formation in Oklahoma, USA. Guar gum represents the most important organic additive used in viscosified fracturing fluids, and Ba constitutes the most common and abundant heavy metal found in unconventional oil and gas (UOG) wastewater. Batch experiments conducted using powdered dolomite rocks (500-600 µm particle size) revealed that at brine salinities of UOG wastewater, chloro-complexation reactions between Ba and Cl ions and pH changes that results from dolomite dissolution are the controlling factors of Ba sorption on dolomite. Competition of Ba with common cations (Ca and Mg) for hydration sites of dolomite, plays a secondary role. Core-flooding experiments conducted to analyze the transport of Ba through natural and synthetic dolomite core plugs are in agreement with the batch sorption experimental results. The transport of Ba through dolomite rocks, increases with increasing brine salinity (0-180,000 mg-NaCl/L). The presence guar gum (50-500 mg/L) does not affect the transport of Ba through dolomite rocks of high flow properties (25-29.6% porosity, 9.6-13.7 mD permeability). However, core-flooding experiments conducted using tight dolomite rocks (6.5-8.6% porosity, 0.06-0.3 mD permeability), revealed that guar gum can retard the transport of Ba by clogging high permeability/porosity regions of tight dolomite rocks. The mechanism of Ba sorption on dolomite can be represented by a sorption model that accounts for both surface complexation reactions on three distinct hydration sites (>CaOHo, >MgOHo, and >CO3Ho), and the kinetic dissolution of dolomite. These results are important in understanding and predicting the fate of Ba present in UOG wastewater disposed into deep dolomite saline aquifers.

Detection of Aß oligomers based on magnetic-field-assisted separation of aptamer-functionalized Fe3O4 magnetic nanoparticles and BaYF5:Yb,Er nanoparticles as upconversion fluorescence labels.

A sensitive and stable bioassay for the detection of Aß oligomer (Aßo), a potentially promising candidate biomarker for Alzheimer's disease (AD) diagnosis, was developed using Fe3O4 magnetic nanoparticles (MNPs) as the recognition and concentration elements and BaYF5:Yb,Er upconversion nanoparticles (UCNPs) as highly sensitive labels, conjugated with the Aßo aptamer (DNA1) and the complementary oligonucleotide of the Aßo aptamer (DNA2), respectively. The DNA1 hybridized with DNA2 to form the duplex structure on the surface of the MNPs/UCNPs nanocomposites probe. When the target Aßo was introduced, the aptamer DNA1 preferentially bound with Aßo and caused the dissociation of some complementary DNA2, liberating some UCNP-labeled complementary DNA2 and leading to a decreased upconversion fluorescent intensity on the surface of MNPs. The decreased fluorescence intensity of UCNPs was related to the concentration of Aßo in the range of 0.2-15nM with a detection limit of 36 pM. The developed method then was successfully applied to measure Aßo in artificial cerebrospinal fluid. Benefiting from the magnetic separation and concentration effect of MNPs, the high sensitivity of UCNPs, as well as the selectivity and stability of the aptamer, the present strategy offered valuable information related to early diagnosis of AD process.

Photoluminescence and electron paramagnetic resonance properties of a potential phototherapic agent: MMgF4 :Gd3+ (M = Ba, Sr) sub-microphosphors.

Novel narrow band UVB-emitting phosphors, BaMgF4 :Gd3+ and SrMgF4 :Gd3+ phosphors, were synthesized using a co-precipitation synthesis method. X-Ray diffraction analysis was carried out to confirm compound formation, phase purity and crystallinity of the phosphor. At 274 nm excitation, phosphors show a sharp narrow band emission at 313 nm that can be assigned to 6 P7/2  â†’ 8 S7/2 transition of the Gd3+ ion. With increasing dopant concentration, intensity enhances and then decreases after a certain concentration, which is an indication of concentration quenching taking place in the phosphor. Scanning electron microscopy images of the phosphor show agglomerated particles in the sub-micron range. Particles range in size from 600 to 800 nm. Electron paramagnetic resonance studies of the phosphors were carried out to detect radicals present in the prepared phosphor. With narrow band UVB emission, phosphor seems to be a good candidate for UV phototherapy application. Copyright © 2016 John Wiley & Sons, Ltd.

Nanoparticles of barium induce apoptosis in human phagocytes.

PURPOSE: Nutrients and immunological factors of breast milk are essential for newborn growth and the development of their immune system, but this secretion can contain organic and inorganic toxins such as barium. Colostrum contamination with barium is an important issue to investigate because this naturally occurring element is also associated with human activity and industrial pollution. The study evaluated the administration of barium nanoparticles to colostrum, assessing the viability and functional activity of colostral mononuclear phagocytes. METHODS: Colostrum was collected from 24 clinically healthy women (aged 18-35 years). Cell viability, superoxide release, intracellular Ca(2+) release, and phagocyte apoptosis were analyzed in the samples. RESULTS: Treatment with barium lowered mononuclear phagocyte viability, increased superoxide release, and reduced intracellular calcium release. In addition, barium increased cell death by apoptosis. CONCLUSION: These data suggest that nanoparticles of barium in colostrum are toxic to cells, showing the importance of avoiding exposure to this element.

Recycling of ladle slag in cement composites: Environmental impacts.

In the present work compact and ground cement composites in which 30% of cement by mass was replaced by ladle slag were investigated for their chemical and physico-mechanical properties. To evaluate long-term environmental impacts, leachability test based on diffusion, which combined both, diffusion and dissolution of contaminants, was performed in water and saline water. Total element concentrations and Cr(VI) were determined in leachates over a time period of 180days. At the end of the experiment, the mineralogical composition and the physico-mechanical stability of cement composites was also assessed. The results revealed that Cr(III) and Cr(VI) were immobilized by the hydration products formed in the cement composites with the addition of ladle slag. Cr(VI) content originating from the cement was also appreciably reduced by Fe(II) from minerals present in the added ladle slag, which thus had significant positive environmental effects. Among metals, only Mo and Ba were leached in elevated concentrations, but solely in ground cement composites with the addition of ladle slag. Lower V concentrations were observed in leachates of ground than compact composite. It was demonstrated that the presence of ladle slag in cement composites can even contribute to improved mortar resistance. The investigated ladle slag can be successfully implemented in cement composites as supplementary cementitious material.

Chemical and structural characterization of glass ionomer cements indicated for atraumatic restorative treatment.

Glass ionomer cements (GICs) are restorative materials, which clinical use has increased significantly during the last decade. The aim of the present study was to analyze the chemical constitution and surface morphology of four glass ionomer cements: Maxxion R, VitroFill, Vidrion R and Vitremer. Twelve polyethylene tubes with an internal diameter of 3 and 3 mm in length were prepared, filled and then transferred to a chamber with 95% relative humidity and a temperature of 37°C. The surface morphology of the tested materials was examined by scanning electron microscopy (SEM) and main components were investigated by energy-dispersive X-ray microanalysis (EDX). Scanning electron microscopy revealed irregular and rough external surface. Cracking was not observed. The main constituents were found to be aluminum, silicon, calcium, sodium and fluoride. Phosphorus, sulfur and barium were only observed in Vidrion R, while chlorine were only observed in Maxxion R. Elemental mapping of the outer surface revealed high concentration of aluminum and silicon. Significant irregularities on the surface of the tested materials were observed. The chemical constitution of all GIC was similar.

Kinetics of copper nanoparticle precipitation in phosphate glass: an isothermal plasmonic approach.

The kinetics of copper nanoparticle (NP) precipitation in melt-quenched barium-phosphate glass has been studied by in situ isothermal optical micro-spectroscopy. A spectroscopically based approximation technique is proposed to obtain information about the activation energies of nucleation and growth in a narrow temperature range (530-570 °C). Pre-plasmonic and plasmonic NP precipitation stages are identified separated in time. The process as a whole is discussed employing classical nucleation/growth theory and the Kolmogorov-Johnson-Mehl-Avrami phase change model. Activation energies of 3.9(7) eV and 2.6(5) eV have been estimated for the pre-plasmonic and plasmonic spectroscopically assessed stages, respectively. High resolution transmission electron microscopy, differential scanning calorimetry, and Raman spectroscopy were used as complementary techniques for studying the nanoparticulate phase and glass host structure. An empirical linear dependence of the diffusion activation energy on the glass transition temperature with broad applicability is suggested.

Photostimulated luminescence properties of Eu2+ -doped barium aluminate phosphor.

An intense green photostimulated luminescence in BaAl2 O4 :Eu(2+) phosphor was prepared. The thermoluminescence results indicate that there are at least three types of traps (T1 , T2 , T3 ) with different trap depths in BaAl2 O4 :Eu(2+) phosphor according to the bands located at 327, 361 and 555 K, respectively, which are closely associated with the phosphor's long persistent luminescence and photostimulated luminescence properties. In addition, as a novel optical read-out form, a photostimulated persistent luminescence signal can be repeatedly obtained in BaAl2 O4 :Eu(2+) phosphor. This shows that re-trapping of the electron released from a deep trap plays an important role in photostimulated persistent luminescence.

Crystal structure of a DNA/Ba2+ G-quadruplex containing a water-mediated C-tetrad.

We have determined the 1.50 Å crystal structure of the DNA decamer, d(CCA(CNV)KGCGTGG) ((CNV)K, 3-cyanovinylcarbazole), which forms a G-quadruplex structure in the presence of Ba(2+). The structure contains several unique features including a bulged nucleotide and the first crystal structure observation of a C-tetrad. The structure reveals that water molecules mediate contacts between the divalent cations and the C-tetrad, allowing Ba(2+) ions to occupy adjacent steps in the central ion channel. One ordered Mg(2+) facilitates 3'-3' stacking of two quadruplexes in the asymmetric unit, while the bulged nucleotide mediates crystal contacts. Despite the high diffraction limit, the first four nucleotides including the (CNV)K nucleoside are disordered though they are still involved in crystal packing. This work suggests that the bulky hydrophobic groups may locally influence the formation of non-Watson-Crick structures from otherwise complementary sequences. These observations lead to the intriguing possibility that certain types of DNA damage may act as modulators of G-quadruplex formation.

Al2O3 influence on structural, elastic, thermal properties of Yb(3+) doped Ba-La-tellurite glass: evidence of reduction in self-radiation trapping at 1µm emission.

Ba-La-tellurite glasses doped with Yb(3+) ions have been prepared through melt quenching technique by modifying their composition with the inclusion of varied concentration of Al2O3 to elucidate its effects on glass structural, elastic, thermal properties and Yb(3+) ion NIR luminescence performance. The FTIR spectral analysis indicates Al2O3 addition is promoting the conversion of BOs from NBOs which have been generated during the process of depolymerisation of main glass forming TeO4 units. The elastic properties of the glass revealed an improved rigidity of the glass network on addition of Al2O3. In concurrence to this, differential thermal analysis showed an increase in glass transition temperature with improved thermal stability factor. Also, Yb(3+) fluorescence dynamics demonstrated that, Al2O3 inclusion helps in restraining the detrimental radiation trapping of ∼1µm emission.

Failed stapled rectal resection in a constipated patient with rectal aganglionosis.

A rare case of a severely constipated patient with rectal aganglionosis is herein reported. The patient, who had no megacolon/megarectum, underwent a STARR, i.e., stapled transanal rectal resection, for obstructed defecation, but her symptoms were not relieved. She started suffering from severe chronic proctalgia possibly due to peri-retained staples fibrosis. Intestinal transit times were normal and no megarectum/megacolon was found at barium enema. A diverting sigmoidostomy was then carried out, which was complicated by an early parastomal hernia, which affected stoma emptying. She also had a severe diverting proctitis, causing rectal bleeding, and still complained of both proctalgia and tenesmus. A deep rectal biopsy under anesthesia showed no ganglia in the rectum, whereas ganglia were present and normal in the sigmoid at the stoma site. As she refused a Duhamel procedure, an intersphincteric rectal resection and a refashioning of the stoma was scheduled. This case report shows that a complete assessment of the potential causes of constipation should be carried out prior to any surgical procedure.

Effect of water and ammonia on surface species formed during NO(x) storage-reduction cycles over Pt-K/Al2O3 and Pt-Ba/Al2O3 catalysts.

The effect of water, in the temperature range 25-350 °C, and ammonia at RT on two different surface species formed on Pt-K/Al2O3 and Pt-Ba/Al2O3 NSR catalysts during NO(x) storage-reduction cycles was investigated. The surface species involved are nitrates, formed during the NO(x) storage step, and isocyanates, which are found to be intermediates in N2 production during reduction by CO. FT-IR experiments demonstrate that the dissociative chemisorption of water and ammonia causes the transformation of the bidentate nitrates and linearly bonded NCO(-) species into more symmetric species that we call ionic species. In the case of water, the effect on nitrates is observable at all the temperatures studied; however, the extent of the transformation decreases upon increasing temperature, consistent with the decreased extent of dissociatively adsorbed water. It was possible to hypothesize that the dissociative chemisorption of water and ammonia takes place in a competitive way on surface sites able to give bidentate nitrates and linearly bonded NCO(-) that are dislocated, remaining on the surface as ionic species.

Safety and efficacy of ethylenediaminetetraacetic acid for removing microcapsules.

BACKGROUND: Microencapsulated islets are used to prevent immune rejection associated with pancreatic islet transplantation, but cellular overgrowth affects transplantation success, necessitating removal of microcapsules prior to retransplantation. This study aimed to investigate the safety and efficacy of ethylendiaminetetraacetic acid (EDTA) for the removal of microcapsules surrounding islet cells. METHODS: Microcapsule dissolution was investigated after in vitro exposure to EDTA for 72 h. Dissolution, blood biochemical markers, and pathologic changes in abdominal organs were observed after intraperitoneal administration of different concentrations of EDTA to rats with abdominally transplanted empty microcapsules. The extent of overgrowth and time to adhesion development were recorded after implantation of microencapsulated islets into the abdominal cavity of diabetic rats. EDTA (0-240 mmol/L) was injected to observe the transplantation effect and ability to dissolve microcapsules. RESULTS: There was a positive correlation between the rate of microcapsule dissolution and EDTA concentration in vitro. Following administration of 60 mmol/L EDTA, the majority of microcapsules within the abdominal cavity were dissolved and the retrieval rate was 2.6%. No adverse effects, abnormal blood biochemical markers, or organ damage were observed in rats 1 mo following intraperitoneal injection with EDTA at doses up to 60 mmol/L. Microcapsule retrieval and blood glucose were significantly higher in cases of grade II cellular overgrowth than in cases of grade 0-I overgrowth. CONCLUSIONS: EDTA (60 mmol/L) dissolved microcapsules in vivo without affecting islet cell viability or secretion capacity, and without affecting blood biochemical markers. Optimal dissolution was achieved with grade 0-I overgrowth after implantation of microencapsulated islets.

Observation of superconductivity at 30~46 K in A(x)Fe2Se2(A = Li, Na, Ba, Sr, Ca, Yb, and Eu).

New iron selenide superconductors by intercalating smaller-sized alkali metals (Li, Na) and alkaline earths using high-temperature routes have been pursued ever since the discovery of superconductivity at about 30 K in KFe2Se2, but all have failed so far. Here we demonstrate that a series of superconductors with enhanced T(c) = 30∼46 K can be obtained by intercalating metals, Li, Na, Ba, Sr, Ca, Yb, and Eu in between FeSe layers by the ammonothermal method at room temperature. Analysis on their powder X-ray diffraction patterns reveals that all the main phases can be indexed based on body-centered tetragonal lattices with a∼3.755-3.831 Å while c∼15.99-20.54 Å. Resistivities show the corresponding sharp transitions at 45 K and 39 K for NaFe2Se2 and Ba0.8Fe2Se2, respectively, confirming their bulk superconductivity. These findings provide a new starting point for studying the properties of these superconductors and an effective synthetic route for the exploration of new superconductors as well.

Barium as a potential indicator of phosphorus in agricultural runoff.

In many catchments, anthropogenic input of contaminants, and in particular phosphorus (P), into surface water is a mixture of agricultural and sewage runoff. Knowledge about the relative contribution from each of these sources is vital for mitigation of major environmental problems such as eutrophication. In this study, we investigated whether the distribution of trace elements in surface waters can be used to trace the contamination source. Water from three groups of streams was investigated: streams influenced only by agricultural runoff, streams influenced mainly by sewage runoff, and reference streams. Samples were collected at different flow regimes and times of year and analyzed for 62 elements using ICP-MS. Our results show that there are significant differences between the anthropogenic sources affecting the streams in terms of total element composition and individual elements, indicating that the method has the potential to trace anthropogenic impact on surface waters. The elements that show significant differences between sources are strontium (p < 0.001), calcium (p < 0.004), potassium (p < 0.001), magnesium (p < 0.001), boron (p < 0.001), rhodium (p = 0.001), and barium (p < 0.001). According to this study, barium shows the greatest potential as a tracer for an individual source of anthropogenic input to surface waters. We observed a strong relationship between barium and total P in the investigated samples (R(2) = 0.78), which could potentially be used to apportion anthropogenic sources of P and thereby facilitate targeting of mitigation practices.