Improving green emission of Tb3+ ions in BaO‐B2O3‐P2O5 glasses by means of Al3+ ions

BaO‐B₂O₃‐P₂O₅ glasses doped with a fixed concentration of Tb³⁺ ions and varying concentrations of Al₂O₃ were synthesized, and the influence of the Al³⁺ ion concentration on the luminescence efficiency of the green emission of Tb³⁺ ions was investigated. The optical absorption, excitation, luminescence spectra and fluorescence decay curves of these glasses were recorded at ambient temperature. The emission spectra of terbium ions when excited at 393 nm exhibited two main groups of bands, corresponding to ⁵D₃ → ⁷F_j (blue region) and ⁵D₄ → 7F_j (green region). From these spectra, the radiative parameters, viz., spontaneous emission probability A, total emission probability A_T, radiative lifetime τ and fluorescent branching ratio β, of different transitions originating from the ⁵D₄ level of Tb³⁺ ions were evaluated based on the Judd‐Ofelt theory. A clear increase in the quantum efficiency and luminescence of the green emission of Tb³⁺ ions corresponding to ⁵D₄ → ⁷F₅ transition is observed with increases in the concentration of Al₂O₃ up to 3.0 mol%. The improvement in emission is attributed to the de‐clustering of terbium ions by Al³⁺ ions and also to the possible admixing of wave functions of opposite parities. Copyright © 2016 John Wiley & Sons, Ltd.     

Barrier properties of glycophorin-phospholipid systems prepared by different methods

Glycophorin was incorporated into large unilamellar dioleoylphosphatidylcholine vesicles by either a detergent dialysis method using octylglucoside or a method avoiding the use of detergents. The vesicles were characterized and the permeability properties and transbilayer movement of lipids in both vesicles were investigated as a function of the protein concentration and were compared to protein-free vesicles. An insight in the permeability properties of the vesicles was obtained by monitoring the ratio potassium (permeant): dextran (impermeant) trap immediately after separation of the vesicles from the external medium. Glycophorin incorporated without the use of detergents in 1:300 protein:lipid molar ratio induces a high potassium permeability for the majority of the vesicles as judged from the low potassium trap (K⁺:dextran trap = 0.21). In contrast, the vesicles in which glycophorin is incorporated via the octylglucoside method (1:500 protein:lipid molar ratio) are much less permeable to potassium (K⁺:dextran trap = 0.67 and $\text{t}\text{1}\text{2}$ of potassium efflux at 22°C is 7.5 h.). The relationship between protein-induced bilayer permeability and lipid transbilayer movement in both vesicle preparations is discussed. Addition of wheat-germ agglutinin to glycophorin-containing vesicles comprised of dioleoylphosphatidylcholine and total erythrocyte lipids caused no or just a small effect (less than 20% release of potassium) on the potassium permeability of these vesicles. Also, addition of lectin to dioleoylphosphatidylethanolamine-glycophorin bilayer vesicles in a 25:1 lipid:glycophorin molar ratio had no effect on the permeability characteristics of the vesicles. In contrast, addition of wheat-germ agglutinin to bilayer vesicles made of dioleoylphosphatidylethanolamine and glycophorin in a 200:1 molar ratio resulted in a release of 74% of the enclosed potassium by triggering a bilayer to hexagonal (H_II) phase transition. The role of protein aggregation and the formation of defects in the lipid bilayer on membrane permeability and lipid transbilayer movement is discussed.     

Structural and luminescence properties of Sm3+‐doped bismuth phosphate glass for orange‐red photonic applications

In the present study, the effect of bismuth oxide (Bi₂O₃) content on the structural and optical properties of 0.5Sm³⁺‐doped phosphate glass and the effect of concentration on structural and optical properties of Sm³⁺‐doped bismuth phosphate (BiP) glass were studied. Structural characterization was accomplished using X‐ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS), Fourier transform infrared (FTIR) spectroscopy and ³¹P nuclear magnetic resonance (NMR) spectroscopy. Optical properties were studied using absorption, photoluminescence and decay measurements. Using optical absorption spectra, Judd–Ofelt parameters were derived to determine the local structure and bonding in the vicinity of Sm³⁺ ions. The emission spectra of Sm³⁺‐doped BiP glass showed two intense emission bands, ⁴G_5/2→⁶H_7/2 (orange) and ⁴G_5/2→⁶H_9/2 (red) for which the stimulated emission cross‐sections (σ_e) and branching ratios (β) were found to be higher. The quantum efficiencies were also calculated from decay measurements recorded for the ⁴G_5/2 level of Sm³⁺ ions. The suitable combination of Bi₂O₃ (10 mol%) and Sm³⁺ (0.5 mol%) ions in these glasses acted as an efficient lasing material and might be suitable for the development of visible orange‐red photonic materials.     

Optical,emission, and excitation dynamics of Eu3+-doped bismuth-based phosphate glass for visible display laser applications

Eu³⁺-doped-bismuth-based phosphate glasses with chemical equation (60 − x)P₂O₅–20Bi₂O₃−10Na₂CO₃–10SrF₂–xEu₂O₃ (PBNSEu), (where x = 0, 0.1, 0.5, 1.0, 1.5 and 2 mol%) were fabricated using the melt-quenching method. Obtain X-ray diffraction (XRD), energy-dispersive X-ray (EDAX), and Fourier transform infrared (FTIR) spectra were used to characterize the structure of the prepared PBNSEu glass. The J–O (Judd–Ofelt) intensity parameters (Ω₂, Ω₄) were estimated using photoluminescence emission spectra. When excited with a xenon lamp at λ_exc = 394 nm, the most intense red-emission transition occurred at ~612 nm (⁵D₀→⁷F₂). J–O intensity parameters were used to calculate radiative properties, whereas the radiative branching ratio (β_R), radiative transition probability (A_R), radiative lifetime (τ_R), and total radiative transition rate (A_τ) were calculated for the transitions ⁵D₀→⁷F_J (where J = 0–4) and were obtained in the emission spectra for europium ion-doped in the current glass. Using the CIE1931 chromaticity coordinates axes, the colours of various concentrations of Eu³⁺ ion-doped PBNS glass were evaluated using the emission spectra. Temperature-dependent luminescence spectra were recorded for the optimized PBNSEu20 glass to calculate the activation energy. These results strongly suggested red components in w-LEDs and visible display laser applications.     

Utilization of phosphate from different sources by six plant species

Summary Six plant species, wheat, paspalum grass (Paspalum plicatulum), maize, molasses grass (Melinis minutiflora), soybean and buckwheat (Fagopyrum esculentum) were compared for their abilities to utilize phosphate from superphosphate, a calcined aluminum phosphate and four rock phosphates.Buckwheat showed an exceptional behaviour in that it could utilize all phosphates. For the other plants, only the calcined aluminum phosphate and one rock phosphate (hyperphosphate) had significant fertilizing values. Their efficiencies, relative to superphosphate, were 0.45 and 0.11 for wheat, 0.73 and 0.43 for paspalum grass, 0.50 and 0.37 for maize, 0.46 and 0.42 for molasses grass, 0.28 and 0.38 for soybean, and 0.72 and 1.08 for buckwheat, respectively.For three P sources, superphosphate, calcined aluminum phosphate and hyperphosphate, a relationship between soil acidity and P uptake was found. Soil pH in its turn was negatively related to the ratio of total equivalents of cations and those of anions absorbed. Consequenly, P uptake was positively related to the ratio of total equivalents of cations to those of anions absorbed. The same effect of plant species on soil pH could also explain the difference in uptake of P from sparingly soluble phosphates. The relative efficiencies of calcined aluminum phosphate and hyperphosphate for the various plant species were closely related to the ratio of total cations and total anions absorbed by these plants.on leave at the Agricultural University during 1977.     

The fate of18O labelled phosphate in soil/plant systems

KH₂PO₄ labelled with¹⁸O and³²P was mixed with soil that was placed in pots in which grass seed was sown. Grass samples were taken after 5, 7, and 12 weeks. The dilution factor (DF) for¹⁸O in the first cut was much greater than the DF for³²P, indicating that the bulk of the¹⁸O in the absorbed phosphate was lost. The DFs for¹⁸O and³²P determined in phosphate extracted from the soil at the end of the pot experiment indicated that half the¹⁸O excess in the applied phosphate was lost.A succeeding experiment showed no loss of¹⁸O when the treated soil was shaken for 3 months with water to which a germicide was added. Thus, the loss of¹⁸O was presumably caused by biochemical processes which brought about the replacement of¹⁸O by¹⁶O. We suggest that the loss of¹⁸O from applied labelled phosphate may be used as a measure of biological activity in soil.     

Quantification of sugar phosphate intermediates of the pentose phosphate pathway by LC-MS/MS: application to two new inherited defects of metabolism

We describe a liquid chromatography tandem mass spectrometry (LC-MS/MS) method to quantify pentose phosphate pathway intermediates (triose-3-phosphates, tetrose-4-phosphate, pentose-5-phosphate, pentulose-5-phosphates, hexose-6-phosphates and sedoheptulose-7-phosphate (sed-7P)) in bloodspots, fibroblasts and lymphoblasts. Liquid chromatography was performed using an ion pair loaded C(18) HPLC column and detection of the sugar phosphates was carried out by tandem mass spectrometry using an electron ion spray source operating in the negative mode and multiple reaction monitoring. Reference values for the pentose phosphate pathway intermediates in blood spots, fibroblasts and lymphoblasts were established. The method was applied to cells from patients affected with a deficiency of transaldolase. The transaldolase-deficient cells showed an increased concentration of sedoheptulose-7-phosphate. (Bloodspots: 5.19 and 5.43 micromol/L [0.49-3.33 micromol/L]; fibroblasts 7.43 and 26.46 micromol/mg protein [0.31-1.14 micromol/mg protein]; lymphoblasts 16.03 micromol/mg protein [0.61-2.09 micromol/mg protein].) The method was also applied to study enzymes of the pentose phosphate pathway by incubating fibroblasts or lymphoblasts homogenates with ribose-5-phosphate or 6-phosphogluconate and the subsequent analysis of the formed sugar phosphates.     

Inhibition of NAD biosynthesis by paraquat in Escherichia coli

Niacin significantly reduced the bacteristatic effect of 1 mM paraquat for Escherichia coli. Without niacin (an intermediate in the salvage pathway for pyridine nucleotide coenzyme biosynthesis), the NAD concentration was decreased rapidly and significantly in E. coli during paraquat poisoning. Niacin prevented the decline in NAD in paraquat-poisoned cells; quinolinate (an intermediate in de novo NAD biosynthesis prior to the entry point of niacin) did not. These data suggest that paraquat poisons the de novo pathway of pyridine nucleotide coenzyme biosynthesis. Similar consequences have been reported to result from hyperbaric oxygen poisoning of E. coli; thus, there is growing evidence for a common mechanism of toxicity for hyperoxia and paraquat.     

Concentration dependence of luminescence efficiency of Dy3+ ions in strontium zinc phosphate glasses mixed with Pb3O4

In this work we synthesized SrO–ZnO–P₂O₅ glasses mixed with Pb₃O₄ (heavy metal oxide) and doped with different amounts of Dy₂O₃ (0.1 to 1.0 mol%). Subsequently their emission and decay characteristics were investigated as a function of Dy₂O₃ concentration. The emission spectra exhibited three principal emission bands in the visible region corresponding to ⁴F_9/2 → ⁶H_15/2 (482 nm), ⁶H_13/2 (574 nm) and ⁶H_11/2 (663 nm) transitions. With increase in the concentration of Dy₂O₃ (upto 0.8 mol%) a considerable increase in the intensity of these bands was observed and, for further increase, quenching of photoluminescence (PL) output was observed. Using emission spectra, various radiative parameters were evaluated and all these parameters were found to increase with increase in Dy₂O₃ concentration. The Y/B integral emission intensity ratio of Dy³⁺ ions evaluated from these spectra exhibited a decreasing trend with increase in the Dy₂O₃ concentration up to 0.8 mol%. Quenching of luminescence observed in the case of the glasses doped with 1.0 mol% is attributed to clustering of Dy³⁺ ions. The quantitative analysis of these results together with infra‐red (IR) spectral studies indicated that 0.8 mol% is the optimum concentration of Dy³⁺ ions needed to achieve maximum luminescence efficiency. Copyright © 2016 John Wiley & Sons, Ltd.     

Thermotropism and hydration properties of POPE and POPE-cholesterol systems as revealed by solid state2H and31P-NMR

The partial phase diagram and the hydration properties of the 1-palmitoyl-2-oleoyl-phosphatidylethanolamine (POPE)-water system, in the absence and presence of 30 mol% cholesterol, have been investigated by solid state phosphorus NMR of the lipid and deuterium NMR of heavy water. The POPE-D₂O phase diagram resembles other phosphatidylethanolamine (PE)-water systems: below water-to-lipid molar ratios (R_i) of 3 the lamellar gel (L or L_c)-to-hexagonal type II (H_II) phase sequence is observed on increasing the temperature. For R_i3 the thermotropic sequence (L or L_c)-L-H_II is detected. On increasing hydration from R_i=3, the H_II phase is detected from 40°C to 85°C whereas the gel phase is observed from 40°C to 30°C. The limiting hydrations of the gel, L and H_II phases are R_i 3, 17 and 20, respectively. The number of bound water molecules per lipid is ca. 8 in both the La and HII phases. The presence of cholesterol stabilizes the hexagonal phase 20°C below temperatures at which it is observed in its absence and reduces the limiting hydration of the fluid and hexagonal phases to Ri 9 and 14, respectively. The structure and/or dynamics of the water bound to the interface are markedly modified on going from the L to the H_II phase.Abbreviations NMR Nuclear magnetic resonance - DDPE 1,2-Didodecyl-rac-glycerol-3-phosphoethanol-amine - DHPE 1,2-Dihexadecyl-sn-glycerol-3-phosphoethanol-amine - DOPE 1,2-Dioleoyl-sn-glycerol-3-phosphoethanol-amine - POPE 1-Palmitoyl-2-oleoyl-sn-glycerol-3-phosphoetha-nolamine - DAPE 1,2-Diarachinoyl-sn-glycerol-3-phosphoethanol-amine - DMPC 1,2-Dimyristol-sn-glycerol-3-phosphocholine - DPPC 1,2-Dipalmitoyl-sn-glycerol-3-phosphocholine - T_c lamellar gel-to-lamellar fluid transition temperature - T_h lamellar fluid-to-hexagonal transition temperature     

The cytochrome P450 2D‐mediated formation of serotonin from 5‐methoxytryptamine in the brain in vivo: a microdialysis study

The cytochrome P450 2D (CYP2D) mediates synthesis of serotonin from 5‐methoxytryptamine (5‐MT), shown in vitro for cDNA‐expressed CYP2D‐isoforms and liver and brain microsomes. We aimed to demonstrate this synthesis in the brain in vivo. We measured serotonin tissue content in brain regions after 5‐MT injection into the raphe nuclei (Model‐A), and its extracellular concentration in rat frontal cortex and striatum using an in vivo microdialysis (Model‐B) in male Wistar rats. Naïve rats served as control animals. 5‐MT injection into the raphe nuclei of PCPA‐(tryptophan hydroxylase inhibitor)‐pretreated rats increased the tissue concentration of serotonin (from 40 to 90% of the control value, respectively, in the striatum), while the CYP2D inhibitor quinine diminished serotonin level in some brain structures of those animals (Model‐A). 5‐MT given locally through a microdialysis probe markedly increased extracellular serotonin concentration in the frontal cortex and striatum (to 800 and 1000% of the basal level, respectively) and changed dopamine concentration (Model‐B). Quinine alone had no effect on serotonin concentration; however, given jointly with 5‐MT, it prevented the 5‐MT‐induced increase in cortical serotonin in naïve rats and in striatal serotonin in PCPA‐treated animals. These results indicate that the CYP2D‐catalyzed alternative pathway of serotonin synthesis from 5‐MT is relevant in the brain in vivo, and set a new target for the action of psychotropics.

     

The luminescence properties of Sr2–1.5x−1.5yP2O7:xDy3+,yCe3+ phosphor for near‐UV‐based white LEDs synthesized by a chemical co‐precipitation method

A series of Sr₂P₂O₇:Dy³⁺, Sr₂P₂O₇:Ce³⁺ and Sr₂P₂O₇:Dy³⁺,Ce³⁺ phosphors was synthesized via the one‐step calcination process for the precursors prepared by co‐precipitation methods. The phases, morphology, quantum efficiency and photoluminescence properties of the obtained phosphors were characterized systematically. These results show that the near‐spherical particles prepared through calcining the precursors by means of ammonium dibasic phosphate co‐precipitation (method 3) have the smallest particle size and strongest emission intensity among the three methods in the paper. With Dy³⁺ concentration increasing in Sr₂P₂O₇:Dy³⁺ phosphors, the luminescence intensity first increases, reaches maximum, and then decreases. A similar trend was followed by Sr₂P₂O₇:Ce³⁺ with Ce³⁺concentration increasing. A successful attempt was made to initiate the energy transfer mechanism from Ce³⁺ to Dy³⁺ in the host lattice and an overlap between the emission band of Ce³⁺ and the excitation band of Dy³⁺ indicated that the Ce³⁺ → Dy³⁺ energy transfer may indeed exist. It is clear that the photoluminescence intensity of Dy³⁺ as well as the quantum efficiency of the phosphor can be enhanced markedly by co‐doping Ce³⁺. Sr₂P₂O₇:Dy³⁺,Ce³⁺ has its (CIE) chromaticity coordinates in the bluish‐white‐light region, near the standard illuminant D₆₅. The CIE 1913 chromaticity coordinates of Sr₂P₂O₇:Dy³⁺ phosphors fall in the white‐light region, and are adjacent to the ideal white‐light coordinates. In addition, the colour temperature and colour tone of Sr₂P₂O₇:Dy³⁺ could be adjusted by changing the relative concentration of Dy³⁺. In short, Sr₂P₂O₇:Dy³⁺ can be a promising single‐phased white‐light emitting phosphor for near‐UV (NUV) w‐LEDs.     

Algal oxidation of aromatic hydrocarbons: formation of 1-naphthol from naphthalene by Agmenellum quadruplicatum, strain PR-6.

Hydroxyurea induces repair replication in human lymphoblastoid NC37 BaEV cells during incubation with liver microsomes and NADPH. Catalase reduces hydroxyurea-induced repair by more than 95%, suggesting that hydrogen peroxide derived from hydroxyurea in the presence of the metabolic activation system is involved in the DNA damage.     

Solution structure of the low-molecular-weight protein tyrosine phosphatase from Tritrichomonas foetus reveals a flexible phosphate binding loop

Eukaryotic low-molecular-weight protein tyrosine phosphatases (LMW PTPs) contain a conserved serine, a histidine with an elevated pKa, and an active site asparagine that together form a highly conserved hydrogen bonding network. This network stabilizes the active site phosphate binding loop for optimal substrate binding and catalysis. In the phosphatase from the bovine parasite Tritrichomonas foetus (TPTP), both the conserved serine (S37) and asparagine (N14) are present, but the conserved histidine has been replaced by a glutamine residue (Q67). Site-directed mutagenesis, kinetic, and spectroscopic experiments suggest that Q67 is located near the active site and is important for optimal catalytic activity. Kinetic experiments also suggest that S37 participates in the active site/hydrogen bonding network. Nuclear magnetic resonance spectroscopy was used to determine the three-dimensional structure of the TPTP enzyme and to further examine the roles of S37 and Q67. The backbone conformation of the TPTP phosphate binding loop is nearly superimposable with that of other tyrosine phosphatases, with N14 existing in a strained, left-handed conformation that is a hallmark of the active site hydrogen bonding network in the LMW PTPs. As expected, both S37 and Q67 are located at the active site, but in the consensus structure they are not within hydrogen bonding distance of N14. The hydrogen bond interactions that are observed in X-ray structures of LMW PTPs may in fact be transient in solution. Protein dynamics within the active site hydrogen bonding network appear to be affected by the presence of substrate or bound inhibitors such as inorganic phosphate.     

The effect of calcium on the secretion of factor VIII-related antigen by cultured human endothelial cells

Cultured human endothelial cells derived from the umbilical cord vein are able to release factor VIII-related antigen into the culture medium. The experiments described in this paper show the presence of two pathways for the secretion of factor VIII-related antigen from endothelial cells. There is a basal release of this antigen, independent of the presence of extracellular calcium ions. This release can be inhibited by cycloheximide and is therefore directly related to de novo protein synthesis. Besides this basal release, there is an extra release of factor VIII-related antigen that can be stimulated by thrombin, the Ca²⁺-ionophore A23187 or phorbol myristate acetate. As demonstrated by immunofluorescence, the stimulus-inducible release originates from storage granules in the cells. This stimulus-inducible release is dependent on extracellular Ca²⁺ but independent of intracellular cAMP.