Faster Synthesis of Beta-Diketonate Ternary Europium Complexes: Elapsed Times & Reaction Yields

β-diketonates are customary bidentate ligands in highly luminescent ternary europium complexes, such as Eu(β-diketonate)₃(L)₂, where L stands for a nonionic ligand. Usually, the syntheses of these complexes start by adding, to an europium salt such as EuCl₃(H₂O)₆, three equivalents of β-diketonate ligands to form the complexes Eu(β-diketonate)₃(H₂O)₂. The nonionic ligands are subsequently added to form the target complexes Eu(β-diketonate)₃(L)₂. However, the Eu(β-diketonate)₃(H₂O)₂ intermediates are frequently both difficult and slow to purify by recrystallization, a step which usually takes a long time, varying from days to several weeks, depending on the chosen β-diketonate. In this article, we advance a novel synthetic technique which does not use Eu(β-diketonate)₃(H₂O)₂ as an intermediate. Instead, we start by adding 4 equivalents of a monodentate nonionic ligand L straight to EuCl₃(H₂O)₆ to form a new intermediate: EuCl₃(L)₄(H₂O)_n, with n being either 3 or 4. The advantage is that these intermediates can now be easily, quickly, and efficiently purified. The β-diketonates are then carefully added to this intermediate to form the target complexes Eu(β-diketonate)₃(L)₂. For the cases studied, the 20-day average elapsed time reduced to 10 days for the faster synthesis, together with an improvement in the overall yield from 42% to 69%.     

A problem encountered in a study of the effects of lanthanide ions on enzyme-catalyzed reactions.

Investigations have been made of the time-dependent loss of the ability of dilute lanthanide solutions to inhibit creatine kinase. Using [¹⁵²Eu]Cl₃, it has been demonstrated that the loss is due to the reduction in concentration that occurs because of the adsorption of lanthanide ions onto walls of containers. Further, it has been shown that the adsorption varies with pH and the composition of the container. The results also indicate that dilute solutions of EuCl₃ do not undergo concentration changes when stored in Pyrex glass vessels either under slightly acidic conditions or in buffered solution at pH 8.0.     

Relationship between Sodium Influx and Salt Tolerance of Nitrogen-Fixing Cyanobacteria

The relationship between sodium uptake and cyanobacterial salt (NaCl) tolerance has been examined in two filamentous, heterocystous, nitrogen-fixing species of Anabaena. During diazotrophic growth at neutral pH of the growth medium, Anabaena sp. strain L-31, a freshwater strain, showed threefold higher uptake of Na⁺ than Anabaena torulosa, a brackish-water strain, and was considerably less salt tolerant (50% lethal dose of NaCl, 55 mM) than the latter (50% lethal dose of NaCl, 170 mM). Alkaline pH or excess K⁺ (>25 mM) in the medium causes membrane depolarization and inhibits Na⁺ influx in both cyanobacteria (S. K. Apte and J. Thomas, Eur. J. Biochem. 154:395-401, 1986). The presence of nitrate or ammonium in the medium caused inhibition of Na⁺ influx accompanied by membrane depolarization. These experimental manipulations affecting Na⁺ uptake demonstrated a good negative correlation between Na⁺ influx and salt tolerance. All treatments which inhibited Na⁺ influx (such as alkaline pH, K⁺ above 25 mM, NO₃⁻, and NH₄⁺), enhanced salt tolerance of not only the brackish-water but also the freshwater cyanobacterium. The results indicate that curtailment of Na⁺ influx, whether inherent or effected by certain environmental factors (e.g., combined nitrogen, alkaline pH), is a major mechanism of salt tolerance in cyanobacteria.     

Chiral Discrimination by Ionic Liquids: Impact of Ionic Solutes

Chiral ionic liquids hold promise in many asymmetric applications. This study explores the impact of ionic solutes on the chiral discrimination of five amino acid methyl ester‐based ionic liquids, including L‐ and D‐alanine methyl ester, L‐proline methyl ester, L‐leucine methyl ester, and L‐valine methyl ester cations combined with bis(trifluoromethanesulfonimide) anion. Circularly polarized luminescence spectroscopy was used to study the chiral discrimination by measuring the racemization equilibrium of a dissymmetric europium complex, Eu(dpa)₃^3? (where dpa = 2,6‐pyridinedicarboxylate). The chiral discrimination measured was dependent on the concentration of Eu(dpa)₃^3? and this concentration‐dependence was different in each of the ionic liquids. Ionic liquids with L‐leucine methyl ester and L‐valine methyl ester even switched enantiomeric preference based on the solute concentration. Changing the cation of the Eu(dpa)₃^3? salt from tetrabutylammonium to tetramethylammonium ion also affected the chiral discrimination demonstrated by the ionic liquids. Chirality 27:320–325, 2015. © 2015 Wiley Periodicals, Inc.     

Enhancing the luminescence of Eu3+/Eu2+ ion‐doped hydroxyapatite by fluoridation and thermal annealing

This paper reports a novel way for the synthesis of a europium (Eu)‐doped fluor‐hydroxyapatite (FHA) nanostructure to control the luminescence of hydroxyapatite nanophosphor, particularly, by applying optimum fluorine concentrations, annealed temperatures and pH value. The Eu‐doped FHA was made using the co‐precipitation method followed by thermal annealing in air and reducing in a H₂ atmosphere to control the visible light emission center of the nanophosphors. The intensities of the OH^? group decreased with the increasing fluorine concentrations. For the specimens annealed in air, the light emission center of the nanophosphor was 615 nm, which was emission from the Eu³⁺ ion. However, when they were annealed in reduced gas (Ar + 5% H₂), a 448 nm light emission center from the Eu²⁺ ion of FHA was observed. The presence of fluorine in Eu‐doped FHA resulted in a significant enhancement of nanophosphor luminescence, which has potential application in light emission and nanomedicine.     

The first example of fluorescence of the solid individual compounds of Eu2+ ion: EuCl2, EuI2, EuBr2

Fluorescence (FL) from Eu²⁺ ion solid individual compounds was observed for the first time using the examples EuCl₂, EuI₂ and EuBr₂. Fluorescence was detected at excitation by ultraviolet (UV) light from powdered samples of Eu (II) halides at room temperature (RT) in an argon atmosphere. In air, FL of all Eu²⁺ compounds studied was stable, and intensity persisted for weeks. Depending on the nature of the halide anion and due to a nephelauxetic effect, the position of the maxima in the FL spectra underwent a red shift in the series: EuCl₂ (409 nm) < EuBr₂ (428 mm) < EuI₂ (432 nm). The lifetimes of the excited states of the Eu²⁺* ions for EuI₂, EuCl₂ and EuBr₂ were 355, 76 and 54 ns, respectively.     

Synthesis and characterization of novel europium β‐diketonate organic complexes for solid‐state lighting

Volatile Eu complexes, namely Eu(TTA)₃Phen, Eu_(x)Y_(1‐x)(TTA)₃ Phen; Eu_(x)Tb_(1‐x)(TTA)₃Phen; Eu, europium; Y, yttrium; Tb, Terbium; TTA, thenoyltrifluoroacetone; and Phen, 1,10 phenanthroline were synthesized by maintaining stichiometric ratio. Various characterization techniques such as X‐ray diffraction (XRD), photoluminescence (PL) and thermo gravimetric analysis/differential thermal analysis (TGA/DTA) were carried out for the synthesized complexes. Diffractograms of all the synthesized complexes showed well‐resolved peaks, which revealed that pure and doped organic Eu³⁺ complexes were crystalline in nature. Of all the synthesized complexes, Eu_0.5 Tb_0.5(TTA)₃Phen showed maximum peak intensity, while the angle of maximum peak intensity for all complexes was almost the same with slightly different d‐values. A prominent sharp red emission line was observed at 611 nm when excited with light at 370 nm. It was observed that the intensity of red emissions increased for doped europium complexes Eu_(x)Y_(1‐x)(TTA)₃Phen and Eu_(x)Tb_(1‐x)(TTA)₃ Phen, when compared with Eu complexes. Emission intensity increased in the following order: Eu(TTA)₃Phen > Eu_0.5 Tb_0.5(TTA)₃Phen > Eu_0.4 Tb_0.6(TTA)₃Phen > Eu_0.5Y_0.5(TTA)₃Phen > Eu_0.4Y_0.6(TTA)₃Phen, proving their potential application in organic light‐emitting diodes (OLEDs). TGA showed that Eu complexes doped in Y³⁺ and Tb³⁺ have better thermal stability than pure Eu complex. DTA analysis showed that the melting temperature of Eu(TTA)₃ Phen was lower than doped Eu complexes. These measurements infer that all complexes were highly stable and could be used as emissive materials for the fabrication of OLEDs. Copyright © 2012 John Wiley & Sons, Ltd.     

Luminescent properties of europium complexes with bis(diphenylphosphino)alkane dioxides

Eu(NO₃)₃?5H₂O and EuCl₃?6H₂O were allowed to react with bis(diphenylphosphino)alkane dioxides Ph₂P(O)(CH₂)_nP(O)Ph₂ (n = 2, 4, 6) to obtain polymeric and binuclear complexes. The prepared compounds were structurally characterized by X‐ray diffraction. Luminescence measurements (emission and excitation spectra, quantum yields, lifetimes) were compared with crystallographic data in order to find a relationship between luminescent properties of the Eu(III) complexes and their structures. The Eu(III) polymers, especially [Eu(dpphO₂)₂Cl₂]⁺Cl^–}_n, have shown extremely long luminescence lifetimes, up to 3.73 ms, as a result of a highly protecting hydrophobic shield. Copyright © 2011 John Wiley & Sons, Ltd.     

Syntheses, structures and luminescence of Europium α-thiophene carboxylates coordination polymer and supramolecular compound

Two europium α-thiophene carboxylic acid (HTPA) compounds, coordination polymer Eu(TPA)₃(HTPA)₂ (1) (TPA=α-thiophene carboxylate) and supramolecular compound Eu(TPA)₃(H₂O)₃ · 0.5H₂O (2) with luminescence and triboluminescence, have been synthesized and structurally characterized. In 1 each europium is bridged by six oxygen atoms from six carboxylates and coordinated with two carboxyl oxygen atoms from two α-thiophene carboxylic acid molecules, resulting in a coordination number of eight to Eu. For 2 each europium is chelated by six oxygen atoms from six carboxylates and coordinated with three oxygen atoms from three coordinated water generating a coordination number nine to Eu; A supramolecular compound is constructed through hydrogen bonds. Both 1 and 2 display strong characteristic emission of Eu³⁺ ion radiated by UV light and produce twinkling red light with an external force.     

Effect of external high potassium and pH on the uptake of choline in glial and neuronal cells in culture

TheV _max of the uptake of choline was increased in nerve cell cultures by lowering (from 7.4 to 6.5) or increasing (from 7.4 to 8.1) the pH. In neurons no effect was observed on the value of theK _m's of the uptake of either the apparent high or low affinity components. In glial cells only a low affinity component was measured at pH 6.5 and diffusion was observed at pH 8.1. An excess of K⁺ ions in the incubation medium reproduced the increase inV _max observed with changes in pH suggesting a possible dependence of the uptake of choline upon the H⁺ and OH^– gradients. Taking into account the characteristics already known of the transport of choline into nerve cells, such a dependence adds new insight in the mechanisms underlying the transport and indicates another possible regulation of choline entry, eventually directed towards the synthesis of acetylcholine.     

Preparation, crystal structure and luminescent properties of lanthanide picrate complexes with N-benzyl-2-{2′-[(benzyl-methyl-carbamoyl)-methoxy]-biphenyl-2-yloxy}-N-methyl-acetamide (L)

A new amide-based ligand derived from biphenyl, N-benzyl-2-{2′-[(benzyl-methyl-carbamoyl)-methoxy]-biphenyl-2-yloxy}-N-methyl-aceamide (L) was synthesized. Solid complexes of lanthanide picrates with this new ligand were prepared and characterized by elemental analysis, conductivity measurements, IR and electronic spectroscopies. The molecular structure of [Eu(pic)₃L] shows that the Eu(III) ion is nine-coordinated by four oxygen atoms from the L and five from two bidentate and one unidentate picrates. All the coordinate picrates and their adjacent equivalent picrates form intermolecular π-π stacking. Furthermore, the [Eu(pic)₃L] complex units are linked by the π-π stacking to form a two-dimensional (2-D) netlike supramolecule. Under excitation, the europium complex exhibited characteristic emissions. The lifetime of the ⁵D₀ level of the Eu(III) ion in the complex is 0.22 ms. The quantum yield Φ of the europium complex was found to be 1.01 × 10⁻³ with quinine sulfate as reference. The lowest triplet state energy level of the ligand indicates that the triplet state energy level of the ligand matches better to the resonance level of Eu(III) than Tb(III) ion.     

Uptake,transfer and metabolism of prostaglandin E2 in the isolated perfused human placental cotyledon

(³H) PGE₂ uptake and transfer in the isolated perfused human placental cotyledon was assessed by a ingle pass paired isotope dilution technique utilising (¹⁴C) sucrose as an extracellular marker. Metabolism of (³H) PGE₂ was measured by analysing maternal and fetal effluents from perfused human placental cotyledons after bolus injection of (³H) PGE₂ into ither the maternal or fetal sides. Maximal uptake of (³H) PGE₂ was greater on the maternal (81 +/- 8%) than the fetal sides (42 +/- 12%) and showed saturation with increasing concentrations of PGE₂ only on the fetal side with an apparent Km of 12 +/- 4.9 nmol/l and v_max of 1.5 +/- 0.2 pmol/min/g. Total recoveries of (³H) PGE₂ were 84.6 +/- 11.8 % and 32.6 +/- 6.3 % of the injected dose after injection on the fetal and maternal sides respectively.Transferof (³H) PGE₂ was the same in both directions being 6.4 +/- 1.2 % of the injected dose in the fetal-maternal direction and 5.8 +/- 2.7 % of the injected dose in the maternal-fetal direction. Metabolism was greater on the maternal side (35% of injected (³H) PGE₂) thanthe fetalside(18% of injected (³H) PGE₂) and was principally to the 13,14-dihydro-15-keto-PGE₂ metabolite. Metabolism of (³H) PGE₂ after passage across the placenta was the same in both directions and was of the order of approximately 60%.     

Structural and optical properties of europium‐ and titanium‐doped Y2O3 nanoparticles

Luminescent nanoparticles of Y₂O₃ doped with europium (Eu) and/or titanium (Ti) were synthesized using modified sol–gel routes. The crystalline cubic phase was confirmed using X‐ray powder diffraction (XRD). Particle morphology and size were evaluated using scanning and transmission electron microscopy. High‐resolution transmission electron microscopy showed that the synthesis method affected the average particle size and the Fourier transform of the images showed the lattice plane distances, indicating that the samples presented high crystallinity degree in accordance with the XRD pattern. The Ti valence was investigated using X‐ray absorption near edge spectroscopy and the tetravalent form was the dominant oxidizing state in the samples, mainly in Eu and Ti co‐doped Y₂O₃. Optical behaviour was investigated through X‐ray excited optical luminescence and photoluminescence under ultraviolet–visible (UV–vis) and vacuum ultraviolet (VUV) excitation. Results indicated that Eu³⁺ is the emitting centre in samples doped with only Eu and with both Eu and Ti with the ⁵D₀→⁷F₂ transition as the most intense, indicating Eu³⁺ in a noncentrosymmetric site. Finally, in the Eu,Ti‐doped Y₂O₃ system, Ti³⁺ (or Ti^IV) excitation was observed but no Ti emission was present, indicating a very efficient energy transfer process from Ti to Eu³⁺. These results can aid the development of efficient nanomaterials, activated using UV, VUV, or X‐rays.     

Growth regulation and amino acid transport in epithelial cells: Influence of culture conditions and transformation on A,ASC, and l transport activities

Amino acid transport in Madin-Darby canine kidney (MDCK) cells, grown in a defined medium, was investigated as a function of cell density, exposure to specific growth factors, and transformation. MDCK cells were found to transport neutral amino acids by systems similar to the A, ASC, L, and N systems which have been characterized using other cell lines. Experimental conditions were developed for MDCK cells which allowed independent measurement of A, ASC, and L transport activities. The activity of the L system was measured as Na⁺-independent leucine or methionine uptake at pH 7.4. The activity of the A system was measured as Na⁺-dependent α(methylamino)isobutyric acid (mAIB) uptake at pH 7.4, the activity of the ASC system was measured as Na⁺-dependent alanine uptake in the presence of 0.1 mM mAIB at pH 6.0, and the activity of system N was observed by measuring Na⁺-dependent glutamine uptake at pH 7.4 in the presence of high concentrations of A and ASC system substrates. The L transport system responded minimally to changes in growth state, but Na⁺-dependent amino add transport responded to regulation by growth factors, cell density, and transformation. The activities of the A and ASC systems both decreased at high cell density, but these activities responded dissimilarly under other conditions. The activity of the A system was stimulated by insulin, was inhibited by PGE₁, and was elevated 3–7 fold in the transformed cell line, MDCK-T₁. The activity of the ASC system was slightly stimulated by insulin and by PGE₁, but was unchanged after chemical transformation. Changes in cellular growth were monitored and were found to correlate best with the activity of the A system. These results suggested that MDCK cell growth may be more closely related to the activity of the A than of the ASC system.     

Photoluminescence imaging of europium (III)‐doped γ‐Al2O3 nanofiber structures

Aluminium oxide (Al₂O₃) has widely been used for catalysts, insulators, and composite materials for diverse applications. Herein, we demonstrated if γ‐Al₂O₃ was useful as a luminescence support material for europium (Eu) (III) activator ion. The hydrothermal method and post‐thermal treatment at 800°C were employed to synthesize Eu(III)‐doped γ‐Al₂O₃ nanofibre structures. Luminescence characteristics of Eu(III) ions in Al₂O₃ matrix were fully understood by taking 2D and 3D‐photoluminescence imaging profiles. Various sharp emissions between 580 to 720 nm were assigned to the ⁵D₀→⁷F_J (J = 0, 1, 2, 3, 4) transitions of Eu(III) activators. On the basis of X‐ray diffraction crystallography, Auger elemental mapping and the asymmetry ratio, Eu(III) ions were found to be well doped into the γ‐Al₂O₃ matrix at a low (1 mol%) doping level. A broad emission at 460 nm was substantially increased upon higher (2 mol%) Eu(III) doping due to defect creation. The first 3D photoluminescence imaging profiles highlight detailed understanding of emission characteristics of Eu(III) ions in Al oxide‐based phosphor materials and their potential applications.     

Role of Cation and Anion Uptake in Salt-stimulated Elongation of Lettuce Hypocotyl Sections

The role of cation and anion uptake in salt-stimulated growth of light-grown, GA₃-treated lettuce (Lactuca sativa L.) hypocotyl sections was investigated. Potassium chloride (10 mm) causes a 2-fold increase in the growth rate of GA₃-treated hypocotyl sections without affecting the growth rate of sections incubated in the absence of GA₃. Salt uptake is the same in both treatments, and furthermore the uptake of cation and anion is stoichiometric during the first 24 hours under all incubation conditions. The importance of the anion for cation uptake is demonstrated in experiments with benzenesulfonate⁻ and iminodiacetate²⁻. When K⁺ and Na⁺ are supplied only as the benzenesulfonate and iminodiacetate salts, growth and cation uptake are markedly reduced compared to KCl and NaCl. Calculation of the osmotic potential of salt-treated sections based on measurement of K⁺ and Cl⁻ uptake suggests that the observed increase in tissue osmolality is a result of salt uptake. Similarly, uptake of ions can account for the shift in water potential when sections are incubated in 10 mm KCl. We conclude that the change in growth rate of light-grown, GA₃-treated sections caused by the addition of KCl or NaCl to the incubation medium results solely from decreased water potential of the tissue due to ion uptake.     

铕标记抗癌胚抗原单克隆抗体C17的研究和应用

用合成的N′-(对-异硫氰基苄基)-二乙三胺-N¹,N²,N³,N³-四乙酸铕钠为螫合剂.用Sephadex G-50凝胶柱层析分离标记C₁₇和过量试剂.分部收集的层析物的光密度图和荧光强度图完全一致.蛋白峰处两管标记C₁₇的比活性分别为5.2和8.9Eu³⁺离子每C₁₇分子,而且C₁₇的标记回收率为64%.标记C₁₇至少在6个月内是稳定的.用铕标记物得到的时间分辨免疫荧光分析的标准曲线具有良好线性和斜率,表明标记物免疫活性良好,而且已用于血清CEA分析.     

Synthesis,photophysics, electrochemistry,thermal stability and electroluminescent performances of a new europium complex with bis(β‐diketone) ligand containing carbazole group

We synthesized a new europium complex [Eu(ecbpd)₃(Phen)] with bis(β‐diketone) ligand containing a carbazole group, in which ecbpd and Phen are dehydro‐3,3′‐(9‐ethyl‐9H‐carbazole‐3,6‐diyl)bis(1‐phenylpropane‐1,3‐dione) and 1,10‐phenanthroline, respectively. Its UV/vis and photoluminescent spectra, quantum yield, luminescence lifetime, electrochemistry, thermal stability and electroluminescent performances were studied. This europium complex showed low efficiency luminescence, which is probably due to the mismatching energy levels of its ligand and Eu³⁺, as well as the double Eu³⁺ core resonance.     

Red emissive ternary europium complexes: synthesis,optical, and luminescence characteristics

Solid ternary europium complexes consisting of fluorinated β-diketone (thenoyltrifluoroacetone, TTFA) and heteroaromatic bidentate auxiliary ligands were synthesized. The luminescence features of the complexes were estimated using various spectral measurements and clearly proved that the Eu³⁺ ion is efficiently sensitized by ligands by an antenna effect. Photoluminescence excitation spectra have shown that Eu(III) complexes are excited effectively in the ultraviolet (UV) region and the corresponding emission spectra consist of characteristic peaks attributed to the ⁵D₀→⁷F_J transitions of the europium ion with the strongest emission peak at 611 nm (⁵D₀→⁷F₂). From photoluminescence (PL) data, decay time, Judd–Ofelt parameters, transition rates, and quantum efficiency of the complexes were also determined. The Commission Internationale de l'éclairage (CIE) colour coordinates indicated the bright red emission of ternary europium complexes. Correlated colour temperature values indicated the utilization of these complexes in display devices. Judd–Ofelt and photophysical parameters were also estimated theoretically using LUMPAC software. Various frontier molecular orbitals and their respective energy were determined. These red emissive europium complexes could be utilized for fabricating solid-state lighting systems.     

Spectroscopic investigation of europium(III) nitrato complexes in anhydrous and aqueous acetonitrile

Electronic absorption and emission spectra, along with lifetime measurements and vibrational spectra, are used to investigate the interaction between nitrate and trivalent europium ions in dilute solutions in anhydrous and aqueous acetonitrile. Upon addition of increasing quantities of nitrate, the complexes [Eu(NO₃)_n]^(3?n)+, with n = 1–5, form quantitatively in anhydrous acetonitrile. In solution, the pentanitrato species is not further solvated and its spectroscopic properties are similar to those of solid samples, indicating a similar structure with five bidentate nitrates bonded to the 10-coordinate Eu(III) ion. The lifetimes of the ⁵D₀ level are 1.35(5) and 1.25(5) ms for Eu(NO₃)₃ and (Me₄N)₂Eu(NO₃)₅ 0.05 M in CH₃CN. The quantum yield of Eu(NO₃)₃ in CH₃CN is 27.4%.The addition of small quantities of water to Eu(NO₃)₃ solutions does not result in the dissociation of the nitrate ions, provided R_w = [H₂O]_t/[Eu³⁺]_t is smaller than 8; the apparent equilibrium rations for [Eu(NO₃)₃(H₂O)_n] are K₃ = 40 ± 15 M^?1 and K₄ = 9 ± 3 M^?1; K₁ and K₂ are too large to be determined. The formation of nitrato complexes is studied in mixtures containing increasing amounts of water and nitrate. Deconvolution of the different components of the ⁵D₀ → ⁷F₀ transition allows a semi-quantitative estimate of the relative concentration of the nitrato complexes. The total number of coordinated nitrate ions per europium ion can be determined on the basis of fluorescence lifetime measurements. The apparent equilibrium ratios for the formation of the mono- and dinitrato species amount to K₁ = 23 ± 3, 15 ± 5 and 5 ± 1 for R_w = 44, 94 and 304, respectively, and to K₂ = 17 ± 8 for R_w = 44 and 94.