Properties of complex of Tb(III) and poly(N-isopropylacrylamide)-g-poly(N-isopropylacrylamide-co-styrene) core-shell nanoparticles

We successfully prepared a new kind of thermoresponsive and fluorescent complex of Tb(III) and PNIPAM-g-P(NIPAM-co-St) (PNNS) core-shell nanoparticle. It was found that Tb(III) mainly bonded to 0 of the carbonyl groups of PNNS, forming the novel (PNIPAM-g-P(NIPAM-co-St))-Tb(III) (PNNS-Tb(III)) complex. The maximum emission intensity of the complex at 545 nm is enhanced about 223 times comparing to that of the pure Tb(III). The intramolecular energy transfer efficiency from PNNS to Tb(III) reaches 50%. When the weight ratio of Tb(III) and the PNNS-Tb(III) complex is 1.2 wt.%, the enhancement of the emission fluorescence intensity at 545 nm is highest.

Crystal structure and luminescent properties of the complex [Eu(III)(TFPB)(3)bpy]

The crystal structure of Eu(TFPB)(3)bpy [TFPB: 4,4,4-trifluoro-1-phenyl-1,3-butanedione, bpy: 2,2'-bipyridyl] has been determined by single crystal X-ray diffraction and the coordination geometry of Eu atom is a square antiprism. The complex can give the characteristic luminescence of Eu3+ upon UV excitation.

Extraction and separation of cadmium(II), iron(III), zinc(II), and europium(III) by Cyanex302 solutions using hollow fiber membrane modules

The mass transfer behaviors of Cd(II), Fe(III), Zn(II), and Eu(III) in sulfuric acid solution using microporous hollow fiber membrane (HFM) containing bis(2,4,4-trimethylpentyl)monothiophosphinic acid (commercial name Cyanex302) were investigated in this paper. The experimental results showed that the values of the mass transfer coefficients (K-w) decreased with an increase of H+ concentration and increased with an increase of extractant Cyanex302 concentration. The mass transfer resistance of Eu3+ was the largest because K-w value of Eu3+ was the smallest. The order of mass transfer rate of metal ions at low pH was Cd > Zn > Fe > Eu. Mixtures of Zn2+ and Eu3+ or of Zn2+ and Cd2+ were well separated in a counter-current circulation experiment using two modules connected in series at different initial acidity and concentration ratio. These results indicate that a hollow fiber membrane extractor is capable of separating the mixture compounds by controlling the acidity of the aqueous solution and by exploiting different mass transfer kinetics. The interfacial activity of Cyanex302 in sulfuric acid solution was measured and interfacial parameters were obtained according to Gibbs adsorption equation.

Kinetics of extraction and stripping of y(III) by Cyanex 272 as an acidic extractant using a constant interfacial cell with laminar flow

The extraction and stripping kinetics of yttrium(III) with bis(2,4,4-trimethylpentyl) phosphinic acid (Cyanex 272, HA) dissolved in heptane as an acid extractant have been investigated by constant interfacial cell with laminar flow. The experimental hydrodynamic conditions have been chosen so that the contribution of diffusion to the measured rate of reaction is minimized. The plot of interfacial area on the rate has shown a linear relationship, which makes the interface the most probable local for the chemical reactions. At the same time, the extraction thermodynamic and kinetic methods are compared to determine the equilibrium extraction constant. A rate equation and the rate-determining step of the extraction and stripping of yttrium(III) have also been obtained, respectively.

Solvent extraction of scandium(III), yttrium(III), lanthanum(III) and gadolinium(III) using Cyanex 302 in heptane from hydrochloric acid solutions

The extractions of the selected rare earths (Sc, Y, La and Gd) from hydrochloric acid solutions have been investigated using bis(2,4,4-trimethylpentyl)-mono thiophosphinic acid (Cyanex 302, HL) in heptane as an extractant. The results demonstrate that the extractions of rare earths occur via the following reaction: Sc(OH)(2+) + 2[(HL)(2)]((O)) double left right arrow [Sc(OH)L-2 (.) 2(HL)]((O)) + 2H(+) Y3+ + 3[(HL)(2)]((O)) double left right arrow [Y(HL2)(3)]((O)) + 3H(+) La(OH)(2)(+) + 3[(HL)(2)](O) double left right arrow [La(OH)(2)L (.) 5(HL)]((O)) + H+ Gd(OH)(2+) + 3[(HL)(2)]((O)) double left right arrow [Gd(OH)L-2 (.) 4(HL)]((O)) + 2H(+) The pH(1/2) values and equilibrium constants of the extracted complexes have been deduced by taking into account the aqueous phase complexation of the metal ion with hydroxyl ligands and plausible complexes extracted into the organic phase. According to the pH(1/2) values, it is possible to realize mutual separation among Sc(III), Y(III), La(III) and Gd(III) with Cyanex 302 by controlling aqueous acidity.

Adsorption of heavy rare earth(III) with extraction resin containing bis(2,4,4-trimethylpentyl) monothiophosphinic acid

In the present paper, the adsorption of thulium(Ill) from chloride medium on an extraction resin containing bis(2,4,4-trimethylpentyl) monothiophosphinic acid (CL302, HL) has been studied. The results show that 1.5 h is enough for the adsorption equilibrium. The distribution coefficients are determined as a function of the acidity of the aqueous phase and the data are analyzed both graphically and numerically. The plots of log D versus pH give a straight line with a slope of about 3, indicating that 3 protons are released in the adsorption reaction of thulium(III). The content of Cyanex302 in the resin is determined to be 48.21%. The total amount of Tm3+ adsorbed up to resin saturation is determined to be 82.46 mg Tm3+/g resin. Therefore, the sorption reactions of Tm3+ from chloride medium with CL302 can be described as: Tm3+ + 3HL((r)) <----> TmL3(r) + 3H(+) The Freundlich's isothermal adsorption equation is also determined as: log Q = 0.73 log C + 3.05 The amounts (Q) of Tm3+ adsorbed with the resin have been studied at different temperatures (15-40degreesC) at fixed concentrations of Tm3+, amounts of extraction resin, ion strength and acidities in the aqueous phase.

Extraction and separation of cerium(IV) from nitric acid solutions containing thorium(IV) and rare earths(III) by DEHEHP

The extraction behaviour of Ce(IV), Th(IV) and part of RE(III), viz., La, Ce, Nd and Yb, has been investigated using di(2-ethylhexyl) 2-ethylhexyl phosphonate (DEHEHP,B) in heptane as an extractant. Results show that extractability varies in the order: Ce(IV) > Th(IV) much greater than RE(III). Therefore, it is possible to find the appropriate conditions under which Ce(IV) can be effectively separated from Th(IV) and RE(III). Furthermore, stripping Ce(IV) from the loaded organic phase can be carried out by dilute H2SO4 with an aliquot of H2O2.Roasted bastnasite made in Baotou (China) by Na2CO3 and leached by HNO3, there is about 50% Ce mainly as tetravalent nitrate along with other RE(III) and Th(IV) in the leachings. Through fractional extraction, taking nitric acid leachings of roasted Bastnasite as feed and DEHEHP as an extractant, we can obtain the CeO2 products with high purity of 99.9-99.99%, with a yield of >85%, in which ThO2/CeO2 < 10(-4).

Computer simulation of Gd(III) speciation in human interstitial fluid

The speciation and distribution of Gd(III) in human interstitial fluid was studied by computer simulation. The results show that at the background concentration, all the Gd(III) species are soluble and no precipitates appear. However as the total concentration of Gd(III) rises above 2.610 x 10(-9) mol/l the insoluble species become predominant. GdPO4 is formed first as a precipitate and then Gd-2(CO3)(3). Among soluble species, free Gd(III), [Gd(HSA)], [Gd(Ox)] and the ternary complexes of Gd(III) with citrate as the primary ligand are main species when the total concentration of Gd(III) is below 2.074 x 10(-2) mol/l. With the total concentration of Gd(III) further rising, [Gd-3(OH)(4)] begins to appear and gradually becomes a predominant species.

Investigation of sandwiched gadolinium(III) complexes with tungstosilicates as potential MRI contrast agents

Two gadolinium-sandwiched complexes with tungstosilicates, K-13[Gd(SiW11O39)(2)] (Gd(SiW11)(2)) and K11H6[Gd2O3(SiW9O34)(2)] (Gd-3(SiW9)(2)), have been investigated by in vitro and in vivo experiments as potential contrast agents for magnetic resonance imaging (MRI). T-1-relaxivity of Gd(SiW11)(2)was 6.59 mM(-1) . s(-1) in aqueous solution and 6.85 mM(-1) . s(-1) in 0.725 mmol . L-1 bovine serum albumin solution at 25degreesC and 9.39 T, respectively. The corresponding T-1-relaxivity of Gd-3(SiW9)(2) was 12.6 and 19.3 mM(-1) . s(-1) per Gd, respectively. MRI for Sprague-Dawley rats showed longer and more remarkable enhancement in rat liver after i.v. injection of these two complexes: 39.4 +/- 3.9% and 57.4 +/- 11.6% within the first 30 min after injection, 31.2 +/- 2.6% and 39.9 +/- 7.6% in the next 60 min for Gd(SiW11)(2) and Gd-3(SiW9)(2) at doses of 0.081 and 0.084 mmol Gd/kg, respectively. Our preliminary in vitro and in vivo study indicates that Gd(SiW11)(2) and Gd-3(SiW9)(2) are favorable candidates for hepatic contrast agents for MRI. However, the two complexes exhibit higher acute toxicity and need to be modified and studied further before clinical use.

Tuning the saturated red emission: synthesis, electrochemistry and photophysics of 2-arylquinoline based iridium(III) complexes and their application in OLEDs

A series of novel iridium(III) complexes with two 2-arylquinoline derivatives as cyclometalated ligands and one monoanionic ligand, such as acetylacetonate (acac), N,N'-diethyldithiocarbamate (Et(2)dtc) and O,O'-diethyldithiophosphate (Et(2)dtp), as ancillary ligands have been synthesized and structurally characterized by H-1 NMR, MS and elemental analysis (EA). The cyclic voltammetry, absorption, emission and electroluminescence properties of these complexes were systematically investigated. Through extending pi-conjugation, introducing electron-donating groups in the ligand frame, or changing the ancillary ligands, the HOMO energy levels of the iridium(III) complexes can be tuned, while their LUMO levels remain little affected; in consequence, the emission wavelengths of the iridium(III) complexes can be tuned in the range 606-653 nm. The highly efficient organic light-emitting diodes (OLEDs) with saturated red emission have been demonstrated. A maximum current efficiency of 10.79 cd A(-1), at a current density of 0.74 mA cm(-2), with an emission wavelength of 616 nm and Commisioon Internationale de L'Eclairage (CIE) coordinates of (0.65, 0.35), which are very close to the National Television System Comittee (NSTC) standard red emission, have been achieved when using complex (DPQ)(2)Ir(acac) as a phosphor dopant.

Syntheses of chromium(III) complexes with Schiff-base ligands and their catalytic behaviors for ethylene polymerization

A series of chromium(III) complexes LCrCl3 (4a-c) bearing chelating 2,2'-iminodiphenyisulfide ligands [L = (2-ArMeC=NAr)(2)S] was synthesized in good yields from the corresponding ligands and CrCl3.(THF). Using modified methylaluminoxane (MMAO) as a cocatalyst, these complexes display moderate activities towards ethylene polymerization, and produce highly linear polyethylenes with broad molecular weight distribution. Polymer yields, catalyst activities and the molecular weights, as well as the molecular weight distributions of the polymers can be controlled over a wide range by the variation of the structures of the chromium(III) complexes and the polymerization parameters, such as Al/Cr molar ratio, reaction temperature and ethylene pressure.

Studies of interaction between iron (III) and intermediates of synthetic neuromelanin by means of cyclic voltammetry of Fe(CN)(3-)(6) and dopamine

Neuromelanin is a complex polymer pigment found primarily in the dopaminergic neurons of the human substantia nigra, whose composition is complex including production of dopamine auto-oxidation, glutathione and a variety of amino acid. Neuromelanin forms stable complex with iron (111). We observed that 5,6-dihydroxyindole and its ramification possessed strong ability of chelating iron (111), and they are the production of dopamine auto-oxidation under physiological pH condition. In the present Of L-Cysteine, the relative yields of electrochemical oxidation of dopamine also had strong ability of chelating iron (111). The experimental results suggest that 5,6-dihydroxyindole and 5-S-cysteineldopamine play important roles in the process of synthetic neuromelanin chelating iron (111).

Synthesis, structure, electrochemistry, photophysics and electroluminescence of 1,3,4-oxadiazole-based ortho-metalated iridium(III) complexes

Four new iridium(III) complexes 1-4, with 1,3,4-oxadiazole derivative as cyclometalated ligand for the first time, have been synthesized and structurally characterized by NMR, EA, MS and X-ray diffraction analysis (except 1). The stronger ligand field strength of the dithiolate ancillary ligands results in higher oxidation potentials and lower HOMO energy levels of complexes than acetylacetone. The absorption spectra of these complexes display low-energy metal-to-ligand charge transfer transition ranging from 350 to 500 nm. Complexes with dithiolate ancillary ligand emit at maximum wavelengths of ca. 500 nm, blue shifting 17 and 11 nm with respect to their counterpart with acetylacetone ligand. The electrophosphorescent devices with 2-4 as phosphorescent dopant in emitting layer have been fabricated. All devices have a low turn-on voltage in the range of 4.5 and 4.9 V. A high-efficiency green emission with maximum luminous efficiency of 5.28 cd/A at current density of 1.37 mA/cm(2) and a maximum brightness of 2592 cd/m(2) at 15.2 V has been achieved in device using 2 as emitter.

Highly efficient iridium(III) complexes with diphenylquinoline ligands for organic light-emitting diodes: Synthesis and effect of fluorinated substitutes on electrochemistry, photophysics and electroluminescence

A series of novel cyclometalated iridium(III) complexes bearing 2,4-diphenylquinoline ligands with fluorinated substituent were prepared and characterized by elemental analysis, NMR and mass spectroscopy. The cyclic voltammetry, absorption, emission and electroluminescent properties of these complexes were systematically investigated. Electrochemical studies showed that the oxidation of the fluorinated complexes occurred at more positive potentials (in the range 0.57-0.69 V) than the unfluorinated complex 1 (0.42 V). In view of the energy level, the lowering of the LUMO by fluorination is significantly less than that of the HOMO. The weak and low energies absorption bands in the range of 300-600 nm are well resolved, likely associated with MLCT and (3)pi-pi* transitions. These complexes show strong orange red emission both in the solution and solid state. The emission maxima of the fluorinated complexes showed blue shift by 9, 24 and 15 nm for 2, 3 and 4, respectively, with respect to the unfluorinated analogous 1. Multilayered organic light-emitting diodes (OLEDs) were fabricated by using the complexes as dopant materials. Significantly higher performance and lower turn-on voltage were achieved using the fluorinated complexes as the emitter than that using the unfluorinated counterpart 1 under the same doping level.

Tuning of emission: Synthesis, structure and photophysical properties of imidazole, oxazole and thiazole-based iridium (III) complexes

Three new iridium (III) complexes with two cyclometalated (CN)-N-boolean AND ligands (imidazole, oxazole and thiazole-based, respectively) and one acetylacetone (acac) ancillary ligand have been synthesized and fully characterized. The structure of the thiazole-based complex has been determined by single crystal X-ray diffraction analysis. The Ir center was located in a distorted octahedral environment by three chelating ligands with the N-N in the trans and C-C in the cis configuration. By changing the hetero-atom of (CN)-N-boolean AND ligands the order S, O and N, a marked and systematic hypsochromic shift of the maximum emission peak of the complexes was realized. The imidazole-based complex emits at a wavelength of 500 nm, which is in the blue to green region. The tuning of emission wavelengths is consistent with the variation of the energy gap estimated front electrochemistry results. An electroluminescent device using the thiazole-based complex as a dopant in the emitting layer has been fabricated. A highly efficient yellow emission with a maximum luminous efficiency of 9.8 cd/A at a current density of 24.2 mA/cm(2) and a maximum brightness of 7985 cd/m(2) at 19.6 V has been achieved.