Synthesis, spectral, and thermal characterizations of Ni(II) and Cu(II) beta-diketone complexes with thenoyltrifluoroacetone ligand

Two kinds of nickel(II) and copper(II) P-diketone complexes derived from thenoyltrifluoroacetone ligand with blue-violet light absorption were synthesized by reacting free ligand and different metal(II) ions in sodium methoxide solution. Their structures were postulated based on elemental analysis, ESI-MS, FT-IR spectra and UV-vis electronic absorption spectra. Smooth films on K9 glass substrates were prepared using the spin-coating method. Their solubility in organic solvents, absorption properties of thin film and thermal stability of these complexes were evaluated. (c) 2006 Elsevier B.V. All rights reserved.

Serine protease inhibition and mitochondrial dysfunction associated with cisplatin resistance in human tumor cell lines : targets for therapy

Indicators of mitochondrial function were studied in two different cell culture models of cis-diamminedichloroplatinum-II (CDDP) resistance: the intrinsically resistant human ovarian cancer cell line CI-80-13S, and resistant clones (HeLa-S1a and HeLa-S1b) generated by stable expression of the serine protease inhibitor—plasminogen activator inhibitor type-2 (PAI-2), in the human cervical cancer cell line HeLa. In both models, CDDP resistance was associated with sensitivity to killing by adriamycin, etoposide, auranofin, bis[1,2-bis(diphenylphosphino)ethane]gold(I) chloride {[Au(DPPE)2]Cl}, CdCl2 and the mitochondrial inhibitors rhodamine-123 (Rhl23), dequalinium chloride (DeCH), tetraphenylphosphonium (TPP), and ethidium bromide (EtBr) and with lower constitutive levels of ATP. Unlike the HeLa clones, CI-80-13S cells were additionally sensitive to chloramphenicol, 1-methyl-4-phenylpyridinium ion (MPP+), rotenone, thenoyltrifluoroacetone (TTFA), and antimycin A, and showed poor reduction of 1-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide (MTT), suggesting a deficiency in NADH dehydrogenase and/or succinate dehydrogenase activities. Total platinum uptake and DNA-bound platinum were slightly lower in CI-80-13S than in sensitive cells. The HeLa-S1a and HeLa-S1b clones, on the other hand, showed poor reduction of triphenyltetrazolium chloride (TTC), indicative of low cytochrome c oxidase activity. Total platinum uptake by HeLa-S1a was similar to HeLa, but DNA-bound platinum was much lower than for the parent cell line. The mitochondria of CI-80-13S and HeLa-S1a showed altered morphology and were fewer in number than those of JAM and HeLa. In both models, CDDP resistance was associated with less platinum accumulation and with mitochondrial and membrane defects, brought about one case with expression of a protease inhibitor which is implicated in tumor progression. Such markers may identify tumors suitable for treatment with gold phosphine complexes or other mitochondrial inhibitors.

Serine protease inhibition and mitochondrial dysfunction associated with cisplatin resistance in human tumor cell lines: targets for therapy

Indicators of mitochondrial function were studied in two different cell culture models of cis-diamminedichloroplatinum-II (CDDP) resistance: the intrinsically resistant human ovarian cancer cell line CI-80-13S, and resistant clones (HeLa-S1a and HeLa-S1b) generated by stable expression of the serine protease inhibitor—plasminogen activator inhibitor type-2 (PAI-2), in the human cervical cancer cell line HeLa. In both models, CDDP resistance was associated with sensitivity to killing by adriamycin, etoposide, auranofin, bis[1,2-bis(diphenylphosphino)ethane]gold(I) chloride {[Au(DPPE)2]Cl}, CdCl2 and the mitochondrial inhibitors rhodamine-123 (Rhl23), dequalinium chloride (DeCH), tetraphenylphosphonium (TPP), and ethidium bromide (EtBr) and with lower constitutive levels of ATP. Unlike the HeLa clones, CI-80-13S cells were additionally sensitive to chloramphenicol, 1-methyl-4-phenylpyridinium ion (MPP+), rotenone, thenoyltrifluoroacetone (TTFA), and antimycin A, and showed poor reduction of 1-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide (MTT), suggesting a deficiency in NADH dehydrogenase and/or succinate dehydrogenase activities. Total platinum uptake and DNA-bound platinum were slightly lower in CI-80-13S than in sensitive cells. The HeLa-S1a and HeLa-S1b clones, on the other hand, showed poor reduction of triphenyltetrazolium chloride (TTC), indicative of low cytochrome c oxidase activity. Total platinum uptake by HeLa-S1a was similar to HeLa, but DNA-bound platinum was much lower than for the parent cell line. The mitochondria of CI-80-13S and HeLa-S1a showed altered morphology and were fewer in number than those of JAM and HeLa. In both models, CDDP resistance was associated with less platinum accumulation and with mitochondrial and membrane defects, brought about one case with expression of a protease inhibitor which is implicated in tumor progression. Such markers may identify tumors suitable for treatment with gold phosphine complexes or other mitochondrial inhibitors.

Synthesis and luminescence properties of hybrid organic-inorganic transparent titania thin film activated by in-situ formed lanthanide complexes

Stable transparent titania thin films were fabricated at room temperature by combining thenoyltrifluoroacetone (TTFA)-modified titanium precursors with amphiphilic triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, P123) copolymers. The obtained transparent titania thin films were systematically investigated by IR spectroscopy, PL emission and excitation spectroscopy and transmission electron microscopy. IR spectroscopy indicates that TTFA coordinates the titanium center during the process of hydrolysis and condensation. Luminescence spectroscopy confirms the in-situ formation of lanthanide complexes in the transparent titania thin film.

Electroluminescence of hole block material caused by electron accumulation and hole penetration

In this study, we investigated the electroluminescence (EL) mechanisms and processes of hole block material in the multilayer devices with Eu(TTA)(3)phen (TTA = thenoyltrifluoroacetone, phen = 1,10-phenanthroline) doped CBP (4,4'-N,N'-dicarbazolebiphenyl) as the light-emitting layer (EML). First, the hole block ability of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) was experimentally confirmed by comparing the EL spectra. With increasing hole injection, BCP emission emerges and increases gradually due to the increasing hole penetration from EML into the hole block layer (HBL).

Near-infrared luminescence from sol-gel materials doped with holmium(III) and thulium(III) complexes

A series of ternary Ln(tta)(3)L complexes (Ln = Ho, Tm; Htta = 2-thenoyltrifluoroacetone; L = 1,10-phenanthroline, 2,2'-bipyridine, or triphenyl phosphate oxide) and their corresponding sol-gel hybrid materials formed via the in situ synthesis process (designated as Ln-T-L gel) were reported. The complexes and the gels were studied in detail, which suggest the complexes have been successfully synthesized in the corresponding gels.

Efficient white organic light-emitting diodes using europium complex as the red unit

Efficient white organic light-emitting diodes (WOLEDs) using europium complex as the red unit are presented. The WOLEDs were fabricated by using the structure of indium tin oxide (ITO)/N, N'-di(naphthalene-1-yl)-N, N'-diphenyl-benzidine (NPB)/4,4-N, N-dicarbazolebiphenyl (CBP) : bis(2,4-diphenylquinolyl-N, C-2) iridium (acetylacetonate) ((PPQ)(2)Ir(acac)) : Eu (III) tris(thenoyltrifluoroacetone) 3,4,7,8-tetramethyl-1,10-phenanthroline (Eu(TTA)(3)(Tmphen))/NPB/2-methyl-9,10-di(2-naphthyl)anthracene (MADN) : p-bis (p-N, N-di-phenyl-aminostyryl)benzene (DSA-Ph)/9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP)/tris(8-hydroxyquinoline) aluminium (Alq3)/LiF/Al.

Mechanisms of efficiency enhancement in the doped electroluminescent devices based on a europium complex

In this study, we investigated the dependence of electroluminescence (EL) efficiency on carrier distribution in the light-emitting layer (EML) of the device based on Eu(TTA)(3)phen (TTA = thenoyltrifluoroacetone, phen = 1, 10-phenanthroline) doped 4,4'-N,N'-dicarbazole- biphenyl (CBP) system. We found that EL efficiency increases monotonously with increasing hole injection even when holes are the majority carriers. This phenomenon was attributed to the accumulation of holes in EML, which improves the balance of holes and electrons on Eu(TTA)(3)phen molecules, thus enhancing the EL efficiency.

Synergistic extraction of rare earths using acid-base coupling extractants of calix[4]arene carboxyl derivative and primary amine N1923

Synergistic effect in the extraction of rare earth (RE) metals by the acid-base coupling (ABC) extractants of calix[4]arene carboxyl derivative Bu-t[4]CH2COOH (H(4)A) and primary amine N1923 (RNH2) has been investigated. The extraction of RE was enhanced by the addition of sodium cations into the aqueous phase not only in the extraction system of Bu-t[4]CH2COOH alone but also in the mixture of Bu-t[4]CH2COOH and N1923. The separation factors (SFs) indicating the extraction selectivity of adjacent RE elements became higher in the mixture system.

Conversion process of the dominant electroluminescence mechanism in a molecularly doped organic light-emitting device with only electron trapping

In this work, the detailed conversion process of the dominant electroluminescence (EL) mechanism in a device with Eu(TTA)(3)phen (TTA=thenoyltrifluoroacetone, phen=1,10-phenanthroline) doped CBP (4,4(')-N,N-'-dicarbazole-biphenyl) film as the emitting layer was investigated by analyzing the evolution of carrier distribution on dye and host molecules with increasing voltage. Firstly, it was confirmed that only electrons can be trapped in Eu(TTA)(3)phen doped CBP. As a result, holes and electrons would be situated on CBP and Eu(TTA)(3)phen molecules, respectively, and thus creates an unbalanced carrier distribution on both dye and host molecules. With the help of EL and photoluminescence spectra, the distribution of holes and electrons on both Eu(TTA)(3)phen and CBP molecules was demonstrated to change gradually with increasing voltage. Therefore, the dominant EL mechanism in this device changes gradually from carrier trapping at relatively low voltage to Forster energy transfer at relatively high voltage.

Improved efficiency by doping blue iridium (III) complex in europium complex-based light-emitting diodes

We demonstrated high-efficiency red organic light-emitting diodes (OLEDs) employing a europium complex, Eu (III) tris( thenoyltrifluoroacetone) 3,4,7,8-tetramethyl-1,10-phenanthroline (Eu(TTA)(3)(Tmphen)), as an emitter and a blue electrophosphorescent complex, Iridium ( III) bis[4,6-di-fluorophenyl-pyridinato-N,C-2] picolinate (FIrpic), as an assistant dopant codoped into 4,4-N, N-dicarbazole-biphenyl (CBP) host as an emissive layer. A pure red electroluminescence (EL) only from Eu3+ ions at 612 nm with a full width at half maximum of 3 nm was observed and the EL efficiency was significantly enhanced. The maximum EL efficiency reached 7.9 cd A(-1) at 0.01 mA cm(-2) current density, which is enhanced by 2.8 times compared with electrophosphorescence-undoped devices. The large improvements are attributed to energy transfer assistance effects of FIrpic, indicating a promising method for obtaining efficient red OLEDs based on rare-earth complexes.

Highly efficient red electroluminescence from stacked organic light-emitting devices based on a europium complex

Stacked organic light-emitting devices (OLEDs) based on a europium complex Eu(TTA)(3) (Tmphen) (TTA = thenoyltrifluoroacetone,Tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline) were fabricated. In this stacked OLEDs, Li:BCP/V2O5 was used the intermediate charge generation layer sandwiched between two identical emissive units consisting of TPD/CBP:DCJTB:Eu(TTA)(3)(Tmphen)/BCP. As expected, the brightness and electroluminescent (EL) current efficiency were approximately enhanced by double times that of conventional single-unit devices. The stacked OLEDs showed the maximum luminance up to 3000 cd/m(2) at a current density of 190 mA/cm(2) and a current efficiency of 14.5 cd/A at a current density of 0.08 mA/cm(2). At the brightness of 100 cd/m(2), the current efficiency reached 10 cd/A at a current density of 1.6 mA/cm2.

Efficient red organic light-emitting devices based on a europium complex

An efficient organic light-emitting device using a trivalent europium (Eu) complex Eu(Tmphen)(TTA)(3) (TTA=thenoyltrifluoroacetone, Tmphen=3,4,7,8-tetramethyl-1,10-phenanthroline) as the dopant emitter was fabricated. The devices were a multilayer structure of indium tin oxide/N,N-diphenyl-N,N-bis(3-methylphenyl)-1,1-biphenyl-4,4-diamine (40 nm)/ Eu complex:4,4-N,N-dicarbazole-biphenyl (1%, 30 nm)/2,9-dimethyl,4,7-diphenyl-1,10phenanthroline (20 nm)/AlQ (30 nm)/LiF (1 nm)/Al (100 nm). A pure red light with a peak of 612 nm and a half bandwidth of 3 nm, which is the characteristic emission of trivalent europium ion, was observed. The devices show the maximum luminance up to 800 cd/m(2), an external quantum efficiency of 4.3%, current efficiency of 4.7 cd/A, and power efficiency of 1.6 lm/W. At the brightness of 100 cd/m(2), the quantum efficiency reaches 2.2% (2.3 cd/A).

Preparation and luminescence properties of ormosil material doped with Eu(TTA)(3)phen complex

The europium complex, Eu(TTA)(3)phen (TTA = thenoyltrifluoroacetone, phen = 1,10-phenanthroline) was successfully doped into organically modified silicate (ormosil) matrix-SiO2/(VTMOS+PMMA) (VTMOS = vinyltrimethoxysilane, PMMA = polymethylmethacrylate) via sol-gel process, and the luminescence properties of the resultant ormosil composite phosphors [ormosil: Eu(TTA)(3)phen were investigated compared with those of the pure Eu(TTA)(3)phen complex powder. The ormosil composite materials incorporated with Eu(TTA)(3)phen show the characteristic red emission of Eu3+ ion. The Eu3+ possesses fewer emission lines and longer lifetime in the hybrid phosphor than in the pure Eu(TTA)(3)phen complex. This has been explained from the viewpoint of the surrounding environment where the Eu3+ ion lies. (C) 2000 Elsevier Science B.V. All rights reserved.