Determination of electron mobility in a blue-emitting alternating block copolymer by space-charge-limited current measurements

In this communication we analyse current versus voltage data obtained using one carrier injection at metal/polymer/metal structures, The used polymer is a soluble blue-emitting alternating block copolymer, Our experimental results demonstrate that the electron current is limited by a large amount of traps with exponential energy distribution in the copolymer. The electron ;mobility of 5.1 x 10(-10) cm(2)/V s is directly determined by space-charge-limited current measurements. The electron mobility is at least three orders of magnitude smaller than that for holes in the copolymer. (C) 1999 Elsevier Science Ltd. All rights reserved.

Hemoglobin conjugated micelles based on triblock biodegradable polymers as artificial oxygen carriers

An artificial oxygen carrier is constructed by conjugating hemoglobin molecules to biodegradable micelles. Firstly a series of triblock copolymers (PEG-PMPC-PLA) in which the middle block contains pendant propargyl groups were synthesized and characterized. After the amphiphilic copolymer was self-assembled into core-shell micelles in aqueous solution, azidized hemoglobin molecules protected by carbon monoxide (CO) were conjugated to the micelles via click reaction between the propargyl and azido groups. The conjugation causes an increase of the micelle's mean diameter. Maximum conjugation ratio is 250 wt% in the hemoglobin-conjugated micelles (HCMs). Oxygen-binding ability of the HCMs was demonstrated by converting the CO-binding state of the HCMs into O-2-binding state.

Synthesis and characterization of new carbazole/fluorene-based derivatives for blue-light-emitting devices

2,7-Bis(9-ethylcarbazol-3-yl)-9,9-di(2-ethylhexyl)fluorene and a segmented copolymer composed of the same chromophores alternated with hexamethylene fragments were synthesized. The obtained materials possess good solubility in common organic solvents, high thermal stability with 1% weight loss temperature of 350-370 degrees C, and suitable glass transition temperatures. Both derivatives show blue fluorescence in dilute solutions as well as in solid state, demonstrating that excimers are not formed in the thin films. The fluorescence spectra of the materials do not show any peaks in the long-wavelength region even after annealing at 200 degrees C in air. An organic LED with the configuration of ITO/copolymer/Al generates blue electroluminescence with the maximum peak at 416 nm, rather low turn-on voltage (4.0 V), and brightness of about 400 cd/m(2). The heterostructure device based on model derivative emitted stable blue light with low operation voltage (100 cd/m(2) at similar to 11 V) and demonstrated luminescence efficiency of 0.8 cd/A.

Novel blue light-emitting PPV-based copolymer containing triazole and carbazole units

A novel alternating conjugated copolymer containing triazole and carbazole units was synthesized by the Wittig reaction. The resulting bipolar conjugated polymer emits a pure light with good thermal stability, which is a promising candidate for polymer light emitting display.

Hydrothermal Synthesis, Structures, and Luminescent Properties of Seven d(10) Metal-Organic Frameworks Based on 9,9-Dipropylfluorene-2,7-Dicarboxylic Acid (H(2)DFDA)

A series of Zn(II) and Cd(II) metal-organic frameworks, namely, [Zn(DFDA)] (1), [Cd(DFDA)(C2H5OH)] (2), [Zn-2(DFDA)(2)(L-1)(2)](2) center dot 3H(2)O (3), [Cd-2(DFDA)(2)(L-1)(2)] (4), [Zn(DFDA)(L-2)] (5), [Cd(DFDA)(L-2)(DMF)] (6), and [Zn(DFDA)(L-3)] (7) (where DFDA = 9,9-dipropylfluorene-2,7-dicarboxylate anion, L-1 = 1,4-bis(imidazol-1-ylmethyl)benzene, L-2 = 1,1'-(1,4-butanediyl) bis(imidazole), L-3 = 2,2'-bipyridine) have been synthesized under hydrothermal conditions and structurally characterized. Compound 1 exhibits a three-dimensional (3D framework containing one-dimensional (1D) Zn(II)-O clusters, with (4(8).6(7)) topology. Compound 2 contains hydrophobic channels built from infinite 1D Cd(II)-O clusters, with (4(8).5(4).6(3)) topology.

Synthesis and Characterization of Coil-Rod-Coil Triblock Copolymers Comprising Fluorene-Based Mesogenic Monodisperse Conjugated Rod and Poly(ethylene oxide) Coil

A series of coil-rod-coil triblock copolymers (i.e., F3T8EO8, F3T8EO17, F3T8EO45, and F3T8EO125) with a mesogenic monodisperse conjugated oligomer comprising 3 fluorene, 8 thiophene, and 2 phenyl units as the rod and poly(ethylene oxide) (PEO) as the coil were synthesized. A reference compound, that is F3T8ME2, with the identical rod but without PEO was also prepared for comparison. The volume fraction of PEO (f(PEO)) was 0, 0.16, 0.28, 0.50, and 0.73 for F3T8ME2, F3T8EO8, F3T8EO17, F3T8EO45, and F3T8EO125, respectively. It was found that the introduction of PEO into the triblock copolymers encouraged the formation of H-type aggregation and f(PEO)-dependent highly ordered mesophases while f(PEO) < 0.73. For F3T8ME2, only nematic mesophase was observed. In contrast, F3T8EO8 and F3T8EO17, with f(PEO) of 0.16 and 0.28, respectively, are smectic A (SA) mesomorphism.

Dye-Sensitized Solar Cells Based on Organic Sensitizers with Different Conjugated Linkers: Furan, Bifuran, Thiophene, Bithiophene, Selenophene, and Biselenophene

Six organic dyes with different conjugated linkers such as furan, bifuran, thiophene, bithiophene, selenophene, and biselenophene have been prepared in combination with the dihexyloxy-substituted triphenylamine donor and the cyanoacrylic acid acceptor. In conjunction with an acetonitrile-based electrolyte and a solvent-free ionic liquid electrolyte, these dyes exhibit 6.88-7.77% and 6.39-7.00% efficiencies, respectively. We have demonstrated that furan and selenophene can be employed as building blocks of sensitizers in stable solar cells for the first time. We have also studied the influence of heteroatoms on photocurrents and photovoltages with the aid of quantum calculations and transient photoelectrical decay measurements. Temperature-dependent electrical impedance experiments have shown that a relatively low external quantum efficiency of the dye with biselenophene linker is not related to the charge collection yield in the case of an acetonitrile electrolyte.

Green light-emitting polyfluorenes with improved color purity incorporated with 4,7-diphenyl-2,1,3-benzothiadiazole moieties

By incorporating 4,7-diphenyl- 2,1,3 benzothiadiazole instead of 2,1,3-benzothiadiazole into the backbone of polyfluorene, we developed a novel series of green light- emitting polymers with much improved color purity. Compared with the state-of-the-art green light-emitting polymer, poly(fluorene-co-benzothiadiazole) (lambda max = 537 nm), the resulting polymers (lambda(max) = 521 nm) showed 10-20 nm blueshifted electroluminescence (EL) spectra and greatly improved color purity because the insertion of two phenylene units between the 2,1,3-benzothiadiazole unit and the fluorene unit reduced the effective conjugation length in the vicinity of the 2,1,3-benzothiadiazole unit. As a result, the resulting polymers emitted pure green light with CIE coordinates of (0.29, 0.63), which are very close to (0.26, 0.65) of standard green emission demanded by the National Television System Committee (NTSC). Moreover, the insertion of the phenylene unit did not affect the photoluminescence (PL) and EL efficiencies of the resulting polymers. PL quantum efficiency in solid films up to 0.82 was demonstrated. Single-layer devices (ITO/PEDOT/ polymer/Ca/Al) of these polymers exhibited a turn-on voltage of 4.2 V, luminous efficiency of 5.96 cd A(-1) and power efficiency of 2.21 lm W-1. High EL efficiencies and good color purities made these polymers very promising for display applications.

Phase identification of triphenylene-based discotic monomer and its main chain polymers

A monomer, 2,3,6,7,10,11-hexakispentyloxy triphenylene (HPT) possesses a triphenylene core as a discotic mesogen. Polymers containing this discotic mesogen have been studied using wide-angle X-ray and electron diffraction. HPT is known to show a discotic liquid crystal phase, noted as D-ho (h for hexagonal bidimensional lattice, o for ordered molecular spacing in each column). In this paper, however, HPT Liquid crystalline phases, heated up from the crystalline state and cooled down from the isotropic state, were characterized in the diameter dimensions. In addition. the diameters of the columns are close to a parameter of two separate crystals. A core orientation was, therefore, proposed in the mesophase obtained by heating the crystalline. In order to distinguish these differences, the D-ho phase was divided to include the D-hcd and D-hco phases. Molecular modeling was performed to help our understanding of the orientation. The D-hcd and D-hco phases were used to characterize the phases of the discotic polymeric analogs by comparing their column diameters to those of the monomers. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

Phylogenetic studies of pantherine cats (Felidae) based on multiple genes, with novel application of nuclear beta-fibrinogen intron 7 to carnivores

The pantherine lineage of the cat family Felidae (order: Carnivora) includes five big cats of genus Panthera and a great many midsized cats known worldwide. Presumably because of their recent and rapid radiation, the evolutionary relationship among pantherines remains ambiguous. We provide an independent assessment of the evolutionary history of pantherine lineage using two complete mitochondrial (mt) genes (ND2 and ND4) and the nuclear beta-fibrmogen intron 7 gene, whose utility in carnivoran phylogeny was first explored. The available four mt (ND5, cytb, 12S, and 16SrRNA) and two nuclear (IRBP and TTR) sequence loci were also combined to reconstruct phylogeny of 14 closely related cat species. Our analyses of combined mt data (six genes; approximate to 3750 bp) and combined mt and nuclear data (nine genes; approximate to 6500 bp) obtained identical tree topologies, which were well-resolved and strongly supported for almost all nodes. Monophyly of Panthera genus in pantherine lineage was confirmed and interspecific affinities within this genus revealed a novel branching pattern, with P. tigris diverging first in Panthera genus, followed by P. onca, P. leo, and last two sister species P. pardus and P. uncia. In addition, close association of Neofelis nebulosa to Panthera, the phylogenetic redefinition of Otocolobus manil within the domestic cat group, and the relatedness of Acinonyx jubatus and Puma concolor were all important findings in the resulting phylogenies. The potential utilities of nine different genes for phylogenetic resolution of closely related pantherine species were also evaluated, with special interest in that of the novel nuclear beta-fibrinogen intron 7. (c) 2005 Elsevier Inc. All rights reserved.

Study on the hydrolysis/precipitation behavior of Keggin Al-13 and Al-30 polymers in polyaluminum solutions

The hydrolysis/precipitation behaviors of Al3+, Al-13 and Al-30 under conditions typical for flocculation in water treatment were investigated by studying the particulates' size development, charge characteristics, chemical species and speciation transformation of coagulant hydrolysis precipitates. The optimal pH conditions for hydrolysis precipitates formation for AlCl3, PAC(A113) and PAC(A130) were 6.5-7.5, 8.5-9.5, and 7.5-9.5, respectively. The precipitates' formation rate increased with the increase in dosage, and the relative rates were AlCl3 >> PAC(A130) > PACA113. The precipitates' size increased when the dosage increased from 50 mu M to 200 mu M, but it decreased when the dosage increased to 800 AM. The Zeta potential of coagulant hydrolysis precipitates decreased with the increase in pH for the three coagulants. The isoelectric points of the freshly formed precipitates for AlCl3, PAC(A113) and PAC(A130) were 7.3, 9.6 and 9.2, respectively. The Zeta potentials of AlCl3 hydrolysis precipitates were lower than those of PAC(A113) and PAC(A130) when pH > 5.0. The Zeta potential of PAC(A130) hydrolysis precipitates was higher than that of PACA113 at the acidic side, but lower at the alkaline side. The dosage had no obvious effect on the Zeta potential of hydrolysis precipitates under fixed pH conditions. The increase in Zeta potential with the increase in dosage under uncontrolled pH conditions was due to the pH depression caused by coagulant addition. Al-Ferron research indicated that the hydrolysis precipitates of AlCl3 were composed of amorphous AI(OH)3 precipitates, but those of PACA113 and PACA130 were composed of aggregates of Al-13 and Al-30, respectively. Al3+ was the most un-stable species in coagulants, and its hydrolysis was remarkably influenced by solution pH. Al-13 and Al-30 species were very stable, and solution pH and aging had little effect on the chemical species of their hydrolysis products. The research method involving coagulant hydrolysis precipitates based on Al-Ferron reaction kinetics was studied in detail. The Al species classification based on complex reaction kinetic of hydrolysis precipitates and Ferron reagent was different from that measured in a conventional coagulant assay using the Al--Ferron method. The chemical composition of Al-a, Al-b and Al-c depended on coagulant and solution pH. The Al-b measured in the current case was different from Keggin Al-13, and the high Alb content in the AlCl3 hydrolysis precipitates could not used as testimony that most of the Al3+ Was converted to highly charged Al-13 species during AlCl3 coagulation.

Novel spiro-fluorenes from tandem radical addition for liquid crystalline monodisperse conjugated oligomers

3'-Nonafluorobutylmethyl-4'-methyl-spiro[cyclopentyl-9,1']fluorenes were successfully synthesized via tandem radical-addition reactions between 9,9-diallylfluorenes and perfluorobutyl iodide in the presence of a radical initiator followed by reduction under mild conditions. Single crystal analysis indicates that two substituents at 3,4-positions of cyclopentane are in a maleinoid form. Accordingly, four oligo(fluorene-co-bithiophene)s with the same molecular length of similar to 10 nm (7 fluorene units and 12 thiophene units) containing one to three novel spiro-fluorene units were synthesized.

Synthesis and properties of soluble poly[bis(benzimidazobenzisoquinolinones)] based on novel aromatic tetraamine monomers

Four aromatic tetraamine monomers possessing flexible ether linkages were successfully synthesized by nucleophilic aromatic substitution of hydroquinone, 4,4'-dihydroxybiphenyl, 2,2'-bis(4-hydroxyphenyl)propane, and 2,7-dihydroxynaphthalene with 5-chloro-2-nitroaniline, followed by reduction, respectively. With these monomers, a new class of soluble poly[ bis(benzimidazobenzisoquinolinones)] was prepared by a one-step, high-temperature solution polycondensation. The resulting polymers were completely soluble in phenolic solvents and had high inherent viscosities ranging from 1.2 to 1.5 g dL(-1). These polymers had glass transition temperatures in the range of 427-449 degrees C. Thermogravimetric analysis showed that all polymers were thermally stable, with 5% weight loss recorded above 510 degrees C in nitrogen.

Effect of ancillary ligands on the properties of heteroleptic green iridium dendrimers functionalized with carbazole dendrons

A series of heteroleptic green iridium dendrimers functionalized with carbazole dendrons, such as G2(pic) and G2(acac), have been synthesized, in which picolinic acid and acetylacetone are used as the ancillary ligands, respectively. Compared with the corresponding homoleptic iridium dendrimer G2 (8%), these heteroleptic ones can be prepared under mild conditions with total yields as high as 55-67%. Both the dendrimer G2(pic) and G2(acac) display bright green emissions with photoluminescence quantum yields higher than 0.80 in toluene solution. As a result, a maximum external quantum efficiency of 7.1% (21.0 cd/A) for G2(pic) and 7.7% (25.8 cd/A) for G2(acac) has been realized based on non-doped device configuration. The state-of-art performance indicates that the heteroleptic dendrimers can be promising candidates used for non-doped electrophosphorescent devices, especially when the ease of synthesis in a large scale is considered.