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.

Nonconjugated Carbazoles: A Series of Novel Host Materials for Highly Efficient Blue Electrophosphorescent OLEDs

A series of carbazole derivatives was synthesized and their electrical and photophysical properties were investigated. It is shown that the triplet energy levels of these hosts are higher than that of the most popular blue phosphorescent material iridium(III) bis[(4,6-difluorophenyl)pyridinato-N,C-2'] picolinate (FIrpic) and the most extensively used phosphorescent host material 4,4'-N,N'-dicarbazole-biphenyl (CBP). These new host materials also showed good thermal stability and high glass transition temperatures (T-g) ranging from 78 to 115 degrees C as the linkage group between the carbazoles was altered. Photophysical measurements indicate that the energy transfer between these new hosts and FIrpic is more efficient than that between CBP and FIrpic. Devices incorporating these novel carbazole derivatives as the host material doped with FIrpic were fabricated with the configurations of ITO/NPB (40 nm)/host:FIrpic (30 nm)/BCP (15 nm)/AlQ (30 nm)/LiF (1 nm)/Al (150 nm). High efficiencies (up to 13.4 cd/A) have been obtained when 1,4-bis (4-(9H-carbazol-9-yl)phenyl)cyclohexane (CBPCH) and bis(4-(9H-carbazol-9-yl)phenyl) ether (CBPE) were used as the host, respectively.

Synthesis of Hyperbranched Polymers with Pendent Norbornene Functionalities via RAFT Polymerization of a Novel Asymmetrical Divinyl Monomer

Hyperbranched polymers with numerous pendent norbornene functionalities have been synthesized via the radical polymerization of a novel asymmetrical divinyl monomer hearing a higher reactivity methacrylate group and it lower reactivity norbornene group. Mediated by a rapid reversible addition-fragmentation chain transfer (RAFT) equilibrium, the concentration of polymeric chain radicals is decreased, and thus the gelation did not occur until higher monomer conversions (ca. 90%). An increase in reaction temperature call also significantly promote the formation of the hyperbranched structure owing to the decreased stability of the intermediate radicals derived from the norbornene group, which was confirmed by a model copolymerization system of two single vinyl monomers with similar structures to the vinyl groups in the asymmetrical divinyl monomer. Furthermore, Tri-SEC and conventional Sin-SEC as well as H-1 NMR.

SYNTHESIS AND CHARACTERIZATION OF HYPERBRANCHED VINYL POLYMERS FROM RAFT POLYMERIZATION OF AN ASYMMETRIC DIVINYL MONOMER

Hyperbranched vinyl polymers were prepared by reversible addition-fragmentation chain transfer ( RAFT) polymerization of a styrenic asymmetric divinyl monomer. This was achieved by using cumyl dithiobenzoate or S-dodecyl-S'-(alpha,alpha'-dimethyl-alpha ''-acetic acid) trithiocarbonate as the chain transfer agent, 1,1'-azobis(cyclohexanecarbonitrile) or thermal initiation as a source of radicals. Cross-linking was inhibited by a rapid RAFT-based equilibrium between active propagation chains and dormant species, and thus a hyperbranched polymer with a monomer conversion as high as 80% was obtained. The hyperbranched structure and properties of the resultant polymers were characterized by a combination of H-1-NMR spectroscopy and a triple detection size exclusion chromatography (TRI-SEC). The hyperbranched vinyl polymer has a broad molecular weight distributions and a low Mark-Houwink exponent alpha value compared with the linear counterpart.

Macrocycle-Terminated Core-Cross-Linked Star Polymers: Synthesis and Characterization

We have synthesized macrocyclic polystyrene- (PS-) terminated PS star polymers via a core-cross-linking approach in this work. A tadpole-shaped macrocyclic PS-linear-PS copolymer was synthesized at first via click chemistry and ATRP polymerization method. The "living" ATRP initiating chain-ends of the tadpole-shaped copolymers were linked together via ATRP polymerization with divinylbenzene to form a core-cross-linked macrocyclic star polymer. The number of arms attached to the macrocyclic star polymers was measured with NMR. and absolute molecular weights with gel permeation chromatography (GPC) with multiangle laser light scattering detector. These macrocyclic star polymers had a highly cross-linked core and many radiating arms. The shorter tadpole-shaped precursors caused core-cross-linked star polymers with higher molecular weights and more arm numbers. The macrocycle-terminated core-cross-linked star polymers showed two glass transition temperatures, one arising from the linear branches and another from the macrocycles.

Effect of main-chain rigidity on the phase transitional behavior of comblike polymers

The influence of the rigidity of polymer backbones on the side-chain crystallization and phase transition behavior was systematically investigated by a combination of differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), Fourier transform infrared spectroscopy (FTIR), and high-resolution solid-state nuclear magnetic resonance spectroscopy (NMR). DSC investigation indicated that the crystallization number of alkyl carbon atoms of the side chains grafted onto the rigid polymer backbone, poly(p-benzamide) (PBA), is much lower than that of the alkyl carbon atoms of the side chains grafted onto the flexible polymer backbone, poly(ethyleneimine) (PEI), implying that the conformational state of the polymer backbones has a strong effect on the side-chain crystallization behavior in comblike polymers. WAXD and FTIR results proved that these two comblike polymers pack into hexagonal (PBA18C) and orthorhombic (PEI18C) crystals, respectively, depending on the adjusting ability of the polymer backbones for particular conformational states. It was also found that the presence of the crystalline-amorphous interphase (delta = 31.6 ppm) in PBA18C detected by solid-state C-13 NMR spectroscopy can be attributed to the rigid PBA backbone, which restricts the mobility of the alkyl side chains.

Order-disorder transition in eicosylated polyethyleneimine comblike polymers

Order-disorder transition (ODT) behavior in eicosylated polyethyleneimine (PEI20C) comblike polymer obtained by grafting n-eicosyl group on polyethyleneimine backbone was systematically investigated by the combination of differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), Fourier transform infrared (FTIR) spectroscopy as well as solid-state high resolution nuclear magnetic resonance (NMR) spectroscopy. DSC investigations showed two obvious transitions, assigned to the transitions (1) from orthorhombic to hexagonal and (2) from hexagonal to amorphous phase, respectively. These transitions are induced by the variations of alkyl side chain conformation and packing structure with temperature changing, which consequently lead to the destruction of original phase equilibrium. The ODT behavior can also be confirmed by spectroscopic methods like WAXD, FTIR and NMR. The ordered structure and the transition behavior of the alkyl side chains confined by the PEI backbone are obviously different from those of pristine normal alkanes. The transition mechanism of ODT and the origin of the phase transition behavior in PEI20C comblike polymer were discussed in detail in this paper.

Solution-processible multi-component cyclometalated iridium phosphors for high-efficiency orange-emitting OLEDs and their potential use as white light sources

The synthesis and photophysical studies of several multifunctional phosphorescent iridium(III) cyclometalated complexes consisting of the hole-transporting carbazole and fluorene-based 2-phenylpyridine moieties are reported. All of them are isolated as thermally and morphological stable amorphous solids. Extension of the pi-conjugation through incorporation of electron- pushing carbazole units to the fluorene fragment leads to bathochromic shifts in the emission profile, increases the highest oc- cupied molecular orbital levels and improves the charge balance in the resulting complexes because of the propensity of the carbazole unit to facilitate hole transport. These iridium-based triplet emitters give a strong orange phosphorescence light at room temperature with relatively short lifetimes in the solution phase. The photo- and electroluminescence properties of these phosphorescent carbazolylfluorene-functionalized metalated complexes have been studied in terms of the coordinating position of carbazole to the fluorene unit. Organic light-emitting diodes (OLEDs) using these complexes as the solution-processed emissive layers have been fabricated which show very high efficiencies even without the need for the typical hole-transporting layer.I These orange-emitting devices can produce a maximum current efficiency of similar to 30 cd A(-1) corresponding to an external quantum efficiency of similar to 10 % ph/el (photons per electron) and a power efficiency of similar to 14 Im W-1.

New carbazole-based copolymers as amorphous hole-transporting materials for multilayer light-emitting diodes

New carbazole-based copolymers, which contain various concentrations of 9-alkyl-3, 6-carbazole fragments in the main chain connected via alkylene spacers, have been synthesized by Ni(0)-catalyzed Yamamoto-type aryl-aryl coupling reactions. Full characterization of the copolymer structure by NMR spectroscopy and elemental analysis is presented. These compounds represent amorphous materials of high thermal stability with glass transition temperatures of 151-162 degrees C and thermal decomposition starting at temperatures > 390 degrees C. UV-Vis absorption and photoluminescence emission of the copolymers confirmed that the effectively conjugated segment in the 3,6-linked carbazole-type copolymers is limited to dyads (dimeric units). However, copolymers with varying concentrations of the oligocarbazole chromophores demonstrate different charge injection and transport properties in multilayer light-emitting diodes with the copolymers as the hole transport and Alq(3) as the electroluminescent/electron transport layer. The device based on a copolymer composed of oligocarbazole blocks with an average length of around four carbazoles exhibited the best overall performance with a turn-on voltage of 3.5 V, a maximal photometric efficiency of 4.1 cd center dot A(-1) and maximum brightness of about 4 200 cd center dot m(-2).

Efficient organic electroluminescent devices based on an organosamarium complex

Several organic electroluminescent devices with different device structures were fabricated based on an organosamarium complex Sm(HFNH)(3)phen[HFNH=4, 4, 5, 5, 6, 6, 6-heptafluoro-l-(2-naphthvl)hexane-1, 3-dione; phen=1, 10-phenanthroline] as emitter. Their electroluminescent properties were investigated in detail. Although the devices with the optimal structure ITO/TPD (50nm)/ Sm(HFNH)(3)phen (xwt%):CBP (50nm)/BCP (20nm)/AIQ (30nm)/LiF (1 nm),/Al (200nm) show high brightness (more than 400cd/m(2)) and high current efficiency (about 1 cd/A), there are emissions from CBP, BCP and even from AIQ existing in the electroluminescence (EL) spectra besides emission from Sm(HFNH)(3)Phen. The reason to this was discussed. The device with the structure ITO/TPD (50 nm)/ Sm(HFNH)(3)phen (50 nm)/AIQ (30 nm)/LiF (1 nm)/Al (200 nm) exhibits the maximum brightness of 118 cd/m(2) and current efficiency of 0.029 cd/A, and shows emissions from AIQ and Sm(HFNH)(3)phen at high voltages. However, with the BCP hole-block layer added, the device [ITO/TPD (50 nm)/Sm(HFNH)(3)phen (50 nm)/BCP (20 nm)/AIQ (30 nm)/LiF (1 nm)/Al (200 nm)] exhibits pure Sm3+ emission in 2 the EL spectra even at high voltages, with the maximum current efficiency of 0.29cd/A and brightness of 82cd/m(2)

Ligand effect on the performance of organic light-emitting diodes based on europium complexes

A series of europium complexes were synthesized and their electroluminescent (EL) characteristics were studied. It was found by comparison that the different substituted groups, such as methyl, chlorine, and nitryl, on ligand 1,10-phenanthroline affect significantly the EL performance of devices based on these complexes. The more methyl-substituted groups on ligand 1,10-phenanthroline led to higher device efficiency. A chlorine-substituted group showed the approximate EL performance as two methyl-substituted groups, whereas a nitryl substituent reduced significantly the EL luminous efficiency. However, beta-diketonate ligand TTA and DBM exhibited similar EL performance. The improved EL luminous efficiency by proper substituted groups on the 1, 10-phenanthroline was attributed to the reduction of the energy loss caused by light hydrogen atom vibration, as well as concentration quenching caused by intermolecular interaction, and the match of energy level between the ligand and Eu3+.

Effect of doped dye on the charge-carrier transport and electroluminescent performance in molecularly doped polymer light-emitting diodes

The effects of the concentration of 10-(2-benzothiazolyl)-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H-(1)-benzopyropyrano(6, 78-i,j)quinolizin-11-one (C545T) as dopant in polyfluorene (PFO) on the charge-carrier transport and electroluminescence (EL) performance were investigated by steady-state and transient EL measurements. A fully green emission from C545T was observed and the EL performance depends strongly on the C545T concentration. The mobility in the C545T-doped PFO film was determined by transient EL. The dopant concentration dependence of the current-voltage relationship indicated clearly the carrier trapping by the C545T molecules. The mobility in C545T:PFO changed significantly with the C545T concentration, and showed a nontrivial dependence on the doping level. The behavior may be understood in terms of the formation of an additional energy disorder due to potential fluctuation caused by the Coulomb interaction of the randomly distributed doping molecules.

Improved color purity and efficiency in polyfluorene-based light-emitting diodes

Polyfluorene (PF) is a class of typical blue electroluminescent (EL) material, but it exhibits undesired feature in the green spectral region under operation condition. We investigated the spectral properties of different device structures of poly(9,9-dioctylfluorene) (PFO)-based light-emitting diodes, and found that the interaction between cathode and PFO is the main origination of green emission in EL devices. The general method of inserting a buffer layer between the PFO and cathode can decrease the low energy band emission to purify the color and improve the EL performance of devices.

Charge carrier transporting, photoluminescent, and electroluminescent properties of zinc(II)-2-(2-hydroxyphenyl)benzothiazolate complex

Zinc(II)-2-(2-hydroxyphenyl)benzothiazolate complex is an excellent white-light-emitting material. Despite some studies devoted to this complex, no information on the real origin of the unusually broad electroluminescent (EL) emission is available. Therefore, we investigate photoluminescent and EL properties of the zinc complex. Orange phosphorescent emission at 580 nm was observed for the complex in thin film at 77 K, whereas only fluorescent emission was obtained at room temperature. Molecular orbitals, excitation energy, and emission energy of the complex were investigated using quantum chemical calculations. We fabricated the device with a structure of ITO/F16CuPc(5.5 nm)/Zn-complex/Al, where F16CuPc is hexadecafluoro copper phthalocyanine. The EL spectra varied strongly with the thickness of the emissive layer. We observed a significant change in the emission spectra with the viewing angles. Optical interference effects and light emission originating both from fluorescence and from phosphorescence can explain all of the observed phenomena, resulting in the broad light emission for the devices based on the Zn complex. We calculated the charge transfer integral and the reorganization energy to explain why the Zn complex is a better electron transporter than a hole transporter.