Aliphatic Poly(ester-carbonate)s Bearing Amino Groups and Its RGD Peptide Grafting

This article deals with (1) synthesis of novel cyclic carbonate monomer (2-oxo [1,3]dioxan-5-yl)carbamic acid benzyl ester (CAB) containing protected amino groups; (2) ring-opening copolymerization of the cyclic monomer with L-lactide (LA) to provide novel degradable poly(ester-carbonate)s with functional groups; (3) removal of the protective benzyloxycarbonyl (Cbz) groups by catalytic hydrogenation to afford the corresponding poly(ester-co-carbonate)s with free amino groups; (4) grafting of oligopeptide Gly-Arg-Gly-Asp-Ser-Tyr (GRGDSY, abbreviated as RGD) onto the copolymer pendant amino groups in the presence of 1,1'-carbonyldiimidazole (CDI).

Synthesis and characterization of functional poly(gamma-benzyl-L-glutamate) (PBLG) as a hydrophobic precursor

Four kinds of functional poly(gamma-benzyl-L-glutamate) (PBLG) copolymers containing chloro, azido, allyl or propargyl groups on the side chains were synthesized through ester exchange reactions of PBLG with functional alcohols without any protection and de-protection process. Hydrolysis of PBLG, which was found during the ester exchange reaction under low ratios of alcohol to the repeat units of PBLG, was thoroughly investigated, and could be successfully depressed by addition of certain amount of benzyl alcohol to the reaction system. Click chemistry reactions of the azidized or propargylated copolymers, thiol-ene reaction of the allyllated copolymer were taken successfully, indicating that the functional groups on the copolymers were still reactive.

White Electroluminescence from a Phosphonate-Functionalized Single-Polymer System with Electron-Trapping Effect

A novel strategy for obtaining white electroluminescence (EL) is based on the mechanism of electron trapping on host. Phosphonate-functionalized polyfluorene is chosen as host owing to its strong electron affinity. Electrons are confined mostly by host pendants in the EL process, which suppresses charge transfer from host to dopant. White EL with CIE coordinates of (0.34,0.35) is achieved.

Red-Emitting Polyfluorenes Grafted with Quinoline-Based Iridium Complex: "Simple Polymeric Chain, Unexpected High Efficiency"

A series of red-light emitting electrophosphorescent polyfluorenes (PFs) with varying content of a quinoline-based iridium complex, (PPQ)(2)Ir(acac) (bis(2,4-diphenylquinolyl-N,C-2') iridium(acetylacetonate)), in the side chain are synthesized by Suzuki polycondensation. Because of the efficient Forster energy transfer from the PF main chain to (PPQ)(2)Ir(acac) and direct charge trapping on the complex, the electroluminescent emission from PF is nearly completely quenched, even though the amount of iridium complex I incorporated into the polymers is as low as 1 mol %. Based on a single-layer device configuration, a luminous efficiency of up to 5.0 cd A(-1) with a luminance of 2000 cd m(-2) and Commission Internationale de L'Eclairage coordinates of (0.63, 0.35) (x, y) is realized, which is far superior to that of previously reported red-light emitting PFs containing benzothiazole- and isoquinoline-based iridium complexes.

Fluorene-Based Copolymers Containing Dinaphtho-s-indacene as New Building Blocks for High-Efficiency and Color-Stable Blue LEDs

By incorporating a new building block, 7,7,15,15-tetraoctyldinaphtho-s-indacene (NSI), into the backbone of poly(9,9-dioctylfluorene) (PFO), a novel series of blue light-emitting copolymers (PFO-NSI) have been developed. The insertion of the NSI unit into the PFO backbone leads to the increase of local effective conjugation length, to form low-energy fluorene-NSI-fluorene (FNF) segments that serve as exciton trapping sites, to which the energy transfers from the high-energy PFO segments. This causes these copolymers to show red-shifted emissions compared with PFO, with a high efficiency and good color stability and purity. The best device performance with a luminance efficiency of 3.43 cd . A(-1), a maximum brightness of 6 539 cd . m(-2) and CIE coordinates of (0.152, 0.164) was achieved.

Starburst substituted hexaazatriphenylene compounds: synthesis, photophysical and electrochemical properties

Starburst-substituted hexaazatriphenylene Compounds have been designed and synthesized by introducing various peripheral aryl substituents to the central heterocyclic core. The effects of various substituent groups on the photophysical and electrochemical properties of the substituted hexaazatriphenylene have been investigated. Significant red-shifts of the absorption peak (from 413 nm to 530 nm) and emission peak (from 432 nm to 700 nm) were observed when the electron-donating ability of the aryl substituents was increased, corresponding to a decrease in the band gap from 2.90 eV to 2.05 eV. Introducing bulky substituents with weak electron-donating ability enhances the fluorescence quantum yield from 23% to 87%. In contrast, incorporating aryl substituents with strong electron-donating ability decreases the fluorescence quantum yield.

Chemical Bonding and Electronic Structure of 4d-Metal Monosulfides

Bond distances, vibrational frequencies, dissociation energies, electron affinities, ionization potentials and dipole moments of the title molecules in neutral and charged ions were studied by use of density functional method. Ground states for each molecule were assigned. The calculated bond distance decreases with the increasing of atomic number of 4d metals, reaches minimum at RhS, then increases. For cationic molecules, the calculated bond distance decreases to the minimum at MoS+, then increases. The calculated vibrational frequency decreases from YS(YS+) to PdS(PdS+) for both neutral and cationic molecules. The bond ionic character decreases from YS(YS+) to PdS(PdS+) for neutral and cationic molecules. The bonding patterns are discussed and compared with the available studies.

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.

The nanocomposite scaffold of poly(lactide-co-glycolide) and hydroxyapatite surface-grafted with L-lactic acid oligomer for bone repair

Nanohydroxyapatite (op-HA) surface-modified with L-lactic acid oligomer (LAc oligomer) was prepared by LAc oligomer grafted onto the hydroxyapatite (HA) surface. The nanocomposite of op-HA/PLGA with different op-HA contents of 5, 10, 20 and 40 wt.% in the composite was fabricated into three-dimensional scaffolds by the melt-molding and particulate leaching methods. PLGA and the nanocomposite of HA/PLGA with 10 wt.% of ungrafted hydroxyapatite were used as the controls. The scaffolds were highly porous with evenly distributed and interconnected pore structures, and the porosity was around 90%. Besides the macropores of 100-300 mu m created by the leaching of NaCl particles, the micropores (1-50 mu m) in the pore walls increased with increasing content of op-HA in the composites of op-HA/PLGA. The op-HA particles could disperse more uniformly than those of pure HA in PLGA matrix. The 20 wt.% op-HA/PLGA sample exhibited the maximum mechanical strength, including bending strength (4.14 MPa) and compressive strength (2.31 MPa). The cell viability and the areas of the attached osteoblasts on the films of 10 wt.% op-HA/PLGA and 20 wt.% op-HA/PLGA were evidently higher than those on the other composites.

Self-Assembly of Hyperbranched Multiarmed PEG-PEI-PLys(Z) Copolymer into Micelles, Rings, and Vesicles

Self-assembling of synthesized novel biodegradable hyperbranched amphiphilic poly(ethylene glycol)-polyethylenimine-poly(epsilon-benzyloxycarbonyl-L-lysine) (PEG-PEI-PLys(Z)) in aqueous media is studied. In aqueous media. PLys(Z) is the hydrophobic segment, with PEG and PEI as the hydrophilic segments. It will self-assemble into spherical shape when the selected solvent water is dropped into the common solvent tetrahydrofuran (THF). And when PEG-PEI-PLYS in common solvent is dropped into mixed solvent water and THF, rings will come into King. The spherical and rings are observed by environmental scanning electron microscopy (ESEM) and transmission electron microscopy ITEM). It shows that the size of the sphere is about 100 nm, and the diameter of ring distributes from 400 nm to 10 mu m and bigger with the time roll around.

Insulin nanoparticle preparation and encapsulation into poly(lactic-co-glycolic acid) microspheres by using an anhydrous system

Insulin has been encapsulated in poly(lactic-co-glycolic acid) (PLGA) microspheres by solid-in-oil-in-oil (S/O/O) emulsion technique using DMF/corn oil as new solvent pairs. To get better encapsulation efficiency, insulin nanoparticles were prepared by the modified isoelectric point precipitation method so that it had good dispersion in the inner oil phase. The resulting microspheres had drug loading of 10% (w/w), while the encapsulation efficiency could be up to 90-100%. And the insulin release from the microspheres could last for 60 days. Microspheres encapsulated original insulin with the same method had lower encapsulation efficiency, and shorter release period. Laser scanning confocal microscopy indicated the insulin nanoparticle and original insulin had different distribution in microspheres. The results suggested that using insulin nanoparticle was better than original insulin for microsphere preparation by S/O/O method.

Preparation of bioactive glass ceramic nanoparticles by combination of sol-gel and coprecipitation method

SiO2-CaO-P2O5 ternary bioactive glass ceramic nanoparticles were prepared via the combination of sol-gel and coprecipitation processes. Precursors of silicon and calcium were hydrolyzed in acidic solution and gelated in alkaline condition together with ammonium dibasic phosphate. Gel particles were separated by centrifugation, followed by freeze drying, and calcination procedure to obtain the bioactive glass ceramic nanoparticles. The investigation of the influence of synthesis temperature on the nanopartilce's properties showed that the reaction temperature played an important role in the crystallinity of nanoparticle. The glass ceramic particles synthesized at 55 degrees C included about 15% crystalline phase, while at 25 degrees C and 40 degrees C the entire amorphous nanopowder could be obtained.

The Study of Electroactive Block Copolymer Containing Aniline Pentamer Isolated from Different Solvents

For the films and powder of polymers containing conductive oligomer are usually obtained from solution, the choice of better solvents for the regular arrangement of oligomers is very important for the higher conductivity. Because of the poor solubility of the oligomers, it is difficult to study the arrangement directly in most common solvents, so, we synthesized a triblock copolymer, mPEG2k-aniline pentamer-mPEG2k, as the model to investigate the arrangement-solvent relationship. For the poor solubility of the AP block in common solvents, the copolymer self-assembled into spheric micelles in toluene and into lamellar crystals in water and THF. The crystallinity (X-c) and crystallization temperature (T-c) values of mPEG blocks in powders prepared from different solvents differed obviously, which may be the effect of different self-assembled structures. From the two-phase model of one-dimensional electron density correlation function of SAXS, the long period of copolymer prepared from THF was presumably equal to the long period of pure mPEG plus the chain length of AP, which demonstrates that the AP blocks arrange regularly in the noncrystalline regions.

Alternating Copolymerization of Carbon Dioxide and Propylene Oxide Catalyzed by Cobalt Schiff Base Complex

Cobalt 2,4-dinitrophenolate (complex 1) based upon a N,N,O,O-tetradentate Schiff base ligand framework was prepared. X-ray diffraction analysis confirmed that complex 1 was triclinic species with a six-coordinated central cobalt octahedron in the solid. Asymmetric alternating copolymerization of carbon dioxide (CO2) with racemic propylene oxide (rac-PO) proceeded effectively by complex 1 in conjunction with (4-dimethylamino)pyridine (DMAP), yielding a perfectly alternating and bimodal molecular weight distribution PO/CO2 poly(propylene carbonate) (PPC) with a small amount of cyclic carbonate byproducts.