Enhanced luminescence of BPO4 by mixing with SiO2 and Al2O3

In this paper, BPO4-xSiO(2) (X: SiO2/BPO4 molar ratio, 0-70%) and BPO4-xAl(2)O(3) (X: Al2O3/BPO4 molar ratio, 0-20%) powder samples were prepared by the Pechini-type sol-gel (PSG) process using glycerol and poly(ethylene glycol) as additives. The structure and optical properties of the resulting samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FESEM), diffuse reflection spectra, photoluminescence (PL) excitation and emission spectra, kinetic decay, and X-ray photoelectron spectra (XPS), respectively. It was found that the Pechini-type sol-gel-derived BPO4-xSiO(2) annealed at 1000 degrees C and BPO4-xAl(2)O(3) annealed at 960 degrees C exhibited bright bluish-white emissions centered at 428 and 413 nm, respectively. The luminescence decay curve analysis indicates that each sample has two kinds of lifetimes (more than 0.4 ms and less than 10 ns) and two types of kinetic decay behaviors, which can be fitted into a double-exponential function and a single-exponential function, respectively.

Multiform oxide optical materials via the versatile Pechini-type sol-gel process: Synthesis and characteristics

This feature article highlights work from the authors' laboratories on the various kinds of oxide optical materials, mainly luminescence and pigment materials with different forms (powder, core-shell structures, thin film and patterning) prepared by the Pechini-type sol-gel (PSG) process. The PSG process, which uses the common metal salts (nitrates, acetates, chlorides, etc.) as precursors and citric acid (CA) as chelating ligands of metal ions and polyhydroxy alcohol (such as ethylene glycol or poly ethylene glycol) as a cross-linking agent to form a polymeric resin on molecular level, reduces segregation of particular metal ions and ensures compositional homogeneity. This process can overcome most of the difficulties and disadvantages that frequently occur in the alkoxides based sol-gel process.

Selective hydrogenation of citral catalyzed with palladium nanoparticles in CO2-in-water emulsion

CO2-in-Water (C/W) emulsion was formed by using a nonionic surfactant of poly (ethylene oxide)-poly (propylene oxide)-poly (ethylene oxide) (P123), and palladium nanoparticles were synthesized in situ in the present work. The catalytic performance of Pd nanoparticles in the C/W emulsion has been discussed for a selective hydrogenation of citral. Much higher activity with a turnover frequency (TOF) of 6313 h(-1) has been obtained in this unique C/W emulsion compared to that in the W/C microemulsion (TOF, 23 h(-1)), since the reaction was taking place not only in the surfactant shell but also on the inner surface of the CO2 core in the C/W emulsion. Moreover, citronellal was obtained with a higher selectivity for that it was extracted to a supercritical carbon dioxide (scCO(2)) phase as formed and thus its further hydrogenation was prohibited. The Pd nanoparticles could be recycled several times and still retain the same selectivity, but it showed a little aggregation leading to a slight decrease in conversion.

Influence of metal particle size on the hydrogenation of maleic anhydride over Pd/C catalysts in scCO(2)

Hydrogenation of maleic anhydride (MAH) with Pd/C catalysts in supercritical carbon dioxide (scCO(2)) was investigated. The selectivity for gamma-butyrolactone (GBL) reached 97.3% in scCO(2) at 100% conversion of MAH, which was notably higher than that of 77.4% obtained in organic solvent of ethylene glycol dimethyl ether (EGDME). The particle size of Pd exhibited large influence on the reaction rate and selectivity of GBL. Higher selectivity of GBL was obtained with Pd/C catalyst of smaller Pd particle size, and the rate of GBL selectivity increase as a function of CO2 pressure was found to be significantly correlated with Pd particle size.

Isothermal Crystallization Behavior of Poly(L-lactic acid)/Organo-Montmorillonite Nanocomposites

The isothermal crystallization behavior of poly(L-lactic acid)/organo-montmorillonite nanocomposites (PLLA/OMMT) with different content of OMMT, using a kind of twice-functionalized organoclay (TFC), prepared by melt intercalation process has been investigated by optical depolarizer. In isothermal crystallization from melt, the induction periods (t(i)) and half times for overall PLLA crystallization (100 degrees C <= T-c <= 120 degrees C) were affected by the temperature and the content of TFC in nanocomposites. The kinetic of isothermal crystallization of PLLA/TFC nanocomposites was studied by Avrami theory. Also, polarized optical photomicrographs supplied a direct way to know the role of TFC in PLLA isothermal crystallization process. Wide angle X-ray diffraction (WAXD) patterns showed the nanostructure of PLLA/TFC material, and the PLLA crystalline integrality was changed as the presence of TFC. Adding TFC led to the decrease of equilibrium melting point of nanocomposites, indicating that the layered structure of clay restricted the full formation of crystalline structure of polymer.

Synthesis of biodegradable thermo- and pH-responsive hydrogels for controlled drug release

Novel intelligent hydrogels composed of biodegradable and pH-sensitive poly(L-glutamic acid) (PGA) and temperature sensitive poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) (PNH) were synthesized and characterized for controlled release of hydrophilic drug. The influence of pH on the equilibrium swelling ratios of the hydrogels was investigated. A higher PNH content resulted in lower equilibrium swelling ratios. Although temperature had little influence on the swelling behaviors of the hydrogels, the changes of optical transmittance of hydrogels as a function of temperature were marked, which showed that the PNH part of hydrogel exhibited hydrophobic property at temperature above the lower critical solution temperature (LCST). The biodegradation rate of the stimuli-sensitive hydrogels in the presence of enzyme was directly proportional to the PGA content. Lysozyme was chosen as a model drug and loaded into the hydrogels.

Reactivity of Rare-Earth Metal Complexes Stabilized by an Anilido-Phosphinimine Ligand

Treatment of anilido-phosphinimine-ligated yttrium mono(alkyl) complex 1a, LY(CH2Si(CH3)(3))(THF) (L = o-(2,6-(C6H3Pr2)-Pr-i)NC6H4P(C6H4)(C6H5)N(2,4,6-C6H2Me3)), with 2 equiv of phenylsilane in DME afforded methoxy-bridged complex 2, [LY(mu-OCH3)](2), via the corresponding hydrido intermediate. When excess isoprene was added to the mixture of la and phenylsilane, a eta(3)-isopentene product, 3, LY(CH2C(CH3)=CHCH3)(THF), was isolated. A lutetium chloride, LLuCl(DME) (4), was generated through the reaction of lutetium mono(alkyl) complex 1b, LLu(CH2Si(CH3)(3))(THF), with [Ph3C]-[B(C6F5)(4)]center dot LiCl accompanied by the formation of [Li(DME)(3)](+)[B(C6F5)(4)](-). Metathesis reaction of 1b with excess AlMe3 at room temperature gave a methyl-terminated counterpart, 5, LLu(CH3)(THF)(2). In all these reactions, the Ln-C-phenyl bonds of complexes 1 remained untouched.

Conducting polyaniline film from aqueous dispersion: Crystallizable side chain forced lamellar structure for high conductivity

Aqueous conducting polyaniline dispersion was prepared employing acidic phosphate ester bearing hydrophilic ethylene glycol segment as dopant, and conducting film with electrical conductivity of 25 S/cm was obtained from the dispersion. Ordered self-assembly lamellar structure with interlamellar distance of 1.2 nm was observed in the film, which consisted of alternating layers of rigid polyaniline chain and flexible phosphate ester side chains, where the phosphate side chain layer was separated by two rigid polyaniline layers. The lamellar structure leading to high conducting film was formed due to the confinement of polyaniline chain by crystallizable phosphate side chain, since the electrical conductivity decreased by four orders of magnitude once the dopant side chain crystalline was destroyed. The crystallizable side chain forced lamellar structure is expected to be a new chance for highly conducting polyaniline.

Synthesis, Structural Characterization, and Olefin Polymerization Behavior of Vanadium(III) Complexes Bearing Tridentate Schiff Base Ligands

Vanadium(III) complexes bearing tridentate salicylaldiminato ligands (2a-f) [OC6H4CH=NL]VCl2(THF) (L = CH2CH2OMe, 2a; CH2CH2NMe2, 2b; CH2C5H4N, 2c; 8-C9H6N (quinoline), 2d; 2-MeSC6H4, 2e; 2-Ph2PC6H4, 2f) and tridentate beta-enaminoketonato ligands [OC6H8CH=N-2-Ph2PC6H4]VCl2(THF) (2g) and [O(Ph)C=CHCH=N-2-Ph2PC6H4]VCl2(THF) (2h) were prepared from VCl3(THF)(3) by treating with 1.0 equiv of the deprotonated ligands in tetrahydrofuran (THF). These complexes were characterized by FTIR and mass spectrometry as well as elemental analysis. Structures of complexes 2e, 2f, and 2h were further confirmed by X-ray crystallographic analysis. These complexes were investigated as catalysts for olefin polymerization in the presence of organoaluminum compounds. On activation with Et2AlCl, complexes 2a-h exhibited high catalytic activities toward ethylene polymerization (up to 20.64 kg PE/mmol(v) center dot h center dot bar) even at high temperature, suggesting these catalysts possess high thermal stability.

A Novel Strategy to Branched Polyacrylonitrile Via One-Pot RAFT Copolymerization of Acrylonitrile and an Asymmetrical Divinyl Monomer

Branched polyacrylonitriles were prepared via the one-pot radical copolymerization of acrylonitirle and an asymmetric divinyl monomer (allyl methacrylate) that possesses both a higher reactive methacrylate and a lower reactive allyl. RAFT technique was used to keep a low-propagation chain concentration via a fast reversible chain transfer euilibration and thus the cross-linking was prevented until a high level of monomer conversions. This novel strategy was demonstrated to engenerate a branched architecture with abundant pendant functional vinyl and nitrile groups, and controlled molecular weight as a behavior of controlled/living radical polymerization characteristics. The effect of the various experimental parameters, including temperature, brancher to monomer molar ratio, and chain transfer agent to initiator molar ratio, on the control Of moleculer dimension (molecular weight and polydispersity indices) and the degree of branching were investigated in detail. Moreover, H-1 NMR and gel permeation chromatography confirm the branched architecture of the resultant polymer. The intrinsic viscosity of the copolymer is also lower than the linear counterpart.

Crystallization Behavior and Mechanical Properties of Crosslinked Plasticized Poly(L-lactic acid)

Enhancing the stability of plasticized poly(L-lactic acid) (PLLA) with poly (ethylene glycol) (PEG) is necessary for its practical application. In this study, plasticized PLLA (PLLA/PEG 80/20 wt/wt) was crosslinked under I-ray (Co-60) in the presence of triallyl isocyanurate (TALC) as crosslinking agent. FTIR analysis revealed that PLLA, PEG, and TALC formed a cocrosslinking structure. Crystallization behavior and mechanical properties of the crosslinked plasticized PLLA were investigated by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), scanning electron microscopy (SEM), and tensile tests. Experimental results indicated that the crystallization behaviors of both PEG and PLLA in the blends were restrained after irradiation. The melting peak of PEG in the crystallized samples disappeared at a low irradiation doses about 10 kGy. Although PLLA still owned the behavior of crystallize, its cold crystallization temperature and glass transition temperature shifted to higher temperature. Mechanical properties of the plasticized PLLA were strengthened through crosslinking. Both yield strength and elastic modulus of the samples increased after crosslinking.

Comparative study of paclitaxel physically encapsulated in and chemically conjugated with PEG-PLA

Paclitaxel-loaded poly(ethylene glycol)-b-poly(L-lactide (LA)) (PEG-PLA) micelles were prepared by two methods. One is physical encapsulation of paclitaxel in micelles composed of a PEG-PLA block copolymer and the other is based on a PEG-PLA-paclitaxel conjugate, abbreviated as "conjugate micelles" Their physicochemical characteristics, e.g. critical micelle concentration (CMC), morphology, and micelle size distribution were then evaluated by means of fluorescence spectroscopy, scanning electron microscopy (SEM), and dynamic light scattering (DLS). The results show that the CMC of PEG-PLA-paclitaxel and PEG-PLA are 6.31 x 10(4) and 1.78 x 10(-3) g L-1, respectively. Both micelles assume a spherical shape with comparable diameters and have unimodal size distribution. Moreover, in vitro drug delivery behavior was studied by high performance liquid chromatography (HPLC). The antitumor activity of the paclitaxel-loaded micelles against human liver cancer H7402 cells was evaluated by 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) method.

Prostate cancer cell-specific VEGF siRNA delivery system using cell targeting peptide conjugated polyplexes

A polymeric gene carrier was developed to deliver vascular endothelial growth factor (VEGF) small interfering RNA (siRNA) for prostate cancer cells in a target-specific manner. Prostate cancer-binding peptide (PCP) was conjugated with polyethylenimine (PEI) via a poly(ethylene glycol) (PEG) linker (PEI-PEG-PCP). The PEI-PEG-PCP conjugate could effectively condense siRNA to form stable polyelectrolyte complexes (polyplexes) with an average diameter of approximately 150 nm in an aqueous solution. VEGF siRNA/PEI-PEG-PCP polyplexes exhibited significantly higher VEGF inhibition efficiency than PCP-unmodified polycationic carriers (PEI-PEG or PEI) in human prostate carcinoma cells (PC-3 cells). The enhanced gene silencing activity of VEGF siRNA/PEI-PEG-PCP was maintained even under serum conditions, owing to the steric stabilization of the polyplexes with hydrophilic PEG grafts. Confocal microscopic studies revealed that the siRNA/PEI-PEG-PCP polyplexes were delivered into PC-3 cells in a PCP ligand-specific manner.

Synthesis, self-assembly in water, and cytotoxicity of MPEG-block-PLLA/DX conjugates

Docetaxel (DX) is one of the most effective antineoplastic drugs. Its current clinical administration is limited because of its hydrophobicity and Serious side effects. A polymer/DX conjugate is designed and successfully prepared to solve these problems. It is monomethoxy-poly(ethylene glycol)-block-poly(L-lactide)/DX (MPEG-PLLA/DX) It was synthesized by reacting DX with carboxyl-terminated copolymer MPEG-PLLA, which was prepared by reacting succinic anhydride with hydroxyl-terminated copolymer monomethoxy-poly(ethylene glycol)-block-poly (L-lactide) (MPEG-PLLA). Its structure and molecular weight was confirmed by H-1 NMR and GPC. The MPEG-PLLA/DX micelles in aqueous solution were prepared Using a SO]vent displacement method and characterized by dynamic light scattering for size and size distribution, and by transmission electron microscopy for surface morphology. Its antitumor activity against HeLa cancer cells evaluated by MTT assay showed that it had a similar antitumor activity to Pure D at the same drug content.

Biodegradable amphiphilic polymer-drug conjugate micelles

The coupling of drugs to macromolecular carriers received an important impetus from Ringsdorf's notion of polymer-drug conjugates. Several water-soluble polymers, poly(ethylene glycol), poly[N-(2-hydroxypropyl) methacrylamidel, poly(L-glutamic acid) and dextran, are studied intensively and have been utilized successfully in clinical research. The promising results arising from clinical trials with polymer-drug conjugates (e.g., paclitaxel, doxorubicin, camptothecins) have provided a firm foundation for other synthetic polymers, especially biodegradable polymers, used as drug delivery vehicles. This review discusses biodegradable polymeric micelles as an alternative drug-conjugate system. Particular focus is on A-B or B-A-B type biodegradable amphiphilic block copolymer such as polylactide, morpholine-2,5-dione derivatives and cyclic carbonates, which can form a core-shell micellar structure, with the hydrophobic drug-binding segment forming the hydrophobic core and the hydrophilic segment as a hydrated outer shell. Polymeric micelles can be designed to avoid uptake by cells of reticuloendothelial system and thus enhance their blood lifetime via the enhanced permeability and retention effect.