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High Thermal Stability (high + thermal_stability)
Selected AbstractsPreparation of Oriented Aluminum Nitride Thin Films on Polyimide Films and Piezoelectric Response with High Thermal Stability and FlexibilityADVANCED FUNCTIONAL MATERIALS, Issue 3 2007M. Akiyama Abstract c -Axis oriented aluminum nitride (AlN) thin films are successfully prepared on amorphous polyimide films by radiofrequency magnetron reactive sputtering at room temperature. Structural analysis shows that the AlN films have a wurtzite structure and consist of c -axis oriented columnar grains about 100,nm wide. The full width at half maximum of the X-ray diffraction rocking curves and piezoelectric coefficient d33 of the AlN films are 8.3° and 0.56,pC,N,1, respectively. The AlN films exhibit a piezoelectric response over a wide temperature range, from ,196 to 300,°C, and can measure pressure within a wide range, from pulse waves of hundreds of pascals to 40,MPa. Moreover, the sensitivity of the AlN films increases with the number of times it was folded, suggesting that we can control the sensitivity of the AlN films by changing the geometric form. These results were achieved by a combination of preparing the oriented AlN thin films on polyimide films, and sandwiching the AlN and polymer films between top and bottom electrodes, such as Pt/AlN/polyimide/Pt. They are thin (less than 10,,m), self powered, adaptable to complex contours, and available in a variety of configurations. Although AlN is a piezoelectric ceramic, the AlN films are flexible and excellent in mechanical shock resistance. [source] Highly Efficient Non-Doped Blue Organic Light-Emitting Diodes Based on Fluorene Derivatives with High Thermal Stability,ADVANCED FUNCTIONAL MATERIALS, Issue 10 2005L. Tao Abstract A new series of blue-light-emitting fluorene derivatives have been synthesized and characterized. The fluorene derivatives have high fluorescence yields, good thermal stability, and high glass-transition temperatures in the range 145,193,°C. Organic light-emitting diodes (OLEDs) fabricated using the fluorene derivatives as the host emitter show high efficiency (up to 5.3,cd,A,1 and 3.0,lm,W,1) and bright blue-light emission (Commission Internationale de L'Eclairage (CIE) coordinates of x,=,0.16, y,=,0.22). The performance of the non-doped fluorene-based devices is among the best fluorescent blue-light-emitting OLEDs. The good performance of the present blue OLEDs is considered to derive from: 1),appropriate energy levels of the fluorene derivatives for good carrier injection; 2),good carrier-transporting properties; and 3),high fluorescence efficiency of the fluorene derivatives. These merits are discussed in terms of the molecular structures. [source] Synthesis and properties of polyimides bearing acid groups on long pendant aliphatic chainsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 13 2006Tomohiro Yasuda Abstract A series of novel polyimide electrolytes having long pendant sulfo- or phosphoalkoxy groups were synthesized for fuel-cell applications. Sulfodecyloxy-, phosphodecyloxy-, and sulfophenoxydodecyloxy-substituted benzidine monomers were synthesized from dihydroxybenzidine. These monomers were copolymerized with naphthalene tetracarboxylic dianhydride and fluorenylidene dianiline to give the corresponding polyimides. A flexible, ductile, and self-standing membrane was obtained via casting from the polyimide solution. Because the acid groups were on long pendant side chains and away from the main chains, the polyimide membrane showed improved oxidative and hydrolytic stability in comparison with the polyimides with sulfonic acid groups on the main chains or on the short side chains. High thermal stability (no glass-transition temperature and a decomposition temperature > 200 °C) was also obtained. The polyimide membrane displayed high proton conductivity of 10,1 S cm,1 at 120 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3995,4005, 2006 [source] Substituent Effects on Crosslike Packing of 2,,7,-Diaryl- spiro(cyclopropane-1,9,-fluorene) Derivatives: Synthesis and Crystallographic, Optical, and Thermal Properties,ADVANCED FUNCTIONAL MATERIALS, Issue 2 2007Z. Wang Abstract A series of 2,,7,-diarylspiro(cyclopropane-1,9,-fluorene) derivatives are efficiently synthesized and characterized to determine the reason for the "green-light" emission of these compounds. These compounds exhibit bright-violet to blue photoluminescence (PL) (,PLmax,=,353,419,nm) with excellent PL quantum efficiencies (,PL,=,83,100,%) in solution and show high thermal stabilities (Td,=,267,474,°C). The variation of the optical properties of these molecules in the solid state depends on the different stacking modes of these compounds containing different substituents, which are revealed by crystallographic analysis. CH,, hydrogen bonds instead of intermolecular ,,, interactions act as the driving force between adjacent fluorenes, even though a very small dialkyl group (cyclopropane) is introduced at the C-9 position of fluorene. The crosslike molecular stacking efficiently reduces the energy transfer between the herring-like aggregates and therefore results in the absence of a "green-light" emission tail. In order to determine the cause of the "green-light" emission tails, the fluorescence spectra of the films annealed in N2 or in air are recorded. Broad green-light emission tails were observed for the films annealed in air, which might be caused by fluorenone defects generated during processing or during the course of the photophysical analysis by reaction with residual oxygen. [source] Synthesis of high-refractive index polyimide containing selenophene unitJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 17 2009Nam-Ho You Abstract A highly refractive and transparent aromatic polyimide (PI) containing a selenophene unit has been developed. The PI was prepared by a two-step polycondensation procedure from 2,5-bis(4-aminophenylenesulfanyl)selenophene (APSP) and 4,4,-[p -thiobis(phenylenesulfanyl)]diphthalic anhydride (3SDEA), and shows high thermal stabilities, such as a relatively high-glass transition temperature of 189 °C and 5% weight loss temperature (T5%) of 418 °C. The optical transmittance of the PI film at 450 nm is higher than 50%. The selenophene unit provides the PI with a refractive index of 1.7594, which is higher than corresponding PIs containing a thiophene or a phenyl unit because of the high polarizability per unit volume of the selenium atom. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4428,4434, 2009 [source] Cyclic Quaternary Ammonium Ionic Liquids with Perfluoroalkyltrifluoroborates: Synthesis, Characterization, and PropertiesCHEMISTRY - A EUROPEAN JOURNAL, Issue 8 2006Zhi-Bin Zhou Dr. Abstract New cyclic quaternary ammonium salts, composed of N -alkyl(alkyl ether)- N -methylpyrrolidinium, -oxazolidinium, -piperidinium, or -morpholinium cations (alkyl=nC4H9, alkyl ether=CH3OCH2, CH3OCH2CH2) and a perfluoroalkyltrifluoroborate anion ([RFBF3],, RF=CF3, C2F5, nC3F7, nC4F9), were synthesized and characterized. Most of these salts are liquids at room temperature. The key properties of these salts,phase transitions, thermal stability, density, viscosity, conductivity, and electrochemical windows,were measured and compared to those of their corresponding [BF4], and [(CF3SO2)2N], salts. The structural effect on all the above properties was intensively studied in terms of the identity of the cation and anion, variation of the side chain in the cation (i.e., alkyl versus alkyl ether), and change in the length of the perfluoroalkyl group (RF) in the [RFBF3], ion. The reduction of Li+ ions and reoxidation of Li metal took place in pure N -butyl- N -methylpyrrolidinium pentafluoroethyltrifluoroborate as the supporting electrolyte. Such comprehensive studies enhance the knowledge necessary to design and optimize ionic liquids for many applications, including electrolytes. Some of these new salts show desirable properties, including low melting points, high thermal stabilities, low viscosities, high conductivities, and wide electrochemical windows, and may thus be potential candidates for use as electrolytes in high-energy storage devices. In addition, many salts are ionic plastic crystals. [source] Benzo[b]phosphole-Containing ,-Electron Systems: Synthesis Based on an Intramolecular trans -Halophosphanylation and Some Insights into Their PropertiesCHEMISTRY - AN ASIAN JOURNAL, Issue 11 2009Aiko Fukazawa Dr. Abstract The intramolecular trans -halophosphanylation of 2-(aminophosphanyl)phenylacetylenes mediated by PBr3 followed by the oxidation with H2O2, produces 3-bromobenzo[b]phosphole oxide derivatives. This cyclization is also used for the synthesis of a 3-iodo derivative by conducting the reaction in the presence of LiI. Based on this synthetic method, various benzophosphole-containing ,-conjugated compounds, including a phosphoryl and methylene-bridged stilbene 10, 2,3,6,7-tetraphenylbenzo[1,2- b:4,5- b,]diphosphole- P,P, -dioxides 11, and their phosphine sulfide derivatives 12, are synthesized. The study of the structure,property relationships in a series of the bridged stilbenes, including a bis(methylene)-bridged stilbene 10, and a bis(phosphoryl)-bridged stilbene, reveals that as the contribution of the phosphoryl groups increased, the absorption and emission maxima substantially shift to longer wavelengths. The intrinsic substituent effects of the phosphoryl group in this skeleton are to decrease the oscillator strength of the electronic transition and thus decrease the radiative decay rate constants from the singlet excited state. Nevertheless, these compounds maintain high fluorescence quantum yields (,F>0.8) owing to the significantly retarded nonradiative decay process. In the study of the benzodiphosphole derivatives 11 and 12, their cyclic voltammetry revealed that both of the phosphoryl and phosphine sulfide derivatives have low reduction potentials (,1.7 to ,1.8,V vs ferrocene/ferrocenium couple) with the high reversibility of the redox waves. These compounds also showed high thermal stabilities with the high glass transition temperatures of 147,159,°C, indicative of their potential utilities as amorphous materials. [source] Thermal Investigation of Al2O3 Thin Films for Application in Cutting Operations,ADVANCED ENGINEERING MATERIALS, Issue 7 2009Kirsten Bobzin Crystalline PVD ,-Al2O3 coatings offer great potential for use in high-speed cutting operations. They offer specific high temperature features, like high hot hardness and high oxidation resistance. However, the reasons for the high thermal stability of this system are not clearly understood. In this paper, the phase and oxidation stability of thin ,-Al2O3 films (as illustrated in the micrograph) are investigated. [source] Layer-by-Layer All-Inorganic Quantum-Dot-Based LEDs: A Simple Procedure with Robust PerformanceADVANCED FUNCTIONAL MATERIALS, Issue 19 2010James S. Bendall Abstract A novel all-inorganic electroluminescent device is demonstrated based on highly luminescent CdTe nanocrystals intercalated within a laminar hydrotalcite-like structure. The laminar scaffold acts to both support and distribute the CdTe nanocrystals. The device is synthesized using simple wet chemical processes at room temperature in ambient conditions. It has high thermal stability, operating continuously up to 90 °C, and a maximum efficiency at J = 0.12 A cm,2. The device is targeted at the automotive industry. [source] Organic Electronics: High Tg Cyclic Olefin Copolymer Gate Dielectrics for N,N,-Ditridecyl Perylene Diimide Based Field-Effect Transistors: Improving Performance and Stability with Thermal Treatment (Adv. Funct.ADVANCED FUNCTIONAL MATERIALS, Issue 16 2010Mater. Abstract A novel application of ethylene-norbornene cyclic olefin copolymers (COC) as gate dielectric layers in organic field-effect transistors (OFETs) that require thermal annealing as a strategy for improving the OFET performance and stability is reported. The thermally-treated N,N, -ditridecyl perylene diimide (PTCDI-C13)-based n-type FETs using a COC/SiO2 gate dielectric show remarkably enhanced atmospheric performance and stability. The COC gate dielectric layer displays a hydrophobic surface (water contact angle = 95° ± 1°) and high thermal stability (glass transition temperature = 181 °C) without producing crosslinking. After thermal annealing, the crystallinity improves and the grain size of PTCDI-C13 domains grown on the COC/SiO2 gate dielectric increases significantly. The resulting n-type FETs exhibit high atmospheric field-effect mobilities, up to 0.90 cm2 V,1 s,1 in the 20 V saturation regime and long-term stability with respect to H2O/O2 degradation, hysteresis, or sweep-stress over 110 days. By integrating the n-type FETs with p-type pentacene-based FETs in a single device, high performance organic complementary inverters that exhibit high gain (exceeding 45 in ambient air) are realized. [source] High Tg Cyclic Olefin Copolymer Gate Dielectrics for N,N,-Ditridecyl Perylene Diimide Based Field-Effect Transistors: Improving Performance and Stability with Thermal TreatmentADVANCED FUNCTIONAL MATERIALS, Issue 16 2010Jaeyoung Jang Abstract A novel application of ethylene-norbornene cyclic olefin copolymers (COC) as gate dielectric layers in organic field-effect transistors (OFETs) that require thermal annealing as a strategy for improving the OFET performance and stability is reported. The thermally-treated N,N, -ditridecyl perylene diimide (PTCDI-C13)-based n-type FETs using a COC/SiO2 gate dielectric show remarkably enhanced atmospheric performance and stability. The COC gate dielectric layer displays a hydrophobic surface (water contact angle = 95° ± 1°) and high thermal stability (glass transition temperature = 181 °C) without producing crosslinking. After thermal annealing, the crystallinity improves and the grain size of PTCDI-C13 domains grown on the COC/SiO2 gate dielectric increases significantly. The resulting n-type FETs exhibit high atmospheric field-effect mobilities, up to 0.90 cm2 V,1 s,1 in the 20 V saturation regime and long-term stability with respect to H2O/O2 degradation, hysteresis, or sweep-stress over 110 days. By integrating the n-type FETs with p-type pentacene-based FETs in a single device, high performance organic complementary inverters that exhibit high gain (exceeding 45 in ambient air) are realized. [source] Probing the role of oligomerization in the high thermal stability of Pyrococcus furiosus ornithine carbamoyltransferase by site-specific mutantsFEBS JOURNAL, Issue 14 2001Bernard Clantin The Pyrococcus furiosus ornithine carbamoyltransferase (OTCase) is extremely heat stable and maintains 50% of its catalytic activity after 60 min at 100 °C. The enzyme has an unusual quaternary structure when compared to anabolic OTCases from mesophilic organisms. It is built up of four trimers arranged in a tetrahedral manner, while other anabolic enzymes are single trimers. Residues Trp21, Glu25, Met29 and Trp33 are located in the main interfaces that occur between the catalytic trimers within the dodecamer. They participate in either hydrophobic clusters or ionic interactions. In order to elucidate the role played by the oligomerization in the enzyme stability at very high temperatures, we performed mutagenesis studies of these residues. All the variants show similar catalytic activities and kinetic properties when compared to the wild-type enzyme, allowing the interpretation of the mutations solely on heat stability and quaternary structure. The W21A variant has only a slight decrease in its stability, and is a dodecamer. The variants E25Q, M29A, W33A, W21A/W33A and E25Q/W33A show that altering more drastically the interfaces results in a proportional decrease in heat stability, correlated with a gradual dissociation of dodecamers into trimers. Finally, the E25Q/M29A/W33A variant shows a very large decrease in heat stability and is a trimer. These results suggest that extreme thermal stabilization of this OTCase is achieved in part through oligomerization. [source] New Stack Design of Micro-tubular SOFCs for Portable Power SourcesFUEL CELLS, Issue 6 2008T. Suzuki Abstract Micro-tubular solid oxide fuel cells (SOFCs) have high thermal stability and higher volumetric power density, which are considered to be ideal features for portable power sources and auxiliary power units for automobile. Here, we report a new stack design using anode supported micro-tubular SOFCs with 2,mm diameter using Gd doped CeO2 (GDC) electrolyte, NiO-GDC anode and (La, Sr)(Co, Fe)O3 (LSCF)-GDC cathode. The new stack consists of three bundles with five tubular cells, sealing layers and interconnects and fuel manifolds. The performance of the stack whose volume is 1,cm3 was shown to be 2.8,V OCV and maximum power output of 1.5,W at 500,°C, applying air only by natural convection. The results also showed strong dependence of the fuel flow rates on the stack performance, which was correlated to the gas diffusion limitation. [source] Synthesis and Characterization of Red-Emitting Iridium(III) Complexes for Solution-Processable Phosphorescent Organic Light-Emitting DiodesADVANCED FUNCTIONAL MATERIALS, Issue 14 2009Seung-Joon Lee Abstract A new series of highly efficient red-emitting phosphorescent Ir(III) complexes, (Et-CVz-PhQ)2Ir(pic-N-O), (Et-CVz-PhQ)2Ir(pic), (Et-CVz-PhQ)2Ir(acac), (EO-CVz-PhQ)2Ir(pic-N-O), (EO-CVz-PhQ)2Ir(pic), and (EO-CVz-PhQ)2Ir(acac), based on carbazole (CVz)-phenylquinoline (PhQ) main ligands and picolinic acid N-oxide (pic-N-O), picolinic acid (pic), and acetylacetone (acac) ancillary ligands, are synthesized for phosphorescent organic light-emitting diodes (PhOLEDs), and their photophysical, electrochemical, and electroluminescent (EL) properties are investigated. All of the Ir(III) complexes have high thermal stability and emit an intense red light with an excellent color purity at CIE coordinates of (0.65,0.34). Remarkably, high-performance solution-processable PhOLEDs were fabricated using Ir(III) complexes with a pic-N-O ancillary ligand with a maximum external quantum efficiency (5.53%) and luminance efficiency (8.89,cd,A,1). The novel use of pic-N-O ancillary ligand in the synthesis of phosphorescent materials is reported. The performance of PhOLEDs using these Ir(III) complexes correlates well with the results of density functional theory calculations. [source] Ordered Mesoporous In2O3: Synthesis by Structure Replication and Application as a Methane Gas SensorADVANCED FUNCTIONAL MATERIALS, Issue 4 2009Thomas Waitz Abstract The synthesis and characterization of ordered mesoporous In2O3 materials by structure replication from hexagonal mesoporous SBA-15 silica and cubic KIT-6 silica is presented. Variation of the synthesis parameters allows for different pore sizes and pore wall thicknesses in the products. The In2O3 samples turn out to be stable up to temperatures between 450,°C and 650,°C; such high thermal stability is necessary for their application as gas sensors. Test measurements show a high sensitivity to methane gas in concentrations relevant for explosion prevention. The sensitivity is shown to be correlated not only with the surface-to-volume ratio, but also with the nanoscopic structural properties of the materials. [source] Multifunctional Microporous MOFs Exhibiting Gas/Hydrocarbon Adsorption Selectivity, Separation Capability and Three-Dimensional Magnetic Ordering,ADVANCED FUNCTIONAL MATERIALS, Issue 15 2008Kunhao Li Abstract Microporous materials [M3(HCOO)6],·,DMF (M,=,Mn, Co, Ni) were synthesized solvothermally and structurally characterized by single crystal and powder X-ray diffraction methods. The metal network exhibits diamondoid connectivity and the overall framework gives rise to zigzag channels along the b axis where guest dimethylformamide molecules reside. The effective pore size of these channels is ,5,6,Å. The materials feature high thermal stability and permanent porosity with relatively small pore diameters which are attributed to the extensive strong dative bonding between the metal centers and formate molecules. The title compounds exhibit interesting multi-fold gas adsorption and magnetic properties. The adsorption study of a series of alcohols, aromatics, and linear hydrocarbons revealed strong control of the adsorbent channel structures on their adsorption capacity and selectivity. The study also indicated possibility of using these materials for separation of close boiling chemicals (e.g., ethylbenzene and p-xylene) via pressure swing adsorption (PSA) process and molecules with different diffusion parameters via kinetic-based process. Three-dimensional spontaneous magnetic ordering was found in all three network structures investigated and at ground states they behave somewhat like soft magnets. [source] Rational Design of Chelating Phosphine Functionalized Os(II) Emitters and Fabrication of Orange Polymer Light-Emitting Diodes Using Solution Process,ADVANCED FUNCTIONAL MATERIALS, Issue 2 2008M. Cheng Abstract A new series of charge neutral Os(II) pyridyl azolate complexes with either bis(diphenylphosphino)methane (dppm) or cis -1,2-bis(diphenylphosphino)ethene (dppee) chelates were synthesized, and their structural, electrochemical, photophysical properties and thermodynamic relationship were established. For the dppm derivatives 3a and 4a, the pyridyl azolate chromophores adopt an eclipse orientation with both azolate segments aligned trans to each other, and with the pyridyl groups resided the sites that are opposite to the phosphorus atoms. In sharp contrast, the reactions with dppee ligand gave rise to the formation of two structural isomers for all three kind of azole chromophores, with both azolate or neutral heterocycles (i.e., pyridyl or isoquinolinyl fragments) located at the mutual trans -disposition around the Os metal (denoted as series of a and b complexes). These chelating phosphines Os(II) complexes show remarkably high thermal stability, among which and several exhibit nearly unitary phosphorescence yield in deaerated solution at RT. A polymer light-emitting device (PLED) prepared using 0.4 mol % of 5a as dopant in a blend of poly(vinylcarbazole) (PVK) and 30 wt % of 2- tert -butylphenyl-5-biphenyl-1,3,4-oxadiazole (PBD) exhibits yellow emission with brightness of 7208 cd m,2, an external quantum efficiency of 10.4 % and luminous efficiency of 36.1 cd A,1 at current density of 20 mA cm,2. Upon changing to 1.6 mol % of 6a, the result showed even better brightness of 9212 cd m,2, external quantum efficiency of 12.5 % and luminous efficiency of 46.1 cd A,1 at 20 mA cm,2, while the max. external quantum efficiency of both devices reaches as high as 11.7 % and 13.3 %, respectively. The high PL quantum efficiency, non-ionic nature, and short radiative lifetime are believed to be the determining factors for this unprecedented achievement. [source] Tris(4-cyanophenyl)amine: Simple Synthesis via Self-assembly; Strong Fluorescence in Solution, Nano/microcrystals, and Solid,ADVANCED FUNCTIONAL MATERIALS, Issue 13 2007A. Patra Abstract The threefold symmetric molecule, tris(4-cyanophenyl)amine (TCPA) is synthesized from 4-fluorocyanobenzene by treatment with potassium carbonate in dimethylsulfoxide; the occurrence of the reaction without any amine reagent suggests the involvement of a novel self-assembly process. A reprecipitation strategy provides stable colloids containing highly monodisperse nano/microcrystals with well-defined cubic morphology and sizes tunable from 250 to 500,nm. The solution, colloid, and solid states of TCPA exhibit strong blue fluorescence; the colloid shows dual emission with an unusually small Stokes shift. Computational investigations are carried out on the molecule and supramolecular assemblies derived from the crystal structure. Coupled with detailed spectroscopic studies, they show that the emission in the colloidal and solid states can be attributed to energy levels resulting from the intermolecular interactions within different aggregation motifs in the condensed phase and energy cascades between them. The computations also reveal the presence of cooperative interactions in the molecular crystal contributing to its high thermal stability. The strong light emission exhibited by TCPA, concurrently in the solution, nano/microcrystal, and solid states establishes it as a novel molecular material of potential practical utility; it has led to the exploration of the underlying mechanism that describes the phenomena observed in the different physical states. [source] New Organic Nonlinear Optical Polyene Crystals and Their Unusual Phase Transitions,ADVANCED FUNCTIONAL MATERIALS, Issue 11 2007O-P. Kwon Abstract A series of new nonlinear optical chromophores based on configurationally locked polyenes (CLPs) with chiral pyrrolidine donors are synthesized. All CLP derivatives exhibit high thermal stability with decomposition temperatures Td at least > ,270,°C. Acentric single crystals of enantiopure D - and L -prolinol-based chromophores with a monoclinic space group P21 exhibit a macroscopic second-order nonlinearity that is twice as large than that of analogous dimethylamino-based crystal. This is attributed to a strong hydrogen-bonded polar polymer-like chain built by these molecules, which is aligned along the polar crystallographic b -axis. Five ,-phase CLP crystals with different donors grown from solution exhibit a reversible or irreversible thermally induced structural phase transition to a ,-phase. These phase transitions are unusual, changing the crystal symmetry from higher to lower at increasing temperatures, for example, from centrosymmetric to non-centrosymmetric, enhancing their macroscopic second-order nonlinear optical properties. [source] Stability of Hoogsteen -Type Triplexes , Electrostatic Attraction between Duplex Backbone and Triplex-Forming Oligonucleotide (TFO) Using an Intercalating ConjugateHELVETICA CHIMICA ACTA, Issue 5 2008Daniel Globisch Abstract Syntheses are described for two novel twisted intercalating nucleic acid (TINA) monomers where the intercalator comprises a benzene ring linked to a naphthalimide moiety via an ethynediyl bridge. The intercalators Y and Z have a 2-(dimethylamino)ethyl and a methyl residue on the naphthalimide moiety, respectively. When used as triplex-forming oligonucleotides (TFOs), the novel naphthalimide TINAs show extraordinary high thermal stability in Hoogsteen -type triplexes and duplexes with high discrimination of mismatch strands. DNA Strands containing the intercalator Y show higher thermal triplex stability than DNA strands containing the intercalator Z. This observation can be explained by the ionic interaction of the protonated dimethylamino group under physiological conditions, targeting the negatively charged phosphate backbone of the duplex. This interaction leads to an extra binding mode between the TFO and the duplex, in agreement with molecular-modeling studies. We believe that this is the first example of an intercalator linking the TFO to the phosphate backbone of the duplex by an ionic interaction, which is a promising tool to achieve a higher triplex stability. [source] Homogeneously Dispersed Ceria Nanocatalyst Stabilized with Ordered Mesoporous AluminaADVANCED MATERIALS, Issue 13 2010Quan Yuan Homogeneously dispersed ceria nanocatalyst can be synthesized and stabilized with ordered mesoporous alumina by a one-step sol,gel method. This novel material possesses high thermal stability and exhibits 100% conversion at room temperature for CO oxidation when loaded with Au. This established approach can be expanded to the controlled synthesis and stabilization of other nanocatalysts with wide applications. [source] New Host Containing Bipolar Carrier Transport Moiety for High-Efficiency Electrophosphorescence at Low VoltagesADVANCED MATERIALS, Issue 6 2009Zhi Qiang Gao A new host material for use in phosphorescent OLEDs with desirable electronic properties has been synthesized. The material exhibits superior carrier-transport properties, a narrow optical band gap, relatively high triplet energy, and high thermal stability. It is synthesized by integrating hole-transporting carbazole groups into an electron-transporting phenanthroline core (see figure), and is demonstrated to be an excellent host for phosphorescent dopant emitters. [source] Mixed Isobutylphobane/N-Heterocyclic Carbene Ruthenium- Indenylidene Complexes: Synthesis and Catalytic Evaluation in Olefin Metathesis ReactionsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-12 2010Xavier Sauvage Abstract Two new second generation ruthenium(II) dichloride-indenylidene complexes [RuCl2(9-isobutylphosphabicyclo[3.3.1]nonane)(NHC)(3-phenyl-1-indenylidene)], where NHC=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) or its unsaturated imidazol-2-ylidene analogue (IMes), were isolated in high yields upon heating a tetrahydrofuran (THF) solution of the diphosphane complex [RuCl2(isobutylphobane)2(3-phenyl-1-indenylidene)] with a two-fold excess of the corresponding imidazol(in)ium-2-carboxylate zwitterions. Both products were characterized by 1H, 13C, and 31P,NMR spectroscopy, and the molecular structure of [RuCl2(isobutylphobane)(SIMes)(3-phenyl-1-indenylidene)] was determined by X-ray diffraction analysis. A close inspection of the packing structure revealed the presence of different types of intra- and intermolecular interactions that enhanced the global stability of the crystals, while low temperature NMR experiments showed the existence of two distinct rotational isomers due to the unsymmetrical nature of the phobane ligand. The catalytic activity of both compounds was assessed in olefin metathesis using benchmark ring-opening metathesis polymerization, ring-closing metathesis (RCM), and cross-metathesis reactions, and compared with those of related first and second generation ruthenium-benzylidene and indenylidene catalyst precursors. Kinetic studies confirmed the high thermal stability of the mixed isobutylphobane/N-heterocyclic carbene complexes, which suffered from a slow initiation efficiency compared to other catalytic systems based on the tricyclohexylphosphane ligand. However, the remarkable robustness of [RuCl2(isobutylphobane)(SIMes)(3-phenyl-1-indenylidene)] was beneficial for performing the RCM of diethyl 2,2-bis(2-methylallyl)malonate. Monitoring the formation of the ruthenium-methylidene active species [RuCl2(isobutylphobane)(SIMes)(CH2)] derived from this precursor further demonstrated its ability to sustain long reaction times and high temperatures required to carry out the RCM of tetrasubstituted olefins. [source] Study on macromolecular lanthanide complexes (V): Synthesis, characterization, and fluorescence properties of lanthanide complexes with the copolymers of styrene and acrylic acidJOURNAL OF APPLIED POLYMER SCIENCE, Issue 2 2009Xing Liang Abstract In this study, the luminescent macromolecular lanthanide complexes Ln-PSt/AA (Ln = Eu and Tb; St = styrene; AA = acrylic acid) have been synthesized, and an extensive characterization has been carried out by means of elemental analysis, FTIR, thermal analysis, and fluorescence determination. The results showed that the carboxylic groups on the chain of the polymers acted as bidentate ligands coordinated to lanthanide ions; and the coordination degree of COO,/Ln3+ in the macromolecular complexes was closely dependent on both the pH value of the solution and the molar ratio of St to AA in the polymeric ligands. Thermal analysis manifested that these Ln-PSt/AA (Ln = Eu and Tb) complexes had high thermal stability and solvent resistance, and these macromolecular complexes were highly crosslinked. The fluorescence determination indicated that Ln-PSt/AA complexes could emit characteristic fluorescence with comparatively high brightness and good monochromaticity, and the fluorescence intensity changed with increasing lanthanide ions content. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Effect of the different rigidity of the chiral crosslinker on phase behaviors of side-chain chiral liquid crystalline elastomersJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2008Bao-Yan Zhang Abstract In the present work, the phase behaviors of two series of side-chain liquid crystalline elastomers (PI and PII series) derived from the same nematic liquid crystalline monomer and the different rigidity of chiral bisolefinic crosslinking units have been compared and studied extensively, and the effect of the different rigidity of crosslinker on the phase behavior of elastomers has been discussed. The chemical structure of the monomers and polymers obtained were confirmed by FTIR and 1H NMR spectroscopy. The phase behaviors were investigated by differential scanning calorimetry, polarizing optical microscopy measurement, thermogravimetric analyses, and X-ray diffraction measurement. The two series of elastomers showed smectic or cholesteric phases. When the amount of different crosslinking units was less than 15 mol %, both of the elastomers displayed elasticity, reversible phase transition with wide mesophase temperature ranges, and high thermal stability. It is shown that the isotropization temperature values of PII series are higher than those of PI series, and the glass transition temperature values of PII series varied smoothly and that of PI series changed smoothly first and then abruptly with increasing the contents of crosslinkers with different rigidity. In addition, PI series showed an interesting change in LC texture near clearing point, but PII series did not. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Synthesis and characterization of novel poly(arylene ether)s based on 9,10-bis-(4-fluoro-3-trifluoromethylphenyl) anthracene and 2,7-bis-(4-fluoro-3-trifluoromethylphenyl) fluoreneJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2007Arun K. Salunke Abstract Two new bisfluoro monomers 9,10-bis-(4-fluoro-3-trifluoromethylphenyl) anthracene and 2,7-bis-(4-fluoro-3-trifluoromethylphenyl) fluorene have been synthesized by the cross-coupling reaction of 2-fluoro-3-trifluoromethyl phenyl boronic acid with 9,10-dibromo anthracene and 2,7-dibromo fluorine, respectively. These two bisfluoro compounds were used to prepare several poly(arylene ether)s by aromatic nucleophilic displacement of fluorine with various bisphenols; such as bisphenol-A, bisphenol-6F, bishydroxy biphenyl, and 9,9-bis-(4-hydroxyphenyl)-fluorene. The products obtained by displacement of the fluorine atoms exhibits weight-average molar masses up to 1.5 ×105 g mol,1 and number average molecular weight up to 6.8 × 104 g mol,1 in GPC. These poly(arylene ether)s show very high thermal stability even up to 490°C for 5% weight loss occurring at this temperature in TGA in synthetic air and showed glass transition temperature observed up to 310°C. All the polymers are soluble in a wide range of organic solvents, e.g., CHCl3, THF, NMP, and DMF. Films cast from DMF solution are brittle in nature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007 [source] Experimental and theoretical investigation of a new rapid switching near-infrared electrochromic conjugated polymerJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 18 2010Han-Yu Wu Abstract A new rapid switching near-IR electrochromic conjugated propeller-shape polymer (PBTPAFL) with lower oxidation potential containing a di-triarylamine group was synthesized via Suzuki coupling approach. The observed UV-vis-NIR absorption changes in the PBTPAFL film at various potentials are fully reversible and associated with strong color changes from the original light green to dark green and then to a Prussian blue. Excellent continuous cyclic stability of the electrochromic characteristics with a rapid color switching time 2.58 s and bleaching time 1.76 s was found as well. Compared with P1 and P2, the introduction of more electron-donating propyl phenyl group in the para position of PBTPAFL lowered the oxidative potential and prevented coupling reaction during the electrochromic procedure. The high molecular weight conjugated polymer having high thermal stability with Td10 more than 450 °C has excellent solubility in common organic solvents such as NMP, THF, chloroform, toluene, xylene, and benzene at room temperature (25 °C) due to the propeller-shape structure and long alkyl chain on fluorene. Herein, from the combination of the experimental and computational study, we proposed a mechanism on the basis of the molecular orbital theory to explain the electrochromic oxidation behavior. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3913,3923, 2010. [source] Synthesis of networked polymers with lithium counter cations from a difunctional epoxide containing poly(ethylene glycol) and an epoxide monomer carrying a lithium sulfonate salt moietyJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 14 2010Kozo Matsumoto Abstract Poly(ethylene glycol)-based networked polymers that had lithium sulfonate salt structures on the network were prepared by heating a mixture of poly(ethylene glycol) diglycidyl ether (PEGGE), poly(ethylene glycol) bis(3-aminopropyl) terminated (PEGBA), and an ionic epoxy monomer, lithium 3-glycidyloxypropanesulfonate (LiGPS). Flexible self-standing networked polymer films showed high thermal stability, low crystallinity, low glass transition temperature, and good mechanical strength. The materials were ion conductive at room temperature even under a dry condition, although the ionic conductivity was rather low (10,6 to 10,5 S/m). The ionic conductivity increased with the increase in temperature to above 1 × 10,4 S/m at 90 °C. The film samples became swollen by immersing in propylene carbonate (PC) or PC solution of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The samples swollen in PC showed higher ionic conductivity (ca.1 × 10,3 S/m at room temperature), and the samples swollen in LiTFSI/PC showed much higher ionic conductivity (nearly 1 S/m at room temperature). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3113,3118, 2010 [source] Development and application of novel ring-opening polymerizations to functional networked polymersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 19 2009Takeshi Endo Abstract This Highlight gives an overview of the recent progress in development of new ring-opening polymerizations (ROPs) and their applications to functional networked polymers in our group. The described ROPs involve thermally induced polymerization of 1,3-benzoxazine, anionic alternating copolymerizations of epoxides and lactones, and those exhibiting equilibrium nature. These ROPs were successfully applied to the syntheses of the relevant networked polymers, leading to their distinctive features such as high thermal stability, small volume shrinkage, and selective decrosslinking ability, which enabled design and development of next generation materials. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4847,4858, 2009 [source] Synthesis and characterization of fluorene-based copolymers containing siloxane or distilbene moieties on their main chainJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 6 2009Hoon-Je Cho Abstract Two novel types of polyfluorene copolymers containing siloxane linkages or distilbene moieties on their main-chains were synthesized by Ni(0)-mediated Yamamoto coupling polymerization. These polymers, designated P2Silo05, P2Silo15, PF-P02, and PF-P05 were prepared by copolymerization between 2,7-dibromo-9,9,-dihexylfluorene and bis(bromobenzene)-terminated disiloxane monomer (for P2Silo05 and P2Silo15) or dibromodistilbene monomer (for PF-P02 and PF-P05). All of the polymers were highly soluble in common organic solvents such as chloroform, toluene, and p -xylene. The glass transition temperatures of the polymers were between 92 and 113 °C, and the decomposition temperatures for a 5% weight loss (Td) were above 420 °C for all of the polymers, demonstrating high thermal stability. The molecular weight (Mw) of the polymers ranged from 4.2 × 104 to 8.8 × 104. The blue shift of the maximum in the UV-visible absorption was greater in polymers with a higher molar percentage of siloxane linkages or distilbene moieties than in homo poly (dihexylfluorene) (PDHF). However, the photoluminescence spectra of the polymers were similar to those of PDHF in terms of the onsets and patterns. Single-layer light-emitting diodes were fabricated with a configuration of ITO/PEDOT:PSS/polymers/Ca/Al. The maximum electroluminescence emission wavelengths of the polymers were 425,450 nm, corresponding to pure blue light. The CIE co-ordinates of the polyfluorenes containing siloxane linkages or distilbene moieties ranged from (0.21, 0.21) to (0.17, 0.10), indicating deeper blue light than that of PDHF {CIE co-ordinates of (0.25, 0.29)}, with P2Silo15 giving the deepest blue-light {CIE co-ordinates of (0.17, 0.10)}. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1595,1608, 2009 [source] | ||||||||||||||||||||||||||||