Cross-linkable aromatic amines as materials for insoluble hole-transporting layers in light-emitting devices

A series of cross-linkable aromatic amines has been synthesized by the multi-step synthetic rout. Full characterization of their structure by H-1 NMR-, IR- and mass spectrometry is presented. The synthesized materials were examined by various techniques including differential scanning calorimetry, thermogravimetry, UV and electron photoemission spectrometry.

Pyrazine-containing Acene-Type Molecular Ribbons with up to 16 Rectilinearly Arranged Fused Aromatic Rings

A series of acene-type conjugated molecules(1-5) containing 2-6 pyrazine units and up to 16 rectilinearly arranged fused aromatic rings were synthesized by condensation coupling of 1,2-diamines and 1,2-diketones. The energy gap of the molecules estimated from absorption edge decreases with an increase in molecular length, indicating the well-delocalized nature of the molecules. The cyclic voltarnmetry measurements suggest that the n-type properties of these ribbonlike pyrazine derivatives are dependent on the molecular length and the number of the pyrazine units.

Determination of Cd2+ and Pb2+ on glassy carbon electrode modified by electrochemical reduction of aromatic diazonium salts

Carbon modified by the reduction of aromatic diazonium derivatives was first used as electrode for the electrochemical stripping analysis of heavy metals. As a model, the glassy carbon electrode was modified with benzoic acid by electrochemical reduction of diazobenzoic acid, and the resulting modified electrodes were used for determination of Cd2+ and Pb2+. The anodic peak currents of cadmium and lead at the benzoic acid-modified glassy carbon electrode are 7.2 and 6 times of that at the bare glassy carbon electrode. A linear response was observed for Pb2+ and Cd2+ in the range of 0.5-50 mu g/l.

A method for quantitative analysis of nitrogen oxides and N2 by means of mass spectrometry with the assistance of a catalytic technique for the reduction of NO with CO or hydrocarbons

Mass spectrometry is not able to differentiate NOx and N2 from other interferences (e.g. CO and C2H4) in the deNOx reactions. In the present study, a quantitative method for analysis of NOx and N2 simultaneously in these reactions with an assisted converter operated at higher temperature under O2-rich condition, which eliminates the interferences, is developed. The NOx conversion from this method is comparable to the one from an Automotive Emission Analyser equipped with NOx electrochemical sensor. Two types of deNOx reactions are tested in terms of selectivity of N2 production. The application of this method is discussed.

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.

Synthesis of Aromatic Oxide-Oxadiazoles Containing Pyridine Ring and Study on Their Spectral Properties

In order to explore new highly organic electroluminescent materials, six symmetrical aromatic oxide-oxadiazoles containing pyridine ring 4a similar to 4f were synthesized through cyclization of substituted benzoic acid (2) with 2,6-dihydrazide pyridine (3) by "one-pot" method in POCl3. Their structures were confirmed by MS, IR, H-1 NMR techniques and elemental analysis. The fluorescence spectra of the target compounds showed that the A,m ranged from 347 to 507 nm, and the maximum A,m were close to 384 nm, which showed that these compounds have good fluorescence with strong fluorescence intensity. When the 5-Br group was introduced into the aromatic ring (4e and 4f), the fluorescent emission wavelength took place Einstein shift, and the fluorescent intensity decreased a little. Using quinine bisulphate as a reference, the fluorescence quantum yields were all tested, and the introduction of 5-Br group had no visible effect on fluorescence quantum yield.

Effects of polymerization conditions on hydrophilic groups in aromatic polyamide thin films

For polyamide used in reverse osmosis (RO) membranes, the content of pendant acid groups is critical to its performance. In this work, FTIR was used to analyze the acid contents in the polyamide films prepared via interfacial polymerization of trimesic acid trichloride (TMC) in hexane and 1,3-phenylenediamine (MPDA) in water, and the effects of reaction conditions, including monomer concentrations, time, and temperature, were studied. It was found that more pendant acid groups are present in the polyramide film at higher TMC concentrations or lower MPDA concentrations, and longer reaction times and lower temperatures also favor the formation of the free acids. These results can be explained by the monomer diffusion in the interfacial polymerization process. This work may help the design and fabrication of RO membranes with different hydrophilicity and target performance.

Rare-earth metal complexes stabilized by amino-phosphine ligand. Reaction with mesityl azide and catalysis of the cycloaddition of organic azides and aromatic alkynes

Stoichiometric reactions between mesityl azide (MesN(3), Mes = 2,4,6-C6H2Me3) and amino-phosphine ligated rare-earth metal alkyl, LLn(CH2SiMe3) (2)(THF) (L = (2,6-C6H3Me2)NCH2C6H4P(C6H5)(2); Ln = Lu (1a), Sc (1b)), amide, LLu(NH(2,6-(C6H3Pr2)-Pr-i))(2)(THF) (2) and acetylide at room temperature gave the amino-phosphazide ligated rare-earth metal bis(triazenyl) complexes, [L(MesN(3))]Ln[(MesN(3))-(CH2SiMe3)](2) (Ln = Lu (3a); Sc (3b)), bis(amido) complex [L(MesN3)] Lu[NH(2,6-C6H3 Pr-i(2))](2) (4), and bis(alkynyl) complex (5) (L(MesN(3))Lu (C CPh)(2))(2), respectively. The triazenyl group in 3 coordinates to the metal ion in a rare eta(2)-mode via N-beta and N-gamma atoms, generating a triangular metallocycle. The amino-phosphazide ligand, L(MesN(3)), in 3, 4 and 5 chelates to the metal ion in a eta(3)-mode via N-alpha and N-gamma atoms. In the presence of excess phenylacetylene, complex 3a isomerized to 3', where the triazenyl group coordinates to the metal ion in a eta(3) mode via Na and Ng atoms.

Tris(2,2 '-bipyridyl)ruthenium(II) electrochemiluminescent detection of coreactants containing aromatic diol group by the interaction between diol and borate anion

Previous studies show that aromatic diols inhibited Ru(bpy)(3)(2+) electrochemiluminescence (ECL), and all reported Ru(bpy)(3)(2+) ECL methods for the determination of aromatic diols-containing coreactants are based on inhibition of Ru(bpy)(3)(2+)/tripropylamine ECL. In this study, the interaction between diol and borate anion was exploited for Ru(bpy)(3)(2+) ECL detection of coreactants containing aromatic diol group using epinephrine as a model analyte. The interaction prevented from the inhibition of Ru(bpy)(3)(2+) ECL by aromatic diol group of epinephrine. As a result, epinephrine was successfully detected in the absence of tripropylamine simply by using borate buffer solution as the supporting electrolyte. Under the optimum conditions, the log of the ECL intensity increases linearly with the log of epinephrine concentrations over the concentration range of 1.0x10(-9)-1.0x10(-4) M. The detection limit is 5.0x10(-10) M at a signal-to-noise ratio of three. The proposed method exhibit wider dynamic range and better detection limit than that by inhibited Ru(bpy)(3)(2+) ECL method. The relative standard deviation for 14 consecutive determinations of 5 mu M epinephrine was 3.5%. The strategy by interaction with borate anion or boronate derivatives is promising for the determination of coreactants containing aromatic diol group or aromatic hydroxyl acid group. Such interaction can also be used to avoid interference from aromatic diols or aromatic hydroxyl acids.

Synthesis and properties of novel organosoluble polyimides derived from 1,4-bis[4-(3,4-dicarboxylphenoxy)]triptycene dianhydride and various aromatic diamines

A novel triptycene-based dianhydride, 1,4-bis[4-(3,4-dicarboxylphenoxy)]triptycene dianhydride, was prepared from 4-nitro-N-methylphthalimide and potassium phenolate of 1,4-dihydroxytriptycene (1). The aromatic nucleophilic substitution reaction between 4-nitro-N-methylphthalimide and I afforded triptycene-based bis(N-methylphthalimide) (2), which hydrolyzed and subsequently dehydrated to give the corresponding dianhydride (3). A series of new polyimides containing triptycene moieties were prepared from the dianhydride monomer (3) and various diamines in in-cresol via conventional one-step polycondensation method. Most of the resulting polyimides were soluble in common organic solvents, such as chloroform, THF, DMAc and DMSO. The polyimides exhibited excellent thermal and thermo-oxidative stabilities with the onset decomposition temperature and 10% weight loss temperature ranging from 448 to 486 degrees C and 526 to 565 degrees C in nitrogen atmosphere, respectively. The glass transition temperatures of the polyimides were in the range of 221-296 degrees C. The polyimide films were found to be transparent, flexible, and tough. The films had tensile strengths, elongations at break, and tensile moduli in the ranges 95-118 MPa, 5.3-16.2%, and 1.03-1.38 GPa, respectively. Wide-angle X-ray diffraction measurements revealed that these polyimides were amorphous.

Nature of the ring-banded spherulites in blends of aromatic poly(ether ketone)s

The ring-banded spherulites in liquid crystalline poly(aryl ether ketone) (LC-PAEK) and poly(aryl ether ether ketone) (PEEK) blends with a higher content (>50%) of LC-PAEK are investigated by polarizing light microscopy (PLM) and atomic force microscopy (AFM) techniques. The results indicate that the light core and rings of the ring-banded spherulites under PLM are mainly composed of an LC-PAEK phase, while the dark rings consist of coexisting phases of PEEK and a small amount of LC-PAEK. The formation of the ring-banded spherulites is attributable to structural discontinuity caused by a rhythmic radial growth.

Structural selectivity of aromatic diamidines

Competition dialysis was used to study the interactions of 13 substituted aromatic diamidine compounds with 13 nucleic acid structures and sequences. The results show a striking selectivity of these compounds for the triplex structure poly dA:(poly dT)(2), a novel aspect of their interaction with nucleic acids not previously described. The triplex selectivity of selected compounds was confirmed by thermal denaturation studies. Triplex selectivity was found to be modulated by the location of amidine substiuents on the core phenyl-furan-phenyl ring scaffold. Molecular models were constructed to rationalize the triplex selectivity of DB359, the most selective compound in the series. Its triplex selectivity was found to arise from optimal ring stacking on base triplets, along with proper positioning of its amidine substituents to occupy the minor and the major-minor grooves of the triplex. New insights into the molecular recognition of nucleic acid structures emerged from these studies, adding to the list of available design principles for selectively targeting DNA and RNA.

The direct synthesis of wholly aromatic poly(p-phenylene)s bearing sulfobenzoyl side groups as proton exchange membranes

Sulfonated poly(p-phenylene)s (SPPs) containing sulfonic acid groups in their side chains had been directly synthesized by Ni(0) catalytic coupling of sodium 3-(2,5-dichlorobenzoyl)benzenesulfonate and 2,5-dichlorobenzophenone. The synthesized copolymers possessed high molecular weights revealed by their high viscosity, and the formation of tough and flexible membranes by casting from DMAc solution. The copolymers exhibited excellent oxidative stability and mechanical properties due to their fully aromatic structure extending through the backbone and pendent groups. Transmission electron microscopic (TEM) analysis revealed that these side-chain type SPP membranes have a microphase-separated structure composed of hydrophilic side-chain domains and hydrophobic polyphenylene main chain domains. The proton conductivities of copolymer membranes increased with the increase of IEC and temperature, reaching values above 3.4 x 10(-1) S/cm at 120 degrees C, which are almost 2-3 times higher than that of Nafion 117 at the same measurement conditions. Consequently, these materials proved to be promising as proton exchange membranes.