Application of ceramic carbon materials for solid-phase extraction of organic compounds

Ceramic carbon materials were developed as new sorbents for solid-phase extraction of organic compounds using chlorpromazine as a representative. The macroporosity and heterogeneity of ceramic carbon materials allow extracting a large amount of chlorpromazine over a short time. Thus, the highly sensitive and selective determination of chlorpromazine in urine sample was achieved by differential pulse voltammograms after only 1-min extraction. The total analysis time was less than 3 min. In comparison with other electrochemical and electrochemi-luminescent methods following 1-min extraction, the proposed method improved sensitivity by about 2 and 1 order of magnitude, respectively. The fast extraction, diversity, and conductivity of ceramic carbon materials make them promising sorbents for various solid-phase extractions, such as solid-phase microextraction, thin-film microextraction, and electrochemically controlled solidphase extraction. The preliminary applications of ceramic carbon materials in chromatography were also studied.

Dependence of charge transfer energy on crystal structure and composition in Eu3+-doped compounds

We report a method for estimating the positions of charge transfer (CT) bands in Eu3+-doped complex crystals. The environmental factor ( he) influencing the CT energy is presented. he consists of four chemical bond parameters: the covalency, the bond volume polarization, the presented charge of the ligand in the chemical bond, and the coordination number of the central ion. These parameters are calculated with the dielectric theory of complex crystals. The relationship between the experimental CT energies and calculated environmental factors was established by an empirical formula. The calculated values are in good agreement with the experimental results. Such a relationship was confirmed by detailed analysis. In addition, our method is also useful to predict the charge-transfer position of any other rare earth ion.

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.

Extended topological indices and prediction of activities of chiral compounds

The activities/properties of two molecules with identical formula but different configuration states of the asymmetric atoms are different. Thus, usually the common topological indices are not suitable. In this study, the chiral topological indices were obtained by extending A(mi) indices suggested by our laboratory and molecular connectivity indices. The modified topologial indices have been used for the studies on D2 for dopamine receptor and a receptor activities of fourteen N-alkylated 3-(3-hydroxypyenyl)-piperidines. It has been observed that selected variables possess low correlations. The results obtained by using multiple regression analysis and artificial neural networks are satisfactory.

Synthesis and characterization of hyperbranched aromatic poly(ether imide)s

The four AB(2) monomers, N-[3- or 4-bis(4-hydroxyphenyl)toluoyl]-4-chlorophthalimide and N-{3- or 4-[1,1-bis(4-hydroxyphenyl)]ethylphenyl}-4-chlorophthalimides, were prepared and used for synthesis of hyperbranched poly(ether imide)s bearing hydroxyl end groups. These hyperbranched poly(ether imide)s had moderate molecular weights with broad distributions and showed glass-transition temperatures (Tgs) between 177 and 230 degreesC. The thermogravimetric analytic measurement revealed the decomposition temperature at 5% weight-loss temperatures (T-d(5%)) ranging from 240 to 281 degreesC. Analysis using H-1 NMR spectroscopy revealed the four types of hyperbranched poly(ether imide)s to have similar degrees of branching (ca. 60%). These polymers were modified by acylation or nucleophilic substitution reaction at the hydroxyl end groups. The conversion effectiveness depended on the type of modification reaction, modifier, and reaction conditions. The thermal stability and solubility of hyperbranched poly(ether imide)s were improved by the modification of the end groups.

Synthesis and characterization of hyperbranched aromatic poly(ester-imide)s

The synthesis and characterization of hyperbranched aromatic poly(ester-imide)s are described. A variety of AB(2) monomers, N-[3- or 4-bis(4-acetoxyphenyl)toluoyl]-4-carboxyl-phthalimide and N-{3- or 4-[1,1-bis(4-acetooxyphenyl)]ethylphenyl}-4-carboxy phthalimides were prepared starting from condensation of nitrobenzaldehydes or nitroacetophenones with phenol and used for synthesis of hyperbranched poly(ester-imide)s containing terminal acetyl groups by transesterification reaction. These hyperbranched poly(ester-imide)s were produced with weight-average molecular weight of up to 6.87 g/mol. Analysis of H-1 NMR and C-13 NMR spectroscopy revealed the structure of the four hyperbranched poly(ester-imide)s. These hyperbranched poly(ester-imide)s exhibited excellent solubility in a variety of solvents such as N,N-dimethylacetamide, dimethyl sulfoxide, and tetrahydrofuran and showed glass-transition temperatures between 217 and 255 degreesC. The thermogravimetric analytic measurement revealed the decomposition temperature at 10% weight-loss temperature (T-d(10)) ranging from 365 to 416 degreesC in nitrogen.

Synthesis, characterization, photoluminescent and electroluminescent properties of new conjugated 2,2 '-(arylenedivinylene)bis-8-substituted quinolines

A series of new PPV oligomers containing 8-substituted quinoline, 2,2'-(arylenedivinylene) bis-8-quinoline derivatives, were designed and synthesized via a Knoevenagel condensation reaction of quinaldine, 8-hydroxy-or 8-methoxy-quinaldine with aromatic dialdehydes. These PPV oligomers were characterized by H-1 and C-13-NMR, X-ray diffraction, elemental analysis, UV-visible and fluorescence spectroscopies. The X-ray diffraction investigation showed that there are intermolecular pi...pi interactions in the solid state in 1 and 3. The optical and photoluminescent properties study demonstrated that the emission color of the resulting materials varies from blue to yellow and is dependent on the substituents (pi-donor and pi-acceptor groups) on both sides of the conjugated molecules and the aromatic core in the middle of the conjugated backbones. The electroluminescent devices using compounds 1-4 as the emitters and electron-transporting layers were fabricated with the structure ITO/NPB/emitter/LiF/Al. The best device performance with the maximum brightness of 5530 cd m(-2) and the luminous efficiency of 2.4 cd A(-1) is achieved by using compound 4, with intramolecular charge transfer character, as the emitter; these values represent a more than 5-fold improvement in brightness and efficiency compared to compound 3 without methoxy groups on the phenyl rings.

Anion coordination and molecular assembly in C2-substituted thiamine-anion systems: effects of the anion and molecular conformation

The compounds (het)(PtCl6)2H(2)O 1, (het)(HgI4).H2O 2 (het = 2-(alpha-hydroxyethyl)thiamine) and (hpt)(Hg2Br6) 3 (hpt = 2-(alpha-hydroxypropyl)thiamine) have been prepared and structurally characterized by X-ray crystallography in order to study the influence of the anion and molecular conformation on the formation of supramolecular architectures that adsorb anionic species. Both het and hpt molecules adopt the usual S conformation for C2-substituted thiamine but differ from the F conformation for C2-free thiamine derivatives. Two types of characteristic ligand-anion complexation are observed, being of the forms C(6')-H...anion...thiazolium-ring (in 1 and 2) and N(4'1)-H...anion...thiazolium-ring (in 3). The reaction of het with PtCl62- or HgI42- gives a 1-D double-chain in 1, consisting of two hydrogen-bonded het chains, which are cross-linked by anions through hydrogen bonding and anion...aromatic-ring interactions, or a cationic 3-D framework in 2 formed by the stacking of hydrogen-bonded sheets with anion-and-water-filled channels. In the case of 3, hydrogen-bonded hpt dimers and HgBr62- anions form alternate cation-anion columns. A comparison with the cases of C2-free thiamine-anion complexes indicates that the change in molecular conformation results in novel supramolecular assemblies in 1 and 2 and an analogous architecture in 3, which also depends on the nature of the anions.

Novel polyoxometalate-templated, 3-D supramolecular networks based on lanthanide dimers: Synthesis, structure, and fluorescent properties of [Ln(2)(DNBA)(4)(DMF)(8)][Mo6O19] (DNBA=3,5-dinitrobenzoate)

The spherical Lindquist type polyoxometalate, Mo6O192-, has been used as a noncoordinating anionic template for the construction of novel three-dimensional lanthanide-aromatic monocarboxylate dimer supramolecular networks [Ln(2)(DNBA)(4)(DMF)(8)][Mo6O19] (Ln = La 1, Ce 2, and Eu 3, DNBA = 3,5-dinitrobenzoate, DMF = dimethylformamide). The title compounds are characterized by elemental analyses, IR, and single-crystal X-ray diffractions. X-ray diffraction experiments reveal that two Ln(III) ions are bridged by four 3,5-dinitrobenzoate anions as asymmetrically bridging ligands, leading to dimeric cores, [Ln(2)(DNBA)(4)(DMF)(8)](2+); [Ln(2)(DNBA)(4)(DMF)(8)](2+) groups are joined together by pi-pi stacking interactions between the aromatic groups to form a two-dimensional grid-like network; the 2-D supramolecular layers are further extended into 3-D supramolecular networks with 1-D box-like channels by hydrogen-bonding interactions, in which hexamolybdate polyanions reside. The compounds represent the first examples of 3-D carboxylate-bridged lanthanide dimer supramolecular "host" networks formed by pi-pi stacking and hydrogen-bonding interactions encapsulating noncoordinating "guest" polyoxoanion species. The fluorescent activity of compound 3 is reported.

Synthesis and evaluation of novel polysaccharide-Gd-DTPA compounds as contrast agent for MRI

Macromolecular conjugates of two kinds of natural polysaccharides, that from Panax quinquefolium linn (PQPS) and Ganoderma applanatum pat (GAPS), with gadolinium-diethylenetriaminepenta-acetic acid (Gd-DTPA) have been synthesized and characterized by means of FTIR, elementary analysis and ICP-AES. Their stability was investigated by competition study with Ca2+, EDTA (ethylenediaminetetraacetic acid) and DTPA. Polysaccharide-bound complexes exhibit T-1 relaxivities of 1.5-1.7 times that of Gd-DTPA in D2O at 25degreesC and 9.4T. MR imaging of Sprague-Dawley (SD) rats showed remarkable enhancement in rat liver and kidney after i.v. injection of these two complexes: liver parenchyma 60.9+/-5.6%, 57.8+/-7.4% at 65-85 min; kidney 144.9+/-14.5%, 199.9+/-25.4% at 10-30 min for PQPS-GdDTPA, GAPS-Gd-DTPA at gadolinium dose of 0.083 and 0.082 mmol/kg, respectively. Our preliminary in vivo and in vitro study indicates that the two kinds of polysaccharide-bound complexes are potential tissue-specific contrast agents for MRI.

Luminescence of the compounds Y0.5-xLi1.5VO4 :(Dy3+,Eu3+)

In this paper for the first time the compounds Y0.5-xLi1.5VO4:(Dy3+, Eu3+),(YLV:Dy,Eu) (0.01

Triplex selective 2-(2-naphthyl)quinoline compounds: Origins of affinity and new design principles

A novel competition dialysis assay was used to investigate the structural selectivity of a series of substituted 2-(2-naphthyl)quinoline compounds designed to target triplex DNA. The interaction of 14 compounds with 13 different nucleic acid sequences and structures was studied. A striking selectivity for the triplex structure poly dA:[poly dT](2) was found for the majority of compounds studied. Quantitative analysis of the competition dialysis binding data using newly developed metrics revealed that these compounds are among the most selective triplex-binding agents synthesized to date. A quantitative structure-affinity relationship (QSAR) was derived using triplex binding data for all 14 compounds used in these studies. The QSAR revealed that the primary favorable determinant of triplex binding free energy is the solvent accessible surface area. Triplex binding affinity is negatively correlated with compound electron affinity and the number of hydrogen bond donors. The QSAR provides guidelines for the design of improved triplex-binding agents.

Liquid crystal alignment generated by linearly polarized UV light on photoactive low molecular mass compounds

Alignment films prepared from low molar mass photo-crosslinkable materials containing the cinnamate group can be used for aligning LCs after irradiating the films with linearly polarized UV light. The high contrast observed in the polarizing optical microscope between dark and bright images indicates that the alignment is quite uniform. As the photoreaction progresses. the average roughness of the films is increased. All the aggregate structures, 'lamellar crystals'. produced by the photo-crosslinking reaction are of a square shape.

Hybrid organic-inorganic compounds doped with terbium carboxyl complexes produced in situ via a sol-gel approach

In situ synthesis of terbium carboxyl complexes in an organic-inorganic hybrid matrix by a sol-gel process has been proposed. The formation of terbium carboxyl complexes in the hybrid matrix is confirmed by the luminescence spectra and IR spectra. It is observed that the location at the amino group in aminobenzoic acid has a large effect on the luminescence properties and lifetimes. Furthermore, the emission intensity decreases with increasing temperature.

Preparation, photo and electroluminescence properties of novel rare earth aromatic carboxylates

Novel soluble rare earth aromatic carboxylates were prepared. The triplet energy level of organic ligand was measured. The photoluminescence properties of the Tb3+ and EU3+ aromatic carboxylates and lifetimes were investigated, which indicated that these rare earth complexes have high quantum efficiency. Because of their excellent solubility, polymer-doping rare earth carboxylates were fabricated as thin Films by spin-coating method and their luminescence properties were studied. Some rare earth organic light-emitting diodes were successfully fabricated which performed high pure color. The maximum luminance of the device of ITO/PVK/PVK :Th (AS)(3)Phen: PBD/PBD/Al is 32 cd(.)m(-2) at 28 V.