Multifunctional organic-inorganic multilayer films of tris(2,2 '-bipyridine)ruthenium and decatungstate

A new multifunctional multilayer films consisting of tris(2,2'-bipyridyl)ruthenium(II) (Rubpy) and sodium decatungstate (W-10) have been prepared by the layer-by-layer (LbL) self-assembly method on ITO substrate. X-ray photoelectron spectra (XPS) confirmed the existence of W10 and Rubpy. Cyclic voltammetry (CV) and UV-Vis spectroscopy demonstrated the uniform assembly of (W-10/Rubpy) multilayer films. The multilayer films possess electrocatalytic activities on the reduction of iodate and oxidation of oxalate. Moreover, the films exhibited electrochemiluminescence (ECL) with tripropylamine (abbreviated as TPA) as the coreactant and the ECL response was proportional to the number of (W-10/Rubpy) layers. These characteristics of the multilayer films might find potential applications in the field of sensors and materials fields.

Simultaneous determination of tramadol and lidocaine in urine by end-column capillary electrophoresis with electrochemiluminescence detection

Tramadol and lidocaine, used as analgesic and local anesthetic in surgery, are partly excreted by kidney. For the first time, we developed a simple and sensitive method, based on capillary electrophoresis with electrochemiluminescence (ECL) detection by end column mode without joint to monitor tramadol and lidocaine in urine. To eliminate the influence of ionic strength of urine sample, analytes were extracted by ether. Tripropylamine (TPA) was used as internal standard. ne recoveries of tramadol and lidocaine were between 94% and 97% at different levels. The method exhibited the linear range for the tramadol and lidocaine from 1.0 X 10(-7) to 1.0 X 10(-4) mol/L with correlation efficient of 0.998. The relative standard deviation (RSD) was 2.9% and 2.7% (n = 8) for tramadol and lidocaine, respectively. The limit of detection (LOD) was 6.0 x 10(-8) mol/L and 4.5 x 10(-8), mol/L (S/N = 3) for tramadol and lidocaine, respectively. The application for detecting tramadol and lidocaine in urine of patients showed that the method was valuable in clinical and biochemical laboratories for detecting tramadol, lidocaine and other tertiary amine pharmaceuticals for various purpose, such as metabolism investigation.

毛细管电泳电化学发光检测体系中正高压进样条件下正负离子电场放大进样效应

毛细管电泳 (CE)正向着实际体系分析和微型化分析的方向发展[1,2 ] .为提高分离效率 ,CE的进样量一般很小 (1 0 - 12 ～ 1 0 - 9L ) ,因此常采用在线样品富集方式以提高检测灵敏度 .电场放大进样 (FASI)是 CE中实现在线样品富集的简便方式[3] ,随着 CE和检测技术的发展 ,其应用范围和研究体系不断扩大[4 ] .三联吡啶钌 [Ru(bpy) 2 + 3]电化学发光 (ECL )作为一种高灵敏、高选择性的检测方法被逐渐应用于 CE分析 (CE-ECL) .我们对这种技术进行了研究 ,并将其应用于临床分析[5～ 7] .实验中发现 ,在施加正高压的条件下 ,不同进样条件和样品基底对正、负离子的电场放大进样具有不同效应 . TPA采用水溶液电场放大进样方式 ,灵敏度提高约 1 0 0倍 ,而负离子 Pro电解质溶液采用预先进水柱 ,正高压电场电动进样也获得显著的电场放大进样效应 ,灵敏度和分离效率分别提高 1 0和 46倍 .本文以三丙胺 (TPA)和脯氨酸 (Pro)为被测物讨论了该现象 .1　实验部分分析纯 TPA(Acros公司 ) ,层析纯 Pro(中国科学院上海生物化...

New technique for capillary electrophoresis directly coupled with end-column electrochemiluminescence detection

capillary electrophoresis (CE) is characterized. A 300 mum diameter Pt working electrode was used to directly couple with a 75 mum inner diameter separation capillary without an electric field decoupler. The hydrodynamic cyclic voltammogram (CV) of Ru(bpy)(3)(2+) showed that electrophoretic current did not affect the ECL reaction. The presence of high-voltage (HV) field only resulted in the shift of the ECL detection potential. The distance of capillary to electrode was an important parameter for optimizing detection performance as it determined the characteristics of mass transport toward the electrode and the actual concentration of Ru(bpy)(3)(2+) in the detection region. The optimum distance of capillary to electrode was decided by the inner diameter of the capillary, too. For a 75 mum capillary, the working electrode should be placed away from the capillary outlet at a distance within the range of 20-260 mum. The effects of pH value of ECL solution and molecular structure of analytes on peak height and theoretical plate numbers were discussed. Using the 75 mum capillary, under the optimum conditions, the method provided a linear range for tripropylamine (TPA) between 1 x 10(-10) and 1 X 10(-5) mol/L with correlation coefficient of 0.998. The detection limit (signal-to-noise ratio S/N = 3) was 5.0 x 10(-11) mol/L. The relative standard deviation in peak height for eight consecutive injections was 5.6%. By this new technique lidocaine spiked in a urine sample was determined. The method exhibited the linear range for lidocaine from 5.0 x 10(-8) to 1.0 X 10(-5) mol/L with correlation efficient of 0.998. The limit of detection (S/N = 3) was 2.0 x 10(-1) mol/L.

Capillary electrophoresis with solid-state electrochemiluminescence detector

We report capillary electrophoresis coupling to a solid-state electrochemiluminescence (ECL) detector for the first time. The solid-state ECL detector was fabricated by immobilizing the ECL reagent tris(2,2'-bipyridyf)ruthenium (TBR) in poly-(p-styrenesulfonate)-silica-poly(vinyl alcohol) grafting 4-vinylpyridine copolymer films. The excellent stability of the solid-state ECL detector in the phosphate solution satisfied application in CE. The CE with solid-state ECL detector system was characterized using tripropylamine (TPA) and proline. The influences of detection potential, the concentration of TBR in the film, and pH value of ECL buffer were investigated. The linear range for TPA and proline was 0.005-10 muM and 5-10 mM with correlation coefficients of 0.997 and 0.998, respectively. The detection limit (signal-to-noise ratio S/N = 3) was estimated to be 0.002 and 2.0 muM for TPA and proline, respectively. The relative standard deviations for 1.0 pm TPA and 1.0 mm proline were 8.7% and 7.5% with theoretical plate numbers of 70 000 and 16 000, respectively. Compared with the CE-ECL of TBR in aqueous solution, the CE coupling with solid-state ECL detector system gave the same sensitivity of analysis.

Electrochemiluminescence of tris(2,2 '-bipyridyl)ruthenium (II) ion-exchanged in polyelectrolyte-silica composite thin-films

The organic-inorganic hybrid, PSS-silica composite material was developed for the immobilization of tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) on glassy carbon electrode via ion-exchange (PSS stands for poly(sodium 4-styrene-sulfonate)). The electrochemiluminescence (ECL) and electrochemistry of Ru(bpy)(3)(2-) immobilized in the composite thin films have been investigated with tripropylamine (TPA) as the coreactant. The immobilized Ru(bpy)(3)(2-) underwent a surface process. The modified electrode was used for the ECL detection of TPA and showed high sensitivity. Detection limit was 0,1 mumol L-1 for TPA (S/N = 3) with a linear range from 0.5 mumol L-1 to 5 mmol L-1 (R = 0.998), Moreover, the resulting modified electrode was stable over six months and the good stability may be due to the strong interaction between Ru(bpy)(3)(2-) and the high ion-exchange able PSS-silica composite films on GCE. Compared with other materials. the PSS-silica composite films containing incorporated Ru(bpy)(3)(2-) showed improved sensitivity and long-term stability, Thus, such composite thin film can be a promising material for the construction of ECL sensor.

Resonant two-photon cross-section calculations for transitions to 4f5d state in Pr3+: YAG using density matrix theory

The density matrix resonant two-photon absorption (TPA) theory is applied to a rare-earth ion-doped laser crystal. TPA cross sections for transitions from the ground state to the first 4f5d state in Pr3+:YAG are calculated. The results indicate the density matrix TPA theory is attractive in studying TPA in laser crystals. (C) 2000 Elsevier Science B.V. All rights reserved.

Electrochemiluminescence of tris(2,2 '-bipyridine)ruthenium(II) immobilized in poly(p-styrenesulfonate)-silica-Triton X-100 composite thin-films

The electrochemiluminescence (ECL) of tris(2,2'-bipyridine)ruthenium(ii) [Ru(bpy)(3)(2+)] immobilized in poly(p-styrenesulfonate) (PSS)-silica-Triton X-100 composite films was investigated. The cooperative action of PSS, sol-gel and Triton X-100 attached Ru(bpy)(3)(2+) to the electrode strongly, and the presence of Triton X-100 prevented drying fractures of the sol-gel films during gelation and even on repeated wet-dry cycles. The modified electrode was used for the ECL detection of oxalate, tripropylamine (TPA) and NADH in a flow injection analysis (FIA) system with a newly designed flow cell. The detection scheme exhibited good stability, short response time and high sensitivity. Detection limits were 0.1, 0.1 and 0.5 mu mol L-1 for oxalate, TPA and NADH, respectively, and the linear concentration range extended from 0.001 to 1 mmol L-1 for the three analytes. Applications of the flow cell in ECL and electrochemical detection, as well as the immobilization of reagents based on the cooperative action, are suggested.

Synthesis and properties of alternating copolymers containing PPV and hole-transporting units for light-emitting devices

A series of alternating copolymers containing triphenylamine (TPA) moieties and oligomeric PPV segments in the main chain have been synthesized by Wittig condensation. The resulting polymers exhibit good thermal stability with decomposition temperatures (Tds) above 305 degreesC under nitrogen at 10 degreesC/min, and high glass transition temperatures (Tgs). They show intense photoluminescence in solution and film. The single-layer electroluminescent device using TAA-PV1 as emissive layer emits green light at 522nm with a turn-on voltage of 6V and maximum brightness of about 200cd/m(2) at 20V.

Calculations of cross sections of resonant two-photon transitions to the second excited 4f5d state in Pr3+: Y3Al5O12 using density matrix theory

The density matrix resonant two-photon absorption (TPA) theory applicable to laser crystals doped with rare earth ions is described. Using this theory, resonant TPA cross sections for transitions from the ground state to the second excited state of the 4f5d configuration in cm(4)s Pr3+:Y3Al5O12 are calculated. The peak value of TPA cross section calculated is 2.75 x 10(-50) cm(4)s which is very close to the previous experimental value 4 x 10(-50) cm(4) s. The good agreement of calculated data with measured values demonstrates that the density matrix resonant TPA theory can predict resonant TPA intensity much better than the standard second-order perturbation TPA theory.

热致液晶三元共聚酯酰亚胺的合成与表征

采用直接熔融缩聚方法由1,6-己撑-双(4-羟基酞酰亚胺)(BHPI)、对羟基苯甲酸(PH-BA)和对苯二甲酸(TPA)合成一系列三元共聚酯酰亚胺。对聚合物进行示差扫描量热(DSC)、偏光显微镜(PLM)、广角X-射线衍射(WAXD)等分析表征，结果表明该系列聚合物具有向列型液晶特征。

Synthesis and properties of thermotropic liquid crystalline copolyesters containing bis(4-hydroxyphenyl)methanone(V)

A new series of fully aromatic thermotropic liquid crystalline copolyesters were synthesized by thermal polycondensation of p-hydroxybenzoic acid (PHB), terephthalic acid (TPA), resorcinol (RES) and bis (4-hydroxyphenyl) methanone (BHP). The DSC traces of copolyesters exhibited two or three endotherms, the low temperature endotherm(Tm) of which indicated the transition from solid state to anisotropic phase. Observation under polarizing microscope and WAXD measurements suggested that the LC-phase formed immediately above Tm had a nematic character.

第二信使介导模拟低氧下丘脑CRF分泌

用模拟高原低氧的方法研究急性低氧条件下促肾上腺皮质激素释放因子(corticotrop in-releasing factor,CRF) 分泌的变化及第二信使参与CRF分泌的作用。低氧(海拔7 km ) 1 h 后, 正中隆起(median eminence,M E) 处CRF 含量明显下降(P < 0. 05) , 下丘脑(hypothalamus, Hy)CRF (不含M E) 含量无明显变化, 而Hy 内cAM P 含量明显增加(P < 0. 01)。脑室注射Forsklin、TPA 后低氧暴露(海拔5 km ) 1 h,M E CRF 含量下降(P < 0. 05; P < 0.05) ,Hy CRF 无明显变化。脑室注射Forsk lin 后Hy cAM P 含量升高(P < 0. 05)。脑室注射H7 和PKA 抑制剂,M ECRF 升高(P < 0. 05; P < 0. 01) ,Hy CRF 和Hy cAM P 均无显著变化。上述结果表明急性低氧应激中CRF 分泌显著增加, 第二信使通路PKA 和PKC 通路均参与CRF 分泌。

Synthesis of titanium silicalites in different template systems and their catalytic performance

Titanium silicalites have been synthesized in the TPABr+ammonia, TPABr+hexanediamine, TPABr+ethylenediamine, TPABr+diethylamine, TPABr+TEAOH, TPABr+n-butylamine, TPABr+TBAOH and TBAOH+n-butylamine systems. As-synthesized titanium silicalites were characterized by XRD, IR and C-13 CP MAS NMR. Catalytic performance in epoxidation of propylene and template effect was investigated. It has been shown that both TPABr and TBAOH serve as templating agent in TPABr+TBAOH system. But in other systems, when there is enough TPABr, organic amines or ammoniums only act as the bases. TEAOH or n-butylamine can take the role of template when less TPABr is added. It indicates that the ability of organic amines or ammoniums to direct the Pentasil structure decreases as follows: TPA(+)>TBA(+)>TEA(+)>n-butylamine. Catalysts exhibiting good performance in epoxidation of propylene can be attained using TPABr as the template and ammonia, n-butylamine, diethylamine, hexanediamine or TBAOH as bases. (C) 1999 Elsevier Science B.V. All rights reserved.

Study of gene expression in thyrotropin-stimulated thyroid cells by cDNA expression array: ID3 transcription modulating factor as an early response protein and tumor marker in thyroid carcinomas.

Induction of cell proliferation by mitogen or growth factor stimulation leads to the specific induction or repression of a large number of genes. To identify genes differentially regulated by the cAMP-dependent transduction pathway, which is poorly characterized so far, we used the cDNA expression array technology. Hybridizations of Atlas human cDNA expression arrays with (32)P-labeled cDNA probes derived from control or thyrotropin (TSH)-stimulated dog thyrocytes in primary culture generated expression profiles of hundreds of genes simultaneously. Among the genes that displayed modified expression, we selected the transcription factor ID3, whose expression was increased by a cAMP-dependent stimulus. ID3 overexpression after TSH stimulation was first verified by Northern blotting analysis, and its mRNA regulation was then investigated in response to a variety of agents acting on thyrocyte proliferation and/or differentiation. We show that: (1) ID3 mRNA induction was stronger after stimulation of the cAMP cascade, but was not restricted to this signaling pathway, as phorbol myristate ester (TPA) and insulin also stimulated mRNA accumulation; (2) in contrast, powerful mitogens for thyroid cells, epidermal growth factor and hepatocyte growth factor, did not significantly modify ID3 mRNA levels; (3) ID3 protein levels closely parallelled mRNA levels, as revealed by immunofluorescence experiments showing a nuclear signal regulated by TSH; (4) in papillary thyroid carcinomas, ID3 mRNA was downregulated. Our results suggest that ID3 expression might be more related to the differentiating process induced by TSH than to the proliferative action of this hormone.