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  • Physical Chemistry  (2)
  • transition metal catalysts  (2)
  • DNA probe assay  (1)
  • 1
    ISSN: 1436-5073
    Keywords: electrogenerated Chemiluminescence ; Ru(bpy) 3 2+ ; detector ; flow injection analysis ; HPLC ; biosensing ; immunoassay ; DNA probe assay
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Ru(bpy) 3 2+ electrogenerated chemiluminescence (CL) has rapidly gained importance as a sensitive and selective detection method in analytical science. The Ru(bpy) 3 2+ ECL is observed when Ru(bpy) 3 3+ reacts with Ru(bpy) 3 + and yields an excited state Ru(bpy) 3 2+* . ECL emission can also be obtained when a variety of oxidants and reductants react with the reduced or oxidized forms of Ru(bpy) 3 2+ . Either the reductant or the oxidant can be treated as an analyte. The Ru(bpy) 3 2+ ECL is used as a detection method for the determination of oxalate and a variety of amine-containing analytes without derivatization in flowing streams such as flow injection and HPLC. When the ECL format is used as a detector for HPLC, unstable post-column reagent addition can often be eliminated and, the problems of both sample dilution and band broadening can be avoided because the Ru(bpy) 3 3+ species are generatedin situ in the reaction/observation flow cell. Since NADH is sensitively detected with the Ru(bpy) 3 2+ ECL, many clinically important analytes can be detected by coupling them to dehydrogenase enzymes that utilize β-nicotinamide adenine cofactors to convert NAD+ to NADH. Ru(bpy) 3 2+ -derivatives are used as CL labels for immunoassay and PCR assay with Ru(bpy) 3 2+ /tripropylamine ECL system. The Ru(bpy) 3 2+ ECL label can be sensitively determined at subpicomolar concentrations, along with an extremely wide dynamic range of greater than six orders of magnitude. Furthermore, it can eliminate disposal and lifetime problems inherent in radio immunoassays. In this paper, basic principles of the Ru(bpy) 3 2+ ECL are discussed. In addition, analytical applications of the Ru(bpy) 3 2+ ECL are illustrated with examples.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of reactions between 2-phenylethyl benzenesulphonates (2-PEB) and benzylamines in acetonitrile at 65·0°C have been studied; the mechanism was examined on the basis of the sign and magnitude of cross-interaction constants ρij and βij. In contrast to the reactions of 2-PEB with anilines in methanol, participation of the aryl-assisted pathway was negligible, with a strong indication that the reaction proceeds largely by an intermolecular SNi mechanism with a four-centre transition state (TS). The effect of substituents on the TS variation was in accord with the predictions of the quantum mechanical model.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0887-624X
    Keywords: poly(propargylamine) ; poly(1,1-diethylpropargylamine) ; polyacetylene derivatives ; transition metal catalysts ; organoaluminum cocatalysts ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Some polyacetylene derivatives containing an amine functional group were prepared by the polymerization of propargylamine (PA) and 1,1-diethylpropargylamine (DEPA) with various transition metal catalysts. In the polymerization of PA, Mo-based catalysts were more effective than that of W-based catalysts, and organoaluminum compounds, especially EtAlCl2, were found to be very effective cocatalysts. In the polymerization of DEPA, Mo-and W-based catalyst systems showed a similar catalytic activity. The polymerization easily proceeded in polar solvents such as nitrobenzene and DMF as well as nonpolar aromatic solvents such as chlorobenzene, toluene, etc. The resulting poly(PA) and poly(DEPA) were insoluble in organic solvents regardless of polymerization catalysts but the polymers were found to be stable to air oxidation. Thermogravimetric analyses and thermal transitions of poly(PA) and poly(DEPA) were also studied. © 1992 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0887-624X
    Keywords: poly(1-ethynylcyclohexene) ; conjugated polymer ; transition metal catalysts ; organoaluminum compounds ; thermal property ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-Ethynylcyclohexene, an acetylene derivative having cyclohexenyl substituent, was polymerized by various W- and Mo-based catalysts. WCl6-EtAlCl2 catalyst system was found to be very effective for this polymerization. The effects of the monomer-to-catalyst mol ratio, the initial monomer concentration, the temperature, and the cocatalysts for the polymerization of 1-ethynylcyclohexene by WCl6 were investigated. The catalytic activity of Mo-based catalysts was found to be similar to that of W-based catalysts. The polymer structure was identified to have a conjugated polymer backbone carrying a cyclohexenyl substituent. The resulting polymers were light-brown powder and completely soluble in aromatic and halogenated hydrocarbon solvents such as chlorobenzene, benzene, chloroform, carbon tetrachloride, etc. Studies of the thermal properties and morphology of poly(1-ethynylcyclohexene) were also carried out. © 1995 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The negative slope (ΔρY+ 〈 0) of the Hammett-type plot using kinetic solvent isotope effect, log kSOH/kSOD versus σ+, for methanolysis of 1-(Y-phenyl)ethyl chlorides is rationalized by an ion-pair mechanism in which a solvent molecule attacks the relatively stable carbocation formed in the pre-equilibrium.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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