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  • 2000-2004  (5)
  • Electron transfer  (3)
  • HPLC  (2)
  • 1
    ISSN: 1434-193X
    Keywords: Triplet recombination ; Electron transfer ; Radical ions ; Photochemistry ; Terpenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The triphenypyrylium tetrafluoroborate (TPT)-sensitized reactions of several terpene donor molecules, including sabinene (1), α-phellandrene (4), α-terpinene (5) and γ-terpinene (6) give rise to significantly different products than reactions induced by other electron-transfer sensitizers, such as 1,4-dicyanobenzene (DCB). The divergent reactions require decidedly different key intermediates; the products obtained with TPT can be explained by dissociative recombination of the intermediate radical-radical cation pair in the triplet state, generating donor-derived biradicals.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1434-193X
    Keywords: Zeolites ; Electron transfer ; Proton transfer ; Radical ions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Incorporation of N,N′-diphenylhydrazine into HZSM-5 led to the formation of azobenzene and aniline (70-80 mol-% mass balance). The formation of azobenzene can be followed by the appearance in diffuse reflectance UV/Vis spectroscopy of a characteristic band (λmax = 420 nm). IR spectra of the extracted solids indicate that some aniline is retained in the zeolite, probably due to acid-base interaction with active sites. The products are rationalized by two competing mechanisms: the formation of azobenzene by electron transfer to an oxidizing site, the generation of aniline by proton transfer from a Brønsted acid site. A long-wavelength diffuse-reflectance band (λmax = 800 nm) in the initial stages of the reaction supports the intermediacy of a radical cation. These results show that acid zeolites can exhibit a dual behavior against basic substrates with low oxidation potential, serving simultaneously as electron acceptor and Brønsted acid.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1434-193X
    Keywords: Zeolites ; Radical ions ; Ring opening ; Electron transfer ; Oxidations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Incorporation of trans-1,2-diphenylcyclopropane (1) and its 3,3-D2-isotopomer into the channels of a redox-active pentasil zeolite (Na-ZSM-5) resulted in the formation of exo,exo-1,3-diphenylallyl radical (2•) and its 2-D1 isotopomer, respectively. This conversion requires oxidation, ring opening, and deprotonation, in an unspecified sequence. The allyl radical 2• is also formed upon incorporation of trans-1,3-diphenylpropene (3). A comparison with the solution photochemistry, in the presence or absence of added base, shows the conversion of 1 into 2• to be a zeolite-specific reaction. Incorporation of arylcyclopropanes 9 (R = H, OCH3) into ZSM-5 generated trans-propenylbenzene radical cations 10•+ (R = H, OCH3); the 2,2-D2 isotopomer of 9 (R = OCH3) gave rise to three different isotopomers of 10•+ (R = OCH3).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 23 (2000), S. 93-99 
    ISSN: 0935-6304
    Keywords: HPLC ; monolithic column ; silica rod column ; fast separations ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The application of a new silica-based, monolithic-type HPLC-column for fast separations is presented. The column is prepared according to a new sol-gel process, which is based on the hydrolysis and polycondensation of alkoxysilanes in the presence of water soluble polymers. The method leads to “rods” made of a single piece of porous silica with a defined pore structure, i. e. macro- and mesopores. The main feature of silica rod columns is a higher total porosity, about 15% higher than of conventional particulate HPLC columns. The resulting column pressure drop is therefore much lower, allowing operation at higher flow rates including flow gradients. Consequently, HPLC analysis can be performed much faster, as it is demonstrated by various applications.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0935-6304
    Keywords: Monolithic column ; silica monolith ; HPLC ; capillary liquid chromatography ; capillary electrochromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Two types of monolithic silica columns derivatized to form an ODS phase, one prepared in a fused silica capillary (SR-FS) and the other prepared in a mold and clad with an engineering plastic (poly-ether-ether-ketone) (SR-PEEK), were evaluated. The column efficiency and pressure drop were compared with those of a column packed with 5-μm ODS-silica particles and of an ODS-silica monolith prepared in a mold and wrapped with PTFE tubing (SR-PTFE). SR-FS gave a lower pressure drop than a column packed with 5-μm particles by a factor of 20, and a plate height of 20 μm at a linear velocity below 1 mm/s. SR-PEEK showed higher flow-resistance than the other monolithic silica columns, but they still showed a minimum plate height of 8-10 μm and a lower pressure drop than popular commercial columns packed with 5-μm particles. The evaluation of SR-FS columns in a CEC mode showed much higher efficiency than in a pressure-driven mode.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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