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  • 1
    Electronic Resource
    Electronic Resource
    Woodbury, NY : American Institute of Physics (AIP)
    Applied Physics Letters 76 (2000), S. 2376-2378 
    ISSN: 1077-3118
    Source: AIP Digital Archive
    Topics: Physics
    Notes: This letter quantifies both experimentally and theoretically the diffusion of low-molecular-weight species across the interface between two aqueous solutions in pressure-driven laminar flow in microchannels at high Péclet numbers. Confocal fluorescent microscopy was used to visualize a fluorescent product formed by reaction between chemical species carried separately by the two solutions. At steady state, the width of the reaction–diffusion zone at the interface adjacent to the wall of the channel and transverse to the direction of flow scales as the one-third power of both the axial distance down the channel (from the point where the two streams join) and the average velocity of the flow, instead of the more familiar one-half power scaling which was measured in the middle of the channel. A quantitative description of reaction–diffusion processes near the walls of the channel, such as described in this letter, is required for the rational use of laminar flows for performing spatially resolved surface chemistry and biology inside microchannels and for understanding three-dimensional features of mass transport in shearing flows near surfaces. © 2000 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1434-193X
    Keywords: Calixarenes ; Chromophores ; Nonlinear optics ; Pre-organization ; Supramolecular chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A systematic investigation of the conceptofpre-organization of nonlinear optical (NLO) active chromophoric groups in calix[4]arene derivatives and the influence on the absolute second-order nonlinear optical coefficients is reported. Several calix[4]arenes were synthesized by modification of the electron-withdrawing groups at the upper rim of the aromatic and extension of the conjugated π system of the pre-organized chromophoric groups. Electrical field induced second harmonic generation (EFISH) experiments showed high μβ(0) values up to 1165·10-48 esu. Compared with the corresponding reference compounds, enhancements of the μβ(0) values varying up to 2.5 times per chromophore were observed which proves the benefit of pre-organization of NLO-active units in a multi-chromophoric system. Another important advantage is that the increase in NLO activity observed for these systems is not accompanied with a shift of the absorption band to longer wavelengths exceeding 20 nm. This makes these calix[4]arene derivatives promising building blocks for the development of stable, NLO-active materials that are suitable for frequency doubling.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0009-2940
    Keywords: Cavitand ; Electrochemistry ; Iron sulfur cluster ; Metalloprotein model ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: NMR and Mössbauer spectroscopy show that a novel tetrathiol ligand, based on the cavitand diphenylglycoluril, encapsulates a 4Fe-4S cluster and induces asymmetry in it. The cluster gives a weak electrochemical current response in DMF, with a half-wave potential for the 2-/3- reduction vs. Fc+/Fc of -1.7 V. Ba2+ ions are adsorbed, according to X-ray analysis of the SEM image of the electrode, and act as modulator and promoter of the electrochemical response. On the basis of cyclic voltammograms it is proposed that this adsorption creates electroactive sites, changing the type of diffusion controlling the mass transport to the electrode from radial to linear, and that it helps the negatively charged complex, which contains a dipole, to approach the negative electrode in an orientation favourable for electron exchange. This feature makes the complex an important model for ferredoxins, in spite of a difference in redox potential.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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