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    Case studies on the aspects of molecular signaling : binding forces, signal generation, and a mature receptor

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    Date
    2007-05
    Author
    Houk, Ronald James Travis, 1979-
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    Abstract
    The field of molecular and atomic sensing has seen a vast growth over the last few decades. Yet many advances still remain to be made. This dissertation takes an in depth look at the two major aspects in a molecular sensing or signaling scaffold—namely the binding of a target followed by the transduction of an observable signal. Chapter 1 will deal with intermolecular binding forces in the form of a case study on electrophilic coordination to carbonyl compounds. Computational studies are performed to determine the optimal geometry of an electrophile interacting with a carbon acid to affect the greatest enhancement in the acidity at the α-carbon. We find that partial interaction through the π-system of the carbonyl and the resulting enolate affords the greatest acidity enhancement. Chapter 2 then switches to studies on the development of a novel signaling method for a molecular signaling assay. Two novel elements—transition metal catalytic signal amplification and peroxyoxalate chemiluminescence—are utilized to generate a signaling motif incorporating two new methodologies for signal generation. The first uses of catalytic signal amplification for the detection of small organic analytes and peroxyoxalate chemiluminescence for signal generation in a molecular recognition event are described. Finally, both elements are brought together in Chapter 3, which describes a mature ionophoric chemodosimeter with both highly sensitive binding and strong signal output. The use of a squaraine dye as a signaling unit for the detection of palladium(II) salts is described in which an aliphatic thiol acts as the theoretical “host” in a covalent displacement type assay. Palladium(II) and other transition metal detection is of importance both industrially and environmentally, and the assay described is sensitive to levels desired in both arenas.
    Department
    Chemistry
    Description
    text
    Subject
    Cellular signal transduction
    URI
    http://hdl.handle.net/2152/13289
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    • facebook
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    • CONTACT US
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    © The University of Texas at Austin