Skip to content
University of Maryland LibrariesDigital Repository at the University of Maryland
    • Login
    View Item 
    •   DRUM
    • Theses and Dissertations from UMD
    • UMD Theses and Dissertations
    • View Item
    •   DRUM
    • Theses and Dissertations from UMD
    • UMD Theses and Dissertations
    • View Item
    JavaScript is disabled for your browser. Some features of this site may not work without it.

    SYNTHESIS AND MOLECULAR RECOGNITION PROPERTIES OF ACYCLIC CUCURBIT[N]URIL AND ITS DERIVATIVES

    Thumbnail
    View/Open
    ZebazeNdendjio_umd_0117E_21063.pdf (38.31Mb)
    No. of downloads: 16

    Date
    2020
    Author
    Zebaze Ndendjio, Sandra
    Advisor
    Isaacs, Lyle
    DRUM DOI
    https://doi.org/10.13016/xrhq-mnz8
    Metadata
    Show full item record
    Abstract
    The study of molecular containers has accelerated dramatically since the 1960's. The introduction of cucurbit[n]urils has contributed tremendously and continues to contribute to the expansion of the field. Chapter 1 introduces cucurbit[n]urils and their molecular recognition properties toward amino acids, peptides, and Insulin. Followed by an overview of the history of CB[n] and their analogs made with modified glycoluril backbone, solubilizing groups, alkyl arm linker, and type of aromatic arms. Chapter 2 describes the application of the acyclic CB[n], Calabadion 1 and 2 for the molecular recognition of amino acids, peptides, and Insulin. The results show that 1 and 2 have preferential binding affinity toward aromatic (e.g. H-Phe-NH2) and di-cationic (e.g. H-Lys-NH2) amino acid amides. Electrostatic interactions between the tetraanionic 1 and 2 with the amino acid guests (in their N-acetylated, zwitterionic, or CO-NH2 forms) was demonstrated to dramatically influence the strength of the recognition process. The binding affinity of 1 and 2 toward insulin was compared to that of CB[7], respectively (Ka= 1.32 × 10^5 M^-1 for 1, 3.47 × 10^5 M^-1 for 2, and 5.59 × 10^5 M^-1 for CB[7]) which showed comparable levels of affinity between these three hosts. Chapter 3 introduces a new acyclic CB[n] featuring a central glycoluril trimer with sulfonated triptycene aromatic sidewalls. It was observed that the binding affinity increases as the alkyl chain length of the guest increases. An x-ray crystal structure reveals an overall out-of-plane distortion of the aromatic sidewalls and intermolecular packing driven by interactions between the external faces of the triptycene sidewalls. Finally, the trimer host was shown to bind strongly to fentanyl which suggests potential usage as in vivo reversal agent. In chapter 4, an analog of 1 was synthesized in which the (CH2)3 linking group was removed. This structural change brings the anionic sulfate substituents closer to the electrostatically negative ureidyl C=O portals. We find that this new host displays preferential binding affinity toward quaternary ammonium ioins and a higher binding affinity toward dications compared to 1. Most impressive are the nanomolar binding affinities toward rocuronium and vecuronium which suggests potential application for in vivo reversal agent.
    URI
    http://hdl.handle.net/1903/26563
    Collections
    • Chemistry & Biochemistry Theses and Dissertations
    • UMD Theses and Dissertations

    DRUM is brought to you by the University of Maryland Libraries
    University of Maryland, College Park, MD 20742-7011 (301)314-1328.
    Please send us your comments.
    Web Accessibility
     

     

    Browse

    All of DRUMCommunities & CollectionsBy Issue DateAuthorsTitlesSubjectsThis CollectionBy Issue DateAuthorsTitlesSubjects

    My Account

    LoginRegister
    Pages
    About DRUMAbout Download Statistics

    DRUM is brought to you by the University of Maryland Libraries
    University of Maryland, College Park, MD 20742-7011 (301)314-1328.
    Please send us your comments.
    Web Accessibility