A DFT-based mechanistic study on the formation of oximes

Serdal Kirmizialtin, Banu Sizirici Yildiz, Ibrahim Yildiz

    Research output: Contribution to journalArticle

    Abstract

    Oxime chemistry has been proven to be a reliable bioconjugation method for biomedical applications. Because of its stable and bio-orthogonal nature, a number of materials have been devised for in vitro and in vivo applications such as drug delivery, imaging, and biochemical assays. Polymers, synthetic molecules, nanoparticles, and biomolecules carrying alkoxyamine and aldehyde/ketone functional groups could be linked to each other through oxime bond, and a variety of modular platforms could be produced. Formation of oximes is catalyzed in acidic medium, and the proposed reaction mechanism follows classical imine formation pathways. Aniline has been found to accelerate the rate of oxime formation several orders of magnitude. In this computational study, we analyzed the proposed mechanism on model systems using DFT calculations including a solvation model. The energetics of the reaction steps in neutral and acidic conditions as well as in the presence of aniline was performed. Explicit water molecules were included in the calculations to study the energetics of solvent assisted proton transfer steps.

    Original languageEnglish (US)
    Article numbere3711
    JournalJournal of Physical Organic Chemistry
    Volume30
    Issue number12
    DOIs
    StatePublished - Dec 1 2017

    Fingerprint

    Oximes
    Discrete Fourier transforms
    aniline
    aldehydes
    ketones
    imines
    Molecules
    Proton transfer
    Imines
    solvation
    molecules
    delivery
    Solvation
    drugs
    Biomolecules
    platforms
    Ketones
    Drug delivery
    Aldehydes
    chemistry

    Keywords

    • carbinolamine
    • DFT
    • hydroxylamine
    • imine
    • oxime
    • proton transfer

    ASJC Scopus subject areas

    • Physical and Theoretical Chemistry
    • Organic Chemistry

    Cite this

    A DFT-based mechanistic study on the formation of oximes. / Kirmizialtin, Serdal; Yildiz, Banu Sizirici; Yildiz, Ibrahim.

    In: Journal of Physical Organic Chemistry, Vol. 30, No. 12, e3711, 01.12.2017.

    Research output: Contribution to journalArticle

    Kirmizialtin, Serdal ; Yildiz, Banu Sizirici ; Yildiz, Ibrahim. / A DFT-based mechanistic study on the formation of oximes. In: Journal of Physical Organic Chemistry. 2017 ; Vol. 30, No. 12.
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