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    Remarkable fluorescence enhancement versus complex formation of cationic porphyrins on the surface of ZnO nanoparticles

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    Type
    Article
    Authors
    Aly, Shawkat Mohammede cc
    Eita, Mohamed Samir
    Khan, Jafar Iqbal
    Alarousu, Erkki
    Mohammed, Omar F. cc
    KAUST Department
    Chemical Science Program
    KAUST Solar Center (KSC)
    Physical Science and Engineering (PSE) Division
    Ultrafast Laser Spectroscopy and Four-dimensional Electron Imaging Research Group
    Date
    2014-05-28
    Online Publication Date
    2014-05-28
    Print Publication Date
    2014-06-12
    Permanent link to this record
    http://hdl.handle.net/10754/563597
    
    Metadata
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    Abstract
    Fluorescence enhancement of organic fluorophores shows tremendous potential to improve image contrast in fluorescence-based bioimaging. Here, we present an experimental study of the interaction of two cationic porphyrins, meso-tetrakis(1-methylpyridinium-4-yl)porphyrin chloride (TMPyP) and meso-tetrakis(4-N,N,N-trimethylanilinium)porphyrin chloride (TMAP), with cationic surfactant-stabilized zinc oxide nanoparticles (ZnO NPs) based on several steady-state and time-resolved techniques. We show the first experimental measurements demonstrating a clear transition from pronounced fluorescence enhancement to charge transfer (CT) complex formation by simply changing the nature and location of the positive charge of the meso substituent of the cationic porphyrins. For TMPyP, we observe a sixfold increase in the fluorescence intensity of TMPyP upon addition of ZnO NPs. Our experimental results indicate that the electrostatic binding of TMPyP with the surface of ZnO NPs increases the symmetry of the porphyrin macrocycle. This electronic communication hinders the rotational relaxation of the meso unit and/or decreases the intramolecular CT character between the cavity and the meso substituent of the porphyrin, resulting in the enhancement of the intensity of the fluorescence. For TMAP, on the other hand, the different type and nature of the positive charge resulting in the development of the CT band arise from the interaction with the surface of ZnO NPs. This observation is confirmed by the femtosecond transient absorption spectroscopy, which provides clear spectroscopic signatures of photoinduced electron transfer from TMAP to ZnO NPs. © 2014 American Chemical Society.
    Citation
    Aly, S. M. B., Eita, M., Khan, J. I., Alarousu, E., & Mohammed, O. F. (2014). Remarkable Fluorescence Enhancement versus Complex Formation of Cationic Porphyrins on the Surface of ZnO Nanoparticles. The Journal of Physical Chemistry C, 118(23), 12154–12161. doi:10.1021/jp5030075
    Sponsors
    S.M.B.A. is grateful for the postdoctoral fellowship provided by Saudi Basic Industries Corporation (SABIC). The research reported in this publication was supported by the King Abdullah University of Science and Technology.
    Publisher
    American Chemical Society (ACS)
    Journal
    The Journal of Physical Chemistry C
    DOI
    10.1021/jp5030075
    ae974a485f413a2113503eed53cd6c53
    10.1021/jp5030075
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Solar Center (KSC)

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