Doctor of Philosophy, University of Akron, 2024, Chemistry
Organic sensors emitting in the near-infrared region (600-900 nm) are desirable for biological applications. Through the combination of different functional groups with Excited State Intramolecular Proton Transfer (ESIPT) segments, novel probes have been crafted to attain large Stokes shift, improved sensitivity, selectivity, and the ability to tune emission towards the NIR region. Chapter I summarizes recent progress in this field, by including the photophysical properties inherent in ESIPT dyes, and investigated the impact of structural and environmental factors to their fluorescence. Furthermore, the potential applications of these probes as imaging reagents are exemplified such as labeling intracellular membranes, mitochondria, lysosomes, and detecting biomolecules.
In Chapter II, four NIR-emitting ESIPT dyes, each featuring distinct cyanine terminal groups, were scrutinized to assess their fluorescence lifetime characteristics in the polar aprotic solvent. By using time–correlated single–photon counting (TCSPC) method, these ESIPT-based dyes revealed a two-component exponential decay in about 2-4 nanoseconds (ns) which was proved to exclusively from keto tautomer. The model compounds (1.10 and 2.2) as well as low-temperature fluorescence spectroscopy (at -189 ℃) identified intramolecular charge transfer (ICT) as a prominent factor influencing the lifetime values. ESIPT simplified lifetime components.
Chapter III includes ESIPT probes with benzoindolium terminal group, which shows large Stokes shift (Δλ≈250 nm) and good quantum yield. The probe also exhibited a minor absorption (~580 nm in DCM) and emission (∼ 610 nm in DCM), attributed to a zwitterionic structure formed through deprotonation of phenolic proton. Fluorescence confocal microscopy investigations highlighted the probe's excellent selectivity for mitochondria, and unusually strong emission in the 595 nm channel rather than the expected 700 nm channel. The study thus illustrated a reaction-based pro (open full item for complete abstract)
Committee: Yi Pang (Advisor); Christopher Ziegler (Committee Member); Chrys Wesdemiotis (Committee Member); Chunming Liu (Committee Member); Tianbo Liu (Committee Member)
Subjects: Analytical Chemistry; Biochemistry; Chemistry; Organic Chemistry; Physical Chemistry