title: Modulation of the Excited-State Dynamics of 2,2'-Bipyridine-3,3'-diol in Crown Ethers: A Possible Way To Control the Morphology of a Glycine Fibril through Fluorescence Lifetime Imaging Microscopy.
abstract: In this article, we have investigated the modulation of excited-state intramolecular double proton transfer (ESIDPT) dynamics of 2,2'-bipyridine-3,3'-diol (BP(OH)2) in two crown ethers (CEs), namely, 18-Crown-6 (18C6) and 15-Crown-5 (15C5). From steady-state UV-visible measurements, we have shown that there is no significant interaction between the dienol tautomeric form of BP(OH)2and two CEs. However, in the presence of CEs, an additional emission band (∼415 nm) is generated along with the diketo tautomer band (∼465 nm). In time-resolved analysis, we have observed the generation of ∼260 ps rise component in the presence of 18C6. Therefore, by combining the results of steady-state and time-resolved emissions, we have proposed that the water-assisted ESIDPT route of BP(OH)2generates a hydronium ion (H3O+) in the excited state. 18C6 binds nicely to this H3O+ion. As a result, retarded ESIDPT dynamics is observed in 18C6. However, as 15C5 cannot bind H3O+properly, no rise component is found. With the addition of potassium chloride (KCl), the contribution of the rise component decreases due to unavailability of free 18C6 cavity to capture the H3O+ion generated in the excited state. Addition of calcium chloride (CaCl2) leads to complete removal of the rise component due to the inhibition of the water-assisted ESIDPT route. From wavelength-dependent behavior, we have observed that the rise component is present only at 465 nm in 18C6. We have also shown that the fibrillar morphology of glycine can be successfully probed through fluorescence lifetime imaging microscopy using BP(OH)2as an imaging agent. Modulation of fibrillar morphology has been found in the presence of two CEs. The interaction of glycine fiber with CEs can be explained by lifetime distribution analysis.
authors.affiliation: Department of Chemistry, Indian Institute of Technology , Kharagpur 721302, West Bengal, India.
authors.forename: Debasis
authors.initials: D
authors.lastname: Banik
authors.affiliation: Department of Chemistry, Indian Institute of Technology , Kharagpur 721302, West Bengal, India.
authors.forename: Arpita
authors.initials: A
authors.lastname: Roy
authors.affiliation: Department of Chemistry, Indian Institute of Technology , Kharagpur 721302, West Bengal, India.
authors.forename: Niloy
authors.initials: N
authors.lastname: Kundu
authors.affiliation: Department of Chemistry, Indian Institute of Technology , Kharagpur 721302, West Bengal, India.
authors.forename: Nilmoni
authors.initials: N
authors.lastname: Sarkar