10.1021/acsomega.8b02761.s001
Reem H. Alzard
Reem H.
Alzard
Muna S. Bufaroosha
Muna S.
Bufaroosha
Noura Al-Shamsi
Noura
Al-Shamsi
Amir Sohail
Amir
Sohail
Naji Al-Dubaili
Naji
Al-Dubaili
Alaa A. Salem
Alaa A.
Salem
Ibrahim M. Abdou
Ibrahim M.
Abdou
Na’il Saleh
Na’il
Saleh
Solubilization of Pyridone-Based Fluorescent Tag by
Complexation in Cucurbit[7]uril
American Chemical Society
2019
UV
enol form
Time-resolved fluorescence results
CB 7 host
time-resolved fluorescence spectra
keto form
CB 7 complexes
TFP
2019-01-10 19:36:07
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Solubilization_of_Pyridone-Based_Fluorescent_Tag_by_Complexation_in_Cucurbit_7_uril/7575338
Aimed
at further exploring the hosting properties of cucurbit[7]uril
(CB7), we have exploited the spectroscopic and photophysical properties
of a known fluorescent label as the guest molecule, namely, 3-cyano-6-(2-thienyl)-4-trifluoromethyl
pyridine (TFP), in neat solvents. The formation of an inclusion host–guest
complex with CB7 was checked by UV–vis absorption spectroscopy,
and the value of binding constant (9.7 × 10<sup>5</sup> M<sup>–1</sup>) was extracted from the spectrophotometric data.
The modulation of keto–enol equilibrium in TFP by the local
environment is governed by the interplay between dimerization through
intermolecular hydrogen bonding between individual solute molecules,
favoring the enol form, and intermolecular hydrogen bonding between
TFP and the surrounding solvents, favoring the keto form. Time-resolved
fluorescence results established that the macromolecular CB7 host
stabilizes preferentially the neutral enol form over the keto form
of TFP. Unprecedentedly, our results reveal a linear dependence of
the amplitudes of the extracted decay-associated spectra from the
time-resolved fluorescence spectra of TFP on the sum of polarity/polarizability
and hydrogen bonding parameters of the local environment, confirming
that TFP at micromolar concentration in the CB7 complexes is experiencing
a methanol-like environment. The results rationalized the 42-fold
enhancement in the solubility of TFP in water media by complexation
in CB7.