Dual relaxation channel in thioflavin-T: An ultrafast spectroscopic study

Puspal Mukherjee, Shahnawaz Rafiq, Pratik Sen

Research output: Contribution to journalArticlepeer-review

12 Scopus citations

Abstract

In the present contribution, the ultrafast excited state dynamics of thioflavin T (ThT) has been investigated in methanol and chloroform. The first hand data of 30 times higher fluorescence quantum yield and observation of slow rise time in fluorescence intensity of ThT in chloroform compared to methanol indicate the complicated photophysics of the molecule. Time resolved fluorescence data along with temperature dependence on fluorescence quantum yield, TD-DFT calculations and femtosecond transient absorption study vividly suggest the involvement of one more twisted intramolecular charge transfer state (TICT-2) along with the TICT-1 state, in the excited state manifold of ThT, which was not identified earlier. It was also established that the depletion of the molecule from the locally excited state to the TICT-1 state probably barrierless in nature, however, an inherent activation energy barrier is present between LE and TICT-2 states. This activation energy barrier in methanol (0.59 kcal mol-1) was found to be exactly same as that available at room temperature, whereas the same in chloroform is found to be quite high (1.58 kcal mol-1). This barrier is proposed to be responsible for the high quantum yield of ThT in chlorinated solvents and we demand a revisit to the mechanism of fibril sensing by ThT.

Original languageEnglish
Pages (from-to)136-147
Number of pages12
JournalJournal of Photochemistry and Photobiology A: Chemistry
Volume328
DOIs
StatePublished - Sep 1 2016

Bibliographical note

Publisher Copyright:
© 2016 Elsevier B.V.

Keywords

  • Excited state relaxation dynamics
  • Femtosecond time resolved fluorescence
  • Femtosecond transient absorption
  • Thioflavin T
  • Twisted intramolecular charge transfer

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering
  • General Physics and Astronomy

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