Ultrafast excited state decay of natural UV filters: From intermolecular hydrogen bonds to a conical intersection

Peter S. Sherin, Yuri P. Tsentalovich, Eric Vauthey, Enrico Benassi

Research output: Contribution to journalArticle

Abstract

Kynurenines (KNs) are natural UV filters of the human eye lens, protecting the eye tissues from solar UV radiation. Key points of their effective protection are the intramolecular charge transfer (ICT) in the excited state and the fast dissipation of absorbed light energy into heat via the intermolecular H-bonds. Herein we report that the introduction of an unsaturated double bond in the amino acid side chain, operating as an ICT-enhancing electron donor group, drastically accelerates the internal conversion (IC) due to a conical intersection (CI) between the potential energy surfaces of the excited and ground states. Our photophysical study of a deaminated KN (carboxyketoalkene, CKA), an intrinsic product of KN thermal decomposition, demonstrates an unusually fast excited state decay in a broad range of solvents of different polarity and proticity. The detailed analysis of interactions in the excited state by different computational techniques revealed that the changes in molecular structure-the twist of the carbonyl group from the plane of the aromatic ring followed by the formation of two mutually orthogonal conjugated substructures-are responsible for the CI of the excited and ground state potential energy surfaces. Intermolecular H-bonds facilitate the transition to the CI, but do not play a crucial role in the fast decay of the excited state. An extremely fast and efficient IC in CKA opens the way for the design of new types of organic UV filters and their applications in material science, cosmetics and medicine.

Original languageEnglish
Pages (from-to)15074-15085
Number of pages12
JournalPhysical Chemistry Chemical Physics
Volume20
Issue number22
DOIs
Publication statusPublished - 1 Jan 2018
Externally publishedYes

Fingerprint

Excited states
intersections
Hydrogen bonds
hydrogen bonds
Kynurenine
filters
decay
excitation
Potential energy surfaces
internal conversion
Ground state
Charge transfer
potential energy
charge transfer
ground state
Cosmetics
Materials science
materials science
Solar radiation
substructures

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Ultrafast excited state decay of natural UV filters : From intermolecular hydrogen bonds to a conical intersection. / Sherin, Peter S.; Tsentalovich, Yuri P.; Vauthey, Eric; Benassi, Enrico.

In: Physical Chemistry Chemical Physics, Vol. 20, No. 22, 01.01.2018, p. 15074-15085.

Research output: Contribution to journalArticle

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