Role of chiral configuration in the photoinduced interaction of d-and l-tryptophan with optical isomers of ketoprofen in linked systems

Aleksandra A. Ageeva, Ilya M. Magin, Alexander B. Doktorov, Victor F. Plyusnin, Polina S. Kuznetsova, Alexander A. Stepanov, Alexander A. Alekseev, Nikolay E. Polyakov, Tatyana V. Leshina

Research output: Contribution to journalArticlepeer-review

Abstract

The study of the L-and D-amino acid properties in proteins and peptides has attracted considerable attention in recent years, as the replacement of even one L-amino acid by its D-analogue due to aging of the body is resulted in a number of pathological conditions, including Alzheimer’s and Parkinson’s diseases. A recent trend is using short model systems to study the peculiarities of proteins with D-amino acids. In this report, the comparison of the excited states quenching of Land D-tryptophan (Trp) in a model donor–acceptor dyad with (R)-and (S)-ketoprofen (KP-Trp) was carried out by photochemically induced dynamic nuclear polarization (CIDNP) and fluorescence spectroscopy. Quenching of the Trp excited states, which occurs via two mechanisms: prevailing resonance energy transfer (RET) and electron transfer (ET), indeed demonstrates some peculiarities for all three studied configurations of the dyad: (R,S)-, (S,R)-, and (S,S)-. Thus, the ET efficiency is identical for (S,R)-and (R,S)-enantiomers, while RET differs by 1.6 times. For (S,S)-, the CIDNP coefficient is almost an order of magnitude greater than for (R,S)-and (S,R)-. To understand the source of this difference, hyperpolarization of (S,S)-and (R,S)-has been calculated using theory involving the electron dipole–dipole interaction in the secular equation.

Original languageEnglish
Article number6198
JournalInternational Journal of Molecular Sciences
Volume22
Issue number12
DOIs
Publication statusPublished - 2 Jun 2021

Keywords

  • Chiral linked systems
  • Diastereomers
  • Electron transfer
  • Enantiomers
  • Magnetic dipole–dipole interaction of electrons
  • Resonance energy transfer
  • Stereoisomerism
  • Ketoprofen/chemistry
  • Tryptophan/chemistry
  • Molecular Structure
  • Energy Transfer
  • Photochemistry

OECD FOS+WOS

  • 1.06.CQ BIOCHEMISTRY & MOLECULAR BIOLOGY
  • 2.04 CHEMICAL ENGINEERING
  • 1.04 CHEMICAL SCIENCES
  • 1.06 BIOLOGICAL SCIENCES

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