Role of Chiral Configuration in the Photoinduced Interaction of D- and L-Tryptophan with Optical Isomers of Ketoprofen in Linked Systems
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 Parkinso...
| Main Authors: | , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2021-06-01
|
| Series: | International Journal of Molecular Sciences |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1422-0067/22/12/6198 |
| _version_ | 1797530914464464896 |
|---|---|
| author | 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 |
| author_facet | 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 |
| author_sort | Aleksandra A. Ageeva |
| collection | DOAJ |
| description | 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 L- and D-tryptophan (Trp) in a model donor–acceptor dyad with (<i>R</i>)- and (<i>S</i>)-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: (<i>R,S</i>)-, (<i>S,R</i>)-, and (<i>S,S</i>)-. Thus, the ET efficiency is identical for (<i>S,R</i>)- and (<i>R,S</i>)-enantiomers, while RET differs by 1.6 times. For (<i>S,S</i>)-, the CIDNP coefficient is almost an order of magnitude greater than for (<i>R,S</i>)- and (<i>S,R</i>)-. To understand the source of this difference, hyperpolarization of (<i>S,S</i>)-and (<i>R,S</i>)- has been calculated using theory involving the electron dipole–dipole interaction in the secular equation. |
| first_indexed | 2024-03-10T10:35:49Z |
| format | Article |
| id | doaj.art-1ac2438d68d04d8a93f2b3683eef70b1 |
| institution | Directory Open Access Journal |
| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-10T10:35:49Z |
| publishDate | 2021-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | International Journal of Molecular Sciences |
| spelling | doaj.art-1ac2438d68d04d8a93f2b3683eef70b12023-11-21T23:17:16ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672021-06-012212619810.3390/ijms22126198Role of Chiral Configuration in the Photoinduced Interaction of D- and L-Tryptophan with Optical Isomers of Ketoprofen in Linked SystemsAleksandra A. Ageeva0Ilya M. Magin1Alexander B. Doktorov2Victor F. Plyusnin3Polina S. Kuznetsova4Alexander A. Stepanov5Alexander A. Alekseev6Nikolay E. Polyakov7Tatyana V. Leshina8Voevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, RussiaVoevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, RussiaVoevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, RussiaVoevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, RussiaVoevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, RussiaVoevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, RussiaVoevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, RussiaVoevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, RussiaVoevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, RussiaThe 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 L- and D-tryptophan (Trp) in a model donor–acceptor dyad with (<i>R</i>)- and (<i>S</i>)-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: (<i>R,S</i>)-, (<i>S,R</i>)-, and (<i>S,S</i>)-. Thus, the ET efficiency is identical for (<i>S,R</i>)- and (<i>R,S</i>)-enantiomers, while RET differs by 1.6 times. For (<i>S,S</i>)-, the CIDNP coefficient is almost an order of magnitude greater than for (<i>R,S</i>)- and (<i>S,R</i>)-. To understand the source of this difference, hyperpolarization of (<i>S,S</i>)-and (<i>R,S</i>)- has been calculated using theory involving the electron dipole–dipole interaction in the secular equation.https://www.mdpi.com/1422-0067/22/12/6198chiral linked systemsdiastereomersenantiomerselectron transferresonance energy transfermagnetic dipole–dipole interaction of electrons |
| spellingShingle | 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 Role of Chiral Configuration in the Photoinduced Interaction of D- and L-Tryptophan with Optical Isomers of Ketoprofen in Linked Systems International Journal of Molecular Sciences chiral linked systems diastereomers enantiomers electron transfer resonance energy transfer magnetic dipole–dipole interaction of electrons |
| title | Role of Chiral Configuration in the Photoinduced Interaction of D- and L-Tryptophan with Optical Isomers of Ketoprofen in Linked Systems |
| title_full | Role of Chiral Configuration in the Photoinduced Interaction of D- and L-Tryptophan with Optical Isomers of Ketoprofen in Linked Systems |
| title_fullStr | Role of Chiral Configuration in the Photoinduced Interaction of D- and L-Tryptophan with Optical Isomers of Ketoprofen in Linked Systems |
| title_full_unstemmed | Role of Chiral Configuration in the Photoinduced Interaction of D- and L-Tryptophan with Optical Isomers of Ketoprofen in Linked Systems |
| title_short | Role of Chiral Configuration in the Photoinduced Interaction of D- and L-Tryptophan with Optical Isomers of Ketoprofen in Linked Systems |
| title_sort | role of chiral configuration in the photoinduced interaction of d and l tryptophan with optical isomers of ketoprofen in linked systems |
| topic | chiral linked systems diastereomers enantiomers electron transfer resonance energy transfer magnetic dipole–dipole interaction of electrons |
| url | https://www.mdpi.com/1422-0067/22/12/6198 |
| work_keys_str_mv | AT aleksandraaageeva roleofchiralconfigurationinthephotoinducedinteractionofdandltryptophanwithopticalisomersofketoprofeninlinkedsystems AT ilyammagin roleofchiralconfigurationinthephotoinducedinteractionofdandltryptophanwithopticalisomersofketoprofeninlinkedsystems AT alexanderbdoktorov roleofchiralconfigurationinthephotoinducedinteractionofdandltryptophanwithopticalisomersofketoprofeninlinkedsystems AT victorfplyusnin roleofchiralconfigurationinthephotoinducedinteractionofdandltryptophanwithopticalisomersofketoprofeninlinkedsystems AT polinaskuznetsova roleofchiralconfigurationinthephotoinducedinteractionofdandltryptophanwithopticalisomersofketoprofeninlinkedsystems AT alexanderastepanov roleofchiralconfigurationinthephotoinducedinteractionofdandltryptophanwithopticalisomersofketoprofeninlinkedsystems AT alexanderaalekseev roleofchiralconfigurationinthephotoinducedinteractionofdandltryptophanwithopticalisomersofketoprofeninlinkedsystems AT nikolayepolyakov roleofchiralconfigurationinthephotoinducedinteractionofdandltryptophanwithopticalisomersofketoprofeninlinkedsystems AT tatyanavleshina roleofchiralconfigurationinthephotoinducedinteractionofdandltryptophanwithopticalisomersofketoprofeninlinkedsystems |