Nonradiative Relaxation Mechanisms of UV Excited Phenylalanine Residues: A Comparative Computational Study
The present work is directed toward understanding the mechanisms of excited state deactivation in three neutral model peptides containing the phenylalanine residue. The excited state dynamics of theγL(g+)folded form of N-acetylphenylalaninylamide (NAPA B) and its amide-N-methylated derivative (NAPMA...
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| Format: | Article |
| Language: | English |
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MDPI AG
2017-03-01
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| Series: | Molecules |
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| Online Access: | http://www.mdpi.com/1420-3049/22/3/493 |
| _version_ | 1818914533793595392 |
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| author | Momir Mališ Nađa Došlić |
| author_facet | Momir Mališ Nađa Došlić |
| author_sort | Momir Mališ |
| collection | DOAJ |
| description | The present work is directed toward understanding the mechanisms of excited state deactivation in three neutral model peptides containing the phenylalanine residue. The excited state dynamics of theγL(g+)folded form of N-acetylphenylalaninylamide (NAPA B) and its amide-N-methylated derivative (NAPMA B) is reviewed and compared to the dynamics of the monohydrated structure of NAPA (NAPAH). The goal is to unravel how the environment, and in particular solvation, impacts the photodynamics of peptides. The systems are investigated using reaction path calculations and surface hopping nonadiabatic dynamics based on the coupled cluster doubles (CC2) method and time-dependent density functional theory. The work emphasizes the role that excitation transfer from the phenylππ*to amidenπ*state plays in the deactivation of the three systems and shows how the ease of out-of-plane distortions of the amide group determines the rate of population transfer between the two electronic states. The subsequent dynamics on thenπ*state is barrierless along several pathways and leads to fast deactivation to the ground electronic state. |
| first_indexed | 2024-12-19T23:47:54Z |
| format | Article |
| id | doaj.art-b88535913c594c07b29262697cc03a91 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-19T23:47:54Z |
| publishDate | 2017-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-b88535913c594c07b29262697cc03a912022-12-21T20:01:15ZengMDPI AGMolecules1420-30492017-03-0122349310.3390/molecules22030493molecules22030493Nonradiative Relaxation Mechanisms of UV Excited Phenylalanine Residues: A Comparative Computational StudyMomir Mališ0Nađa Došlić1Ruđer Bošković Institute, HR-10000 Zagreb, CroatiaRuđer Bošković Institute, HR-10000 Zagreb, CroatiaThe present work is directed toward understanding the mechanisms of excited state deactivation in three neutral model peptides containing the phenylalanine residue. The excited state dynamics of theγL(g+)folded form of N-acetylphenylalaninylamide (NAPA B) and its amide-N-methylated derivative (NAPMA B) is reviewed and compared to the dynamics of the monohydrated structure of NAPA (NAPAH). The goal is to unravel how the environment, and in particular solvation, impacts the photodynamics of peptides. The systems are investigated using reaction path calculations and surface hopping nonadiabatic dynamics based on the coupled cluster doubles (CC2) method and time-dependent density functional theory. The work emphasizes the role that excitation transfer from the phenylππ*to amidenπ*state plays in the deactivation of the three systems and shows how the ease of out-of-plane distortions of the amide group determines the rate of population transfer between the two electronic states. The subsequent dynamics on thenπ*state is barrierless along several pathways and leads to fast deactivation to the ground electronic state.http://www.mdpi.com/1420-3049/22/3/493nonadiabatic molecular dynamicsnonradiative deactivationpeptidephenylalanine |
| spellingShingle | Momir Mališ Nađa Došlić Nonradiative Relaxation Mechanisms of UV Excited Phenylalanine Residues: A Comparative Computational Study Molecules nonadiabatic molecular dynamics nonradiative deactivation peptide phenylalanine |
| title | Nonradiative Relaxation Mechanisms of UV Excited Phenylalanine Residues: A Comparative Computational Study |
| title_full | Nonradiative Relaxation Mechanisms of UV Excited Phenylalanine Residues: A Comparative Computational Study |
| title_fullStr | Nonradiative Relaxation Mechanisms of UV Excited Phenylalanine Residues: A Comparative Computational Study |
| title_full_unstemmed | Nonradiative Relaxation Mechanisms of UV Excited Phenylalanine Residues: A Comparative Computational Study |
| title_short | Nonradiative Relaxation Mechanisms of UV Excited Phenylalanine Residues: A Comparative Computational Study |
| title_sort | nonradiative relaxation mechanisms of uv excited phenylalanine residues a comparative computational study |
| topic | nonadiabatic molecular dynamics nonradiative deactivation peptide phenylalanine |
| url | http://www.mdpi.com/1420-3049/22/3/493 |
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