2020
Conformational Control of the Photodynamics of a Bilirubin Dipyrrinone Subunit: Femtosecond Spectroscopy Combined with Nonadiabatic Simulations
JANOŠ, Jiří, Dominik MADEA, Sadegh MAHVIDI, Taufiqueahmed Pirsah MUJAWAR, Jakub ŠVENDA et. al.Základní údaje
Originální název
Conformational Control of the Photodynamics of a Bilirubin Dipyrrinone Subunit: Femtosecond Spectroscopy Combined with Nonadiabatic Simulations
Autoři
JANOŠ, Jiří, Dominik MADEA (203 Česká republika, domácí), Sadegh MAHVIDI (364 Írán, domácí), Taufiqueahmed Pirsah MUJAWAR (356 Indie, domácí), Jakub ŠVENDA (203 Česká republika, domácí), Jiří SUCHAN, Petr SLAVÍČEK (203 Česká republika) a Petr KLÁN (203 Česká republika, garant, domácí)
Vydání
Journal of Physical Chemistry, Washington, D.C. American Chemical Society, 2020, 1089-5639
Další údaje
Jazyk
angličtina
Typ výsledku
Článek v odborném periodiku
Obor
10400 1.4 Chemical sciences
Stát vydavatele
Spojené státy
Utajení
není předmětem státního či obchodního tajemství
Odkazy
Impakt faktor
Impact factor: 2.781
Kód RIV
RIV/00216224:14310/20:00117372
Organizační jednotka
Přírodovědecká fakulta
UT WoS
000608855900006
Klíčová slova anglicky
Quantum yield; Photoisomerization; Cyclization; Molecular structure; Excited states
Štítky
Příznaky
Mezinárodní význam, Recenzováno
Změněno: 17. 2. 2023 21:12, Mgr. Michaela Hylsová, Ph.D.
Anotace
V originále
The photochemistry of bilirubin has been extensively studied due to its importance in the phototherapy of hyperbilirubinemia. In the present work, we investigated the ultrafast photodynamics of a bilirubin dipyrrinone subunit, vinylneoxanthobilirubic acid methyl ester. The photoisomerization and photocyclization reactions of its (E) and (Z) isomers were studied using femtosecond transient absorption spectroscopy and by multireference electronic structure theory, where the nonadiabatic dynamics was modeled with a Landau–Zener surface hopping technique. The following picture has emerged from the combined theoretical and experimental approach. Upon excitation, dipyrrinone undergoes a very fast vibrational relaxation, followed by an internal conversion on a picosecond time scale. The internal conversion leads either to photoisomerization or regeneration of the starting material. Further relaxation dynamics on the order of tens of picoseconds was observed in the ground state. The nonadiabatic simulations revealed a strong conformational control of the photodynamics. The ultrafast formation of a cyclic photochemical product from a less-populated conformer of the studied subunit was predicted by our calculations. We discuss the relevance of the present finding for the photochemistry of native bilirubin. The work has also pointed to the limits of semiclassical nonadiabatic simulations for simulating longer photochemical processes, probably due to the zero-point leakage issue.
Návaznosti
EF17_043/0009632, projekt VaV |
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LM2015063, projekt VaV |
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LM2018121, projekt VaV |
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LM2018140, projekt VaV |
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NV18-07-00342, projekt VaV |
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