Conformational Control of the Photodynamics of a Bilirubin
Dipyrrinone Subunit: Femtosecond Spectroscopy Combined with
Nonadiabatic Simulations

J 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; Sadegh MAHVIDI; Taufiqueahmed Pirsah MUJAWAR; Jakub ŠVENDA; Jiří SUCHAN; Petr SLAVÍČEK a Petr KLÁN

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

URL

Impakt faktor

Impact factor: 2.781

Označené pro přenos do RIV

Ano

Kód RIV

RIV/00216224:14310/20:00117372

Organizační jednotka

Přírodovědecká fakulta

Klíčová slova anglicky

Quantum yield; Photoisomerization; Cyclization; Molecular structure; Excited states

Štítky

14313010, 143180, rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 2. 6. 2025 11:24, 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

Název: CETOCOEN Excellence

LM2015063, projekt VaV

Název: Národní infrastruktura chemické biologie (Akronym: CZ-OPENSCREEN)

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, CZ-OPENSCREEN: National Infrastructure for Chemical Biology

LM2018140, projekt VaV

Název: e-Infrastruktura CZ (Akronym: e-INFRA CZ)

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, e-Infrastruktura CZ

NV18-07-00342, projekt VaV

Název: Studium degradačních produktů bilirubinu vznikajících při fototerapii novorozenecké žloutenky

Investor: Ministerstvo zdravotnictví ČR, Studium degradačních produktů bilirubinu vznikajících při fototerapii novorozenecké žloutenky

90121, velká výzkumná infrastruktura

Název: RECETOX RI

Citovat

JANOŠ, Jiří; Dominik MADEA; Sadegh MAHVIDI; Taufiqueahmed Pirsah MUJAWAR; Jakub ŠVENDA; Jiří SUCHAN; Petr SLAVÍČEK a Petr KLÁN. Conformational Control of the Photodynamics of a Bilirubin Dipyrrinone Subunit: Femtosecond Spectroscopy Combined with Nonadiabatic Simulations. Journal of Physical Chemistry. Washington, D.C.: American Chemical Society, 2020, roč. 124, č. 50, s. 10457-10471. ISSN 1089-5639. Dostupné z: https://doi.org/10.1021/acs.jpca.0c08945.

@article{1710416,
   author = {Janoš, Jiří and Madea, Dominik and Mahvidi, Sadegh and Mujawar, Taufiqueahmed Pirsah and Švenda, Jakub and Suchan, Jiří and Slavíček, Petr and Klán, Petr},
   article_location = {Washington, D.C.},
   article_number = {50},
   doi = {https://doi.org/10.1021/acs.jpca.0c08945},
   keywords = {Quantum yield; Photoisomerization; Cyclization; Molecular structure; Excited states},
   language = {eng},
   issn = {1089-5639},
   journal = {Journal of Physical Chemistry},
   title = {Conformational Control of the Photodynamics of a Bilirubin Dipyrrinone Subunit: Femtosecond Spectroscopy Combined with Nonadiabatic Simulations},
   url = {https://doi.org/10.1021/acs.jpca.0c08945},
   volume = {124},
   year = {2020}
}

TY  - JOUR
ID  - 1710416
AU  - Janoš, Jiří - Madea, Dominik - Mahvidi, Sadegh - Mujawar, Taufiqueahmed Pirsah - Švenda, Jakub - Suchan, Jiří - Slavíček, Petr - Klán, Petr
PY  - 2020
TI  - Conformational Control of the Photodynamics of a Bilirubin Dipyrrinone Subunit: Femtosecond Spectroscopy Combined with Nonadiabatic Simulations
JF  - Journal of Physical Chemistry
VL  - 124
IS  - 50
SP  - 10457-10471
EP  - 10457-10471
PB  - American Chemical Society
SN  - 10895639
KW  - Quantum yield
KW  - Photoisomerization
KW  - Cyclization
KW  - Molecular structure
KW  - Excited states
UR  - https://doi.org/10.1021/acs.jpca.0c08945
L2  - https://doi.org/10.1021/acs.jpca.0c08945
N2  - 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.
ER  -

JANOŠ, Jiří; Dominik MADEA; Sadegh MAHVIDI; Taufiqueahmed Pirsah MUJAWAR; Jakub ŠVENDA; Jiří SUCHAN; Petr SLAVÍČEK a Petr KLÁN. Conformational Control of the Photodynamics of a Bilirubin Dipyrrinone Subunit: Femtosecond Spectroscopy Combined with Nonadiabatic Simulations. \textit{Journal of Physical Chemistry}. Washington, D.C.: American Chemical Society, 2020, roč.~124, č.~50, s.~10457-10471. ISSN~1089-5639. Dostupné z: https://doi.org/10.1021/acs.jpca.0c08945.

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