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.

Basic information

Original name

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

Authors

JANOŠ, Jiří, Dominik MADEA (203 Czech Republic, belonging to the institution), Sadegh MAHVIDI (364 Islamic Republic of Iran, belonging to the institution), Taufiqueahmed Pirsah MUJAWAR (356 India, belonging to the institution), Jakub ŠVENDA (203 Czech Republic, belonging to the institution), Jiří SUCHAN, Petr SLAVÍČEK (203 Czech Republic) and Petr KLÁN (203 Czech Republic, guarantor, belonging to the institution)

Edition

Journal of Physical Chemistry, Washington, D.C. American Chemical Society, 2020, 1089-5639

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10400 1.4 Chemical sciences

Country of publisher

United States of America

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

Impact factor

Impact factor: 2.781

RIV identification code

RIV/00216224:14310/20:00117372

Organization unit

Faculty of Science

DOI

http://dx.doi.org/10.1021/acs.jpca.0c08945

UT WoS

000608855900006

Keywords in English

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

Abstract

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.

Links

EF17_043/0009632, research and development project

Name: CETOCOEN Excellence

LM2015063, research and development project

Name: Národní infrastruktura chemické biologie (Acronym: CZ-OPENSCREEN)

Investor: Ministry of Education, Youth and Sports of the CR

LM2018121, research and development project

Name: Výzkumná infrastruktura RECETOX (Acronym: RECETOX RI)

Investor: Ministry of Education, Youth and Sports of the CR, RECETOX RI

LM2018140, research and development project

Name: e-Infrastruktura CZ (Acronym: e-INFRA CZ)

Investor: Ministry of Education, Youth and Sports of the CR

NV18-07-00342, research and development project

Name: Studium degradačních produktů bilirubinu vznikajících při fototerapii novorozenecké žloutenky

Investor: Ministry of Health of the CR

Citovat

JANOŠ, Jiří, Dominik MADEA, Sadegh MAHVIDI, Taufiqueahmed Pirsah MUJAWAR, Jakub ŠVENDA, Jiří SUCHAN, Petr SLAVÍČEK and 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, vol. 124, No 50, p. 10457-10471. ISSN 1089-5639. Available from: https://dx.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 = {http://dx.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 and 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, vol.~124, No~50, p.~10457-10471. ISSN~1089-5639. Available from: https://dx.doi.org/10.1021/acs.jpca.0c08945.

Detailed Information on Publication Record