Molecular Mechanism of Diaminomaleonitrile to
Diaminofumaronitrile Photoisomerization: An Intermediate Step
in the Prebiotic Formation of Purine Nucleobases

J 2014

Molecular Mechanism of Diaminomaleonitrile to Diaminofumaronitrile Photoisomerization: An Intermediate Step in the Prebiotic Formation of Purine Nucleobases

SZABLA, Rafal Kazimierz, Robert W. GÓRA, Jiří ŠPONER a Judit ŠPONEROVÁ

Základní údaje

Originální název

Molecular Mechanism of Diaminomaleonitrile to Diaminofumaronitrile Photoisomerization: An Intermediate Step in the Prebiotic Formation of Purine Nucleobases

Autoři

SZABLA, Rafal Kazimierz (616 Polsko), Robert W. GÓRA (616 Polsko), Jiří ŠPONER (203 Česká republika, garant, domácí) a Judit ŠPONEROVÁ (348 Maďarsko, domácí)

Vydání

Chemistry - A European Journal, Weinheim, WILEY- VCH VERLAG GMBH, 2014, 0947-6539

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10403 Physical chemistry

Stát vydavatele

Německo

Utajení

není předmětem státního či obchodního tajemství

Odkazy

URL

Impakt faktor

Impact factor: 5.731

Kód RIV

RIV/00216224:14740/14:00075641

Organizační jednotka

Středoevropský technologický institut

DOI

http://dx.doi.org/10.1002/chem.201304224

UT WoS

000331729700018

Klíčová slova anglicky

isomerization; nucleobases; nucleotides; photochemistry; quantum chemistry

Štítky

kontrola MP, MP, rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 10. 6. 2014 11:00, Martina Prášilová

Anotace

V originále

The photoinduced isomerization of diaminomaleonitrile (DAMN) to diaminofumaronitrile (DAFN) was suggested to play a key role in the prebiotically plausible formation of purine nucleobases and nucleotides. In this work we analyze two competitive photoisomerization mechanisms on the basis of state-of-the-art quantum-chemical calculations. Even though it was suggested that this process might occur on the triplet potential-energy surface, our results indicate that the singlet reaction channel should not be disregarded either. In fact, the peaked topography of the S-1/S-0 conical intersection suggests that the deexcitation should most likely occur on a sub-picosecond timescale and the singlet photoisomerization mechanism might effectively compete even with a very efficient intersystem crossing. Such a scenario is further supported by the relatively small spin-orbit coupling of the S-1 and T-2 states in the Franck-Condon region, which does not indicate a very effective triplet bypass for this photoreaction. Therefore, we conclude that the triplet reaction channel in DAMN might not be as prominent as was previously thought.

Návaznosti

ED1.1.00/02.0068, projekt VaV

Název: CEITEC - central european institute of technology

Citovat

SZABLA, Rafal Kazimierz, Robert W. GÓRA, Jiří ŠPONER a Judit ŠPONEROVÁ. Molecular Mechanism of Diaminomaleonitrile to Diaminofumaronitrile Photoisomerization: An Intermediate Step in the Prebiotic Formation of Purine Nucleobases. Chemistry - A European Journal. Weinheim: WILEY- VCH VERLAG GMBH, 2014, roč. 20, č. 9, s. 2515-2521. ISSN 0947-6539. Dostupné z: https://dx.doi.org/10.1002/chem.201304224.

@article{1184820,
   author = {Szabla, Rafal Kazimierz and Góra, Robert W. and Šponer, Jiří and Šponerová, Judit},
   article_location = {Weinheim},
   article_number = {9},
   doi = {http://dx.doi.org/10.1002/chem.201304224},
   keywords = {isomerization; nucleobases; nucleotides; photochemistry; quantum chemistry},
   language = {eng},
   issn = {0947-6539},
   journal = {Chemistry - A European Journal},
   title = {Molecular Mechanism of Diaminomaleonitrile to Diaminofumaronitrile Photoisomerization: An Intermediate Step in the Prebiotic Formation of Purine Nucleobases},
   url = {http://onlinelibrary.wiley.com/doi/10.1002/chem.201304224/pdf},
   volume = {20},
   year = {2014}
}

TY  - JOUR
ID  - 1184820
AU  - Szabla, Rafal Kazimierz - Góra, Robert W. - Šponer, Jiří - Šponerová, Judit
PY  - 2014
TI  - Molecular Mechanism of Diaminomaleonitrile to Diaminofumaronitrile Photoisomerization: An Intermediate Step in the Prebiotic Formation of Purine Nucleobases
JF  - Chemistry - A European Journal
VL  - 20
IS  - 9
SP  - 2515-2521
EP  - 2515-2521
PB  - WILEY- VCH VERLAG GMBH
SN  - 09476539
KW  - isomerization
KW  - nucleobases
KW  - nucleotides
KW  - photochemistry
KW  - quantum chemistry
UR  - http://onlinelibrary.wiley.com/doi/10.1002/chem.201304224/pdf
L2  - http://onlinelibrary.wiley.com/doi/10.1002/chem.201304224/pdf
N2  - The photoinduced isomerization of diaminomaleonitrile (DAMN) to diaminofumaronitrile (DAFN) was suggested to play a key role in the prebiotically plausible formation of purine nucleobases and nucleotides. In this work we analyze two competitive photoisomerization mechanisms on the basis of state-of-the-art quantum-chemical calculations. Even though it was suggested that this process might occur on the triplet potential-energy surface, our results indicate that the singlet reaction channel should not be disregarded either. In fact, the peaked topography of the S-1/S-0 conical intersection suggests that the deexcitation should most likely occur on a sub-picosecond timescale and the singlet photoisomerization mechanism might effectively compete even with a very efficient intersystem crossing. Such a scenario is further supported by the relatively small spin-orbit coupling of the S-1 and T-2 states in the Franck-Condon region, which does not indicate a very effective triplet bypass for this photoreaction. Therefore, we conclude that the triplet reaction channel in DAMN might not be as prominent as was previously thought.
ER  -

SZABLA, Rafal Kazimierz, Robert W. GÓRA, Jiří ŠPONER a Judit ŠPONEROVÁ. Molecular Mechanism of Diaminomaleonitrile to Diaminofumaronitrile Photoisomerization: An Intermediate Step in the Prebiotic Formation of Purine Nucleobases. \textit{Chemistry - A European Journal}. Weinheim: WILEY- VCH VERLAG GMBH, 2014, roč.~20, č.~9, s.~2515-2521. ISSN~0947-6539. Dostupné z: https://dx.doi.org/10.1002/chem.201304224.

Podrobný výpis o publikaci