Formamide-Based Prebiotic Synthesis of Nucleobases: A
Kinetically Accessible Reaction Route

J 2012

Formamide-Based Prebiotic Synthesis of Nucleobases: A Kinetically Accessible Reaction Route

ŠPONEROVÁ, Judit, Arnošt MLÁDEK, Jiří ŠPONER a Miguel FUENTES-CABRERA

Základní údaje

Originální název

Formamide-Based Prebiotic Synthesis of Nucleobases: A Kinetically Accessible Reaction Route

Název česky

Prebioticka synteza nukleobazi zalozena na formamidu: Kineticky dostupna reakcni draha

Autoři

ŠPONEROVÁ, Judit (348 Maďarsko, domácí), Arnošt MLÁDEK (203 Česká republika), Jiří ŠPONER (203 Česká republika, garant, domácí) a Miguel FUENTES-CABRERA (724 Španělsko)

Vydání

The Journal of Physical Chemistry A, Washington, American Chemical Society, 2012, 1089-5639

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10403 Physical chemistry

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

URL

Impakt faktor

Impact factor: 2.771

Kód RIV

RIV/00216224:14740/12:00057255

Organizační jednotka

Středoevropský technologický institut

DOI

http://dx.doi.org/10.1021/jp209886b

UT WoS

000298978000076

Klíčová slova anglicky

CHEMICAL EVOLUTION; HYDROGEN-CYANIDE; PRIMITIVE EARTH; RING FORMATION; ADENINE; ORIGIN; PURINE; MECHANISM; ENERGIES; WATER

Štítky

ok, rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 7. 4. 2013 13:11, Olga Křížová

Anotace

V originále

Synthesis of nucleobases in nonaqueous environments is an alternative way for the emergence of terrestrial life, which could solve the fundamental problem connected to the hydrolytic instability of nucleic acid components in an aqueous environment. In this contribution, we present a plausible reaction route for the prebiotic synthesis of nucleobases in formamide, which does not require participation of the formamide trimer and aminoimidazole-carbonitrile intermediates. The computed activation energy of the proposed pathway is noticeably higher than that of the HCN-based synthetic route, but it is still feasible under the experimental conditions of the Saladino synthesis. We show that, albeit both the pyrimidine and purine ring formation utilizes the undissociated form of formamide, the dehydration product of formamide, HCN, may also play a key role in the mechanism. The rate determining step of the entire reaction path is the cyclization of the diaza-pentanimine precursor. The subsequent formation of the imidazole ring proceeds with a moderate activation energy. Our calculations thus demonstrate that the experimentally suggested reaction path without the involvement of aminoimidazole-carbonitrile intermediates is also a viable alternative for the nonaqueous synthesis of nucleobases.

Návaznosti

ED1.1.00/02.0068, projekt VaV

Název: CEITEC - central european institute of technology

GD203/09/H046, projekt VaV

Název: Biochemie na rozcestí mezi in silico a in vitro

Investor: Grantová agentura ČR, Biochemie na rozcestí mezi in silico a in vitro

LC06030, projekt VaV

Název: Biomolekulární centrum

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, Biomolekulární centrum

Citovat

ŠPONEROVÁ, Judit, Arnošt MLÁDEK, Jiří ŠPONER a Miguel FUENTES-CABRERA. Formamide-Based Prebiotic Synthesis of Nucleobases: A Kinetically Accessible Reaction Route. The Journal of Physical Chemistry A. Washington: American Chemical Society, 2012, roč. 116, č. 1, s. 720-726. ISSN 1089-5639. Dostupné z: https://dx.doi.org/10.1021/jp209886b.

@article{969344,
   author = {Šponerová, Judit and Mládek, Arnošt and Šponer, Jiří and FuentesandCabrera, Miguel},
   article_location = {Washington},
   article_number = {1},
   doi = {http://dx.doi.org/10.1021/jp209886b},
   keywords = {CHEMICAL EVOLUTION; HYDROGEN-CYANIDE; PRIMITIVE EARTH; RING FORMATION; ADENINE; ORIGIN; PURINE; MECHANISM; ENERGIES; WATER},
   language = {eng},
   issn = {1089-5639},
   journal = {The Journal of Physical Chemistry A},
   title = {Formamide-Based Prebiotic Synthesis of Nucleobases: A Kinetically Accessible Reaction Route},
   url = {http://pubs.acs.org/doi/full/10.1021/jp209886b},
   volume = {116},
   year = {2012}
}

TY  - JOUR
ID  - 969344
AU  - Šponerová, Judit - Mládek, Arnošt - Šponer, Jiří - Fuentes-Cabrera, Miguel
PY  - 2012
TI  - Formamide-Based Prebiotic Synthesis of Nucleobases: A Kinetically Accessible Reaction Route
JF  - The Journal of Physical Chemistry A
VL  - 116
IS  - 1
SP  - 720-726
EP  - 720-726
PB  - American Chemical Society
SN  - 10895639
KW  - CHEMICAL EVOLUTION
KW  - HYDROGEN-CYANIDE
KW  - PRIMITIVE EARTH
KW  - RING FORMATION
KW  - ADENINE
KW  - ORIGIN
KW  - PURINE
KW  - MECHANISM
KW  - ENERGIES
KW  - WATER
UR  - http://pubs.acs.org/doi/full/10.1021/jp209886b
L2  - http://pubs.acs.org/doi/full/10.1021/jp209886b
N2  - Synthesis of nucleobases in nonaqueous environments is an alternative way for the emergence of terrestrial life, which could solve the fundamental problem connected to the hydrolytic instability of nucleic acid components in an aqueous environment. In this contribution, we present a plausible reaction route for the prebiotic synthesis of nucleobases in formamide, which does not require participation of the formamide trimer and aminoimidazole-carbonitrile intermediates. The computed activation energy of the proposed pathway is noticeably higher than that of the HCN-based synthetic route, but it is still feasible under the experimental conditions of the Saladino synthesis. We show that, albeit both the pyrimidine and purine ring formation utilizes the undissociated form of formamide, the dehydration product of formamide, HCN, may also play a key role in the mechanism. The rate determining step of the entire reaction path is the cyclization of the diaza-pentanimine precursor. The subsequent formation of the imidazole ring proceeds with a moderate activation energy. Our calculations thus demonstrate that the experimentally suggested reaction path without the involvement of aminoimidazole-carbonitrile intermediates is also a viable alternative for the nonaqueous synthesis of nucleobases.
ER  -

ŠPONEROVÁ, Judit, Arnošt MLÁDEK, Jiří ŠPONER a Miguel FUENTES-CABRERA. Formamide-Based Prebiotic Synthesis of Nucleobases: A Kinetically Accessible Reaction Route. \textit{The Journal of Physical Chemistry A}. Washington: American Chemical Society, 2012, roč.~116, č.~1, s.~720-726. ISSN~1089-5639. Dostupné z: https://dx.doi.org/10.1021/jp209886b.

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