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 and Miguel FUENTES-CABRERA

Basic information

Original name

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

Name in Czech

Prebioticka synteza nukleobazi zalozena na formamidu: Kineticky dostupna reakcni draha

Authors

ŠPONEROVÁ, Judit (348 Hungary, belonging to the institution), Arnošt MLÁDEK (203 Czech Republic), Jiří ŠPONER (203 Czech Republic, guarantor, belonging to the institution) and Miguel FUENTES-CABRERA (724 Spain)

Edition

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

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10403 Physical chemistry

Country of publisher

United States of America

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

Impact factor

Impact factor: 2.771

RIV identification code

RIV/00216224:14740/12:00057255

Organization unit

Central European Institute of Technology

DOI

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

UT WoS

000298978000076

Keywords in English

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

Abstract

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.

Links

ED1.1.00/02.0068, research and development project

Name: CEITEC - central european institute of technology

GD203/09/H046, research and development project

Name: Biochemie na rozcestí mezi in silico a in vitro

Investor: Czech Science Foundation

LC06030, research and development project

Name: Biomolekulární centrum

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

Citovat

ŠPONEROVÁ, Judit, Arnošt MLÁDEK, Jiří ŠPONER and 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, vol. 116, No 1, p. 720-726. ISSN 1089-5639. Available from: 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 and 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, vol.~116, No~1, p.~720-726. ISSN~1089-5639. Available from: https://dx.doi.org/10.1021/jp209886b.

Detailed Information on Publication Record