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@article{1299543,
author = {Šponerová, Judit and Šponer, Jiří and Giorgi, Alessandra and Di Mauro, Ernesto and Pino, Samanta and Costanzo, Giovanna},
article_location = {WASHINGTON},
article_number = {7},
doi = {http://dx.doi.org/10.1021/acs.jpcb.5b00601},
keywords = {GAUSSIAN-BASIS SETS; PREBIOTIC CHEMISTRY; RNA WORLD; ATOMS LI; ORIGIN; MODEL; ENERGIES; GMP; MONTMORILLONITE; STABILITY},
language = {eng},
issn = {1520-6106},
journal = {Journal of Physical Chemistry B},
title = {Untemplated Nonenzymatic Polymerization of 3 ',5 ' cGMP: A Plausible Route to 3 ',5 '-Linked Oligonucleotides in Primordia},
url = {http://pubs.acs.org/doi/pdf/10.1021/acs.jpcb.5b00601},
volume = {119},
year = {2015}
}
TY - JOUR
ID - 1299543
AU - Šponerová, Judit - Šponer, Jiří - Giorgi, Alessandra - Di Mauro, Ernesto - Pino, Samanta - Costanzo, Giovanna
PY - 2015
TI - Untemplated Nonenzymatic Polymerization of 3 ',5 ' cGMP: A Plausible Route to 3 ',5 '-Linked Oligonucleotides in Primordia
JF - Journal of Physical Chemistry B
VL - 119
IS - 7
SP - 2979-2989
EP - 2979-2989
PB - AMER CHEMICAL SOC
SN - 15206106
KW - GAUSSIAN-BASIS SETS
KW - PREBIOTIC CHEMISTRY
KW - RNA WORLD
KW - ATOMS LI
KW - ORIGIN
KW - MODEL
KW - ENERGIES
KW - GMP
KW - MONTMORILLONITE
KW - STABILITY
UR - http://pubs.acs.org/doi/pdf/10.1021/acs.jpcb.5b00601
L2 - http://pubs.acs.org/doi/pdf/10.1021/acs.jpcb.5b00601
N2 - The high-energy 3',5' phosphodiester linkages conserved in 3',5' cyclic GMPs offer a genuine solution for monomer activation required by the transphosphorylation reactions that could lead to the emergence of the first simple oligonucleotide sequences on the early Earth. In this work we provide an in-depth characterization of the effect of the reaction conditions on the yield of the polymerization reaction of 3',5' cyclic GMPs both in aqueous environment as well as under dehydrating conditions. We show that the threshold temperature of the polymerization is about 30 degrees C lower under dehydrating conditions than in solution. In addition, we present a plausible exergonic reaction pathway for the polymerization reaction, which involves transient formation of anionic centers at the O3' positions of the participating riboses. We suggest that excess Na+ cations inhibit the polymerization reaction because they block the anionic mechanism via neutralizing the negatively charged O3'. Our experimental findings are compatible with a prebiotic scenario, where gradual desiccation of the environment could induce polymerization of 3',5' cyclic GMPs synthesized in liquid.
ER -
ŠPONEROVÁ, Judit, Jiří ŠPONER, Alessandra GIORGI, Ernesto DI MAURO, Samanta PINO a Giovanna COSTANZO. Untemplated Nonenzymatic Polymerization of 3 ',5 ' cGMP: A Plausible Route to 3 ',5 '-Linked Oligonucleotides in Primordia. \textit{Journal of Physical Chemistry B}. WASHINGTON: AMER CHEMICAL SOC, roč.~119, č.~7, s.~2979-2989. ISSN~1520-6106. doi:10.1021/acs.jpcb.5b00601. 2015.
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