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Statements

Subject Item
n2:RIV%2F61388963%3A_____%2F13%3A00394881%21RIV14-AV0-61388963
rdf:type
skos:Concept n13:Vysledek
dcterms:description
Photoconversion of HCN tetramer into an imidazole derivative is one of the most likely routes for prebiotics. Although this reaction is known since the 1960’s, its photochemical intermediates have never been revealed. Using a combination of theoretical methods (excited and ground state reaction paths; QM/MM dynamics; RRKM chemical kinetics), it was shown that, among a number of different reaction pathways, only a specific sequence of steps is compatible with the experimental conditions. Multi-step mechanism for the DAMNAICN reaction that is thermodynamically and kinetically compatible with the available experimental data was identified. This mechanism rationalizes the observed ketenimine absorption and its disappearance upon heating as well as the preference for the trans isomer in the photostationary state. It is consistent with a cold environment that is required to support a high HCN concentration, and it is also consistent with the lack of luminescence during the reaction. Finally, from a more general perspective, the ultrafast energy dissipation revealed by simulations provides insight into the time scales that are relevant in photochemical prebiotic reactions. Photoconversion of HCN tetramer into an imidazole derivative is one of the most likely routes for prebiotics. Although this reaction is known since the 1960’s, its photochemical intermediates have never been revealed. Using a combination of theoretical methods (excited and ground state reaction paths; QM/MM dynamics; RRKM chemical kinetics), it was shown that, among a number of different reaction pathways, only a specific sequence of steps is compatible with the experimental conditions. Multi-step mechanism for the DAMNAICN reaction that is thermodynamically and kinetically compatible with the available experimental data was identified. This mechanism rationalizes the observed ketenimine absorption and its disappearance upon heating as well as the preference for the trans isomer in the photostationary state. It is consistent with a cold environment that is required to support a high HCN concentration, and it is also consistent with the lack of luminescence during the reaction. Finally, from a more general perspective, the ultrafast energy dissipation revealed by simulations provides insight into the time scales that are relevant in photochemical prebiotic reactions.
dcterms:title
Photochemical Steps in the Prebiotic Synthesis of Purine Precursors from HCN Photochemical Steps in the Prebiotic Synthesis of Purine Precursors from HCN
skos:prefLabel
Photochemical Steps in the Prebiotic Synthesis of Purine Precursors from HCN Photochemical Steps in the Prebiotic Synthesis of Purine Precursors from HCN
skos:notation
RIV/61388963:_____/13:00394881!RIV14-AV0-61388963
n13:predkladatel
n14:ico%3A61388963
n4:aktivita
n15:I
n4:aktivity
I
n4:cisloPeriodika
31
n4:dodaniDat
n10:2014
n4:domaciTvurceVysledku
n9:9831339
n4:druhVysledku
n11:J
n4:duvernostUdaju
n18:S
n4:entitaPredkladatele
n16:predkladatel
n4:idSjednocenehoVysledku
96084
n4:idVysledku
RIV/61388963:_____/13:00394881
n4:jazykVysledku
n12:eng
n4:klicovaSlova
computational chemistry; hydrogen cyanide chemistry; photochemistry; prebiotic synthesis; simulations
n4:klicoveSlovo
n5:hydrogen%20cyanide%20chemistry n5:simulations n5:computational%20chemistry n5:prebiotic%20synthesis n5:photochemistry
n4:kodStatuVydavatele
DE - Spolková republika Německo
n4:kontrolniKodProRIV
[09E5C8A9309F]
n4:nazevZdroje
Angewandte Chemie. International Edition in English
n4:obor
n8:CF
n4:pocetDomacichTvurcuVysledku
1
n4:pocetTvurcuVysledku
5
n4:rokUplatneniVysledku
n10:2013
n4:svazekPeriodika
52
n4:tvurceVysledku
Thiel, W. Anoop, A. Nachtigallová, Dana Barbatti, M. Boulanger, E.
n4:wos
000322126900024
s:issn
1433-7851
s:numberOfPages
4
n17:doi
10.1002/anie.201303246