Kinetic Barriers and the Self‐organization of Life

Pascal, Robert

doi:10.1002/ijch.201400193

Cited by 23 publications

(21 citation statements)

References 72 publications

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“…Their early role in chemical evolution could therefore have been to act as aminoacylating agents rather than as activated precursors of peptides. The possibility of an intramolecular transfer of the aminoacyl moiety from adenylate anhydrides to the 3′-hydroxyl group is an additional example of the importance of intramolecular reactions in a prebiotic context and of induced intramolecularity for the emergence of catalysis (Pascal 2003 , 2015 ).…”

Section: Resultsmentioning

confidence: 99%

The Chemical Likelihood of Ribonucleotide-α-Amino acid Copolymers as Players for Early Stages of Evolution

et al. 2019

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How ribosomal translation could have evolved remains an open question in most available scenarios for the early developments of life. Rather than considering RNA and peptides as two independent systems, this work is aimed at assessing the possibility of formation and stability of co-polymers or co-oligomers of α-amino acids and nucleotides from which translation might have evolved. Here we show that the linkages required to build such mixed structures have lifetimes of several weeks to months at neutral pH and 20 °C owing to the mutual protecting effect of both neighboring phosphoramidate and ester functional groups increasing their stability by factors of about 1 and 3 orders of magnitude, respectively. This protecting effect is reversible upon hydrolysis allowing the possibility of subsequent reactions. These copolymer models, for which an abiotic synthesis pathway is supported by experiments, form a basis from which both polymerization and translation could have logically evolved. Low temperatures were identified as a critical parameter for the kinetic stability of the aminoacylated nucleotide facilitating the synthesis of the model. This observation independently supports the views that any process involving RNA aminoacyl esters, outstandingly including the emergence of translation, was more probable at 0 °C or below and might be considered a kinetic marker constraining the environment in which translation has evolved. Electronic supplementary material The online version of this article (10.1007/s00239-019-9887-7) contains supplementary material, which is available to authorized users.

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Section: Resultsmentioning

confidence: 99%

The Chemical Likelihood of Ribonucleotide-α-Amino acid Copolymers as Players for Early Stages of Evolution

et al. 2019

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“…In fact the presence of kinetic barriers is actually a requirement for the system to be held far from equilibrium [43–44] so that life can only evolve from systems tightly bound, typically through covalent bonds [55–56]. Activated chemical species involved in these systems would not rapidly evolve at low temperature allowing the selection of efficient catalytic processes [50]. This observation therefore can explain the emergence of processes that lead to increased rates of transformation, and therefore energy dissipation.…”

Section: Resultsmentioning

confidence: 99%

How and why kinetics, thermodynamics, and chemistry induce the logic of biological evolution

Pross¹,

Pascal²

2017

Beilstein J. Org. Chem.

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Thermodynamic stability, as expressed by the Second Law, generally constitutes the driving force for chemical assembly processes. Yet, somehow, within the living world most self-organisation processes appear to challenge this fundamental rule. Even though the Second Law remains an inescapable constraint, under energy-fuelled, far-from-equilibrium conditions, populations of chemical systems capable of exponential growth can manifest another kind of stability, dynamic kinetic stability (DKS). It is this stability kind based on time/persistence, rather than on free energy, that offers a basis for understanding the evolutionary process. Furthermore, a threshold distance from equilibrium, leading to irreversibility in the reproduction cycle, is needed to switch the directive for evolution from thermodynamic to DKS. The present report develops these lines of thought and argues against the validity of a thermodynamic approach in which the maximisation of the rate of energy dissipation/entropy production is considered to direct the evolutionary process. More generally, our analysis reaffirms the predominant role of kinetics in the self-organisation of life, which, in turn, allows an assessment of semi-quantitative constraints on systems and environments from which life could evolve.

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“…It confirms the view that intramolecular pathways weree ssential in the absence of enzyme catalysts because they could divertc hemicalp rocesses from the regulardecay of reactants through kinetically efficient routes. [57,58]…”

Section: Resultsmentioning

confidence: 99%

Mixed Anhydride Intermediates in the Reaction of 5(4H)‐Oxazolones with Phosphate Esters and Nucleotides

Liu

Rigger

Rossi

et al. 2016

Chemistry A European J

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Abstract5(4H)‐Oxazolones can be formed through the activation of acylated α‐amino acids or of peptide C termini. They constitute potentially activated intermediates in the abiotic chemistry of peptides that preceded the origin of life or early stages of biology and are capable of yielding mixed carboxylic‐phosphoric anhydrides upon reaction with phosphate esters and nucleotides. Here, we present the results of a study aimed at investigating the chemistry that can be built through this interaction. As a matter of fact, the formation of mixed anhydrides with mononucleotides and nucleic acid models is shown to take place at positions involving a mono‐substituted phosphate group at the 3’‐ or 5’‐terminus but not at the internal phosphodiester linkages. In addition to the formation of mixed anhydrides, the subsequent intramolecular acyl or phosphoryl transfers taking place at the 3’‐terminus are considered to be particularly relevant to the common prebiotic chemistry of α‐amino acids and nucleotides.

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Kinetic Barriers and the Self‐organization of Life

Cited by 23 publications

References 72 publications

The Chemical Likelihood of Ribonucleotide-α-Amino acid Copolymers as Players for Early Stages of Evolution

The Chemical Likelihood of Ribonucleotide-α-Amino acid Copolymers as Players for Early Stages of Evolution

How and why kinetics, thermodynamics, and chemistry induce the logic of biological evolution

Mixed Anhydride Intermediates in the Reaction of 5(4H)‐Oxazolones with Phosphate Esters and Nucleotides

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