Isotope effects at the origin of life: Fingerprints of the Strecker synthesis

Chimiak, Laura; Eiler, John M.; Sessions, Alex L.; Blumenfeld, C.; Klatte, M.; Stoltz, Brian M.

doi:10.1016/j.gca.2022.01.015

Cited by 6 publications

(6 citation statements)

References 45 publications

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“…1). In contrast to the 13 C-enrichment at the C-1 position noted for autotrophically synthesized alanine, alanine produced abiotically via Strecker synthesis is 13 C-depleted at the C-1 position [24] compared to its source carbon pool (cyanide in this case), suggesting that abiotic and biotic synthesis pathways impart distinct intramolecular signals that can be traced back to their source (Fig. 1).…”

Section: Tablementioning

confidence: 85%

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Analysis of intramolecular carbon isotope distributions in alanine by electrospray ionization Orbitrap mass spectrometry

Weiss,

Sessions,

Julien

et al. 2023

International Journal of Mass Spectrometry

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Section: Tablementioning

confidence: 85%

“…Ref. [24], and found on meteorites [18,25,26]. Their carbon skeletons collectively sample a broad swath of central metabolic pathways, providing excellent potential for reconstructing metabolisms.…”

Section: Introductionmentioning

confidence: 99%

Analysis of intramolecular carbon isotope distributions in alanine by electrospray ionization Orbitrap mass spectrometry

Weiss,

Sessions,

Julien

et al. 2023

International Journal of Mass Spectrometry

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“…While Strecker synthesis would produce a 15 N-enrichment relative to ammonia (Pizzarello et al, 1994;Pizzarello and Holmes, 2009;Elsila et al, 2012), these enrichments span a 100 ‰ range, which is above that which could be explained by the synthesis alone. The equilibrium between the amine and imine in Strecker synthesis has an equilibrium isotope effect that enriches the imine (i.e., the nitrogen that is inherited by amino acids) by 56 ‰ relative to the ammonia (Chimiak et al, 2022), so either there are multiple nitrogen sources or secondary chemistries must impact the final δ 15 N of amino acids to create the observed range. As the EIE between the α-aminonitrile's amine nitrogen and ammonia results in α-aminonitrile's amine nitrogen being 56 ‰ enriched in δ 15 N relative to ammonia, amino acids that react first will deplete the δ 15 N of the remaining ammonia by 10s of ‰, potentially leading to large variations in δ 15 N of products and ammonia over the course of reaction.…”

Section: Possible Inclusion Of Nitrogen Isotope Data In the Hypothesi...mentioning

confidence: 99%

Prebiotic Synthesis on Meteorite Parent Bodies: Insights from Hydrogen and Carbon Isotope Models

Chimiak

Eiler

2022

Preprint

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Several mechanisms could produce the biorelevant compounds in carbonaceous meteorites. These include radiation-driven reactions in the interstellar medium, gas-phase mineral-catalyzed reactions in the solar nebula, and aqueous chemistry in meteorite parent bodies. The ratio of heavy-to-light isotopes in a compound can constrains its formation history: a reaction’s substrates, mechanisms, and physiochemical conditions impact isotope ratios. Studies of the stable isotope compositions of meteoritic organic compounds have focused on sample- and molecular-average isotope measurements and have interpreted those data via qualitative or semi-quantitative models. Here we create quantitative models (i.e., explicitly fit to measurements) for hydrogen and carbon isotope compositions of organic compounds in primitive carbonaceous meteorites and use these models to reach broader conclusions regarding the environments, substrates, and chemical processes that contributed to pre- and early-solar-system organic synthesis. The hydrogen model fits measured molecular-average deuterium concentrations in a compound class (e.g., amines, carboxylic acids) as linear combinations of hydrogens with similar chemical environments. In the chondrites studied, methyl hydrogens are amongst the most deuterium-enriched moiety and hydrogens attached to α-carbons are the least. Deuterium enrichment is inversely related to both a compound class’s water solubility and a meteorite sample’s degree of aqueous alteration and terrestrial weathering. These values suggest that ISM-sourced compounds reacted to form deuterium-enriched molecules on meteorites’ parent bodies and the enrichments were attenuated through exchange with water during aqueous alteration on the parent body and subsequent terrestrial processing. The carbon model fits the δ13CVPDB of products from various reaction mechanisms by applying isotope effects to reactant δ13C measurements. The model with the most accurate δ13C fits of the compounds in the Murchison meteorite (62 % of previous measurements fit by model) and the lowest average residuals (5 ‰) uses the integrated aldehyde network (oxidation, reductive amination, and Strecker synthesis on aldehydes and ketones) to produce straight-chain compounds that undergo formaldehyde addition to create branched-chain compounds. Formaldehyde addition has not been previously considered in prebiotic chemical reaction networks, but the best-fit network’s ability to fit compounds that span over 100 ‰ in carbon isotope abundances makes it an attractive chemistry to explore.

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“…5,6 The fractionation of isotopes between a molecule and its precursors is controlled by key rate-determining steps and major branching points in the flow of carbon and nitrogen. 7 The origin of biological N isotope discrimination might be closely related to the synthesis and evolution of prebiotic proteinogenic amino acids, 8 peptides, and proteins.…”

Section: Introductionmentioning

confidence: 99%

“…Substitution of 12 C, 14 N, and 1 H by 13 C, 15 N, and 2 H atoms might slow down protein pico-to-femtosecond dynamics, and effect the system’s electrostatics. − Heavier isotopologue reactants participate in a reaction more slowly than lighter ones, regardless of the reaction type (i.e., physical, chemical, or biochemical), therefore resulting in isotopic effects. , The fractionation of isotopes between a molecule and its precursors is controlled by key rate-determining steps and major branching points in the flow of carbon and nitrogen . The origin of biological N isotope discrimination might be closely related to the synthesis and evolution of prebiotic proteinogenic amino acids, peptides, and proteins.…”

Section: Introductionmentioning

confidence: 99%

Demonstrating Prebiotic Peptide Evolution by Nitrogen Isotope Discrimination in an Autocatalytic Chemical Reaction Network

Bao,

Wu,

et al. 2024

ACS Earth Space Chem.

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Nitrogen isotope discrimination may be closely related to the prebiotic evolution of peptides that occurred in the origin of life from chemical reaction networks (CRNs). We deduce that autocatalytic Sammox (sulfurous reduction coupled to anaerobic ammonium oxidation)-driven CRN is a feasible scenario for life origin. To demonstrate prebiotic peptide evolution, we investigated N isotope discrimination in proteinogenic amino acids and peptide synthesis in Sammox-driven CRNs, combining mathematical and physical models. The species and amounts of proteinogenic amino acids generated in Sammox-driven CRNs with 14 NH 4 + as the N source were all significantly higher than those in Sammox-driven CRNs with 15 NH 4 + as the N source for both hydrothermal and microaerobic eutectic freezing conditions. The low yield of 15 N-amino acids, both species and amounts, will lead to the formation of 15 N-peptides with poor structure and function and slow peptide dynamics; these peptides might be preferentially degraded in Sammox-driven CRNs. We then explored the nitrogen isotopic effects during the synthesis process from ammonia to glycine, from glycine to glycine-containing peptides, and during the process of glycine-containing peptide hydrolysis. 15 N are eliminated in competition with 14 N during the process of glycine synthesis, glycine-containing peptide synthesis, and glycinecontaining peptide hydrolysis under hydrothermal conditions as determined by the maximum entropy production principle, which is a prebiotic evolution process. In addition, pyrrole as the building block of the prosthetic group, which is generated from Sammoxdriven CRNs under hydrothermal conditions, may provide a more evolutionary possibility of prebiotic peptides.

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Isotope effects at the origin of life: Fingerprints of the Strecker synthesis

Cited by 6 publications

References 45 publications

Analysis of intramolecular carbon isotope distributions in alanine by electrospray ionization Orbitrap mass spectrometry

Analysis of intramolecular carbon isotope distributions in alanine by electrospray ionization Orbitrap mass spectrometry

Prebiotic Synthesis on Meteorite Parent Bodies: Insights from Hydrogen and Carbon Isotope Models

Demonstrating Prebiotic Peptide Evolution by Nitrogen Isotope Discrimination in an Autocatalytic Chemical Reaction Network

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