A Plausible Prebiotic Origin of Glyoxylate: Nonenzymatic Transamination Reactions of Glycine with Formaldehyde

Mohammed, F.; Chen, Ke; Mojica, Mike; Conley, Mark; Napoline, J. Wesley; Butch, Christopher J.; Pollet, Paméla; Krishnamurthy, Ramanarayanan; Liotta, Charles L.

doi:10.1055/s-0036-1588657

Cited by 11 publications

(6 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Additionally, the identification of glyoxylic acid (c8) in insoluble polymers 1 and 6 is interesting. These results extend the experimental conditions that can lead to the prebiotic production of glyoxylic acid (c8) (Menor-Salvan and Marin-Yaseli, 2013;Marín-Yaseli et al, 2016;Mohammed et al, 2017;Mompeán et al, 2019) and may be interesting for the further development of the "glyoxylic acid scenario" proposed by Eschenmoser (2007), as will be discussed later. The yields of glyoxylic acid (c8) for the experiments 1 and 6 were 1.1•10 −4 % (13 mg/L) and 9.5•10 −4 % (169 mg/L), respectively.…”

Section: Gc-ms Analyses Of Insoluble Nh 4 Cn Polymerssupporting

confidence: 72%

Reactivity of Cyanide at Water-Ice Interfaces: Implications for the Search for Organics on Icy Worlds

Marín-Yaseli

González-Toril

Ruíz-Bermejo

2020

Front. Astron. Space Sci.

View full text Add to dashboard Cite

Icy moons in our solar system are targets of interest to search for signs of life and habitability beyond Earth. They are the astrobiological aim for several developing space missions (JUICE, Europa Clipper, and Europa Lander). A further understanding of the processes that force a planetary object to develop a biological system and to develop habitability conditions could be obtained by adopting a prebiotic chemistry point of view. In this regard, it is highly interesting to search for organic compounds synthesized from cyanide since it has been proposed that polymerization of NH 4 CN would be applicable to icy planetary environments. Thus, the effect of water freeze-thaw cycles, UV-radiation and salts on the polymerization of NH 4 CN was explored as an approach to understand the possible organic chemistry of icy worlds. As a result, insoluble and soluble NH 4 CN polymers, synthesized under multiple conditions, were analyzed by GC-MS. A diverse set of amino acids, carboxylic acids, and several N-heterocycles were identified. Glyoxylic acid was detected under particular reaction conditions, extending the plausible favorable conditions for the emergence of this molecule, referred to as the "glyoxylate scenario." In addition, the GC-MS results were studied by multivariate analysis, showing that the ice-water interfaces may be ideal places to develop complex organic chemistry from a carbon source as simple as cyanide.

show abstract

Section: Gc-ms Analyses Of Insoluble Nh 4 Cn Polymerssupporting

confidence: 72%

Reactivity of Cyanide at Water-Ice Interfaces: Implications for the Search for Organics on Icy Worlds

Marín-Yaseli

González-Toril

Ruíz-Bermejo

2020

Front. Astron. Space Sci.

View full text Add to dashboard Cite

show abstract

“…Indeed, when we carried out a reaction of glyoxylate with hydantoin in water at neutral pH (Scheme 2), it afforded orotate in greater than 10 % yield. In a prebiotic context, hydantoin and glyoxylate are both derived from glycine, the simplest α‐amino acid, by reaction with cyanate [16] and formaldehyde, [17] respectively. This hydantoin and glyoxylate route to orotate has been proposed previously, by Ivin et al in 1976, [18] and in a subsequent 1978 US patent, [19] but neither work was in the context of prebiotic chemistry.…”

Section: Methodsmentioning

confidence: 99%

A Plausible Prebiotic One‐Pot Synthesis of Orotate and Pyruvate Suggestive of Common Protometabolic Pathways

et al. 2022

View full text Add to dashboard Cite

A reaction between two prebiotically plausible building blocks, hydantoin and glyoxylate, generates both the nucleobase orotate, a precursor of biological pyrimidines, and pyruvate, a core metabolite in the citric acid cycle and amino acid biosynthesis. The reaction proceeds in water to provide significant yields of the two widely divergent chemical motifs. Additionally, the reaction of thiohydantoin and glyoxylate produces thioorotate in high yield under neutral aqueous conditions. The use of an open‐chain thiohydantoin derivative also enables the potential pre‐positioning of a nucleosidic bond prior to the synthesis of an orotate nucleoside. The observation that diverse building blocks of modern metabolism can be produced in a single reaction pot, from common reactants under mild conditions, supports the plausibility of orthogonal chemistries operating at the origins of chemical evolution.

show abstract

“…2A). This conversion, mimicking the reductive step of oxalacetate to malate in the rTCA pathway, also works at moderate pHs (5)(6), and various concentrations (10-500 mM) in good yields (68-75% conversion, Supplementary Table S1 and Figs. S1-S5).…”

mentioning

confidence: 87%

“…46 Lastly, the chemistry outlined here depends on the prebiotic availability of glyoxylate and malonate for which there is some support. [4][5][6][7]47 It is plausible that as the experimental demonstration grows for the central role of glyoxylate and malonate chemistry, it will spur more efforts to put constraints on their prebiotic provenance.…”

mentioning

confidence: 99%

Cyanide as a Primordial Reductant enables a Protometabolic Reductive Glyoxylate Pathway

Krishnamurthy

Yadav

Pulletikurti

et al. 2021

Preprint

Self Cite

View full text Add to dashboard Cite

Investigation of prebiotic chemical pathways leading to protometabolic forerunners of metabolism has been largely based on bio-inspired (iron-mediated) reductive conversion of carbon dioxide and of carboxylic acid substrates.1,2 While attractive from a parsimony point of view, this approach has been challenging with debatable outcomes.3,4 Herein, we show that cyanide reacts with citric acid cycle (TCA) intermediates and derivatives and acts as a primordial reducing agent mediating abiotic reductive transformations. The hydrolysis of the cyanide adducts followed by decarboxylation enables the efficient reductive-decarboxylative transformation of oxaloacetate to malate and fumarate to succinate while pyruvate and α-ketoglutarate are not reduced. In the presence of glyoxylate,5,6 malonate7 and malononitrile,8 alternative pathways emerge, which after decarboxylation produce metabolic intermediates and related compounds also found in meteorites.9 These results, along with the previous demonstration of the metal-free alpha-keto analog of the reverse-TCA cycle,4,6 suggest that (a) alternative paradigms of cyanide-based protometabolic reactions bypassing the abiotic reductive-carboxylation steps can be prebiotically viable, (b) a novel reductive glyoxylate pathway can be a precursor to the r-TCA cycle and (c) the type of sophisticated carboxylation and reduction chemistries which are part of extant metabolic cycles10,11 are an evolutionary invention mediated by complex metalloproteins11.

show abstract

A Plausible Prebiotic Origin of Glyoxylate: Nonenzymatic Transamination Reactions of Glycine with Formaldehyde

Cited by 11 publications

References 11 publications

Reactivity of Cyanide at Water-Ice Interfaces: Implications for the Search for Organics on Icy Worlds

Reactivity of Cyanide at Water-Ice Interfaces: Implications for the Search for Organics on Icy Worlds

A Plausible Prebiotic One‐Pot Synthesis of Orotate and Pyruvate Suggestive of Common Protometabolic Pathways

Cyanide as a Primordial Reductant enables a Protometabolic Reductive Glyoxylate Pathway

Contact Info

Product

Resources

About