Sulfur Analogs of the Core Formose Cycle: A Free Energy Map DOI Creative Commons
Jeremy Kua, Manuel Pena,

Samantha N. Cotter

et al.

Life, Journal Year: 2024, Volume and Issue: 15(1), P. 1 - 1

Published: Dec. 24, 2024

Using computational methods, we examine if the presence of H2S can tame unruly formose reaction by generating a free energy map thermodynamics and kinetics sulfur analogs within core cycle. With mercaptoaldehyde as linchpin C2 species, feeding cycle with CH2O, selected aldol additions enolizations are kinetically more favorable. Thione formation is thermodynamically less favored compared to aldehydes ketones, but all these species be connected enolization reactions. In some analogs, retroaldol transformation C4 back into favorable, have found one route incorporating where selects for specific pathway over others. However, CH2O diminishes, addition larger favorable analogs. Our results also suggest that competing Cannizzaro side reactions disfavored when abundant.

Language: Английский

The Second Wave of Formose Research DOI Creative Commons
Akihito Hashidzume

BBA Advances, Journal Year: 2025, Volume and Issue: 7, P. 100141 - 100141

Published: Jan. 1, 2025

Language: Английский

Citations

0
Abiotic aldol reactions of formaldehyde with ketoses and aldoses—Implications for the prebiotic synthesis of sugars by the formose reaction DOI

Scot M. Sutton,

Sunil Pulletikurti,

Huacan Lin

et al.

Chem, Journal Year: 2025, Volume and Issue: unknown, P. 102553 - 102553

Published: April 1, 2025

Language: Английский

Citations

0
Exploring the Core Formose Cycle: Catalysis and Competition DOI Creative Commons
Jeremy Kua,

L. Philip Tripoli

Life, Journal Year: 2024, Volume and Issue: 14(8), P. 933 - 933

Published: July 25, 2024

The core autocatalytic cycle of the formose reaction may be enhanced or eroded by presence simple molecules at life’s origin. Utilizing quantum chemistry, we calculate thermodynamics and kinetics reactions both within those that deplete reactants intermediates, such as Cannizzaro reaction. We find via disproportionation aldehydes into carboxylic acids alcohols, furnishes catalysts for a variety reactions. also ammonia can catalyze in-cycle while hydrogen sulfide does not; both, however, play role in sequestering intermediates web potential

Language: Английский

Citations

3
Evidence of Selection in Mineral Mediated Polymerization Reactions Executed in a Robotic Chemputer System DOI Creative Commons
Silke Asche, Robert Pow, S. Hessam M. Mehr

et al.

ChemSystemsChem, Journal Year: 2024, Volume and Issue: 6(3)

Published: March 8, 2024

Abstract It has long been thought that abiogenesis requires a process of selection and evolution at the molecular level, but this is hard to explore experimentally. One solution could be use automation in experiments which allow for traceability ability larger reaction space. We report fully programmable automated platform reactions amino acids presence mineral environments. The robotic system based upon Chemputer well defined modules, software, chemical programming language orchestrate processes, including analysis. mixtures were analysed with tandem mass spectrometry peptide sequencing algorithm. Each experiment was screened 1,398,100 possible unique sequences, more than 550 specifically sequences confirmed This work aimed develop new understanding repeated cycles polymerisation emergence well‐defined acid sequences. found outcome oligomerisation significantly influenced by different minerals, serpentine environment selects glycine phenylalanine rich fragments enable formation longer oligomers as function cycle number.

Language: Английский

Citations

2
Combined Network and High Resolution Mass Spectrometry Analysis of the Formose Reaction Reveals Mechanisms for Emergent Behaviors DOI Creative Commons
Romulo Cruz-Simbron, Siddhant Sharma, Aayush Arya

et al.

Published: Feb. 2, 2024

The formose reaction (FR) autocatalytically converts simple plausibly prebiotic feedstocks into molecules of biological interest, including ribose. Autocatalysis is a hallmark life, thus various studies have explored the with respect to origins life. FR robust under appropriate conditions, occurring readily at low temperatures from substrates, and has been implicated in generation meteoritic organic compounds. We here using combination silico modeling techniques high resolution mass spectrometry. models match experimental results well, point being much more complex than previously modeled or measured, help explain FR’s potential generate homochirality primitive compartments, both which are also hallmarks before emergence directed molecular encoding suggested by RNA World model. These suggest requires further study regard its importance may lie way it enables coordinates emergent chemistries, rather particular products generates, such as

Language: Английский

Citations

0
Combined Network and High Resolution Mass Spectrometry Analysis of the Formose Reaction Reveals Mechanisms for Emergent Behaviors DOI Creative Commons
Romulo Cruz-Simbron, Siddhant Sharma, Aayush Arya

et al.

Published: Feb. 5, 2024

The formose reaction (FR) autocatalytically converts simple plausibly prebiotic feedstocks into molecules of biological interest, including ribose. Autocatalysis is a hallmark life, thus various studies have explored the with respect to origins life. FR robust under appropriate conditions, occurring readily at low temperatures from substrates, and has been implicated in generation meteoritic organic compounds. We here using combination silico modeling techniques high resolution mass spectrometry. models match experimental results well, point being much more complex than previously modeled or measured, help explain FR’s potential generate homochirality primitive compartments, both which are also hallmarks before emergence directed molecular encoding suggested by RNA World model. These suggest requires further study regard its importance may lie way it enables coordinates emergent chemistries, rather particular products generates, such as

Language: Английский

Citations

0
Sulfur Analogs of the Core Formose Cycle: A Free Energy Map DOI Creative Commons
Jeremy Kua, Manuel Pena,

Samantha N. Cotter

et al.

Life, Journal Year: 2024, Volume and Issue: 15(1), P. 1 - 1

Published: Dec. 24, 2024

Using computational methods, we examine if the presence of H2S can tame unruly formose reaction by generating a free energy map thermodynamics and kinetics sulfur analogs within core cycle. With mercaptoaldehyde as linchpin C2 species, feeding cycle with CH2O, selected aldol additions enolizations are kinetically more favorable. Thione formation is thermodynamically less favored compared to aldehydes ketones, but all these species be connected enolization reactions. In some analogs, retroaldol transformation C4 back into favorable, have found one route incorporating where selects for specific pathway over others. However, CH2O diminishes, addition larger favorable analogs. Our results also suggest that competing Cannizzaro side reactions disfavored when abundant.

Language: Английский

Citations

0