Formation, stabilization and fate of acetaldehyde and higher aldehydes in an autonomously changing prebiotic system emerging from acetylene

Diederich, Philippe; Geisberger, Thomas; Yan, Yingfei; Seitz, Christian; Ruf, Alexander; Huber, Claudia; Hertkorn, Norbert; Schmitt‐Kopplin, Philippe

doi:10.1038/s42004-023-00833-5

Cited by 10 publications

(4 citation statements)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, due to kinetic effects and experimental limitations such as imperfect mixing and fast cooling, certain amounts of unreacted ammonia and acetylene can be expected in the sample as molecular solids and have been observed in Figures and . This situation is frequently observed in the synthesis of numerous cocrystals. ,− …”

Section: Resultsmentioning

confidence: 87%

“…Furthermore, these binary solids are also relevant in the studies of other planetary bodies. For example, both materials have been detected as constituents of the comets, such as Hyakutake. − Both molecules are also believed to be present in prebiotic Earth. − The intermolecular interactions within condensed phases of such simple organic systems can be relevant for the studies of planetary bodies and as well as modeling of processes occurring on young prebiotic Earth. Such interactions are indeed strong between ammonia and acetylene , resulting in a stable 1:1 cocrystal that was reported in 2009 .…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Neutron Vibrational Spectroscopic Study of the Acetylene: Ammonia (1:1) Cocrystal Relevant to Titan, Saturn’s Moon

Kramer,

Trump,

Daemen

et al. 2024

J. Phys. Chem. A

View full text Add to dashboard Cite

The surface of Titan, Saturn's icy moon, is believed to be composed of various molecular minerals with a great diversity in structure and composition. Under the surface conditions, 93 K and 1.45 atm, most small molecules solidify and form minerals, including acetylene and ammonia. These two compounds can not only form single-component solids but also a 1:1 binary cocrystal that exhibits intriguing rotor phase behavior. This cocrystal is a putative mineral on Titan and other planetary bodies such as comets. In addition, the structure of the cocrystal is relevant to fundamental science as it can help better understand the emergence of rotor phases. Here, we present a detailed vibrational neutron spectroscopic study supported by a neutron powder diffraction study on the cocrystal and the single-phase solids. The experimentally observed spectral bands were assigned based on theoretical calculations. The established spectra−properties correlations for the cocrystal corroborate the observed properties. To the best of our knowledge, this study presents the first example of the application of neutron vibrational spectroscopy in studying Titan-relevant organic minerals.

show abstract

Section: Resultsmentioning

confidence: 87%

Section: Introductionmentioning

confidence: 99%

Neutron Vibrational Spectroscopic Study of the Acetylene: Ammonia (1:1) Cocrystal Relevant to Titan, Saturn’s Moon

Kramer,

Trump,

Daemen

et al. 2024

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…16 Both molecules are also believed to be present in prebiotic Earth. [17][18][19] The intermolecular interactions within condensed phases of such simple organic systems can be relevant for the studies of planetary bodies and as well as modeling of processes occurring on young prebiotic Earth. Such interactions are indeed strong between ammonia and acetylene, [21][22] resulting in a stable 1:1 cocrystal that was reported in 2009.…”

Section: Introductionmentioning

confidence: 99%

Neutron Vibrational Spectroscopic Study of the Acetylene:Ammonia (1:1) Cocrystal Relevant to Titan, Saturn’s Moon

Kramer,

Trump,

Daemen

et al. 2024

Preprint

View full text Add to dashboard Cite

The surface of Titan, Saturn’s icy moon, is believed to be comprised of various molecular minerals with a great diversity in structure and composition. Under the surface conditions, 93 K and 1.45 atm, most small molecules solidify and form minerals, including acetylene and ammonia. These two compounds can form single-component solids but also a 1:1 binary cocrystal that exhibits intriguing rotor phase behavior. This cocrystal is a putative mineral on Titan and other planetary bodies such as comets. In addition, the structure of the cocrystal is relevant to fundamental science as it can help better understand the emergence of rotor phases. Here we present a detailed vibrational neutron spectroscopic study supported by neutron powder diffraction study on the cocrystal and the single-phase solids. The experimentally observed spectral bands were assigned based on theoretical calculations. The established spectra–properties correlations for the cocrystal corroborate the observed properties. To the best of our knowledge, this study presents the first example of the application of neutron vibrational spectroscopy in studying Titan-relevant organic minerals.

show abstract

“…The study of the origin of life addresses one of the most fundamental research questions of our time, but despite many interdisciplinary attempts, the final step to clarifying how life evolved remains unsolved. In the field of prebiotic chemistry, reaction pathways and networks of biologically relevant molecules and the corresponding reaction conditions are studied, 5 mostly with a focus on elucidating individual pathways. 6 As a result, these pathways are often examined separately to address the different requirements of a particular prebiotic environment.…”

Section: ■ Introductionmentioning

confidence: 99%

(Photoredox) Organocatalysis in the Emergence of Life: Discovery, Applications, and Molecular Evolution

Bechtel,

Ebeling,

Huber

et al. 2023

Acc. Chem. Res.

View full text Add to dashboard Cite

Conspectus Life as we know it is built on complex and perfectly interlocking processes that have evolved over millions of years through evolutionary optimization processes. The emergence of life from nonliving matter and the evolution of such highly efficient systems therefore constitute an enormous synthetic and systems chemistry challenge. Advances in supramolecular and systems chemistry are opening new perspectives that provide insights into living and self-sustaining reaction networks as precursors for life. However, the ab initio synthesis of such a system requires the possibility of autonomous optimization of catalytic properties and, consequently, of an evolutionary system at the molecular level. In this Account, we present our discovery of the formation of substituted imidazolidine-4-thiones (photoredox) organocatalysts from simple prebiotic building blocks such as aldehydes and ketones under Strecker reaction conditions with ammonia and cyanides in the presence of hydrogen sulfide. The necessary aldehydes are formed from CO2 and hydrogen under prebiotically plausible meteoritic or volcanic iron-particle catalysis in the atmosphere of the early Earth. Remarkably, the investigated imidazolidine-4-thiones undergo spontaneous resolution by conglomerate crystallization, opening a pathway for symmetry breaking, chiral amplification, and enantioselective organocatalysis. These imidazolidine-4-thiones enable α-alkylations of aldehydes and ketones by photoredox organocatalysis. Therefore, these photoredox organocatalysts are able to modify their aldehyde building blocks, which leads in an evolutionary process to mutated second-generation and third-generation catalysts. In our experimental studies, we found that this mutation can occur not only by new formation of the imidazolidine core structure of the catalyst from modified aldehyde building blocks or by continuous supply from a pool of available building blocks but also by a dynamic exchange of the carbonyl moiety in ring position 2 of the imidazolidine moiety. Remarkably, it can be shown that by incorporating aldehyde building blocks from their environment, the imidazolidine-4-thiones are able to change and adapt to altering environmental conditions without undergoing the entire formation process. The selection of the mutated catalysts is then based on the different catalytic activities in the modification of the aldehyde building blocks and on the catalysis of subsequent processes that can lead to the formation of molecular reaction networks as progenitors for cellular processes. We were able to show that these imidazolidine-4-thiones not only enable α-alkylations but also facilitate other important transformations, such as the selective phosphorylation of nucleosides to nucleotides as a key step leading to the oligomerization to RNA and DNA. It can therefore be expected that evolutionary processes have already taken place on a small molecular level and have thus developed chemical tools that change over time, representing a hidden layer on the path to enzyma...

show abstract

Formation, stabilization and fate of acetaldehyde and higher aldehydes in an autonomously changing prebiotic system emerging from acetylene

Cited by 10 publications

References 46 publications

Neutron Vibrational Spectroscopic Study of the Acetylene: Ammonia (1:1) Cocrystal Relevant to Titan, Saturn’s Moon

Neutron Vibrational Spectroscopic Study of the Acetylene: Ammonia (1:1) Cocrystal Relevant to Titan, Saturn’s Moon

Neutron Vibrational Spectroscopic Study of the Acetylene:Ammonia (1:1) Cocrystal Relevant to Titan, Saturn’s Moon

(Photoredox) Organocatalysis in the Emergence of Life: Discovery, Applications, and Molecular Evolution

Contact Info

Product

Resources

About