Search for: All records

Abstract Oxygen-containing complex organic molecules are key precursors to biorelevant compounds fundamental for the origins of life. However, the untangling of their interstellar formation mechanisms has just scratched the surface, especially for oxygen-containing cyclic molecules. Here, we present the first laboratory simulation experiments featuring the formation of all three C₂H₄O isomers—ethylene oxide (c–C₂H₄O), acetaldehyde (CH₃CHO), and vinyl alcohol (CH₂CHOH)—in low-temperature model interstellar ices composed of carbon monoxide (CO) and ethanol (C₂H₅OH). Ice mixtures were exposed to galactic cosmic-ray proxies with an irradiation dose equivalent to a cold molecular cloud aged (7 ± 2) × 10⁵yr. These biorelevant species were detected in the gas phase through isomer-selective photoionization reflectron time-of-flight mass spectrometry during temperature-programmed desorption. Isotopic labeling experiments reveal that ethylene oxide is produced from ethanol alone, providing the first experimental evidence to support the hypothesis that ethanol serves as a precursor to the prototype epoxide in interstellar ices. These findings reveal feasible pathways for the formation of all three C₂H₄O isomers in ethanol-rich interstellar ices, offering valuable constraints on astrochemical models for their formation. Our results suggest that ethanol is a critical precursor to C₂H₄O isomers in interstellar environments, representing a critical step toward unraveling the formation mechanisms of oxygen-containing cyclic molecules, aldehydes, and their enol tautomers from alcohols in interstellar ices. 

Abstract Aldehydes are ubiquitous in star-forming regions and carbonaceous chondrites, serving as essential intermediates in metabolic pathways and molecular mass growth processes to vital biomolecules necessary for the origins of life. However, their interstellar formation mechanisms have remained largely elusive. Here, we unveil the formation of lactaldehyde (CH₃CH(OH)CHO) by barrierless recombination of formyl (HĊO) and 1-hydroxyethyl (CH₃ĊHOH) radicals in interstellar ice analogs composed of carbon monoxide (CO) and ethanol (CH₃CH₂OH). Lactaldehyde and its isomers 3-hydroxypropanal (HOCH₂CH₂CHO), ethyl formate (CH₃CH₂OCHO), and 1,3-propenediol (HOCH₂CHCHOH) are identified in the gas phase utilizing isomer-selective photoionization reflectron time-of-flight mass spectrometry and isotopic substitution studies. These findings reveal fundamental formation pathways for complex, biologically relevant aldehydes through non-equilibrium reactions in interstellar environments. Once synthesized, lactaldehyde can act as a key precursor to critical biomolecules such as sugars, sugar acids, and amino acids in deep space. 

The molecular framework for protometabolism—chemical reactions in a prebiotic environment preceding modern metabolism—has remained unknown in evolutionary biology. Mono-, di-, and tricarboxylic acids that comprise contemporary metabolism, such as the Krebs cycle, are of particular prebiotic relevance and are theorized to predate life on Earth. Researchers have struggled to unravel the molecular origins of respiration, with theories pointing toward abiotic origins later co-opted by the earliest living organisms; however, the molecular network of these molecules has remained elusive. Recent detections of carboxylic acids linked to the Krebs cycle on the Ryugu asteroid and Murchison meteorite rekindled interest in their extraterrestrial origins. Replicating conditions analogous to the environment of dense molecular clouds in laboratory simulation experiments, our work provides compelling evidence on the abiotic synthesis of the complete suite of biorelevant molecules central to the Krebs cycle. The opportunity for these biomolecules forming in deep space could provide molecular origins of protometabolism on early Earth and also provide the molecular feedstock to worlds beyond our own.