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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. 

Abstract Enols—tautomers of ketones or aldehydes—are considered key intermediates in the formation of prebiotic sugars and sugar acids. Although laboratory simulation experiments suggest that enols should be ubiquitous in the interstellar medium, the underlying formation mechanisms of enols in interstellar environments are largely elusive. Here, we present the laboratory experiments on the formation of glyoxal (HCOCHO) along with its ynol tautomer acetylenediol (HOCCOH) in interstellar ice analogs composed of carbon monoxide (CO) and water (H₂O) upon exposure to energetic electrons as a proxy for secondary electrons generated from Galactic cosmic rays. Utilizing tunable vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry, glyoxal and acetylenediol were detected in the gas phase during temperature-programmed desorption. Our results reveal the formation pathways of glyoxal via radical–radical recombination of two formyl (HĊO) radicals, and that of acetylenediol via keto-enol-ynol tautomerization. Due to the abundance of carbon monoxide and water in interstellar ices, glyoxal and acetylenediol are suitable candidates for future astronomical searches. Furthermore, the detection of acetylenediol in astrophysically relevant ices advances our understanding for the formation pathways of high-energy tautomers such as enols in deep space. 

Abstract Glycinal (HCOCH₂NH₂) and acetamide (CH₃CONH₂) are simple molecular building blocks of biomolecules in prebiotic chemistry, though their origin on early Earth and formation in interstellar media remain a mystery. These molecules are formed with their tautomers in low temperature interstellar model ices upon interaction with simulated galactic cosmic rays. Glycinal and acetamide are accessed via barrierless radical‐radical reactions of vinoxy (⋅CH₂CHO) and acetyl (⋅C(O)CH₃), and then undergo keto‐enol tautomerization. Exploiting tunable photoionization reflectron time‐of‐flight mass spectroscopy and photoionization efficiency (PIE) curves, these results demonstrate fundamental reaction pathways for the formation of complex organics through non‐equilibrium ice reactions in cold molecular cloud environments. These molecules demonstrate an unconventional starting point for abiotic synthesis of organics relevant to contemporary biomolecules like polypeptides and cell membranes in deep space.