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Abstract The chemical evolution in star forming regions is driven by the interplay between gas and ice mantles. Identifying the ice compositions at the early stage of star formation thus provides constraints on the chemical processes inaccessible from gas-phase characterizations. As part of the CORINOS program, spectra from the James Webb Space Telescope (JWST) Mid-Infrared Instruments Medium Resolution Spectroscopy were taken toward four Class 0 protostars: IRAS 15398-3359, Ser-emb7, L483, and B335. The spectra were processed with simultaneous fitting of a continuum and silicate absorption to produce optical depth mid-infrared spectra of the ices at 5–28μm (360–2000 cm⁻¹) toward these four sources. Simple molecules such as water (H₂O), carbon dioxide (CO₂), methanol (CH₃OH), formic acid/formate (HCOOH/HCOO⁻), ammonia/ammonium (NH₃/NH₄⁺), and formaldehyde (H₂CO) are the most abundant features in these ices, while complex organic molecules (COMs) represent a smaller contribution. Likely COMs include hydroxylamine (NH₂OH), methylamine (CH₃NH₂), and ethanol (CH₃CH₂OH). Absorption features belonging to functional groups such as –CH₃and –OH suggest that additional COMs are present, but these cannot be unambiguously assigned due to overlapping bands. Formation pathways toward these COMs utilizing radical–radical combination reactions based on laboratory simulation experiments is presented. By extension, COMs predicted by these reactions, but absent from the spectra, are discussed. The results provide insight into the chemical environment of these ices and also highlight the critical need for caution and sufficient evidence in order to confidently identify COMs in ice. 

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. 

Abstract For the last century, the source of sulfur in Earth’s very first organisms has remained a fundamental, unsolved enigma. While sulfates and their organic derivatives with sulfur in the S(+VI) oxidation state represent core nutrients in contemporary biochemistry, the limited bioavailability of sulfates during Earth’s early Archean period proposed that more soluble S(+IV) compounds served as the initial source of sulfur for the first terrestrial microorganisms. Here, we reveal via laboratory simulation experiments that the three simplest alkylsulfonic acids—water soluble organic S(+IV) compounds—can be efficiently produced in interstellar, sulfur-doped ices through interaction with galactic cosmic rays. This discovery opens a previously elusive path into the synthesis of vital astrobiological significance and untangles fundamental mechanisms of a facile preparation of sulfur-containing, biorelevant organics in extraterrestrial ices; these molecules can be eventually incorporated into comets and asteroids before their delivery and detection on Earth such as in the Murchison, Tagish Lake, and Allende meteorites along with the carbonaceous asteroid Ryugu. 

Organosulfur molecules methanethiol, ethanethiol, and dimethyl sulfide—all identified in the interstellar medium—were first prepared in astrophysically relevant ices of methane and hydrogen sulfide exposed to proxies of galactic cosmic rays. Image from ESA/Hubble & NASA. 

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. 

Thiocarbonic acid was formed in low-temperature interstellar ice analogs composed of hydrogen sulfide (H₂S) and carbon disulfide (CS₂), exposed to electron irradiation simulating the impact of galactic cosmic rays.