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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. 

The global symmetries of a $D$-dimensional quantum field theory (QFT) can, in many cases, be captured in terms of a ( $D+1$)-dimensional symmetry topological field theory (SymTFT). In this work we construct a ( $D+1$)-dimensional theory which governs the symmetries of QFTs with multiple sectors which have connected correlators that admit a decoupling limit. The associated symmetry field theory decomposes into a SymTree, namely a treelike structure of SymTFTs fused along possibly nontopological junctions. In string-realized multisector QFTs, these junctions are smoothed out in the extradimensional geometry, as we demonstrate in examples. We further use this perspective to study the fate of higher-form symmetries in the context of holographic large $M$averaging where the topological sectors of different large $M$replicas become dressed by additional extended operators associated with the SymTree. Published by the American Physical Society2024 

Abstract The North American craton interior preserves a >1 Ga history of near surface processes that inform ongoing debates regarding timing and drivers of continental‐scale deformation and erosion associated with far‐field orogenesis. We tested various models of structural inversion on a major segment of the Midcontinent Rift along the Douglas Fault in northern Wisconsin, which accommodated ≳10 km of total vertical displacement. U‐Pb detrital zircon and vein calcite Δ₄₇/U‐Pb thermochronometry from the hanging wall constrain the majority of uplift (≳8.5 km) and deformation to 1052–1036 Ma during the Ottawan phase of the Grenvillian orogeny. Combined U‐Pb zircon dates, Δ₄₇/U‐Pb calcite thermochronometry, and field data that document syn‐ to early post‐depositional deformation in the footwall constrain a second stage of uplift (1–1.5 km) ca. 995–980 Ma during the Rigolet phase of the Grenvillian orogeny. A minor phase of Appalachian far‐field orogenesis is associated with minimal thrust reactivation. Our combined analyses identified the 995–980 Ma Bayfield Group as a Grenvillian foreland basin with an original thickness 0.5–2 km greater than currently preserved. By quantifying flexural loading and other subsidence mechanisms along the Douglas Fault, we identify dynamic subsidence as a mechanism that could be consistent with the development of late‐Grenvillian transcontinental fluvial systems. Minimal post‐Grenvillian erosion (0.5–2 km) in this part of the craton interior has preserved the Bayfield Group and equivalent successions, limiting the magnitude of regional erosion that can be attributed to Neoproterozoic glaciation. 

Tropical epibenthic dinoflagellate communities produce a plethora of bioactive secondary metabolites, including the toxins ciguatoxins (CTXs) and potentially gambierones, that can contaminate fishes, leading to ciguatera poisoning (CP) when consumed by humans. Many studies have assessed the cellular toxicity of causative dinoflagellate species to better understand the dynamics of CP outbreaks. However, few studies have explored extracellular toxin pools which may also enter the food web, including through alternative and unanticipated routes of exposure. Additionally, the extracellular exhibition of toxins would suggest an ecological function and may prove important to the ecology of the CP-associated dinoflagellate species. In this study, semi-purified extracts obtained from the media of a Coolia palmyrensis strain (DISL57) isolated from the U.S. Virgin Islands were assessed for bioactivity via a sodium channel specific mouse neuroblastoma cell viability assay and associated metabolites evaluated by targeted and non-targeted liquid chromatography tandem and high-resolution mass spectrometry. We found that extracts of C. palmyrensis media exhibit both veratrine enhancing bioactivity and non-specific bioactivity. LC-HR-MS analysis of the same extract fractions identified gambierone and multiple undescribed peaks with mass spectral characteristics suggestive of structural similarities to polyether compounds. These findings implicate C. palmyrensis as a potential contributor to CP and highlight extracellular toxin pools as a potentially significant source of toxins that may enter the food web through multiple exposure pathways. 

Oxirene was prepared and stabilized in matrices through resonant energy transfer prior to identification in the gas phase. 

We unravel, for the very first time, the formation pathways of hydroxyacetone (CH 3 COCH 2 OH), methyl acetate (CH 3 COOCH 3 ), and 3-hydroxypropanal (HCOCH 2 CH 2 OH), as well as their enol tautomers within mixed ices of methanol (CH 3 OH) and acetaldehyde (CH 3 CHO) analogous to interstellar ices in the ISM exposed to ionizing radiation at ultralow temperatures of 5 K. Exploiting photoionization reflectron time-of-flight mass spectrometry (PI-ReToF-MS) and isotopically labeled ices, the reaction products were selectively photoionized allowing for isomer discrimination during the temperature-programmed desorption phase. Based on the distinct mass-to-charge ratios and ionization energies of the identified species, we reveal the formation pathways of hydroxyacetone (CH 3 COCH 2 OH), methyl acetate (CH 3 COOCH 3 ), and 3-hydroxypropanal (HCOCH 2 CH 2 OH) via radical–radical recombination reactions and of their enol tautomers (prop-1-ene-1,2-diol (CH 3 C(OH)CHOH), prop-2-ene-1,2-diol (CH 2 C(OH)CH 2 OH), 1-methoxyethen-1-ol (CH 3 OC(OH)CH 2 ) and prop-1-ene-1,3-diol (HOCH 2 CHCHOH)) via keto-enol tautomerization. To the best of our knowledge, 1-methoxyethen-1-ol (CH 3 OC(OH)CH 2 ) and prop-1-ene-1,3-diol (HOCH 2 CHCHOH) are experimentally identified for the first time. Our findings help to constrain the formation mechanism of hydroxyacetone and methyl acetate detected within star-forming regions and suggest that the hitherto astronomically unobserved isomer 3-hydroxypropanal and its enol tautomers represent promising candidates for future astronomical searches. These enol tautomers may contribute to the molecular synthesis of biologically relevant molecules in deep space due to their nucleophilic character and high reactivity.