Solvent constraints for biopolymer folding and evolution in extraterrestrial environments.

We propose that spontaneous folding and molecular evolution of biopolymers are two universal aspects that must concur for life to happen. These aspects are fundamentally related to the chemical composition of biopolymers and crucially depend on the solvent in which they are embedded. We show that molecular information theory and energy landscape theory allow us to explore the limits that solvents impose on biopolymer existence. We consider 54 solvents, including water, alcohols, hydrocarbons, halogenated solvents, aromatic solvents, and low molecular weight substances made up of elements abundant in the universe, which may potentially take part in alternative biochemistries. We find that along with water, there are many solvents for which the liquid regime is compatible with biopolymer folding and evolution. We present a ranking of the solvents in terms of biopolymer compatibility. Many of these solvents have been found in molecular clouds or may be expected to occur in extrasolar planets.

Dimethylformamide dimethyl acetal reagent for in situ chiral analyses of organic molecules on Titan with the Dragonfly mass spectrometer space instrument (Dragonfly mission).

Thanks to the Cassini-Huygens space mission between 2004 and 2017, a lot was learned about Titan, the biggest satellite of Saturn, and its intriguing atmosphere, surface, and organic chemistry complexity. However, key questions about the potential for the atmosphere and surface chemistry to produce organic molecules of direct interest for prebiotic chemistry and life did not find an answer. Due to Titan potential as a habitable world, NASA selected the Dragonfly space mission to be launched in 2027 to Titan's surface and explore the Shangri-La surface region for minimum 3 years. One of the main goals of this mission will be to understand the past and actual abundant prebiotic chemistry on Titan, especially using the Dragonfly Mass Spectrometer (DraMS). Two recently used sample pre-treatments for Gas Chromatography - Mass Spectrometry (GC-MS mode of DraMS) analyses are planned prior analysis to extract refractory organic molecules of interest for prebiotic chemistry and astrobiology. The dimethylformamide dimethylacetal (DMF-DMA) derivatization reaction offers undoubtedly an opportunity to detect biosignatures by volatilizing refractory biological or prebiotic molecules and conserving the chiral carbons' conformation while an enantiomeric excess indicates a chemical feature induced primarily by life (and may be aided on the primitive systems by light polarization). The goal of this study is to investigate the ageing of DMF-DMA in DraMS (and likely MOMA) capsules prior to in situ analysis on Titan (or Mars). The main results highlighted by our work on DMF-DMA are first its satisfactory stability for space requirements through time (no significant degradation over a year of storage and less than 30 % of lost under thermal stress) to a wide range of temperature (0 °C to 250 °C), or the presence of water and oxidants during the derivatization reaction (between 0 and 10 % of DMF-DMA degradation). Moreover, this reagent derivatized very well amines and carboxylic acids in high or trace amounts (ppt to hundreds of ppm), conserving their molecular conformation during the heat at 145 °C for 3 min (0 to 4% in the enantiomeric form change).

Formation of extraterrestrial peptides and their derivatives.

The formation of protein precursors, due to the condensation of atomic carbon under the low-temperature conditions of the molecular phases of the interstellar medium, opens alternative pathways for the origin of life. We perform peptide synthesis under conditions prevailing in space and provide a comprehensive analytic characterization of its products. The application of 13C allowed us to confirm the suggested pathway of peptide formation that proceeds due to the polymerization of aminoketene molecules that are formed in the C + CO + NH3 reaction. Here, we address the question of how the efficiency of peptide production is modified by the presence of water molecules. We demonstrate that although water slightly reduces the efficiency of polymerization of aminoketene, it does not prevent the formation of peptides.

Chapter 9: Life as We Don't Know It.

While Earth contains the only known example of life in the universe, it is possible that life elsewhere is fundamentally different from what we are familiar with. There is an increased recognition in the astrobiology community that the search for life should steer away from terran-specific biosignatures to those that are more inclusive to all life-forms. To start exploring the space of possibilities that life could occupy, we can try to dissociate life from the chemistry that composes it on Earth by envisioning how different life elsewhere could be in composition, lifestyle, medium, and form, and by exploring how the general principles that govern living systems on Earth might be found in different forms and environments across the Solar System. Exotic life-forms could exist on Mars or Venus, or icy moons like Europa and Enceladus, or even as a shadow biosphere on Earth. New perspectives on agnostic biosignature detection have also begun to emerge, allowing for a broader and more inclusive approach to seeking exotic life with unknown chemistry that is distinct from life as we know it on Earth.

Chapter 3: The Origins and Evolution of Planetary Systems.

The materials that form the diverse chemicals and structures on Earth-from mountains to oceans and biological organisms-all originated in a universe dominated by hydrogen and helium. Over billions of years, the composition and structure of the galaxies and stars evolved, and the elements of life, CHONPS, were formed through nucleosynthesis in stellar cores. Climactic events such as supernovae and stellar collisions produced heavier elements and spread them throughout the cosmos, often to be incorporated into new, more metal-rich stars. Stars typically form in molecular clouds containing small amounts of dust through the collapse of a high-density core. The surrounding nebular material is then pulled into a protoplanetary disk, from which planets, moons, asteroids, and comets eventually accrete. During the accretion of planetary systems, turbulent mixing can expose matter to a variety of different thermal and radiative environments. Chemical and physical changes in planetary system materials occur before and throughout the process of accretion, though many factors such as distance from the star, impact history, and level of heating experienced combine to ultimately determine the final geophysical characteristics. In Earth's planetary system, called the Solar System, after the orbits of the planets had settled into their current configuration, large impacts became rare, and the composition of and relative positions of objects became largely fixed. Further evolution of the respective chemical and physical environments of the planets-geosphere, hydrosphere, and atmosphere-then became dependent on their local geochemistry, their atmospheric interactions with solar radiation, and smaller asteroid impacts. On Earth, the presence of land, air, and water, along with an abundance of important geophysical and geochemical phenomena, led to a habitable planet where conditions were right for life to thrive.

Chapter 7: Assessing Habitability Beyond Earth.

All known life on Earth inhabits environments that maintain conditions between certain extremes of temperature, chemical composition, energy availability, and so on (Chapter 6). Life may have emerged in similar environments elsewhere in the Solar System and beyond. The ongoing search for life elsewhere mainly focuses on those environments most likely to support life, now or in the past-that is, potentially habitable environments. Discussion of habitability is necessarily based on what we know about life on Earth, as it is our only example. This chapter gives an overview of the known and presumed requirements for life on Earth and discusses how these requirements can be used to assess the potential habitability of planetary bodies across the Solar System and beyond. We first consider the chemical requirements of life and potential feedback effects that the presence of life can have on habitable conditions, and then the planetary, stellar, and temporal requirements for habitability. We then review the state of knowledge on the potential habitability of bodies across the Solar System and exoplanets, with a particular focus on Mars, Venus, Europa, and Enceladus. While reviewing the case for the potential habitability of each body, we summarize the most prominent and impactful studies that have informed the perspective on where habitable environments are likely to be found.

A recently quenched galaxy 700 million years after the Big Bang.

Local and low-redshift (z < 3) galaxies are known to broadly follow a bimodal distribution: actively star-forming galaxies with relatively stable star-formation rates and passive systems. These two populations are connected by galaxies in relatively slow transition. By contrast, theory predicts that star formation was stochastic at early cosmic times and in low-mass systems1-4. These galaxies transitioned rapidly between starburst episodes and phases of suppressed star formation, potentially even causing temporary quiescence-so-called mini-quenching events5,6. However, the regime of star-formation burstiness is observationally highly unconstrained. Directly observing mini-quenched galaxies in the primordial Universe is therefore of utmost importance to constrain models of galaxy formation and transformation7,8. Early quenched galaxies have been identified out to redshift z < 5 (refs. 9-12) and these are all found to be massive (M⋆ > 1010 M⊙) and relatively old. Here we report a (mini-)quenched galaxy at z = 7.3, when the Universe was only 700 Myr old. The JWST/NIRSpec spectrum is very blue (U-V = 0.16 ± 0.03 mag) but exhibits a Balmer break and no nebular emission lines. The galaxy experienced a short starburst followed by rapid quenching; its stellar mass (4-6 × 108 M⊙) falls in a range that is sensitive to various feedback mechanisms, which can result in perhaps only temporary quenching.

Multi-Technique Characterization of 3.45 Ga Microfossils on Earth: A Key Approach to Detect Possible Traces of Life in Returned Samples from Mars.

The NASA Mars 2020 Perseverance rover is actively exploring Jezero crater to conduct analyses on igneous and sedimentary rock targets from outcrops located on the crater floor (Máaz and Séítah formations) and from the delta deposits, respectively. The rock samples collected during this mission will be recovered during the Mars Sample Return mission, which plans to bring samples back to Earth in the 2030s to conduct in-depth studies using sophisticated laboratory instrumentation. Some of these samples may contain traces of ancient martian life that may be particularly difficult to detect and characterize because of their morphological simplicity and subtle biogeochemical expressions. Using the volcanic sediments of the 3.45 Ga Kitty's Gap Chert (Pilbara, Australia), containing putative early life forms (chemolithotrophs) and considered as astrobiological analogues for potential early Mars organisms, we document the steps required to demonstrate the syngenicity and biogenicity of such biosignatures using multiple complementary analytical techniques to provide information at different scales of observation. These include sedimentological, petrological, mineralogical, and geochemical analyses to demonstrate macro- to microscale habitability. New approaches, some unavailable at the time of the original description of these features, are used to verify the syngenicity and biogenicity of the purported fossil chemolithotrophs. The combination of elemental (proton-induced X-ray emission spectrometry) and molecular (deep-ultraviolet and Fourier transform infrared) analyses of rock slabs, thin sections, and focused ion beam sections reveals that the carbonaceous matter present in the samples is enriched in trace metals (e.g., V, Cr, Fe, Co) and is associated with aromatic and aliphatic molecules, which strongly support its biological origin. Transmission electron microscopy observations of the carbonaceous matter documented an amorphous nanostructure interpreted to correspond to the degraded remains of microorganisms and their by-products (extracellular polymeric substances, filaments…). Nevertheless, a small fraction of carbonaceous particles has signatures that are more metamorphosed. They probably represent either reworked detrital biological or abiotic fragments of mantle origin. This study serves as an example of the analytical protocol that would be needed to optimize the detection of fossil traces of life in martian rocks.

Bacterial model membranes under the harsh subsurface conditions of Mars.

Biomembranes are a key component of all living systems. Most research on membranes is restricted to ambient physiological conditions. However, the influence of extreme conditions, such as the deep subsurface on Earth or extraterrestrial environments, is less well understood. The deep subsurface of Mars is thought to harbour high concentrations of chaotropic salts in brines, yet we know little about how these conditions would influence the habitability of such environments. Here, we investigated the combined effects of high concentrations of Mars-relevant salts, including sodium and magnesium perchlorate and sulphate, and high hydrostatic pressure on the stability, structure, and function of a bacterial model membrane. To this end, several biophysical techniques have been employed, including calorimetry, fluorescence and CD spectroscopy, confocal microscopy, and small-angle X-ray scattering. We demonstrate that sulphate and perchlorate salts affect the properties of the membrane differently, depending on the counterion present (Na+vs. Mg2+). We found that the perchlorates, which are believed to be abundant salts in the Martian environment, induce a more hydrated and less ordered membrane, strongly favouring the physiologically relevant fluid-like phase of the membrane even under high-pressure stress. Moreover, we show that the activity of the phospholipase A2 is strongly modulated by both high pressure and salt. Compellingly, in the presence of the chaotropic perchlorate, the enzymatic reaction proceeded at a reasonable rate even in the presence of condensing Mg2+ and at high pressure, suggesting that bacterial membranes could still persist when challenged to function in such a highly stressed Martian environment.

Solid-State Single-Molecule Sensing with the Electronic Life-Detection Instrument for Enceladus/Europa (ELIE).

Growing evidence of the potential habitability of Ocean Worlds across our solar system is motivating the advancement of technologies capable of detecting life as we know it-sharing a common ancestry or physicochemical origin with life on Earth-or don't know it, representing a distinct emergence of life different than our one known example. Here, we propose the Electronic Life-detection Instrument for Enceladus/Europa (ELIE), a solid-state single-molecule instrument payload that aims to search for life based on the detection of amino acids and informational polymers (IPs) at the parts per billion to trillion level. As a first proof-of-principle in a laboratory environment, we demonstrate the single-molecule detection of the amino acid L-proline at a 10 µM concentration in a compact system. Based on ELIE's solid-state quantum electronic tunneling sensing mechanism, we further propose the quantum property of the HOMO-LUMO gap (energy difference between a molecule's highest energy-occupied molecular orbital and lowest energy-unoccupied molecular orbital) as a novel metric to assess amino acid complexity. Finally, we assess the potential of ELIE to discriminate between abiotically and biotically derived α-amino acid abundance distributions to reduce the false positive risk for life detection. Nanogap technology can also be applied to the detection of nucleobases and short sequences of IPs such as, but not limited to, RNA and DNA. Future missions may utilize ELIE to target preserved biosignatures on the surface of Mars, extant life in its deep subsurface, or life or its biosignatures in a plume, surface, or subsurface of ice moons such as Enceladus or Europa. One-Sentence Summary: A solid-state nanogap can determine the abundance distribution of amino acids, detect nucleic acids, and shows potential for detecting life as we know it and life as we don't know it.

Sustained wet-dry cycling on early Mars.

The presence of perennially wet surface environments on early Mars is well documented1,2, but little is known about short-term episodicity in the early hydroclimate3. Post-depositional processes driven by such short-term fluctuations may produce distinct structures, yet these are rarely preserved in the sedimentary record4. Incomplete geological constraints have led global models of the early Mars water cycle and climate to produce diverging results5,6. Here we report observations by the Curiosity rover at Gale Crater indicating that high-frequency wet-dry cycling occurred in early Martian surface environments. We observe exhumed centimetric polygonal ridges with sulfate enrichments, joined at Y-junctions, that record cracks formed in fresh mud owing to repeated wet-dry cycles of regular intensity. Instead of sporadic hydrological activity induced by impacts or volcanoes5, our findings point to a sustained, cyclic, possibly seasonal, climate on early Mars. Furthermore, as wet-dry cycling can promote prebiotic polymerization7,8, the Gale evaporitic basin may have been particularly conducive to these processes. The observed polygonal patterns are physically and temporally associated with the transition from smectite clays to sulfate-bearing strata, a globally distributed mineral transition1. This indicates that the Noachian-Hesperian transition (3.8-3.6 billion years ago) may have sustained an Earth-like climate regime and surface environments favourable to prebiotic evolution.

Organic Catalytic Activity as a Method for Agnostic Life Detection.

An ideal life detection instrument would have high sensitivity but be insensitive to abiotic processes and would be capable of detecting life with alternate molecular structures. In this study, we propose that catalytic activity can be the basis of a nearly ideal life detection instrument. There are several advantages to catalysis as an agnostic life detection method. Demonstrating catalysis does not necessarily require culturing/growing the alien life and in fact may persist even in dead biomass for some time, and the amplification by catalysis is large even by minute amounts of catalysts and, hence, can be readily detected against abiotic background rates. In specific, we propose a hydrolytic catalysis detection instrument that could detect activity in samples of extraterrestrial organic material from unknown life. The instrument uses chromogenic assay-based detection of various hydrolytic catalytic activities, which are matched to corresponding artificial substrates having the same, chromogenic (preferably fluorescent) upon release, group; D- and L-enantiomers of these substrates can be used to also answer the question whether unknown life is chiral. Since catalysis is a time-proportional product-concentration amplification process, hydrolytic catalytic activity can be measured on a sample of even a minute size, and with instruments based on, for example, optofluidic chip technology.

No thick carbon dioxide atmosphere on the rocky exoplanet TRAPPIST-1 c.

Seven rocky planets orbit the nearby dwarf star TRAPPIST-1, providing a unique opportunity to search for atmospheres on small planets outside the Solar System1. Thanks to the recent launch of the James Webb Space Telescope (JWST), possible atmospheric constituents such as carbon dioxide (CO2) are now detectable2,3. Recent JWST observations of the innermost planet TRAPPIST-1 b showed that it is most probably a bare rock without any CO2 in its atmosphere4. Here we report the detection of thermal emission from the dayside of TRAPPIST-1 c with the Mid-Infrared Instrument (MIRI) on JWST at 15 µm. We measure a planet-to-star flux ratio of fp/f⁎ = 421 ± 94 parts per million (ppm), which corresponds to an inferred dayside brightness temperature of 380 ± 31 K. This high dayside temperature disfavours a thick, CO2-rich atmosphere on the planet. The data rule out cloud-free O2/CO2 mixtures with surface pressures ranging from 10 bar (with 10 ppm CO2) to 0.1 bar (pure CO2). A Venus-analogue atmosphere with sulfuric acid clouds is also disfavoured at 2.6σ confidence. Thinner atmospheres or bare-rock surfaces are consistent with our measured planet-to-star flux ratio. The absence of a thick, CO2-rich atmosphere on TRAPPIST-1 c suggests a relatively volatile-poor formation history, with less than [Formula: see text] Earth oceans of water. If all planets in the system formed in the same way, this would indicate a limited reservoir of volatiles for the potentially habitable planets in the system.

Influence of pH and salts on DMF-DMA derivatization for future Space Applications.

For gas chromatography - mass spectrometry (GC-MS) analyses performed in situ, pH and salts (e.g., chlorides, sulfates) may enhance or inhibit the detection of targeted molecules of interest for astrobiology (e.g. amino acids, fatty acids, nucleobases). Obviously, salts influence the ionic strength of the solutions, the pH value, and the salting effect. But the presence of salts may also produce complexes or mask ions in the sample (masking effect on hydroxide ion, ammonia, etc.). For future space missions, wet chemistry will be conducted before GC-MS analyses to detect the full organic content of a sample. The defined organic targets for space GC-MS instrument requirements are generally strongly polar or refractory organic compounds, such as amino acids playing a role in the protein production and metabolism regulations for life on Earth, nucleobases essential for DNA and RNA formation and mutation, and fatty acids that composed most of the eukaryote and prokaryote membranes on Earth and resist to environmental stress long enough to still be observed on Mars or ocean worlds in geological well-preserved records. The wet-chemistry chemical treatment consists of reacting an organic reagent with the sample to extract and volatilize polar or refractory organic molecules (i.e. dimethylformamide dimethyl acetal (DMF-DMA) in this study). DMF-DMA derivatizes functional groups with labile H in organics, without modifying their chiral conformation. The influence of pH and salt concentration of extraterrestrial materials on the DMF-DMA derivatization remains understudied. In this research, we studied the influence of different salts and pHs on the derivatization of organic molecules of astrobiological interest with DMF-DMA, such as amino acids, carboxylic acids, and nucleobases. Results show that salts and pH influence the derivatization yield, and that their effect depend on the nature of the organics and the salts studied. Second, monovalent salts lead to a higher or similar organic recovery compared to divalent salts regardless of pH below 8. However, a pH above 8 inhibits the DMF-DMA derivatization influencing the carboxylic acid function to become an anionic group without labile H. Overall, considering the negative effect of the salts on the detection of organic molecules, future space missions may have to consider a desalting step prior to derivatization and GC-MS analyses.