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Hydrogen sulfate protic ionic liquids may exhibit exceptional stability under warm, low-pressure planetary conditions, where conventional solvents would evaporate, making them plausible persistent fluids on sulfur-rich planetary surfaces. Yet their physicochemical behavior under hydration remains poorly constrained. We investigate glycinium hydrogen sulfate ionic liquid [GlyH+][ HSO4− ] mixed with 0%–80% water by volume using infrared spectroscopy, cryogenic electron microscopy (cryo-EM), and molecular dynamics simulations. We identify two distinct phases separated by a critical transition at ∼3 water molecules per ion pair (35% v/v water). Below this threshold, water molecules integrate into ionic liquid polar domains without disrupting HSO4− – HSO4− hydrogen-bonded networks, maintaining a homogeneous phase visible by cryo-EM. Above this threshold, the mixture undergoes phase inversion, forming 10 ± 2 nm ionic liquid aggregates dispersed in continuous water. Infrared spectroscopy reveals a sharp decrease in the strong/weak hydrogen bonding ratio at this transition point. At 70% water, cryo-EM shows uniform spherical nanodomains, each containing ∼3100 ion pairs with hydrated shells surrounding neat ionic liquid cores. Molecular dynamics simulations confirm spontaneous segregation into pure water regions and intact ionic liquid domains separated by interfacial zones. These findings demonstrate that hydrogen sulfate ionic liquids exposed to episodic water on planetary surfaces would persist as functional nanoscale compartments rather than fully mixing and dissolving in water. Our work has implications for planetary solvent availability, solute aggregation, and prebiotic chemistry in nonaqueous brines.

The atmosphere of Venus remains mysterious, with many outstanding chemical connundra. These include the unexpected presence of ∼10 ppm O₂ in the cloud layers, an unknown composition of large particles in the lower cloud layers, and hard to explain measured vertical abundance profiles of SO₂ and H₂O. We propose a hypothesis for the chemistry in the clouds that largely addresses all of the above anomalies. We include ammonia (NH₃), a key component that has been tentatively detected both by the Venera 8 and Pioneer Venus probes. NH₃ dissolves in some of the sulfuric acid cloud droplets, effectively neutralizing the acid and trapping dissolved SO₂ as ammonium sulfite salts. This trapping of SO₂ in the clouds, together with the release of SO₂ below the clouds as the droplets settle out to higher temperatures, explains the vertical SO₂ abundance anomaly. A consequence of the presence of NH₃ is that some Venus cloud droplets must be semisolid ammonium salt slurries, with a pH of ∼1, which matches Earth acidophile environments, rather than concentrated sulfuric acid. The source of NH₃ is unknown but could involve biological production; if so, then the most energy-efficient NH₃-producing reaction also creates O₂, explaining the detection of O₂ in the cloud layers. Our model therefore predicts that the clouds are more habitable than previously thought, and may be inhabited. Unlike prior atmospheric models, ours does not require forced chemical constraints to match the data. Our hypothesis, guided by existing observations, can be tested by new Venus in situ measurements.

Life on Earth is known to rarely make fluorinated carbon compounds, as compared to other halocarbons. We quantify this rarity, based on our exhaustive natural products database curated from available literature. We build on explanations for the scarcity of fluorine chemistry in life on Earth, namely that the exclusion of the C–F bond stems from the unique physico-chemical properties of fluorine, predominantly its extreme electronegativity and strong hydration shell. We further show that the C–F bond is very hard to synthesize and when it is made by life its potential biological functions can be readily provided by alternative functional groups that are much less costly to incorporate into existing biochemistry. As a result, the overall evolutionary cost-to-benefit balance of incorporation of the C–F bond into the chemical repertoire of life is not favorable. We argue that the limitations of organofluorine chemistry are likely universal in that they do not exclusively apply to specifics of Earth’s biochemistry. C–F bonds, therefore, will be rare in life beyond Earth no matter its chemical makeup.

Phosphorous-containing molecules are essential constituents of all living cells. While the phosphate functional group is very common in small molecule natural products, nucleic acids, and as chemical modification in protein and peptides, phosphorous can form P–N (phosphoramidate), P–S (phosphorothioate), and P–C (e.g., phosphonate and phosphinate) linkages. While rare, these moieties play critical roles in many processes and in all forms of life. In this review we thoroughly categorize P–N, P–S, and P–C natural organophosphorus compounds. Information on biological source, biological activity, and biosynthesis is included, if known. This review also summarizes the role of phosphorylation on unusual amino acids in proteins (N- and S-phosphorylation) and reviews the natural phosphorothioate (P–S) and phosphoramidate (P–N) modifications of DNA and nucleotides with an emphasis on their role in the metabolism of the cell. We challenge the commonly held notion that nonphosphate organophosphorus functional groups are an oddity of biochemistry, with no central role in the metabolism of the cell. We postulate that the extent of utilization of some phosphorus groups by life, especially those containing P–N bonds, is likely severely underestimated and has been largely overlooked, mainly due to the technological limitations in their detection and analysis.

Recent renewed interest in the possibility of life in the acidic clouds of Venus has led to new studies on organic chemistry in concentrated sulfuric acid. We have previously found that the majority of amino acids are stable in the range of Venus’ cloud sulfuric acid concentrations (81% and 98% w/w, the rest being water). The natural next question is whether dipeptides, as precursors to larger peptides and proteins, could be stable in this environment. We investigated the reactivity of the peptide bond using 20 homodipeptides and find that the majority of them undergo solvolysis within a few weeks, at both sulfuric acid concentrations. Notably, a few exceptions exist. HH and GG dipeptides are stable in 98% w/w sulfuric acid for at least 4 months, while II, LL, VV, PP, RR and KK resist hydrolysis in 81% w/w sulfuric acid for at least 5 weeks. Moreover, the breakdown process of the dipeptides studied in 98% w/w concentrated sulfuric acid is different from the standard acid-catalyzed hydrolysis that releases monomeric amino acids. Despite a few exceptions at a single concentration, no homodipeptides have demonstrated stability across both acid concentrations studied. This indicates that any hypothetical life on Venus would likely require a functional substitute for the peptide bond that can maintain stability throughout the range of sulfuric acid concentrations present.

Recent findings demonstrate that concentrated sulfuric acid supports rich organic chemistry, including the stability of the canonical DNA bases adenine, thymine, guanine and cytosine. Yet, due to full protonation in concentrated sulfuric acid, these bases may not pair as effectively as they do in water. We are therefore motivated to study nucleic acid bases that pair via hydrophobic and van der Waals interactions instead of canonical hydrogen bonding. Here, we investigate the stability of 14 selected, commercially available alternative nucleobases in concentrated sulfuric acid to evaluate their potential for forming DNA-like polymers in this solvent. The reactivity of compounds 1–14 have not been previously investigated in concentrated sulfuric acid. We incubate the selected compounds in 98% and 81% w/w sulfuric acid and monitor their stability using 1H and 13C NMR spectroscopy over 3 weeks at room temperature. In 98% w/w sulfuric acid, six bases—benzo[c][1,2,5]thiadiazole (1), 2,2′-bipyridine (2), 1,1′-biphenyl (3), 1-methoxy-3-methylbenzene (MMO2) (7) and 1-chloro-3-methoxybenzene (ClMO) (13), and 2,4-difluorotoluene (14)—remain soluble and stable with no detectable degradation. A few compounds show non-destructive reactivity, like sulfonation (compound 3) or H/D exchange (compounds 7, 13, 14). The other compounds react rapidly or are insoluble in 98% w/w sulfuric acid. In 81% w/w sulfuric acid, only compounds 1 and 2 remain stable and soluble, while other selected compounds are insoluble or unstable. Our findings identify a subset of alternative bases stable in concentrated sulfuric acid, advancing efforts towards the design of an example genetic-like polymer in this unusual solvent. Our work further highlights sulfuric acid’s potential for supporting complex organic chemistry, with implications for astrobiology, planetary science of Venus and synthetic biology.

About 2.5 billion years ago, microbes learned to harness plentiful solar energy to reduce CO2 with H2O, extracting energy and producing O2 as waste. O2 production from this metabolic process was so vigorous that it saturated its photochemical sinks, permitting it to reach “runaway” conditions and rapidly accumulate in the atmosphere despite its reactivity. Here we argue that O2 may not be unique: diverse gases produced by life may experience a “runaway” effect similar to O2. This runaway occurs because the ability of an atmosphere to photochemically cleanse itself of trace gases is generally finite. If produced at rates exceeding this finite limit, even reactive gases can rapidly accumulate to high concentrations and become potentially detectable. Planets orbiting smaller, cooler stars, such as the M dwarfs that are the prime targets for the James Webb Space Telescope (JWST), are especially favorable for runaway, due to their lower UV emission compared to higher-mass stars. As an illustrative case study, we show that on a habitable exoplanet with an H2–N2 atmosphere and net surface production of NH3 orbiting an M dwarf (the “Cold Haber World” scenario), the reactive biogenic gas NH3 can enter runaway, whereupon an increase in the surface production flux of one order of magnitude can increase NH3 concentrations by three orders of magnitude and render it detectable by JWST in just two transits. Our work on this and other gases suggests that diverse signs of life on exoplanets may be readily detectable at biochemically plausible production rates.

Waste gas products from technological civilizations may accumulate in an exoplanet atmosphere to detectable levels. We propose nitrogen trifluoride (NF 3 ) and sulfur hexafluoride (SF 6 ) as ideal technosignature gases. Earth life avoids producing or using any N–F or S–F bond-containing molecules and makes no fully fluorinated molecules with any element. NF 3 and SF 6 may be universal technosignatures owing to their special industrial properties, which unlike biosignature gases, are not species-dependent. Other key relevant qualities of NF 3 and SF 6 are: their extremely low water solubility, unique spectral features, and long atmospheric lifetimes. NF 3 has no non-human sources and was absent from Earth’s pre-industrial atmosphere. SF 6 is released in only tiny amounts from fluorine-containing minerals, and is likely produced in only trivial amounts by volcanic eruptions. We propose a strategy to rule out SF 6 ’s abiotic source by simultaneous observations of SiF 4 , which is released by volcanoes in an order of magnitude higher abundance than SF 6 . Other fully fluorinated human-made molecules are of interest, but their chemical and spectral properties are unavailable. We summarize why life on Earth—and perhaps life elsewhere—avoids using F. We caution, however, that we cannot definitively disentangle an alien biochemistry byproduct from a technosignature gas.

Exoplanet atmospheres are expected to vary significantly in thickness and chemical composition, leading to a continuum of differences in surface pressure and atmospheric density. This variability is exemplified within our Solar System, where the four rocky planets exhibit surface pressures ranging from 1 nPa on Mercury to 9.2 MPa on Venus. The direct effects and potential challenges of atmospheric pressure and density on life have rarely been discussed. For instance, atmospheric density directly affects the possibility of active flight in organisms, a critical factor since without it, dispersing across extensive and inhospitable terrains becomes a major limitation for the expansion of complex life. In this paper, we propose the existence of a critical atmospheric density threshold below which active flight is unfeasible, significantly impacting biosphere development. To qualitatively assess this threshold and differentiate it from energy availability constraints, we analyze the limits of active flight on Earth, using the common fruit fly,  Drosophila melanogaster , as a model organism. We subjected Drosophila melanogaster to various atmospheric density scenarios and reviewed previous data on flight limitations. Our observations show that flies in an N 2 -enriched environment recover active flying abilities more efficiently than those in a helium-enriched environment, highlighting behavioral differences attributable to atmospheric density vs. oxygen deprivation.

Searches for phosphine in Venus' atmosphere have sparked a debate. Cordiner et al. (2022, https://doi.org/10.1029/2022gl101055) analyze spectra from the Stratospheric Observatory For Infrared Astronomy (SOFIA) and infer <0.8 ppb of PH3. We noticed that some spectral artifacts arose from non‐essential calibration‐load signals. By‐passing these signals allows simpler post‐processing and a 5.7σ candidate detection, suggesting ∼3 ppb of PH3 above the clouds. Compiling six phosphine results hints at an inverted abundance trend: decreasing above the clouds but rising again in the mesosphere from some unexplained source. However, no such extra source is needed if phosphine is undergoing destruction by sunlight (photolysis), to a similar degree as on Earth. Low phosphine values/limits are found where the viewed part of the super‐rotating Venusian atmosphere had passed through sunlight, while high values are from views moving into sunlight. We suggest Venusian phosphine is indeed present, and so merits further work on models of its origins. Plain Language Summary Cordiner et al. (2022, https://doi.org/10.1029/2022gl101055) find no phosphine in Venus' atmosphere, using the airborne SOFIA telescope. By‐passing some instrumental effects, we extract a detection with 5.7σ‐confidence from the same data. We can resolve the tension between high and low PH3 abundance values by noticing that the former are from “mornings” in Venus' atmosphere and the latter from “evenings.” Sunlight reduces the amount of phosphine in Earth's atmosphere by an order of magnitude, so similarly on Venus, we might expect lower abundances in data taken when the part of the atmosphere observed has passed through sunlight. If the six available data sets can be reconciled in this way, further modeling of possible sources of PH3 (e.g., volcanic, disequilibrium chemistry, extant life) seem worthwhile. Key Points We recover Venusian phosphine in SOFIA spectra by reducing contaminating signals; the PH3 abundance is ∼3 part‐per billion (ppb) Six recoveries/limits show PH3 depleting between clouds and mesosphere, which would require an unknown re‐formation process or extra source Recoveries and upper limits can instead be reconciled by PH3 photolysis, as high/low abundances correspond to Venusian mornings/evenings