Search

Phosphorus (III) oxide (P$_4$O$_6$) has been suggested to be a major component of the gas phase phosphorus chemistry in the atmospheres of gas giant planets and of Venus. However, P$_4$O$_6$'s proposed role is based on thermodynamic modeling, itself based on values for the free energy of formation of P$_4$O$_6$ estimated from limited experimental data. Values of the standard Gibbs free energy of formation ($\Delta$Go(g)) of P$_4$O$_6$ in the literature differ by up to ~656 kJ/mol, a huge range. Depending on which value is assumed, P$_4$O$_6$ may either be the majority phosphorus species present or be completely absent from modeled atmospheres. Here, we critically review the literature thermodynamic values and compare their predictions to observed constraints on P$_4$O$_6$ geochemistry. We conclude that the widely used values from the NIST/JANAF database are almost certainly too low (predicting that P$_4$O$_6$ is more stable than is plausible). We show that, regardless of the value of $\Delta$Go(g) for P$_4$O$_6$ assumed, the formation of phosphine from P$_4$O$_6$ in the Venusian atmosphere is thermodynamically unfavorable. We conclude that there is a need for more robust data on both the thermodynamics of phosphorus chemistry for astronomical and geological modeling in general and for understanding the atmosphere of Venus and the gas giant planets in particular., Comment: Article published in ACS Earth Space Chem. https://pubs.acs.org/doi/full/10.1021/acsearthspacechem.3c00016

Measurements of trace gases in planetary atmospheres help us explore chemical conditions different to those on Earth. Our nearest neighbour, Venus, has cloud decks that are temperate but hyperacidic. Here we report the apparent presence of phosphine (PH3) gas in Venus’s atmosphere, where any phosphorus should be in oxidized forms. Single-line millimetre-waveband spectral detections (quality up to ~15σ) from the JCMT and ALMA telescopes have no other plausible identification. Atmospheric PH3 at ~20 ppb abundance is inferred. The presence of PH3 is unexplained after exhaustive study of steady-state chemistry and photochemical pathways, with no currently known abiotic production routes in Venus’s atmosphere, clouds, surface and subsurface, or from lightning, volcanic or meteoritic delivery. PH3 could originate from unknown photochemistry or geochemistry, or, by analogy with biological production of PH3 on Earth, from the presence of life. Other PH3 spectral features should be sought, while in situ cloud and surface sampling could examine sources of this gas. The detection of ~20 ppb of phosphine in Venus clouds by observations in the millimetre-wavelength range from JCMT and ALMA is puzzling, because according to our knowledge of Venus, no phosphine should be there. As the most plausible formation paths do not work, the source could be unknown chemical processes—maybe even life?

Theory and observation for the search for life on exoplanets via atmospheric "biosignature gases" is accelerating, motivated by the capabilities of the next generation of space- and ground-based telescopes. The most observationally accessible rocky planet atmospheres are those dominated by molecular hydrogen gas, because the low density of H$_2$-gas leads to an expansive atmosphere. The capability of life to withstand such exotic environments, however, has not been tested in this context. We demonstrate that single-celled microorganisms ($\textit{E. coli}$ and yeast) that normally do not inhabit H$_2$-dominated environments can survive and grow in a 100% H$_2$ atmosphere. We also describe the astonishing diversity of dozens of different gases produced by $\textit{E. coli}$, including many already proposed as potential biosignature gases (e.g., nitrous oxide, ammonia, methanethiol, dimethylsulfide, carbonyl sulfide, and isoprene). This work demonstrates the utility of lab experiments to better identify which kinds of alien environments can host some form of possibly detectable life., Nature Astronomy https://doi.org/10.1038/s41550-020-1069-4. V2 has a typo correction

A long-term goal of exoplanet studies is the identification and detection of biosignature gases. Beyond the most discussed biosignature gas O$_2$, only a handful of gases have been considered in detail. Here we evaluate phosphine (PH$_3$). On Earth, PH$_3$ is associated with anaerobic ecosystems, and as such is a potential biosignature gas on anoxic exoplanets. We simulate CO$_2-$ and H$_2-$dominated habitable terrestrial planet atmospheres. We find that PH$_3$ can accumulate to detectable concentrations on planets with surface production fluxes of 10$^{10}$-10$^{14}$ cm$^{-2}$ s$^{-1}$ (corresponding to surface concentrations of 10s of ppb to 100s of ppm), depending on atmospheric composition and UV flux. While high, such surface fluxes are comparable to the global terrestrial production rate of CH$_4$ (10$^{11}$ cm$^{-2}$ s$^{-1}$) and below the maximum local terrestrial PH$_3$ production rate (10$^{14}$ cm$^{-2}$ s$^{-1}$). As with other gases, PH$_3$ can more readily accumulate on low-UV planets, e.g. planets orbiting quiet M-dwarfs or with a photochemical UV shield. If detected, PH$_3$ is a promising biosignature gas, as it has no known abiotic false positives on terrestrial planets that could generate the high fluxes required for detection. PH$_3$ also has 3 strong spectral features such that in any atmosphere scenario 1 of the 3 will be unique compared to other dominant spectroscopic molecules. PH$_3$'s weakness as a biosignature gas is its high reactivity, requiring high outgassing for detectability. We calculate that 10s of hours of JWST time are required for a potential detection of PH$_3$. Yet because PH$_3$ is spectrally active in the same wavelength regions as other atmospherically important molecules (e.g., H$_2$O and CH$_4$), searches for PH$_3$ can be carried out at no additional observational cost to searches for other molecules relevant to exoplanet habitability., Accepted to Astrobiology. Expected publication info: Volume 20, Issue 2

In our previous paper we have modelled a dielectrophoretic force (DEP) and cell particle behavior in a microfluidic channel (Weber MU et al 2023 Chip for dielectrophoretic microbial capture, separation and detection I: theoretical basis of electrode design Nanotechnology this issue). Here we test and confirm the results of our modeling work by experimentally validating the theoretical design constraints of the ring electrode architecture. We have compared and tested the geometry and particle capture and separation performance of the two separate electrode designs (the ring and dot electrode structures) by investigating bacterial motion in response to the applied electric field. We have quantitatively evaluated the electroosmosis (EO) to positive DEP (PDEP) transition in both electrode designs and explained the differences in capture efficiency of the ring and dot electrode systems. The ring structure shows 99% efficiency of bacterial capture both for PDEP and for EO. Moreover, the ring structure shows an over 200 faster bacterial response to the electric field. We have also established that the ring electrode architecture, with appropriate structure periodicity and spacing, results in efficient capture and separation of microbial cells. We have identified several critical design constraints that are required to achieve high efficiency bacterial capture. We have established that the spacing between consecutive DEP traps smaller than the length of the depletion zone will ensure that the DEP force dominates bacterial motion over motility and Brownian motion.

Significance This research provides a transformative hypothesis for the chemistry of the atmospheric cloud layers of Venus while reconciling decades-long atmosphere anomalies. Our model predicts that the clouds are not entirely made of sulfuric acid, but are partially composed of ammonium salt slurries, which may be the result of biological production of ammonia in cloud droplets. As a result, the clouds are no more acidic than some extreme terrestrial environments that harbor life. Life could be making its own environment on Venus. The model’s predictions for the abundance of gases in Venus’ atmosphere match observation better than any previous model, and are readily testable., 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.

Bacterial culture methods, e.g. Plate Counting Method (PCM), are a gold standard in the assessment of microbial contamination in multitude of human industries. They are however slow, labor intensive, and prone to manual errors. Dielectrophoresis (DEP) has shown great promise for particle separation for decades; however, it has not yet been widely applied in routine laboratory setting. This paper provides an overview of a new DEP microbial capture and separation method called Fluid-Screen (FS), that achieves very fast, efficient, reliable and repeatable capture and separation of microbial cells. Method verification experiments demonstrated that the FS system captured 100% of bacteria in test samples, a capture efficiency much higher than previously reported for similar technology. Data generated supports the superiority of the FS method as compared to the established Plate Counting Method (PCM), that is routinely used to detect bacterial contamination in healthcare, pharmacological and food industries. We demonstrate that the FS method is universal and can capture and separate different species of bacteria and fungi to viruses, from various sample matrices (i.e. human red blood cells, mammalian cells).

The potential detection of ppb levels phosphine (PH3) in the clouds of Venus through millimeter-wavelength astronomical observations is extremely surprising as PH3 is an unexpected component of an oxidized environment of Venus. A thorough analysis of potential sources suggests that no known process in the consensus model of Venus' atmosphere or geology could produce PH3 at anywhere near the observed abundance. Therefore, if the presence of PH3 in Venus' atmosphere is confirmed, it is highly likely to be the result of a process not previously considered plausible for Venusian conditions. The source of atmospheric PH3 could be unknown geo- or photochemistry, which would imply that the consensus on Venus' chemistry is significantly incomplete. An even more extreme possibility is that strictly aerial microbial biosphere produces PH3. This paper summarizes the Venusian PH3 discovery and the scientific debate that arose since the original candidate detection one year ago., A short overview of the Venusian PH3 discovery and the scientific debate that arose since the original candidate detection in September 2020. Additional discussion of possible non-canonical sources of PH3 on Venus is also included. arXiv admin note: text overlap with arXiv:2009.06499

Phosphorus is an essential element for all life on Earth, yet trivalent phosphorus (e.g., in phosphines) appears to be almost completely absent from biology. Instead phosphorus is utilized by life almost exclusively as phosphate, apart from a small contingent of other pentavalent phosphorus compounds containing structurally similar chemical groups. In this work, we address four previously stated arguments as to why life does not explore trivalent phosphorus: (1) precedent (lack of confirmed instances of trivalent phosphorus in biochemicals suggests that life does not have the means to exploit this chemistry), (2) thermodynamic limitations (synthesizing trivalent phosphorus compounds is too energetically costly), (3) stability (phosphines are too reactive and readily oxidize in an oxygen (O2)-rich atmosphere), and (4) toxicity (the trivalent phosphorus compounds are broadly toxic). We argue that the first two of these arguments are invalid, and the third and fourth arguments only apply to the O2-rich environment of modern Earth. Specifically, both the reactivity and toxicity of phosphines are specific to aerobic life and strictly dependent on O2-rich environment. We postulate that anaerobic life persisting in anoxic (O2-free) environments may exploit trivalent phosphorus chemistry much more extensively. We review the production of trivalent phosphorus compounds by anaerobic organisms, including phosphine gas and an alkyl phosphine, phospholane. We suggest that the failure to find more such compounds in modern terrestrial life may be a result of the strong bias of the search for natural products toward aerobic organisms. We postulate that a more thorough identification of metabolites of the anaerobic biosphere could reveal many more trivalent phosphorus compounds. We conclude with a discussion of the implications of our work for the origin and early evolution of life, and suggest that trivalent phosphorus compounds could be valuable markers for both extraterrestrial life and the Shadow Biosphere on Earth.

The chemistry of life requires a solvent, which for life on Earth is water. Several alternative solvents have been suggested, but there is little quantitative analysis of their suitability as solvents for life. To support a novel (non-terrestrial) biochemistry, a solvent must be able to form a stable solution of a diverse set of small molecules and polymers, but must not dissolve all molecules. Here, we analyze the potential of concentrated sulfuric acid (CSA) as a solvent for biochemistry. As CSA is a highly effective solvent but a reactive substance, we focused our analysis on the stability of chemicals in sulfuric acid, using a model built from a database of kinetics of reaction of molecules with CSA. We consider the sulfuric acid clouds of Venus as a test case for this approach. The large majority of terrestrial biochemicals have half-lives of less than a second at any altitude in Venus’s clouds, but three sets of human-synthesized chemicals are more stable, with average half-lives of days to weeks at the conditions around 60 km altitude on Venus. We show that sufficient chemical structural and functional diversity may be available among those stable chemicals for life that uses concentrated sulfuric acid as a solvent to be plausible. However, analysis of meteoritic chemicals and possible abiotic synthetic paths suggests that postulated paths to the origin of life on Earth are unlikely to operate in CSA. We conclude that, contrary to expectation, sulfuric acid is an interesting candidate solvent for life, but further work is needed to identify a plausible route for life to originate in it.

We describe a dataset of the quantitative reactivity of organic chemicals with concentrated sulfuric acid. As well as being a key industrial chemical, sulfuric acid is of environmental and planetary importance. In the absence of measured reaction kinetics, the reaction rate of a chemical with sulfuric acid can be estimated from the reaction rate of structurally related chemicals. To allow an approximate prediction, we have collected 589 sets of kinetic data on the reaction of organic chemicals with sulfuric acid from 262 literature sources and used a functional group-based approach to build a model of how the functional groups would react in any sulfuric acid concentration from 60–100%, and between −20 °C and 100 °C. The data set provides the original reference data and kinetic measurements, parameters, intermediate computation steps, and a set of first-order rate constants for the functional groups across the range of conditions −20 °C–100 °C and 60–100% sulfuric acid. The dataset will be useful for a range of studies in chemistry and atmospheric sciences where the reaction rate of a chemical with sulfuric acid is needed but has not been measured.

Research for possible biosignature gases on habitable exoplanet atmosphere is accelerating. We add isoprene, C5H8, to the roster of biosignature gases. We found that formation of isoprene geochemical formation is highly thermodynamically disfavored and has no known abiotic false positives. The isoprene production rate on Earth rivals that of methane (~ 500 Tg yr-1). On Earth, isoprene is rapidly destroyed by oxygen-containing radicals, but its production is ubiquitous to a diverse array of evolutionarily distant organisms, from bacteria to plants and animals-few, if any at all, volatile secondary metabolite has a larger evolutionary reach. While non-photochemical sinks of isoprene may exist, the destruction of isoprene in an anoxic atmosphere is mainly driven by photochemistry. Motivated by the concept that isoprene might accumulate in anoxic environments, we model the photochemistry and spectroscopic detection of isoprene in habitable temperature, rocky exoplanet anoxic atmospheres with a variety of atmosphere compositions under different host star UV fluxes. Limited by an assumed 10 ppm instrument noise floor, habitable atmosphere characterization using JWST is only achievable with transit signal similar or larger than that for a super-Earth sized exoplanet transiting an M dwarf star with an H2-dominated atmosphere. Unfortunately, isoprene cannot accumulate to detectable abundance without entering a run-away phase, which occurs at a very high production rate, ~ 100 times Earth's production rate. In this run-away scenario isoprene will accumulate to > 100 ppm and its spectral features are detectable with ~ 20 JWST transits. One caveat is that some spectral features are hard to be distinguished from that of methane. Despite these challenges, isoprene is worth adding to the menu of potential biosignature gases., 62 pages, 24 figures

The search for signs of life on other worlds has largely focused on terrestrial planets. Recent work, however, argues that life could exist in the atmospheres of temperate sub-Neptunes. Here, we evaluate the usefulness of carbon dioxide isotopologues as evidence of aerial life. Carbon isotopes are of particular interest as metabolic processes preferentially use the lighter $^{12}$C over $^{13}$C. In principle, the upcoming James Webb Space Telescope (JWST) will be able to spectrally resolve the $^{12}$C and $^{13}$C isotopologues of CO$_{2}$, but not CO and CH$_{4}$. We simulated observations of CO$_{2}$ isotopologues in the H$_{2}$-dominated atmospheres of our nearest ($< 40$ pc), temperate (equilibrium temperature of 250-350 K) sub-Neptunes with M dwarf host stars. We find $^{13}$CO$_{2}$ and $^{12}$CO$_{2}$ distinguishable if the atmosphere is H$_{2}$-dominated with a few percentage points of CO$_{2}$ for the most idealized target with an Earth-like composition of the two most abundant isotopologues, $^{12}$CO$_{2}$ and $^{13}$CO$_{2}$. With a Neptune-like metallicity of 100$\times$ solar and a C/O of 0.55, we are unable to distinguish between $^{13}$CO$_{2}$ and $^{12}$CO$_{2}$ in the atmospheres of temperate sub-Neptunes. If atmospheric composition largely follows metallicity scaling, the concentration of CO$_{2}$ in a H$_{2}$-dominated atmosphere will be too low to distinguish CO$_{2}$ isotopologues with JWST. In contrast, at higher metallicities, there will be more CO$_{2}$, but the smaller atmospheric scale height makes the measurement impossible. Carbon dioxide isotopologues are unlikely to be useful biosignature gases for the JWST era. Instead, isotopologue measurements should be used to evaluate formation mechanisms of planets and exoplanetary systems., 11 pages, 3 figures. Published in the Astrophysical Journal on May 4, 2022. The final authenticated version is available online at: https://iopscience.iop.org/article/10.3847/1538-4357/ac625f/meta

The recent candidate detection of ~1 ppb of phosphine in the middle atmosphere of Venus is so unexpected that it requires an exhaustive search for explanations of its origin. Phosphorus-containing species have not been modelled for Venus' atmosphere before and our work represents the first attempt to model phosphorus species in the Venusian atmosphere. We thoroughly explore the potential pathways of formation of phosphine in a Venusian environment, including in the planet's atmosphere, cloud and haze layers, surface, and subsurface. We investigate gas reactions, geochemical reactions, photochemistry, and other non-equilibrium processes. None of these potential phosphine production pathways are sufficient to explain the presence of ppb phosphine levels on Venus. If PH3's presence in Venus' atmosphere is confirmed, it therefore is highly likely to be the result of a process not previously considered plausible for Venusian conditions. The process could be unknown geochemistry, photochemistry, or even aerial microbial life, given that on Earth phosphine is exclusively associated with anthropogenic and biological sources. The detection of phosphine adds to the complexity of chemical processes in the Venusian environment and motivates in situ follow up sampling missions to Venus. Our analysis provides a template for investigation of phosphine as a biosignature on other worlds., v2 is in press in Astrobiology, Special Collection: Venus; v2 also expands on the potential of phosphides from the deep mantle volcanism as a source of PH3 (as suggested by Truong and Lunine 2021: https://www.pnas.org/content/118/29/e2021689118) and shows the volcanic source of PH3 to be unlikely

We revisit the hypothesis that there is life in the Venusian clouds to propose a life cycle that resolves the conundrum of how life can persist aloft for hundreds of millions to billions of years. Most discussions of an aerial biosphere in the Venus atmosphere temperate layers never address whether the life-small microbial-type particles-is free floating or confined to the liquid environment inside cloud droplets. We argue that life must reside inside liquid droplets such that it will be protected from a fatal net loss of liquid to the atmosphere, an unavoidable problem for any free-floating microbial life forms. However, the droplet habitat poses a lifetime limitation: Droplets inexorably grow (over a few months) to large enough sizes that are forced by gravity to settle downward to hotter, uninhabitable layers of the Venusian atmosphere. (Droplet fragmentation-which would reduce particle size-does not occur in Venusian atmosphere conditions.) We propose for the first time that the only way life can survive indefinitely is with a life cycle that involves microbial life drying out as liquid droplets evaporate during settling, with the small desiccated 'spores' halting at, and partially populating, the Venus atmosphere stagnant lower haze layer (33-48 km altitude). We, thus, call the Venusian lower haze layer a 'depot' for desiccated microbial life. The spores eventually return to the cloud layer by upward diffusion caused by mixing induced by gravity waves, act as cloud condensation nuclei, and rehydrate for a continued life cycle. We also review the challenges for life in the extremely harsh conditions of the Venusian atmosphere, refuting the notion that the 'habitable' cloud layer has an analogy in any terrestrial environment., Open Access Astrobiology Article

Despite more than one hundred years of work on organosilicon chemistry, the basis for the plausibility of silicon-based life has never been systematically addressed nor objectively reviewed. We provide a comprehensive assessment of the possibility of silicon-based biochemistry, based on a review of what is known and what has been modeled, even including speculative work. We assess whether or not silicon chemistry meets the requirements for chemical diversity and reactivity as compared to carbon. To expand the possibility of plausible silicon biochemistry, we explore silicon&rsquo, s chemical complexity in diverse solvents found in planetary environments, including water, cryosolvents, and sulfuric acid. In no environment is a life based primarily around silicon chemistry a plausible option. We find that in a water-rich environment silicon&rsquo, s chemical capacity is highly limited due to ubiquitous silica formation, silicon can likely only be used as a rare and specialized heteroatom. Cryosolvents (e.g., liquid N2) provide extremely low solubility of all molecules, including organosilicons. Sulfuric acid, surprisingly, appears to be able to support a much larger diversity of organosilicon chemistry than water.

Only about 100 natural products are known to contain a nitrogen-sulfur (N-S) bond. This review thoroughly categorizes N-S bond-containing compounds by structural class. Information on biological source, biological activity, and biosynthesis is included, if known. We also review the role of N-S bond functional groups as post-translational modifications of amino acids in proteins and peptides, emphasizing their role in the metabolism of the cell.

A subset of B-cell lymphoma patients have dominant mutations in the histone H3 lysine 27 (H3K27) methyltransferase EZH2, which change it from a monomethylase to a trimethylase. These mutations occur in aromatic resides surrounding the active site and increase growth and alter transcription. We study the N-terminal trimethylase NRMT1 and the N-terminal monomethylase NRMT2. They are 50% identical, but differ in key aromatic residues in their active site. Given how these residues affect EZH2 activity, we tested whether they are responsible for the distinct catalytic activities of NRMT1/2. Additionally, NRMT1 acts as a tumor suppressor in breast cancer cells. Its loss promotes oncogenic phenotypes but sensitizes cells to DNA damage. Mutations of NRMT1 naturally occur in human cancers, and we tested a select group for altered activity. While directed mutation of the aromatic residues had minimal catalytic effect, NRMT1 mutants N209I (endometrial cancer) and P211S (lung cancer) displayed decreased trimethylase and increased monomethylase/dimethylase activity. Both mutations are located in the peptide-binding channel and indicate a second structural region impacting enzyme specificity. The NRMT1 mutants demonstrated a slower rate of trimethylation and a requirement for higher substrate concentration. Expression of the mutants in wild type NRMT backgrounds showed no change in N-terminal methylation levels or growth rates, demonstrating they are not acting as dominant negatives. Expression of the mutants in cells lacking endogenous NRMT1 resulted in minimal accumulation of N-terminal trimethylation, indicating homozygosity could help drive oncogenesis or serve as a marker for sensitivity to DNA damaging chemotherapeutics or γ-irradiation.

Unambiguously identifying molecules in spectra is of fundamental importance for a variety of scientific and industrial uses. Interpreting atmospheric spectra for the remote detection of volatile compounds requires information about the spectrum of each relevant molecule. However, spectral data currently exist for a few hundred molecules and only a fraction of those have complete spectra (e.g. H2O, NH3). Consequently, molecular detections in atmospheric spectra remain vulnerable to false positives, false negatives, and missassignments. There is a key need for spectral data for a broad range of molecules. Given how challenging it is to obtain high-resolution molecular spectra, there is great value in creating intermediate approximate spectra that can provide a starting point for the analysis of atmospheric spectra. Using a combination of experimental measurements, organic chemistry, and quantum mechanics, RASCALL (Rapid Approximate Spectral Calculations for ALL) is a computational approach that provides approximate spectral data for any given molecule, including thousands of potential atmospheric gases. RASCALL is a new theoretical chemistry method for the simulation of spectral data. RASCALL 1.0, presented here, is capable of simulating molecular spectral data, in a few seconds, by interpreting functional group data from experimental and theoretical sources to estimate the position and strength of molecular bands. The RASCALL 1.0 spectra consist of approximate band centers and qualitative intensities. RASCALL 1.0 is also able to assess hundreds of molecules simultaneously, which will inform prioritization protocols for future, computationally and experimentally costly, high-accuracy physical chemistry studies. Finally, RASCALL can be used to study spectral patterns between molecules, highlighting ambiguities in molecular detections and also directing observations towards spectral regions that reduce the degeneracy in molecular identification. The RASCALL catalogue, and its preliminary version RASCALL 1.0, contains spectral data for more molecules than any other publicly available database, with applications in all fields interested in the detection of molecules in the gas phase (e.g., medical imaging, petroleum industry, pollution monitoring, astrochemistry). The preliminary catalogue of molecular data and associated documentation are freely available online and will be routinely updated.

Thousands of exoplanets are known to orbit nearby stars. Plans for the next generation of space-based and ground-based telescopes are fueling the anticipation that a precious few habitable planets can be identified in the coming decade. Even more highly anticipated is the chance to find signs of life on these habitable planets by way of biosignature gases. But which gases should we search for? Although a few biosignature gases are prominent in Earth's atmospheric spectrum (O2, CH4, N2O), others have been considered as being produced at or able to accumulate to higher levels on exo-Earths (e.g., dimethyl sulfide and CH3Cl). Life on Earth produces thousands of different gases (although most in very small quantities). Some might be produced and/or accumulate in an exo-Earth atmosphere to high levels, depending on the exo-Earth ecology and surface and atmospheric chemistry. To maximize our chances of recognizing biosignature gases, we promote the concept that all stable and potentially volatile molecules should initially be considered as viable biosignature gases. We present a new approach to the subject of biosignature gases by systematically constructing lists of volatile molecules in different categories. An exhaustive list up to six non-H atoms is presented, totaling about 14,000 molecules. About 2500 of these are CNOPSH compounds. An approach for extending the list to larger molecules is described. We further show that about one-fourth of CNOPSH molecules (again, up to N = 6 non-H atoms) are known to be produced by life on Earth. The list can be used to study classes of chemicals that might be potential biosignature gases, considering their accumulation and possible false positives on exoplanets with atmospheres and surface environments different from Earth's. The list can also be used for terrestrial biochemistry applications, some examples of which are provided. We provide an online community usage database to serve as a registry for volatile molecules including biogenic compounds.Astrobiology-Atmospheric gases-Biosignatures-Exoplanets. Astrobiology 16, 465-485.

A fundamental goal of biology is to understand the rules behind life's use of chemical space. Established work focuses on why life uses the chemistry that it does. Given the enormous scope of possible chemical space, we postulate that it is equally important to ask why life largely avoids certain areas of chemical space. The nitrogen-sulfur bond is a prime example, as it rarely appears in natural molecules, despite the very rich N-S bond chemistry applied in various branches of industry (e.g., industrial materials, agrochemicals, pharmaceuticals). We find that, out of more than 200,000 known, unique compounds made by life, only about 100 contain N-S bonds. Furthermore, the limited number of N-S bond-containing molecules that life produces appears to fall into a few very distinctive structural groups. One may think that industrial processes are unrelated to biochemistry because of a greater possibility of solvents, catalysts, and temperatures available to industry than to the cellular environment. However, the fact that life does rarely make N-S bonds, from the plentiful precursors available, and has evolved the ability to do so independently several times, suggests that the restriction on life's use of N-S chemistry is not in its synthesis. We present a hypothesis to explain life's extremely limited usage of the N-S bond: that the N-S bond chemistry is incompatible with essential segments of biochemistry, specifically with thiols. We support our hypothesis by (1) a quantitative analysis of the occurrence of N-S bond-containing natural products and (2) reactivity experiments between selected N-S compounds and key biological molecules. This work provides an example of a reason why life nearly excludes a distinct region of chemical space. Combined with future examples, this potentially new field of research may provide fresh insight into life's evolution through chemical space and its origin and early evolution.

We present a new model for the biological production of phosphine (PH3). Phosphine is found globally, in trace amounts, in the Earth's atmosphere. It has been suggested as a key molecule in the phosphorus cycle, linking atmospheric, lithospheric and biological phosphorus chemistry. Phosphine's production is strongly associated with marshes, swamps and other sites of anaerobic biology. However the mechanism of phosphine's biological production has remained controversial, because it has been believed that reduction of phosphate to phosphine is endergonic. In this paper we show through thermodynamic calculations that, in specific environments, the combined action of phosphate reducing and phosphite disproportionating bacteria can produce phosphine. Phosphate-reducing bacteria can capture energy from the reduction of phosphate to phosphite through coupling phosphate reduction to NADH oxidation. Our hypothesis describes how the phosphate chemistry in an environmental niche is coupled to phosphite generation in ground water, which in turn is coupled to the phosphine production in water and atmosphere, driven by a specific microbial ecology. Our hypothesis provides clear predictions on specific complex environments where biological phosphine production could be widespread. We propose tests of our hypothesis in fieldwork.