The exclusive presence of β-D-ribofuranose in nucleic acids is still a conundrum in prebiotic chemistry, given that pyranose species are substantially more stable at equilibrium. However, a precise ...characterisation of the relative furanose/pyranose fraction at temperatures higher than about 50 °C is still lacking. Here, we employ a combination of NMR measurements and statistical mechanics modelling to predict a population inversion between furanose and pyranose at equilibrium at high temperatures. More importantly, we show that a steady temperature gradient may steer an open isomerisation network into a non-equilibrium steady state where furanose is boosted beyond the limits set by equilibrium thermodynamics. Moreover, we demonstrate that nonequilibrium selection of furanose is maximum at optimal dissipation, as gauged by the temperature gradient and energy barriers for isomerisation. The predicted optimum is compatible with temperature drops found in hydrothermal vents associated with extremely fresh lava flows on the seafloor.
We constrained the origin and genetic environment of modern iron ooids (sand-sized grains with a core and external cortex of concentric laminae) providing new tools for the interpretation of their ...fossil counterparts as well as the analogous particles discovered on Mars. Here, we report an exceptional, unique finding of a still active deposit of submillimetric iron ooids, under formation at the seabed at a depth of 80 m over an area characterized by intense hydrothermal activity off Panarea, a volcanic island north of Sicily (Italy). An integrated analysis, carried out by X-ray Powder Diffraction, Environmental Scanning Electron Microscopy, X-ray Fluorescence and Raman spectroscopy reveals that Panarea ooids are deposited at the seafloor as concentric laminae of primary goethite around existing nuclei. The process is rapid, and driven by hydrothermal fluids as iron source. A sub-spherical, laminated structure resulted from constant agitation and by degassing of CO
-dominated fluids through seafloor sediments. Our investigations point the hydrothermal processes as responsible for the generation of the Panarea ooids, which are neither diagenetic nor reworked. The presence of ooids at the seawater-sediments interface, in fact, highlights how their development and growth is still ongoing. The proposed results show a new process responsible for ooids formation and gain a new insight into the genesis of iron ooids deposits that are distributed at global scale in both modern and past sediments.
The search for traces of life is one of the principal objectives of Mars exploration. Central to this objective is the concept of habitability, the set of conditions that allows the appearance of ...life and successful establishment of microorganisms in any one location. While environmental conditions may have been conducive to the appearance of life early in martian history, habitable conditions were always heterogeneous on a spatial scale and in a geological time frame. This "punctuated" scenario of habitability would have had important consequences for the evolution of martian life, as well as for the presence and preservation of traces of life at a specific landing site. We hypothesize that, given the lack of long-term, continuous habitability, if martian life developed, it was (and may still be) chemotrophic and anaerobic. Obtaining nutrition from the same kinds of sources as early terrestrial chemotrophic life and living in the same kinds of environments, the fossilized traces of the latter serve as useful proxies for understanding the potential distribution of martian chemotrophs and their fossilized traces. Thus, comparison with analog, anaerobic, volcanic terrestrial environments (Early Archean >3.5-3.33 Ga) shows that the fossil remains of chemotrophs in such environments were common, although sparsely distributed, except in the vicinity of hydrothermal activity where nutrients were readily available. Moreover, the traces of these kinds of microorganisms can be well preserved, provided that they are rapidly mineralized and that the sediments in which they occur are rapidly cemented. We evaluate the biogenicity of these signatures by comparing them to possible abiotic features. Finally, we discuss the implications of different scenarios for life on Mars for detection by in situ exploration, ranging from its non-appearance, through preserved traces of life, to the presence of living microorganisms.
Mars-Early Earth-Anaerobic chemotrophs-Biosignatures-Astrobiology missions to Mars.
Modern biological dependency on trace elements is proposed to be a consequence of their enrichment in the habitats of early life together with Earth's evolving physicochemical conditions; the ...resulting metallic biological complement is termed the metallome. Herein, we detail a protocol for describing metallomes in deep time, with applications to the earliest fossil record. Our approach extends the metallome record by more than 3 Ga and provides a novel, non-destructive method of estimating biogenicity in the absence of cellular preservation. Using microbeam particle-induced X-ray emission (µPIXE), we spatially quantify transition metals and metalloids within organic material from 3.33 billion-year-old cherts of the Barberton greenstone belt, and demonstrate that elements key to anaerobic prokaryotic molecular nanomachines, including Fe, V, Ni, As and Co, are enriched within carbonaceous material. Moreover, Mo and Zn, likely incorporated into enzymes only after the Great Oxygenation Event, are either absent or present at concentrations below the limit of detection of µPIXE, suggesting minor biological utilisation in this environmental setting. Scanning and transmission electron microscopy demonstrates that metal enrichments do not arise from accumulation in nanomineral phases and thus unambiguously reflect the primary composition of the carbonaceous material. This carbonaceous material also has δ
C between -41.3‰ and 0.03‰, dominantly -21.0‰ to -11.5‰, consistent with biological fractionation and mostly within a restricted range inconsistent with abiotic processes. Considering spatially quantified trace metal enrichments and negative δ
C fractionations together, we propose that, although lacking cellular preservation, this organic material has biological origins and, moreover, that its precursor metabolism may be estimated from the fossilised "palaeo-metallome". Enriched Fe, V, Ni and Co, together with petrographic context, suggests that this kerogen reflects the remnants of a lithotrophic or organotrophic consortium cycling methane or nitrogen. Palaeo-metallome compositions could be used to deduce the metabolic networks of Earth's earliest ecosystems and, potentially, as a biosignature for evaluating the origin of preserved organic materials found on Mars.
The Middle Marker – horizon H1 of the Hooggenoeg Formation – is the oldest sedimentary horizon in the Barberton greenstone belt and one of the oldest sedimentary horizons on Earth. Herein, we ...describe a range of carbonaceous microstructures in this unit which bear resemblance to phototrophic microbial biofilms, biosedimentary structures, and interpreted microfossils in contemporaneous greenstone belts from the Early Archaean. Post-depositional iron-rich fluid cycling through these sediments has resulted in the precipitation of pseudo-laminated structures, which also bear resemblance, at the micron-scale, to certain microbial mat-like structures, although are certainly abiogenic. Poor preservation of multiple putative microbial horizons due to coarse volcaniclastic sedimentation and synsedimentary fragmentation by hydrothermal fluid also makes a conclusive assessment of biogenicity challenging. Nonetheless, several laminated morphologies within volcaniclastic sandstones and siltstones and coarse-grained volcaniclastic sandstones are recognisable as syngenetic photosynthetic microbial biofilms and microbially induced sedimentary structures; therefore, the Middle Marker preserves the oldest evidence for life in the Barberton greenstone belt. Among these biosignatures are fine, crinkly, micro-tufted, laminated microbial mats, pseudo-tufted laminations and wisp-like carbonaceous fragments interpreted as either partially formed biofilms or their erosional products. In the same sediments, lenticular objects, which have previously been interpreted as bona fide microfossils, are rare but recurrent finds whose biogenicity we question. The Middle Marker preserves an ancient record of epibenthic microbial communities flourishing, struggling and perishing in parallel with a waning volcanic cycle, an environment upon which they depended and through which they endured. Direct comparisons can be made between environment-level characters of the Middle Marker and other Early Archaean cherts, suggesting that shallow-water, platformal, volcanogenic-hydrothermal biocoenoses were major microbial habitats throughout the Archaean.
Micro‐Raman spectrometers are used in various domains, from archaeology to space exploration. These systems use microscope objectives to focus the laser onto the sample to be analysed. Although this ...method drastically increases the spatial resolution down to a few hundreds of nanometres, it is also commonly admitted that this focused laser beam may heat and alter the studied material. The setting of the laser power is thus a universal problem for any micro‐Raman spectroscopy user who has to find a compromise between the Raman signal intensity and the risk of thermal alteration. This parameter is not easy to set based on bibliographic references because, depending on the architecture of the system used, on the laser wavelength and on the sample, damage may occur at very different laser power levels. Here, we describe the different parameters that influence thermal increase induced by the laser and propose easy to make experiments to measure them. A series of experiments is then carried out to study the thermal alteration of various materials when exposed to a laser beam focused with the different microscope objectives of a micro‐Raman system. It is shown that, except for very thin samples or powdered materials, the relevant parameters to consider are the laser power at the sample surface and the duration of exposure to the laser beam, whatever the objective used. We also demonstrate that the risk of sample alteration is almost non‐existent for thick transparent materials. Interestingly, it is shown that, for semi‐transparent materials, alteration may occur at lower laser power for low magnification objectives than for high magnification objectives. These results are explained by the high aperture angle of microscope objectives which induces high dispersion of the laser within the sample.
The different parameters to consider in order to evaluate the thermal increase induced by the laser during micro‐Raman analyses are described and illustrated using a series of experiments. It is shown that the risk of sample alteration is quasi‐null for transparent materials and that, except for very opaque or very thin samples, the relevant parameter to consider is the laser power, whatever the objective.
BIOMEX (BIOlogy and Mars EXperiment) is an ESA/Roscosmos space exposure experiment housed within the exposure facility EXPOSE-R2 outside the Zvezda module on the International Space Station (ISS). ...The design of the multiuser facility supports-among others-the BIOMEX investigations into the stability and level of degradation of space-exposed biosignatures such as pigments, secondary metabolites, and cell surfaces in contact with a terrestrial and Mars analog mineral environment. In parallel, analysis on the viability of the investigated organisms has provided relevant data for evaluation of the habitability of Mars, for the limits of life, and for the likelihood of an interplanetary transfer of life (theory of lithopanspermia). In this project, lichens, archaea, bacteria, cyanobacteria, snow/permafrost algae, meristematic black fungi, and bryophytes from alpine and polar habitats were embedded, grown, and cultured on a mixture of martian and lunar regolith analogs or other terrestrial minerals. The organisms and regolith analogs and terrestrial mineral mixtures were then exposed to space and to simulated Mars-like conditions by way of the EXPOSE-R2 facility. In this special issue, we present the first set of data obtained in reference to our investigation into the habitability of Mars and limits of life. This project was initiated and implemented by the BIOMEX group, an international and interdisciplinary consortium of 30 institutes in 12 countries on 3 continents. Preflight tests for sample selection, results from ground-based simulation experiments, and the space experiments themselves are presented and include a complete overview of the scientific processes required for this space experiment and postflight analysis. The presented BIOMEX concept could be scaled up to future exposure experiments on the Moon and will serve as a pretest in low Earth orbit.
•Extraterrestrial organic matter is detected by EPR in 3.33 Ga sediments.•It is associated with Ni-Cr-rich ferrite “cosmic” spinel nanoparticles.•A challenge for the research for organic traces of ...extinct life in Mars.
Electron paramagnetic resonance (EPR) analysis of carbonaceous, volcanic, tidal sediments from the 3.33 Ga-old Josefsdal Chert (Kromberg Formation, Barberton Greenstone Belt), documents the presence of two types of insoluble organic matter (IOM): (1) IOM similar to that previously found in Archean cherts from numerous other sedimentary rocks in the world and of purported biogenic origin; (2) anomalous IOM localized in a 2 mm-thick sedimentary horizon. Detailed analysis by continuous-wave-EPR and pulse-EPR reveals that IOM in this layer is similar to the insoluble component of the hydrogenated organic matter in carbonaceous chondrites, suggesting that this narrow sedimentary horizon has preserved organic matter of extraterrestrial origin. This conclusion is supported by the presence in this thin layer of another anomalous EPR signal at g = 3 attributed to Ni-Cr-Al ferrite spinel nanoparticles, which are known to form during atmospheric entry of cosmic objects. From this EPR analysis, it was deduced that the anomalous sedimentary layer originates from deposition, in a nearshore environment, of a cloud of tiny dust particles originating from a flux of micrometeorites falling through the oxygen-poor Archean atmosphere.
Cell fixation is an essential approach for preserving cell morphology, allowing the targeting and labelling of biomolecules with fluorescent probes. One of the key requirements for more efficient ...fluorescent labelling is the preservation of cell morphology, which usually requires a combination of several fixation techniques. In addition, the use of a counter stain is often essential to improve the contrast of the fluorescent probes. Current agents possess significant limitations, such as low resistance toward photobleaching and sensitivity to changes in the microenvironment. Luminescent Ln
'encapsulated sandwich' metallacrowns (MCs) overcome these drawbacks and offer complementary advantages. In particular, they emit sharp emission bands, possess a large difference between excitation and emission wavelengths and do not photobleach. Herein, MCs formed with pyrazinehydroxamic acid (Ln
Zn(ii)MC
, Ln
= Yb, Nd) were used, combined with near-infrared (NIR) counter staining and fixation agents for HeLa cells upon an initial five minute exposure to UV-A light. The validity and quality of the cell fixation were assessed with Raman spectroscopy. Analysis of the NIR luminescence properties of these MCs was performed under different experimental conditions, including in a suspension of stained cells. Moreover, the high emission intensity of Ln
Zn(ii)MC
in the NIR region allows these MCs to be used for imaging with standard CCD cameras installed on routine fluorescence microscopes. Finally, the NIR-emitting Ln
Zn(ii)MC
compounds combine, within a single molecule, features such as cell fixation and staining abilities, good photostability and minimal sensitivity of the emission bands to the local microenvironment, and they are highly promising for establishing the next generation of imaging agents with a single biodistribution.
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