Formation of nucleobases from formamide in the presence of iron oxides: implication in chemical evolution and origin of life

Simple compounds like HCN, which have one C and one N, are proposed as the probable precursors for biomonomers. Formamide, a hydrolysis product of HCN, is known as the precursor of various biologically important compounds, for example, nucleobases (purines and pyrimidines). In this paper, we report our results on the synthesis of nucleobases, adenine, cytosine, purine, 9-(hydroxyacetyl) purine, and 4(3H)-pyrimidinone from formamide, using iron oxide (hematite) and oxide hydroxides (goethite and akaganeite) as a catalyst. Goethite and hematite produced purine in higher yield. The products formed were characterized by high-performance liquid chromatography and electrospray ionization mass spectrometry techniques. Results of our study reveal that iron oxides might have worked as efficient prebiotic catalysts.     

Archaeal genome organization and stress responses: implications for the origin and evolution of cellular life

For DNA to be used as an informational molecule it must exist in the cell on the edge of stability because all genomic processes require local controlled melting. This presents mechanistic opportunities and problems for genomic DNA from hyperthermophilic organisms, whose unpackaged DNA could melt at optimal temperatures for growth. Hyperthermophiles are suggested to employ the novel positively supercoiling topoisomerase enzyme reverse gyrase (RG) to form positively supercoiled DNA that is intrinsically resistant to thermal denaturation. RG is presently the only archaeal gene that is uniquely found in hyperthermophiles and therefore is central to hypotheses suggesting a hypothermophilic origin of life. However, the suggestion that RG has evolved by the fusion of two pre-existing enzymes has led to hypotheses for a lower temperature for the origin of life. In addition to the action of topoisomerases, DNA packaging and the intracellular ionic environment can also manipulate DNA topology significantly. In the Euryarchaeota, nucleosomes containing minimal histones can adopt two alternate DNA topologies in a salt-dependent manner. From this we hypothesize that since internal salt concentrations are increased following an increase in temperature, the genomic effects of temperature fluctuations could also be accommodated by changes in nucleosome organization. In addition, stress-induced changes in the nucleoid proteins could also play a role in maintaining the genome in the optimal topological state in changing environments. The function of these systems could therefore be central to temperature adaptation and thus be implicated in origin of life scenarios involving hyperthermophiles.     

Pumice as a remarkable substrate for the origin of life

The context for the emergence of life on Earth sometime prior to 3.5 billion years ago is almost as big a puzzle as the definition of life itself. Hitherto, the problem has largely been addressed in terms of theoretical and experimental chemistry plus evidence from extremophile habitats like modern hydrothermal vents and meteorite impact structures. Here, we argue that extensive rafts of glassy, porous, and gas-rich pumice could have had a significant role in the origin of life and provided an important habitat for the earliest communities of microorganisms. This is because pumice has four remarkable properties. First, during eruption it develops the highest surface-area-to-volume ratio known for any rock type. Second, it is the only known rock type that floats as rafts at the air-water interface and then becomes beached in the tidal zone for long periods of time. Third, it is exposed to an unusually wide variety of conditions, including dehydration. Finally, from rafting to burial, it has a remarkable ability to adsorb metals, organics, and phosphates as well as to host organic catalysts such as zeolites and titanium oxides. These remarkable properties now deserve to be rigorously explored in the laboratory and the early rock record.     

A microbial oasis in the hypersaline Atacama subsurface discovered by a life detector chip: implications for the search for life on Mars

The Atacama Desert has long been considered a good Mars analogue for testing instrumentation for planetary exploration, but very few data (if any) have been reported about the geomicrobiology of its salt-rich subsurface. We performed a Mars analogue drilling campaign next to the Salar Grande (Atacama, Chile) in July 2009, and several cores and powder samples from up to 5?m deep were analyzed in situ with LDChip300 (a Life Detector Chip containing 300 antibodies). Here, we show the discovery of a hypersaline subsurface microbial habitat associated with halite-, nitrate-, and perchlorate-containing salts at 2?m deep. LDChip300 detected bacteria, archaea, and other biological material (DNA, exopolysaccharides, some peptides) from the analysis of less than 0.5?g of ground core sample. The results were supported by oligonucleotide microarray hybridization in the field and finally confirmed by molecular phylogenetic analysis and direct visualization of microbial cells bound to halite crystals in the laboratory. Geochemical analyses revealed a habitat with abundant hygroscopic salts like halite (up to 260?g kg(-1)) and perchlorate (41.13?μg g(-1) maximum), which allow deliquescence events at low relative humidity. Thin liquid water films would permit microbes to proliferate by using detected organic acids like acetate (19.14?μg g(-1)) or formate (76.06?μg g(-1)) as electron donors, and sulfate (15875?μg g(-1)), nitrate (13490?μg g(-1)), or perchlorate as acceptors. Our results correlate with the discovery of similar hygroscopic salts and possible deliquescence processes on Mars, and open new search strategies for subsurface martian biota. The performance demonstrated by our LDChip300 validates this technology for planetary exploration, particularly for the search for life on Mars.     

Hydrothermal simulation experiments as a tool for studies of the origin of life on Earth and other terrestrial planets: a review

The potential of life's origin in submarine hydrothermal systems has been evaluated by a number of investigators by conducting high temperature-high pressure experiments involving organic compounds. In the majority of these experiments little attention has been paid to the importance of constraining important parameters, such as the pH and the redox state of the system. This is particularly revealed in the apparent difficulties in interpreting experimental data from hydrothermal organic synthesis and stability studies. However, in those cases where common mineral assemblages have been used in an attempt to buffer the pH and redox conditions to geologically and geochemically realistic values, theoretical and experimental data seem to converge. The use of mineral buffer assemblages provides a convenient way by which to constrain the experimental conditions. Studies at high temperatures and pressure in the laboratory have revealed a number of reactions that proceed rapidly in hydrothermal fluids, including the Strecker synthesis of amino acids. In other cases, the verification of postulated abiotic reaction mechanisms has not been possible, at least for large molecules such as large fatty acids and hydrocarbons. This includes the Fischer-Tropsch synthesis reaction. High temperature-high pressure experimental methods have been developed and used successfully for a long time in, for example, mineral solubility studies under hydrothermal conditions. By taking advantage of this experimental experience new and, at times, unexpected directions can be taken in bioorganic geochemistry, one being, for instance, primitive two-dimensional information coding. This article critically reviews some of the organic synthesis and stability experiments that have been conducted under simulated submarine hydrothermal conditions. We also discuss some of the theoretical and practical considerations that apply to hydrothermal laboratory studies of organic molecules related to the origin of life on Earth and probably also to the other terrestrial planets.     

Oxidant enhancement in martian dust devils and storms: implications for life and habitability

We investigate a new mechanism for producing oxidants, especially hydrogen peroxide (H2O2), on Mars. Large-scale electrostatic fields generated by charged sand and dust in the martian dust devils and storms, as well as during normal saltation, can induce chemical changes near and above the surface of Mars. The most dramatic effect is found in the production of H2O2 whose atmospheric abundance in the "vapor" phase can exceed 200 times that produced by photochemistry alone. With large electric fields, H2O2 abundance gets large enough for condensation to occur, followed by precipitation out of the atmosphere. Large quantities of H2O2 would then be adsorbed into the regolith, either as solid H2O2 "dust" or as re-evaporated vapor if the solid does not survive as it diffuses from its production region close to the surface. We suggest that this H2O2, or another superoxide processed from it in the surface, may be responsible for scavenging organic material from Mars. The presence of H2O2 in the surface could also accelerate the loss of methane from the atmosphere, thus requiring a larger source for maintaining a steady-state abundance of methane on Mars. The surface oxidants, together with storm electric fields and the harmful ultraviolet radiation that readily passes through the thin martian atmosphere, are likely to render the surface of Mars inhospitable to life as we know it.     

Origin of informational polymers and the search for non-terran life: protection of the polymeric state of DNA by phosphate minerals

An in-depth analysis of the effects exerted on the DNA backbone by 25 crystal phosphate minerals is reported. Degradation of DNA oligomers was performed with two different reactions: Hydrolysis following Nucleophilic Degradation (HND), initiated by the nucleophilic addition of formamide on both purine and pyrimidine nucleobases, and Hydrolysis following Nucleophilic Substitution (HNS) carried on by water and starting with the removal of a nondegraded base. A complete panel of effects on the phosphoester bonds, from protection to enhanced instability to absence of interference, is described. These effects differ in the different degradation pathways and in different physical-chemical conditions. The relationship between the hardness of the mineral and its protective ability is discussed. In addition to its interest per se, this study was prompted by the observed catalytic abilities of soluble and mineral phosphates (Saladino et al., 2006c) on the synthetic reactions by formamide. The relevance of these observations in the search for nonterran life is discussed.     

Experimentally tracing the key steps in the origin of life: The aromatic world

Life is generally believed to emerge on Earth, to be at least functionally similar to life as we know it today, and to be much simpler than modern life. Although minimal life is notoriously difficult to define, a molecular system can be considered alive if it turns resources into building blocks, replicates, and evolves. Primitive life may have consisted of a compartmentalized genetic system coupled with an energy-harvesting mechanism. How prebiotic building blocks self-assemble and transform themselves into a minimal living system can be broken into two questions: (1) How can prebiotic building blocks form containers, metabolic networks, and informational polymers? (2) How can these three components cooperatively organize to form a protocell that satisfies the minimal requirements for a living system? The functional integration of these components is a difficult puzzle that requires cooperation among all the aspects of protocell assembly: starting material, reaction mechanisms, thermodynamics, and the integration of the inheritance, metabolism, and container functionalities. Protocells may have been self-assembled from components different from those used in modern biochemistry. We propose that assemblies based on aromatic hydrocarbons may have been the most abundant flexible and stable organic materials on the primitive Earth and discuss their possible integration into a minimal life form. In this paper we attempt to combine current knowledge of the composition of prebiotic organic material of extraterrestrial and terrestrial origin, and put these in the context of possible prebiotic scenarios. We also describe laboratory experiments that might help clarify the transition from nonliving to living matter using aromatic material. This paper presents an interdisciplinary approach to interface state of the art knowledge in astrochemistry, prebiotic chemistry, and artificial life research.     

Key science questions from the second conference on early Mars: geologic, hydrologic, and climatic evolution and the implications for life

In October 2004, more than 130 terrestrial and planetary scientists met in Jackson Hole, WY, to discuss early Mars. The first billion years of martian geologic history is of particular interest because it is a period during which the planet was most active, after which a less dynamic period ensued that extends to the present day. The early activity left a fascinating geological record, which we are only beginning to unravel through direct observation and modeling. In considering this time period, questions outnumber answers, and one of the purposes of the meeting was to gather some of the best experts in the field to consider the current state of knowledge, ascertain which questions remain to be addressed, and identify the most promising approaches to addressing those questions. The purpose of this report is to document that discussion. Throughout the planet's first billion years, planetary-scale processes-including differentiation, hydrodynamic escape, volcanism, large impacts, erosion, and sedimentation-rapidly modified the atmosphere and crust. How did these processes operate, and what were their rates and interdependencies? The early environment was also characterized by both abundant liquid water and plentiful sources of energy, two of the most important conditions considered necessary for the origin of life. Where and when did the most habitable environments occur? Did life actually occupy them, and if so, has life persisted on Mars to the present? Our understanding of early Mars is critical to understanding how the planet we see today came to be.     

Immunological detection of small organic molecules in the presence of perchlorates: relevance to the life marker chip and life detection on Mars

The proposed ExoMars mission, due to launch in 2018, aims to look for evidence of extant and extinct life in martian rocks and regolith. Previous attempts to detect organic molecules of biological or abiotic origin on Mars have been unsuccessful, which may be attributable to destruction of these molecules by perchlorate salts during pyrolysis sample extraction techniques. Organic molecules can also be extracted and measured with solvent-based systems. The ExoMars payload includes the Life Marker Chip (LMC) instrument, capable of detecting biomarker molecules of extant and extinct Earth-like life in liquid extracts of martian samples with an antibody microarray assay. The aim of the work reported here was to investigate whether the presence of perchlorate salts, at levels similar to those at the NASA Phoenix landing site, would compromise the LMC extraction and detection method. To test this, we implemented an LMC-representative sample extraction process with an LMC-representative antibody assay and used these to extract and analyze a model sample that consisted of a Mars analog sample matrix (JSC Mars-1) spiked with a representative organic molecular target (pyrene, an example of abiotic meteoritic infall targets) in the presence of perchlorate salts. We found no significant change in immunoassay function when using pyrene standards with added perchlorate salts. When model samples spiked with perchlorate salts were subjected to an LMC-representative liquid extraction, immunoassays functioned in a liquid extract and detected extracted pyrene. For the same model sample matrix without perchlorate salts, we observed anomalous assay signals that coincided with yellow coloration of the extracts. This unexpected observation is being studied further. This initial study indicates that the presence of perchlorate salts, at levels similar to those detected at the NASA Phoenix landing site, is unlikely to prevent the LMC from extracting and detecting organic molecules from martian samples.     

Chiral symmetry breaking and complete chiral purity by thermodynamic-kinetic feedback near equilibrium: implications for the origin of biochirality

Chiral symmetry breaking occurs when a physical or chemical process spontaneously generates a large excess of one of the two enantiomers--left-handed (L) or right-handed (D)--with no preference as to which of the two enantiomers is produced. From the viewpoint of energy, these two enantiomers can exist with an equal probability, and inorganic processes that involve chiral products commonly yield a racemic mixture of both. The fact that biologically relevant molecules exist only as one of the two enantiomers is a fascinating example of complete symmetry breaking in chirality and has long intrigued the science community. The origin of this selective chirality has remained a fundamental enigma with regard to the origin of life since the time of Pasteur, some 140 years ago. Here, it is shown that two populations of chiral crystals of left and right hand cannot coexist in solution: one of the chiral populations disappears in an irreversible autocatalytic process that nurtures the other one. Final and complete chiral purity seems to be an inexorable fate in the course of the common process of growth-dissolution. This unexpected chiral symmetry breaking can be explained by the feedback between the thermodynamic control of dissolution and the kinetics of the growth process near equilibrium. This "thermodynamic-kinetic feedback near equilibrium" is established as a mechanism to achieve complete chiral purity in solid state from a previously solid racemic medium. The way in which this mechanism could operate in solutions of chiral biomolecules is described. Finally, based on this mechanism, experiments designed to search for chiral purity in a new way are proposed: chiral purity of amino acids or biopolymers is predicted in solid phase from a previously solid racemic medium. This process may have played a key role in the origin of biochirality.     

Averaged relative states for spacecraft formation control in the presence of J2 disturbances

The method of controlling a spacecraft formation using mean relative states as the inputs is an effective technique if control actuation is sought to be reduced. In this paper, we extend the efficacy of this method by including the linearized J2 terms in the system dynamics and derive the linear mapping between the actual and the mean relative states. The resultant control equation has J2 related gains that are shown to improve the tracking of the states and increase system performance for a phase plane-based controller performing formation maneuvering.     

With a grain of salt: what halite has to offer to discussions on the origin of life

This experimental study investigated how the dynamics of the crystallization of the evaporite mineral halite could affect the accumulation and preservation of organic macromolecules present in the crystallizing solution. Halite was grown under controlled conditions in the presence of polymer nanoparticles that acted as an analog to protocellular material. Optical microscopy, atomic force microscopy, and laser scanning confocal fluorescence microscopy were used to trace the localization of the nanoparticles during and after growth of halite crystals. The present study revealed that the organic nanoparticles were not regularly incorporated within the halite, but were very concentrated on its surfaces. Their distribution was controlled dominantly by the morphologic surface features of the mineral rather than by specific molecular interactions with an atomic plane of the mineral. This means that the distribution of organic molecules was controlled by surfaces like those of halite's evaporitic growth forms. The experiments with halite also demonstrated that a mineral need not continuously incorporate organic molecules during its crystallization to preserve those molecules: After rejection by (non-incorporation into) the crystallizing halite, the organic nanoparticles increased in concentration in the evaporating brine. They ultimately either adsorbed in rectilinear patterns onto the hopper-enhanced surfaces and along discontinuities within the crystals, or they were encapsulated within fluid inclusions. Of additional importance in origin-of-life considerations is the fact that halite in the natural environment rapidly can change its role from that of a protective repository (in the absence of water) to that of a source of organic particles (as soon as water is present) when the mineral dissolves.     

Acetylene as fast food: implications for development of life on anoxic primordial Earth and in the outer solar system

Acetylene occurs, by photolysis of methane, in the atmospheres of jovian planets and Titan. In contrast, acetylene is only a trace component of Earth's current atmosphere. Nonetheless, a methane-rich atmosphere has been hypothesized for early Earth; this atmosphere would also have been rich in acetylene. This poses a paradox, because acetylene is a potent inhibitor of many key anaerobic microbial processes, including methanogenesis, anaerobic methane oxidation, nitrogen fixation, and hydrogen oxidation. Fermentation of acetylene was discovered approximately 25 years ago, and Pelobacter acetylenicus was shown to grow on acetylene by virtue of acetylene hydratase, which results in the formation of acetaldehyde. Acetaldehyde subsequently dismutates to ethanol and acetate (plus some hydrogen). However, acetylene hydratase is specific for acetylene and does not react with any analogous compounds. We hypothesize that microbes with acetylene hydratase played a key role in the evolution of Earth's early biosphere by exploiting an available source of carbon from the atmosphere and in so doing formed protective niches that allowed for other microbial processes to flourish. Furthermore, the presence of acetylene in the atmosphere of a planet or planetoid could possibly represent evidence for an extraterrestrial anaerobic ecosystem.     

考虑J2项摄动的星座相对运动控制

利用轨道某些要素(偏心率，升交点赤经和倾角)的差别可以构成由一颗中心星和几个环绕星组成的近距离星座。在理想中心引力场下，环绕星运行轨迹在水平面投影可以呈现封闭圆形。在地球引力摄动时，这种空间形状将逐渐发散。为此，本文考虑J2项摄动的影响，设计了对其具有鲁棒性的环绕星相对轨道；进而导出了带有J2项摄动的环绕星相对运动方程，并给出了基于惯性笛卡尔坐标系运动学变量的相对轨道控制方法。分析和仿真结果表明，这种控制方法能够实现星座相对运动的高精度控制。     

Ultrastructural and geochemical characterization of Archean-Paleoproterozoic graphite particles: implications for recognizing traces of life in highly metamorphosed rocks

Abundant graphite particles occur in amphibolite-grade quartzite of the Archean-Paleoproterozoic Wutai Metamorphic Complex in the Wutaishan area of North China. Petrographic thin section observations suggest that the graphite particles occur within and between quartzite clasts and are heterogeneous in origin. Using HF maceration techniques, the Wutai graphite particles were extracted for further investigation. Laser Raman spectroscopic analysis of a population of extracted graphite discs indicated that they experienced a maximum metamorphic temperature of 513 +/- 50 degrees C, which is consistent with the metamorphic grade of the host rock and supports their indigenicity. Scanning and transmission electron microscopy revealed that the particles bear morphological features (such as hexagonal sheets of graphite crystals) related to metamorphism and crystal growth, but a small fraction of them (graphite discs) are characterized by a circular morphology, distinct marginal concentric folds, surficial wrinkles, and complex nanostructures. Ion microprobe analysis of individual graphite discs showed that their carbon isotope compositions range from -7.4 per thousand to -35.9 per thousand V-PDB (Vienna Pee Dee Belemnite), with an average of -20.3 per thousand, which is comparable to bulk analysis of extracted carbonaceous material. The range of their size, ultrastructures, and isotopic signatures suggests that the morphology and geochemistry of the Wutai graphite discs were overprinted by metamorphism and their ultimate carbon source probably had diverse origins that included abiotic processes. We considered both biotic and abiotic origins of the carbon source and graphite disc morphologies and cannot falsify the possibility that some circular graphite discs characterized by marginal folds and surficial wrinkles represent deflated, compressed, and subsequently graphitized organic-walled vesicles. Together with reports by other authors of acanthomorphic acritarchs from greenschist-amphibolite-grade metamorphic rocks, this study suggests that it is worthwhile to examine carbonaceous materials preserved in highly metamorphosed rocks for possible evidence of ancient life.     

The possible origin and persistence of life on Enceladus and detection of biomarkers in the plume

The jets of icy particles and water vapor issuing from the south pole of Enceladus are evidence for activity driven by some geophysical energy source. The vapor has also been shown to contain simple organic compounds, and the south polar terrain is bathed in excess heat coming from below. The source of the ice and vapor, and the mechanisms that accelerate the material into space, remain obscure. However, it is possible that a liquid water environment exists beneath the south polar cap, which may be conducive to life. Several theories for the origin of life on Earth would apply to Enceladus. These are (1) origin in an organic-rich mixture, (2) origin in the redox gradient of a submarine vent, and (3) panspermia. There are three microbial ecosystems on Earth that do not rely on sunlight, oxygen, or organics produced at the surface and, thus, provide analogues for possible ecologies on Enceladus. Two of these ecosystems are found deep in volcanic rock, and the primary productivity is based on the consumption by methanogens of hydrogen produced by rock reactions with water. The third ecosystem is found deep below the surface in South Africa and is based on sulfur-reducing bacteria consuming hydrogen and sulfate, both of which are ultimately produced by radioactive decay. Methane has been detected in the plume of Enceladus and may be biological in origin. An indicator of biological origin may be the ratio of non-methane hydrocarbons to methane, which is very low (0.001) for biological sources but is higher (0.1-0.01) for nonbiological sources. Thus, Cassini's instruments may detect plausible evidence for life by analysis of hydrocarbons in the plume during close encounters.     

Glycine identification in natural jarosites using laser desorption Fourier transform mass spectrometry: implications for the search for life on Mars

The jarosite group minerals have received increasing attention since the discovery of jarosite on the martian surface by the Mars Exploration Rover Opportunity. Given that jarosite can incorporate foreign ions within its structure, we have investigated the use of jarosite as an indicator of aqueous and biological processes on Earth and Mars. The use of laser desorption Fourier transform mass spectrometry has revealed the presence of organic matter in several jarosite samples from various locations worldwide. One of the ions from the natural jarosites has been attributed to glycine because it was systematically observed in combinations of glycine with synthetic ammonium and potassium jarosites, Na(2)SO(4) and K(2)SO(4). The ability to observe these organic signatures in jarosite samples with an in situ instrumental technique, such as the one employed in this study, furthers the goals of planetary geologists to determine whether signs of life (e.g., the presence of biomolecules or biomolecule precursors) can be detected in the rock record of terrestrial and extraterrestrial samples.     

The formation of sulfate and elemental sulfur aerosols under varying laboratory conditions: implications for early earth

The presence of sulfur mass-independent fractionation (S-MIF) in sediments more than 2.45?×?10(9) years old is thought to be evidence for an early anoxic atmosphere. Photolysis of sulfur dioxide (SO(2)) by UV light with λ?相似文献   

Influence of ionic inorganic solutes on self-assembly and polymerization processes related to early forms of life: implications for a prebiotic aqueous medium

A commonly accepted view is that life began in a marine environment, which would imply the presence of inorganic ions such as Na+, Cl-, Mg2+, Ca2+, and Fe2+. We have investigated two processes relevant to the origin of life--membrane self-assembly and RNA polymerization--and established that both are adversely affected by ionic solute concentrations much lower than those of contemporary oceans. In particular, monocarboxylic acid vesicles, which are plausible models of primitive membrane systems, are completely disrupted by low concentrations of divalent cations, such as magnesium and calcium, and by high sodium chloride concentrations as well. Similarly, a nonenzymatic, nontemplated polymerization of activated RNA monomers in ice/eutectic phases (in a solution of low initial ionic strength) yields oligomers with > 80% of the original monomers incorporated, but polymerization in initially higher ionic strength aqueous solutions is markedly inhibited. These observations suggest that cellular life may not have begun in a marine environment because the abundance of ionic inorganic solutes would have significantly inhibited the chemical and physical processes that lead to self-assembly of more complex molecular systems.