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Formation of bioorganic compounds in planetary atmospheres by cosmic radiation.

Simulated planetary atmospheres (mixtures of simple gases) were irradiated with high energy particles to simulate an action of cosmic rays. When a mixture of carbon monoxide, nitrogen and water was irradiated with 2.8-40 MeV protons, a wide variety of bioorganic compounds including amino acids, imidazole, and uracil were identified in the products. The amount of amino acids was proportional to the energy deposit to the system. Various kinds of simulated planetary atmospheres, such as "Titan type" and "Jovian type", were also irradiated with high energy protons, and gave amino acids in the hydrolyzed products. Since cosmic rays are a universal energy source in space, it was suggested that formation of bioorganic compounds in planetary atmospheres is inevitable in the course of cosmic evolution.

Amino Acids↗

X-ray astronomy in the new millennium: a summary.

Recent X-ray observations have had a major impact on topics ranging from proto-stars to cosmology. They have also drawn attention to important and general physical processes that currently limit our understanding of thermal and non-thermal X-ray sources. These include unmeasured atomic astrophysics data (wavelengths, oscillator strengths, etc.), basic hydromagnetic processes (e.g. shock structure, reconnection), plasma processes (such as electron-ion equipartition and heat conduction) and radiative transfer (in discs and accretion columns). Progress on these problems will probably come from integrative studies that draw upon observations, throughout the electromagnetic spectrum, of different classes of source. X-ray observations are also giving a new perspective on astronomical subjects, like the nature of galactic nuclei and the evolution of stellar populations. In addition, they are helping us to address central cosmological questions, including the measurement of the matter content of the Universe, understanding its overall luminosity density, describing its chemical evolution and locating the first luminous objects. X-ray astronomy has a healthy future with several international space missions under construction and in development.

Journal Article↗

NASA's Exobiology Program.

The goal of NASA's Exobiology Program is to understand the origin, evolution, and distribution of life, and life-related molecules, on Earth and throughout the universe. Emphasis is focused on determining how the rate and direction of these processes were affected by the chemical and physical environment of the evolving planet, as well as by planetary, solar, and astrophysical phenomena. This is accomplished by a multi-disciplinary program of research conducted by over 60 principal investigators in both NASA and university laboratories. Major program thrusts are in the following research areas: biogenic elements; chemical evolution; origin of life; organic geochemistry; evolution of higher life forms; solar system exploration; and the search for extraterrestrial intelligence (SETI).

Biological Evolution↗

The macrolide-bacterium interaction and its biological basis.

Erythromycin, the first antibacterial macrolide introduced into the clinical setting over 50 years ago, was used extensively not only for the treatment of respiratory tract infections in both adults and children, but also for bone and soft tissue infections, and specific sexually transmitted diseases. Macrolide antibiotics have undergone a dramatic chemical evolution over the past 50 years, culminating in the improved 14- and 16-membered macrolides, acylides and new ketolides. In all cases, improvements in antibacterial activity involved changes in the interplay between the chemical structure of the macrolide and the components of the bacterial cell that dictate ultimate antibacterial activity and efficacy. Target site modification by methylation of ribosomal RNA, the so-called Macrolide-Streptogramin-Lincosamide, (MLS0 resistance and active efflux are the two most common forms of resistance present in the clinic today; however, other resistance mechanisms are known. The first macrolide that bound to MLS-resistant ribosomes was reported in 1989, demonstrating that appropriate structural changes could regain access to the modified ribosome-binding site. In addition, macrolide analogs with reduced affinity for the active efflux pump were identified in 1990, demonstrating that features of pump recognition could be separated from ribosome binding site recognition. Progressive medicinal chemistry led to the synthesis and development of the more recent ketolide class, which combines attributes of both prototypes into one molecule, i.e. non-recognition by the efflux pump and regaining some access to the modified ribosome binding site. Ketolide also lack of induction of erm methylase as do 16-member macrolides.

Animals↗

Exobiology, the study of the origin, evolution and distribution of life within the context of cosmic evolution: a review.

The primary goal of exobiological research is to reach a better understanding of the processes leading to the origin, evolution and distribution of life on Earth or elsewhere in the universe. In this endeavour, scientists from a wide variety of disciplines are involved, such as astronomy, planetary research, organic chemistry, palaeontology and the various subdisciplines of biology including microbial ecology and molecular biology. Space technology plays an important part by offering the opportunity for exploring our solar system, for collecting extraterrestrial samples, and for utilizing the peculiar environment of space as a tool. Exobiological activities include comparison of the overall pattern of chemical evolution of potential precursors of life, in the interstellar medium, and on the planets and small bodies of our solar system; tracing the history of life on Earth back to its roots; deciphering the environments of the planets in our solar system and of their satellites, throughout their history, with regard to their habitability; searching for other planetary systems in our Galaxy and for signals of extraterrestrial civilizations; testing the impact of space environment on survivability of resistant life forms. This evolutionary approach towards understanding the phenomenon of life in the context of cosmic evolution may eventually contribute to a better understanding of the processes regulating the interactions of life with its environment on Earth.

Astronomical Phenomena↗

Circadian variations of adenosine and of its metabolism. Could adenosine be a molecular oscillator for circadian rhythms?

The present review describes the biological implications of the periodic changes of adenosine concentrations in different tissues of the rat. Adenosine is a purine molecule that could have been formed in the prebiotic chemical evolution and has been preserved. The rhythmicity of this molecule, as well as its metabolism and even the presence of specific receptors, suggests a regulatory role in eukaryotic cells and in multicellular organisms. Adenosine may be considered a chemical messenger and its action could take place at the level of the same cell (autocrine), the same tissue (paracrine), or on separate organs (endocrine). Exploration of the circadian variations of adenosine was planned considering the liver as an important tissue for purine formation, the blood as a vehicle among tissues, and the brain as the possible acceptor for hepatic adenosine or its metabolites. The rats used in these studies were adapted to a dark-light cycle of 12 h with an unrestrained feeding and drinking schedule. The metabolic control of adenosine concentration in the different tissues studied through the 24-h cycle is related to the activity of adenosine-metabolizing enzyme: 5'-nucleotidase adenosine deaminase, adenosine kinase, and S-adenosylhomocysteine hydrolase. Some possibilities of the factors modulating the activity of these enzymes are commented upon. The multiphysiological action of adenosine could be mediated by several actions: (i) by interaction with extracellular and intracellular receptors and (ii) through its metabolism modulating the methylation pathway, possibly inducing physiological lipoperoxidation, or participating in the energetic homeostasis of the cell. The physiological meaning of the circadian variations of adenosine and its metabolism was focused on: maintenance of the energetic homeostasis of the tissues, modulation of membrane structure and function, regulation of fasting and feeding metabolic pattern, and its participation in the sleep-wake cycle. From these considerations, we suggest that adenosine could be a molecular oscillator involved in the circadian pattern of biological activity in the rat.

Adenosine↗

Formation of prebiochemical compounds in models of the primitive earth's atmosphere. I: CH4 NH3 and CH4 N2 atmospheres.

In order to understand the formation of organic compounds in the primitive atmosphere, the first steps of evolution in models of the primitive atmosphere were investigated. Mixtures containing C-H-N elements were subjected to a low pressure silent electric discharge for several seconds, and the resulting effluents were analysed mainly by gas chromatography, infrared spectrometry and chemical analysis. The formation of hydrocarbon (i.e. ethylene, acetylene, methylacetylene) and of nitrogen containing compounds (i.e. hydrogen cyanide, cyanogen, saturated nitriles, acylonitrile, cyanoacetylene) is reported. The influence of the initial mixture composition on the amount of compounds formed was systematically studied. The nature of the nitrogen source (N2 or NH3) in the primitive atmosphere has a great influence on the amount and on the very nature of the synthesized products. It is shown that important precursors such as cyanogen and cyanoacetylene are formed only in very rich N2 mediums. These results show the important role played by the nature of the primitive atmosphere in the determination of the chemical evolution pathways.

Ammonia↗

Photochemical synthesis of simple organic free radicals on simulated planteary surfaces-an ESR study.

Electron spin resonance spectroscopy provided evidence for formation of hydroxyl radicals during ultraviolet photolysis (254 nm) at -170C of H2O adsorbed on silica gel or of silica gel alone. The carboxyl radical was observed when CO or CO2 or a mixture of CO and CO2 absorbed on silica gel at -170C was irradiated. The ESR signals of these radicals slowly disappeared when the irradiated samples were warmed to room temperature. However, re-irradiation of CO or CO2, or the mixture CO and CO2 on silica gel at room temperature then produced a new species, the carbon dioxide anion radical, which slowly decayed and which was identical with that produced by direct photolysis of formic acid adsorbed on silica gel. The primary photochemical process may involve formation of hydrogen and hydroxyl radicals by means of (1) photodissociation of H2O physically adsorbed on the silica gel, or (2) absorption of the excitation energy by the silica gel surface with subsequent cleavage of the silanol bonds, or (3) dissociation of H2O molecules throug photosensitization by the surfaces or a combination of (1) to (3). Subsequent reactions of these radicals with adsorbed CO or CO2 or both yield carboxyl radicals, CO2H, the precsursors of formic acid. Our results confirm the formation of formic acid under simulated Martian conditions and provide a mechanistic basis for gauging the potential importance of gas-solid photochemistry for chemical evolution on other extraterrestrial bodies, on the primitive earth and on dust grains in the interstellar medium.

Adsorption↗

The computational challenges of Earth-system science.

The Earth system--comprising atmosphere, ocean, land, cryosphere and biosphere--is an immensely complex system, involving processes and interactions on a wide range of space- and time-scales. To understand and predict the evolution of the Earth system is one of the greatest challenges of modern science, with success likely to bring enormous societal benefits. High-performance computing, along with the wealth of new observational data, is revolutionizing our ability to simulate the Earth system with computer models that link the different components of the system together. There are, however, considerable scientific and technical challenges to be overcome. This paper will consider four of them: complexity, spatial resolution, inherent uncertainty and time-scales. Meeting these challenges requires a significant increase in the power of high-performance computers. The benefits of being able to make reliable predictions about the evolution of the Earth system should, on their own, amply repay this investment.

Atmosphere↗

Computational mineral physics and the physical properties of perovskite.

The inherent uncertainties in modern first-principles calculations are reviewed using geophysically relevant examples. The elastic constants of perovskite at lower-mantle temperatures and pressures are calculated using ab initio molecular dynamics. These are used in conjunction with seismic tomographic models to estimate that the lateral temperature contrasts in the Earth's lower mantle are 800 K at a depth of 1000 km, and 1500 K at a depth of 2000 km. The effect of Al(3+) on the compressibility of MgSiO(3) perovskite is calculated using three different pseudopotentials. The results confirm earlier work and show that the compressibility of perovskites with Al(3+) substituted for both Si(4+) and Mg(2+) is very similar to the compressibility of Al(3+)-free perovskite. Even when 100% of the Si(4+) and Mg(2+) ions are replaced with Al(3+), the bulk modulus is only 7% less than that for Al(3+)-free perovskite. In contrast, perovskites where Al(3+) substitutes for Si(4+) only and that are charge balanced by oxygen vacancies do show higher compressibilities. When corrected to similar concentrations of Al(3+), the calculated compressibilities of the oxygen-vacancy-rich perovskites are in agreement with experimental results.

Aluminum↗

The atmosphere of Titan.

The discovery that Titan had an atmosphere was made by the identification of methane in the satellite's spectrum in 1944. But the abundance of this gas and the identification of other major constituents required the 1980 encounter by the Voyager 1 spacecraft. in the intervening years, traces of C2H2, C2H4, C2H6 and CH3D had been posited to interpret emission bands in Titan's IR spectrum. The Voyager infrared Spectrometer confirmed that these gases were present and added seven more. The atmosphere is now known to be composed primarily of molecular nitrogen. But the derived mean molecular weight suggests the presence of a significant amount of some heavier gas, most probably argon. It is shown that this argon must be primordial, and that one can understand the evolution of Titan's atmosphere in terms of degassing of a mixed hydrate dominated by CH4, N2 and 36Ar. This model satisfactorily explains the absence of neon and makes no special requirements on the satellite's surface temperature. The organic chemistry taking place on Titan today invites comparison with chemical evolution on the primitive Earth prior to the origin of life.

Biological Evolution↗

Evolution as a collective phenomenon.

The quantum mechanical description of biosystems, which emphasise their dielectric properties and the presence of an uncorrelated condensate of phonons, (in analogy with Bose-Einstein condensation), is extended to a description of biosystems, in which the condensed phonons show anomalous averages, (in analogy with superconductivity). The theory is used to show that a quantum ultraviolet defence mechanism may have been present at the origin of chemical evolution, removing a difficulty in the standard scenario. Suggestions are made as to how to proceed experimentally to show the existence of a correlated phonon condensate.

Biological Evolution↗

The chemical end-ligation of homopyrimidine oligodeoxyribonucleotides within a DNA triple helix.

BACKGROUND: Triple-helical nucleic acids, first reported in the late 1950s, are receiving attention for their possible involvement in controlling gene expression. Certain sequences of DNA are believed to form local triple-helical structures (H-form DNA), although this has not been directly observed in vivo. Studies carried out in our laboratories have suggested that self-replicating oligonucleotides could have been involved in chemical evolution via triple-helical intermediates. In addition to self-replication mechanisms, elucidating processes for the nonenzymatic elongation of biologically relevant polymers remains an important challenge in understanding the origin of life. To this end, we have studied a novel ligation of oligodeoxyribonucleotides that lie within a triple helix. RESULTS: The chemical end-ligation of homopyrimidine oligodeoxyribonucleotides on a triple helix is reported. This selective process, induced by cyanoimidazole, is facilitated by a template effect of the DNA aggregate and occurs between the 3' end (hydroxyl) of the third minor-groove-bound strand and the 5' end (phosphate) of the antiparallel oligopyrimidine strand. CONCLUSIONS: Double-helical homopurine/homopyrimidine DNA can serve as a template for the elongation of oligonucleotides in a manner that has not been described previously. The end-ligation of homopyrimidine oligomers, a nonenzymatic process, proceeds via a requisite triple-helical intermediate and constitutes an efficient and selective method for the template-directed elongation of nucleic acids. Such a process could conceivably have been involved in the elongation of primordial information-bearing biopolymers.

DNA↗

Emergence of adaptable systems and evolution of a translation device.

An over-all organizational framework for the origin of life is outlined and attempts for realization are given. Evolution can be described as a process resulting in an increase of "knowledge" where knowledge is the number of carriers of genetic information discarded, on the average, until the evolutionary state under consideration is reached. A model for the evolution of a translation device, a crucial event in the origin of life, is described in detail. Aggregates of short polynucleotide strands in a hairpin conformation play a major role in this model. Experimental evidence for the selectivity of aggregation supports the idea of aggregates as error filters. Chromatographic separation as selection process during chemical evolution supports the model of the early translation device leading to the origin of the genetic code.

Amino Acids↗

The evolution of the prebiotic atmosphere.

One-dimensional radiative convective and photochemical models are used to estimate the vertical temperature structure and composition of the earth's prebiotic atmosphere. Greatly enhanced CO2 levels (100-1000 times present) are required to keep the mean surface temperature above freezing in the face of decreased solar luminosity during the earth's early history. Such high CO2 partial pressures would have affected the atmospheric oxidation state by facilitating the photochemical production of soluble species including H2O2 and H2CO. Oxidation of ferrous iron in the oceans by H2O2 dissolved in rainwater should have kept the atmospheric H2 mixing ratio above 2x10(-4) and the ground-level O2 mixing ratio below 10(-11), regardless of the magnitude of the rate of volcanic release of reduced gases.

Atmosphere↗

The thermochemical structure and evolution of Earth's mantle: constraints and numerical models.

Geochemical observations place several constraints on geophysical processes in the mantle, including a requirement to maintain several distinct reservoirs. Geophysical constraints limit plausible physical locations of these reservoirs to a thin basal layer, isolated deep 'piles' of material under large-scale mantle upwellings, high-viscosity blobs/plums or thin strips throughout the mantle, or some combination of these. A numerical model capable of simulating the thermochemical evolution of the mantle is introduced. Preliminary simulations are more differentiated than Earth but display some of the proposed thermochemical processes, including the generation of a high-mu mantle reservoir by recycling of crust, and the generation of a high-(3)He/(4)He reservoir by recycling of residuum, although the resulting high-(3)He/(4)He material tends to aggregate near the top, where mid-ocean-ridge melting should sample it. If primitive material exists as a dense basal layer, it must be much denser than subducted crust in order to retain its primitive (e.g. high-(3)He) signature. Much progress is expected in the near future.

Computer Simulation↗

Analysis of complex mixtures recovered from space missions statistical approach to the study of Titan atmosphere analogues (tholins).

To study Titan, the largest moon of Saturn, laboratory simulation experiments have been performed to obtain analogues of Titan's aerosols (named tholins) using different energy sources. Tholins, which have been demonstrated to represent aerosols in Titan's haze layers, are a complex mixture, resulting from the chemical evolution of several hydrocarbons and nitriles. Their chromatographic analysis yields complex chromatograms, which require the use of mathematical procedures to extract from them all the information they contain. Two different chemometric approaches (the Fourier analysis approach and the statistical model of peak overlapping) have been successfully applied to pyrolysis-GC-MS chromatogram of a tholin sample. Fundamental information on the mixture's chemical composition (number of components, m) and on the separation system performance (separation efficiency, sigma) can be easily estimated: the excellent correspondence between the data calculated by the two independent procedures proves the reliability of the statistical approaches in characterizing a tholin chromatogram. Moreover, the plot of autocorrelation function contains, in a simplified form, all the information on the retention pattern: retention recursivities can be easily singled out and related to specific molecular structure variations. Therefore, the autocorrelation function (ACF) plot constitutes a simplified fingerprint of the pyrolysis products of tholins, which can be used as a powerful tool to characterize a tholin sample.

Aerosols↗