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Amino acid condensation catalyzed by inorganic oxides is a widely recognized way for prebiotic peptide formation. Silica and alumina are widely distributed in the Earth-like planets' crust as minerals of different complexity, and thus are attractive model catalysts for the studies of abiotic peptide synthesis. Experiments performed in other laboratories have shown that this process can be efficient at > 80 degrees C, which is not easy to find on the planetary surface in combination with sufficient concentrations of amino acids and necessary catalysts. In the present work we tested catalytic activity of three forms of alumina (which proved to be an efficient catalyst for this process) in the intermolecular condensation of L-alanine. We expanded the temperature interval down to 55 degrees C and used the simplest permanent heating procedure, without employing fluctuating drying/wetting conditions. The most important finding is that even under the lowest temperature considered (i.e. 55 degrees C), short peptide formation can be detected already after 10-30 days of heating. This fact implies that the abiotic peptide formation might occur in a wide variety of planetary environments, without need for high temperatures, given the presence of amino acid building blocks and alumina-containing minerals.
Some results, recently obtained from laboratory experiments of ion irradiation of ice mixtures containing H, C, N, and O, are here summarized. They are relevant to the formation and evolution of complex organics on interstellar dust, comets and other small bodies in the external Solar System. In particular the formation of CN-bearing species is discussed. Interstellar dust incorporated into primitive Solar System bodies and subsequently delivered to the early Earth, may have contributed to the origin of life. The delivery of CN-bearing species seems to have been necessary because molecules containing the cyanogen bond are difficult to be produced in an environment that is not strongly reducing as that of the early Earth probably was. Moreover we report on an ongoing research program concerning the interaction between refractory materials produced by ion irradiation of simple ices and biological materials (amino acids, proteins, cells).
Our discovery of high degrees of circular polarisation in some star-forming regions provides an attractive mechanism for the origin of homochirality. The largest degrees of circular polarisation, so far observed at near-infrared wavelengths, are thought to arise from the scattering of stellar radiation from aligned dust grains and are calculated to extend down to UV wavelengths. The extent of the region where circularly polarised light (CPL) of a single handedness originates is very large, and it is likely that the whole of a planetary system would see a single handedness of CPL also. We present the observational data, models of the scattering that leads to the production of CPL, and a model for the origin of homochirality. We also discuss briefly future laboratory and space-based experiments.
In the last years extraterrestrial scenarios for the origin of homochirality in biological structures received considerable attention in the topical literature: Rubenstein and Bonner postulated a rapidly rotating neutron star emitting circularly polarised synchrotron radiation responsible for the first asymmetric synthesis; the group of Bailey published the observation of circular polarisation caused by Mie scattering from aligned dust grains in the Orion OMC-1 star-formation region that might provide an enantioselective effect on prochiral or racemic organic molecules. Rikken and Raupach observed a magnetochiral effect and considered extraterrestrial magnetic fields of sufficient strengths to introduce biomoleculars parity violation. With the aim to investigate these hypotheses among other theories describing the origin of biological asymmetry, our laboratory participates in the conception and development of ROSETTA's COSAC Experiment, that is designed to identify organic molecules in the cometary matter in situ. Within COSAC's 'Chirality Module' enantiomers will be separated gas chromatographically with the help of capillary columns coated with chirally active liquid films. This technique will allow the separation of specific chiral organic compounds out of the analysed cometary matter into their enantiomeric constituents. Both thermo conductivity and mass spectrometric detectors will be used to determine each enantiomer's amount and therefore the corresponding enantiomeric excesses. As a consequence of COSAC's 'Chirality-Experiment' far-reaching results are expected to investigate the various hypotheses about the first asymmetric synthesis.
Modern studies now favor the fact that extraterrestrial organic molecules served as an important source of biological important substances on the primitive Earth. It is presumed that these space-made organic molecules could be transported safely to the Earth surface being associated with mineral grains. It is important to test whether nucleotides synthesized in Earth orbit could be protected by lunar surface regolite. The phosphorylation of adenosine, uridine and thymidine has been studied with respect of their further transformations and degradation in presence of mineral bed. After retrieval, HPLC analysis is used to identify all the mononucleotides of certain nucleosides. It has been shown, that exposure of the investigated nucleosides as dry films in space conditions in the presence of Lunar soil increases the yield of synthesized nucleotides in 1.1-3.0 times as compared with the exposure of the same samples in absence of Lunar soil. To identify and evaluate the principal source of energy in open space responsible for nucleotide synthesis reaction laboratory experiments were performed. It has been shown, that vacuum ultra violet (VUV 145 nm) radiation promotes nucleotide synthesis more effectively than ultra violet (UV 254 nm) while the presence of Lunar soil increases reaction yield in 1.5-2.0 times. Formation of 5'-mononucleotides seemed to be the most effective reaction both in flight and in laboratory experiments. Protective action of lunar soil on synthesized nucleotides against UV radiation has been shown in open Space conditions.
High molecular weight organic compounds are involved in the chemistry and physics of many astrophysical and planetary objects. They are or should be present in interstellar dust, in comets and meteorites, in the Giant planets and Titan, in asteroids Triton and icy satellites. They represent a class of very complex organic material, part of which may have played a role in the origin of life on Earth. Thus they directly concern prebiotic chemistry and exobiology.
The principal observational properties of silicate core-organic refractory mantle interstellar dust grains in the infrared at 3.4 microns and at 10 microns and 20 microns are discussed in terms of the cyclic evolution of particles forming in stellar atmospheres and undergoing subsequent accretion, photoprocessing and destruction (erosion). Laboratory plus space emulation of the photoprocessing of laboratory analog ices and refractories are discussed. The aggregated interstellar dust model of comets is summarized. The same properties required to explain the temperature and infrared properties of comet coma dust are shown to be needed to account for the infrared silicate and continuum emission of the beta Pictoris disk as produced by a cloud of comets orbiting the star.
We present the photochemical and thermal evolution of both non-polar and polar ices representative of interstellar and pre-cometary grains. Ultraviolet photolysis of the non-polar ices comprised of O2, N2, and CO produces CO2, N2O, O3, CO3, HCO, H2CO, and possibly NO and NO2. When polar ice analogs (comprised of H2O, CH3OH, CO, and NH3) are exposed to UV radiation, simple molecules are formed including: H2, H2CO, CO2, CO, CH4, and HCO (the formyl radical). Warming produces moderately complex species such as CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), R-CN and/or R-NC (nitriles and/or isonitriles). Several of these are already known to be in the interstellar medium, and their presence indicates the importance of grain processing. Infrared spectroscopy, 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry demonstrate that after warming to room temperature what remains is an organic residue composed primarily of hexamethylenetetramine (HMT, C6H12N4) and other complex organics including the amides above and polyoxymethylene (POM) and its derivatives. The formation of these organic species from simple starting mixtures under conditions germane to astrochemistry may have important implications for the organic chemistry of interstellar ice grains, comets and the origins of life.
The abiogenic synthesis of pyrimidine nucleotides in solid state has been investigated. Our experiment indicates that natural nucleotides are produced in thin films prepared from nucleoside and inorganic phosphate by irradiating with vacuum ultraviolet light (VUV, lambda=100-200 nm). We have investigated the influence of the type of nucleic acids base (thymidine, cytosine, uracil) and the structure of sugar moiety (ribose or deoxyribose) on the course and yield of reaction. We compared the action of vacuum ultraviolet light with action of gamma-radiation, heat and biology significant UV (254 nm) which have been investigated earlier. The occurrence of these reaction in open space is discussed.
The present experiment indicates that oligopeptides are easily produced in solid state from mixtures of simple amino acids by irradiating with high energy charged particles. We investigated such amino acids and their mixtures as tryptophan, tyrosine and glycine. The thin films was irradiated with protons (6.6 MeV). Such dipeptides as Trp-Trp, Gly-Tyr, Tyr-Gly, and Tyr-Tyr have been detected as products of irradiation. Cosmic rays might be an effective energy source for abiotic formation of bioorganic compounds on the surface of small bodies in the solar system on early stage of formation of planets as well as at present day.
Ion irradiation of carbon containing ices produces several effects among which the formation of complex molecules and even refractory organic materials whose spectral color and molecular complexity both depend on the amount of deposited energy. Here results from laboratory experiments are summarized. Their relevance for the formation and evolution of simple molecules and complex organic materials on planetary bodies in the external Solar System is outlined.
Hydrogen cyanide polymers--heterogeneous solids ranging in color from yellow to orange to brown to black--may be among the organic macromolecules most readily formed within the Solar System. The non-volatile black crust of comet Halley, for example, as well as the extensive orange-brown streaks in the atmosphere of Jupiter, might consist largely of such polymers synthesized from HCN formed by photolysis of methane and ammonia. Laboratory studies of these ubiquitous compounds point to the presence of polyamidine structures synthesized directly from hydrogen cyanide. These would be converted by water to polypeptides which can be further hydrolyzed to alpha-amino acids. Other polymers and multimers with ladder structures derived from HCN would also be present and might well be the source of the many nitrogen heterocycles, adenine included, detected by thermochemolytic analysis. The dark brown color arising from the impacts of comet P/Shoemaker-Levy 9 on Jupiter could therefore be mainly caused by the presence of HCN polymers, whether originally present, deposited by the impactor or synthesized from freshly formed HCN. Spectroscopic detection of these predicted macromolecules and their hydrolytic and pyrolytic by-products would strengthen significantly the hypothesis that cyanide polymerization is a preferred pathway for prebiotic and extraterrestrial chemistry.
The idea of extraterrestrial delivery of organic matter to the early Earth is especially attractive at present and is strongly supported by the detection of a large variety of organic compounds, including amino acids and nucleobases, in carbonaceous chondrites. Whether these compounds can be delivered by other space bodies is unclear and depends primarily on capability of the biomolecules to survive high temperatures during atmospheric deceleration and impacts to the terrestrial surface. In the present study we estimated survivability of simple amino acids (alpha-aminoisobutyric acid, L-alanine, L-valine and L-leucine), purines (adenine and guanine) and pyrimidines (uracil and cytosine) under rapid heating to temperatures of 400 to 1000 degrees C under N2 or CO2 atmosphere. We have found that most of the compounds studied cannot survive the temperatures substantially higher than 700 degrees C; however at 500-600 degrees C, the recovery can be at a per cent level (or even 10%-level for adenine, uracil, alanine, and valine). Implications of the data for extraterrestrial delivery of the biomolecules are discussed.
Comets in our solar system appear to have provided a bridge between the cold, volatile-rich outer solar system, and the warm, but volatile-poor inner solar system. Excluding tidal and possible extinct radionuclide heating sources, only in the inner solar system are temperatures high enough for liquid water, and therefore life as we know it, to exist for times comparable to the age of the solar system. Comets may have been crucial for providing biogenic volatiles and perhaps organic molecules to this warm environment. It is therefore interesting from an exobiological point of view to ask if comets exist in other planetary systems. Most attempts to detect comets around other stars or in interstellar space have failed. However, there is growing spectroscopic evidence for comet-like bodies orbiting the star Beta Pictoris.
Eight characteristics of the unique suite of amino acids and hydroxy acids found in the Murchison meteorite can be recognized on the basis of detailed molecular and isotopic analyses. The marked structural correspondence between the alpha-amino acids and alpha-hydroxy acids and the high deuterium/hydrogen ratio argue persuasively for their formation by aqueous phase Strecker reactions in the meteorite parent body from presolar, i.e., interstellar, aldehydes, ketones, ammonia, and hydrogen cyanide. The characteristics of the meteoritic suite of amino acids and hydroxy acids are briefly enumerated and discussed with regard to their consonance with this interstellar-parent body formation hypothesis. The hypothesis has interesting implications for the organic composition of both the primitive parent body and the presolar nebula.
A combined gas chromatography/isotope ratio mass spectrometry (GC/IRMS) method has been developed that permits the direct stable carbon isotope analysis of N(O)-trifluoroacetyl-isopropyl esters of individual amino acids and their respective enantiomers at nanomole abundances. Calculation of the original delta 13C values of the amino acids is accomplished via a correction for the carbon introduced during the derivatization process. Previous GC/IRMS analyses of individual amino acids in the non-hydrolyzed water extract of an interior sample of a Murchison meteorite stone revealed an enrichment in 13C relative to terrestrial organic matter, in agreement with previous findings for bulk extracts. The range of amino acid delta 13C values (+5 to +30%, PDB) suggests possible kinetic effects during synthesis. In this study, an apparent kinetic isotope effect was also observed for the amino acid products of a spark discharge experiment. These preliminary results are supportive of a similar mechanism for the abiotic synthesis of amino acids in the Murchison meteorite.
Synthesis of meteoritic amino acids probably took place in the aqueous sub-surface regions of one or more asteroid-sized parent bodies. Starting material for those reactions apparently consisted of a population of more simple compounds including a suite of aliphatic precursors characterised by (1) complete structural diversity, (2) prevalence of branched- over straight-chain species, (3) exponential decrease in abundance with increasing C number, (4) large enrichment in D, and, probably, (5) systematic decrease in 13C/12C with increasing C number. Those properties were apparently acquired during synthesis of the precursors by ion-molecule reactions in a presolar molecular cloud.