Characteristics and formation of amino acids and hydroxy acids of the Murchison meteorite.

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.     

Similarity of the infrared spectrum of an Orgueil organic polymer with interstellar organic compounds in the line of sight towards IRS 7.

We present a comparison between the IR spectrum of the galactic center source IRS 7 and the spectrum of a carbonaceous polymer from the Orgueil meteorite. We have obtained an almost perfect match between the two spectra in the region between 3020-2790 cm-1, which suggests that the chemical composition of the interstellar organic matter and that of the meteorite polymer are similar or that the meteoritic polymer could be a well preserved interstellar organic molecule. Assuming that the meteoritic polymer has the same C/H ratio as these interstellar molecules, we find that 45 % of the total abundance of carbon in the line of sight toward IRS 7 is trapped in such an interstellar organic grain material.     

The chemical conditions on the parent body of the murchison meteorite: Some conclusions based on amino, hydroxy and dicarboxylic acids

Amino and hydroxy acids have been identified in the Murchison meteorite. Their presence is consistent with a synthetic pathway involving aldehydes, hydrogen cyanide and ammonia in an aqueous environment (Strecker-cyanohydrin synthesis). From the various equilibrium and rate constants involved in this synthesis, four independent estimates of the ammonium ion concentrations on the parent body at the time of compound synthesis are obtained; all values are about 2 × 10^?3 M. Succinic acid and β-alanine have also been detected in the Murchison meteorite. Their presence is consistent with a synthesis from acrylonitrile, hydrogen cyanide and ammonia. Using the equilibrium and rate constants for this synthetic pathway, and the succinic acid/β-alanine ratio measured in the Murchison meteorite, an estimate of the hydrogen cyanide concentration of 10^?3 to 10^?2 M is obtained. Since hydrogen cyanide hydrolyzes relatively rapidly in an aqueous environment ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{< 10}{}^4\text{yrs}$) this high concentration implies a period of synthesis of organic compounds as short as 10⁴ years on the Murchison meteorite parent body.     

Formation of amino acid precursors in cometary ice environments by cosmic radiation.

Cometary ices are believed to contain water, carbon monoxide, methane and ammonia, and are possible sites for the formation and preservation of organic compounds relating to the origin of life. Cosmic rays, together with ultraviolet light, are among the most effective energy sources for the formation of organic compounds in space. In order to study the possibility of the formation of amino acids in comets or their precursory bodies (interstellar dust grains), several types of ice mixtures made in a cryostat at 10 K ("simulated cometary ices") were irradiated with high energy protons. After irradiation, the volatile products were analyzed with a quadrupole mass spectrometer, while temperature of the cryostat was raised to room temperature. The non-volatile products remaining in the cryostat at room temperature were collected with water. They were acid-hydrolyzed, and analyzed by ion-exchange chromatography. When an ice mixture of carbon monoxide (or methane), ammonia and water was irradiated, some hydrocarbons were formed, and amino acids such as glycine and alanine were detected in the hydrolyzate. These results suggest the possible formation of "amino acid precursors" (compounds yielding amino acids after hydrolysis) in interstellar dust grains by cosmic radiation. We previously reported that amino acid precursors were formed when simulated primitive planetary atmospheres were irradiated with cosmic ray particles. It will be of great interest to compare the amount of bioorganic compounds that were formed in the primitive earth and that brought by comets to the earth.     

吉林陨石的形成和演化过程

在对吉林陨石进行多学科综合研究所取得的成果基础上,我们对吉林陨石的形成演化过程作了如下讨论:(1)太阳星云的凝聚过程:根据吉林陨石的凝聚和固化年龄和矿物的组合,探讨了太阳星云凝聚的过程;(2)吉林陨石母体的热变质过程:从稀有气体的丢失,全岩化学成分的特征,稀土元素的自纯化过程和橄榄石、斜方辉石成分的稳定性,讨论了热变质过程的特征;(3)吉林陨石母体的冷却过程:根据镍纹石的镍含量和宽度,还根据矿物中Ar和裂变径迹的保存性,分析了吉林陨石母体的冷却史;(4)吉林陨石母体的破碎和宇宙线照射历史:根据对宇宙成因He3、Ne20,21,22、Ar38、Na22、Al26、Mn54、Mn53和Co60的测定结果,提出了吉林陨石的两阶段照射历史的模式。第一阶段的吉林陨石母体,年龄10—11my,r=10m,确定了各样品在母体中的相对位置;第二阶段的吉林陨石母体,年龄0.3—0.5my,r=80—90cm确定了各样品的埋藏深度及通过大气层后的烧失量;(5)吉林陨石的降落过程:讨论了吉林陨星在太阳系空间和大气层中的轨道及降落过程。      

Prebiotic syntheses of purines and pyrimidines

The work done in many laboratories during the last two decades has confirmed that hydrogen cyanide and cyanoacetylene are the two major precursors for the prebiotic synthesis of purines and pyrimidines, respectively. Although several different pathways for the synthesis of purines have been described, they are all variations of the initial mechanism proposed by Oró and Kimball, where hydrogen cyanide leads first to the formation of a 4,5-disubstituted imidazole derivative, and then to the closing of the purine ring with a C₁ compound. A number of experiments have shown that purines and pyrimidines can also be obtained from methane, ammonia (nitrogen), and water mixtures, provided an activating source of energy (radiation, electric discharges, etc.) is available. However, in this case the yields are lower by about two orders of magnitude because of the intermediate formation of hydrogen cyanide and cyanoacetylene. The latter two compounds have been found in interstellar space, Titan and other bodies of the solar system. They were probably present in the primordial parent bodies from the solar nebula in concentrations of 10⁻² to 10⁻³ M as inferred from recent calculations by Miller and coworkers obtained for the Murchison meteorite. These concentrations should have been sufficient to generate relatively large amounts of purine and pyrimidine bases on the primitive Earth.     

Amino acids in meteorites.

Carbonaceous chondrites carry a record of chemical evolution that is unparalleled among presently accessible natural materials. Within the complex suite of organic compounds that characterize these meteorites, amino acids occur at a total concentration that may reach 0.6 micromole g-1 meteorite (approximately 60 ppm). Both free amino acids and acid-labile amino acid derivatives have been found in hot-water extracts of a CI1 and seven CM2 chondrites. Although the amino acid composition of all CM2 chondrites is not the same, differences may be largely explicable on the basis of spontaneous and biologically-caused decomposition occurring during their terrestrial residence. The amino acids of the Murchison meteorite (CM2) have been extensively analyzed and 52 amino acids have been positively identified. Thirty three of these amino acids are unknown in natural materials other than carbonaceous chondrites. Thus the Murchison meteorite has recently been the major source of new naturally-occurring amino acids. The Murchison amino acids comprise a mixture of C2 through C8 cyclic and acyclic monoamino alkanoic and alkandioic acids of nearly complete structural diversity. Within the acyclic monoamino alkanoic acid series, primary alpha-amino alpha-branched amino acids are predominant. The concentrations of individual amino acids decline exponentially with increasing carbon number within homologous series. Amino acid enantiomers are found in approximately equal amounts. Eight of the terrestrial protein amino acids have been found.     

Comets and life.

Some of the chemical species which have been detected in comets include H2O, HCN, CH3CN, CO, CO2, NH3, CS, C2 and C3. All of these have also been detected in the interstellar medium, indicating a probable relationship between interstellar dust and gas clouds and comets. Laboratory experiments carried out with different mixtures of these molecules give rise to the formation of the biochemical compounds which are necessary for life, such as amino acids, purines, pyrimidines, monosaccharides, etc. However, in spite of suggestions to the contrary, the presence of life in comets is unlikely. On the other hand, the capture of cometary matter by the primitive Earth is considered essential for the development of life on this planet. The amount of cometary carbon-containing matter captured by the Earth, as calculated by different authors, is several times larger than the total amount of organic matter present in the biosphere (10(18)g). The major classes of reactions which were probably involved in the formation of key biochemical compounds are discussed. Our tentative conclusions are that: 1) comets played a predominant role in the emergence of life on our planet, and 2) they are the cosmic connection with extraterrestrial life.     

Complex organics in meteorites.

Complex macromolecular organic matter is present in carbonaceous chondrites as the most abundant organic matter and may be present in interstellar dusts and comets. With this view, our studies of the complex organic matter isolated from six CM2 chondrites, namely Yamato-74662, Yamato-791198, Yamato-793321, Yamato-86720, Belgica-7904, and Murchison are introduced and discussed in the text. The complex organic matter is acid-insoluble and organic solvent-insoluble, and therefore, it was examined by heating experiments to obtain information on its chemical constituents and characteristics. Three chondrites, Yamato-74662, Yamato-791198, and Murchison which have solvent-extractable organic compounds, such as amino acids, carboxylic acid, hydrocarbons, etc. possess thermally labile organic fraction in the complex organic matter. Organic compounds detected in the pyrolyzate of the complex organic matter number over 130 of which aromatic hydrocarbons are dominant. They appeared around 300 degrees C, and disappeared at about 600 degrees C with a maximum at 400-500 degrees C during the heating. On the other hand, the other three chondrites do not have the extractable organic compounds nor a thermally labile organic fraction. The presence or absence of the fraction in the complex organic matter likely indicates the presence or absence of the solvent-extractable organic compounds and relates to thermal history of the chondrite.     

Chemical evolution of primitive solar system bodies.

In this paper we summarize some of the most salient observations made recently on the organic molecules and other compounds of the biogenic elements present in the interstellar medium and in the primitive bodies of the solar system. They include the discovery of the first phosphorus molecular species in dense interstellar clouds, the presence of complex organic ions in the dust and gas phase of Halley's coma, the finding of unusual, probably presolar, deuterium-hydrogen ratios in the amino acids of carbonaceous chondrites, and new developments on the chemical evolution of Titan, the primitive Earth, and early Mars. Some of the outstanding problems concerning the synthesis of organic molecules on different cosmic bodies are also discussed from an exobiological perspective.     

吉林陨石稀有气体的分布特征及其热历史的初步探讨

吉林陨石的宇成和放射成因稀有气体存在大幅度的变化.宇成3He、20, 21, 22Ne和38Ar_c之间彼此近似线性相关, 放射成因4He和40Ar之间近似线性相关.放射成因4He、40Ar与作为陨星深度标尺的宇成60Co间近似线性相关, 但与作为吉林陨石母体深度标尺的21Ne之间不存在线性相关.上述事实表明:4He和40Ar在吉林陨石中的分布是不均匀的, 在吉林母体中的分布是不规则的, 而在吉林流星中, 由表面至中心呈现递增的倾向.我们试图用吉林陨石母体与小行星间的碰撞效应解释用4He和40Ar的上述独特分布特征.      

Chemical evolution and the origin of life.

During the last three decades major advances have been made in our understanding of the formation of carbon compounds in the universe and of the occurence of processes of chemical evolution. 1) Carbon and other biogenic elements (C,H,N,O,S and P) are some of the most abundant in the universe. 2) The interstellar medium has been found to contain a diversity of molecules of these elements. 3) Some of these molecules have also been found in comets which are considered the most primordial bodies of the solar system. 4) The atmospheres of the outer planets and their satellites, for example, Titan, are actively involved in the formation of organic compounds which are the precursors of biochemical molecules. 5) Some of these biochemical molecules, such as amino acids, purines and pyrimidines, have been found in carbonaceous chondrites. 6) Laboratory experiments have shown that most of the monomers and oligomers necessary for life can be synthesized under hypothesized but plausible primitive Earth conditions from compounds found in the above cosmic bodies. 7) It appears that the primitive Earth had the necessary and sufficient conditions to allow the chemical synthesis of biomacromolecules and to permit the processes required for the emergence of life on our planet. 8) It is unlikely that the emergence of life occurred in any other body of the solar system, although the examination of the Jovian satellite Europa may provide important clues about the constraints of this evolutionary process. Some of the fundamental principles of chemical evolution are briefly discussed.     

Observational astrochemistry

Astronomers have identified some 70 molecular species in dense interstellar clouds and the envelopes expelled by evolved stars. Some 75% of these are organic, including molecules with up to 13 atoms and with weights up to 147 daltons. Elements found in interstellar compounds include H, C, N, O, S, Si, and probably Cℓ. A recent addition to the list of interstellar molecules is the first hydrocarbon ring, cyclopropenylidene (C₃H₂). Current research in astrochemistry is concentrating on the determination of accurate chemical abundances as a function of environment. Both basic similarities and intriguing differences among clouds are found, which may provide clues to processes associated with cloud evolution and star formation.     

From the interstellar clouds, through the inner to the outer solar system: a universally distributed complex organic chemistry. Preface.

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.     

Fullerenes in space.

The discovery and synthesis of fullerenes led to the hypothesis that they may be present and stable in interstellar space. Fullerenes have been reported in an impact crater on the LDEF spacecraft. Investigations of fullerenes in carbonaceous meteorites have yielded only small upper limits. Fullerene compounds and their ions could be interesting carrier molecules for some of the "diffuse interstellar bands" (DIBs), a long standing mystery in astronomy. We have detected two new diffuse bands that are consistent with laboratory measurements of the C60+, as first evidence for the largest molecule ever detected in space. Criteria for this identification are discussed. The inferred abundance (up to 0.9 % of cosmic carbon locked in C60+) suggests that fullerenes may play an important role in interstellar chemistry. We present new observations on DIB substructures consistent with fullerene compounds, and the search for neutral C60 in the diffuse medium.     

Possible complex organic compounds on Mars.

It is suggested that primitive Mars had somehow similar environments as primitive Earth. If life was born on the primitive earth using organic compounds which were produced from the early Earth environment, the same types of organic compounds were also formed on primitive Mars. Such organic compounds might have been preserved on Mars still now. We are studying possible organic formation on primitive and present Mars. A gaseous mixture of CO2, CO, N2 and H2O with various mixing ratios were irradiated with high energy protons (major components of cosmic rays). Hydrogen cyanide and formaldehyde were detected among volatile products, and yellow-brown-colored water-soluble non-volatile substances were produced, which gave amino acids after acid-hydrolysis. Major part of "amino acid precursors" were not simple molecules like aminonitriles, but complex compounds which eluted earlier than free amino acids in cation-exchange HPLC. These organic compounds should be major targets in the future Mars mission. Strategy for the detection of the complex organics on Mars will be discussed.     

The Kumtag meteorite strewn field

The Kumtag meteorite strewn field was found in the Kumtag desert, 132 km south of Hami city in the Xinjiang province, China. It is an ellipse of 2.5 × 7.9 km, with a long axis extending along the northeast-southwest direction. The largest individual meteorite of the strewn field weighs about 10 kg; the smallest individual has a mass of only 27 g. In total, more than 100 individuals with a total mass of more than 180 kg were collected. The location and the distribution of the fragments suggest that the Kumtag meteoroid entered the atmosphere in the direction Northeast-Southwest. All meteorites collected in this strewn field are samples from the same unique meteorite shower. The Kumtag meteorite is an H5 ordinary chondrite with a shock stage S2, and a weathering grade W2. The cosmic ray exposure age of Kumtag is 6.7 ± 0.8 Ma, which is rather typical for H chondrites and which indicates that Kumtag was derived from the massive impact event on its parent body ~7 Ma ago. A significant amount of He has been lost during certain unknown processe(s) before the Kumtag meteorite was ejected from its parent body.     

Stable isotope analysis at the molecular level: a new approach for determining the origins of amino acids in the Murchison meteorite.

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.     

Complex organics in laboratory simulations of interstellar/cometary ices.

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.     

吉林陨石的熔融实验研究及其在地球化学中的应用

组成地球的初始物质很可能是IAB铁陨石及H群球粒陨石,非均匀吸积形成地球以后,除由岩浆分异作用使幔中金属-硫化物下沉到原始地核外,在还原条件下还有部分Fe是由橄榄石中的FeO还原为Fe0而提供的并加入于地核内.对于大的陨石母体,由于内部加热或其表面受冲击加热而发生熔融和岩浆分异,导致形成某些铁陨石及无球粒陨石或7型岩石类型的球粒岩石.实验产物中的Fe-Ni-S相可作为判别宇宙球粒的标志之一.