Carbon isotope composition of individual amino acids in the Murchison meteorite

A significant portion of prebiotic organic matter on the early Earth may have been introduced by carbonaceous asteroids and comets. The distribution and stable-isotope composition of individual organic compounds in carbonaceous meteorites, which are thought to be derived from asteroidal parent bodies, may therefore provide important information concerning mechanistic pathways for prebiotic synthesis and the composition of organic matter on Earth before living systems developed. Previous studies have shown that meteorite amino acids are enriched in 13C relative to their terrestrial counterparts, but individual species were not distinguished. Here we report the 13C contents of individual amino acids in the Murchison meteorite. The amino acids are enriched in 13C, indicating an extraterrestrial origin. Alanine is not racemic, and the 13C enrichment of its D- and L-enantiomers implies that the excess of the L-enantiomer is indigenous rather than terrestrial contamination, suggesting that optically active materials were present in the early Solar System before life began.     

Amino-acid synthesis in carbonaceous meteorites by aqueous alteration of polycyclic aromatic hydrocarbons

It has been suggested that amino acids and other organic compounds found in carbonaceous meteorites formed by aqueous alteration in the meteorite parent bodies. Observations of carbonaceous material in interstellar grains and interplanetary dust particles indicate that condensed organic compounds may have been present in meteorite parent bodies at the time of aqueous alteration. One group of compounds thought to be representative of this carbonaceous material is the polycyclic aromatic hydrocarbons (PAHs). Recently it was proposed that PAHs condense on SiC grains in the molecular envelopes of carbon-rich red-giant stars, which would allow for their subsequent incorporation into meteorite parent bodies during accretion. This incorporation mechanism is supported by the identification of SiC grains in carbonaceous chondrites. The possibility therefore exists that PAHs, and/or other condensed organic compounds, represent the starting material for aqueous alteration which leads to the formation of amino acids and other water-soluble organic compounds. Here we present calculations of the distribution of aqueous organic compounds in metastable equilibrium with representative PAHs as functions of the fugacities of O2, CO2 and NH3. The results reported here for pyrene and fluoranthene, two PAHs with different structures but the same stoichiometry, differ greatly but indicate that the formation of amino and carboxylic acids is energetically favourable at probable parent-body alteration conditions. The actual reaction mechanisms involved could be revealed by consideration of isotope data for PAHs, amino acids, other organic compounds and carbonates in carbonaceous chondrites.     

Carbonaceous meteorites as a source of sugar-related organic compounds for the early Earth.

The much-studied Murchison meteorite is generally used as the standard reference for organic compounds in extraterrestrial material. Amino acids and other organic compounds important in contemporary biochemistry are thought to have been delivered to the early Earth by asteroids and comets, where they may have played a role in the origin of life. Polyhydroxylated compounds (polyols) such as sugars, sugar alcohols and sugar acids are vital to all known lifeforms-they are components of nucleic acids (RNA, DNA), cell membranes and also act as energy sources. But there has hitherto been no conclusive evidence for the existence of polyols in meteorites, leaving a gap in our understanding of the origins of biologically important organic compounds on Earth. Here we report that a variety of polyols are present in, and indigenous to, the Murchison and Murray meteorites in amounts comparable to amino acids. Analyses of water extracts indicate that extraterrestrial processes including photolysis and formaldehyde chemistry could account for the observed compounds. We conclude from this that polyols were present on the early Earth and therefore at least available for incorporation into the first forms of life.     

Unusual stable isotope ratios in amino acid and carboxylic acid extracts from the Murchison meteorite

Much effort has been directed to analyses of organic compounds in carbonaceous chondrites because of their implications for organic chemical evolution and the origin of life. We have determined the isotopic composition of hydrogen, nitrogen and carbon in amino acid and monocarboxylic acid extracts from the Murchison meteorite. The unusually high D/H and 15N/14N ratios in the amino acid fraction (delta D = 1,370% after correction for isotope exchange; delta 15N = 90) are uniquely characteristic of known interstellar organic materials. The delta D value of the monocarboxylic acid fraction is lower (377%), but still consistent with an interstellar origin. These results confirm the extraterrestrial origin of both classes of compound, and provide the first evidence suggesting a direct relationship between the massive organo-synthesis occurring in interstellar clouds and the presence of pre-biotic compounds in primitive planetary bodies. The isotope data also bear on the historical problem of distinguishing indigenous material from terrestrial contaminants.     

Amino acids from ultraviolet irradiation of interstellar ice analogues

Amino acids are the essential molecular components of living organisms on Earth, but the proposed mechanisms for their spontaneous generation have been unable to account for their presence in Earth's early history. The delivery of extraterrestrial organic compounds has been proposed as an alternative to generation on Earth, and some amino acids have been found in several meteorites. Here we report the detection of amino acids in the room-temperature residue of an interstellar ice analogue that was ultraviolet-irradiated in a high vacuum at 12 K. We identified 16 amino acids; the chiral ones showed enantiomeric separation. Some of the identified amino acids are also found in meteorites. Our results demonstrate that the spontaneous generation of amino acids in the interstellar medium is possible, supporting the suggestion that prebiotic molecules could have been delivered to the early Earth by cometary dust, meteorites or interplanetary dust particles.     

Detection of carbonates in dust shells around evolved stars.

Carbonates on large Solar System bodies like Earth and Mars (the latter represented by the meteorite ALH84001) form through the weathering of silicates in a watery (CO3)2- solution. The presence of carbonates in interplanetary dust particles and asteroids (again, represented by meteorites) is not completely understood, but has been attributed to aqueous alteration on a large parent body, which was subsequently shattered into smaller pieces. Despite efforts, the presence of carbonates outside the Solar System has hitherto not been established. Here we report the discovery of the carbonates calcite and dolomite in the dust shells of evolved stars, where the conditions are too primitive for the formation of large parent bodies with liquid water. These carbonates, therefore, are not formed by aqueous alteration, but perhaps through processes on the surfaces of dust or ice grains or gas phase condensation. The presence of carbonates which did not form by aqueous alteration suggests that some of the carbonates found in Solar System bodies no longer provide direct evidence that liquid water was present on large parent bodies early in the history of the Solar System.     

Early Solar System aqueous activity: Sr isotope evidence from the Orgueil CI meteorite

The CI meteorites are rare but important objects because they may represent our best sample of chemically unfractionated Solar System material. Despite the fact the these meteorites apparently retain their original chemical composition, they clearly contain secondary mineral phases, some at least believed to have been produced through the action of liquid water on the parent body. The timing of this event, however, was unknown. In an attempt to solve this problem, we have measured the Sr isotopic composition and 87Rb/86Sr in carbonates and sulphate separated from the Orgueil meteorite. Both of these phases probably precipitated from aqueous solution. Our first results, reported here, show that carbonate deposition occurred contemporaneously with parent body formation or shortly after it probably within 100 Myr. On the other hand, at least some of the calcium sulphate seems to have been formed recently.     

Carbon isotope composition of low molecular weight hydrocarbons and monocarboxylic acids from Murchison meteorite

The origin of the organic matter in carbonaceous meteorites remains controversial despite extensive study over the past 20 yr. Motivated by the expectation that the patterns of isotopic variation with molecular structure among the organic compounds would contain important clues to their origin, we have measured the carbon isotopic compositions for individual hydrocarbons and monocarboxylic acids from Murchison meteorite, a C2 carbonaceous chondrite which fell in Australia in 1969. With few exceptions, notably benzene, the volatile products are substantially isotopically heavier than their terrestrial counterparts, signifying their extraterrestrial origin. For both classes of compounds, the ratio of 13C to 12C decreases with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic ratio than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with the kinetically controlled synthesis of higher homologues from lower ones. The results suggest the possibility that the production mechanisms for hydrocarbons and carboxylic acids may be similar; they also impose constraints on the identity of the reactant species.     

Hydrogen isotope geochemistry of lherzolitic shergottite in Martian meteorite GRV99027 from the Grove Mountains in Antarctica

Whether life vestige existed in Martian meteorites or not has provoked a hot tide toward Mars exploration. Among the other things, whether water existed in Marsor not again becomes a hot point of contemporary sci- entific exploration. Analyzing the hydrog…     

氘过量参数及其水文地质学意义--以四川九寨沟和冶勒水文地质研究为例

根据四川九寨沟和冶勒地区各种水体的同位素资料,讨论了反映大气降水蒸发、凝结过程的不平衡程度的氘过量参数(d=δD-8δ18O)在降水和地下水中的主要变化特点及影响因素,对比了岩溶水和非岩溶水中氘过量参数d值的变化情况以及与水体氚含量变化的相关规律性.指出氘过量参数d值,是研究水/岩作用、地下水动力学和地表径流动态组成的一个十分重要的参数指标,具有极为重要的水文地质学意义.     

Comet dust as a source of amino acids at the Cretaceous/Tertiary boundary

Large amounts of apparently extraterrestrial amino acids have been detected recently in rocks at the Cretaceous/Tertiary (K/T) boundary at Stevns Klint, Denmark. The amino acids were found a few tens of centimetres above and below the boundary layer, but were absent in the boundary clay itself. If one supposes that these compounds were carried to the Earth by the giant meteorite thought to have impacted at the end of the Cretaceous, some puzzling questions are raised: why weren't the amino acids incinerated in the impact, and why are they not present in the boundary clay itself? Here we suggest that the amino acids were actually deposited with the dust from a giant comet trapped in the inner Solar System, a fragment of which comprised the K/T impactor. Amino acids or their precursors in the comet dust would have been swept up by the Earth both before and after the impact, but any conveyed by the impactor itself would have been destroyed. The observed amino acid layers would thus have been deposited without an impact.     

Large differences in the helix propensities of alanine and glycine

The standard view of alpha helix formation in water, based on helix propensities determined by the host-guest method, is that differences in helix propensity among the amino acids are small, except for proline, and that the average value of the helix propagation parameter s is near 1. A contradictory view of alpha helix formation in water is emerging from substitution experiments with short, unique-sequence peptides that contain only naturally occurring amino acids. Short peptides that contain only alanine and lysine, or alanine and glutamate, form surprisingly stable monomeric helices in water and substitution of a single alanine residue by another amino acid in these or related peptides produces a wide range of changes in helix content, depending on which amino acid is substituted for alanine. We show here that the ratio of the helix propensities of alanine to glycine is large, about 100, in substitution experiments with a 17-residue reference peptide containing alanine and lysine. The helix propensity is identified with s, the helix propagation parameter of the statistical mechanics model for alpha helix formation, and the results are interpreted by the Lifson-Roig theory. Single alanine----glycine substitutions have been made at a series of positions in individual peptides. The helix-destabilizing effect of an Ala----Gly substitution depends strongly on its position in the helix, as predicted by the Lifson-Roig theory if the ratio of s values for Ala:Gly is large.     

Ultraviolet-radiation-induced methane emissions from meteorites and the Martian atmosphere

Almost a decade after methane was first reported in the atmosphere of Mars there is an intensive discussion about both the reliability of the observations--particularly the suggested seasonal and latitudinal variations--and the sources of methane on Mars. Given that the lifetime of methane in the Martian atmosphere is limited, a process on or below the planet's surface would need to be continuously producing methane. A biological source would provide support for the potential existence of life on Mars, whereas a chemical origin would imply that there are unexpected geological processes. Methane release from carbonaceous meteorites associated with ablation during atmospheric entry is considered negligible. Here we show that methane is produced in much larger quantities from the Murchison meteorite (a type CM2 carbonaceous chondrite) when exposed to ultraviolet radiation under conditions similar to those expected at the Martian surface. Meteorites containing several per cent of intact organic matter reach the Martian surface at high rates, and our experiments suggest that a significant fraction of the organic matter accessible to ultraviolet radiation is converted to methane. Ultraviolet-radiation-induced methane formation from meteorites could explain a substantial fraction of the most recently estimated atmospheric methane mixing ratios. Stable hydrogen isotope analysis unambiguously confirms that the methane released from Murchison is of extraterrestrial origin. The stable carbon isotope composition, in contrast, is similar to that of terrestrial microbial origin; hence, measurements of this signature in future Mars missions may not enable an unambiguous identification of biogenic methane.     

Relative helix-forming tendencies of nonpolar amino acids

An important issue in understanding the relationship between protein sequence and structure is the degree to which different amino acids favour the formation of particular types of secondary structure. Estimates of the 'helix-forming tendency' of amino acids have been made based on 'host-guest' experiments, in which copolymers are made of the amino acid of interest (the 'guest') and a host residue (typically hydroxypropyl- or hydroxybutyl-L-glutamine). Recently, however, short alanine-based peptides were found to form stable monomeric helices in water, contrary to the result predicted from host-guest experiments. We have now measured the helix-forming tendency of five different nonpolar amino acids (Ala, Ile, Leu, Phe, Val) by substituting each in turn for alanine in a 17-residue alanine-based peptide and determining the extent of alpha-helix formation. Our results differ from those of host-guest experiments both in the degree of variation in helix-forming tendency of different amino acids, and in the rank order of the helix-forming tendency. We conclude that the helix-forming tendency of a particular amino acid depends on the sequence context in which it occurs; and the restriction of side-chain rotamer conformations is important in determining the helix-forming tendency.     

Asymmetric additions to dienes catalysed by a dithiophosphoric acid

Chiral Br?nsted acids (proton donors) have been shown to facilitate a broad range of asymmetric chemical transformations under catalytic conditions without requiring additional toxic or expensive metals. Although the catalysts developed thus far are remarkably effective at activating polarized functional groups, it is not clear whether organic Br?nsted acids can be used to catalyse highly enantioselective transformations of unactivated carbon-carbon multiple bonds. This deficiency persists despite the fact that racemic acid-catalysed 'Markovnikov' additions to alkenes are well known chemical transformations. Here we show that chiral dithiophosphoric acids can catalyse the intramolecular hydroamination and hydroarylation of dienes and allenes to generate heterocyclic products in exceptional yield and enantiomeric excess. We present a mechanistic hypothesis that involves the addition of the acid catalyst to the diene, followed by nucleophilic displacement of the resulting dithiophosphate intermediate; we also report mass spectroscopic and deuterium labelling studies in support of the proposed mechanism. The catalysts and concepts revealed in this study should prove applicable to other asymmetric functionalizations of unsaturated systems.     

Possible in situ formation of meteoritic nanodiamonds in the early Solar System

Grains of dust that pre-date the Sun provide insights into their formation around other stars and into the early evolution of the Solar System. Nanodiamonds recovered from meteorites, which originate in asteroids, have been thought to be the most abundant type of presolar grain. If that is true, then nanodiamonds should be at least as abundant in comets, because they are thought to have formed further out in the early Solar System than the asteroid parent bodies, and because they should be more pristine. Here we report that nanodiamonds are absent or very depleted in fragile, carbon-rich interplanetary dust particles, some of which enter the atmosphere at speeds within the range of cometary meteors. One interpretation of the results is that some (perhaps most) nanodiamonds formed within the inner Solar System and are not presolar at all, consistent with the recent detection of nanodiamonds within the accretion discs of other young stars. An alternative explanation is that all meteoritic nanodiamonds are indeed presolar, but that their abundance decreases with heliocentric distance, in which case our understanding of large-scale transport and circulation within the early Solar System is incomplete.     

天然有机酸催化Pechmann缩合反应合成香豆素衍生物的研究

开展了几种天然有机酸催化Pechmann缩合反应的研究,结果表明,草酸能够有效催化-酮酸酯与取代酚的缩合反应,成功合成了一系列香豆素衍生物.这种方法具有催化剂价廉易得、环境友好、条件温和、能够容忍底物中的多种官能团等优点.     

Hexanoyl Chitosan-based Gel Electrolyte for Lithium-ion Cell

1 Introduction Fig.1 Chemical structure of hexanoyl chitosanChitosan is soluble in dilute acid solutions as a result of salt formation by the amino groups with various inorganic and organic acids~([1,2]). Due to the reactivity of water and other protic solvents such as methanol and acetic acid with the electrode material in the lithium-based electrochemical devices~([3]), the insolubility of chitosan in aprotic solvents is inadequate to meet the requirements to be used as the electrolyte mater…     

Structure and thermal history of the H-chondrite parent asteroid revealed by thermochronometry

Our Solar System formed approximately 4.6 billion years ago from the collapse of a dense core inside an interstellar molecular cloud. The subsequent formation of solid bodies took place rapidly. The period of &<10 million years over which planetesimals were assembled can be investigated through the study of meteorites. Although some planetesimals differentiated and formed metallic cores like the larger terrestrial planets, the parent bodies of undifferentiated chondritic meteorites experienced comparatively mild thermal metamorphism that was insufficient to separate metal from silicate. There is debate about the nature of the heat source as well as the structure and cooling history of the parent bodies. Here we report a study of 244Pu fission-track and 40Ar-39Ar thermochronologies of unshocked H chondrites, which are presumed to have a common, single, parent body. We show that, after fast accretion, an internal heating source (most probably 26Al decay) resulted in a layered parent body that cooled relatively undisturbed: rocks in the outer shells reached lower maximum metamorphic temperatures and cooled faster than the more recrystallized and chemically equilibrated rocks from the centre, which needed approximately 160 Myr to reach 390K.     

S-process krypton of variable isotopic composition in the Murchison meteorite

Current theories on the origin of the chemical elements explain the abundance of medium-heavy and heavy nuclides to be due to the capture by pre-existing lighter nuclides of free neutrons on either a slow timescale (s-process) or a rapid timescale (r-process). Experimental evidence in support of these theories comes from the analysis of carbonaceous chondrites. In acid-resistant residues of these meteorites a kind of xenon has been found, the isotopic composition of which matches almost perfectly that predicted for s-process xenon. We report data that allow us, for the first time, to derive with reasonable precision the full isotopic spectrum of s-process krypton as well. We show that this s-Kr in a residue from Murchison meteorite did not originate in one single s-process but rather is a mixture of contributions from stellar environments where the density of free neutrons was not the same. The astrophysical conditions under which this Krypton has been produced were distinct from those that have been invoked to explain the Solar System s-process abundance. Similar to the 13C-rich carbon component in an aliquot of the same residue, the s-process Kr from different astrophysical sites has retained its identity during the accumulation and subsequent history of the meteorite.