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1.
The role and relative contributions of different forms of energy to the synthesis of amino acids and other organic compounds on the primitive earth, in the parent bodies or carbonaceous chondrites, and in the solar nebula are examined. A single source of energy or a single process would not account for all the organic compounds synthesized in the solar system. Electric discharges appear to produce amino acids more efficiently than other sources of energy and the composition of the synthesized amino acids is qualitatively similar to those found in the Murchison meteorite. Ultraviolet light is also likely to have played a major role in prebiotic synthesis. Although the energy in the sun's spectrum that can be absorbed by the major constituents of the primitive atmosphere is not large, reactive trace components such as H2S and formaldehyde absorb at longer wavelengths where greater amounts of energy are available and produce amino acids by reactions involving hot hydrogen atoms. The thermal reaction of CO + H2 + NH3 on Fischer-Tropsch catalysts generates intermediates that lead to amino acids and other organic compounds that have been found in meteorites. However, this synthesis appears to be less efficient than electric discharges and to require a special set of reaction conditions. It should be emphasized that after the reactive organic intermediates are generated by the above processes, the subsequent reactions which produce the more complete biochemical compounds are low temperature homogenous reactions occurring in an aqueous environment.  相似文献   

2.
Summary Six of the seven chain isomers of six-carbon acyclic primary-amino alkanoic acids (leucine isomers) have been either identified or confirmed in hot-water extracts of the Murchison meteorite using combined gas chromatography-mass spectrometry (GC-MS) and ion exchange chromatography. 2-Amino-2-ethylbutyric acid, 2-amino-2,3-dimethylbutyric acid, pseudoleucine, and 2-methylnorvaline were positively identified by GC-MS. These amino acids have not been previously reported to occur in natural materials and may be uniquely meteoritic in origin. The presence of leucine and isoleucine (including the diastereoisomer, alloisoleucine) was confirmed. Peaks corresponding to norleucine were seen by ion-exchange and gas chromatography but characteristic mass spectra were not obtained. The-branched chain isomers in this series are quantitatively the most significant. These results are compared with literature data on amino acid synthesis by electrical discharge and Fischer-Tropsch-type catalysis. Neither model system produces an amino acid suite that is completely comparable to that found in the Murchison meteorite.Contribution 113 from the Center for Meteorite Studies  相似文献   

3.
For almost 20 years laboratory experiments have advanced the concepts of chemical evolution, particularly with regard to formation of the amino acids. What has been generally lacking is concrete natural evidence for this chemical evolution hypothesis. The recent development of sophisticated analytical techniques and availability of carbonaceous chondrites with a minimum of terrestrial contamination has resulted in the identification of amino acids which provide strong evidence for a natural extraterrestrial chemical synthesis. Since the initial find in the Murchison meteorite (a type II carbonaceous chondrite) of both protein and nonprotein amino acids and amino acids with nearly equal abundances of D and L isomers, further studies have been carried out. These studies have revealed the presence of at least 35 amino acids; the population consists of a wide variety of linear, cyclic and polyfunctional amino acids which shows a trend of decreasing concentration with increasing carbon number. Investigations of the Murray meteorite (a type II carbonaceous chondrite) has produced similar results, but studies of the Orgueil meteorite (a type I carbonaceous chondrite) show only a limited suite of amino acids, some of which appear to be indigenous while others appear to be terrestrial contaminants. A sample of the Murchison meteorite was extracted with D2O and in addition to free amino acids, showing no deuterium incorporation, some amino acids showed the presence of deuterium suggesting either a precursor(s) or hydrogendeuterium exchange which require(s) formation of carbon-hydrogen bonds.  相似文献   

4.
For almost 20 years laboratory experiments have advanced the concepts of chemical evolution, particularly with regard to formation of the amino acids. What has been generally lacking is concrete natural evidence for this chemical evolution hypothesis. The recent development of sophisticated analytical techniques and availability of carbonaceous chondrites with a minimum of terrestrial contamination has resulted in the identification of amino acids which provide strong evidence for a natural extraterrestrial chemical synthesis. Since the initial find in the Murchison meteorite (a type II carbonaceous chondrite) of both protein and nonprotein amino acids with nearly equal abundances of D and L isomers, further studies have been carried out. These studies have revealed the presence of at least 35 amino acids; the population consists of a wide variety of linear, cyclic and polyfunctional amino acids which shows a trend of decreasing concentration with increasing carbon number. Investigations of the Murray meteorite (a type II carbonaceous chondrite) has produced similar results, but studies of the Orgueil meteorite (a type I carbonaceous chondrite) show only a limited suite of amino acids, some of which appear to be indigenous while others appear to be terrestrial contaminanats. A sample of the Murchison meteorite was extracted with D2O and in addition of 'free' amino acids, showing no deuterium incorporation, some amino acids showed the presence of deuterium suggesting either a 'precursor(s)' or hydrogen-deuterium exchange which require(s) formation of carbon-hydrogen bonds.  相似文献   

5.
Stanley Miller’s 1958 H2S-containing experiment, which included a simulated prebiotic atmosphere of methane (CH4), ammonia (NH3), carbon dioxide (CO2), and hydrogen sulfide (H2S) produced several alkyl amino acids, including the α-, β-, and γ-isomers of aminobutyric acid (ABA) in greater relative yields than had previously been reported from his spark discharge experiments. In the presence of H2S, aspartic and glutamic acids could yield alkyl amino acids via the formation of thioimide intermediates. Radical chemistry initiated by passing H2S through a spark discharge could have also enhanced alkyl amino acid synthesis by generating alkyl radicals that can help form the aldehyde and ketone precursors to these amino acids. We propose mechanisms that may have influenced the synthesis of certain amino acids in localized environments rich in H2S and lightning discharges, similar to conditions near volcanic systems on the early Earth, thus contributing to the prebiotic chemical inventory of the primordial Earth.  相似文献   

6.
The spark discharge synthesis of amino acids using an atmosphere of CH4 + N2 + H2O + NH3 has been investigated with variable pNH3. The amino acids produced using higher hydrocarbons (ethane, ethylene, acetylene, propane, butane, and isobutane) instead of CH4 were also investigated. There was considerable range in the absolute yields of amino acids, but the yields relative to glycine (or -amino-n-butyric acid) were more uniform. The relative yields of the C3 to C6 aliphatic -amino acids are nearly the same (with a few exceptions) with all the hydrocarbons. The glycine yields are more variable. The precursors to the C3-C6 aliphatic amino acids seem to be produced in the same process, which is separate from the synthesis of glycine precursors. It may be possible to use these relative yields as a signature for a spark discharge synthesis provided corrections can be made for subsequent decomposition events (e.g. in the Murchison meteorite).  相似文献   

7.
Summary The amino acid composition and the pyrolyzable organic content of the Antarctic Allan Hills meteorite (ALHA 77306.9 and ALHA 77306.17) was examined. The pyrolysis products are very similar to those of the Murchison meteorite. The identified amino acids are present at quite low levels, they are racemic and are structurally similar to those observed in the Murchison meteorite. This indicates the possible chemical synthesis of these compounds in the meteorite parent body. The Allan Hills meteorite is not detectably contaminated.  相似文献   

8.
Primitive terrestrial life – defined as a chemical system able to transfer its molecular information via self-replication and to evolve – probably originated from the evolution of reduced organic molecules in liquid water. Several sources have been proposed for the prebiotic organic molecules: terrestrial primitive atmosphere (methane or carbon dioxide), deep-sea hydrothermal systems, and extraterrestrial meteoritic and cometary dust grains. The study of carbonaceous chondrites, which contain up to 5% by weight of organic matter, has allowed close examination of the delivery of extraterrestrial organic material. Eight proteinaceous amino acids have been identified in the Murchison meteorite among more than 70 amino acids. Engel reported that l-alanine was surprisingly more abundant than d-alanine in the Murchison meteorite. Cronin also found excesses of l-enantiomers for nonprotein amino acids. A large collection of micrometeorites has been recently extracted from Antarctic old blue ice. In the 50- to 100-μm size range, carbonaceous micrometeorites represent 80% of the samples and contain 2% of carbon, on average. They might have brought more carbon than that involved in the present surficial biomass. The early histories of Mars and Earth clearly show similarities. Liquid water was once stable on the surface of Mars, attesting the presence of an atmosphere capable of deccelerating C-rich micrometeorites. Therefore, primitive life may have developed on Mars as well and fossilized microorganisms may still be present in the near subsurface. The Viking missions to Mars in 1976 did not find evidence of either contemporary or past life, but the mass spectrometer on the lander aeroshell determined the atmospheric composition, which has allowed a family of meteorites to be identified as Martian. Although these samples are essentially volcanic in origin, it has been recognized that some of them contain carbonate inclusions and even veins that have a carbon isotopic composition indicative of an origin from Martian atmospheric carbon dioxide. The oxygen isotopic composition of these carbonate deposits allows calculation of the temperature regime existing during formation from a fluid that dissolved the carbon dioxide. As the composition of the fluid is unknown, only a temperature range can be estimated, but this falls between 0° and 90°C, which would seem entirely appropriate for life processes. It was such carbonate veins that were found to host putative microfossils. Irrespective of the existence of features that could be considered to be fossils, carbonate-rich portions of Martian meteorites tend to have material, at more than 1000 ppm, that combusts at a low temperature; i.e., it is an organic form of carbon. Unfortunately, this organic matter does not have a diagnostic isotopic signature so it cannot be unambiguously said to be indigenous to the samples. However, many circumstantial arguments can be made to the effect that it is cogenetic with the carbonate and hence Martian. If it could be proved that the organic matter was preterrestrial, then the isotopic fractionation between it and the carbon is in the right sense for a biological origin. Received: January 22, 1998 / Accepted: February 16, 1998  相似文献   

9.
To date, explanations for the origin and emergence of the alphabet of amino acids encoded by the standard genetic code have been largely qualitative and speculative. Here, with the help of computational chemistry, we present the first quantitative exploration of nature's “choices” set against various models for plausible alternatives. Specifically, we consider the chemical space defined by three fundamental biophysical properties (size, charge, and hydrophobicity) to ask whether the amino acids that entered the genetic code exhibit a higher diversity than random samples of similar size drawn from several different definitions of amino acid possibility space.We found that in terms of the properties studied, the full, standard set of 20 biologically encoded amino acids is indeed significantly more diverse than an equivalently sized group drawn at random from the set of plausible, prebiotic alternatives (using the Murchison meteorite as a model for pre-biotic plausibility). However, when the set of possible amino acids is enlarged to include those that are produced by standard biosynthetic pathways (reflecting the widespread idea that many members of the standard alphabet were recruited in this way), then the genetically encoded amino acids can no longer be distinguished as more diverse than a random sample. Finally, if we turn to consider the overlap between biologically encoded amino acids and those that are prebiotically plausible, then we find that the biologically encoded subset are no more diverse as a group than would be expected from a random sample, unless the definition of “random sample” is adjusted to reflect possible prebiotic abundance (again, using the contents of the Murchison meteorite as our estimator). This final result is contingent on the accuracy of our computational estimates for amino acid properties, and prebiotic abundances, and an exploration of the likely effect of errors in our estimation reveals that our results should be treated with caution. We thus present this work as a first step in quantifying and thus testing various origin-of-life hypotheses regarding the origin and evolution of life's amino acid alphabet, and advocate the progress that would add valuable information in the future.  相似文献   

10.
Prebiotic oceans might have contained abundant amino acids, and were subjected to meteorite impacts, especially during the late heavy bombardment. It is so far unknown how meteorite impacts affected amino acids in the early oceans. Impact experiments were performed under the conditions where glycine was synthesized from carbon, ammonia, and water, using aqueous solutions containing 13C-labeled glycine and alanine. Selected amino acids and amines in samples were analyzed with liquid chromatography-mass spectrometry (LC/MS). In particular, the 13C-labeled reaction products were analyzed to distinguish between run products and contaminants. The results revealed that both amino acids survived partially in the early ocean through meteorite impacts, that part of glycine changed into alanine, and that large amounts of methylamine and ethylamine were formed. Fast decarboxylation was confirmed to occur during such impact processes. Furthermore, the formation of n-butylamine, detected only in the samples recovered from the solutions with additional nitrogen and carbon sources of ammonia and benzene, suggests that chemical reactions to form new biomolecules can proceed through marine impacts. Methylamine and ethylamine from glycine and alanine increased considerably in the presence of hematite rather than olivine under similar impact conditions. These results also suggest that amino acids present in early oceans can contribute further to impact-induced reactions, implying that impact energy plays a potential role in the prebiotic formation of various biomolecules, although the reactions are complicated and depend upon the chemical environments as well.  相似文献   

11.
A large collection of micrometeorites has been recently extracted from Antarctic old blue ice. In the 50 to 100 micrometers size range, the carbonaceous micrometeorites represent 80% of the samples and contain 2% of carbon. They might have brought more carbon to the surface of the primitive Earth than that involved in the present surficial biomass. Amino acids such as "-amino isobutyric acid have been identified in these Antarctic micrometeorites. Enantiomeric excesses of L-amino acids have been detected in the Murchison meteorite. A large fraction of homochiral amino acids might have been delivered to the primitive Earth via meteorites and micrometeorites. Space technology in Earth orbit offers a unique opportunity to study the behaviour of amino acids required for the development of primitive life when they are exposed to space conditions, either free or associated with tiny mineral grains mimicking the micrometeorites. Our objectives are to demonstrate that porous mineral material protects amino acids in space from photolysis and racemization (the conversion of L-amino acids into a mixture of L- and D-molecules) and to test whether photosensitive amino acids derivatives can polymerize in mineral grains under space conditions. The results obtained in BIOPAN-1 and BIOPAN-2 exposure experiments on board unmanned satellite FOTON are presented.  相似文献   

12.
The synthesis of adenine from the polymerization of concentrated ammonium cyanide solutions is well known. We show here that guanine is also produced by this reaction but at yields ranging from 10 to 40 times less than that of adenine. This synthesis is effective at both +80 and −20°C. Since high concentrations of NH4CN are obtainable only by freezing, this prebiotic synthesis would be applicable to frozen regions of the primitive Earth, the Jovian satellite Europa and other icy satellites, and the parent body of the Murchison meteorite. Received: 18 September 1998 / Accepted: 31 March 1999  相似文献   

13.
The action of an electric discharge on reduced gas mixtures such as H2O, CH4 and NH3 (or N2) results in the production of several biologically important organic compounds including amino acids. However, it is now generally held that the early Earth’s atmosphere was likely not reducing, but was dominated by N2 and CO2. The synthesis of organic compounds by the action of electric discharges on neutral gas mixtures has been shown to be much less efficient. We show here that contrary to previous reports, significant amounts of amino acids are produced from neutral gas mixtures. The low yields previously reported appear to be the outcome of oxidation of the organic compounds during hydrolytic workup by nitrite and nitrate produced in the reactions. The yield of amino acids is greatly increased when oxidation inhibitors, such as ferrous iron, are added prior to hydrolysis. Organic synthesis from neutral atmospheres may have depended on the oceanic availability of oxidation inhibitors as well as on the nature of the primitive atmosphere itself. The results reported here suggest that endogenous synthesis from neutral atmospheres may be more important than previously thought. Stanley L. Miller died May 20, 2007.  相似文献   

14.
It is generally thought that the terrestrial atmosphere at the time of the origin of life was CO2-rich and that organic compounds such as amino acids would not have been efficiently formed abiotically under such conditions. It has been pointed out, however, that the previously reported low yields of amino acids may have been partially due to oxidation by nitrite/nitrate during acid hydrolysis. Specifically, the yield of amino acids was found to have increased significantly (by a factor of several hundred) after acid hydrolysis with ascorbic acid as an oxidation inhibitor. However, it has not been shown that CO2 was the carbon source for the formation of the amino acids detected after acid hydrolysis with ascorbic acid. We therefore reinvestigated the prebiotic synthesis of amino acids in a CO2-rich atmosphere using an isotope labeling experiment. Herein, we report that ascorbic acid does not behave as an appropriate oxidation inhibitor, because it contributes amino acid contaminants as a consequence of its reactions with the nitrogen containing species and formic acid produced during the spark discharge experiment. Thus, amino acids are not efficiently formed from a CO2-rich atmosphere under the conditions studied.  相似文献   

15.
Prebiotic electric discharge and ultraviolet light experiments are usually reported in terms of carbon yields and involve a large input of energy to maximize yields. Experiments using lower energy inputs are more realistic prebiotic models and give energy yields which can be used to estimate the relative importance of the different energy sources on the primitive earth. Simulated prebiotic atmospheres containing either CH4, CO or CO2 with N2, H2O and variable amounts of H2 were subjected to the spark from a high frequency Tesla coil. The energy yields for the synthesis of HCN and H2CO were estimated. CH4 mixtures give the highest yields of HCN while H2CO is most efficiently produced with the CO mixtures. These results are a model for atmospheric corona discharges, which are more abundant than lightning and different in character. Preliminary experiments using artificial lightning are also reported. The energy yields from these experiments combined with the corona discharge available on the earth, allows a yearly production rate to be estimated. These are compared with other experiments and model calculations. From these production rates of HCN (e.g. 100 nmoles cm−2 yr−1) and the experimental hydrolysis rates, the steady state concentration in the primitive ocean can be calculated (e.g., 4 × 10−6 M at pH 8 and 0°). A steady state amino acid concentration of 3 × 10−4 M is estimated from the HCN production rate and the rate of decomposition of the amino acids by passage through the submarine vents.  相似文献   

16.
Summary A suite of sixteen monocarboxylic acids having carbon numbers 2 to 7, formed by the Miller-Urey spark discharge process, were identified and quantified by gas chromatography and mass fragmentography using a deuterium spiking technique. The molar concentration and isomeric distribution of these laboratory synthesized monocarboxylic acids are compared to those previously reported for the Murchison meteorite. They show similar trends, namely, decreasing molar concentration with increasing molecular weight, and, the ratio of normal/branched isomers tend toward smaller with increasing carbon numbers.  相似文献   

17.
Mineral components of the Murchison meteorite were investigated in terms of potential catalytic effects on synthetic and hydrolytic reactions related to ribonucleic acid. We found that the mineral surfaces catalyzed condensation reactions of formamide to form carboxylic acids, amino acids, nucleobases and sugar precursors. These results suggest that formamide condensation reactions in the parent bodies of carbonaceous meteorites could give rise to multiple organic compounds thought to be required for the emergence of life. Previous studies have demonstrated similar catalytic effects for mineral assemblies likely to have been present in the early Earth environment. The minerals had little or no effect in promoting hydrolysis of RNA (24mer of polyadenylic acid) at 80°C over a pH range from 4.2 to 9.3. RNA was most stable in the neutral pH range, with a half-life ~5 h, but at higher and lower pH ranges the half-life decreased to ~1 h. These results suggest that if RNA was somehow incorporated into a primitive form of RNA-based thermophilic life, either it must be protected from random hydrolytic events, or the rate of synthesis must exceed the rate of hydrolysis.  相似文献   

18.
In 1959, Miller and Urey (Science 130, 245) published their classic compilation of energy sources for indigenous prebiotic organic synthesis on the early Earth. Much contemporary origins of life research continues to employ their original estimates for terrestrial energy dissipation by lightning and coronal discharges, 2 × 1019 J yr–1 and 6 × 1019 J yr–1, respectively. However, more recent work in terrestrial lightning and point discharge research suggests that these values are overestimates by factors of about 20 and 120, respectively. Calculated concentrations of amino acids (or other prebiotic organic products) in the early terrestrial oceans due to electrical discharge sources may therefore have been equally overestimated. A review of efficiencies for those experiments that provide good analogues to naturally-occurring lightning and coronal discharges suggests that lightning energy yields for organic synthesis (nmole J–1) are about one order of magnitude higher than those for coronal discharge. Therefore organic production by lightning may be expected to have dominated that due to coronae on early Earth. Limited data available for production of nitric oxide in clouds suggests that coronal emission within clouds, a source of energy heretofore too uncertain to be included in the total coronal energy inventory, is insufficient to change this conclusion. Our recommended valves for lightning and coronal discharge dissipation rates on the early Earth are, respectively, 1 × 1018 J yr–1 and 5 × 1017 J yr–1.  相似文献   

19.
The reaction of guanidine hydrochloride with cyanoacetaldehyde gives high yields (40–85%) of 2,4-diaminopyrimidine under the concentrated conditions of a drying lagoon model of prebiotic synthesis, in contrast to the low yields previously obtained under more dilute conditions. The prebiotic source of cyanoacetaldehyde, cyanoacetylene, is produced from electric discharges under reducing conditions. The effect of pH and concentration of guanidine hydrochloride on the rate of synthesis and yield of diaminopyrimidine were investigated, as well as the hydrolysis of diaminopyrimidine to cytosine, isocytosine, and uracil. Thiourea also reacts with cyanoacetaldehyde to give 2-thiocytosine, but the pyrimidine yields are much lower than with guanidine hydrochloride or urea. Thiocytosine hydrolyzes to thiouracil and cytosine and then to uracil. This synthesis would have been a significant prebiotic source of 2-thiopyrimidines and 5-substituted derivatives of thiouracil, many of which occur in tRNA. The applicability of these results to the drying lagoon model of prebiotic synthesis was tested by dry-down experiments where dilute solutions of cyanoacetaldehyde, guanidine hydrochloride, and 0.5m NaCl were evaporated over varying periods of time. The yields of diaminopyrimidine varied from 1 to 7%. These results show that drying lagoons and beaches may have been major sites of prebiotic syntheses.  相似文献   

20.
Keeping in mind the importance of amphiphilic lipids for the formation of semipermeable membranes, a review summary of the sources of appropriate precursors, and chemical reactions for the abiotic synthesis of lipids is presented here within the framework of the theory of chemical evolution. It covers the presence in different cosmic environments of precursors for the formation of the biochemical molecules necessary for the emergence of life on Earth. It starts (1) with a short introduction. Then the following matters are briefly reviewed: (2) The circumstellar and interstellar molecules, some of which, could generate straight chain fatty acids through C9. (3) The possible reactions of hydrogenation and hydrolysis of cyanopolyynes which in the presence first of hydrogen and then liquid water could lead to the formation of aliphatic acids. (4) The composition of comets, where the preliminary analysis by mass spectrometry indicate straight chain hydrocarbons through only C5. (5) The organic compounds in carbonaceous chondrites where aliphatic acids through C12 have been identified, although the branched chain isomers are abundant. (6) The synthesis of some biochemical compounds, such as amino acids present in carbonaceous chondrites, which were probably formed by condensation of presolar precursors, aldehydes and ketones, with HCN in the presence of ammonia and liquid water in the meteorite parent body. The isotopic evidence seems to support this interpretation. (7) The formation of the Earth-Moon system by the catastrophic impact of a Mars-size body with the proto-Earth. (8) The subsequent capture of cometary water, organic and inorganic compounds, which must have led to a very reactive primitive Earth's atmospheric environment. The cometary iron-nickel grains could have catalyzed the formation of fatty acids by Fischer-Tropsch reactions. (9) The laboratory synthesis of straight chain fatty acids from C5 through C20 by Fischer-Tropsch processes. The amounts are usually in excess of the yields of aliphatic hydrocarbons. The chemical synthesis of glycerophospholipids including phosphatidylcholine. (10) The formation of liposomes, primarily, from phosphatidylcholine and the encapsulation within them of biopolymers. (11) Speculations on protocellular models of increasing complexity based on liposomes enclosing catalytic biomolecules. (12) Finally, some of the important problems remaining to be solved concerning the experimental approach to the study of the origin of life are briefly considered. It is hoped that in the next century, significant advances will be made in our understanding of the origin of life on Earth.  相似文献   

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