Pre-cometary ice composition from hot core chemistry

Pre-cometary ice located around star-forming regions contains molecules that are pre-biotic compounds or pre-biotic precursors. Molecular line surveys of hot cores provide information on the composition of the ice since it sublimates near these sites. We have combined a hydrostatic hot core model with a complex network of chemical reactions to calculate the time-dependent abundances of molecules, ions, and radicals. The model considers the interaction between the ice and gas phase. It is applied to the Orion hot core where high-mass star formation occurs, and to the solar-mass binary protostar system IRAS 16293-2422. Our calculations show that at the end of the hot core phase both star-forming sites produce the same prebiotic CN-bearing molecules. However, in the Orion hot core these molecules are formed in larger abundances. A comparison of the calculated values with the abundances derived from the observed line data requires a chemically unprocessed molecular cloud as the initial state of hot core evolution. Thus, it appears that these objects are formed at a much younger cloud stage than previously thought. This implies that the ice phase of the young clouds does not contain CN-bearing molecules in large abundances before the hot core has been formed. The pre-biotic molecules synthesized in hot cores cause a chemical enrichment in the gas phase and in the pre-cometary ice. This enrichment is thought to be an important extraterrestrial aspect of the formation of life on Earth and elsewhere.     

Amino acids from ion-irradiated nitrile-containing ices

Solid CH(3)CN and solid H(2)O + CH(3)CN were ion irradiated near 10 K to initiate chemical reactions thought to occur in extraterrestrial ices. The infrared spectra of these samples after irradiation revealed the synthesis of new molecules. After the irradiated ices were warmed to remove volatiles, the resulting residual material was extracted and analyzed. Both unhydrolyzed and acid-hydrolyzed residues were examined by both liquid and gas chromatographic-mass spectral methods and found to contain a rich mixture of products. The unhydrolyzed samples showed HCN, NH(3), acetaldehyde (formed by reaction with background and atmospheric H(2)O), alkyamines, and numerous other compounds, but no amino acids. However, reaction products in hydrolyzed residues contained a suite of amino acids that included some found in carbonaceous chondrite meteorites. Equal amounts of D- and L-enantiomers were found for each chiral amino acid detected. Extensive use was made of (13)C-labeled CH(3)CN to confirm amino acid identifications and discriminate against possible terrestrial contaminants. The results reported here show that ices exposed to cosmic rays can yield products that, after hydrolysis, form a set of primary amino acids equal in richness to those made by other methods, such as photochemistry.     

Stability of amino acids and their oligomerization under high-pressure conditions: implications for prebiotic chemistry

The polymerization of amino acids leading to the formation of peptides and proteins is a significant problem for the origin of life. This problem stems from the instability of amino acids and the difficulty of their oligomerization in aqueous environments, such as seafloor hydrothermal systems. We investigated the stability of amino acids and their oligomerization reactions under high-temperature (180-400°C) and high-pressure (1.0-5.5?GPa) conditions, based on the hypothesis that the polymerization of amino acids occurred in marine sediments during diagenesis and metamorphism, at convergent margins on early Earth. Our results show that the amino acids glycine and alanine are stabilized by high pressure. Oligomers up to pentamers were formed, which has never been reported for alanine in the absence of a catalyst. The yields of peptides at a given temperature and reaction time were higher under higher-pressure conditions. Elemental, infrared, and isotopic analyses of the reaction products indicated that deamination is a key degradation process for amino acids and peptides under high-pressure conditions. A possible NH(3)-rich environment in marine sediments on early Earth may have further stabilized amino acids and peptides by inhibiting their deamination.     

Temporal changes in fluid chemistry and energy profiles in the vulcano island hydrothermal system

In June 2003, the geochemical composition of geothermal fluids was determined at 9 sites in the Vulcano hydrothermal system, including sediment seeps, geothermal wells, and submarine vents. Compositional data were combined with standard state reaction properties to determine the overall Gibbs free energy (DeltaG(r) ) for 120 potential lithotrophic and heterotrophic reactions. Lithotrophic reactions in the H-O-N-S-C-Fe system were considered, and exergonic reactions yielded up to 120 kJ per mole of electrons transferred. The potential for heterotrophy was characterized by energy yields from the complete oxidation of 6 carboxylic acids- formic, acetic, propanoic, lactic, pyruvic, and succinic-with the following redox pairs: O(2)/H(2)O, SO(4) (2)/H(2)S, NO(3) ()/NH(4) (+), S(0)/H(2)S, and Fe(3)O(4)/Fe(2+). Heterotrophic reactions yielded 6-111 kJ/mol e(). Energy yields from both lithotrophic and heterotrophic reactions were highly dependent on the terminal electron acceptor (TEA); reactions with O(2) yielded the most energy, followed by those with NO(3) (), Fe(III), SO(4) (2), and S(0). When only reactions with complete TEA reduction were included, the exergonic lithotrophic reactions followed a similar electron tower. Spatial variability in DeltaG(r) was significant for iron redox reactions, owing largely to the wide range in Fe(2+) and H(+) concentrations. Energy yields were compared to those obtained for samples collected in June 2001. The temporal variations in geochemical composition and energy yields observed in the Vulcano hydrothermal system between 2001 and 2003 were moderate. The largest differences in DeltaG(r) over the 2 years were from iron redox reactions, due to temporal changes in the Fe(2+) and H(+) concentrations. The observed variations in fluid composition across the Vulcano hydrothermal system have the potential to influence not only microbial diversity but also the metabolic strategies of the resident microbial communities.     

The PROCESS experiment: exposure of amino acids in the EXPOSE-E experiment on the international space station and in laboratory simulations

To understand the chemical behavior of organic molecules in the space environment, amino acids and a dipeptide in pure form and embedded in meteorite powder were exposed in the PROCESS experiment in the EXPOSE-E facility mounted on the European Technology Exposure Facility (EuTEF) platform on board the International Space Station (ISS). After exposure to space conditions for 18 months, the samples were returned to Earth and analyzed in the laboratory for reactions caused by solar UV and cosmic radiation. Chemical degradation and possible racemization and oligomerization, the main reactions caused by photochemistry in the vacuum ultraviolet domain (VUV, wavelength range 100-200?nm for photon energy from 6.2 to 12.4?eV) were examined in particular. The molecules were extracted and derivatized by silylation and analyzed by gas chromatograph coupled to a mass spectrometer (GC-MS) to quantify the rate of the degradation of the compounds. Laboratory exposure in several wavelength ranges from UV to VUV was carried out in parallel in the Cologne Deutsches Zentrum für Luft- und Raumfahrt (DLR) Center and Centre de biophysique moléculaire (CBM) laboratories. The results show that resistance to irradiation is a function of the chemical nature of the exposed molecules and the wavelengths of the UV light. The most altered compounds were the dipeptide, aspartic acid, and aminobutyric acid. The most resistant were alanine, valine, glycine, and aminoisobutyric acid. Our results also demonstrate the protective effect of meteorite powder, which reemphasizes the importance of exogenic contribution to the inventory of prebiotic organics on early Earth.     

真空羽流气相沉积污染初步研究

从固体表面对气体分子的作用着手分析气相羽流沉积污染的内在机理,阐述了固体表面对气体分子的物理吸附、化学吸附特性,给出吸附速率方程、脱附速率方程以及沉积速率方程,并通过区分贴壁吸附层、物理吸附层,重点研究了物理吸附层的脱附速率。选取有代表性的CO₂、NH₃、H₂O以及N₂H₄等气体,确定其物理吸附层脱附模型的参数,得到了与经验脱附率曲线较为一致的理论脱附率曲线。分析了单组元肼催化分解姿控发动机对太阳能帆板的气相沉积污染。     

LIFE: Life Investigation For Enceladus A Sample Return Mission Concept in Search for Evidence of Life

Abstract Life Investigation For Enceladus (LIFE) presents a low-cost sample return mission to Enceladus, a body with high astrobiological potential. There is ample evidence that liquid water exists under ice coverage in the form of active geysers in the "tiger stripes" area of the southern Enceladus hemisphere. This active plume consists of gas and ice particles and enables the sampling of fresh materials from the interior that may originate from a liquid water source. The particles consist mostly of water ice and are 1-10?μ in diameter. The plume composition shows H(2)O, CO(2), CH(4), NH(3), Ar, and evidence that more complex organic species might be present. Since life on Earth exists whenever liquid water, organics, and energy coexist, understanding the chemical components of the emanating ice particles could indicate whether life is potentially present on Enceladus. The icy worlds of the outer planets are testing grounds for some of the theories for the origin of life on Earth. The LIFE mission concept is envisioned in two parts: first, to orbit Saturn (in order to achieve lower sampling speeds, approaching 2 km/s, and thus enable a softer sample collection impact than Stardust, and to make possible multiple flybys of Enceladus); second, to sample Enceladus' plume, the E ring of Saturn, and the Titan upper atmosphere. With new findings from these samples, NASA could provide detailed chemical and isotopic and, potentially, biological compositional context of the plume. Since the duration of the Enceladus plume is unpredictable, it is imperative that these samples are captured at the earliest flight opportunity. If LIFE is launched before 2019, it could take advantage of a Jupiter gravity assist, which would thus reduce mission lifetimes and launch vehicle costs. The LIFE concept offers science returns comparable to those of a Flagship mission but at the measurably lower sample return costs of a Discovery-class mission. Key Words: Astrobiology-Habitability-Enceladus-Biosignatures. Astrobiology 12, 730-742.     

Prebiotic significance of extraterrestrial ice photochemistry: detection of hydantoin in organic residues

The delivery of extraterrestrial organic materials to primitive Earth from meteorites or micrometeorites has long been postulated to be one of the origins of the prebiotic molecules involved in the subsequent apparition of life. Here, we report on experiments in which vacuum UV photo-irradiation of interstellar/circumstellar ice analogues containing H(2)O, CH(3)OH, and NH(3) led to the production of several molecules of prebiotic interest. These were recovered at room temperature in the semi-refractory, water-soluble residues after evaporation of the ice. In particular, we detected small quantities of hydantoin (2,4-imidazolidinedione), a species suspected to play an important role in the formation of poly- and oligopeptides. In addition, hydantoin is known to form under extraterrestrial, abiotic conditions, since it has been detected, along with various other derivatives, in the soluble part of organic matter of primitive carbonaceous meteorites. This result, together with other related experiments reported recently, points to the potential importance of the photochemistry of interstellar "dirty" ices in the formation of organics in Solar System materials. Such molecules could then have been delivered to the surface of primitive Earth, as well as other telluric (exo-) planets, to help trigger first prebiotic reactions with the capacity to lead to some form of primitive biomolecular activity.     

Nucleobases and prebiotic molecules in organic residues produced from the ultraviolet photo-irradiation of pyrimidine in NH(3) and H(2)O+NH(3) ices

Although not yet identified in the interstellar medium (ISM), N-heterocycles including nucleobases-the information subunits of DNA and RNA-are present in carbonaceous chondrites, which indicates that molecules of biological interest can be formed in non-terrestrial environments via abiotic pathways. Recent laboratory experiments and ab initio calculations have already shown that the irradiation of pyrimidine in pure H(2)O ices leads to the formation of a suite of oxidized pyrimidine derivatives, including the nucleobase uracil. In the present work, NH(3):pyrimidine and H(2)O:NH(3):pyrimidine ice mixtures with different relative proportions were irradiated with UV photons under astrophysically relevant conditions. Liquid- and gas-chromatography analysis of the resulting organic residues has led to the detection of the nucleobases uracil and cytosine, as well as other species of prebiotic interest such as urea and small amino acids. The presence of these molecules in organic residues formed under abiotic conditions supports scenarios in which extraterrestrial organics that formed in space and were subsequently delivered to telluric planets via comets and meteorites could have contributed to the inventory of molecules that triggered the first biological reactions on their surfaces.     

HNIW中间体纯度测定方法

建立了测定六硝六氮杂异戊兹烷基(HNIW)两个主要中间体四乙酰基六氮杂异戊兹烷(TAIW)和四乙酰基二苄基六氮杂异戊兹烷(TADB IW)纯度的高效液相色谱法。采用二极管阵列紫外检测器检测,检测波长230 nm;中间体TAIW采用水作溶剂,DE-613反相色谱柱,甲醇流动相分离;中间体TADB IW采用冰醋酸溶解后水稀释,Symm etry-C18反相色谱柱,甲醇-水流动相分离。结果表明,两中间体分析方法标准偏差均小于1.0%,标准样品回收率均在100.0%左右,准确度和精密度较好,满足HNIW生产工艺和质量控制要求。     

Adsorption of amino acids (ALA, CYS, HIS, MET) on zeolites: fourier transform infrared and Raman spectroscopy investigations

Minerals adsorb more amino acids with charged R-groups than amino acids with uncharged R-groups. Thus, the peptides that form from the condensation of amino acids on the surface of minerals should be composed of amino acid residues that are more charged than uncharged. However, most of the amino acids (74%) in today's proteins have an uncharged R-group. One mechanism with which to solve this paradox is the use of organophilic minerals such as zeolites. Over the range of pH (pH 2.66-4.50) used in these experiments, the R-group of histidine (His) is positively charged and neutral for alanine (Ala), cysteine (Cys), and methionine (Met). In acidic hydrothermal environments, the pH could be even lower than those used in this study. For the pH range studied, the zeolites were negatively charged, and the overall charge of all amino acids was positive. The conditions used here approximate those of prebiotic Earth. The most important finding of this work is that the relative concentrations of each amino acid (X=His, Met, Cys) to alanine (X/Ala) are close to 1.00. This is an important result with regard to prebiotic chemistry because it could be a solution for the paradox stated above. Pore size did not affect the adsorption of Cys and Met on zeolites, and the Si/Al ratio did not affect the adsorption of Cys, His, and Met. ZSM-5 could be used for the purification of Cys from other amino acids (Student-Newman-Keuls test, p<0.05), and mordenite could be used for separation of amino acids from each other (Student-Newman-Keuls test, p<0.05). As shown by Fourier transform infrared (FT-IR) spectra, Ala interacts with zeolites through the [Formula: see text] group, and methionine-zeolite interactions involve the COO, [Formula: see text], and CH(3) groups. FT-IR spectra show that the interaction between the zeolites and His is weak. Cys showed higher adsorption on all zeolites; however, the hydrophobic Van der Waals interaction between zeolites and Cys is too weak to produce any structural changes in the Cys groups (amine, carboxylic, sulfhydryl, etc.); thus, the FT-IR and Raman spectra are the same as those of solid Cys.     

有烧蚀气体产物影响的化学非平衡粘性流数值计算研究

本文是针对高超声速绕流钝锥体再入飞行器，研究有烧蚀气体产物影响的化学非平衡反应粘性流ＮＳ方程数值计算方法。通过带有化学源项的ＮＳ方程对流动作数值模拟，总的连续方程由单个组元守恒方程组代替。对１３个化学组元，２６个气相化学反应，以及２个气相－固相化学反应，研究烧烛碳－空气的化学反应系统，并与纯空气化学反应系统的计算结果进行比较。利用二阶迎风ＴＶＤ差分格式和激波捕捉法，计算球锥体头部和身部化学非平衡粘性流场     

Radiant ignition of a combustible solid with gas-phase exothermicity

An asymptotic analysis is presented for the ignition of a solid fuel that gasifies endothermically then reacts exothermically in the gas phase through a one-step Arrhenius process. The endothermic gasification was analyzed in an earlier paper; the present paper employs those results in treating the gas-phase reaction. It is shown that depending on values of the chemical parameters, the gas-phase ignition reaction may begin either at the time that gasification begins or during the later stage of transport-controlled gasification. In the former case, results for the gas-phase ignition time are similar to those for condensed-phase ignitions. In the latter case, a mixing layer develops in the gas-phase and moves away from the surface, the exothermic reaction being negligible until thermal runaway occurs somewhere within the mixing layer. Both early-time and late-time ignitions within the mixing layer are analyzed by solving partial differential equations derived from perturbations for large activation energies and a small ratio of gas to solid thermal responsivity. The theory serves to indicate how ignition by gas-phase reactions may be distinguished experimentally from ignition by condensed-phase or heterogenous reactions.     

The formation of sulfate and elemental sulfur aerosols under varying laboratory conditions: implications for early earth

The presence of sulfur mass-independent fractionation (S-MIF) in sediments more than 2.45?×?10(9) years old is thought to be evidence for an early anoxic atmosphere. Photolysis of sulfur dioxide (SO(2)) by UV light with λ?相似文献   

The determination of ice composition with instruments on cometary landers

The determination of the composition of materials that make up comets is essential in trying to understand the origin of these primitive objects. The ices especially could be made in several different astrophysical settings including the solar nebula, protosatellite nebulae of the giant planets, and giant molecular clouds that predate the formation of the solar system. Each of these environments makes different ices with different composition. In order to understand the origin of comets, one needs to determine the composition of each of the ice phases. For example, it is of interest to know that comets contain carbon monoxide, CO, but it is much more important to know how much of it is a pure solid phase, is trapped in clathrate hydrates, or is adsorbed on amorphous water ice. In addition, knowledge of the isotopic composition of the constituents will help determine the process that formed the compounds. Finally, it is important to understand the bulk elemental composition of the nucleus. When these data are compared with solar abundances, they put strong constraints on the macro-scale processes that formed the comet. A differential scanning calorimeter (DSC) and an evolved gas analyzer (EGA) will make the necessary association between molecular constituents and their host phases. This combination of instruments takes a small (tens of mg) sample of the comet and slowly heats it in a sealed oven. As the temperature is raised, the DSC precisely measures the heat required, and delivers the gases to the EGA. Changes in the heat required to raise the temperature at a controlled rate are used to identify phase transitions, e.g., crystallization of amorphous ice or melting of hexagonal ice, and the EGA correlates the gases released with the phase transition. The EGA consists of two mass spectrometers run in tandem. The first mass spectrometer is a magnetic-sector ion-momentum analyzer (MAG), and the second is an electrostatic time-of-flight analyzer (TOF). The TOF acts as a detector for the MAG and serves to resolve ambiguities between fragments of similar mass such as CO and N2. Because most of the compounds of interest for the volatile ices are simple, a gas chromatograph is not needed and thus more integration time is available to determine isotopic ratios. A gamma-ray spectrometer (GRS) will determine the elemental abundances of the bulk cometary material by determining the flux of gamma rays produced from the interaction of the cometary material with cosmic ray produced neutrons. Because the gamma rays can penetrate a distance of several tens of centimeters a large volume of material is analyzed. The measured composition is, therefore, much more likely to be representative of the bulk comet than a very small sample that might have lost some of its volatiles. Making these measurements on a lander offers substantial advantages over trying to address similar objectives from an orbiter. For example, an orbiter instrument can determine the presence and isotopic composition of CO in the cometary coma, but only a lander can determine the phase(s) in which the CO is located and separately determine the isotopic composition of each reservoir of CO. The bulk composition of the nucleus might be constrained from separate orbiter analyses of dust and gas in the coma, but the result will be very model dependent, as the ratio of gas to dust in the comet will vary and will not necessarily be equal to the bulk value.     

An examination of the carbon isotope effects associated with amino acid biosynthesis

Stable carbon isotope ratios (delta(13)C) were determined for alanine, proline, phenylalanine, valine, leucine, isoleucine, aspartate (aspartic acid and asparagine), glutamate (glutamic acid and glutamine), lysine, serine, glycine, and threonine from metabolically diverse microorganisms. The microorganisms examined included fermenting bacteria, organotrophic, chemolithotrophic, phototrophic, methylotrophic, methanogenic, acetogenic, acetotrophic, and naturally occurring cryptoendolithic communities from the Dry Valleys of Antarctica. Here we demonstrated that reactions involved in amino acid biosynthesis can be used to distinguish amino acids formed by life from those formed by nonbiological processes. The unique patterns of delta(13)C imprinted by life on amino acids produced a biological bias. We also showed that, by applying discriminant function analysis to the delta(13)C value of a pool of amino acids formed by biological activity, it was possible to identify key aspects of intermediary carbon metabolism in the microbial world. In fact, microorganisms examined in this study could be placed within one of three metabolic groups: (1) heterotrophs that grow by oxidizing compounds containing three or more carbon-to-carbon bonds (fermenters and organotrophs), (2) autotrophs that grow by taking up carbon dioxide (chemolitotrophs and phototrophs), and (3) acetoclastic microbes that grow by assimilation of formaldehyde or acetate (methylotrophs, methanogens, acetogens, and acetotrophs). Furthermore, we demonstrated that cryptoendolithic communities from Antarctica grouped most closely with the autotrophs, which indicates that the dominant metabolic pathways in these communities are likely those utilized for CO(2 )fixation. We propose that this technique can be used to determine the dominant metabolic types in a community and reveal the overall flow of carbon in a complex ecosystem.     

Abiotic nitrogen fixation on terrestrial planets: reduction of NO to ammonia by FeS

Understanding the abiotic fixation of nitrogen and how such fixation can be a supply of prebiotic nitrogen is critical for understanding both the planetary evolution of, and the potential origin of life on, terrestrial planets. As nitrogen is a biochemically essential element, sources of biochemically accessible nitrogen, especially reduced nitrogen, are critical to prebiotic chemistry and the origin of life. Loss of atmospheric nitrogen can result in loss of the ability to sustain liquid water on a planetary surface, which would impact planetary habitability and hydrological processes that shape the surface. It is known that NO can be photochemically converted through a chain of reactions to form nitrate and nitrite, which can be subsequently reduced to ammonia. Here, we show that NO can also be directly reduced, by FeS, to ammonia. In addition to removing nitrogen from the atmosphere, this reaction is particularly important as a source of reduced nitrogen on an early terrestrial planet. By converting NO directly to ammonia in a single step, ammonia is formed with a higher product yield (~50%) than would be possible through the formation of nitrate/nitrite and subsequent conversion to ammonia. In conjunction with the reduction of NO, there is also a catalytic disproportionation at the mineral surface that converts NO to NO? and N?O. The NO? is then converted to ammonia, while the N?O is released back in the gas phase, which provides an abiotic source of nitrous oxide.     

Advanced technologies available for future solid propellant grains

Significant advances have been made during the last decade in several fields of solid propulsion: the advances have enabled new savings in the motor development phase and recurring costs, because they help limit the number of prototypes and tests.The purpose of the paper is to describe the improvements achieved by SNPE in solid grain technologies, making these technologies available for new developments in more efficient and reliable future SRMs: new energetic molecules, new solid propellants, new processes for grain manufacturing, quick response grain design tools associated with advanced models for grain performance predictions.Using its expertise in chemical synthesis, SNPE develops new molecules to fit new energetic material requirements.Tests based on new propellant formulations have produced good results in the propellant performance/safety behavior ratio. New processes have been developed simultaneously to reduce the manufacturing costs of the new propellants.In addition, the grain design has been optimized by using the latest generation of predictive theoretical tools supported by a large data bank of experimental parameters resulting from over 30 years' experience in solid propulsion:

• Computer-aided method for the preliminary grain design

• Advanced models for SRM operating and performance predictions