Effect of temperature on the adsorption of adenine

Equilibrium adsorption isotherms for the purine base adenine on the surface of graphite crystals have been obtained at 30, 40, 50, and 60 degrees C by frontal analysis using water as a mobile phase. These data were fitted to the Langmuir isotherm model and interpreted in terms of the well-characterized adsorbate monolayer structure. A van't Hoff plot was used to estimate the adsorption enthalpy, -delta H degree which we determined to be 20 kJ mol-1. The susceptibility of nucleic acid bases to aqueous-phase hydrolysis may have been a limiting feature for their inclusion in the primordial genetic architecture; our results suggest that the effects of temperature and the presence of inorganic solids must also be included when assessing the prebiotic availability of adenine.     

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.     

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.     

少烟复合改性双基推进剂燃烧性能研究

采用外加燃速催化剂的方式,通过淤浆浇注工艺制备了13个少烟CMDB推进剂配方的样品。研究了芳香酸铅-铜盐,芳香酸铅-铜盐-碳黑以及PbCO_3-过渡金属氧化物-碳黑对燃烧性能的影响。在8～10MPa的压强变化范围内,加入4％芳香酸铅-铜盐和芳香酸铅-铜盐-碳黑,能够普遍提高基础配方的燃速,尤其后者的催化效果最为明显。随着压强的增高,催化剂的作用逐渐减弱。用4％PEG代替部分NC和用HDI代替TDI,与NC为单一粘合剂的基础配方对比,在8～12MPa压强区间内,PbCO_3-过渡金属氧化物-碳黑三元催化剂明显地降低了CMDB推进剂的燃速。同时观察到当有TDI存在时,加入1.5％的邻氨基苯甲酸铅,药浆适用期明显缩短。     

Analysis of underivatized amino acids in geological samples using ion-pairing liquid chromatography and electrospray tandem mass spectrometry

The capability of detecting biomarkers, such as amino acids, in chemically complex field samples is essential to establishing the knowledge required to search for chemical signatures of life in future planetary explorations. However, due to the complexities of in situ investigations, it is important to establish a new analytical scheme that utilizes a minimal amount of sample preparation. This paper reports the feasibility of a novel and sensitive technique, which has been established to quantitate amino acids in terrestrial crust samples directly without derivatization using volatile ion-pairing liquid chromatography and tandem mass spectrometry equipped with an electrospray ionization source. Adequate separation of 20 underivatized amino acids was achieved on a C(18) capillary column within 26 min with nonafluoropentanoic acid (NFPA) as ion-pairing reagent. Each amino acid was identified from its retention time as well as from its characteristic parent-to-daughter ion transition. Using tandem mass spectrometry as a detection technique allows co-elution of some amino acids, as it is more specific than traditional spectrophotometric methods. In the present study, terrestrial samples collected from 3 different locations were analyzed for their water-extractable free amino acid contents, following the removal of metal and organic interferences via ion exchange procedures. This is the first time that amino acids in geological samples were directly determined quantitatively without complicated derivatization steps. Depending on the amino acid, the detection limits varied from 0.02 to 5.7 pmol with the use of a 1 microl sample injection loop.     

离子推力器羽流特性及其污染分析

介绍了与电推进系统有关的空间环境效应的形成原因及其对航天器性能、寿命等的影响。阐述了离子火箭发动机羽流内束离子、中性推进剂原子、交换电荷（CEX）离子和电子等主要成分与航天器相互作用的过程及机理。分析表明，离子推力器出口处的中性推进剂原子与高速束离子流碰撞后产生的CEX离子Xe^＋，以及带电离子轰击推力器组件特别是加速极所产生的金属CEX离子，是造成离子火箭发动机羽流污染的主要成分。在此基础上提出了若干防污染措施。     

Generation of experimental plasma parameter maps around the baffle aperture of a Kaufman (UK-25) ion thruster

The plasma produced by a Kaufman (UK-25) ion thruster possesses four distinct regions. The interaction of two of these regions, the coupling and discharge plasmas, is important for thruster design and efficiency, since it controls the production of the primary electrons responsible for most of the ionisation in the thruster. This paper details the measurement and analysis techniques used to obtain two-dimensional experimental plasma parameter maps across a plasma double layer in the baffle aperture region of this type of ion thruster. This plasma-interaction region was mapped experimentally using Langmuir probes.The Langmuir probe data were collected and analysed to produce maps of plasma potential, Maxwellian and primary electron energy and number density. Detailed static magnetic field measurements using Hall-effect probes were also obtained. A number of derived plasma parameter maps were then made possible, such as electron pressure. The application of the analysis techniques used here allowed ion thruster plasma property maps to be constructed of a spatial extent and resolution previously unseen. Two-dimensional maps of the spatial location of primary electrons are presented, as effected by applied magnetic field changes, along with the detection of regions showing depletion of primary electron energies.     

三元乙丙橡胶防热材料传热试验方法与温度数值计算

三元乙丙橡胶(EPDM)由于具有导热系数低的特点,在测量其背面温度时会产生比较大的测量误差.为减少测量误差,在热电偶测温端与被测表面之间增加具有高热导率的金属片作为集热片,对加与不加集热片、集热片选取不同材料(铜片和铝片),以及同厚度不同直径与同直径不同厚度分别进行了试验研究和瞬态传热数值计算,分析了集热片材料与尺寸对温度测量准确性及动态响应的影响.计算结果与试验结果吻合较好,表明铝片比铜片响应稍快,但强度没有铜片高,从而选用铜片;直径大与厚度小的铜片比直径小与厚度大的铜片响应快.     

Biochemical constraints in a protobiotic earth devoid of basic amino acids: the "BAA(-) world"

It has been hypothesized in this journal and elsewhere, based on surveys of published data from prebiotic synthesis experiments and carbonaceous meteorite analyses, that basic amino acids such as lysine and arginine were not abundant on prebiotic Earth. If the basic amino acids were incorporated only rarely into the first peptides formed in that environment, it is important to understand what protobiotic chemistry is possible in their absence. As an initial test of the hypothesis that basic amino acid negative [BAA(-)] proteins could have performed at least a subset of protobiotic chemistry, the current work reports on a survey of 13 archaeal and 13 bacterial genomes that has identified 61 modern gene sequences coding for known or putative proteins not containing arginine or lysine. Eleven of the sequences found code for proteins whose functions are well known and important in the biochemistry of modern microbial life: lysine biosynthesis protein LysW, arginine cluster proteins, copper ion binding proteins, bacterial flagellar proteins, and PE or PPE family proteins. These data indicate that the lack of basic amino acids does not prevent peptides or proteins from serving useful structural and biochemical functions. However, as would be predicted from fundamental physicochemical principles, we see no fossil evidence of prebiotic BAA(-) peptide sequences capable of interacting directly with nucleic acids.     

Elucidation of an iterative process of carbon-carbon bond formation of prebiotic significance

Laboratory experiments carried out under plausible prebiotic conditions (under conditions that might have occurred at primitive deep-sea hydrothermal vents) in water and involving constituents that occur in the vicinity of submarine hydrothermal vents (e.g., CO, H(2)S, NiS) have disclosed an iterative Ni-catalyzed pathway of C-C bond formation. This pathway leads from CO to various organic molecules that comprise, notably, thiols, alkylmono- and disulfides, carboxylic acids, and related thioesters containing up to four carbon atoms. Furthermore, similar experiments with organic compounds containing various functionalities, such as thiols, carboxylic acids, thioesters, and alcohols, gave clues to the mechanisms of this novel synthetic process in which reduced metal species, in particular Ni(0), appear to be the key catalysts. Moreover, the formation of aldehydes (and ketones) as labile intermediates via a hydroformylation-related process proved to be at the core of the chain elongation process. Since this process can potentially lead to organic compounds with any chain length, it could have played a significant role in the prebiotic formation of lipidic amphiphilic molecules such as fatty acids, potential precursors of membrane constituents.     

Formation of replicating saponite from a gel in the presence of oxalate: implications for the formation of clay minerals in carbonaceous chondrites and the origin of life

The potential role of clay minerals in the abiotic origin of life has been the subject of ongoing debate for the past several decades. At issue are the clay minerals found in a class of meteorites known as carbonaceous chondrites. These clay minerals are the product of aqueous alteration of anhydrous mineral phases, such as olivine and orthopyroxene, that are often present in the chondrules. Moreover, there is a strong correlation in the occurrence of clay minerals and the presence of polar organic molecules. It has been shown in laboratory experiments at low temperature and ambient pressure that polar organic molecules, such as the oxalate found in meteorites, can catalyze the crystallization of clay minerals. In this study, we show that oxalate is a robust catalyst in the crystallization of saponite, an Al- and Mg-rich, trioctahedral 2:1 layer silicate, from a silicate gel at 60°C and ambient pressure. High-resolution transmission electron microscopy analysis of the saponite treated with octadecylammonium (n(C)=18) cations revealed the presence of 2:1 layer structures that have variable interlayer charge. The crystallization of these differently charged 2:1 layer silicates most likely occurred independently. The fact that 2:1 layer silicates with variable charge formed in the same gel has implications for our understanding of the origin of life, as these 2:1 clay minerals most likely replicate by a mechanism of template-catalyzed polymerization and transmit the charge distribution from layer to layer. If polar organic molecules like oxalate can catalyze the formation of clay-mineral crystals, which in turn promote clay microenvironments and provide abundant adsorption sites for other organic molecules present in solution, the interaction among these adsorbed molecules could lead to the polymerization of more complex organic molecules like RNA from nucleotides on early Earth.     

Metallic and Oxidized Aluminum Debris Impacting the Trailing Edge of the Long Duration Exposure Facility (LDEF)

A total of 87 microcraters >30 m in diameter that were found in gold substrates exposed on the trailing edge of the non-spinning Long Duration Exposure Facility (LDEF) yielded analyzable projectile residues in their interiors. Using qualitative SEM-EDS analysis methods, some 60 of these craters were formed by natural cosmic-dust particles, while 27 residues (31%) were assigned to orbital debris (Hörz et al., 1993). The far majority of the orbital-debris impacts, 24 (89%) of the 27 events, contained only aluminum in their X-ray spectra. The present study evaluates these aluminum-rich residues in detail and employs a windowless X-ray detector, which permits for the analysis of low-Z elements and specifically of oxygen. This makes it possible to discriminate between oxidized (Al₂O₃) and metallic (Al) projectiles from dramatically different sources, the former produced during solid-fuel rocket firings, the latter resulting from explosively or collisionally disrupted spacecraft.Of the 24 craters analyzed with the windowless detector, 13 (54%) contained Al₂O₃ and 11 (46%) yielded structurally disintegrated Al metal. The oxidized residues preferentially occur in the smaller craters, all <60 m in diameter. Corresponding particles on LDEF's trailing edge are <35 m in diameter. Some 70% of this particle population is composed of Al₂O₃. Although solid-fuel rocket exhaust products are typically <5 m in size, they tend to coagulate into crusts at the rocket nozzle to be shed occasionally as relatively large, aggregate particles. Structurally disintegrated, metallic fragments compose one-third of all particles <35 m, but they dominate all particles >35 m, and thus all craters >60 m. These findings clearly establish that solid-rocket exhaust particles, as well as explosively or collisionally produced debris, exist in low-inclination, high-eccentricity orbits in sufficient quantities that they must be accounted for in models describing the present and future orbital-debris population at typical Shuttle and Space Station altitudes.     

Hydrodynamics during melting of an electroconductive sample in microgravity conditions under contactless positioning by electromagnetic forces

MHD-flow during melting of a spherical metal sample under contactless positioning by alternating magnetic field produced by two circular turns with currents, is investigated. It is shown that when the currents supplying the turns are opposite in direction, electromagnetic forces, originating from the interaction of the Foucault currents with alternating magnetic field, induce two torus-like eddies in the interior of the molten metal drop.     

Did evolution select a nonrandom "alphabet" of amino acids?

The last universal common ancestor of contemporary biology (LUCA) used a precise set of 20 amino acids as a standard alphabet with which to build genetically encoded protein polymers. Considerable evidence indicates that some of these amino acids were present through nonbiological syntheses prior to the origin of life, while the rest evolved as inventions of early metabolism. However, the same evidence indicates that many alternatives were also available, which highlights the question: what factors led biological evolution on our planet to define its standard alphabet? One possibility is that natural selection favored a set of amino acids that exhibits clear, nonrandom properties-a set of especially useful building blocks. However, previous analysis that tested whether the standard alphabet comprises amino acids with unusually high variance in size, charge, and hydrophobicity (properties that govern what protein structures and functions can be constructed) failed to clearly distinguish evolution's choice from a sample of randomly chosen alternatives. Here, we demonstrate unambiguous support for a refined hypothesis: that an optimal set of amino acids would spread evenly across a broad range of values for each fundamental property. Specifically, we show that the standard set of 20 amino acids represents the possible spectra of size, charge, and hydrophobicity more broadly and more evenly than can be explained by chance alone.     

FeS/S/FeS(2) redox system and its oxidoreductase-like chemistry in the iron-sulfur world

The iron-sulfur world (ISW) theory is an intriguing prediction regarding the origin of life on early Earth. It hypothesizes that life arose as a geochemical process from inorganic starting materials on the surface of sulfide minerals in the vicinity of deep-sea hot springs. During the last two decades, many experimental studies have been carried out on this topic, and some interesting results have been achieved. Among them, however, the processes of carbon/nitrogen fixation and biomolecular assembly on the mineral surface have received an inordinate amount of attention. To the present, an abiotic model for the oxidation-reduction of intermediates participating in metabolic pathways has been ignored. We examined the oxidation-reduction effect of a prebiotic FeS/S/FeS(2) redox system on the interconversion between several pairs of α-hydroxy acids and α-keto acids (i.e., lactate/pyruvate, malate/oxaloacetate, and glycolate/glyoxylate). We found that, in the absence of FeS, elemental sulfur (S) oxidized α-hydroxy acids to form corresponding keto acids only at a temperature higher than its melting point (113°C); in the presence of FeS, such reactions occurred more efficiently through a coupled reaction mechanism, even at a temperature below the phase transition point of S. On the other hand, FeS was shown to have the capacity to reversibly reduce the keto acids. Such an oxidoreductase-like chemistry of the FeS/S/FeS(2) redox system suggests that it can determine the redox homeostasis of metabolic intermediates in the early evolutionary phase of life. The results provide a possible pathway for the development of primordial redox biochemistry in the iron-sulfur world. Key Words: Iron-sulfur world-FeS/S/FeS(2) redox system-Oxidoreductase-like chemistry. Astrobiology 11, 471-476.     

卫星导电铜箔接地性能退化机理研究

接地网的接地性能关系整星电磁兼容性的优劣。文章从接地网导电铜箔的搭接现状入手,分析铜箔本身和导电胶的电阻以及铜箔接地电阻退化的机理;通过温湿度加速试验验证指出,在导电铜箔接地性能退化中导电胶的性能退化起主导作用;通过工艺试验得出电焊可以显著改善铜箔接地性能,以满足型号任务需求。     

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.     

空气环境中镀银表面二次电子发射劣化机理

暴露于空气中的金属受环境影响，表面会产生吸附、沾污和氧化等表面改性作用，引起二次电子产额（secondary electron yield,SEY）变化。为探究银表面改性对SEY的影响，使用加热、有机清洗、离子清洗实现了多种银表面状态。实验结果显示，加热能够去除部分表面吸附和沾污，并使得SEY降低；离子清洗在去除表面吸附和沾污的同时还能够剥离表面氧化层，获得高度洁净的表面。离子清洗10/30分钟后SEY峰值由2.61降至1.73/1.70，说明剥离银表面的吸附、沾污和氧化层能使得SEY明显降低。为验证氧化对SEY的影响，使用磁控溅射制备氧化银薄膜。结果表明，氧化银SEY仅比银高0.1左右，且在斜入射下两者SEY差异更小，该结果证明银表面发生氧化不会使得SEY明显升高，并间接说明表面吸附和沾污是使得银表面SEY升高的主要因素。     

用Langmuir探针诊断MPT羽流

为了探索微波等离子推力器(MPT)羽流的特性,建立了一套Langmuir探针诊断系统并对MPT的羽流进行了诊断,得出了MPT喷管羽流的电子温度和电子数密度等重要特性参数。实验结果表明,所测参数反映了等离子体的特性。与理论计算结果基本相符,并且诊断手段简单易行,为MPT羽流诊断提供了一种实验手段。     

石墨渗铜喉衬材料的微观结构与抗热震性能

采用粗粒级高强石墨加压渗铜工艺，制备了石墨渗铜(CIG：copper-impregnated graphite)喉衬材料。对其微观结构与抗热震性能的关系进行了研究。结果表明，由于渗铜提高了原石墨的热导率及整体增韧的综合效果，使石墨渗铜材料比通用的5种石墨材料具有更好的抗热震性能，更好地适应了小型高性能战术导弹、航天飞行器高压强大流量SRM对喉衬材料的要求。