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.     

The reactions of nitrogen heterocycles with acrolein: scope and prebiotic significance

It has been suggested that life began with a self-replicating RNA molecule. However, after much research into the prebiotic synthesis of RNA, the difficulties encountered have lead some to hypothesize that RNA was preceded by a simpler molecule, one more easily synthesized prebiotically. Many of the proposed alternative molecules are based on acrolein, since it reacts readily with nucleophiles, such as the nucleobases, via Michael addition and is readily synthesized from formaldehyde and acetaldehyde. Reports regarding the reactions of nucleobases with concentrated acrolein solutions suggest that this is a plausible reaction mechanism, though there are also reports that the "incorrect" isomers are obtained. The scope and kinetics of the reaction of acrolein with various nitrogen heterocycles are reported here. Reactions of pyrimidines often give N(1) adducts as the major products. Reactions of purines often give N(9) adducts in good yield. The reactions are rapid under neutral to slightly alkaline conditions, and proceed at low temperatures and dilutions. The implications of these findings for the origin of life are discussed.     

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.     

Adenine synthesis in interstellar space: mechanisms of prebiotic pyrimidine-ring formation of monocyclic HCN-pentamers

The question whether the nucleobases can be synthesized in interstellar space is of fundamental significance in considerations of the origin of life. Adenine is formally the HCN pentamer, and experiments have demonstrated that adenine is formed under certain conditions by HCN pentamerization in gas, liquid, and condensed phases. Most mechanistic proposals invoke the intermediacy of the HCN tetramer AICN (4), and it is thought that adenine synthesis is completed by addition of the 5(th) HCN to 4 to form amidine 5 and subsequent pyrimidine cyclization. In this context, we have been studying the mechanism for prebiotic pyrimidine-ring formation of monocyclic HCN-pentamers with ab initio electronic structure theory. The calculations model gas phase chemistry, and the results primarily inform discussions of adenine synthesis in interstellar space. Purine formation requires tautomerization of 5 to the conjugated amidine 6 (via hydrogen-tunneling, thermally with H(+) -catalysis, or by photolysis) or to keteneimine 7 (by photolysis). It was found that 5-(N'-formamidinyl)-1H-imidazole-4-carbonitrile (6) can serve as a substrate for proton-catalyzed purine formation under photolytic conditions and N-(4-(iminomethylene)-1H-imidazol-5(4H)-ylidene)formamidine (7) can serve as a substrate for uncatalyzed purine formation under photolytic conditions. The absence of any sizeable activation barrier for the cyclization of 7 to the (Z)-imino form of 9H-adenine (Z)-2 is quite remarkable, and it is this feature that allows for the formation of the purine skeleton from 7 without any further activation.     

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.     

Nitrogen reduction under hydrothermal vent conditions: implications for the prebiotic synthesis of C-H-O-N compounds

Dinitrogen is reduced in dilute hydrogen sulfide (H2S) solutions to ammonium at 120 degrees C. Experiments with dissolved dinitrogen (partial pressure 50 bar) in a 12 x 10(-3) mol/L H2S(aq) solution yield approximately 10(-5) mol/L NH4+ within 2-7 days. These yields are consistent with the equilibrium NH4+ concentration for the N-S-H system under these conditions. The formation of ammonium is catalyzed by the presence of freshly precipitated iron monosulfide. These results indicate that dinitrogen can be reduced at moderate temperatures in hydrothermal vent systems. Abiotic nitrogen reduction could have taken place within primordial hydrothermal vents, supplying some ammonia for the synthesis of C-H-O-N compounds via abiotic processes. The yield of ammonia via dinitrogen reduction by hydrogen sulfide, however, is so low that it is doubtful this process could have produced enough ammonia to sustain prebiotic hydrothermal synthesis of C-H-O-N compounds in or around vent systems.     

The catalytic potential of cosmic dust: implications for prebiotic chemistry in the solar nebula and other protoplanetary systems

The synthesis of important prebiotic molecules is fundamentally reliant on basic starting ingredients: water, organic species [e.g., methane (CH(4))], and reduced nitrogen compounds [e.g., ammonia (NH(3)), methyl cyanide (CH(3)CN) etc.]. However, modern studies conclude that the primordial Earth's atmosphere was too rich in CO, CO(2), and water to permit efficient synthesis of such reduced molecules as envisioned by the classic Miller-Urey experiment. Other proposed sources of terrestrial nitrogen reduction, like those within submarine vent systems, also seem to be inadequate sources of chemically reduced C-H-O-N compounds. Here, we demonstrate that nebular dust analogs have impressive catalytic properties for synthesizing prebiotic molecules. Using a catalyst analogous to nebular iron silicate condensate, at temperatures ranging from 500K to 900K, we catalyzed both the Fischer-Tropsch conversion of CO and H(2) to methane and water, and the corresponding Haber-Bosch synthesis of ammonia from N(2) and H(2). Remarkably, when CO, N(2), and H(2) were allowed to react simultaneously, these syntheses also yielded nitrogen-containing organics such as methyl amine (CH(3)NH(2)), acetonitrile (CH(3)CN), and N-methyl methylene imine (H(3)CNCH(2)). A fundamental consequence of this work for astrobiology is the potential for a natural chemical pathway to produce complex chemical building blocks of life throughout our own Solar System and beyond.     

Aqueous corrosion of phosphide minerals from iron meteorites: a highly reactive source of prebiotic phosphorus on the surface of the early Earth

We present the results of an experimental study of aqueous corrosion of Fe-phosphide under conditions relevant to the early Earth. The results strongly suggest that iron meteorites were an important source of reactive phosphorus (P), a requirement for the formation of P-based life. We further demonstrate that iron meteorites were an abundant source of phosphide minerals early in Earth history. Phosphide corrosion was studied in five different solutions: deionized water, deionized water buffered with sodium bicarbonate, deionized water with dissolved magnesium and calcium chlorides, deionized water containing ethanol and acetic acid, and deionized water containing the chlorides, ethanol, and acetic acid. Experiments were performed in the presence of both air and pure Ar gas to evaluate the effect of atmospheric chemistry. Phosphide corrosion in deionized water results in a metastable mixture of mixed-valence, P-bearing ions including pyrophosphate and triphosphate, key components for metabolism in modern life. In a pH-buffered solution of NaHCO(3), the condensed and reduced species diphosphonate is an abundant corrosion product. Corrosion in ethanol- and acetic acid-containing solutions yields additional P-bearing organic molecules, including acetyl phosphonate and a cyclic triphosphorus molecule. Phosphonate is a major corrosion product of all experiments and is the only P-bearing molecule that persists in solutions with high concentrations of magnesium and calcium chlorides, which suggests that phosphonate may have been a primitive oceanic source of P. The stability and reactivity of phosphonate and hypophosphite in solution were investigated to elucidate reaction mechanisms and the role of mineral catalysts on P-solution chemistry. Phosphonate oxidation is rapid in the presence of Fe metal but negligible in the presence of magnetite and in the control sample. The rate of hypophosphite oxidation is independent of reaction substrate.     

Influence of ionic inorganic solutes on self-assembly and polymerization processes related to early forms of life: implications for a prebiotic aqueous medium

A commonly accepted view is that life began in a marine environment, which would imply the presence of inorganic ions such as Na+, Cl-, Mg2+, Ca2+, and Fe2+. We have investigated two processes relevant to the origin of life--membrane self-assembly and RNA polymerization--and established that both are adversely affected by ionic solute concentrations much lower than those of contemporary oceans. In particular, monocarboxylic acid vesicles, which are plausible models of primitive membrane systems, are completely disrupted by low concentrations of divalent cations, such as magnesium and calcium, and by high sodium chloride concentrations as well. Similarly, a nonenzymatic, nontemplated polymerization of activated RNA monomers in ice/eutectic phases (in a solution of low initial ionic strength) yields oligomers with > 80% of the original monomers incorporated, but polymerization in initially higher ionic strength aqueous solutions is markedly inhibited. These observations suggest that cellular life may not have begun in a marine environment because the abundance of ionic inorganic solutes would have significantly inhibited the chemical and physical processes that lead to self-assembly of more complex molecular systems.     

Rate measurements of the hydrolysis of complex organic macromolecules in cold aqueous solutions: implications for prebiotic chemistry on the early Earth and Titan

Organic macromolecules ("complex tholins") were synthesized from a 0.95 N(2)/0.05 CH(4) atmosphere in a high-voltage AC flow discharge reactor. When placed in liquid water, specific water soluble compounds in the macromolecules demonstrated Arrhenius type first order kinetics between 273 and 313 K and produced oxygenated organic species with activation energies in the range of approximately 60+/-10 kJ mol(-1). These reactions displayed half lives between 0.3 and 17 days at 273 K. Oxygen incorporation into such materials--a necessary step toward the formation of biological molecules--is therefore fast compared to processes that occur on geologic timescales, which include the freezing of impact melt pools and possible cryovolcanic sites on Saturn's organic-rich moon Titan.     

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.     

基于刚体转动四元数模型的航天器再定向方案

介绍了一种新的刚体转动的四元数模型。这些模型可以提高再定向控制的对边界条件的适应能力，在此基础上还介绍了这些模型的一些实际应用。     

Determination of parameters of attitude motion of a small communication satellite using the data of measurements of current of solar panels

A communication satellite (small spacecraft) injected into a geosynchronous orbit is considered. Flywheel engines are used to control the rotational spacecraft motion. The spacecraft after the emergency situation has passed into a state of uncontrolled rotation. In this case, no direct telemetric information about parameters of its rotational motion was accessible. As a result, the problem arose to determine the rotational satellite motion according to the available indirect information: current taken from the solar panels. Telemetric measurements of solar panel current obtained on the time interval of a few hours were simultaneously processed by the least squares method integrating the equations of rotational satellite motion. We present the results of processing 10 intervals of the measurement data allowing one to determine the real rotational spacecraft motion and to estimate the total angular momentum of flywheel engines.     

攻角变化对超音速进气道再起动特性的影响

以二维非定常可压缩流的N-S方程为控制方程,采用SST k-ω湍流模型对攻角变化引起的超音速进气道再起动过程进行了数值模拟,研究了攻角变化对超音速进气道再起动特性的影响.结果表明,当超音速进气道不起动时,可通过合理改变攻角实现进气道的再起动工作;超音速进气道的再起动攻角随攻角变化速率的增大近似呈线性增加;攻角变化速率较...     

多通道功率放大器中幅度和相位一致性影响分析

文章利用传输矩阵方法,建立了MPA分析模型,并通过引入幅度和相位随机性,结合各路放大器幅度和相位组合概率,对通道隔离度的影响进行了计算和分析。     

多自由度微振动环境时域波形复现的数值仿真

为满足航天器微振动环境模拟的需要,开展了多自由度微振动时域波形复现控制方法研究。首先,介绍了基于时域波形复现的多自由度微振动环境模拟控制理论方法。其次,针对六自由度微振动激励系统,应用MATLAB软件建立了基于实测传递函数矩阵的多输入多输出微振动激励仿真系统,针对微振动时域波形复现闭环控制过程进行了算法编程,并给出了仿真的闭环控制流程图。最后,通过算例对多自由度微振动时域波形复现进行了数值仿真,以给定的白噪声为输入,模拟对实际存在的系统非线性、测量误差等影响因素的控制效果。仿真结果验证了多自由度微振动时域波形复现控制方法的可行性及有效性,所得结论可以为研究多自由度微振动时域波形复现控制系统提供参考。     

Determination of an Estimation of Parameters of Motion of a Spacecraft on the Stage of Its Descent on the Basis of Integration of Inertial and Optoelectronic Navigation Systems

The problem of determining an estimation of current spacecraft motion parameters on the stage of its descent is solved on the basis of readings of an optoelectronic navigation system and additional information from the self-contained inertial navigation system at the most general assumptions on the nature of motion of the object and the statistical properties of the noise of the measuring devices.     

On solving the problems of optimization of trajectories of many-revolution orbit transfers of spacecraft

The problem of optimal control over many-revolution spacecraft orbit transfers between circular coplanar orbits of satellites is considered. The spacecraft flight is controlled by a thrust vector of a jet engine with restricted thrust (JERT). The mass expenditure is minimized at a limited time of flight. The optimal control problem is solved based on the maximum principle. The boundary value problem of the maximum principle is solved numerically using the shooting method. A modified computation scheme of the shooting method is suggested (multi-point shooting), as well as a method (correlated with the scheme) of choosing the initial approximation with the use of a solution to the optimization problem in the impulse formulation. The scheme and method allow one to construct many-revolution spacecraft orbit transfers.     

热变形对一种天线指向机构指向精度的影响分析

热变形对天线指向机构的指向精度具有重要影响,但利用传统的设计方法很难实现对指向精度的准确计算,尤其是热变形对指向精度影响的研究工作更是少见。为此建立了机构的三维实体热-结构耦合有限元分析模型,根据有限元分析结果并结合机构的运动链关系,构建了各关键运动副运动误差的计算方法;在此基础上实现了机构指向误差的计算,研究了运动副名义、最大以及最小配合间隙条件下,温度载荷对各关键运动副运动误差和指向精度的影响。研究结果表明,温度载荷对关键运动副的运动误差以及机构的指向精度具有重要影响,随着温度载荷偏离常温数值的增加,指向误差不断增大,名义配合间隙条件下的指向误差最大。     

国际空间大学董事会主席访问航天科技集团公司

10月14日,国际空间大学董事会主席拉姆·哈迪姆访问中国航天科技集团公司,就集团公司承办国际空间大学2007年暑期进修项目的筹备情况与集团公司人力资源部部长陈学钏、副部长白燕强交换了意见。陈学钏部长向哈迪姆通报了集团公司筹备这次活动的工作进展情况。据陈部长介绍,中国