Fate of prebiotic adenine

Equilibrium adsorption isotherm data for the purine base adenine has been obtained on several prebiotically relevant minerals by frontal analysis using water as a mobile phase. Adenine is far displaced toward adsorption on pyrite (FeS2), quartz (SiO2), and pyrrhotite (FeS), but somewhat less for magnetite (Fe3O4) and forsterite (Mg2SiO4). The prebiotic prevalence of these minerals would have allowed them to act as a sink for adenine; removal from the aqueous phase would confer protection from hydrolysis as well, establishing a nonequilibrium thermodynamic framework for increased adenine synthesis. Our results provide evidence that adsorption phenomena may have been critical for the primordial genetic architecture.     

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.     

Interaction of tryptophan and phenylalanine with metal ferrocyanides and its relevance in chemical evolution

The interaction of two naturally occurring aromatic alpha-amino acids, namely, tryptophan and phenylalanine, with zinc, nickel, cobalt, and copper ferrocyanides has been studied. Both amino acids showed a high adsorption affinity toward metal ferrocyanides at neutral pH (7.0). Adsorption trends followed the Langmuir adsorption isotherm. Values of the Langmuir constants K(L) and X(m) suggest tryptophan is a better adsorbate than phenylalanine. Zinc ferrocyanide showed the highest adsorption, while the minimum adsorption was found in the case of copper ferrocyanide. Infrared spectral studies of adsorbate, adsorbent, and adsorption adducts indicate that adsorption occurs because of the interaction of adsorbate molecules with outer divalent metal ions present in the lattice of metal ferrocyanides. The present investigation supports the hypothesis that metal ferrocyanides might have concentrated the biomonomers on their surface in primeval seas during the course of chemical evolution.     

Adsorption water-related potential chemical and biological processes in the upper martian surface

Mars Odyssey has given strong evidence for the existence of water in the upper martian surface at equatorial latitudes. The water content, which corresponds to the hydrogen in the soil, can regionally reach values up to about 15%. This water is mainly in the form of structurally and partially irreversibly bound "crystal" water, and of reversibly bound and partially unfrozen adsorption water. This adsorption water, which has "liquid-like" properties as a two dimensional fluid or film, can trigger-in the presence of ultraviolet light and in concentrations similar to what has been measured on Mars-photocatalytic processes that are important for martian surface chemistry. The consequences of the diurnally variable presence of adsorption water on the chemistry and hypothetical biological processes at and in the upper martian surface at equatorial and mid-latitudes are discussed in terms of water-related environmental aspects for chemical and hypothetical life processes on Mars.     

Formation of nucleobases from formamide in the presence of iron oxides: implication in chemical evolution and origin of life

Simple compounds like HCN, which have one C and one N, are proposed as the probable precursors for biomonomers. Formamide, a hydrolysis product of HCN, is known as the precursor of various biologically important compounds, for example, nucleobases (purines and pyrimidines). In this paper, we report our results on the synthesis of nucleobases, adenine, cytosine, purine, 9-(hydroxyacetyl) purine, and 4(3H)-pyrimidinone from formamide, using iron oxide (hematite) and oxide hydroxides (goethite and akaganeite) as a catalyst. Goethite and hematite produced purine in higher yield. The products formed were characterized by high-performance liquid chromatography and electrospray ionization mass spectrometry techniques. Results of our study reveal that iron oxides might have worked as efficient prebiotic catalysts.     

A regenerable carbon dioxide removal and oxygen recovery system for the Japanese Experiment Module

The Japanese Space Station Program is now under Phase B study by the National Space Development Agency of Japan in participation with the U.S. Space Station Program. A Japanese Space Station participation will be a dedicated pressurized module to be attached to the U.S. Space Station, and is called Japanese Experiment Module (JEM). Astronaut scientists will conduct various experimental operations there. Thus an environment control and life support system is required. Regenerable carbon dioxide removal and collection technique as well as oxygen recovery technique has been studied and investigated for several years. A regenerable carbon dioxide removal subsystem using steam desorbed solid amine and an oxygen recovery subsystem using Sabatier methane cracking have a good possibility for the application to the Japanese Experiment Module. Basic performance characteristics of the carbon dioxide removal and oxygen recovery subsystem are presented according to the results of a fundamental performance test program. The trace contaminant removal process is also investigated and discussed. The solvent recovery plant for the regeneration of various industrial solvents, such as hydrocarbons, alcohols and so on, utilizes the multi-bed solvent adsorption and steam desorption process, which is very similar to the carbon dioxide removal subsystem. Therefore, to develop essential components including adsorption tank (bed), condenser. process controller and energy saving system, the technology obtained from the experience to construct solvent recovery plant can be easily and effectively applicable to the carbon dioxide removal subsystem. The energy saving efficiency is evaluated for blower power reduction, steam reduction and waste heat utilization technique. According to the above background, the entire environment control and life support system for the Japanese Experiment Module including the carbon dioxide removal and oxygen recovery subsystem is evaluated and proposed.     

溶剂对石英/酚醛复合材料浸润过程的影响

通过研究不同溶荆对于石英／酚醛复合材料溶液浸润过程的影响,得出酚醛树脂及溶荆在石英表面的竞争性吸附机理。漫反射红外光谱研究表明,强极性溶剂由于能够与石英表面Si-OH形成氢键,从而与酚醛树脂在石英表面形成竞争性吸附;粘度和表面张力测量证实强极性溶剂被优先吸附;热失重分析表明,不同溶剂与酚醛树脂的竞争性吸附导致树脂在石英表面平衡吸附量存在差异。     

陶瓷基分子吸附器的航天器污染控制性能试验研究

为验证陶瓷基分子吸附器利用多孔材料的吸附性能降低航天器一定区域内污染水平的能力,试验研究真空环境中13X分子筛材料的分子污染物吸/脱附特性,以及以13X分子筛为吸附剂的陶瓷基分子吸附器对航天器用电缆放气产物的吸附性能。试验结果表明:13X分子筛可以有效捕获污染物分子,陶瓷基分子吸附器的吸附能力在3.1×10-2～3.4×10-2 g/cm2之间。陶瓷基分子吸附器可以应用于航天器热真空试验和在轨运行时的污染控制,有利于延长航天器寿命、提高航天器可靠性。     

Simulation of hydrogen adsorption in carbon nanotube arrays

The hydrogen adsorption in carbon nanotubes arrays was studied through molecular dynamics simulation. The interactions are described by the Lennard–Jones potential. The relative mass content and density of hydrogen are obtained as functions of the pressure, temperature and the distance between the tubes in the array. The formation of a second adsorption layer at low temperatures is detected. The cluster geometry optimal for adsorption is found.     

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.     

ZnO纳米棒阵列/QCM超疏水空间污染气敏传感器性能研究

空间环境污染监测中,石英晶体微天平（QCM）传感器可通过增加比表面积增强对有机污染分子的吸附能力,通过表面超疏水化减小水分子的影响,从而提高传感器的探测精度。文章采用水热法在QCM表面制备 ZnO纳米棒阵列膜,并对其形貌和物化性能进行实验测试。研究结果表明:ZnO纳米棒的顶端呈六边形,属于六方纤锌矿结构;ZnO纳米棒沿(002)晶面择优生长,具有较低的表面自由能;纳米棒之间存在空隙,表面接触角可达150°,表现出超疏水性能;ZnO纳米棒阵列增加了有机分子的吸附位点,使石英晶振吸附有机分子的能力更强;同时,ZnO纳米棒阵列具有一定的光催化性能,140 min内光催化降解罗丹明B的效率约为35.5%。以上研究工作可为空间环境有机分子污染监测提供技术参考。     

Analysis of volatile lunar compounds: The study of gas retention time on Carbosieve SIII adsorbent with respect to temperature

This work presents the study of the characteristic retention times on Carbosieve SIII adsorbent for several permanent gases CO₂, CO, CH₄, N₂ with respect to the temperature of cooling of adsorption accumulators. To perform this work, a laboratory model of a gas chromatograph that included all key components of a standard instrument has been designed.     

Can enantiomorphic crystals like quartz play a role in the origin of homochirality on earth?

This communication reviews the possible actions of enantiomorphic crystals on the surface of Earth as sources of homochirality of organic compounds. The discovery of asymmetric adsorption and asymmetric catalysis involving optically active quartz crystals has led some authors to conclude that this source of asymmetry played an important role as a source of homochirality in nature, a concept that later proved erroneous. Moreover, data regarding the preponderance in nature of l-quartz crystals have been used to confirm calculations of the parity violation energy difference (PVED) for l-quartz and, hence, to explain the prevalence of L-amino acids and D-sugars in living matter. As discussed here, quartz and other enantiomorphs such as sodium chlorate can produce chiral intermediates active in autocatalytical processes. Our most recent compilation of the literature, however, reveals that the distribution of d- and l-quartz crystals at the surface of the Earth when all possible locations are included is quite random. Although quartz can serve as an effective asymmetric inductor in autocatalytic processes, it cannot be the source of homochirality of living matter because of the random occurrence of the two types of enantiomorphs. The calculations of PVED values for quartz therefore lack a sound physical basis.     

沸石分子筛对航天器分子污染物的吸附性能研究

针对空间环境中有机污染物沉积在航天器敏感部件上造成相关功能失效问题,提出一种利用沸石分子筛多孔结构在轨清除有机污染物的新方法。研究了真空环境中,Naβ、NaY、13X三种分子筛对某型号电缆真空放气产物的吸附能力,结果表明13X的吸附能力优于其它两种分子筛,饱和吸收率为14.03%。将其作为分子吸附器的吸附材料应用到航天器易污染的部位,将会有效控制航天器在轨运行的污染水平,提高可靠性。     

硝基氧化剂废气污染治理

硝基氧化剂在使用过程中会产生大量的氮氧化物废气。对于氮氧化物的污染治理技术目前主要有化学吸收法，液膜法，催化脱除法，高能辐射法，冷冻法和吸附法等。这些方法各有其特点及合适的应用场合，在处理时要综合考虑废气的来源，组成，强度及费用，效果等各方面的因素，并在此 选择最佳处理方法。     

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。     

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.     

航天服材料的静电吸附效应地面试验研究

航天员在轨出舱作业时，其穿戴的航天服面临空间尘粒污染的静电吸附增强效应问题，空间尘粒污染会对航天员的健康及仪器设备的安全稳定运行造成威胁。文章分析了空间站–航天服静电起电模型，研究了污染物粒子带电机理及带电尘粒在电场作用下的静电吸附过程；在此基础上搭建空间站–航天服电场的静电吸附效应地面模拟装置，并开展了4种航天服表面典型材料对空间中尘埃粒子的静电吸附效应试验验证。通过对试验结果的分析，提出后续应在航天员出舱活动中设计静电消除装置、处理航天服主体材料表面保持航天服洁净等建议。     

总装材料对氦气吸附性能的试验研究

文章对卫星总装中所使用的部分吸附性材料进行了氦气吸附性能试验研究。通过试验及分析证明了所采用的吸附性材料对氦气的吸附很小,在采用累积法进行卫星检漏时,吸附性材料对检漏结果的影响可以忽略。     

Dynamics of debye-scale nonstationary plasma structures in the region of auroral field-aligned currents

We consider the formation of small-scale nonstationary plasma structures in the region of relatively strong field-aligned electric currents. The formation of these structures has been shown to be associated with the density instability developed when the current velocity exceeds a critical value. The conditions for the development of this instability can be most favorable in the region of low-density plasma. Numerical calculations have been performed for the initial nonlinear stage of the structure development. The main parameters of the structure, i.e., the times of its formation and destruction, spatial scales, and electric field, have been estimated. The features of the structures are consistent with the existing data from space experiments in the region of auroral field-aligned currents of the Earth.