Prebiotic oligodeoxynucleotide synthesis in a cyclic evaporating system at low temperatures.

Deoxynucleoside 5'-monophosphates were condensed by cyanamide or by l-ethyl-3-(3-dimethylaminopropyl) carbodiimide in the presence of ammonium chloride at 0 degree, 37 degrees or 60 degrees C through several cycles of evaporation to dryness with replenishment of all reactants at each cycle. We found that at 37 degrees or 60 degrees cyanamide gives distinctly more high molecular weight material than does carbodiimide. Indeed, the yield of condensed products for the cyanamide reaction (dimers and higher oligomers) was found to be between 60 percent and 80 percent. The molecular weight distribution of the product shifts to higher molecular weights as cycling continues at 37 degrees or 60 degrees for both condensing agents. The water soluble carbodiimide gives higher yields of low molecular weight product but much lower yields of the higher molecular weight products. At 0 degree yields of high molecular weight product were low for both condensing agents. Results of characterization of the products demonstrate the synthesis of oligodeoxynucleotides including tetramers, with 3'-5' phosphodiester linkages.     

Progress in demonstrating homochiral selection in prebiotic RNA synthesis

The dual properties of RNA as an enzyme catalyst (ribozyme) and its ability to store genetic information suggest that early life could have been based on RNA. We have synthesized RNA oligomers up to 50-mer chain lengths by Na⁺-montmorillonite catalyzed reactions of 5′-activated mononucleotides. For studying chiral selectivity, the reactions of racemic mixtures of D, L-ImpA and D, L-ImpU were carried out on Na⁺-montmorillonite. The dimer, trimer, tetramer and pentamer fractions (yields 43.3%, 14.5%, 5.8% and 3.0%, respectively) were investigated for homochiral selection. These products were collected via ion exchange HPLC, their terminal 5′-phosphate was cleaved by alkaline phosphatase and further analyzed by reverse phase HPLC. Twelve linear and three cyclic dimers were isolated and characterized. The homochirality of dimers was 63.5 ± 0.8%. Out of the sixteen trimers isolated, ten were homochiral with an overall homochirality of 74.2 ± 1.6%. The tetramers and pentamers were separated into 24 and 20 isomers, respectively. Their co-elution with those formed in the binary reactions of D-ImpA with D-ImpU on Na⁺-montmorillonite revealed 92.7 ± 2.0% and 97.2 ± 0.5% homochirality, respectively. These results suggest that Na⁺-montmorillonite not only catalyzes the prebiotic synthesis of RNA but it also facilitates homochiral selection. Work is in progress to determine chiral selectivity in the reaction mixtures of activated nucleotides of racemic A, U, G and C on Na⁺-montmorillonite.     

Prebiotic synthesis and reactions of nucleosides and nucleotides.

Diiminosuccinonitrile (DISN) has been investigated as a potential prebiotic phosphorylating agent. It is formed readily by the oxidation of diaminomaleonitrile (DAMN), a tetramer of HCN. DISN effects the cyclization of 3'-adenosine monophosphate to adenosine 2',3'-cyclic phosphace in up to 40% yield. The DISN-mediated phosphorylation of uridine to uridine mono-phosphate does not proceed efficiently in aqueous solution. The reaction of DISN and BrCN with uridine-5'-phosphate and uridine results in the formation of 2,2'-anhydronucleotides and 2,2'-anhydronucleosides respectively, and other reaction products resulting from an initial reaction at the 2'- and 3'-hydroxyl groups. The clay mineral catalysis of the cyclization of adenosine-3'-phosphate was investigated using homoionic montmorillonites.     

可体内降解的骨固定材料的制备研究

为制备强度和韧性都适中且可体内降解的骨固定材料,首先借助聚D,L丙交酯与聚己内酯的扩链反应获得一系列扩链反应聚合物;然后通过测定聚合物拉伸强度和降解性能随扩链剂和扩链反应条件的变化规律,来选择扩链剂和制定最佳制备工艺.利用按上述方法选定的扩链剂和制备工艺,最终制备出了拉伸强度为24.47MPa,延伸率为1091%,降解时间为6个月,且对人体无害的骨固定材料.      

Mechanism of radiation-induced strand break formation in DNA and polynucleotides.

The present state of our knowledge of the OH radical-induced strand break (sb) formation in presence and absence of oxygen in aqueous solution is reviewed for poly(U), poly(C), poly(A) and single- and double-stranded DNA as substrates. It was shown earlier that a single OH radical can induce a double-strand break in DNA. As a key step in the mechanism an interstrand radical transfer is postulated. The OH radical reaction is part of the indirect effect of gamma-irradiation. In addition recent results are presented concerning sb formation by the direct effect of high-energy irradiation using laser-induced photoionization for the formation of radical cations.     

硅溶胶在镁合金阳极氧化反应中的成膜作用

采用溶胶化学与电化学相结合的新型表面处理方法——将自制的硅溶胶添加到电解质溶液中进行阳极氧化.以AZ91D镁合金及镁锂合金为研究基材,研究体系分别为硅酸钠和氢氧化钠溶液,通过对不同溶胶添加量下的溶液电导率、反应击穿电压、氧化膜层厚度及微观形貌、膜层表面成分及XRD结果分析,来探讨溶胶粒子在成膜过程中的作用.结果表明:溶胶粒子的加入增大了阳极表面的电阻,使得反应的击穿电压升高,从而导致了膜层厚度增加;同时硅溶胶粒子参与了阳极氧化反应,其在高温高压的条件下与MgO生成了Mg₂SiO₄.      

Exposure of animals to artificial gravity conditions leads to the alteration of the glutamate release from rat cerebral hemispheres nerve terminals.

The biochemical basis underlying the effects of altered gravity on the process of nervous signal transmission is not clear. We have investigated the effect of hypergravity stress (created by centrifugation of rats at l0 g for 1 h) on the basal and stimulated release of L-[14C]glutamate (a chemical transmitter of excitatory signals) from isolated rat brain nerve terminals (synaptosomes). It has been shown that the hypergravity stress exerted a different influence on the Ca(2+)-dependent and the Ca(2+)-independent component of neurotransmitter release. The Ca(2+)-dependent L-[14C]glutamate release evoked by potassium chloride was equal to 14.4 +/- 0.7% of total synaptosomal label for control animals and 6.2 +/- 1.9% for animals, exposed to hypergravity (P < or = 0.05) and was more than twice decreased as a result of the hypergravity stress. We observed no statistically significant difference in the Ca(2+)-independent component of L-[14C]glutamate release. For control group and animals exposed to the hypergravity stress it was equal to 7.7 +/- 2.8% and 12.9 +/- 2.0%, respectively. We have also investigated the effect of the hypergravity stress on the activity of high-affinity Na(+)-dependent glutamate transporters. Km and Vmax of L-[14C]glutamate uptake have been determined. The maximal velocity of glutamate uptake was decreased as a result of hypergravity loading, but no difference in the Km values between control rats and hypergravity exposed animals was observed. These findings indicate that hypergravity stress alters neurotransmitter reuptake and exocytotic neurotransmitter release processes.     

Abiogenic synthesis of pyrimidine nucleotides in solid state by vacuum ultraviolet radiation.

The abiogenic synthesis of pyrimidine nucleotides in solid state has been investigated. Our experiment indicates that natural nucleotides are produced in thin films prepared from nucleoside and inorganic phosphate by irradiating with vacuum ultraviolet light (VUV, lambda=100-200 nm). We have investigated the influence of the type of nucleic acids base (thymidine, cytosine, uracil) and the structure of sugar moiety (ribose or deoxyribose) on the course and yield of reaction. We compared the action of vacuum ultraviolet light with action of gamma-radiation, heat and biology significant UV (254 nm) which have been investigated earlier. The occurrence of these reaction in open space is discussed.     

Transport of extraterrestrial biomolecules to the Earth: problem of thermal stability.

The idea of extraterrestrial delivery of organic matter to the early Earth is especially attractive at present and is strongly supported by the detection of a large variety of organic compounds, including amino acids and nucleobases, in carbonaceous chondrites. Whether these compounds can be delivered by other space bodies is unclear and depends primarily on capability of the biomolecules to survive high temperatures during atmospheric deceleration and impacts to the terrestrial surface. In the present study we estimated survivability of simple amino acids (alpha-aminoisobutyric acid, L-alanine, L-valine and L-leucine), purines (adenine and guanine) and pyrimidines (uracil and cytosine) under rapid heating to temperatures of 400 to 1000 degrees C under N2 or CO2 atmosphere. We have found that most of the compounds studied cannot survive the temperatures substantially higher than 700 degrees C; however at 500-600 degrees C, the recovery can be at a per cent level (or even 10%-level for adenine, uracil, alanine, and valine). Implications of the data for extraterrestrial delivery of the biomolecules are discussed.     

Polycyclic aromatic hydrocarbons: primitive pigment systems in the prebiotic environment.

Polycyclic aromatic hydrocarbons (PAH) in the form of polymerized derivatives represent over 90% of the organic material of carbonaceous chondrites. It now appears likely that there was substantial survival of the organic content of meteoritic and cometary infall during late accretion, so that PAH would presumably be major components of the organic inventory present on the prebiotic Earth. An important question relative to chemical evolution and energy transduction is the nature of pigments which could be available to make light energy available to the earliest cellular forms of life. PAH and their derivatives all absorb light in the near UV and blue wavelengths, and are candidates for primitive pigments. We have explored this possibility in a model system consisting of mixtures of pyrene, fluoranthene and pyrene derivatives with hexadecane, dispersed in dilute salt solutions. Upon illumination, photochemical oxidation of the hexadecane occurs, with long-chain amphiphiles such as 2-hexadecanone and 2-hexadecanol as products. Because the reaction proceeds under strictly anaerobic conditions, the source of oxygen is apparently water. We also observed acid pH shifts during illumination. Photochemical production of hydrogen ion is significant, in that chemiosmotic proton gradients across membranes are used by all contemporary cells as a source of energy for ATP synthesis and nutrient transport. To test whether the protons could be used to transduce light energy into a useful form, PAH derivatives were included in lipid bilayer membranes (liposomes). Upon illumination, protons (or acidic products) were produced and accumulated inside the vesicles, so that substantial pH gradients were established across the membranes, acid inside. We conclude that PAH dissolved in aliphatic hydrocarbons absorb light energy and use it to oxidize the hydrocarbon to long-chain amphiphilic molecules. The oxidation is accompanied by release of protons. If PAH derivatives are included in the bilayer membrane of lipid vesicles, protons accumulate within the membrane-bounded volumes to form proton gradients. This system provides a useful model of a primitive photochemical reaction in which light energy is transduced into potentially useable forms.     

Effect of condensation agents and minerals for oligopeptide formation under mild and hydrothermal conditions in related to chemical evolution of proteins

The role of condensation agents and minerals for oligopeptide formation was inspected to see whether minerals possess catalytic activity under mild and hydrothermal conditions. Under mild conditions, oligopeptide formation from negatively charged amino acids (Asp and Glu) using different minerals and the elongation of alanine oligopeptides ((Ala)₂–(Ala)₅) were attempted using apatite minerals. Oligo(Asp) up to 10 amino acid units from Asp were observed in the presence of 1-ethyl-3-(3-dimethylaminopropyl carbodiimide (EDC). Notable influence of minerals was not detected for the oligo(Asp) formation. Oligo(Asp) was gradually degraded by the further incubation in the presence of EDC in both the absence and presence of minerals. The formation of oligo(Glu) was less efficient in the presence of carbonyldiimidazole. The elongation from (Ala)₃, (Ala)₄, and (Ala)₅ and the formation of diketopiperazine from (Ala)₂ proceeded immediately in the presence of EDC in the meantime of the sample preparations. In addition, it was unexpected that the disappearance of the products and the reformation of the reactants occurred by the further incubation for 24 h; for instance, (Ala)₅ decreased but (Ala)₄ increased with increasing the reaction time in the reaction of (Ala)₄ with EDC. These facts suggest that the activation of the reactant amino acids or peptides immediately occurs. Under the simulated hydrothermal conditions, EDC did not enhance the formation of oligopeptides from Asp, Glu or Ala nor the spontaneous formation of (Ala)₅ from (Ala)₄.     

高含量卡托辛合成的理论与实验研究

2,2'-双（乙基二茂铁）丙烷（卡托辛）是一种综合性能优良的高效液体燃速催化剂,主要包含4种乙基取代位置不同、物理和化学性质均很相近的卡托辛同分异构体和不同取代基的双二茂铁丙烷,其中卡托辛同分异构体与其他双二茂铁丙烷很难分离。首先,采用密度泛函理论（DFT）方法模拟确定了4种同分异构体的结构,分别获得4种同分异构体的1H-NMR和13C-NMR理论谱图。其次,计算研究了合成过程中温度对产物中4种同分异构体含量的影响。最后,在理论合成条件的指导下,以高纯度乙基二茂铁和丙酮为原料、浓硫酸为催化剂,合成了卡托辛粗品。结果表明:利用惰性气体辅助蒸汽蒸馏法得到纯度大于99.0%的卡托辛同分异构体,收率高于94.0%,并通过核磁共振法确定了其结构。      

Analysis of GNSS clock prediction performance with different interrupt intervals and application to real-time kinematic precise point positioning

Continuous and timely real-time satellite orbit and clock products are mandatory for real-time precise point positioning (RT-PPP). Real-time high-precision satellite orbit and clock products should be predicted within a short time in case of communication delay or connection breakdown in practical applications. For prediction, historical data describing the characteristics of the real-time orbit and clock can be used as the basis for performing the prediction. When historical data are scarce, it is difficult for many existing models to perform precise predictions. In this paper, a linear regression model is used to predict clock products. Seven-day GeoForschungsZentrum (GFZ) final clock products sampled at 30 s are used to analyze the characteristics of GNSS clocks. It is shown that the linear regression model can be used as the prediction model for the satellite clock products. In addition, the accuracy of the clock prediction for different satellites are analyzed using historical data with different periods (such as 2 and 10 epochs). Experimental results show that the accuracy of the clock with the linear regression prediction model using historical data with 10 epochs is 1.0 ns within 900 s. This is higher accuracy than that achieved using historical data of 2 epochs. Finally, the performance analysis for real-time kinematic precise point positioning (PPP) is provided using GFZ final clock prediction results and state space representation (SSR) clock prediction results when communication delay or connection breakdown occur. Experimental results show that the positioning accuracy without prediction is better than that with prediction in general, whether using the final clock product or the SSR clock product. For the final clock product, the positioning accuracy in the north (N), east (E), and up (U) directions is better than 10.0 cm with all visible GNSS satellites with prediction. In comparison, the 3D positioning accuracy of N, E, and U directions with visible GNSS satellites whose prediction accuracy is better than 0.1 ns using historical data of 10 epochs is improved from 15.0 cm to 7.0 cm. For the SSR clock product, the positioning accuracy of N, E, and U directions is better than 12.0 cm with visible GNSS satellites with prediction. In comparison, the 3D positioning accuracy of N, E, and U directions with visible GNSS satellites whose prediction accuracy is better than 0.1 ns using historical data of 10 epochs is improved from 12.0 cm to 9.0 cm.     

Direct interaction between amino acids and nucleotides as a possible physicochemical basis for the origin of the genetic code.

A study of the association of homocodonic amino acids and selected heterocodonic amino acids with selected nucleotides in aqueous solution was undertaken to examine a possible physical basis for the origin of codon assignments. These interactions were studied using 1H nuclear magnetic resonance spectroscopy (NMR). Association constants for the various interactions were determined by fitting the changes in the chemical shifts of the anomeric and ring protons of the nucleoside moieties as a function of amino acid concentration to an isotherm which described the binding interaction. The strongest association of all homocodonic amino acids were with their respective anticodonic nucleotide sequences. The strength of association was seen to increase with increase in the chain length of the anticodonic nucleotide. The association of these amino acids with different phosphate esters of nucleotides suggests that a definite isomeric structure is required for association with a specified amino acid; the 5'-mononucleotides and (3'-5')-linked dinucleotides are the favored geometries for strong associations. Use of heterocodonic amino acids and nonprotein amino acids supports these findings. We conclude that there is at least a physicochemical, anticodonic contribution to the origin of the genetic code.     

二甲醚部分氧化重整制氢热力学分析及实验

用元素势能法对二甲醚(DME)部分氧化重整制氢进行了热力学分析与计算,在定压绝热条件下计算了产物中各组分的体积分数随空醚比(0.5~4)和压强(0.1~0.5MPa)的变化关系.结果表明:H₂的体积分数随压强的增大而减小;在标准大气压和空醚比为3的条件下,由二甲醚部分氧化反应得到的氢气体积分数最大,约为35%;H₂的体积分数随空醚比的增大先增后减,CO的体积分数变化不明显,CO₂和CH₄的体积分数随空醚比的增大而减小.最后,在自制实验台上进行二甲醚等离子体重整制氢的实验,将该实验结果与热力学分析结果进行了对比分析,结果证明用元素势能法分析得到的H₂,CO,CH₄和CO₂的体积分数随空醚比的变化趋势与实验结果较为一致.      

Search for millisecond rotational periods in some low-mass X-ray binaries observed by EXOSAT

We present the results of a search for millisecond rotational pulsations in the X-ray emission of five low-mass X-ray binaries: MXB1728-34, 4U1702-42, 4U1705-44, 4U1755-33 and GX17+2. The data were obtained by the EXOSAT Medium Energy Experiment Argon Counters (1–20 keV) with a time resolution of 7.8125 milliseconds. We searched for periods in the range from 16 msec to 8 sec. Upper limits of 1.5 – 5% were found at a 3 sigma level.     

Chemical evolution of RNA under hydrothermal conditions and the role of thermal copolymers of amino acids for the prebiotic degradation and formation of RNA.

The roles of thermal copolymers of amino acids (TCAA) were studied for the prebiotic degradation of RNA. A weak catalytic ability of TCAA consisted of Glu, L-Ala, L-Val, L-Glu, L-Asp, and optionally L-His was detected for the cleavage of the ribose phosphodiester bond of a tetranucleotide (5'-dCrCdGdG) in aqueous solution at 80 degees C. The rate constants of the disappearance of 5'-dCrCdGdG were determined in aqueous solutions using different pH buffer and TCAA. The degradation rates were enhanced 1.3-3.0 times in the presence of TCAA at pH 7.5 and 8.0 at 80 degrees C, while the hydrolysis of oligoguanylate (oligo(G)) was accelerated about 1.6 times at pH 8.0. A weak inhibitory activity for the cleavage of oligo(G) was detected in the presence of 0.055 M TCAA-Std. On the other hand, our recent study on the influences of TCAA for the template-directed reaction of oligo(G) on a polycytidylic acid template showed that TCAA has an acceleration activity for the degradation of the activated nucleotide monomer and an acceleration activity for the formation of G5' ppG capped oligo(G). This series of studies suggest that efficient and selective catalytic or inhibitory activities for either the degradation or formation of RNA under hydrothermal conditions could have hardly emerged from the simple thermal condensation products of amino acids. A scenario is going to be deduced on the chemical evolution of enzymatic activities and RNA molecules concerning hydrothermal earth conditions.     

A strategy for mineral and energy resource independence

Data acquired by Landsats 1, 2, and 3, are beginning to provide the information on which an improved mineral and energy resource exploration strategy can be based. Landsat 4 is expected to augment this capability with its higher resolution (30 m) and additional spectral bands in the Thematic Mapper (TM) designed specifically to discriminate clay minerals associated with mineral alteration. In addition, a new global magnetic anomaly map, derived from the recent Magsat mission, has recently been compiled by the National Aeronautics and Space Administration (NASA), the U.S. Geological Survey (USGS), and others. Preliminary, extremely small-scale renditions of this map indicate that global coverage is nearly complete and that the map will improve upon a previous one derived from Polar Orbiting Geophysical Observatory (POGO) data. Digital processing of the Landsat image data and Magsat geophysical data can be used to create three-dimensional stereoscopic models for which Landsat images provide surface reference to deep structural anomalies.Comparative studies of national Landsat lineament maps, Magsat stereoscopic models, and metallogenic information derived from the Computerized Resources Information Bank (CRIB) inventory of U.S. mineral resources, provide a way of identifying and selecting exploration areas that have mineral resource potential. Landsat images and computer-compatible tapes can provide new and better mosaics and also provide the capability for a closer look at promising sites.     

Photolysis of phosphine in the presence of acetylene and propyne, gas mixtures of planetary interest.

Phosphine (PH3) 1 has been observed in the atmospheres of Jupiter and Saturn. We have studied the photochemical reactions of this compound with acetylene (C2H2), an alkyne also detected in these atmospheres. The volatile products formed in these reactions were characterized by H, 31P and 13C NMR. The ethenylphosphine 2 is the first product formed in the photolysis of PH3 in the presence Of C2H2. Photolysis of PH3 in the presence of propyne (C3H4) led to the formation of the Z- and E-prop-1-enylphosphines and traces of 1-methylethenylphosphine. A reaction pathway is proposed. The initial step is the dissociation of PH3 to hydrogen and PH2 radicals. Addition of the phosphinyl radical on alkyne occurs as the next step. Vinylphosphines are then formed by radical combination. This proposed reaction pathway takes into account the nature of the products and studies devoted to the photolysis of germane (GeH4) or hydrogen sulfide (H2S) in the presence of alkyne. Attempts to detect the methylidynephosphine HC triple bond P (the isoelectronic compound of HC triple bond N), in the photolysis products of PH3-C2H2 mixtures were unsuccessful. The application of these findings to Jovian and Saturn atmospheric chemistry is discussed.