Amino-acid synthesis in carbonaceous meteorites by aqueous alteration of polycyclic aromatic hydrocarbons

It has been suggested that amino acids and other organic compounds found in carbonaceous meteorites formed by aqueous alteration in the meteorite parent bodies. Observations of carbonaceous material in interstellar grains and interplanetary dust particles indicate that condensed organic compounds may have been present in meteorite parent bodies at the time of aqueous alteration. One group of compounds thought to be representative of this carbonaceous material is the polycyclic aromatic hydrocarbons (PAHs). Recently it was proposed that PAHs condense on SiC grains in the molecular envelopes of carbon-rich red-giant stars, which would allow for their subsequent incorporation into meteorite parent bodies during accretion. This incorporation mechanism is supported by the identification of SiC grains in carbonaceous chondrites. The possibility therefore exists that PAHs, and/or other condensed organic compounds, represent the starting material for aqueous alteration which leads to the formation of amino acids and other water-soluble organic compounds. Here we present calculations of the distribution of aqueous organic compounds in metastable equilibrium with representative PAHs as functions of the fugacities of O2, CO2 and NH3. The results reported here for pyrene and fluoranthene, two PAHs with different structures but the same stoichiometry, differ greatly but indicate that the formation of amino and carboxylic acids is energetically favourable at probable parent-body alteration conditions. The actual reaction mechanisms involved could be revealed by consideration of isotope data for PAHs, amino acids, other organic compounds and carbonates in carbonaceous chondrites.     

Carbon isotope composition of low molecular weight hydrocarbons and monocarboxylic acids from Murchison meteorite

The origin of the organic matter in carbonaceous meteorites remains controversial despite extensive study over the past 20 yr. Motivated by the expectation that the patterns of isotopic variation with molecular structure among the organic compounds would contain important clues to their origin, we have measured the carbon isotopic compositions for individual hydrocarbons and monocarboxylic acids from Murchison meteorite, a C2 carbonaceous chondrite which fell in Australia in 1969. With few exceptions, notably benzene, the volatile products are substantially isotopically heavier than their terrestrial counterparts, signifying their extraterrestrial origin. For both classes of compounds, the ratio of 13C to 12C decreases with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic ratio than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with the kinetically controlled synthesis of higher homologues from lower ones. The results suggest the possibility that the production mechanisms for hydrocarbons and carboxylic acids may be similar; they also impose constraints on the identity of the reactant species.     

Racemic amino acids from the ultraviolet photolysis of interstellar ice analogues

The delivery of extraterrestrial organic molecules to Earth by meteorites may have been important for the origin and early evolution of life. Indigenous amino acids have been found in meteorites-over 70 in the Murchison meteorite alone. Although it has been generally accepted that the meteoritic amino acids formed in liquid water on a parent body, the water in the Murchison meteorite is depleted in deuterium relative to the indigenous organic acids. Moreover, the meteoritical evidence for an excess of laevo-rotatory amino acids is hard to understand in the context of liquid-water reactions on meteorite parent bodies. Here we report a laboratory demonstration that glycine, alanine and serine naturally form from ultraviolet photolysis of the analogues of icy interstellar grains. Such amino acids would naturally have a deuterium excess similar to that seen in interstellar molecular clouds, and the formation process could also result in enantiomeric excesses if the incident radiation is circularly polarized. These results suggest that at least some meteoritic amino acids are the result of interstellar photochemistry, rather than formation in liquid water on an early Solar System body.     

Paleoecological implications of the nitrogen isotope signatures in the sediments amended by Antarctic seal excrements

The nitrogen isotope signatures in the sediments amended by seal excrements, from Fildes Peninsula of King George Islands, Antarctica, were examined for their paleoecological application potential. The contents of total organic carbon (TOC) and total nitrogen (TN) and the atomic C/N ratios in the sediments show that the organic carbon and nitrogen are predominantly of marine origin and derived from seal excrements. The remarkably high δ15N values in the sediments may be related to at least two important factors of trophic enrichment and NH3 volatilization, which requires further studies. The large variations in the seal hair abundances and the determinedδ15N values in the sediments signify similar changes of the historical seal populations around the study site. A significant negative correlation between the δ15N values and seal hair abundance was observed, and this suggests that the δ15N values, like the number of seal hairs,can be used as a paleoecological proxy for the historical seal populations. The time-integrated δ15N signatures in the sediments with predominantly animal-derived nitrogen source thus provide a new tool for estimating historical populations of seals and penguins and interpretlng the underlying paleoecological processes.     

苏州河和黄浦江颗粒态氨基酸的季节变化简

于2007年1、4、7、10月在苏州河、黄浦江4个采样点采集表层水样,分析了颗粒态氨基酸（Particulate Amino Acids, PAA）的组成及含量;并对比分析了北新泾、河南路桥、十六铺和嫩江码头4个站点氨基酸的季节变化特征;结合颗粒有机碳（POC）、颗粒有机氮（PON）及颗粒态氨基酸的构型特征（D和L型）等参数,探讨了该区域颗粒有机氮的来源和降解情况.结果表明：苏州河氨基酸季节变化比黄浦江大;氨基酸降解系数(DI)分析表明研究区域的氨基酸主要来自现场过程和细菌贡献,其中7月份氨基酸最为新鲜;氨基酸降解系数DI和D构型氨基酸成负相关性关系,表明自然细菌来源的D-氨基酸在降解过程中的变化.     

制备型高效液相色谱法分离纯化绿原酸

采用制备高效液相色谱技术,从杜仲叶提取物中分离纯化得到高纯活性成分绿原酸.对制备色谱的洗脱方式、洗脱剂组成、浓度、洗脱速度等参数进行优化,提出并应用了流动相速度梯度洗脱方法.最佳操作条件为:采用流速梯度进行洗脱,流速先为28 mL/min,然后为45 mL/min;流动相为15%的有机酸B和 0.1%的有机酸E(体积分数);测定波长为254 nm;进样体积为10 mL;进样量为2500 mg.通过该工艺分离纯化,制备回收率为83.3%,相对标准偏差为3.1%,绿原酸的纯度达98.61%,同时可得到杜仲叶黄酮、桃叶珊瑚甙等副产品.     

5—磺基水杨酸存在下两相合成二茂钛氨基酸配合物

在两相体系（H2O／CHCl3)中,利用二氯二茂钛与5－磺基水杨酸形成的水溶液和N－（取代苯基）氨基乙酸反应,简便全盛了三种二茂钛氨基酸配合物,采用元素分析、IR及^1H NMR等对其进行了表征。结果表明,氨基酸的羧基以单齿氧原子与钛配位,形成了双分子取代的二茂钛配合物。     

The synthesis of organic and inorganic compounds in evolved stars

Recent isotopic analysis of meteorites and interplanetary dust has identified solid-state materials of pre-solar origin. We can now trace the origin of these inorganic grains to the circumstellar envelopes of evolved stars. Moreover, organic (aromatic and aliphatic) compounds have been detected in proto-planetary nebulae and planetary nebulae, which are the descendants of carbon stars. This implies that molecular synthesis is actively happening in the circumstellar environment on timescales as short as several hundred years. The detection of stellar grains in the Solar System suggests that they can survive their journey through the interstellar medium and that they are a major contributor of interstellar grains.     

Anomalous 17O compositions in massive sulphate deposits on the Earth

The variation of delta 18O that results from nearly all physical, biological and chemical processes on the Earth is approximately twice as large as the variation of delta 17O. This so-called 'mass-dependent' fractionation is well documented in terrestrial minerals. Evidence for 'mass-independent' fractionation (delta 17O = delta 17O-0.52 delta 18O), where deviation from this tight relationship occurs, has so far been found only in meteoritic material and a few terrestrial atmospheric substances. In the rock record it is thought that oxygen isotopes have followed a mass-dependent relationship for at least the past 3.7 billion years, and no exception to this has been encountered for terrestrial solids. Here, however, we report oxygen-isotope values of two massive sulphate mineral deposits, which formed in surface environments on the Earth but show large isotopic anomalies (delta 17O up to 4.6%). These massive sulphate deposits are gypcretes from the central Namib Desert and the sulphate-bearing Miocene volcanic ash-beds in North America. The source of this isotope anomaly might be related to sulphur oxidation reactions in the atmosphere and therefore enable tracing of such oxidation. These findings also support the possibility of a chemical origin of variable isotope anomalies on other planets, such as Mars.     

Amino acids from ultraviolet irradiation of interstellar ice analogues

Amino acids are the essential molecular components of living organisms on Earth, but the proposed mechanisms for their spontaneous generation have been unable to account for their presence in Earth's early history. The delivery of extraterrestrial organic compounds has been proposed as an alternative to generation on Earth, and some amino acids have been found in several meteorites. Here we report the detection of amino acids in the room-temperature residue of an interstellar ice analogue that was ultraviolet-irradiated in a high vacuum at 12 K. We identified 16 amino acids; the chiral ones showed enantiomeric separation. Some of the identified amino acids are also found in meteorites. Our results demonstrate that the spontaneous generation of amino acids in the interstellar medium is possible, supporting the suggestion that prebiotic molecules could have been delivered to the early Earth by cometary dust, meteorites or interplanetary dust particles.     

Identification of molecular-cloud material in interplanetary dust particles

Interplanetary dust particles (IDPs) collected in the Earth's stratosphere and meteorites are fragments of comets and asteroids. These are 'primitive' meteorites in part because they have preserved materials which predate the formation of the Solar System. The most primitive (least altered) meteorites contain a few parts per million of micrometre-sized dust which formed in the atmospheres of giant stars. Some meteorites have elevated D/H and 15N/14N ratios that are attributed to surviving interstellar organic molecules which have probably been strongly diluted and altered by parent-body processes. Most IDPs are chemically, mineralogically, and texturally primitive in comparison to meteorites. Here I show that H and N isotopic anomalies among fragile 'cluster' IDPs are far larger, more common, and less equilibrated than those previously observed in other IDPs or meteorites. In some cases, the D/H ratios that we measure reach the values of interstellar molecules, suggesting that molecular-cloud material has survived intact. These observations indicate that cluster IDPs are the most primitive class of Solar System materials currently available for laboratory analysis.     

溶剂抽提分离烷硫化反应混合物

以铵盐和磷酸作为萃取剂抽提分离甲苯二氨烷硫化反应的反应混合物,重点考察在单级抽提分离过程中,工艺条件对萃取分离效果的影响。研究发现适宜的分离条件为：混合时间为15min,萃取温度为常温,萃取剂与原料的体积比为2,萃取剂的质量分数为0．025。在此条件下,二甲硫基甲苯二胺的质量分数可以由0．814提高到0．949,回收率为95．1％。     

Nickel solvent extraction from cold purification filter cakes of Angouran mine concentrate using LIX984N

Cold purification filter cakes generated in the hydrometallurgical processing of Angouran mine zinc concentrate commonly contain significant amounts of Zn, Cd, and Ni ions and thus are valuable resources for metal recovery. In this research, a nickel containing solution that was obtained from sulfuric acid leaching of the filter cake following cadmium and zinc removal was subjected to solvent extraction experiments using 10vol% LIX984N diluted in kerosene. Under optimum experimental conditions (pH 5.3, volume ratio of organic/aqueous (O:A) = 2:1, and contact time = 5 min), more than 97.1% of nickel was extracted. Nickel was stripped from the loaded organic by contacting with a 200 g/L sulfuric acid solution, from which 77.7% of nickel was recovered in a single contact at the optimum conditions (pH 1–1.5, O:A = 5:1, and contact time = 15 min).     

高能宇宙线C,N和O的反常同位素的解释

近期观测和理论表明,宇宙线可源于类太阳恒星,且在星际空间中有净能量增益,由此,本文提出了在太阳域内用厚板模型,在星际介质中用泄漏箱模型描述的传播模型,可以解释实验观测到的高能宇宙线C、N和O的同位素反常。     

The nature and origin of interstellar diamond

Microscopic diamond was recently discovered in oxidized acid residues from several carbonaceous chondrite meteorites (for example, the C delta component of the Allende meteorite). Some of the reported properties of C delta seem in conflict with those expected of diamond. Here we present high spatial resolution analytical data which may help to explain such results. The C delta diamond is an extremely fine-grained (0.5-10 nm) single-phase material, but surface and interfacial carbon atoms, which may comprise as much as 25% of the total, impart an 'amorphous' character to some spectral data. These data support the proposed high-pressure conversion of amorphous carbon and graphite into diamonds due to grain-grain collisions in the interstellar medium although a low-pressure mechanism of formation cannot be ruled out.     

超分子C14H14N4O8的合成及结构表征

以反丁烯二酸和咪唑为原料,采用缓慢蒸发溶剂法合成了新的有机加合物C14H14N4O8,并获得了其单晶体.通过红外、热化学分析、X-射线单晶衍射等技术对该加合物进行了结构测定和性质表征.晶体中分子通过分子间氢键相互连接构成超分子网络结构.该加合物属于三斜晶系,P-1空间群,a=0.746 77(15), b=7.736 3(15),c=8.405 5(17),α=69.73(3)°,β=80.40(3)°,γ=66.19(3)°,Z=1,V=416.75(14)A3,D=1.468 (mg/m3),F(000)=190.     

云南烤烟中上部叶片氮化合物代谢规律研究

针对目前部分烟区烤烟中、上部叶片含氮化合物含量偏高,影响烟叶（特别是上部叶）可用性的实际,在不同施氮量和氮素形态下,研究了烤烟K326大田中后期中、上部叶片含氮化合物总氮、烟碱、蛋白质和氨基酸含量变化规律。中部叶中,施氮量增加,叶片总氮、蛋白质、氨基酸含量增加,烟碱含量变化不明显;氮素形态对总氮、蛋白质、氨基酸的影响不明显,成熟期烟碱含量随硝态肥施用比例增加有下降趋势,上部叶中,施氮量剧烈影响叶片各种含氮化合物含量,施氮量越高,含氮化合物含量越高,高氮量处理明显高于中、低氮量处理;氮素形态对上部叶含氮化合物影响与对中部叶的影响基本一致,因此,生产中降低中、上部烟叶含氮化合物含量,提高烟叶可用性应严格控制施氮量;增加硝氮施用比例可促进烟株对氮素的前期吸收,一定程度降低上部叶烟碱含量。     

Sublimation from icy jets as a probe of the interstellar volatile content of comets

Comets are some of the most primitive bodies left over from the Solar System's early history. They may preserve both interstellar material and material from the proto-solar nebula, and so studies of their volatile components can provide clues about the evolution of gases and ices, as a collapsing molecular cloud transforms into a mature planetary system. Previous observations of emission from rotational transitions in molecules have averaged over large areas of the inner coma, and therefore include both molecules that sublimed from the nucleus and those that result from subsequent chemical processes in the coma Here we present high-resolution observations of emission from the molecules HNC, DCN and HDO associated with comet Hale-Bopp. Our data reveal arc-like structures-icy jets-offset from (but close to) the nucleus. The measured abundance ratios on 1-3" scales are substantially different from those on larger scales, and cannot be accounted for by models of chemical processes in the coma; they are, however, similar to the values observed in the cores of dense interstellar clouds and young stellar objects. We therefore propose that sublimation from millimetre-sized icy grains ejected from the nucleus provides access to relatively unaltered volatiles. The D/H ratios inferred from our data suggest that, by mass, Hale-Bopp (and by inference the outer regions of the early solar nebula) consists of > or =15-40% of largely unprocessed interstellar material.     

咪唑基阳离子-Strandberg型钼磷酸盐的合成及电催化活性探讨

利用常规和水热合成法得到2个咪唑基阳离子-Strandberg型钼磷酸盐的有机-无机杂化化合物,H8（H2biim）5[（HPO4）2Mo5O15]2.4H2O（1）和H4（Hbeim）5[（HPO4）2Mo5O15].4H2O（2）（H2biim=2,2′-联咪唑;Hbeim=苯并咪唑）.通过IR光谱、ICP、元素分析、CV和单晶X-射线衍射分析进行了表征,并研究了该杂化材料对H2O2还原的电催化活性.结果表明,化合物1和2在酸性条件下对H2O2具有电催化还原作用.分子间通过多阴离子单元与有机物基团间的静电作用、N—H…O和O—H…O氢键作用形成无限的三维网络结构.     

Ultraviolet-radiation-induced methane emissions from meteorites and the Martian atmosphere

Almost a decade after methane was first reported in the atmosphere of Mars there is an intensive discussion about both the reliability of the observations--particularly the suggested seasonal and latitudinal variations--and the sources of methane on Mars. Given that the lifetime of methane in the Martian atmosphere is limited, a process on or below the planet's surface would need to be continuously producing methane. A biological source would provide support for the potential existence of life on Mars, whereas a chemical origin would imply that there are unexpected geological processes. Methane release from carbonaceous meteorites associated with ablation during atmospheric entry is considered negligible. Here we show that methane is produced in much larger quantities from the Murchison meteorite (a type CM2 carbonaceous chondrite) when exposed to ultraviolet radiation under conditions similar to those expected at the Martian surface. Meteorites containing several per cent of intact organic matter reach the Martian surface at high rates, and our experiments suggest that a significant fraction of the organic matter accessible to ultraviolet radiation is converted to methane. Ultraviolet-radiation-induced methane formation from meteorites could explain a substantial fraction of the most recently estimated atmospheric methane mixing ratios. Stable hydrogen isotope analysis unambiguously confirms that the methane released from Murchison is of extraterrestrial origin. The stable carbon isotope composition, in contrast, is similar to that of terrestrial microbial origin; hence, measurements of this signature in future Mars missions may not enable an unambiguous identification of biogenic methane.