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默奇森陨石中含氮化合物的同位素分析:氨、胺、氨基酸和极性碳氢化合物。

Isotopic analyses of nitrogenous compounds from the Murchison meteorite: ammonia, amines, amino acids, and polar hydrocarbons.

作者信息

Pizzarello S, Feng X, Epstein S, Cronin J R

机构信息

Department of Chemistry and Biochemistry, Arizona State University, Tempe 85287-1604, USA.

出版信息

Geochim Cosmochim Acta. 1994 Dec;58(24):5579-87. doi: 10.1016/0016-7037(94)90251-8.

Abstract

The combined volatile bases (ammonia, aliphatic amines, and possibly other bases), ammonia, amino acids, and polar hydrocarbons were prepared from the Murchison meteorite for isotopic analyses. The volatile bases were obtained by cryogenic transfer after acid-hydrolysis of a hot-water extract and analyzed by combined gas chromatography-mass spectrometry of pentafluoropropionyl derivatives. The aliphatic amines present in this preparation comprise a mixture that includes both primary and secondary isomers through C5 at a total concentration of > or = 100 nmoles g-1. As commonly observed for meteoritic organic compounds, almost all isomers through C5 are present, and the concentrations within homologous series decrease with increasing chain length. Ammonia was chromatographically separated from the other volatile bases and found at a concentration of 1.1-1.3 micromoles g-1 meteorite. The ammonia analyzed includes contributions from ammonium salts and the hydrolysis of extractable organic compounds, e.g., carboxamides. Stable isotope analyses showed the volatile bases to be substantially enriched in the heavier isotopes, relative to comparable terrestrial compounds delta D < or = +1221%; delta 13C = +22%; delta 15N = +93%). Ammonia, per se, was found to have a somewhat lower delta 15N value (+69%) than the total volatile bases; consequently, a higher delta 15N (>93%) can be inferred for the other bases, which include the amines. Solvent-extractable polar hydrocarbons obtained separately were found to be enriched in 15N (delta 15N = +104%). Total amino acids, prepared from a hydrolyzed hot-water extract by cation exchange chromatography, gave a delta 15N of +94%, a value in good agreement with that obtained previously. Nitrogen isotopic data are also given for amino acid fractions separated chromatographically. The delta 15N values of the Murchison soluble organic compounds analyzed to date fall within a rather narrow range (delta 15N = +94 +/- 8%), an observation consistent with their formation, or formation of their precursors, by interstellar chemistry.

摘要

从默奇森陨石中制备了挥发性碱(氨、脂肪族胺以及可能的其他碱)、氨、氨基酸和极性碳氢化合物用于同位素分析。挥发性碱是通过对热水提取物进行酸水解后低温转移获得的,并通过五氟丙酰衍生物的气相色谱 - 质谱联用进行分析。该制剂中存在的脂肪族胺是一种混合物,包括直至C5的伯异构体和仲异构体,总浓度≥100纳摩尔/克。正如陨石有机化合物中常见的那样,几乎所有直至C5的异构体都存在,并且同系物系列中的浓度随链长增加而降低。氨通过色谱法与其他挥发性碱分离,发现其在陨石中的浓度为1.1 - 1.3微摩尔/克。所分析的氨包括铵盐和可提取有机化合物(如羧酰胺)水解的贡献。稳定同位素分析表明,相对于地球上的可比化合物,挥发性碱在较重同位素中显著富集(δD≤ +1221%;δ13C = +22%;δ15N = +93%)。发现氨本身的δ15N值(+69%)略低于总挥发性碱;因此,可以推断其他碱(包括胺)的δ15N值更高(>93%)。单独获得的可溶剂提取的极性碳氢化合物被发现15N富集(δ15N = +104%)。通过阳离子交换色谱法从水解的热水提取物中制备的总氨基酸,其δ15N为 +94%,该值与先前获得的值非常一致。还给出了通过色谱法分离的氨基酸馏分的氮同位素数据。迄今为止分析的默奇森可溶性有机化合物的δ15N值落在相当窄的范围内(δ15N = +94 ± 8%),这一观察结果与它们通过星际化学形成或其前体形成一致。

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