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The Origin of Amino Acids in Lunar Regolith Samples

机译:月球样品中氨基酸的来源

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摘要

We analyzed the amino acid content of seven lunar regolith samples returned by the Apollo 16 and Apollo 17 missions and stored under NASA curation since collection using ultrahigh-performance liquid chromatography with fluorescence detection and time-of-flight mass spectrometry. Consistent with results from initial analyses shortly after collection in the 1970s, we observed amino acids at low concentrations in all of the curated samples, ranging from 0.2 parts-per-billion (ppb) to 42.7 ppb in hot-water extracts and 14.5–651.1 ppb in 6 M HCl acid-vapor-hydrolyzed, hot-water extracts. Amino acids identified in the Apollo soil extracts include glycine, D- and L-alanine, D- and L-aspartic acid, D- and L-glutamic acid, D- and L-serine, L-threonine, and L-valine, all of which had previously been detected in lunar samples, as well as several compounds not previously identified in lunar regoliths: α-aminoisobutyric acid (AIB), D- and L-β-amino-n-butyric acid (β-ABA), DL-α-amino-n-butyric acid, γ-amino-n-butyric acid, β-alanine, and ε-amino-n-caproic acid. We observed an excess of the L enantiomer in most of the detected proteinogenic amino acids, but racemic alanine and racemic β-ABA were present in some samples.We also examined seven samples from Apollo 15, 16, and 17 that had been previously allocated to a non-curation laboratory, as well as two samples of terrestrial dunite from studies of lunar module engine exhaust that had been stored in the same laboratory. The amino acid content of these samples suggested that contamination had occurred during non-curatorial storage.We measured the compound-specific carbon isotopic ratios of glycine, β-alanine, and L-alanine in Apollo regolith sample 70011 and found values of ‒21‰ to ‒33‰. These values are consistent with those seen in terrestrial biology and, together with the enantiomeric compositions of the proteinogenic amino acids, suggest that terrestrial biological contamination is a primary source of the amino acids in these samples. However, the presence of the non-proteinogenic amino acids such as AIB and β -ABA suggests the possibility of some contribution from exogenous sources.We did not observe a correlation of amino acid content with proximity to the Apollo 17 lunar module, implying that lunar module exhaust was not a primary source of amino acid precursors. Solar-wind-implanted precursors such as HCN also appear to be at most a minor contributor, given a lack of correlation between amino acid content and soil maturity (as measured by Is/FeO ratio) and the differences between the δ13C values of the amino acids and the solar wind.
机译:我们分析了由Apollo 16和Apollo 17任务返回并在NASA策展下存储的七个月球长石样本的氨基酸含量,这是因为使用了具有荧光检测和飞行时间质谱的超高效液相色谱仪进行收集。与1970年代收集后不久的初步分析结果一致,我们在所有精选样品中观察到了低浓度的氨基酸,热水提取物中的氨基酸含量范围为十亿分之0.2(ppb)至42.7 ppb,14.5–651.1 ppb在6 M HCl酸-蒸汽水解的热水提取物中。阿波罗土壤提取物中鉴定出的氨基酸包括甘氨酸,D-和L-丙氨酸,D-和L-天冬氨酸,D-和L-谷氨酸,D-和L-丝氨酸,L-苏氨酸和L-缬氨酸,所有这些先前都已在月球样品中检测到,以及先前在月球白垩纪中未发现的几种化合物:α-氨基异丁酸(AIB),D-和L-β-氨基-正丁酸(β-ABA), DL-α-氨基-正丁酸,γ-氨基-正丁酸,β-丙氨酸和ε-氨基-正己酸。我们在大多数检测到的蛋白原氨基酸中观察到了过量的L对映异构体,但一些样品中存在外消旋的丙氨酸和外消旋的β-ABA。我们还检查了七个阿波罗15、16和17样品,这些样品先前已分配给一个非治疗实验室,以及两个月球舱发动机废气研究样品,这些样品已存储在同一实验室中。这些样品中的氨基酸含量表明在非策展品存储期间发生了污染。我们测量了Apollo regolith样品70011中甘氨酸,β-丙氨酸和L-丙氨酸的化合物特异性碳同位素比,发现值为‒21‰至‒33‰。这些值与在陆地生物学中观察到的值一致,并且与蛋白原氨基酸的对映异构体组成一起表明,陆地生物污染是这些样品中氨基酸的主要来源。然而,非蛋白氨基酸如AIB和β-ABA的存在表明可能有外源的贡献。我们没有观察到氨基酸含量与阿波罗17号月球模块的接近性相关,这表明月球组件排气不是氨基酸前体的主要来源。由于氨基酸含量与土壤成熟度(通过Is / FeO比测量)之间缺乏相关性,并且氨基酸的δ13C值之间没有相关性,因此太阳风植入的前体(例如HCN)似乎也起了很小的作用。酸和太阳风。

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