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在太空中寻找生命的证据:通过 N,N-二甲基甲酰胺二甲缩醛衍生物依赖气相色谱-质谱法分析对映有机分子。

Search for evidence of life in space: analysis of enantiomeric organic molecules by N,N-dimethylformamide dimethylacetal derivative dependant Gas Chromatography-Mass Spectrometry.

机构信息

Laboratoire de Génie des Procédés et Matériaux (LGPM), Ecole Centrale Paris, Grande voie des vignes, 92295 chatenay-Malabry, PressUniverSud, France.

出版信息

J Chromatogr A. 2010 Jan 29;1217(5):731-40. doi: 10.1016/j.chroma.2009.11.009. Epub 2009 Nov 10.

Abstract

Within the context of the future space missions to Mars (MSL 2011 and Exomars 2016), which aim at searching for traces of life at the surface, the detection and quantitation of enantiomeric organic molecules is of major importance. In this work, we have developed and optimized a method to derivatize and analyze chiral organic molecules suitable for space experiments, using N,N-dimethylformamide dimethylacetal (DMF-DMA) as the derivatization agent. The temperature, duration of the derivatization reaction, and chromatographic separation parameters have been optimized to meet instrument design constraints imposed upon space experiment devices. This work demonstrates that, in addition to its intrinsic qualities, such as production of light-weight derivatives and a great resistance to drastic operating conditions, DMF-DMA facilitates simple and fast derivatization of organic compounds (three minutes at 140 degrees C in a single-step) that is suitable for an in situ analysis in space. By using DMF-DMA as the derivatization agent, we have successfully identified 19 of the 20 proteinic amino acids and been able to enantiomerically separate ten of the potential 19 (glycine being non-chiral). Additionally, we have minimized the percentage of racemized amino acid compounds produced by optimizing the conditions of the derivatization reaction itself. Quantitative linearity studies and the determination of the limit of detection show that the proposed method is also suitable for the quantitative determination of both enantiomeric forms of most of the tested amino acids, as limits of detection obtained are lower than the ppb level of organic molecules already detected in Martian meteorites.

摘要

在未来的火星任务(MSL2011 和 Exomars2016)中,旨在寻找表面生命的痕迹,检测和定量对映有机分子变得尤为重要。在这项工作中,我们开发并优化了一种方法,使用 N,N-二甲基甲酰胺二甲缩醛(DMF-DMA)作为衍生化试剂,衍生和分析适合空间实验的手性有机分子。优化了衍生化反应的温度、时间和色谱分离参数,以满足空间实验设备对仪器设计的限制。这项工作表明,除了其固有特性(如生成轻量级衍生物和对恶劣操作条件的高抵抗力)外,DMF-DMA 还可以方便地对有机化合物进行简单快速的衍生化(在 140°C 下一步反应只需三分钟),适合在空间进行原位分析。通过使用 DMF-DMA 作为衍生化试剂,我们成功地鉴定了 20 种蛋白质氨基酸中的 19 种,并能够对其中的 10 种进行对映体分离(甘氨酸是非手性的)。此外,通过优化衍生化反应本身的条件,我们最大限度地减少了产生外消旋氨基酸化合物的百分比。定量线性研究和检测限的确定表明,该方法也适用于大多数测试氨基酸对映异构体的定量测定,因为获得的检测限低于已在火星陨石中检测到的有机分子的 ppb 水平。

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