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Anal Chim Acta

Title:		Influence of pH and salts on DMF-DMA derivatization for future Space Applications
Author(s):		Boulesteix D; Buch A; Samson J; Millan M; Jomaa J; Coscia D; Moulay V; McIntosh O; Freissinet C; Stern JC; Szopa C;
Address:		"Laboratoire Genie des Procedes et Materiaux, CentraleSupelec, University Paris-Saclay, 8-10 Rue Joliot-Curie, 91190, Gif-sur-Yvette, France. Electronic address: david.boulesteix@centralesupelec.fr. Laboratoire Genie des Procedes et Materiaux, CentraleSupelec, University Paris-Saclay, 8-10 Rue Joliot-Curie, 91190, Gif-sur-Yvette, France. Electronic address: arnaud.buch@centralesupelec.fr. Laboratoire Genie des Procedes et Materiaux, CentraleSupelec, University Paris-Saclay, 8-10 Rue Joliot-Curie, 91190, Gif-sur-Yvette, France. LATMOS/IPSL, UVSQ University Paris-Saclay, Sorbonne University, CNRS, 11 Bd d'Alembert, 78280, Guyancourt, France. Planetary Environments Laboratory (Code 699), NASA Goddard Space Flight Center, Greenbelt, MD, 20771, USA; School of Medicine, Wayne State University, 42 W. Warren Ave, Detroit, MI, 48202, USA. Space Science Exploration Division (Code 690), NASA, Goddard Space Flight Center, Greenbelt, MD, 20771, USA"
Journal Title:		Anal Chim Acta
Year:		2023
Volume:		20230505
Issue:
Page Number:		341270 -
DOI:		10.1016/j.aca.2023.341270
ISSN/ISBN:		1873-4324 (Electronic) 0003-2670 (Linking)
Abstract:		"For gas chromatography - mass spectrometry (GC-MS) analyses performed in situ, pH and salts (e.g., chlorides, sulfates) may enhance or inhibit the detection of targeted molecules of interest for astrobiology (e.g. amino acids, fatty acids, nucleobases). Obviously, salts influence the ionic strength of the solutions, the pH value, and the salting effect. But the presence of salts may also produce complexes or mask ions in the sample (masking effect on hydroxide ion, ammonia, etc.). For future space missions, wet chemistry will be conducted before GC-MS analyses to detect the full organic content of a sample. The defined organic targets for space GC-MS instrument requirements are generally strongly polar or refractory organic compounds, such as amino acids playing a role in the protein production and metabolism regulations for life on Earth, nucleobases essential for DNA and RNA formation and mutation, and fatty acids that composed most of the eukaryote and prokaryote membranes on Earth and resist to environmental stress long enough to still be observed on Mars or ocean worlds in geological well-preserved records. The wet-chemistry chemical treatment consists of reacting an organic reagent with the sample to extract and volatilize polar or refractory organic molecules (i.e. dimethylformamide dimethyl acetal (DMF-DMA) in this study). DMF-DMA derivatizes functional groups with labile H in organics, without modifying their chiral conformation. The influence of pH and salt concentration of extraterrestrial materials on the DMF-DMA derivatization remains understudied. In this research, we studied the influence of different salts and pHs on the derivatization of organic molecules of astrobiological interest with DMF-DMA, such as amino acids, carboxylic acids, and nucleobases. Results show that salts and pH influence the derivatization yield, and that their effect depend on the nature of the organics and the salts studied. Second, monovalent salts lead to a higher or similar organic recovery compared to divalent salts regardless of pH below 8. However, a pH above 8 inhibits the DMF-DMA derivatization influencing the carboxylic acid function to become an anionic group without labile H. Overall, considering the negative effect of the salts on the detection of organic molecules, future space missions may have to consider a desalting step prior to derivatization and GC-MS analyses"
Keywords:		*Extraterrestrial Environment/chemistry *Dimethylformamide Salts Amino Acids/analysis Carboxylic Acids Fatty Acids And perchlorate salts Chloride DMF-DMA derivatization Space applications Sulfate pH;
Notes:		"MedlineBoulesteix, D Buch, A Samson, J Millan, M Jomaa, J Coscia, D Moulay, V McIntosh, O Freissinet, C Stern, J C Szopa, C eng Netherlands 2023/05/28 Anal Chim Acta. 2023 Jul 25; 1266:341270. doi: 10.1016/j.aca.2023.341270. Epub 2023 May 5"