Influence of pH and salts on DMF-DMA derivatization for future Space Applications

• Published in: Analytica chimica acta Vol. 1266; p. 341270
• Main Authors: Boulesteix, D., Buch, A., Samson, J., Millan, M., Jomaa, J., Coscia, D., Moulay, V., McIntosh, O., Freissinet, C., Stern, J.C., Szopa, C.
• Format: Journal Article
• Language: English
• Published: Netherlands Elsevier B.V 25-07-2023; Elsevier Masson
• Subjects: Amino Acids - analysis; And perchlorate salts; Carboxylic Acids; Chloride; Dimethylformamide; DMF-DMA derivatization; Extraterrestrial Environment - chemistry; Fatty Acids; Salts; Sciences of the Universe; Space applications; Sulfate; pH; DMF-DMA derivatization; Chloride; Sulfate; Space applications; And perchlorate salts
• ISSN: 0003-2670; 1873-4324
• DOI: 10.1016/j.aca.2023.341270

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.
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•DMF-DMA derivatization is a fast one-pot reaction helpful to break the matrix, desorb, derivatize, and volatilize analytes.•DMF-DMA derivatizes polar and refractory organic molecules as well as enantiomeric forms separated with a chiral column.•GC-MS with a DMF-DMA extraction identifies hundreds of organic compounds (from pmol to mmol of molecule) in a bulk sample.•DMF-DMA is suited for space applications (spaceflight and return sample missions) and (biogeo)chemistry laboratory work.