Coupling trapped ion mobility spectrometry to mass spectrometry: trapped ion mobility spectrometry–time‐of‐flight mass spectrometry versus trapped ion mobility spectrometry–Fourier transform ion cyclotron resonance mass spectrometry

Hupin

Carrasco

et al. 2020

Icarus

The origin and evolution of organic matter in the solar system intertwines astrobiology and planetary geochemistry issues. To observe the contribution of atmospheric processes in the formation of complex organic matter, one of the most intensively studied objects in the outer solar system is Titan, the largest moon of Saturn. Its reducing atmosphere of methane and nitrogen hosts a thick, permanent, nitrogen-rich, organic haze, whose complex composition remains largely unknown. Due to the measurement of species at large mass-to-charge ratio and infrared information from the Cassini-Huygens mission, polyaromatic hydrocarbons (PAHs) based structure for this haze has been suggested. Here, we propose a snapshot of the global chemical structure based on the analysis of laboratory analogue of Titan's haze with ion mobility spectrometry coupled with mass spectrometry. This robust analysis, validated with other geochemical complex mixtures, such as petroleum, allows for the observation of the size and three-dimensional structure of detected species. By comparison, with standards molecules, we exclude several structures such as pure PolyHCN and pure polycyclic aromatic hydrocarbons to be present in the principal trend of the laboratory tholins. Using theoretical calculations, we propose a plausible structure consistent with our results, which is a branched triazine-pyrazole. We observe that the larger the aerosols molecules are, the more they tend towards a structure containing small aromatics cores linked together by short chains. We suggest that the use of such an analytical approach could help advance our understanding of other complex organic compounds in the Solar System such as soluble organic matter in meteorites.

Section: Introductionmentioning

confidence: 99%

Structural elucidation of soluble organic matter: Application to Titan's haze

Hupin

Carrasco

et al. 2020

Icarus

“…The unique information derived by ion mobility separation -i.e., such as mobility peak position, width, and shape, provides more detailed structural insight than mass spectrometry alone. [13,14] Experimental Tholins were produced according to the PAMPRE process. [3] Briefly, after a few hours of cold plasma discharge of a nitrogen/methane mixture, a brown powder, the tholins sample material, was recovered.…”

mentioning

confidence: 99%

Structural Study of Analogues of Titan’s Haze by Trapped Ion Mobility Coupled with a Fourier Transform Ion Cyclotron Mass Spectrometer

Rueger

J. Am. Soc. Mass Spectrom.

Maitre

et al. 2019

Self Cite

The aerosols present in the atmosphere of the Saturn's moon Titan are of particular planetary science interest and several spacecraft missions already allowed to gather spectroscopic data. Titan haze's analogs, so-called tholins, were produced on earth to push forward the comprehension of their formation and properties. In this study, this highly complex mixture was analyzed here for the first time by trapped ion mobility spectrometry coupled to ultra-high resolution mass spectrometry (FTICR MS). Electrospray ionization revealed the characteristic CHN x -class components, with CHN 5-6 and DBE 6-7 most abundant. Deploying specialized visualization, enabled by accurate mass measurements and elemental composition assignments, the adapted Kendrick mass defect analysis highlights the C 2 H 3 N homolog series, whereas the nitrogen-modified van Krevelen diagram exhibits a clear trend towards H/C 1.5 and N/C 0.5. More interestingly, the representation of m/z versus collision cross section (CCS) allowed hypothesizing a ramified N-PAH structural motif. State-of-the-art IMS is currently not able to resolve the isomeric continuum of ultra-complex mixtures; thus peak parameter other than the CCS-value are explored. As such, analyzing the mobility peak width versus m/z shows a linear increase in isomeric diversity between m/z 170 and 350 and a near plateau in diversity at higher m/z for the N-PAH-like structure. Due to the high complexity of the sample, these structural insights are only to be revealed by TIMS-FTICR MS.

“…A further issue to go deeper in the analysis will be to solve isomers and provide structural identification, as preliminary work by Gautier et al 2016 demonstrated the need for with such complex samples using laboratory LC-Orbitrap. More complex configurations of the CosmOrbitrap could be proposed in that context, and the one that seems most suitable for this new challenge is the trapped ion mobility spectrometry (TIMS) (Castellanos et al, 2014;Tose et al, 2018). This technique, located before the mass spectrometer, allows to estimate the number of isomers present in a mixture.…”

Section: Discussionmentioning

confidence: 99%

High‐resolution mass spectrometry for future space missions: Comparative analysis of complex organic matter with LAb‐CosmOrbitrap and laser desorption/ionization Fourier transform ion cyclotron resonance

Selliez¹,

Rapid Comm Mass Spectrometry

Cherville³

et al. 2020

(RATIONALE) Mass spectrometers are regularly boarded on spacecraft for the exploration of the Solar System. A better understanding of the origin, distribution and evolution of organic matter and its relationships with inorganic matter in different extra-terrestrial environments requires the development of innovative space tools, described as Ultra High Resolution Mass Spectrometry (UHRMS) instruments. (METHODS) Analyses of a complex organic material simulating extraterrestrial matter (Titan's tholins) are performed with a homemade space-designed Orbitrap TM equipped with a laser ablation ionization source at 266 nm: the LAb-CosmOrbitrap. Mass spectra are obtained using only one laser shot and transient duration of 838 ms. A comparison is made on the same sample with a laboratory benchmark mass spectrometer: a Fourier Transform Ion Cyclotron Resonance equipped with a laser desorption ionization at 355 nm (LDI-FTICR) allowing accumulation of 20,000 laser shots. (RESULTS) Mass spectra and attributions of molecular formulae based on the peaks detected by both techniques show significant similarities. Detection and identification of the same species are validated. The formation of clusters ions with the LAb-CosmOrbitrap is also presented. This specific feature brings informative and unusual indirect detections about the chemical compounds constituting Titan's tholins. In particular, the detection of HCN confirms previous results obtained with laboratory Electrospray Ionization (ESI)-UHRMS studies about the understanding of polymeric patterns for the formation of tholins. (CONCLUSION) Capabilities of the LAb-CosmOrbitrap to decipher complex organic mixtures using single laser shot and a short transient are highlighted. In agreement with results provided by a commercial FTICR instrument in the laboratory, we demonstrate in this work the relevance of a space laser-CosmOrbitrap instrument for the future planetary exploration.