Valorisation
MassLor est une Infrastructure de Recherche en Spectrométrie de Masse de l’Université de Lorraine et du Pôle Scientifique CPM.
Elle a pour objectif de proposer son expertise et son savoir-faire à des partenaires académiques et industriels, Lorrains et nationaux, dans le domaine de la Recherche & Développement, des prestations de service et de la formation.
Retrouvez l'ensemble des publications de la plateforme ICI
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« We thank XX from the mass spectrometry MassLor platform of Lorraine University ».
La publication des travaux et expériences menées dans le cadre de l’accès à l’IR Infranalytics devra faire mention du soutien accordé par ce programme, en incluant au minimum la phrase suivante dans les remerciements :
"Financial support from the IR INFRANALYTICS FR2054 for conducting the research is gratefully acknowledged."
Les dernières publications :
Concealed by darkness: Combination of NMR and HRMS reveal the molecular nature of dissolved organic matter in fractured-rock groundwater and connected surface waters
M.C. Bridoux a,* , G. Gaiffe a , P. Pacholski a,b , S. Cangemi c , G. Vinci c , R. Spaccini c , S. Schramm b
Water Research 243 (2023) 120392 ; https://doi.org/10.1016/j.watres.2023.120392
Detailed molecular composition of solid phase extracted dissolved organic matter (SPEDOM) collected from fractured-rock groundwater was compared to connected surface river water at two different watersheds in the unconfined chalk aquifer of Champagne in France using full scan ultrahigh resolution electrospray and photoionization Fourier transform ion cyclotron mass spectrometry (FT-ICR MS), Orbitrap tandem MS (MS/MS) and 1 H magnetic resonance spectroscopy (NMR). 1 H NMR spectroscopy indicated that groundwater SPEDOM carried a higher contribution of aliphatic compounds while surface river waters SPEDOM were enriched in carboxyl-rich alicyclic molecules (CRAM), acetate derivatives and oxygenated units. Furthermore, we show here that use of photoionization (APPI(+)) in aquifer studies is key, ionizing about eight times more compounds than ESI in surface river water samples, specifically targeting the dissolved organic nitrogen pool, accounting for more than 50% of the total molecular space, as well as a non-polar, more aromatic fraction; with little overlap with compounds detected by ESI(-) FT-ICR MS. On the other hand, groundwater SPEDOM samples did not show similar selectivity as less molecular diversity was observed in APPI compared to ESI. Mass-difference transformation networks (MDiNs) applied to ESI(-) and APPI(+) FT-ICR MS datasets provided an overview of the biogeochemical relationships within the aquifer, revealing chemical diversity and microbial/abiotic reactions. Finally, the combination of ESI(-) FT-ICR MS and detailed Orbitrap MS/MS analysis revealed a pool of polar, anthropogenic sulfur-containing surfactants in the groundwaters, likely originating from agricultural runoff. Overall, our study shows that in this aquifer, groundwater SPEDOM contains a significantly reduced pool of organic compounds compared to surface river waters, possibly related to a combination of lack of sunlight and adsorption of high O/ C formulas to mineral surfaces.
Alumina-embedded HZSM-5 with enhanced behavior for the catalytic cracking of biomass pyrolysis bio-oil: Insights into the role of mesoporous matrix in the deactivation by coke
Iratxe Crespo a , Jasmine Hertzog b , Vincent Carre b , Frederic Aubriet b , Beatriz Valle a,*
J.aap. 172 (2023) 106009 ; https://doi.org/10.1016/j.jaap.2023.106009
The behavior of HZSM-5 zeolite embedded in γ-Al2O3/α-Al2O3 matrix in the catalytic cracking of biomass pyrolysis bio-oil was studied with special focus on the role of the matrix in the deactivation by coke. The runs were conducted at 450 ºC, space-time of 0.35 gzeolite.h.gfeed − 1 and 0.5 h, 1 h, and 2 h on stream. The analysis of reaction products was conducted by in-line GC and GC/MS, and deactivated catalyst samples were extensively characterized by N2 physisorption, NH3-TPD, TPD-TPO, TPD-GC/MS and LDI FT-ICR MS. The alumina-embedded catalyst (Cat− Z30) exhibited greater stability, keeping the bio-oil conversion above 88 % for 0.5 h on stream, in comparison to the bulk HZSM-5 that deactivated rapidly entailing a bio-oil conversion plunge (from 95 % to 40 %). Consequently, the yield of gasoline-range hydrocarbons (> 70 % MAH monoaromatics) was boosted from 18 % to 26 % for the same reaction time. The aqueous liquid byproduct concurrently produced has a suitable composition for H2 production by further steam reforming. The enhanced behavior was caused by the weak-acid mesoporous structure of the matrix playing a dual function: i) diffusive-shell (inwards) role by promoting fragmentation/deoxygenation of bulky molecules (e.g., saccharides and guaiacols) into reactive oxygenates, and deposition of thermally-induced coke away from the zeolite micropores; ii) spread-growth (outwards) role by enhancing the diffusion of hydrocarbons outwards from zeolite crystals, and by promoting the development of heavy polycyclic structures that delay the blockage of active sites in micropores. The results are useful to progress towards the integral valorization of raw bio-oil, the development of active and stable catalysts, and the proposal of regeneration strategies necessary for the scaling up.
Next Challenges for the Comprehensive Molecular Characterization of Complex Organic Mixtures in the Field of Sustainable Energy
Anthony Abou-Dib , Frédéric Aubriet * , Jasmine Hertzog , Lionel Vernex-Loset, Sébastien Schramm and Vincent Carré *
Molecules 2022, 27, 8889 ; https://doi.org/10.3390/molecules27248889
The conversion of lignocellulosic biomass by pyrolysis or hydrothermal liquefaction gives access to a wide variety of molecules that can be used as fuel or as building blocks in the chemical industry. For such purposes, it is necessary to obtain their detailed chemical composition to adapt the conversion process, including the upgrading steps. Petroleomics has emerged as an integral approach to cover a missing link in the investigation bio-oils and linked products. It relies on ultra-high-resolution mass spectrometry to attempt to unravel the contribution of many compounds in complex samples by a non-targeted approach. The most recent developments in petroleomics partially alter the discriminating nature of the non-targeted analyses. However, a peak referring to one chemical formula possibly hides a forest of isomeric compounds, which may present a large chemical diversity concerning the nature of the chemical functions. This identification of chemical functions is essential in the context of the upgrading of bio-oils. The latest developments dedicated to this analytical challenge will be reviewed and discussed, particularly by integrating ion source features and incorporating new steps in the analytical workflow. The representativeness of the data obtained by the petroleomic approach is still an important issue.
Nucleos’ID: A New Search Engine Enabling the Untargeted Identification of RNA Post-transcriptional Modifications from Tandem Mass Spectrometry Analyses of Nucleosides
Clarisse Gosset-Erard, Mévie Didierjean, Jérome Pansanel, Antony Lechner, Philippe Wolff, Lauriane Kuhn, Frédéric Aubriet, Emmanuelle Leize-Wagner, Patrick Chaimbault, and Yannis-Nicolas François*
Anal. Chem. 2023, 95, 2, 1608–1617 ; https://doi.org/10.1021/acs.analchem.2c04722
As RNA post-transcriptional modifications are of growing interest, several methods were developed for their characterization. One of them established for their identification, at the nucleosidic level, is the hyphenation of separation methods, such as liquid chromatography or capillary electrophoresis, to tandem mass spectrometry. However, to our knowledge, no software is yet available for the untargeted identification of RNA post-transcriptional modifications from MS/MS data-dependent acquisitions. Thus, very long and tedious manual data interpretations are required. To meet the need of easier and faster data interpretation, a new user-friendly search engine, called Nucleos’ID, was developed for CE-MS/MS and LC–MS/MS users. Performances of this new software were evaluated on CE-MS/MS data from nucleoside analyses of already well-described Saccharomyces cerevisiae transfer RNA and Bos taurus total tRNA extract. All samples showed great true positive, true negative, and false discovery rates considering the database size containing all modified and unmodified nucleosides referenced in the literature. The true positive and true negative rates obtained were above 0.94, while the false discovery rates were between 0.09 and 0.17. To increase the level of sample complexity, untargeted identification of several RNA modifications from Pseudomonas aeruginosa 70S ribosome was achieved by the Nucleos’ID search following CE-MS/MS analysis.
Differentiation of Four Polyvinylidene Fluoride Polymers Based on Their End Groups by DART-FT-ICR MS and Kendrick Plots
Pierre Pacholski, Sébastien Schramm*, Frédéric Progent*, and Frédéric Aubriet*
J. Am. Soc. Mass Spectrom. 2023, 34, 10, 2278–2288 ; https://doi.org/10.1021/jasms.3c00202
Nowadays, synthetic polymers are produced and used in many materials for different applications. Matrix-assisted laser desorption/ionization or electrospray mass spectrometry are classically used to investigate them, but these techniques require sample preparation steps, which are not always suitable for the study of insoluble or formulated polymers. Alternatively, direct real-time (DART) ionization analysis may be conducted without sample preparation. Four polyvinylidene fluoride (PVDF) polymers involving the C2H2F2 repeating unit coming from different suppliers have been analyzed by DART Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) in negative-ion mode. The obtained mass spectra systematically displayed an oligomeric distribution between m/z 400 and 1300 of [M – H]−, [M + O2]•–, and [M + NO2]− ions. Kendrick plots were used to ease the identification of PVDF end-groups and establish a difference between the samples. Both commercial PVDF polymers shared the same α+ω end groups formula, which confirmed a similar polymerization process for their synthesis. The two other PVDFs were clearly different from the commercial ones by the occurrence of specific end-groups. MS/MS and MS3 experiments were conducted to obtain structural information on these end-groups.
