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Poster De Conférence Année : 2023

Off-line LC×SFC-HRMS/MS method development for the non-target analysis of depolymerized lignin

Résumé

Lignin is an abundant renewable resource that is mainly obtained as a by-product of the wood industry. Isolated lignin is typically considered a waste, and approximately only 2% is commercialized. However, because of the phenolic structure, it has high potential to be used even more as a natural resource for the production of bio-materials or isolation of various compounds. The BIOPOLIOL (Bio-based Polymers from Lignin Oligomers) project aims to valorize lignin to manufacture polyhydroxyurethanes (PHU) that could replace polyurethane (whose synthesis requires toxic isocyanates) foams applied in construction. In this joint project, lignin is depolymerized using soft catalysis into monomers and oligomers, which in turn are demethylated to increase the number of hydroxyl groups beneficial to the PHU synthesis. The complex mixture has to be analyzed to monitor and improve the valorization of the processed lignin via a powerful chromatographic and mass-spectrometric technique. Depolymerized lignin consists of numerous compounds that are often structurally highly similar, which means that one-dimensional chromatography might not provide a sufficiently high peak capacity for the full characterization. Therefore, in this study, an off-line comprehensive two-dimensional reversed-phase liquid chromatography combined with supercritical fluid chromatography (RPLCxSFC) was developed and applied for the non-target analysis of depolymerized lignin. In our knowledge, this is the first study to apply this kind of two-dimensional setup for the analysis of monomers but also oligomers in the organic fraction of processed lignin. A set of 33 lignin monomer standards were used to separately optimize the two dimensions, including the injection conditions. The theoretical 2D plots demonstrated that higher orthogonality could be obtained with RPLCxSFC than with RPLCxRPLC. In the case of RPLCxSFC, the highest orthogonality and best separation of compounds could be achieved with a set of pentafluorophenyl (PFP) and 1-aminoanthracene (1-AA) columns in the two dimensions. In addition to optimizing the chromatographic separation, mass-spectrometric (MS) detection was optimized to suit the method and sample. In our knowledge, this is the first time that MS has been applied with the RPLCxSFC analysis of depolymerized lignin. The same lignin monomers were used to study the influence of the SFC make-up additives on the ESI(-) signal. As the mass analyzer, a quadrupole time-of-flight mass spectrometer (qTOF-MS) was used, which enabled to determine the exact mass, formula, and double-bond equivalent (DBE) for the separated compounds. The overall peak capacity, detected compounds, and ability to distinguish compounds with the same m/z ratio was compared with optimized 1D-LC. A valuable advantage of using the RPLCxSFC method off-line (in addition to the much easier implementation compared to the on-line version and the possibility to change the injection solvent before the second dimension) is the possibility to perform high-resolution MS/MS. The application of fragmentation demonstrated that some compounds, which were separated thanks to the second dimension, had the same mass but a different fragmentation pattern. Therefore, this study demonstarted that an orthogonal two-dimensional separation with HRMS/MS detection is advantageous for the comprehensive non-target analysis of depolymerized lignin.
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Dates et versions

hal-04241269 , version 1 (13-10-2023)

Identifiants

  • HAL Id : hal-04241269 , version 1

Citer

Eliise Tammekivi, Magali Batteau, D. Laurenti, Hugo Lilti, Karine Faure. Off-line LC×SFC-HRMS/MS method development for the non-target analysis of depolymerized lignin. HPLC2023, Jun 2023, Dusseldorf, Germany. ⟨hal-04241269⟩
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