Matrix-assisted laser desorption/ionization time-of-flight/time-of-flight tandem mass spectrometry (negative ion mode) of French Oak lignin: A novel series of lignin and tricin derivatives attached to carbohydrate and shikimic acid moieties.

RATIONALE: We report the top-down lignomic analysis of the virgin released lignin (VRL) small oligomers obtained from French Oak wood. METHODS: We have used MALDI-TOF-MS in the negative ion mode for the analysis of the complex mixture of lignin oligomers extracted from French Oak wood. High-energy CID-TOF/TOF-MS/MS analyses were used to support the postulated precursor ion structures. RESULTS: Twenty compounds were identified using MALDI-TOF-MS/MS of the VRL extracted from French Oak wood: seven tricin derivatives and/or flavonoids, three syringylglycerol derivatives, two syringol derivatives, two flavonolignin derivatives, and six miscellaneous compounds: luteoferol, lariciresinol isomer, 5-hydroxy guaiacyl derivative, syringyl -C10 H10 O2 dimer, trihydroxy benzaldehyde derivative, and aryl tetralin lignan derivative. Most of the identified compounds were in the form of carbohydrate and/or shikimic acid complexes. CONCLUSIONS: The analysis of this complex mixture led to the identification of a series of lignin dimers, novel lignin-carbohydrate complexes (LCC), and unique tricin derivatives linked to different types of carbohydrates and shikimic acid moieties. This finding supports the presence of lignin-carbohydrate complexes in the isolated VRL. These analyses also showed that French Oak lignin is abundant in syringol moieties present in the lignin syringyl units or tricin derivatives. Moreover, the identification of some lignin-carbohydrate and/or flavonoid-shikimic acid complexes could provide new insight into the relationship between the biosynthesis of lignin and tricin.

Top-down lignomics analysis of the French pine lignin by atmospheric pressure photoionization quadrupole time-of-flight tandem mass spectrometry: Identification of a novel series of lignin-carbohydrate complexes.

RATIONALE: We report the top-down lignomics analysis of the virgin released lignin (VRL) extracted from French pine wood by using atmospheric pressure photoionization quadrupole time-of-flight mass spectrometry (APPI-QqTOF-MS) and low-energy collision-induced dissociation tandem mass spectrometry (CID-MS/MS). METHODS: We used APPI-QqTOF-MS (positive ion mode) for the analysis of the complex mixture of VRL oligomers extracted from French pine wood. Some of the major precursor ions were fished out from the complex VRL oligomeric mixture and subjected to low-energy CID-MS/MS analyses. RESULTS: Fourteen novel lignin-carbohydrate complexes (LCCs) were identified using APPI-QqTOF-MS/MS of the very complex mixture of virgin released lignins (VRLs), directly extracted from French pine wood without any kind of purification. The low-energy CID-MS/MS analyses allowed us to establish the fragmentation patterns of the precursor ions and to identify the complex structures of the identified LCC molecules. These novel identified series of LCCs were composed of one or two carbohydrate rings to which one, two, or three lignin units were covalently attached. In addition to the fourteen LCCs, acetyl eugenol was identified in the French pine VRL sample. The identification of acetyl eugenol indicates possible lignin degradation and modification (acetylation) during the mild extraction method developed by the Compagnie Industrielle de la Matière Végétale (CIMV). CONCLUSIONS: The top-down lignomics analysis of the French pine VRLs using APPI-QqTOF-MS and low energy CID-MS/MS allowed us to identify acetylated eugenol and a novel series of fourteen LCCs. These series of LCCs provide evidence that lignins are covalently linked to carbohydrates in the native wood network and act as cross-linkers between cellulose and hemicellulose components of wood.

Top-down lignomic matrix-assisted laser desorption/ionization time-of-flight tandem mass spectrometry analysis of lignin oligomers extracted from date palm wood.

RATIONALE: We report for the first time the top-down lignomic analysis of the virgin released lignin (VRL) oligomers obtained from the Saudi date palm wood (SDPW), using a matrix-assisted laser desorption/ionization time-of-flight/time-of-flight (MALDI-TOF/TOF) instrument. In addition, we are proposing new collision-induced dissociation tandem mass spectrometry (CID-MS/MS) fragmentation routes for this series of unreported VRL oligomers. METHODS: We have used direct MALDI-TOF-MS analysis of the mixture of lignin oligomers without any chromatographic pre-separation. High-energy CID-MS/MS analyses were used to confirm the precursor ion structures. RESULTS: Six protonated lignin oligomer molecules were identified: [C19 H24 O8  + H]+ as H(8-O-4')G; [C50 H52 O19  + H]+ as H(8-O-4')H(8-O-4'')S(8-O-4''')S(8-O-4'''')G; [C58 H54 O18 + H]+ as H(8-O-4')H(8-O-4'')H(8-O-4''')G(8-O-4'''')S(8-O-4''''')G; [C58 H54 O19  + H]+ as H(8-O-4')H(8-O-4'')H(8-O-4''')S(8-O-4'''')S(8-O-4''''')G; [C61 H68 O25  + H]+ as H(8-O-4')G(8-O-4'')G(8-O-4''')S(8-O-4'''')S(8-O-4''''')G; and [C61 H68 O26  + H]+ as C(8-O-4')G(8-O-4'')G(8-O-4''')S(8-O-4'''')S(8-O-4''''')G units (H = coniferyl, S = sinapyl, and G = p-coumaryl). Two distonic cations were identified as [C39 H43 O15  + H]+• and [C40 H43 O16  + H]+• deriving from two tetrameric lignin oligomers. The high-energy MS/MS analyses allowed the confirmation of the proposed structures of this series of lignin oligomers. CONCLUSIONS: To our knowledge, this is the first elucidation of the lignin structure of the Saudi seedling date palm wood that was accomplished using a top-down lignomic strategy that has not previously been published. The complex high-energy CID-MS/MS fragmentations presented herein are novel and have never been described before.

Renewable and high-purity hydrogen from lignocellulosic biomass in a biorefinery approach.

Unprecedented efforts are being deployed to develop hydrogen production from bioresources in a circular economy approach, yet their implementation remains scarce. Today's Challenges are associated with the shortage in the value chain, lack of large-scale production infrastructure, high costs, and low efficiency of current solutions. Herein, we report a hydrogen production route from cellulose pulp, integrating biomass fractionation and gasification in a biorefinery approach. Softwood sawdust undergoes formic acid organosolv treatment to extract cellulose, followed by steam gasification. High-purity hydrogen-rich syngas at a concentration of 56.3 vol% and a yield of 40 gH2/kgcellulose was produced. Char gasification offers the advantage of producing free-tar syngas reducing cleaning costs and mitigating downstream issues. A comprehensive assessment of mass and energy balance along the hydrogen value chain revealed an efficiency of 26.5% for hydrogen production, with an energy requirement of 111.1 kWh/kgH2. Optimizing solvent recovery and valorization of other constituents as added-value products in a biorefinery approach would further improve the process and entice its industrial takeoff.

Towards efficient and greener processes for furfural production from biomass: A review of the recent trends.

As mentioned in several recent reviews, biomass-based furfural is attracting increasing interest as a feasible alternative for the synthesis of a wide range of non-petroleum-derived compounds. However, the lack of environmentally friendly, cost-effective, and sustainable industrial procedures is still evident. This review describes the chemical and biological routes for furfural production. The mechanisms proposed for the chemical transformation of xylose to furfural are detailed, as are the current advances in the manufacture of furfural from biomass. The main goal is to overview the different ways of improving the furfural synthesis process. A pretreatment process, particularly chemical and physico-chemical, enhances the digestibility of biomass, leading to the production of >70 % of available sugars for the production of valuable products. The combination of heterogeneous (zeolite and polymeric solid) catalyst and biphasic solvent system (water/GVL and water/CPME) is regarded as an attractive approach, affording >75 % furfural yield for over 80 % of selectivity with the possibility of catalyst reuse. Microwave heating as an activation technique reduces reaction time at least tenfold, making the process more sustainable. The state of the art in industrial processes is also discussed. It shows that, when sulfuric acid is used, the furfural yields do not exceed 55 % for temperatures close to 180 °C. However, the MTC process recently achieved an 83 % yield by continuously removing furfural from the liquid phase. Finally, the CIMV process, using a formic acid/acetic acid mixture, has been developed. The economic aspects of furfural production are then addressed. Future research will be needed to investigate scaling-up and biological techniques that produce acceptable yields and productivities to become commercially viable and competitive in furfural production from biomass.

Structural determination by atmospheric pressure photoionization tandem mass spectrometry of some compounds isolated from the SARA fractions obtained from bitumen.

We have identified compounds obtained from the SARA fractions of bitumen by using atmospheric pressure photoionization mass spectrometry and low-energy collision tandem mass spectrometric analyses with a QqToF-MS/MS hybrid instrument. The identified compounds were isolated from the maltene saturated oil and the aromatic fractions of the SARA components of a bitumen. The QqToF instrument had sufficient mass resolution to provide accurate molecular weight information and to enhance the tandem mass spectrometry results. The APPI-QqToF-MS analysis of the separated compounds showed a series of protonated molecules [M + H](+) and molecular ions [M](+▪) of the same mass but having different chemical structures, in the maltene saturated oil and the aromatic SARA fractions. These isobaric ions were a molecular ion [M2 ](+▪) at m/z 418.2787 and a protonated molecule [M5 + H](+) at m/z 287.1625 in the saturated oil fraction, and molecular ions [M6 ](+▪) at m/z 418.1584 and [M7 ](+▪) at m/z 287.1285 in the aromatic fraction. The identification of this series of chemical compounds was achieved by performing CID-MS/MS analyses of the molecular ions [M](+▪) ([M1 ](+▪) at m/z 446. 2980, [M2 ](+▪) at m/z 418.2787, [M3 ](+▪) at m/z 360.3350 and [M4 ](+▪) at m/z 346.2095) in the saturated oil fraction and of the [M5 + H](+) ion at m/z 287.1625 also in the saturated oil fraction. The observed CID-MS/MS fragmentation differences were explained by proposed different breakdown processes of the precursor ions. The presented tandem mass spectrometric study shows the capability of MS/MS experiments to differentiate between different classes of chemical compounds of the SARA components of bitumen and to explain the reasons for the observed mass spectrometric differences. However, greater mass resolution than that provided by the QqToF-MS/MS instrument would be required for the analysis of the asphaltene fraction of bitumen.

Top-down lignomics analysis of the French oak lignin by atmospheric pressure photoionization and electrospray ionization quadrupole time-of-flight tandem mass spectrometry: Identification of a novel series of lignans.

We report herein the top-down lignomic analysis of virgin released lignin (VRL) extracted from the French oak wood using atmospheric pressure photoionization quadrupole orthogonal time-of-flight mass spectrometry (APPI-QqTOF-MS) (+ ion mode). Eight major protonated lignin oligomers were identified using the APPI-QqTOF-MS/MS of this complex VRL mixture without any kind of purification. This series of protonated oligomer ions were identified as neolignan cedrusin (1), five different aryltetralin lignans dimers (2-6), one lignan-dehydroshikimic acid complex (7), and a lignan trimer (8). Similarly, electrospray ionization (ESI)-QqTOF-MS (+ ion mode) allowed us to identify three extra aryltetralin lignan derivatives (9-11). The Kendrick mass defect analysis was used for the simplification of this complex APPI-QqTOF-MS into a compositional map, which displayed clustering points of associated ions possessing analogous elemental composition. This series of novel protonated molecules were selected and subjected to low-energy collision-induced dissociation (CID)-MS/MS analyses. The obtained gas-phase fragmentation patterns helped to tentatively assign their most likely structures. Also, it was found that the use of different APPI and ESI ambient ionization techniques enhances the ionization of different types of lignin oligomers.

A critique on the structural analysis of lignins and application of novel tandem mass spectrometric strategies to determine lignin sequencing.

This review is devoted to the application of MS using soft ionization methods with a special emphasis on electrospray ionization, atmospheric pressure photoionization and matrix-assisted laser desorption/ionization MS and tandem MS (MS/MS) for the elucidation of the chemical structure of native and modified lignins. We describe and critically evaluate how these soft ionization methods have contributed to the present-day knowledge of the structure of lignins. Herein, we will introduce new nomenclature concerning the chemical state of lignins, namely, virgin released lignins (VRLs) and processed modified lignins (PML). VRLs are obtained by liberation of lignins through degradation of vegetable matter by either chemical hydrolysis and/or enzymatic hydrolysis. PMLs are produced by subjecting the VRL to a series of further chemical transformations and purifications that are likely to alter their original chemical structures. We are proposing that native lignin polymers, present in the lignocellulosic biomass, are not made of macromolecules linked to cellulose fibres as has been frequently reported. Instead, we propose that the lignins are composed of vast series of linear related oligomers, having different lengths that are covalently linked in a criss-cross pattern to cellulose and hemicellulose fibres forming the network of vegetal matter. Consequently, structural elucidation of VRLs, which presumably have not been purified and processed by any other type of additional chemical treatment and purification, may reflect the structure of the native lignin. In this review, we present an introduction to a MS/MS top-down concept of lignin sequencing and how this technique may be used to address the challenge of characterizing the structure of VRLs. Finally, we offer the case that although lignins have been reported to have very high or high molecular weights, they might not exist on the basis that such polymers have never been identified by the mild ionizing techniques used in modern MS.

Elucidation of the complex molecular structure of wheat straw lignin polymer by atmospheric pressure photoionization quadrupole time-of-flight tandem mass spectrometry.

Wheat straw lignin was extracted using the novel CIMV procedure which selectively separates the cellulose, hemicelluloses and lignin. Solid-state (13)C NMR experiments using cross polarization/magic angle spinning (CP/MAS) were carried out on the extracted wheat straw lignin and some structural indices were revealed. Atmospheric pressure photoionization mass spectrometry (APPI-MS) has proven to be a powerful analytical tool capable of ionizing small to large lignin oligomers, which cannot be ionized efficiently by atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI). The APPI mass spectra of the extracted wheat straw lignin were recorded in the positive and negative ion modes. Positive ion mode APPI-MS indicated the exact presence of 39 specific oligomeric ions. Negative ion APPI-MS indicated the additional presence of at least 18 specific oligomeric ions. The structural characterization of this novel and complete series of 57 specific related oligomers was achieved by calculating the exact molecular masses measured by high-resolution quadrupole time-of-flight mass spectrometry (QqToF-MS). Some oligomeric species photoionized in both the positive and negative ion modes to form the respective protonated and deprotonated molecules. Low-energy collision-induced dissociation tandem mass spectrometric analyses performed with a QqToF-MS/MS hybrid instrument provided unique dissociation patterns of the complete series of novel precursor ions. These MS/MS analyses provided diagnostic product ions, which enabled us to determine the exact molecular structures and arrangement of the selected 57 different related ionic species.