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

Albishi, Tasahil; Mikhael, Abanoub; Shahidi, Fereidoon; Fridgen, Travis D.; Delmas, M.; Banoub, Joseph

doi:10.1002/rcm.8368

Cited by 13 publications

(12 citation statements)

References 41 publications

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“…71 The distribution of these bonds in a lignin molecule is a key characteristic and significantly contributes to the observed chemistry. The presence of these weak and strong bonds opens the door to a description of lignin structure by clusters oligomeric units with ether and/or ester covalent links 87 that could be used to describe lignin thermal behavior. The widely accepted polymerization process for lignin construction involves oxidative radicalization of phenols, followed by combinatorial radical coupling.…”

Section: Lignin Structure Overviewmentioning

confidence: 99%

A Review on Lignin Liquefaction: Advanced Characterization of Structure and Microkinetic Modeling

Terrell

Dellon

Dufour

et al. 2019

Ind. Eng. Chem. Res.

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Lignin liquefaction microkinetics is a move toward a more first-principles (i.e., ab initio)-based understanding at the molecular level in reaction engineering. While the microkinetic modeling of reactions to obtain kinetic rate parameters of chemical reactions have been widely used in the field of gas phase combustion and heterogeneous catalysis, this approach has not been as thoroughly developed in the area of biomass thermochemical reactions (e.g., lignin pyrolysis, hydrothermal liquefaction). The difficulties in establishing the structure of complex heterogeneous materials, like lignin, is perhaps the main challenge in developing rational microkinetic descriptions of biomass thermochemical reactions. In this manuscript, we review the current state of the art and the challenges to develop microkinetic models for lignin liquefaction technologies (e.g., pyrolysis, hydrothermal liquefaction, solvolysis). A general strategy for the development of microkinetic models for lignin liquefaction technologies is discussed. The first hurdle is to obtain sufficiently rich experimental data of lignin underlying polymeric structure and methodologies to use this data to build realistic lignin structural representations. Some analytical techniques for lignin structural characterization and their associated data, as well as a correlation for calculating the degree of macromolecular lignin branching, are discussed. The presence of small lignin oligomeric structures and the role of these structures in lignin pyrolysis is also addressed. The ways in which elementary deconstruction and repolymerization reactions occur within this structure to form a liquid intermediate and how these deconstruction products continue to interact with each other until they are removed from the liquid intermediate is thoroughly discussed. Further, experimental work with model compounds and the effect of reaction parameters (e.g., temperature, pressure, vapor residence time) are reviewed. Another major challenge to develop microkinetic models of lignin liquefaction is to describe product removal mechanisms (e.g., evaporation, solubilization, thermal ejection) from the liquid intermediate. Group contribution methods are presented for estimation of thermophysical parameters, like normal boiling point and heat of vaporization for model structures. Once the products have been removed from the liquid intermediate, they continue reacting in the aerosol droplets, in vapor phase, or in the solvent depending on the liquefaction technology studied. These “secondary reactions” need to be included in realistic microkinetic models. Based on this review, we can state that with careful implementation, high-quality microkinetic models can be developed to simulate thermochemical lignin liquefaction.

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Section: Lignin Structure Overviewmentioning

confidence: 99%

A Review on Lignin Liquefaction: Advanced Characterization of Structure and Microkinetic Modeling

Terrell

Dellon

Dufour

et al. 2019

Ind. Eng. Chem. Res.

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“…An estimated list including in total 172 lignin‐related phenolic compounds was prepared based on previous reports (Table S81) . The estimated list included 43 monomers, 58 dimers, 40 trimers, 16 tetramers, 6 pentamers, and 7 hexamers, alongside their exact mass, chemical formula, RDB, type of lignin‐related phenolic compound, a compound label, a literature reference for all Los, and the name of the included LMs.…”

Section: Methodsmentioning

confidence: 99%

Nontargeted Analysis Strategy for the Identification of Phenolic Compounds in Complex Technical Lignin Samples

Prothmann

Hulteberg

et al. 2020

ChemSusChem

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Lignin is the second most abundant biopolymer in nature and a promising renewable resource for aromatic chemicals. For the understanding of different lignin isolation and conversion processes, the identification of phenolic compounds is of importance. However, given the vast number of possible chemical transformations, the prediction of produced phenolic structures is challenging and a nontargeted analysis method is therefore needed. In this study, a nontargeted analysis method has been developed for the identification of phenolic compounds by using an ultrahigh‐performance supercritical fluid chromatography–high‐resolution multiple stage tandem mass spectrometry method, combined with a Kendrick mass defect‐based classification model. The method is applied to a Lignoboost Kraft lignin (LKL), a sodium lignosulfonate lignin (SLS), and a depolymerized Kraft lignin (DKL) sample. In total, 260 tentative phenolic compounds are identified in the LKL sample, 50 in the SLS sample, and 77 in the DKL sample.

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“…Recently, the group performed a top-down sequencing of LOs extracted from date palm wood via MALDI-TOF analysis (Albishi et al, 2019). They identified six novel VRL oligomer molecules, describing their structure in detail via never-before-reported CID-MS/MS fragmentations.…”

Section: Matrix-assisted Laser Desorption/ Ionization Mass Spectrometry (Maldi-ms)mentioning

confidence: 99%

Mass spectrometry‐based methods for the advanced characterization and structural analysis of lignin: A review

Letourneau

Volmer

2021

Mass Spectrometry Reviews

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Lignin is currently one of the most promising biologically derived resources, due to its abundance and application in biofuels, materials and conversion to value aromatic chemicals. The need to better characterize and understand this complex biopolymer has led to the development of many different analytical approaches, several of which involve mass spectrometry and subsequent data analysis. This review surveys the most important analytical methods for lignin involving mass spectrometry, first looking at methods involving gas chromatography, liquid chromatography and then continuing with more contemporary methods such as matrix assisted laser desorption ionization and time-of-flight-secondary ion mass spectrometry. Following that will be techniques that directly ionize lignin mixtures-without chromatographic separation-using softer atmospheric ionization techniques that leave the lignin oligomers intact. Finally, ultra-high resolution mass analyzers such as FT-ICR have enabled lignin analysis without major sample preparation and chromatography steps. Concurrent with an increase in the resolution of mass spectrometers, there have been a wealth of complementary data analyses and visualization methods that have allowed researchers to probe deeper into the "lignome" than ever before. These approaches extract trends such as compound series and even important analytical information about lignin substructures without performing lignin degradation either chemically or during MS analysis. These innovative methods are paving the way for a more comprehensiveThis is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

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

Cited by 13 publications

References 41 publications

A Review on Lignin Liquefaction: Advanced Characterization of Structure and Microkinetic Modeling

A Review on Lignin Liquefaction: Advanced Characterization of Structure and Microkinetic Modeling

Nontargeted Analysis Strategy for the Identification of Phenolic Compounds in Complex Technical Lignin Samples

Mass spectrometry‐based methods for the advanced characterization and structural analysis of lignin: A review

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