Characterization of model compounds of processed lignin and the lignome by using atmospheric pressure ionization tandem mass spectrometry

Haupert, Laura J.; Owen, Benjamin C.; Marcum, Christopher L.; Jarrell, Tiffany M.; Pulliam, Christopher J.; Amundson, Lucas M.; Narra, Padmaja; Aqueel, Mohammad Sabir; Parsell, Trenton H.; Abu‐Omar, Mahdi M.; Kenttämaa, Hilkka I.

doi:10.1016/j.fuel.2011.12.015

Cited by 50 publications

(98 citation statements)

References 32 publications

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“…When the model compounds were studied by traditional negative mode APCI ionization (methanol and water as solvents), they gave ions with poor abundances. The lack in sensitivity and the weak observed fragmentation make this a poor ionization method for the characterization of lignin degradation products …”

Section: Atmospheric Pressure Ionization Ms Methods As Powerful Toolsmentioning

confidence: 99%

“…Using the model compounds, Haupert et al have shown that it was possible to use ESI‐MS (+ion mode) doped with sodium chloride, to generate abundant [M + Na] + sodiated molecules without any fragmentation. This approach allowed the direct determination of the molecular weights of the lignin degradation products in mixtures . However, as expected, no structural information could be obtained by examining the CID‐MS/MS of the sodiated molecules using either triple quadrupole or QIT tandem mass spectrometric instruments because the sodiated molecules are known not to fragment during MS/MS analysis.…”

Section: Atmospheric Pressure Ionization Ms Methods As Powerful Toolsmentioning

confidence: 99%

“…The CID‐MS n analysis of this series of precursor deprotonated molecules established the connectivities between precursor and product ions; these were obtained by measuring multiple consecutive ion isolation and CID‐MS n (up to MS 7 ). This methodology has since been found to improve significantly the information that can be obtained by mass spectrometric analysis for lignin degradation products and lignome (Table ) …”

Section: Atmospheric Pressure Ionization Ms Methods As Powerful Toolsmentioning

confidence: 99%

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

et al. 2015

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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.

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Section: Atmospheric Pressure Ionization Ms Methods As Powerful Toolsmentioning

confidence: 99%

Section: Atmospheric Pressure Ionization Ms Methods As Powerful Toolsmentioning

confidence: 99%

Section: Atmospheric Pressure Ionization Ms Methods As Powerful Toolsmentioning

confidence: 99%

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

et al. 2015

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“…[43] Further, this method was shown to be amenable to high-performance liquid chromatographic separation, which opens the door for the separation of complex mixtures prior to mass spectrometric analysis. The ions were generated by using negative-ion mode electrospray ionizationd oped with NaOH, as this method was previously demonstrated to produce only deprotonated molecules for different phenolic analytes at almost equali onization efficiencies.…”

Section: Introductionmentioning

confidence: 99%

A Fundamental Tandem Mass Spectrometry Study of the Collision‐Activated Dissociation of Small Deprotonated Molecules Related to Lignin

et al. 2016

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The collision-activated fragmentation pathways and reaction mechanisms of 34 deprotonated model compounds representative of lignin degradation products were explored experimentally and computationally. The compounds were evaporated and ionized by using negative-ion mode electrospray ionization doped with NaOH to produce abundant deprotonated molecules. The ions were isolated and subjected to collision-activated dissociation (CAD). Their fragment ions were then isolated and also subjected to CAD. This was repeated until no further fragmentation was observed (up to MS ). This approach enabled the identification of characteristic reaction pathways and delineation of reasonable fragmentation mechanisms for deprotonated molecules containing various functional groups. The varying fragmentation patterns observed for different types of compounds allow for the identification of the functionalities in these compounds. This information was utilized to identify the presence of specific functionalities and their combinations in molecules in an organosolv lignin sample.

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“…Negative ion mode electrospray ionization (ESI) with sodium hydroxide dopant has been identified as the best ionization method for degraded lignin as it exclusively forms deprotonated molecules with no fragmentation for lignin model compounds [11]. Other ionization methods, such as positive ion mode ESI or atmospheric pressure chemical ionization (APCI), either cause extensive fragmentation or form multiple ion types for each compound [11]. When used in HPLC/ tandem mass spectrometry experiments, negative ion mode ESI facilitates the analysis of complex lignin degradation product mixtures [12,13].…”

Section: Introductionmentioning

confidence: 99%

Identification of the Phenol Functionality in Deprotonated Monomeric and Dimeric Lignin Degradation Products via Tandem Mass Spectrometry Based on Ion–Molecule Reactions with Diethylmethoxyborane

Zhu

Max

Marcum

et al. 2016

J. Am. Soc. Mass Spectrom.

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Characterization of model compounds of processed lignin and the lignome by using atmospheric pressure ionization tandem mass spectrometry

Cited by 50 publications

References 32 publications

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

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

A Fundamental Tandem Mass Spectrometry Study of the Collision‐Activated Dissociation of Small Deprotonated Molecules Related to Lignin

Identification of the Phenol Functionality in Deprotonated Monomeric and Dimeric Lignin Degradation Products via Tandem Mass Spectrometry Based on Ion–Molecule Reactions with Diethylmethoxyborane

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