Lignin is the most abundant natural resource of aromatic moieties and the second most abundant natural biopolymer. Analytical techniques that obtain as much information as possible on the exact structural content of lignin species are essential for developing efficient processes that transform highly complex lignin wastes into value chemicals and biofuels. For mass spectrometric analysis of lignin samples, usually electrospray ionization, atmospheric pressure chemical ionization, or atmospheric pressure photoionization are used as ionization techniques. Matrix-assisted laser desorption/ionization (MALDI) is less frequently applied but offers a much more rapid screening option for lignin mixtures. In this study, we compared several common MALDI matrices for analysis of alkali lignin and discovered that different chemical matrices exhibited very different ionization efficiencies and selectivity with respect to the structures of the lignin-related compounds as well as the presence of heteroatoms. Importantly, the results highlight that the choice of matrix strongly determines the analytical coverage of molecular species in the complex lignin degradation mixtures.
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Calvo-Flores FG, Dobado JA. Lignin as renewable raw material. ChemSusChem. 2010;3:1227–35. https://doi.org/10.1002/cssc.201000157.
Tolbert A, Akinosho H, Khunsupat R, Naskar AK, Ragauskas AJ. Characterization and analysis of the molecular weight of lignin for biorefining studies. Biofuels Bioprod Biorefin. 2014;8:836–56. https://doi.org/10.1002/bbb.1500.
De Wild PJ, Huijgen WJJ, Gosselink RJA. Lignin pyrolysis for profitable lignocellulosic biorefineries. Biofuels Bioprod Biorefin. 2014;8:645–57. https://doi.org/10.1002/bbb.1474.
Li C, Zhao X, Wang A, Huber GW, Zhang T. Catalytic transformation of lignin for the production of chemicals and fuels. Chem Rev. 2015;115:11559–624. https://doi.org/10.1021/acs.chemrev.5b00155.
Sticklen MB. Plant genetic engineering for biofuel production: towards affordable cellulosic ethanol. Nat Rev Genet. 2008;9:433–43. https://doi.org/10.1038/nrg2336.
Simmons BA, Loqué D, Ralph J. Advances in modifying lignin for enhanced biofuel production. Curr Opin Plant Biol. 2010;13:313–20. https://doi.org/10.1016/j.pbi.2010.03.001.
Ragauskas AJ, Beckham GT, Biddy MJ, Chandra R, Chen F, Davis MF, et al. Lignin valorization: improving lignin processing in the biorefinery. Science. 2014;80(344):1246843. https://doi.org/10.1126/science.1246843.
Qi Y, Volmer DA. Rapid mass spectral fingerprinting of complex mixtures of decomposed lignin: data-processing methods for high-resolution full-scan mass spectra. Rapid Commun Mass Spectrom accepted. 2018. https://doi.org/10.1002/rcm.8254.
Bozell JJ, O’Lenick CJ, Warwick S. Biomass fractionation for the biorefinery: heteronuclear multiple quantum coherence-nuclear magnetic resonance investigation of lignin isolated from solvent fractionation of switchgrass. J Agric Food Chem. 2011;59:9232–42. https://doi.org/10.1021/jf201850b.
Hanson SK, Baker RT, Gordon JC, Scott BL, Thorn DL. Aerobic oxidation of lignin models using a base metal vanadium catalyst. Inorg Chem. 2010;49:5611–8. https://doi.org/10.1021/ic100528n.
Hasegawa I, Inoue Y, Muranaka Y, Yasukawa T, Mae K. Selective production of organic acids and depolymerization of lignin by hydrothermal oxidation with diluted hydrogen peroxide. Energy Fuel. 2011;25:791–6. https://doi.org/10.1021/ef101477d.
Fox RH, Myers RJK, Vallis I. The nitrogen mineralization rate of legume residues in soil as influenced by their polyphenol, lignin, and nitrogen contents. Plant Soil. 1990;129:251–9. https://doi.org/10.1007/BF00032420.
Tu L, Hu H, Chen G, Peng Y, Xiao Y, Hu T, et al. Nitrogen addition significantly affects forest litter decomposition under high levels of ambient nitrogen deposition. PLoS One. 2014;9:e88752.
Brinkmann K, Blaschke L, Polle A Comparison of different methods for lignin determination as a basis for calibration of near-infrared reflectance spectroscopy and implications of lignoproteins. J Chem Ecol 28:2483–2501 . doi: https://doi.org/10.1023/A:1021484002582.
Qi Y, O’Connor PB. Data processing in Fourier transform ion cyclotron resonance mass spectrometry. Mass Spectrom Rev. 2014;33:333–52. https://doi.org/10.1002/mas.21414.
Qi Y, Hempelmann R, Volmer DA. Two-dimensional mass defect matrix plots for mapping genealogical links in mixtures of lignin depolymerisation products. Anal Bioanal Chem. 2016;408:4835–43. https://doi.org/10.1007/s00216-016-9598-5.
Qi Y, Hempelmann R, Volmer DA. Shedding light on the structures of lignin compounds: photo-oxidation under artificial UV light and characterization by high resolution mass spectrometry. Anal Bioanal Chem. 2016;408:8203–10. https://doi.org/10.1007/s00216-016-9928-7.
Morreel K, Kim H, Lu F, Dima O, Akiyama T, Vanholme R, et al. Mass spectrometry-based fragmentation as an identification tool in lignomics. Anal Chem. 2010;82:8095–105. https://doi.org/10.1021/ac100968g.
Jarrell TM, Marcum CL, Sheng H, Owen BC, O’Lenick CJ, Maraun H, et al. Characterization of organosolv switchgrass lignin by using high performance liquid chromatography/high resolution tandem mass spectrometry using hydroxide-doped negative-ion mode electrospray ionization. Green Chem. 2014;16:2713–27. https://doi.org/10.1039/C3GC42355G.
Owen BC, Haupert LJ, Jarrell TM, Marcum CL, Parsell TH, Abu-Omar MM, et al. High-performance liquid chromatography/high-resolution multiple stage tandem mass spectrometry using negative-ion-mode hydroxide-doped electrospray ionization for the characterization of lignin degradation products. Anal Chem. 2012;84:6000–7. https://doi.org/10.1021/ac300762y.
Hughey CA, Rodgers RP, Marshall AG. Resolution of 11 000 compositionally distinct components in a single electrospray ionization Fourier transform ion cyclotron resonance mass spectrum of crude oil. Anal Chem. 2002;74:4145–9. https://doi.org/10.1021/ac020146b.
Hertkorn N, Frommberger M, Witt M, Koch BP, Schmitt-Kopplin P, Perdue EM. Natural organic matter and the event horizon of mass spectrometry. Anal Chem. 2008;80:8908–19. https://doi.org/10.1021/ac800464g.
Cho Y, Na J-G, Nho N-S, Kim S, Kim S. Application of saturates, aromatics, resins, and asphaltenes crude oil fractionation for detailed chemical characterization of heavy crude oils by Fourier transform ion cyclotron resonance mass spectrometry equipped with atmospheric pressure photoionization. Energy Fuel. 2012;26:2558–65. https://doi.org/10.1021/ef201312m.
Barrow MP, Witt M, Headley JV, Peru KM. Athabasca oil sands process water: characterization by atmospheric pressure photoionization and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Anal Chem. 2010;82:3727–35. https://doi.org/10.1021/ac100103y.
Headley JV, Peru KM, Barrow MP. Advances in mass spectrometric characterization of naphthenic acids fraction compounds in oil sands environmental samples and crude oil-a review. Mass Spectrom Rev. 2015;35:311–28. https://doi.org/10.1002/mas.21472.
Headley JV, Peru KM, Barrow MP. Mass spectrometric characterization of naphthenic acids in environmental samples: a review. Mass Spectrom Rev. 28:121–34. https://doi.org/10.1002/mas.20185.
Qi Y, Bortoli S, Volmer DA. Detailed study of cyanobacterial microcystins using high performance tandem mass spectrometry. J Am Soc Mass Spectrom. 2014;25:1253–62. https://doi.org/10.1007/s13361-014-0893-0.
Qi Y, Volmer DA. Structural analysis of small to medium-sized molecules by mass spectrometry after electron-ion fragmentation (ExD) reactions. Analyst. 2016;141:794–806. https://doi.org/10.1039/c5an02171e.
Kew W, Mackay CL, Goodall I, Clarke DJ, Uhrín D. Complementary ionization techniques for the analysis of scotch whisky by high resolution mass spectrometry. Anal Chem. 2018;90:11265–72. https://doi.org/10.1021/acs.analchem.8b01446.
Blackburn JWT, Kew W, Graham MC, Uhrín D. Laser desorption/ionization coupled to FTICR mass spectrometry for studies of natural organic matter. Anal Chem. 2017;89:4382–6. https://doi.org/10.1021/acs.analchem.6b04817.
Kosyakov DS, Ul’yanovskii NV, Sorokina EA, Gorbova NS. Optimization of sample preparation conditions in the study of lignin by MALDI mass spectrometry. J Anal Chem. 2014;69:1344–50. https://doi.org/10.1134/S1061934814140056.
Kosyakov DS, Anikeenko EA, Ul’yanovskii NV, Khoroshev OY, Shavrina IS, Gorbova NS. Ionic liquid matrices for MALDI mass spectrometry of lignin. Anal Bioanal Chem. 2018. https://doi.org/10.1007/s00216-018-1353-7.
Albishi T, Mikhael A, Shahidi F, Fridgen TD, Delmas M, Banoub J. Top-down lignomic matrix-assisted laser desorption/ionization time-of-flight tandem mass spectrometry analysis of lignin oligomers extracted from date palm wood. Rapid Commun Mass Spectrom. 2019;33:539–60. https://doi.org/10.1002/rcm.8368.
Bowman AS, Asare SO, Lynn BC. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis for characterization of lignin oligomers using cationization techniques and 2,5-dihydroxyacetophenone (DHAP) matrix. Rapid Commun Mass Spectrom. 2019;33:811–9. https://doi.org/10.1002/rcm.8406.
Kew W, Blackburn JWT, Clarke DJ, Uhrín D. Interactive van Krevelen diagrams – advanced visualisation of mass spectrometry data of complex mixtures. Rapid Commun Mass Spectrom. 2017;31:658–62. https://doi.org/10.1002/rcm.7823.
Moyer SC, Budnik BA, Pittman JL, Costello CE, O’Connor PB. Attomole peptide analysis by high-pressure matrix-assisted laser desorption/ionization Fourier transform mass spectrometry. Anal Chem. 2003;75:6449–54. https://doi.org/10.1021/ac034938x.
Lex A, Gehlenborg N, Strobelt H, Vuillemot R, Pfister H. UpSet: visualization of intersecting sets. IEEE Trans Vis Comput Graph. 2014;20:1983–92. https://doi.org/10.1109/TVCG.2014.2346248.
Qi Y, Luo R, Schrader W, Volmer DA. Application of phase correction to improve the characterization of photooxidation products of lignin using 7 Tesla Fourier-transform ion cyclotron resonance mass spectrometry. FACETS. 2017;2:461–75. https://doi.org/10.1139/facets-2016-0069.
Lange H, Decina S, Crestini C. Oxidative upgrade of lignin – recent routes reviewed. Eur Polym J. 2013;49:1151–73. https://doi.org/10.1016/j.eurpolymj.2013.03.002.
Gellerstedt G. Softwood kraft lignin: raw material for the future. Ind Crop Prod. 2015;77:845–54. https://doi.org/10.1016/j.indcrop.2015.09.040.
Bennett KL, Kussmann M, Mikkelsen M, Roepstorff P, Björk P, Godzwon M, et al. Chemical cross-linking with thiol-cleavable reagents combined with differential mass spectrometric peptide mapping—a novel approach to assess intermolecular protein contacts. Protein Sci. 2000;9:1503–18. https://doi.org/10.1110/ps.9.8.1503.
Huwiler KG, Mosher DF, Vestling MM. Optimizing the MALDI-TOF-MS observation of peptides containing disulfide bonds. J Biomol Tech. 2003;14:289–97.
Chendo C, Rollet M, Phan TNT, Viel S, Gigmes D, Charles L. Successful MALDI mass spectrometry of poly(4-vinylpyridine) using a solvent-free sample preparation. Int J Mass Spectrom. 2015;376:90–6. https://doi.org/10.1016/j.ijms.2014.12.004.
Zhang Y, Lu H. Enhanced ionization of phosphatidylcholines during MALDI mass spectrometry using DCTB as matrix. Chinese J Chem. 2012;30:2091–6. https://doi.org/10.1002/cjoc.201200600.
Lou X, de Waal BFM, van Dongen JLJ, Vekemans JAJM, Meijer EW. A pitfall of using 2-[(2E)-3-(4-tert-butylphenyl)-2-methylprop-2-enylidene] malononitrile as a matrix in MALDI TOF MS: chemical adduction of matrix to analyte amino groups. J Mass Spectrom. 2010;45:1195–202. https://doi.org/10.1002/jms.1814.
Purcell JM, Merdrignac I, Rodgers RP, Marshall AG, Gauthier T, Guibard I. Stepwise structural characterization of asphaltenes during deep hydroconversion processes determined by atmospheric pressure photoionization (APPI) Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Energy Fuel. 2010;24:2257–65. https://doi.org/10.1021/ef900897a.
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Qi, Y., Volmer, D.A. Chemical diversity of lignin degradation products revealed by matrix-optimized MALDI mass spectrometry. Anal Bioanal Chem 411, 6031–6037 (2019). https://doi.org/10.1007/s00216-019-01984-y
- Lignin degradation products
- Mass spectrometry
- Chemical matrices