Lignin Degradation & Analysis

Lignin is a fundamental building block and structural support of vascular plants’ tissues and algae contributing up to 30% of their biomass.

Thus, lignin is one of the most abundant sources of renewable carbon, a potential feedstock for renewable liquid fuel and valuable phenolic chemicals. Various approaches to transform lignin into commercially beneficial substances are being investigated including extraction as well as thermal, catalytic and biological degradation. In order to pursue an efficient use of lignin, full understanding of its complex heteropolymeric structure is essential in a variety of feedstocks including native and processed lignin.

While working on biomass, I have noted the incompleteness of carbonaceous materials’ characterization using traditional chromatographic methods. In addition, such methods are tedious as well as time- and cost demanding. Thus, I have broadened my research portfolio by developing comprehensive thermal desorption – pyrolysis with GC detection (TD-Pyr), the method which at low temperatures evolves and characterizes volatile species while the pyrolytic temperatures break the remainder of organics into smaller components providing valuable structural information on non-GC-elutable (polymer) components. Furthermore, while combining this method with thermal carbon analysis (TCA) we can close mass balance not only for the whole sample but also within each temperature fraction, thus quantitatively verifying the obtained characterization.

Besides carbon mass balance, the molecular weight distribution appears to be key to understanding the produced species. However, size exclusion methods have to be carefully validated to ensure an effective characterization of heteropolymeric lignin structure. Similarly, mass spectrometry can provide information on mass range, yet fragmentation, ionization suppression and formation of multiple charges may complicate the data interpretation – so, these phenomena must be investigated.

Relevant selected publications

• Andrianova, A., Di Prospero, T., Geib, C., Smoliakova, I., Kozliak, E., Kubatova, A. Electrospray ionization with high-resolution mass spectrometry as a tool for lignomics: Lignin mass spectrum deconvolution. J. Am. S. Mass Spectrom, 2018 29(5), 1044-1059.
  DOI: 10.1007/s13361-018-1916-z
• Andrianova, A., Yeudakimenka, N., Lilak, S., Kozliak, E., Ugrinov, A., Sibi, M., Kubatova, A.. Size exclusion chromatography of lignin: The mechanistic aspects and elimination of undesired secondary interactions. J. Chromatogr. A, 2017, 1534, 101-110.
  DOI: 10.1016/j.chroma.2017.12.051
• Brzonova, I., Ji, Y., Kozliak, E., Andrianova, A. A., LaVallie, A., Kubatova, A. Production of lignin-based insoluble polymers (anionic hydrogels) by C. versicolor. Science. Rep. 2017. 7(1), 17507.
  DOI: 10.1038/s41598-017-17696-1
• Voeller, K., Bilek, H., Kreft, J., Dostalkova, A., Kozliak, E., Kubatova, A. Thermal carbon analysis enabling the comprehensive characterization of lignin and its degradation products. ACS Sustain. Chem. Eng. 2017, 5, 1110334-10341
  DOI: 10.1021/acssuschemeng.7b02392

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