Utilising Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to track the oxidation of lignin by an alkaliphilic laccase

• Published in: Analyst (London) 2024-04, Vol.149 (8), p.2399-2411
• Main Authors: Towle, Zak, Cruickshank, Faye, Mackay, C. Logan, Clarke, David J, Horsfall, Louise E
• Format: Article
• Language: English
• Subjects: Biopolymers; Chemical analysis; Chemistry; Complexity; Cyclotron resonance; Cyclotrons; Fine chemicals; Fourier Analysis; Fourier transforms; Furans; Gas Chromatography-Mass Spectrometry; Laccase; Laccase - metabolism; Lignans; Lignin; Lignin - chemistry; Lignin - metabolism; Mass spectrometry; Mass Spectrometry - methods; NMR; Nuclear magnetic resonance; Oxidation; Raw materials; Scientific imaging
• ISSN: 0003-2654; 1364-5528
• DOI: 10.1039/d4an00124a

Lignin is a complex heteroaromatic polymer which is one of the most abundant and diverse biopolymers on the planet. It comprises approximately one third of all woody plant matter, making it an attractive candidate as an alternative, renewable feedstock to petrochemicals to produce fine chemicals. However, the inherent complexity of lignin makes it difficult to analyse and characterise using common analytical techniques, proving a hindrance to the utilisation of lignin as a green chemical feedstock. Herein we outline the tracking of lignin degradation by an alkaliphilic laccase in a semi-quantitative manner using a combined chemical analysis approach using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to characterise shifts in chemical diversity and relative abundance of ions, and NMR to highlight changes in the structure of lignin. Specifically, an alkaliphilic laccase was used to degrade an industrially relevant lignin, with compounds such as syringaresinol being almost wholly removed (95%) after 24 hours of treatment. Structural analyses reinforced these findings, indicating a >50% loss of NMR signal relating to β-β linkages, of which syringaresinol is representative. Ultimately, this work underlines a combined analytical approach that can be used to gain a broader semi-quantitative understanding of the enzymatic activity of laccases within a complex, non-model mixture. Herein, we outline a method to semi-quantitatively analyse and track the enzymatic oxidation of lignin using high resolution mass spectrometry.