Monitoring Molecular Weight Changes During Technical Lignin Depolymerization by Operando Attenuated Total Reflectance Infrared Spectroscopy and Chemometrics

Overview

Journal ChemSusChem

Specialty Chemistry

Date 2021 Nov 23

PMID 34812582

Citations 6

Authors

Khaled N M Khalili

Peter de Peinder

Jacqueline Donkers

Richard J A Gosselink

Pieter C A Bruijnincx

Bert M Weckhuysen

Affiliations

Soon will be listed here.

Abstract

Technical lignins are increasingly available at industrial scale, offering opportunities for valorization, such as by (partial) depolymerization. Any downstream lignin application requires careful tailoring of structural properties, such as molecular weight or functional group density, properties that are difficult to control or predict given the structure variability and recalcitrance of technical lignins. Online insight into changes in molecular weight (M ), to gauge the extent of lignin depolymerization and repolymerization, would be highly desired to improve such control, but cannot be readily provided by the standard ex-situ techniques, such as size exclusion chromatography (SEC). Herein, operando attenuated total reflectance infrared (ATR-IR) spectroscopy combined with chemometrics provided temporal changes in M during lignin depolymerization with high resolution. More specifically, ex-situ SEC-derived M and polydispersity data of kraft lignin subjected to aqueous phase reforming conditions could be well correlated with ATR-IR spectra of the reaction mixture as a function of time. The developed method showed excellent regression results and relative error, comparable to the standard SEC method. The method developed has the potential to be translated to other lignin depolymerization processes.

Citing Articles

A translatable IR-chemometrics model for the rapid prediction of structural and material properties of technical lignins.

Riddell L, de Peinder P, Lindner J, Meirer F, Bruijnincx P Nat Protoc. 2025; .

PMID: 40075188 DOI: 10.1038/s41596-025-01139-7.

Quantifying the Abundance of Alkane Moieties in Lignins with FTIR Spectroscopy and PLS Regression; Estimating Grafting Degree of Esterification.

Heen Blindheim F, Ruwoldt J ChemSusChem. 2024; 18(3):e202400938.

PMID: 39301760 PMC: 11789983. DOI: 10.1002/cssc.202400938.

Predicting Molecular Weight Characteristics of Reductively Depolymerized Lignins by ATR-FTIR and Chemometrics.

Riddell L, de Peinder P, Polizzi V, Vanbroekhoven K, Meirer F, Bruijnincx P ACS Sustain Chem Eng. 2024; 12(23):8968-8977.

PMID: 38872958 PMC: 11167637. DOI: 10.1021/acssuschemeng.4c03100.

Interfacial Adsorption of Oil-Soluble Kraft Lignin and Stabilization of Water-in-Oil Emulsions.

Ruwoldt J, Handiso B, Oksnes Dalheim M, Solberg A, Simon S, Syverud K Langmuir. 2024; 40(10):5409-5419.

PMID: 38424003 PMC: 10938882. DOI: 10.1021/acs.langmuir.3c03950.

Functional surfaces, films, and coatings with lignin - a critical review.

Ruwoldt J, Heen Blindheim F, Chinga-Carrasco G RSC Adv. 2023; 13(18):12529-12553.

PMID: 37101953 PMC: 10123495. DOI: 10.1039/d2ra08179b.

References

Lancefield C, Constant S, de Peinder P, Bruijnincx P . Linkage Abundance and Molecular Weight Characteristics of Technical Lignins by Attenuated Total Reflection-FTIR Spectroscopy Combined with Multivariate Analysis. ChemSusChem. 2019; 12(6):1139-1146. PMC: 6563701. DOI: 10.1002/cssc.201802809. View

Upton B, Kasko A . Strategies for the Conversion of Lignin to High-Value Polymeric Materials: Review and Perspective. Chem Rev. 2015; 116(4):2275-306. DOI: 10.1021/acs.chemrev.5b00345. View

Cortright R, Davda R, Dumesic J . Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water. Nature. 2002; 418(6901):964-7. DOI: 10.1038/nature01009. View

Bruijnincx P, Weckhuysen B . Biomass conversion: Lignin up for break-down. Nat Chem. 2014; 6(12):1035-6. DOI: 10.1038/nchem.2120. View

Britt P, Buchanan 3rd A, Cooney M, Martineau D . Flash vacuum pyrolysis of methoxy-substituted lignin model compounds. J Org Chem. 2000; 65(5):1376-89. DOI: 10.1021/jo991479k. View

Via B, Zhou C, Acquah G, Jiang W, Eckhardt L . Near infrared spectroscopy calibration for wood chemistry: which chemometric technique is best for prediction and interpretation?. Sensors (Basel). 2014; 14(8):13532-47. PMC: 4179028. DOI: 10.3390/s140813532. View

Zakzeski J, Bruijnincx P, Jongerius A, Weckhuysen B . The catalytic valorization of lignin for the production of renewable chemicals. Chem Rev. 2010; 110(6):3552-99. DOI: 10.1021/cr900354u. View

Zakzeski J, Jongerius A, Bruijnincx P, Weckhuysen B . Catalytic lignin valorization process for the production of aromatic chemicals and hydrogen. ChemSusChem. 2012; 5(8):1602-9. DOI: 10.1002/cssc.201100699. View

Li C, Zhao X, Wang A, Huber G, Zhang T . Catalytic Transformation of Lignin for the Production of Chemicals and Fuels. Chem Rev. 2015; 115(21):11559-624. DOI: 10.1021/acs.chemrev.5b00155. View

10.

Robinson A, Mansfield S . Rapid analysis of poplar lignin monomer composition by a streamlined thioacidolysis procedure and near-infrared reflectance-based prediction modeling. Plant J. 2009; 58(4):706-14. DOI: 10.1111/j.1365-313X.2009.03808.x. View

11.

Sun Z, Fridrich B, De Santi A, Elangovan S, Barta K . Bright Side of Lignin Depolymerization: Toward New Platform Chemicals. Chem Rev. 2018; 118(2):614-678. PMC: 5785760. DOI: 10.1021/acs.chemrev.7b00588. View

12.

Schutyser W, Renders T, van den Bosch S, Koelewijn S, Beckham G, Sels B . Chemicals from lignin: an interplay of lignocellulose fractionation, depolymerisation, and upgrading. Chem Soc Rev. 2018; 47(3):852-908. DOI: 10.1039/c7cs00566k. View

13.

Rinaldi R, Jastrzebski R, Clough M, Ralph J, Kennema M, Bruijnincx P . Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis. Angew Chem Int Ed Engl. 2016; 55(29):8164-215. PMC: 6680216. DOI: 10.1002/anie.201510351. View

14.

Khalili K, de Peinder P, Donkers J, Gosselink R, Bruijnincx P, Weckhuysen B . Monitoring Molecular Weight Changes during Technical Lignin Depolymerization by Operando Attenuated Total Reflectance Infrared Spectroscopy and Chemometrics. ChemSusChem. 2021; 14(24):5517-5524. PMC: 9299174. DOI: 10.1002/cssc.202101853. View

15.

Liao Y, Koelewijn S, Van den Bossche G, Van Aelst J, Van den Bosch S, Renders T . A sustainable wood biorefinery for low-carbon footprint chemicals production. Science. 2020; 367(6484):1385-1390. DOI: 10.1126/science.aau1567. View

16.

Misson M, Haron R, Ahmad Kamaroddin M, Saidina Amin N . Pretreatment of empty palm fruit bunch for production of chemicals via catalytic pyrolysis. Bioresour Technol. 2009; 100(11):2867-73. DOI: 10.1016/j.biortech.2008.12.060. View

17.

Zhou G, Taylor G, Polle A . FTIR-ATR-based prediction and modelling of lignin and energy contents reveals independent intra-specific variation of these traits in bioenergy poplars. Plant Methods. 2011; 7:9. PMC: 3094334. DOI: 10.1186/1746-4811-7-9. View

18.

Lancefield C, Wienk H, Boelens R, Weckhuysen B, Bruijnincx P . Identification of a diagnostic structural motif reveals a new reaction intermediate and condensation pathway in kraft lignin formation. Chem Sci. 2018; 9(30):6348-6360. PMC: 6115679. DOI: 10.1039/c8sc02000k. View