The DOI matches its Crossref record; 68 of the 68 references it cites were found in a registry or an index.
A Mechanistic Investigation of Acid-Catalyzed Cleavage of Aryl-Ether Linkages: Implications for Lignin Depolymerization in Acidic Environments
Open accessAbstract
Abstract Acid catalysis has long been used to depolymerize plant cell wall polysaccharides, and the mechanisms by which acid affects carbohydrates have been extensively studied. Lignin depolymerization, however, is not as well understood, primarily due to the heterogeneity and reactivity of lignin. We present an experimental and theoretical study of acid-catalyzed cleavage of two non-phenolic and two phenolic dimers that exhibit the β-O-4 ether linkage, the most common intermonomer bond in lignin. This work demonstrates that the rate of acid-catalyzed β-O-4 cleavage in dimers exhibiting a phenolic hydroxyl group is 2 orders of magnitude faster than in non-phenolic dimers. The experiments suggest that the major product distribution is similar for all model compounds, but a stable phenyl-dihydrobenzofuran species is observed in the acidolysis of two of the γ-carbinol containing model compounds. The presence of a methoxy substituent, commonly found in native lignin, prevents the formation of this intermediate. Reaction pathways were examined with quantum mechanical calculations, which aid in explaining the substantial differences in reactivity. Moreover, we use a radical scavenger to show that the commonly proposed homolytic cleavage pathway of phenolic β-O-4 linkages is unlikely in acidolysis conditions. Overall, this study explains the disparity between rates of β-O-4 cleavage seen in model compound experiments and acid pretreatment of biomass, and implies that depolymerization of lignin during acid-catalyzed pretreatment or fractionation will proceed via a heterolytic, unzipping mechanism wherein β-O-4 linkages are cleaved from the phenolic ends of branched, polymer chains inward toward the core of the polymer.
Overview
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
Integrity signals
Registry
Cites
Statistics
Verification
Claims the paper makes
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
Self-check
Percentages, sums and reported differences re-computed from the paper’s own numbers.
The self-check needs the paper’s full text.
Citations
Cites
Features of promising technologies for pretreatment of lignocellulosic biomass
MOSIER, N. (2005) · Bioresource Technology · doi:10.1016/j.biortech.2004.06.025 · Cited by 6,251
The Path Forward for Biofuels and Biomaterials
Ragauskas, A. J., Williams, C. K., Davison, B. H., Britovsek, G., Cairney, J., Eckert, C. A., Frederick, W. J., Hallett, J. P., Leak, D. J., Liotta, C. L., et al. (2006) · Science · doi:10.1126/science.1114736 · Cited by 5,741
Bozell, J. J., & Petersen, G. R. (2010) · Green Chemistry · doi:10.1039/b922014c · Cited by 4,566
Biomass Recalcitrance: Engineering Plants and Enzymes for Biofuels Production
Himmel, M. E., Ding, S.-Y., Johnson, D. K., Adney, W. S., Nimlos, M. R., Brady, J. W., & Foust, T. D. (2007) · Science · doi:10.1126/science.1137016 · Cited by 4,533
Self-citationBoerjan, W., Ralph, J., & Baucher, M. (2003) · Annual Review of Plant Biology · doi:10.1146/annurev.arplant.54.031902.134938 · Cited by 4,504
The Catalytic Valorization of Lignin for the Production of Renewable Chemicals
Zakzeski, J., Bruijnincx, P. C. A., Jongerius, A. L., & Weckhuysen, B. M. (2010) · Chemical Reviews · doi:10.1021/cr900354u · Cited by 4,468
Lignin Biosynthesis and Structure
Vanholme, R., Demedts, B., Morreel, K., Ralph, J., & Boerjan, W. (2010) · Plant Physiology · doi:10.1104/pp.110.155119 · Cited by 2,664
Coordinated development of leading biomass pretreatment technologies
Wyman, C. E., Dale, B. E., Elander, R. T., Holtzapple, M., Ladisch, M. R., & Lee, Y. Y. (2005) · Bioresource Technology · doi:10.1016/j.biortech.2005.01.010 · Cited by 1,432
Lignin modification improves fermentable sugar yields for biofuel production
Chen, F., & Dixon, R. A. (2007) · Nature Biotechnology · doi:10.1038/nbt1316 · Cited by 1,330
How biotech can transform biofuels
Lynd, L. R., Laser, M. S., Bransby, D., Dale, B. E., Davison, B., Hamilton, R., Himmel, M., Keller, M., McMillan, J. D., Sheehan, J., et al. (2008) · Nature Biotechnology · doi:10.1038/nbt0208-169 · Cited by 1,121
Cited by
Catalytic Transformation of Lignin for the Production of Chemicals and Fuels
Li, C., Zhao, X., Wang, A., Huber, G. W., & Zhang, T. (2015) · Chemical Reviews · doi:10.1021/acs.chemrev.5b00155 · Cited by 2,951
Guidelines for performing lignin-first biorefining
Abu-Omar, M. M., Barta, K., Beckham, G. T., Luterbacher, J. S., Ralph, J., Rinaldi, R., Román-Leshkov, Y., Samec, J. S. M., Sels, B. F., & Wang, F. (2021) · Energy & Environmental Science · doi:10.1039/d0ee02870c · Cited by 913
Self-citationTunable and functional deep eutectic solvents for lignocellulose valorization
Liu, Y., Deak, N., Wang, Z., Yu, H., Hameleers, L., Jurak, E., Deuss, P. J., & Barta, K. (2021) · Nature Communications · doi:10.1038/s41467-021-25117-1 · Cited by 452
A review on biopolymer production via lignin valorization
Rajesh Banu, J., Kavitha, S., Yukesh Kannah, R., Poornima Devi, T., Gunasekaran, M., Kim, S.-H., & Kumar, G. (2019) · Bioresource Technology · doi:10.1016/j.biortech.2019.121790 · Cited by 319
Self-citationRecent advances in the valorization of plant biomass
Ning, P., Yang, G., Hu, L., Sun, J., Shi, L., Zhou, Y., Wang, Z., & Yang, J. (2021) · Biotechnology for Biofuels · doi:10.1186/s13068-021-01949-3 · Cited by 296
Metadata
- Authors
- Sturgeon, M. R., Kim, S., Lawrence, K., Paton, R. S., Chmely, S. C., Nimlos, M., Foust, T. D., & Beckham, G. T.
- Venue
- ACS Sustainable Chemistry & Engineering
- Publisher
- American Chemical Society (ACS)
- Published
- 2013-11-18
- Volume
- 2
- Issue
- 3
- Pages
- 472-485
- ISSN
- 2168-0485 (ISSN-L)
- OpenAlex
- W1998548865
- Cited by
- 414
- References
- 68
- FWCI
- 9.39
- Type
- journal article
- Language
- en
- Open access
- hybrid
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review
How to cite
Cite CoChat for the checks on this page, and the paper for its own findings.
- This page
- CoChat. (2026). Citation check: A Mechanistic Investigation of Acid-Catalyzed Cleavage of Aryl-Ether Linkages: Implications for Lignin Depolymerization in Acidic Environments. https://app.cochat.ai/papers/10.1021/sc400384w
- The paper
- Sturgeon, M. R., Kim, S., Lawrence, K., Paton, R. S., Chmely, S. C., Nimlos, M., Foust, T. D., & Beckham, G. T. (2014). A Mechanistic Investigation of Acid-Catalyzed Cleavage of Aryl-Ether Linkages: Implications for Lignin Depolymerization in Acidic Environments. ACS Sustainable Chemistry & Engineering. https://doi.org/10.1021/sc400384w
Data sources
Bibliographic data: Semantic Scholar, OpenAlex, Crossref.
Contains information from the Semantic Scholar Academic Graph Datasets, made available under the ODC Attribution License (ODC-BY 1.0).
Semantic Scholar’s data is described in: Kinney, R., et al. (2023). The Semantic Scholar Open Data Platform. arXiv:2301.10140.
