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Title: Ferricyanide-based analysis of aqueous lignin suspension revealed sequestration of water-soluble lignin moieties

This study describes the application of a ferricyanide-based assay as a simple and inexpensive assay for rapid analysis of aqueous lignin samples. The assay measures the formation of Prussian blue from the redox reaction between a mixture of potassium ferricyanide and ferric chloride, and phenolic hydroxyl groups of lignin or lignin-derived phenolic moieties. This study revealed that soluble lignin moieties exhibited stronger ferricyanide reactivity than insoluble aggregates. The soluble lignin moieties exhibited higher ferricyanide reactivity because of increased access of the phenolic hydroxyl groups to the ferricyanide reagents. Ferricyanide reactivity of soluble lignin moieties correlated inversely with the molecular weight distributions of the molecules, probably due to the involvement of phenolic hydroxyl groups in bond formation. The insoluble lignin aggregates exhibited low ferricyanide reactivity due to sequestration of the phenolic hydroxyl groups within the solid matrix. The study also highlighted the sequestration of polydispersed water-soluble lignin moieties by insoluble aggregates. The sequestered moieties were released by treatment with 0.01 M NaOH at 37 °C for 180 min. The redox assay was effective on different types of lignin extracts such as Klason lignin from switchgrass, ionic-liquid derived lignin from Eucalyptus and alkali lignin extracts. The assay generated a distinct profile formore » each lignin sample that was highly reproducible. The assay was also used to monitor consumption of syringic acid by Sphingobium sp. SYK-6. The simplicity and reproducibility of this assay makes it an excellent and versatile tool for qualitative and semi-quantitative characterization and comparative profiling of aqueous lignin samples.« less
Authors:
 [1] ;  [1] ;  [1]
  1. Joint BioEnergy Institute, Emeryville, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
RSC Advances
Additional Journal Information:
Journal Volume: 6; Journal Issue: 59; Journal ID: ISSN 2046-2069
Publisher:
Royal Society of Chemistry
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
OSTI Identifier:
1378712

Joshua, C. J., Simmons, B. A., and Singer, S. W.. Ferricyanide-based analysis of aqueous lignin suspension revealed sequestration of water-soluble lignin moieties. United States: N. p., Web. doi:10.1039/c6ra04443c.
Joshua, C. J., Simmons, B. A., & Singer, S. W.. Ferricyanide-based analysis of aqueous lignin suspension revealed sequestration of water-soluble lignin moieties. United States. doi:10.1039/c6ra04443c.
Joshua, C. J., Simmons, B. A., and Singer, S. W.. 2016. "Ferricyanide-based analysis of aqueous lignin suspension revealed sequestration of water-soluble lignin moieties". United States. doi:10.1039/c6ra04443c. https://www.osti.gov/servlets/purl/1378712.
@article{osti_1378712,
title = {Ferricyanide-based analysis of aqueous lignin suspension revealed sequestration of water-soluble lignin moieties},
author = {Joshua, C. J. and Simmons, B. A. and Singer, S. W.},
abstractNote = {This study describes the application of a ferricyanide-based assay as a simple and inexpensive assay for rapid analysis of aqueous lignin samples. The assay measures the formation of Prussian blue from the redox reaction between a mixture of potassium ferricyanide and ferric chloride, and phenolic hydroxyl groups of lignin or lignin-derived phenolic moieties. This study revealed that soluble lignin moieties exhibited stronger ferricyanide reactivity than insoluble aggregates. The soluble lignin moieties exhibited higher ferricyanide reactivity because of increased access of the phenolic hydroxyl groups to the ferricyanide reagents. Ferricyanide reactivity of soluble lignin moieties correlated inversely with the molecular weight distributions of the molecules, probably due to the involvement of phenolic hydroxyl groups in bond formation. The insoluble lignin aggregates exhibited low ferricyanide reactivity due to sequestration of the phenolic hydroxyl groups within the solid matrix. The study also highlighted the sequestration of polydispersed water-soluble lignin moieties by insoluble aggregates. The sequestered moieties were released by treatment with 0.01 M NaOH at 37 °C for 180 min. The redox assay was effective on different types of lignin extracts such as Klason lignin from switchgrass, ionic-liquid derived lignin from Eucalyptus and alkali lignin extracts. The assay generated a distinct profile for each lignin sample that was highly reproducible. The assay was also used to monitor consumption of syringic acid by Sphingobium sp. SYK-6. The simplicity and reproducibility of this assay makes it an excellent and versatile tool for qualitative and semi-quantitative characterization and comparative profiling of aqueous lignin samples.},
doi = {10.1039/c6ra04443c},
journal = {RSC Advances},
number = 59,
volume = 6,
place = {United States},
year = {2016},
month = {6}
}

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