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

Joshua, C. J.; Simmons, B. A.; Singer, S. W.

doi:10.1039/c6ra04443c

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

Journal Article · Thu Jun 02 00:00:00 EDT 2016 · RSC Advances

DOI:https://doi.org/10.1039/c6ra04443c· OSTI ID:1378712

Joshua, C. J. ^[1]; Simmons, B. A. ^[1]; Singer, S. W. ^[1]

Joint BioEnergy Institute, Emeryville, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

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.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1378712

Journal Information:: RSC Advances, Vol. 6, Issue 59; ISSN 2046-2069

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 4 works

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References (67)

Accuracy of Klason Lignin and Acid Detergent Lignin Methods As Assessed by Bomb Calorimetry ^† Jung, Hans-Joachim G.; Varel, Vincent H.; Weimer, Paul J. Journal of Agricultural and Food Chemistry, Vol. 47, Issue 5 https://doi.org/10.1021/jf981250q	journal	May 1999
Influence of pectins on the solubility and the molar mass distribution of dehydrogenative polymers (DHPs, lignin model compounds) Cathala, Bernard; Monties, Bernard International Journal of Biological Macromolecules, Vol. 29, Issue 1 https://doi.org/10.1016/S0141-8130(01)00145-3	journal	July 2001
Lignin Biosynthesis Boerjan, Wout; Ralph, John; Baucher, Marie Annual Review of Plant Biology, Vol. 54, Issue 1, p. 519-546 https://doi.org/10.1146/annurev.arplant.54.031902.134938	journal	June 2003
Chemical profiles of switchgrass Hu, Zhoujian; Sykes, Robert; Davis, Mark F. Bioresource Technology, Vol. 101, Issue 9 https://doi.org/10.1016/j.biortech.2009.12.033	journal	May 2010
Lignin monomer composition affects Arabidopsis cell-wall degradability after liquid hot water pretreatment Li, Xu; Ximenes, Eduardo; Kim, Youngmi Biotechnology for Biofuels, Vol. 3, Issue 1 https://doi.org/10.1186/1754-6834-3-27	journal	January 2010
Characterization of Lignin Structures and Lignin–Carbohydrate Complex (LCC) Linkages by Quantitative ¹³ C and 2D HSQC NMR Spectroscopy Yuan, Tong-Qi; Sun, Shao-Ni; Xu, Feng Journal of Agricultural and Food Chemistry, Vol. 59, Issue 19 https://doi.org/10.1021/jf2031549	journal	October 2011
Evaluation of the bioavailability and metabolism in the rat of punicalagin, an antioxidant polyphenol from pomegranate juice Cerd�, Bego�a; Llorach, Rafael; Cer�n, Jos� J. European Journal of Nutrition, Vol. 42, Issue 1 https://doi.org/10.1007/s00394-003-0396-4	journal	February 2003
Extraction and Isolation of Lignin for Utilization as a Standard to Determine Lignin Concentration Using the Acetyl Bromide Spectrophotometric Method Fukushima, Romualdo S.; Hatfield, Ronald D. Journal of Agricultural and Food Chemistry, Vol. 49, Issue 7 https://doi.org/10.1021/jf010449r	journal	July 2001
Enzymatic conversion of lignocellulose into fermentable sugars: challenges and opportunities Jørgensen, Henning; Kristensen, Jan Bach; Felby, Claus Biofuels, Bioproducts and Biorefining, Vol. 1, Issue 2 https://doi.org/10.1002/bbb.4	journal	October 2007
A comparison of the insoluble residues produced by the Klason lignin and acid detergent lignin procedures Hatfield, Ronald D.; Jung, Hans-Joachim G.; Ralph, John Journal of the Science of Food and Agriculture, Vol. 65, Issue 1, p. 51-58 https://doi.org/10.1002/jsfa.2740650109	journal	May 1994
Evidence for cleavage of lignin by a brown rot basidiomycete Yelle, Daniel J.; Ralph, John; Lu, Fachuang Environmental Microbiology, Vol. 10, Issue 7 https://doi.org/10.1111/j.1462-2920.2008.01605.x	journal	July 2008
Isolation and characterization of novel bacterial strains exhibiting ligninolytic potential Bandounas, Luaine; Wierckx, Nick JP; de Winde, Johannes H. BMC Biotechnology, Vol. 11, Issue 1 https://doi.org/10.1186/1472-6750-11-94	journal	January 2011
Recent Advances in Understanding Lignin Biosynthesis Whetten, Ross W.; MacKay, John J.; Sederoff, Ronald R. Annual Review of Plant Physiology and Plant Molecular Biology, Vol. 49, Issue 1 https://doi.org/10.1146/annurev.arplant.49.1.585	journal	June 1998
Can Lignin Be Accurately Measured? Hatfield, Ronald; Fukushima, Romualdo S. Crop Science, Vol. 45, Issue 3 https://doi.org/10.2135/cropsci2004.0238	journal	January 2005
Enzymatic "Combustion": The Microbial Degradation of Lignin Kirk, T. K.; Farrell, R. L. Annual Review of Microbiology, Vol. 41, Issue 1, p. 465-501 https://doi.org/10.1146/annurev.mi.41.100187.002341	journal	October 1987
FT-IR determination of lignin degradation in wheat straw by white rot fungus Stropharia rugosoannulata with different oxygen concentrations Buta, J. George; Zadrazil, Frantisek; Galletti, Guido C. Journal of Agricultural and Food Chemistry, Vol. 37, Issue 5 https://doi.org/10.1021/jf00089a038	journal	September 1989
Self-similar multiscale structure of lignin revealed by neutron scattering and molecular dynamics simulation Petridis, Loukas; Pingali, Sai Venkatesh; Urban, Volker Physical Review E, Vol. 83, Issue 6 https://doi.org/10.1103/PhysRevE.83.061911	journal	June 2011
Deposition of Lignin Droplets Produced During Dilute Acid Pretreatment of Maize Stems Retards Enzymatic Hydrolysis of Cellulose Selig, M. J.; Viamajala, S.; Decker, S. R. Biotechnology Progress, Vol. 23, Issue 6 https://doi.org/10.1021/bp0702018	journal	December 2007
Elucidation of new structures in lignins of CAD- and COMT-deficient plants by NMR Ralph, John; Lapierre, Catherine; Marita, Jane M. Phytochemistry, Vol. 57, Issue 6 https://doi.org/10.1016/S0031-9422(01)00109-1	journal	July 2001
Comparative evaluation of Fe(III) reducing power-based antioxidant capacity assays in the presence of phenanthroline, batho-phenanthroline, tripyridyltriazine (FRAP), and ferricyanide reagents Berker, Kadriye Işıl; Güçlü, Kubilay; Tor, İzzet Talanta, Vol. 72, Issue 3 https://doi.org/10.1016/j.talanta.2007.01.019	journal	May 2007
Lignin-modifying enzymes from selected white-rot fungi: production and role from in lignin degradation Hatakka, Annele FEMS Microbiology Reviews, Vol. 13, Issue 2-3 https://doi.org/10.1111/j.1574-6976.1994.tb00039.x	journal	March 1994
Recent innovations in analytical methods for the qualitative and quantitative assessment of lignin Lupoi, Jason S.; Singh, Seema; Parthasarathi, Ramakrishnan Renewable and Sustainable Energy Reviews, Vol. 49 https://doi.org/10.1016/j.rser.2015.04.091	journal	September 2015
Studies on dietary fiber. 3. Improved procedures for analysis of dietary fiber Theander, Olof; Westerlund, Eric A. Journal of Agricultural and Food Chemistry, Vol. 34, Issue 2 https://doi.org/10.1021/jf00068a045	journal	March 1986
The mechanism of the ferric ferricyanide reduction reaction Lillie, R. D.; Donaldson, P. T. The Histochemical Journal, Vol. 6, Issue 6 https://doi.org/10.1007/BF01011507	journal	November 1974
Determination of Molecular Weight Distribution of Lignin Derivatives by Aqueous Phase High Performance Size Exclusion Chromatography (HPSEC) González, A. M.; Salager, J. L.; Brunetto, M. R. Journal of High Resolution Chromatography, Vol. 23, Issue 12 https://doi.org/10.1002/1521-4168(20001201)23:12<693::AID-JHRC693>3.0.CO;2-T	journal	December 2000
The emerging role for bacteria in lignin degradation and bio-product formation Bugg, Timothy DH; Ahmad, Mark; Hardiman, Elizabeth M. Current Opinion in Biotechnology, Vol. 22, Issue 3 https://doi.org/10.1016/j.copbio.2010.10.009	journal	June 2011
Lignin Biosynthesis and Structure Vanholme, R.; Demedts, B.; Morreel, K. Plant Physiology, Vol. 153, Issue 3, p. 895-905 https://doi.org/10.1104/pp.110.155119	journal	May 2010
Lignin Composition and Structure in Young versus Adult Eucalyptus globulus Plants Rencoret, Jorge; Gutiérrez, Ana; Nieto, Lidia Plant Physiology, Vol. 155, Issue 2 https://doi.org/10.1104/pp.110.167254	journal	November 2010
Milled Wood Lignin: A Linear Oligomer Crestini, Claudia; Melone, Federica; Sette, Marco Biomacromolecules, Vol. 12, Issue 11 https://doi.org/10.1021/bm200948r	journal	November 2011
Lignin Valorization: Improving Lignin Processing in the Biorefinery Ragauskas, A. J.; Beckham, G. T.; Biddy, M. J. Science, Vol. 344, Issue 6185, p. 1246843-1246843 https://doi.org/10.1126/science.1246843	journal	May 2014
A simple and sensitive assay for ascorbate using potassium ferricyanide as spectroscopic probe reagent Zhang, Hua; Li, Jing; Wang, Kui Analytical Biochemistry, Vol. 388, Issue 1 https://doi.org/10.1016/j.ab.2009.01.039	journal	May 2009
Breakdown of Cell Wall Nanostructure in Dilute Acid Pretreated Biomass Pingali, Sai Venkatesh; Urban, Volker S.; Heller, William T. Biomacromolecules, Vol. 11, Issue 9 https://doi.org/10.1021/bm100455h	journal	September 2010
Methods to Reveal the Structure of Lignin Brunow, Gosta Biopolymers Online: Biology https://doi.org/10.1002/3527600035.bpol1003	book	January 2001
Accurate and Reproducible Determination of Lignin Molar Mass by Acetobromination Asikkala, Janne; Tamminen, Tarja; Argyropoulos, Dimitris S. Journal of Agricultural and Food Chemistry, Vol. 60, Issue 36 https://doi.org/10.1021/jf303003d	journal	March 2012
Chemical composition, antioxidant activity and bioaccessibility studies in phenolic extracts of two Hericium wild edible species Heleno, Sandrina A.; Barros, Lillian; Martins, Anabela LWT - Food Science and Technology, Vol. 63, Issue 1 https://doi.org/10.1016/j.lwt.2015.03.040	journal	September 2015
Pathways for degradation of lignin in bacteria and fungi Bugg, Timothy D. H.; Ahmad, Mark; Hardiman, Elizabeth M. Natural Product Reports, Vol. 28, Issue 12, p. 1883-1896 https://doi.org/10.1039/c1np00042j	journal	January 2011
Development of novel assays for lignin degradation: comparative analysis of bacterial and fungal lignin degraders Ahmad, Mark; Taylor, Charles R.; Pink, David Molecular BioSystems, Vol. 6, Issue 5 https://doi.org/10.1039/b908966g	journal	January 2010
Alkylperoxyl Radical-Scavenging Activity of Various Flavonoids and Other Phenolic Compounds: Implications for the Anti-Tumor-Promoter Effect of Vegetables Sawa, Tomohiro; Nakao, Mayumi; Akaike, Takaaki Journal of Agricultural and Food Chemistry, Vol. 47, Issue 2 https://doi.org/10.1021/jf980765e	journal	February 1999
Antioxidant activity of grape seed (Vitis vinifera) extracts on peroxidation models in vitro Jayaprakasha, G. K.; Singh, R. P.; Sakariah, K. K. Food Chemistry, Vol. 73, Issue 3 https://doi.org/10.1016/S0308-8146(00)00298-3	journal	May 2001
Electrochemical Behavior and Antioxidant and Prooxidant Activity of Natural Phenolics Simić, Aleksandra; Manojlović, Dragan; Šegan, Dejan Molecules, Vol. 12, Issue 10 https://doi.org/10.3390/12102327	journal	October 2007
Anodic methoxylation of cinnamate esters Pardini, Vera L.; Sakata, Solange K.; Vargas, Reinaldo R. Journal of the Brazilian Chemical Society, Vol. 12, Issue 2 https://doi.org/10.1590/S0103-50532001000200016	journal	January 2001
Substrate-Specific Development of Thermophilic Bacterial Consortia by Using Chemically Pretreated Switchgrass Eichorst, Stephanie A.; Joshua, Chijioke; Sathitsuksanoh, Noppadon Applied and Environmental Microbiology, Vol. 80, Issue 23 https://doi.org/10.1128/AEM.02795-14	journal	September 2014
Modeling the Lignin Degradation Kinetics in an Ethanol/Formic Acid Solvolysis Approach. Part 1. Kinetic Model Development Gasson, James R.; Forchheim, Daniel; Sutter, Tatjana Industrial & Engineering Chemistry Research, Vol. 51, Issue 32 https://doi.org/10.1021/ie301487v	journal	July 2012
Free radical scavenging activity from leaves of Acacia nilotica (L.) Wild. ex Delile, an Indian medicinal tree Kalaivani, T.; Mathew, Lazar Food and Chemical Toxicology, Vol. 48, Issue 1 https://doi.org/10.1016/j.fct.2009.10.013	journal	January 2010
Lignin. 19. Kraft lignin component conformation and associated complex configuration in aqueous alkaline solution Sarkanen, Simo; Teller, David C.; Abramowski, Edward Macromolecules, Vol. 15, Issue 4 https://doi.org/10.1021/ma00232a027	journal	July 1982
Characterization and genomic analysis of kraft lignin biodegradation by the beta-proteobacterium Cupriavidus basilensis B-8 Shi, Yan; Chai, Liyuan; Tang, Chongjian Biotechnology for Biofuels, Vol. 6, Issue 1 https://doi.org/10.1186/1754-6834-6-1	journal	January 2013
Mass spectrometry in the biosynthetic and structural investigation of lignins Reale, Samantha; Di Tullio, Alessandra; Spreti, Nicoletta Mass Spectrometry Reviews, Vol. 23, Issue 2 https://doi.org/10.1002/mas.10072	journal	January 2004
Use of Lignin Extracted from Different Plant Sources as Standards in the Spectrophotometric Acetyl Bromide Lignin Method Fukushima, Romualdo S.; Kerley, Monty S. Journal of Agricultural and Food Chemistry, Vol. 59, Issue 8 https://doi.org/10.1021/jf104826n	journal	April 2011
Using the Acetyl Bromide Assay To Determine Lignin Concentrations in Herbaceous Plants: Some Cautionary Notes Hatfield, R. D.; Grabber, J.; Ralph, J. Journal of Agricultural and Food Chemistry, Vol. 47, Issue 2, p. 628-632 https://doi.org/10.1021/jf9808776	journal	February 1999
Comparison of the Acetyl Bromide Spectrophotometric Method with Other Analytical Lignin Methods for Determining Lignin Concentration in Forage Samples Fukushima, Romualdo S.; Hatfield, Ronald D. Journal of Agricultural and Food Chemistry, Vol. 52, Issue 12, p. 3713-3720 https://doi.org/10.1021/jf035497l	journal	June 2004
Elucidation of Lignin Structure by Quantitative 2D NMR Sette, Marco; Wechselberger, Rainer; Crestini, Claudia Chemistry - A European Journal, Vol. 17, Issue 34 https://doi.org/10.1002/chem.201003045	journal	June 2011
Chemical Studies on the Composition of Fiber Fractions and Lignin Determination Residues Reeves, James B. Journal of Dairy Science, Vol. 76, Issue 1 https://doi.org/10.3168/jds.S0022-0302(93)77331-2	journal	January 1993
Free radical scavenging activity and reducing power of Acacia nilotica wood lignin Aadil, Keshaw Ram; Barapatre, Anand; Sahu, Sudha International Journal of Biological Macromolecules, Vol. 67 https://doi.org/10.1016/j.ijbiomac.2014.03.040	journal	June 2014
Pathway of p-Coumaric Acid Incorporation into Maize Lignin As Revealed by NMR Ralph, John; Hatfield, Ronald D.; Quideau, Stephane Journal of the American Chemical Society, Vol. 116, Issue 21, p. 9448-9456 https://doi.org/10.1021/ja00100a006	journal	October 1994
Characterization of the water-insoluble fraction from fast pyrolysis liquids (pyrolytic lignin) Bayerbach, Rolf; Nguyen, Van Dy; Schurr, Ulrich Journal of Analytical and Applied Pyrolysis, Vol. 77, Issue 2 https://doi.org/10.1016/j.jaap.2006.02.002	journal	October 2006
High-performance size exclusion chromatography of low-molecular-weight lignins and model compounds Himmel, M. E.; Oh, K. K.; Sopher, D. W. Journal of Chromatography A, Vol. 267 https://doi.org/10.1016/S0021-9673(01)90845-3	journal	January 1983
The Ferric Ferricyanide Reduction test in Histochemistry Lillie, R. D.; Burtner, Helen J. Journal of Histochemistry & Cytochemistry, Vol. 1, Issue 2 https://doi.org/10.1177/1.2.87	journal	March 1953
Rapid determination of syringyl: Guaiacyl ratios using FT-Raman spectroscopy Sun, Lan; Varanasi, Patanjali; Yang, Fan Biotechnology and Bioengineering, Vol. 109, Issue 3 https://doi.org/10.1002/bit.24348	journal	November 2011
Cyano Compounds, Inorganic Gail, Ernst; Gos, Stephen; Kulzer, Rupprecht Ullmann's Encyclopedia of Industrial Chemistry https://doi.org/10.1002/14356007.a08_159.pub3	book	January 2011
Enzymatic co-polymerization of lignin with low-molecular mass compounds Milstein, Oleg; Hüttermann, Aloys; Fründ, Rüdiger Applied Microbiology and Biotechnology, Vol. 40, Issue 5 https://doi.org/10.1007/BF00173342	journal	January 1994
Multidimensional NMR analysis reveals truncated lignin structures in wood decayed by the brown rot basidiomycete Postia placenta: Ligninolysis during fungal brown rot of wood Yelle, Daniel J.; Wei, Dongsheng; Ralph, John Environmental Microbiology, Vol. 13, Issue 4 https://doi.org/10.1111/j.1462-2920.2010.02417.x	journal	January 2011
Structure and Action Mechanism of Ligninolytic Enzymes Wong, Dominic W. S. Applied Biochemistry and Biotechnology, Vol. 157, Issue 2 https://doi.org/10.1007/s12010-008-8279-z	journal	June 2008
Lignin dehydrogenative polymerization mechanism: a poplar cell wall peroxidase directly oxidizes polymer lignin and produces in vitro dehydrogenative polymer rich in β- O -4 linkage Sasaki, Shinya; Nishida, Tomoaki; Tsutsumi, Yuji FEBS Letters, Vol. 562, Issue 1-3 https://doi.org/10.1016/S0014-5793(04)00224-8	journal	March 2004
Diversity and structure of bacterial communities associated with P hanerochaete chrysosporium during wood decay : Bacteria of the white-rot mycosphere Hervé, Vincent; Le Roux, Xavier; Uroz, Stéphane Environmental Microbiology, Vol. 16, Issue 7 https://doi.org/10.1111/1462-2920.12347	journal	December 2013
Lignin Degradation by Streptomyces viridosporus: Isolation and Characterization of a New Polymeric Lignin Degradation Intermediate † Crawford, Don L.; Pometto, Anthony L.; Crawford, Ronald L. Applied and Environmental Microbiology, Vol. 45, Issue 3 https://doi.org/10.1128/AEM.45.3.898-904.1983	journal	January 1983
Requirement for a Growth Substrate During Lignin Decomposition by Two Wood-Rotting Fungi Kirk, T. Kent; Connors, W. J.; Zeikus, J. Gregory Applied and Environmental Microbiology, Vol. 32, Issue 1 https://doi.org/10.1128/AEM.32.1.192-194.1976	journal	January 1976
Production and Characterization of Polymeric Lignin Degradation Intermediates from Two Different Streptomyces spp. † Borgmeyer, Jeffry R.; Crawford, Don L. Applied and Environmental Microbiology, Vol. 49, Issue 2 https://doi.org/10.1128/AEM.49.2.273-278.1985	journal	January 1985

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