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Comprehensive Analysis of Monomeric Phenolics in Dilute Acid Plant Hydrolysates

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Abstract

We carried out a comprehensive analysis of the phenolic compounds in hydrolysate produced by dilute acid pretreatment of 20 potential lignocellulosic biofuel feedstocks, including grasses, hardwoods and softwood, and agaves. We find that the phenolic fraction is dominated by Hibbert's ketones, most of which had not so far been characterized in hydrolysate. Using gas chromatography/mass spectrometry, a range of 43–68 monomeric phenolic compounds were identified in each of the feedstocks, including from 13 to 20 Hibbert's ketones and related structures, which represented 28–82 % of phenolics formed during pretreatment. The total concentration of phenolics ranged from 87 to 1,077 μg/mL (equivalent to 78–969 mg phenolics released per 100 g of biomass used) across the feedstocks studied. While total amount of phenolics produced does not correlate with the Klason lignin in the feedstock, the distribution of compound types produced is reflective of the S and G monolignol ratios of the feedstock. Since phenolic compounds are particularly inhibitory to microbial processes and cellulolytic enzymes, our results indicate there is sufficient variation across feedstocks that design strategies are likely to benefit from both general and targeted approaches to detoxification.

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References

  1. Somerville C, Youngs H, Taylor C, Davis SC, Long SP (2010) Feedstocks for lignocellulosic biofuels. Science 329:790–792

    Article  CAS  PubMed  Google Scholar 

  2. Wyman CE, Dale BE, Elander RT, Holtzapple M, Ladisch MR, Lee YY (2005) Coordinated development of leading biomass pretreatment technologies. Biores Technol 96:1959–1966

    Article  CAS  Google Scholar 

  3. Mood SH, Golfeshan AH, Tabatabaei M, Jouzani GS, Najafi GH, Gholami M, Ardjmand M (2013) Lignocellulosic biomass to bioethanol, a comprehensive review with a focus on pretreatment. Renew Sust Energy Rev 27:77–93

    Article  Google Scholar 

  4. Wyman CE (ed) (2013) Aqueous pretreatment of plant biomass for biological and chemical conversion to fuels and chemicals. Wiley, New York

    Google Scholar 

  5. Palmqvist E, Hahn-Hägerdal B (2000) Fermentation of lignocellulosic hydrolysates. II: inhibition and mechanisms of inhibition. Biores Technol 74:25–33

    Article  CAS  Google Scholar 

  6. Elander RT, Dale BE, Holtzapple M, Ladisch MR, Lee YY, Mitchinson C, Saddler JN, Wyman CE (2009) Summary of findings from the biomass refining consortium for applied fundamentals and innovation (CAFI): corn stover pretreatment. Cellulose 16:649–659

    Article  CAS  Google Scholar 

  7. Kim Y, Mosier NS, Ladisch MR, Pallapolu VR, Lee YY, Garlock R, Balan V, Dale BE, Donohoe BS, Vinzant TB, Elander RT, Falls M, Sierra R, Holtzapple MT, Shi J, Ebrik MA, Redmond T, Yang B, Wyman CE, Warner RE (2011) Comparative study on enzymatic digestibility of switchgrass varieties and harvests processed by leading pretreatment technologies. Biores Technol 102:11089–11096

    Article  CAS  Google Scholar 

  8. Wyman CE, Dale BE, Balan V, Elander RT, Holtzapple MT, Ramirez RS, Ladisch MR, Mosier NS, Lee YY, Gupta R (2013) Comparative performance of leading pretreatment technologies for biological conversion of corn stover, poplar wood, and switchgrass to sugars. In: Wyman CE (ed) Aqueous pretreatment of plant biomass for biological and chemical conversion to fuels and chemicals. Wiley, New York, pp 239–259

    Chapter  Google Scholar 

  9. Klinke HB, Thomsen AB, Ahring BK (2004) Inhibition of ethanol-producing yeast and bacteria by degradation products produced during pre-treatment of biomass. Appl Microbiol Biotechnol 66:10–26

    Article  CAS  PubMed  Google Scholar 

  10. Du B, Sharma LN, Becker C, Chen S-F, Mowery RA, van Walsum GP, Chambliss CK (2010) Effect of varying feedstock-pretreatment chemistry combinations on the formation and accumulation of potentially inhibitory degradation products in biomass hydrolysates. Biotechnol Bioeng 107:430–440

    Article  CAS  PubMed  Google Scholar 

  11. Humbird D, Davis R, Tao L, Kinchin C, Hsu D, Aden A, Schoen P, Lukas J, Olthof B, Worley M, Sexton D, Dudgeon D (2011) Process design and economics for biochemical conversion of lignocellulosic biomass to ethanol: dilute-acid pretreatment and enzymatic hydrolysis of corn stover. Technical Report NREL/TP-5100-47764. United States National Renewable Energy Laboratory, US Department of Energy. May 2011

  12. Popoff T, Theander O (1972) Formation of aromatic compounds from carbohydrates. Part I. Reaction of D-glucuronic acid, D-galacturonic acid, D-xylose, and L-arabinose in slightly acidic, aqueous solution. Carbohydr Res 22:135–149

    Article  CAS  Google Scholar 

  13. Ralph J, Brunow G, Boerjan W (2007) Lignins. In: Rose F, Osborne K (eds) Encyclopedia of life sciences. Wiley, Chichester, pp 1–10

    Google Scholar 

  14. Sun Y, Cheng J (2002) Hydrolysis of lignocellulosic materials for ethanol production: a review. Biores Technol 83:1–11

    Article  CAS  Google Scholar 

  15. del Río JC, Rencoret J, Marques G, Gutiérrez A, Ibarra D, Santos JI, Jiménez-Barbero J, Zhang L, Martínez AT (2008) Highly acylated (acetylated and/or p-coumaroylated) native lignins from diverse herbaceous plants. J Agric Food Chem 56:9525–9534

    Article  PubMed  Google Scholar 

  16. Clark TA, Mackie KL (1984) Fermentation inhibitors in wood hydrolysates derived from the softwood Pinus radiata. J Chem Tech Biotechnol 34B:101–110

    CAS  Google Scholar 

  17. Tran AV, Chambers RP (1986) Lignin and extractives derived inhibitors in the 2,3-butanediol fermentation of mannose-rich prehydrolysates. Appl Microbiol Biotechnol 23:191–197

    CAS  Google Scholar 

  18. Jönsson LJ, Palmqvist E, Nilvebrant N-O, Hahn-Hägerdal B (1998) Detoxification of wood hydrolysates with laccase and peroxidase from the white-rot fungus Trametes versicolor. Appl Microbiol Biotechnol 49:691–697

    Article  Google Scholar 

  19. Luo C, Brink DL, Blanch HW (2002) Identification of potential fermentation inhibitors in conversion of hybrid poplar hydrolyzate to ethanol. Biomass Bioenergy 22:125–138

    Article  CAS  Google Scholar 

  20. Larsson S, Reimann A, Nilvebrant N-O, Jönsson LJ (1999) Comparison of different methods for the detoxification of lignocellulose hydrolyzates of spruce. App Biochem Biotechnol 77–79:91–103

    Article  Google Scholar 

  21. Buchert J, Niemelä K, Puls J, Poutanen K (1990) Improvement in the fermentability of steamed hemicellulose hydrolysate by ion exclusion. Process Biochem Int 176–180

  22. Ximenes E, Kim Y, Ladisch MR (2013) Biological conversion of plants to fuels and chemicals and the effects of inhibitors. In: Wyman CE (ed) Aqueous pretreatment of plant biomass for biological and chemical conversion to fuels and chemicals. Wiley, New York, pp 39–60

    Chapter  Google Scholar 

  23. Fenske JJ, Griffin DA, Penner MH (1998) Comparison of aromatic monomers in lignocellulosic biomass prehydrolysates. J Ind Microbiol Biotechnol 20:364–368

    Article  CAS  Google Scholar 

  24. Bauer S, Sorek H, Mitchell VD, Ibáñez AB, Wemmer DE (2012) Characterization of Miscanthus giganteus lignin isolated by ethanol organosolv process under reflux condition. J Agric Food Chem 60:8203–8212

    Article  CAS  PubMed  Google Scholar 

  25. Higuchi T, Tanahashi M, Sato A (1972) Acidolysis of bamboo lignin. I. Gas–liquid chromatography and mass spectrometry of acidolysis monomers. Mokuzai Gakkaishi (J Japan Wood Res Soc) 18:183–189

    Google Scholar 

  26. Lapierre C, Rolando C, Monties B (1983) Characterization of poplar lignins acidolysis products: capillary gas–liquid and liquid–liquid chromatography of monomeric compounds. Holzforschung 37:189–198

    Article  CAS  Google Scholar 

  27. Jin Z, Matsumoto Y, Tange T, Iiyama K (2007) Structural characteristics of lignin in primitive pteridophytes: Selaginella species. J Wood Sci 53:412–418

    Article  CAS  Google Scholar 

  28. Niemelä K (1991) Unusual propiophenones formed during hydrolysis of birch lignin. Holzforschung 45:233–235

    Article  Google Scholar 

  29. Lundquist K, Kirk TK (1971) Acid degradation of lignin. IV. Analysis of lignin acidolysis products by gas chromatography, using trimethylsilyl derivatives. Acta Chem Scand 25:889–894

    Article  CAS  PubMed  Google Scholar 

  30. Niemelä K, Sjöström E (1986) Simultaneous identification of aromatic and aliphatic low molecular weight compounds from alkaline pulping liquor by capillary gas–liquid chromatography–mass spectrometry. Holzforschung 40:361–368

    Article  Google Scholar 

  31. Allerdings E, Ralph J, Steinhart H, Bunzel M (2006) Isolation and structural identification of complex feruloyated heteroxylan side-chains from maize bran. Phytochem 67:1276–1286

    Article  CAS  Google Scholar 

  32. Hatfield RD, Marita JM, Frost K (2008) Characterization of p-coumarate accumulation, p-coumaroyl transferase, and cell wall changes during the development of corn stems. J Sci Food Agric 88:2529–2537

    Article  CAS  Google Scholar 

  33. Appeldoorn MM, Kabel MA, van Eylen D, Gruppen H, Schols HA (2010) Characterization of oligomeric xylan structures from corn fiber resistant to pretreatment and simultaneous saccharification and fermentation. J Agric Food Chem 58:11294–11301

    Article  CAS  PubMed  Google Scholar 

  34. Carrasco C, Solano C, Peñarrieta JM, Baudel HM, Galbe M, Lidén G (2012) Arabinosylated phenolics obtained from SO2-steam-pretreated sugarcane bagasse. J Chem Technol Biotechnol 87:1723–1726

    Article  CAS  Google Scholar 

  35. Bunzel M, Schüssler A, Saha GT (2011) Chemical characterization of Klason lignin preparations from plant-based foods. J Agric Food Chem 59:12506–12513

    Article  CAS  PubMed  Google Scholar 

  36. Kuiters AT, Sarink HM (1986) Leaching of phenolic compounds from leaf and needle litter of several deciduous and coniferous trees. Soil Biol Biochem 18:475–480

    Article  CAS  Google Scholar 

  37. Bardet M, Robert DR (1985) On the reactions and degradation of the lignin during steam hydrolysis of aspen wood. Sven Papperstidn 6:R61–R67

    Google Scholar 

  38. Klemola A (1968) Steam hydrolysis of birchwood. Part III. Investigation of low-molecular aromatic degradation products. Suom Kemistil B 41:83–98

    CAS  Google Scholar 

  39. Ando S, Arai I, Kiyoto K, Hanai S (1986) Identification of aromatic monomers in steam-exploded poplar and their influences on ethanol fermentation by Saccharomyces cerevisiae. J Ferment Technol 64:567–570

    Article  CAS  Google Scholar 

  40. Tran AV, Chambers RP (1985) Red oak wood derived inhibitors in the ethanol fermentation of xylose by Pichia stipitis CBS 5776. Biotechnol Lett 7:841–846

    Article  CAS  Google Scholar 

  41. Tran AV, Chambers RP (1986) Ethanol fermentation of red oak acid prehydrolysate by the yeast Pichia stipitis CBS 5776. Enzyme Microb Technol 8:439–444

    Article  CAS  Google Scholar 

  42. Wilson JJ, Deschatelets L, Nishikawa NK (1989) Comparative fermentability of enzymatic and acid hydrolysates of steam-pretreated aspenwood hemicellulose by Pichia stipitis CBS 5776. Appl Microbiol Biotechnol 31:592–596

    Article  CAS  Google Scholar 

  43. Lim W-S, Kim J-Y, Kim H-Y, Choi J-W, Choi I-G, Lee J-W (2013) Structural properties of pretreated biomass from different acid pretreatments and their effects on simultaneous saccharification and ethanol fermentation. Biores Technol 139:214–219

    Article  CAS  Google Scholar 

  44. Kim Y, Kreke T, Hendrickson R, Parenti J, Ladisch MR (2013) Fractionation of cellulose and fermentation inhibitors from steam pretreated mixed hardwood. Biores Technol 135:30–38

    Article  CAS  Google Scholar 

  45. Humpula JF, Chundawat RV, Jones AD, Balan V, Dale BE (2011) Rapid quantification of major reaction products formed during thermochemical pretreatment of lignocellulosic biomass using GC-MS. J Chromatogr B 879:1018–1022

    Article  CAS  Google Scholar 

  46. Zhang Y, Wang L, Chen H (2013) Formation of kinetics of potential fermentation inhibitors in a steam explosion process of corn straw. Appl Biochem Biotechnol 169:359–367

    Article  CAS  PubMed  Google Scholar 

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Acknowledgments

This work was funded by the Energy Biosciences Institute. The authors would like to thank Dr. Sanil Sreekumar (UC Berkeley) for the preparation of 3-syringylpropanol; Tim Mies (University of Illinois at Urbana-Champaign), Dr. Sarah Davis (University of Illinois at Urbana-Champaign; now at Ohio University), and Dr. Jason Lupoi (Joint Bio-Energy Institute, Emeryville) for providing biomass samples; and Dr. Mirko Bunzel (University of Minnesota, St. Paul) for the mixture of 5-O-trans-feruloyl- and 5-O- trans-p-coumaroyl-arabinose.

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Correspondence to Stefan Bauer.

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Mitchell, V.D., Taylor, C.M. & Bauer, S. Comprehensive Analysis of Monomeric Phenolics in Dilute Acid Plant Hydrolysates. Bioenerg. Res. 7, 654–669 (2014). https://doi.org/10.1007/s12155-013-9392-6

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