期刊论文详细信息
Biotechnology for Biofuels
Effect of lignin content on changes occurring in poplar cellulose ultrastructure during dilute acid pretreatment
Qining Sun5  Marcus Foston1  Xianzhi Meng5  Daisuke Sawada2  Sai Venkatesh Pingali2  Hugh M O’Neill2  Hongjia Li3  Charles E Wyman4  Paul Langan2  Art J Ragauskas6  Rajeev Kumar4 
[1] Department of Energy, Environmental and Chemical Engineering, Washington University, 1 Brookings Drive, Saint Louis 63130, MO, USA
[2] Center for Structural Molecular Biology and the Biology and Soft Matter Division, Oak Ridge National Laboratory, Oak Ridge 37831, TN, USA
[3] Center for Environmental Research and Technology (CE-CERT), Bourns College of Engineering, University of California, 1084 Columbia Avenue, Riverside 92507, CA, USA
[4] BioEnergy Science Center (BESC), Oak Ridge National Laboratory (ORNL), Oak Ridge 37831, TN, USA
[5] School of Chemistry and Biochemistry, Renewable Bioproducts Institute, Georgia Institute of Technology, 500 10th Street, N.W. Atlanta 30332-0620, GA, USA
[6] Department of Chemical and Biomolecular Engineering, Department of Forestry, Wildlife, and Fisheries, Center for Renewable Carbon, University of Tennessee, Knoxville 37996-2200, TN, USA
关键词: Biomass recalcitrance;    Enzymatic sugar release;    Delignification;    Dilute acid pretreatment;    Lignin content;    Cellulose ultrastructure;   
Others  :  1084378
DOI  :  10.1186/s13068-014-0150-6
 received in 2014-05-17, accepted in 2014-09-25,  发布年份 2014
【 摘 要 】

Background

Obtaining a better understanding of the complex mechanisms occurring during lignocellulosic deconstruction is critical to the continued growth of renewable biofuel production. A key step in bioethanol production is thermochemical pretreatment to reduce plant cell wall recalcitrance for downstream processes. Previous studies of dilute acid pretreatment (DAP) have shown significant changes in cellulose ultrastructure that occur during pretreatment, but there is still a substantial knowledge gap with respect to the influence of lignin on these cellulose ultrastructural changes. This study was designed to assess how the presence of lignin influences DAP-induced changes in cellulose ultrastructure, which might ultimately have large implications with respect to enzymatic deconstruction efforts.

Results

Native, untreated hybrid poplar (Populus trichocarpa x Populus deltoids) samples and a partially delignified poplar sample (facilitated by acidic sodium chlorite pulping) were separately pretreated with dilute sulfuric acid (0.10 M) at 160°C for 15 minutes and 35 minutes, respectively . Following extensive characterization, the partially delignified biomass displayed more significant changes in cellulose ultrastructure following DAP than the native untreated biomass. With respect to the native untreated poplar, delignified poplar after DAP (in which approximately 40% lignin removal occurred) experienced: increased cellulose accessibility indicated by increased Simons’ stain (orange dye) adsorption from 21.8 to 72.5 mg/g, decreased cellulose weight-average degree of polymerization (DPw) from 3087 to 294 units, and increased cellulose crystallite size from 2.9 to 4.2 nm. These changes following DAP ultimately increased enzymatic sugar yield from 10 to 80%.

Conclusions

Overall, the results indicate a strong influence of lignin content on cellulose ultrastructural changes occurring during DAP. With the reduction of lignin content during DAP, the enlargement of cellulose microfibril dimensions and crystallite size becomes more apparent. Further, this enlargement of cellulose microfibril dimensions is attributed to specific processes, including the co-crystallization of crystalline cellulose driven by irreversible inter-chain hydrogen bonding (similar to hornification) and/or cellulose annealing that converts amorphous cellulose to paracrystalline and crystalline cellulose. Essentially, lignin acts as a barrier to prevent cellulose crystallinity increase and cellulose fibril coalescence during DAP.

【 授权许可】

   
2014 Sun et al.; licensee BioMed Central Ltd.

附件列表
Files Size Format View
Figure 1. 54KB Image download
Figure 8. 24KB Image download
Figure 7. 37KB Image download
Figure 6. 25KB Image download
Figure 5. 24KB Image download
Figure 4. 54KB Image download
Figure 3. 25KB Image download
Figure 2. 23KB Image download
Figure 1. 30KB Image download
【 图 表 】

Figure 1.

Figure 2.

Figure 3.

Figure 4.

Figure 5.

Figure 6.

Figure 7.

Figure 8.

Figure 1.

【 参考文献 】
  • [1]Caffall KH, Mohnen D: The structure, function, and biosynthesis of plant cell wall pectic polysaccharides. Carbohydr Res 2009, 344:1879-1900.
  • [2]Klemm D, Heublein B, Fink HP, Bohn A: Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem Int Ed Engl 2005, 44:3358-3393.
  • [3]Pu YQ, Zhang DC, Singh PM, Ragauskas AJ: The new forestry biofuels sector. Biofuels Bioprod Biorefining 2008, 2:58-73.
  • [4]Murphy JD, McCarthy K: Ethanol production from energy crops and wastes for use as a transport fuel in Ireland. Appl Energy 2005, 82:148-166.
  • [5]Sannigrahi P, Pu Y, Ragauskas A: Cellulosic biorefineries - unleashing lignin opportunities. Curr Opin Environ Sustain 2010, 2:383-393.
  • [6]Foston M, Ragauskas AJ: Biomass characterization: recent progress in understanding biomass recalcitrance. Ind Biotechnol 2012, 8:191-208.
  • [7]Himmel ME, Ding SY, Johnson DK, Adney WS, Nimlos MR, Brady JW, Foust TD: Biomass recalcitrance: engineering plants and enzymes for biofuels production. Science 2007, 315:804-807.
  • [8]Hsu TA, Ladisch MR, Tsao GT: Alcohol from cellulose. Chemtech 1980, 10:315-319.
  • [9]Lacayo CI, Hwang MS, Ding S-Y, Thelen MP: Lignin depletion enhances the digestibility of cellulose in cultured xylem cells. PLoS One 2013, 8:e68266.
  • [10]Lee SB, Kim IH, Ryu DDY, Taguchi H: Structural-properties of cellulose and cellulase reaction-mechanism. Biotechnol Bioeng 1983, 25:33-51.
  • [11]Puri VP: Effect of crystallinity and degree of polymerization of cellulose on enzymatic saccharification. Biotechnol Bioeng 1984, 26:1219-1222.
  • [12]Fan LT, Lee YH, Beardmore DH: Mechanism of the enzymatic-hydrolysis of cellulose - effects of major structural features of cellulose on enzymatic-hydrolysis. Biotechnol Bioeng 1980, 22:177-199.
  • [13]Mansfield SD, Mooney C, Saddler JN: Substrate and enzyme characteristics that limit cellulose hydrolysis. Biotechnol Prog 1999, 15:804-816.
  • [14]Yang B, Dai Z, Ding S-Y, Wyman CE: Enzymatic hydrolysis of cellulosic biomass. Biofuels 2011, 2:421-450.
  • [15]Del Rio LF, Chandra RP, Saddler JN: Fibre size does not appear to influence the ease of enzymatic hydrolysis of organosolv-pretreated softwoods. Bioresour Technol 2012, 107:235-242.
  • [16]Hall M, Bansal P, Lee JH, Realff MJ, Bommarius AS: Cellulose crystallinity - a key predictor of the enzymatic hydrolysis rate. FEBS J 2010, 277:1571-1582.
  • [17]Foston M, Ragauskas AJ: Changes in lignocellulosic supramolecular and ultrastructure during dilute acid pretreatment of Populus and switchgrass. Biomass Bioenerg 2010, 34:1885-1895.
  • [18]Pu Y, Hu F, Huang F, Davison BH, Ragauskas AJ: Assessing the molecular structure basis for biomass recalcitrance during dilute acid and hydrothermal pretreatments. Biotechnol Biofuels 2013, 6:1-13. BioMed Central Full Text
  • [19]Meng X, Foston M, Leisen J, DeMartini J, Wyman CE, Ragauskas AJ: Determination of porosity of lignocellulosic biomass before and after pretreatment by using Simons’ stain and NMR techniques. Bioresour Technol 2013, 144:467-476.
  • [20]Jeoh T, Ishizawa CI, Davis MF, Himmel ME, Adney WS, Johnson DK: Cellulase digestibility of pretreated biomass is limited by cellulose accessibility. Biotechnol Bioeng 2007, 98:112-122.
  • [21]O’sullivan AC: Cellulose: the structure slowly unravels. Cellulose 1997, 4:173-207.
  • [22]Yamamoto H, Horii F: CPMAS carbon-13 NMR analysis of the crystal transformation induced for Valonia cellulose by annealing at high temperatures. Macromolecules 1993, 26:1313-1317.
  • [23]Yamamoto H, Horii F, Odani H: Structural changes of native cellulose crystals induced by annealing in aqueous alkaline and acidic solutions at high temperatures. Macromolecules 1989, 22:4130-4132.
  • [24]Horii F, Yamamoto H, Kitamaru R, Tanahashi M, Higuchi T: Transformation of native cellulose crystals induced by saturated steam at high temperatures. Macromolecules 1987, 20:2946-2949.
  • [25]Debzi E, Chanzy H, Sugiyama J, Tekely P, Excoffier G: The Iα → Iβ transformation of highly crystalline cellulose by annealing in various mediums. Macromolecules 1991, 24:6816-6822.
  • [26]Rinaldi R, Schuth F: Acid hydrolysis of cellulose as the entry point into biorefinery schemes. ChemSusChem 2009, 2:1096-1107.
  • [27]Langan P, Petridis L, O’Neill HM, Pingali SV, Foston M, Nishiyama Y, Schulz R, Lindner B, Hanson BL, Harton S: Common processes drive the thermochemical pretreatment of lignocellulosic biomass. Green Chem 2014, 16:63-68.
  • [28]Sun Q, Foston M, Sawada D, Pingali SV, O’Neill HM, Li H, Wyman CE, Langan P, Pu Y, Ragauskas AJ: Comparison of changes in cellulose ultrastructure during different pretreatments of poplar. Cellulose 2014, 21:2419-2431.
  • [29]DeMartini JD, Pattathil S, Miller JS, Li HJ, Hahn MG, Wyman CE: Investigating plant cell wall components that affect biomass recalcitrance in poplar and switchgrass. Energy Environ Sci 2013, 6:898-909.
  • [30]Ishizawa CI, Jeoh T, Adney WS, Himmel ME, Johnson DK, Davis MF: Can delignification decrease cellulose digestibility in acid pretreated corn stover? Cellulose 2009, 16:677-686.
  • [31]Sannigrahi P, Kim DH, Jung S, Ragauskas A: Pseudo-lignin and pretreatment chemistry. Energy Environ Sci 2011, 4:1306-1310.
  • [32]Marchessault RH: Applications of infrared spectroscopy to the study of wood polysaccharides. Spectrochim Acta 1962, 18:876.
  • [33]Yin YF, Berglund L, Salmen L: Effect of steam treatment on the properties of wood cell walls. Biomacromolecules 2011, 12:194-202.
  • [34]Kumar R, Mago G, Balan V, Wyman CE: Physical and chemical characterizations of corn stover and poplar solids resulting from leading pretreatment technologies. Bioresour Technol 2009, 100:3948-3962.
  • [35]He JX, Cui SZ, Wang SY: Preparation and crystalline analysis of high-grade bamboo dissolving pulp for cellulose acetate. J Appl Polym Sci 2008, 107:1029-1038.
  • [36]Zhang J, Siika-aho M, Tenkanen M, Viikari L: The role of acetyl xylan esterase in the solubilization of xylan and enzymatic hydrolysis of wheat straw and giant reed. Biotechnol Biofuels 2011, 4:1-10. BioMed Central Full Text
  • [37]Jonsson LJ, Alriksson B, Nilvebrant N-O: Bioconversion of lignocellulose: inhibitors and detoxification. Biotechnol Biofuels 2013, 6:16. BioMed Central Full Text
  • [38]Sun XF, Xu F, Sun RC, Fowler P, Baird MS: Characteristics of degraded cellulose obtained from steam-exploded wheat straw. Carbohydr Res 2005, 340:97-106.
  • [39]Hubbell CA, Ragauskas AJ: Effect of acid-chlorite delignification on cellulose degree of polymerization. Bioresour Technol 2010, 101:7410-7415.
  • [40]Larsson PT, Hult EL, Wickholm K, Pettersson E, Iversen T: CP/MAS C-13-NMR spectroscopy applied to structure and interaction studies on cellulose I. Solid State Nucl Magn Reson 1999, 15:31-40.
  • [41]Newman RH: Carbon-13 NMR evidence for cocrystallization of cellulose as a mechanism for hornification of bleached kraft pulp. Cellulose 2004, 11:45-52.
  • [42]Lindgren T, Edlund U, Iversen T: A multivariate characterization of crystal transformations of cellulose. Cellulose 1995, 2:273-288.
  • [43]Ioelovich M, Leykin A, Figovsky O: Study of cellulose paracrystallinity. Bioresource 2010, 5:1393-1407.
  • [44]Wickholm K, Hult EL, Larsson PT, Iversen T, Lennholm H: Quantification of cellulose forms in complex cellulose materials: a chemometric model. Cellulose 2001, 8:139-148.
  • [45]Wickholm K, Larsson PT, Iversen T: Assignment of non-crystalline forms in cellulose I by CP/MAS C-13 NMR spectroscopy. Carbohydr Res 1998, 312:123-129.
  • [46]Hult EL, Larsson PT, Iversen T: Cellulose fibril aggregation - an inherent property of kraft pulps. Polymer 2001, 42:3309-3314.
  • [47]Sturcova A, His I, Apperley DC, Sugiyama J, Jarvis MC: Structural details of crystalline cellulose from higher plants. Biomacromolecules 2004, 5:1333-1339.
  • [48]Simons FL: A stain for use in the microscopy of beaten fibers. Tappi J 1950, 33:312-314.
  • [49]Arantes V, Saddler JN: Cellulose accessibility limits the effectiveness of minimum cellulase loading on the efficient hydrolysis of pretreated lignocellulosic substrates. Biotechnol Biofuels 2011, 4:1-17. BioMed Central Full Text
  • [50]Kumar R, Wyman CE: Physical and chemical features of pretreated biomass that influence macro‐/micro‐accessibility and biological processing. In Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion to Fuels and Chemicals. John Wiley & Sons, Ltd, Chichester, West Sussex, United Kingdom; 2013:281-310.
  • [51]Hallac BB, Sannigrahi P, Pu Y, Ray M, Murphy RJ, Ragauskas AJ: Effect of ethanol organosolv pretreatment on enzymatic hydrolysis of Buddleja davidii stem biomass. Ind Eng Chem Res 2010, 49:1467-1472.
  • [52]Pan XJ, Xie D, Yu RW, Saddler JN: The bioconversion of mountain pine beetle-killed lodgepole pine to fuel ethanol using the organosolv process. Biotechnol Bioeng 2008, 101:39-48.
  • [53]Foston M, Ragauskas AJ: Changes in the structure of the cellulose fiber wall during dilute acid pretreatment in populus studied by H-1 and H-2 NMR. Energy Fuels 2010, 24:5677-5685.
  • [54]Chen W-H, Tu Y-J, Sheen H-K: Disruption of sugarcane bagasse lignocellulosic structure by means of dilute sulfuric acid pretreatment with microwave-assisted heating. Appl Energy 2011, 88:2726-2734.
  • [55]Öhgren K, Bura R, Saddler J, Zacchi G: Effect of hemicellulose and lignin removal on enzymatic hydrolysis of steam pretreated corn stover. Bioresour Technol 2007, 98:2503-2510.
  • [56]Converse A, Ooshima H, Burns D: Kinetics of enzymatic hydrolysis of lignocellulosic materials based on surface area of cellulose accessible to enzyme and enzyme adsorption on lignin and cellulose. Appl Biochem Biotechnol 1990, 24:67-73.
  • [57]Sluiter A, Hames B, Ruiz R, Scarlata C, Sluiter J, Templeton D, Crocker D: Determination of structural carbohydrates and lignin in biomass. In Laboratory Analytical Procedure. National Renewable Energy Laboratory, 1617 Cole Boulevard, Golden, Colorado; 2008:80401-83393.
  • [58]Zhang D, Pu Y, Chai X-S, Naithani V, Jameel H, Ragauskas AJ: Elucidating carboxylic acid profiles for extended oxygen delignification of high-kappa softwood kraft pulps. Holzforschung 2006, 60:123-129.
  • [59]Virtanen T, Maunu SL, Tamminen T, Hortfing B, Liitia T: Changes in fiber ultrastructure during various kraft pulping conditions evaluated by C-13 CPMAS NMR spectroscopy. Carbohydr Polym 2008, 73:156-163.
  • [60]Pu YQ, Ziemer C, Ragauskas AJ: CP/MAS C-13 NMR analysis of cellulase treated bleached softwood kraft pulp. Carbohydr Res 2006, 341:591-597.
  • [61]Cullity BD, Stock SR: Elements of X-ray Diffraction. Prentice Hall, Upper Saddle River, New Jersey; 2001.
  • [62]Klug HP, Alexander LE: X-ray diffraction procedures: for polycrystalline and amorphous materials. In X-Ray Diffraction Procedures: for Polycrystalline and Amorphous Materials. 2nd edition. Edited by Klug HP, Alexander LE. Wiley, New York; 1974.
  • [63]Yu X, Atalla RH: A staining technique for evaluating the pore structure variations of microcrystalline cellulose powders. Powder Technol 1998, 98:135-138.
  • [64]Esteghlalian AR, Bilodeau M, Mansfield SD, Saddler JN: Do enzymatic hydrolyzability and Simons’ stain reflect the changes in the accessibility of lignocellulosic substrates to cellulase enzymes? Biotechnol Prog 2001, 17:1049-1054.
  • [65]Chandra R, Ewanick S, Hsieh C, Saddler JN: The characterization of pretreated lignocellulosic substrates prior to enzymatic hydrolysis, part 1: a modified Simons’ staining technique. Biotechnol Prog 2008, 24:1178-1185.
  文献评价指标  
  下载次数:23次 浏览次数:13次