Chemical and structural changes associated with Cu-catalyzed alkaline-oxidative delignification of hybrid poplar

Biotechnology for Biofuels

Zhenglun Li⁵  Namita Bansal²  Ali Azarpira⁶  Aditya Bhalla²  Charles H Chen⁴  John Ralph¹  Eric L Hegg²  David B Hodge³ 

[1] Department of Biochemistry, University of Wisconsin, Madison, WI, USA

[2] Department of Biochemistry and Molecular Biology, Michigan State University, East Lansing, MI, USA

[3] Division of Sustainable Process Engineering, Luleå University of Technology, Luleå, Sweden

[4] Department of Materials Science and Engineering, Johns Hopkins University, Baltimore, MD, USA

[5] College of Agricultural Sciences, Oregon State University, Corvallis, OR, USA

[6] DOE-Great Lakes Bioenergy Research Center, University of Wisconsin, Madison, WI, USA

关键词: Electron microscopy;    NMR spectroscopy;    Alkaline hydrogen peroxide (AHP) pretreatment;    Lignin;    Catalytic oxidation;    Pretreatment;    Plant cell walls;   

Others  :  1228157
DOI  :  10.1186/s13068-015-0300-5

 received in 2015-04-14, accepted in 2015-07-30,  发布年份 2015

【 摘 要 】

Background

Alkaline hydrogen peroxide pretreatment catalyzed by Cu(II) 2,2′-bipyridine complexes has previously been determined to substantially improve the enzymatic hydrolysis of woody plants including hybrid poplar as a consequence of moderate delignification. In the present work, cell wall morphological and lignin structural changes were characterized for this pretreatment approach to gain insights into pretreatment outcomes and, specifically, to identify the extent and nature of lignin modification.

Results

Through TEM imaging, this catalytic oxidation process was shown to disrupt cell wall layers in hybrid poplar. Cu-containing nanoparticles, primarily in the Cu(I) oxidation state, co-localized with the disrupted regions, providing indirect evidence of catalytic activity whereby soluble Cu(II) complexes are reduced and precipitated during pretreatment. The concentration of alkali-soluble polymeric and oligomeric lignin was substantially higher for the Cu-catalyzed oxidative pretreatment. This alkali-soluble lignin content increased with time during the catalytic oxidation process, although the molecular weight distributions were unaltered. Yields of aromatic monomers (including phenolic acids and aldehydes) were found to be less than 0.2 % (wt/wt) on lignin. Oxidation of the benzylic alcohol in the lignin side-chain was evident in NMR spectra of the solubilized lignin, whereas minimal changes were observed for the pretreatment-insoluble lignin.

Conclusions

These results provide indirect evidence for catalytic activity within the cell wall. The low yields of lignin-derived aromatic monomers, together with the detailed characterization of the pretreatment-soluble and pretreatment-insoluble lignins, indicate that the majority of both lignin pools remained relatively unmodified. As such, the lignins resulting from this process retain features closely resembling native lignins and may, therefore, be amenable to subsequent valorization.

【 授权许可】

   
2015 Li et al.

【 图 表 】

Fig.1.

Fig.2.

Fig.3.

Fig.4.

Fig.5.

Fig.6.

Fig.1.

Fig.2.

Fig.3.

Fig.4.

Fig.5.

Fig.6.

【 参考文献 】

• [1]Dale BE: Energy consumption, wealth, and biofuels: helping human beings achieve their potential. Biofuel Bioprod Biorefin 2012, 6:1-3.
• [2]Solomon BD: Biofuels and sustainability. Ann NY Acad Sci 2010, 1185:119-134.
• [3]Davison BH, Parks J, Davis MF, Donohoe BS (2013) Plant cell walls: basics of structure, chemistry, accessibility and the influence on conversion. In: Wyman CE (ed) Aqueous pretreatment of plant biomass for biological and chemical conversion to fuels and chemicals. Wiley, New York, pp 23–38
• [4]Walton JD: Deconstructing the cell wall. Plant Physiol 1994, 104:1113.
• [5]Cortright RD, Davda RR, Dumesic JA: Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water. Nature 2002, 418:964-967.
• [6]Himmel ME, Ding SY, Johnson DK, Adney WS, Nimlos MR, Brady JW, et al.: Biomass recalcitrance: engineering plants and enzymes for biofuels production. Science 2007, 315:804-807.
• [7]Chaudhuri SK, Lovley DR: Electricity generation by direct oxidation of glucose in mediatorless microbial fuel cells. Nat Biotechnol 2003, 21:1229-1232.
• [8]Stoklosa RJ, Hodge DB: Fractionation and improved enzymatic deconstruction of hardwoods with alkaline delignification. Bioenergy Res 2015.
• [9]Ong RG, Chundawat SP, Hodge DB, Keskar S, Dale BE (2014) Linking plant biology and pretreatment: understanding the structure and organization of the plant cell wall and interactions with cellulosic biofuel production. In: McCannMC, Buckeridge MS, Carpita NC (eds) Plants and bioenergy. Springer, Berlin, pp 231–253
• [10]Zhang C, Lei X, Scott CT, Zhu J, Li K: Comparison of dilute acid and sulfite pretreatment for enzymatic saccharification of earlywood and latewood of Douglas fir. Bioenergy Res 2014, 7:362-370.
• [11]Sperry JS: Evolution of water transport and xylem structure. Int J Plant Sci 2003, 164:S115-S127.
• [12]Li X, Luo X, Li K, Zhu JY, Fougere JD, Clarke K: Effects of SPORL and dilute acid pretreatment on substrate morphology, cell physical and chemical wall structures, and subsequent enzymatic hydrolysis of lodgepole pine. Appl Biochem Biotechnol 2012, 168:1556-1567.
• [13]Gao J, Anderson D, Levie B: Saccharification of recalcitrant biomass and integration options for lignocellulosic sugars from Catchlight Energy’s sugar process (CLE Sugar). Biotechnol Biofuels 2013, 6:10. BioMed Central Full Text
• [14]Rødsrud G, Lersch M, Sjöde A: History and future of world’s most advanced biorefinery in operation. Biomass Bioenergy 2012, 46:46-59.
• [15]Stoklosa RJ, Hodge DB: Integration of (hemi)-cellulosic biofuels technologies with chemical pulp production. In Biorefineries: integrated biochemical processes for liquid biofuels. Edited by Qureshi N, Hodge DB, Vertès A. Elsevier Press, Amsterdam; 2014.
• [16]Pan XJ, Gilkes N, Kadla J, Pye K, Saka S, Gregg D, et al.: Bioconversion of hybrid poplar to ethanol and co-products using an organosolv fractionation process: optimization of process yields. Biotechnol Bioeng 2006, 94:851-861.
• [17]Tucker M, Farmer J, Keller F, Schell D, Nguyen Q: Comparison of yellow poplar pretreatment between NREL digester and sunds hydrolyzer. Appl Biochem Biotechnol 1998, 70–72:25-35.
• [18]Kim Y, Mosier NS, Ladisch MR: Enzymatic digestion of liquid hot water pretreated hybrid poplar. Biotechnol Prog 2009, 25:340-348.
• [19]Garrote G, Domínguez H, Parajó JC: Mild autohydrolysis: an environmentally friendly technology for xylooligosaccharide production from wood. J Chem Technol Biotechnol 1999, 74:1101-1109.
• [20]Allen SG, Schulman D, Lichwa J, Antal MJ, Jennings E, Elander R: A comparison of aqueous and dilute-acid single-temperature pretreatment of yellow poplar sawdust. Ind Eng Chem Res 2001, 40:2352-2361.
• [21]Bajpai P: Environmentally benign approaches for pulp bleaching. Elsevier, Amsterdam; 2005.
• [22]Dignum MJ, Kerler J, Verpoorte R: Vanilla production: technological, chemical, and biosynthetic aspects. Food Rev Int 2001, 17:119-120.
• [23]Fackler K, Srebotnik E, Watanabe T, Lamaipis P, Humar M, Tavzes C et al (2002) Biomimetic pulp bleaching with copper complexes and hydroperoxides. In: Viikari L, Lantto R (eds) Progress in biotechnology, vol 21. Elsevier, Amsterdam, pp 223–230
• [24]Hage R, Iburg JE, Kerschner J, Koek JH, Lempers ELM, Martens RJ, et al.: Efficient manganese catalysts for low-temperature bleaching. Nature 1994, 369:637-639.
• [25]Hage R, Lienke A: Applications of transition-metal catalysts to textile and wood-pulp bleaching. Angew Chem Int Ed 2006, 45:206-222.
• [26]Odermatt J, Kordsachia O, Patt R, Kühne L, Chen CL, Gratzl JS (2001) A manganese-based catalyst for alkaline peroxide bleaching. In: Argyropoulos DS (ed) Oxidative delignification chemistry, vol 785, pp 235–254
• [27]Perng YS, Oloman CW, Watson PA, James BR: Catalytic oxygen bleaching of wood pulp with metal prophyrin and phthalocyanine complexes. Tappi J 1994, 77:119-125.
• [28]Rahmawati N, Ohashi Y, Honda Y, Kuwahara M, Fackler K, Messner K, et al.: Pulp bleaching by hydrogen peroxide activated with copper 2,2′-dipyridylamine and 4-aminopyridine complexes. Chem Eng J 2005, 112:167-171.
• [29]Xu C, Long X, Du J, Fu S: A critical reinvestigation of the TAED-activated peroxide system for low-temperature bleaching of cotton. Carb Polym 2013, 92:249-253.
• [30]Korpi H, Lahtinen P, Sippola V, Krause O, Leskelä M, Repo T: An efficient method to investigate metal–ligand combinations for oxygen bleaching. Appl Catal A 2004, 268:199-206.
• [31]Rovio S, Kallioinen A, Tamminen T, Hakola M, Leskela M, Siika-Aho M: Catalyzed alkaline oxidation as a wood fractionation technique. BioRes 2012, 7:756-776.
• [32]Das S, Lachenal D, Marlin N: Production of pure cellulose from Kraft pulp by a totally chlorine-free process using catalyzed hydrogen peroxide. Ind Crop Prod 2013, 49:844-850.
• [33]Gueneau B, Marlin N, Deronzier A, Lachenal D: Pulp delignification with oxygen and copper(II)-polyimine complexes. Holzforschung 2014, 68:377-384.
• [34]Hakola M, Kallioinen A, Kemell M, Lahtinen P, Lankinen E, Leskelä M, et al.: Liberation of cellulose from the lignin cage: a catalytic pretreatment method for the production of cellulosic ethanol. ChemSusChem 2010, 3:1142-1145.
• [35]Argyropoulos DS, Suchy M, Akim L: Nitrogen-centered activators of peroxide-reinforced oxygen delignification. Ind Chem Eng Res 2004, 43:1200-1205.
• [36]Li Z, Chen CH, Liu T, Mathrubootham V, Hegg EL, Hodge DB: Catalysis with Cu II (bpy) improves alkaline hydrogen peroxide pretreatment. Biotechnol Bioeng 2013, 110(1078–1086):37.
• [37]Li Z, Chen C, Hegg E, Hodge DB: Rapid and effective oxidative pretreatment of woody biomass at mild reaction conditions and low oxidant loadings. Biotechnol Biofuel 2013, 6:119. BioMed Central Full Text
• [38]Chang V, Holtzapple M: Fundamental factors affecting biomass enzymatic reactivity. Appl Biochem Biotechnol 2000, 84–86:5-37.
• [39]Li M, Pattathil S, Hahn MG, Hodge DB: Identification of features associated with plant cell wall recalcitrance to pretreatment by alkaline hydrogen peroxide in diverse bioenergy feedstocks using glycome profiling. RSC Adv 2014, 4:17282-17292.
• [40]Ruffell J, Levie B, Helle S, Duff S: Pretreatment and enzymatic hydrolysis of recovered fibre for ethanol production. Biores Technol 2010, 101:2267-2272.
• [41]Li M, Foster C, Kelkar S, Pu YQ, Holmes D, Ragauskas A, et al.: Structural characterization of alkaline hydrogen peroxide pretreated grasses exhibiting diverse lignin phenotypes. Biotechnol Biofuels 2012, 5:38. BioMed Central Full Text
• [42]Foston M, Ragauskas A: Biomass characterization: recent progress in understanding biomass recalcitrance. Ind Biotechnol 2012, 8:191-208.
• [43]Donohoe BS, Vinzant TB, Elander RT, Pallapolu VR, Lee YY, Garlock RJ, et al.: Surface and ultrastructural characterization of raw and pretreated switchgrass. Biores Technol 2011, 102:11097-11104.
• [44]Chundawat SP, Donohoe BS, da Costa Sousa L, Elder T, Agarwal UP, Lu F, et al.: Multi-scale visualization and characterization of lignocellulosic plant cell wall deconstruction during thermochemical pretreatment. Energ Environ Sci 2011, 4:973-984.
• [45]Ding S-Y, Liu Y-S, Zeng Y, Himmel ME, Baker JO, Bayer EA: How does plant cell wall nanoscale architecture correlate with enzymatic digestibility? Science 2012, 338:1055-1060.
• [46]Fromm J, Rockel B, Lautner S, Windeisen E, Wanner G: Lignin distribution in wood cell walls determined by TEM and backscattered SEM techniques. J Struct Biol 2003, 143:77-84.
• [47]Fahlén J, Salmén L: Pore and matrix distribution in the fiber wall revealed by atomic force microscopy and image analysis. Biomacromolecules 2005, 6:433-438.
• [48]Donohoe BS, Decker SR, Tucker MP, Himmel ME, Vinzant TB: Visualizing lignin coalescence and migration through maize cell walls following thermochemical pretreatment. Biotechnol Bioeng 2008, 101:913-925.
• [49]Donaldson L: Delamination of Wood at the Microscopic Scale: current knowledge and methods. In Delamination in wood, wood products and wood-based composites. Edited by Bucur V. Springer, The Netherlands; 2011:123-144.
• [50]Irvine GM: The significance of the glass transition of lignin in thermomechanical pulping. Wood Sci Technol 1985, 19:139-149.
• [51]Lin HC, Ohuchi T, Murase Y, Shiah TC, Gu LT, Lee MJ, et al.: Application of TGA and EDX analysis to evaluate the process of preservative-treated woods. J Fac Agr Kyushu U 2006, 51:337-344.
• [52]Jauneau A, Quentin M, Driouich A: Micro-heterogeneity of pectins and calcium distribution in the epidermal and cortical parenchyma cell walls of flax hypocotyl. Protoplasma 1997, 198:9-19.
• [53]Goldstein S, Czapski G: Kinetics of oxidation of cuprous complexes of substituted phenanthroline and 2,2′-bipyridyl by molecular oxygen and by hydrogen peroxide in aqueous solution. Inorg Chem 1985, 24:1087-1092.
• [54]Sigel H, Flierl C, Griesser R: Metal ions and hydrogen peroxide. XX. On the kinetics and mechanism of the decomposition of hydrogen peroxide, catalyzed by the Cu 2+ -2,2′-bipyridyl complex. J Am Chem Soc 1969, 91:1061-1064.
• [55]Barnett SM, Goldberg KI, Mayer JM: A soluble copper–bipyridine water-oxidation electrocatalyst. Nat Chem 2012, 4:498-502.
• [56]Lapierre C, Jouin D, Monties B: On the molecular origin of the alkali solubility of Gramineae lignins. Phytochem 1989, 28:1401-1403.
• [57]Robinson AR, Mansfield SD: Rapid analysis of poplar lignin monomer composition by a streamlined thioacidolysis procedure and near-infrared reflectance-based prediction modeling. Plant J 2009, 58:706-714.
• [58]Werhan H, Mir JM, Voitl T, Rudolf von Rohr P: Acidic oxidation of kraft lignin into aromatic monomers catalyzed by transition metal salts. Holzforschung 2011, 65:703-709.
• [59]Zakzeski J, Jongerius AL, Weckhuysen BM: Transition metal catalyzed oxidation of Alcell lignin, soda lignin, and lignin model compounds in ionic liquids. Green Chem 2010, 12:1225-1236.
• [60]Azarpira A, Ralph J, Lu F: Catalytic alkaline oxidation of lignin and its model compounds: a pathway to aromatic biochemicals. Bioenergy Res 2014, 7:78-86.
• [61]Rencoret J, Ralph J, Marques G, Gutiérrez A, Martínez AT, del Río JC: Structural characterization of lignin isolated from coconut (Cocos nucifera) coir fibers. J Agric Food Chem 2013, 61:2434-2445.
• [62]Lu F, Karlen SD, Regner M, Kim H, Ralph SA, Sun R-C, et al.: Naturally p-hydroxybenzoylated lignins in palms. Bioenergy Res 2015.
• [63]Pacek AW, Ding P, Garrett M, Sheldrake G, Nienow AW: Catalytic conversion of sodium lignosulfonate to vanillin: engineering aspects. Part 1. Effects of processing conditions on vanillin yield and selectivity. Ind Chem Eng Res 2013, 52:8361-8372.
• [64]Santos SG, Marques AP, Lima DLD, Evtuguin DV, Esteves VI: Kinetics of eucalypt lignosulfonate oxidation to aromatic aldehydes by oxygen in alkaline medium. Ind Chem Eng Res 2011, 50:291-298.
• [65]Kirk TK, Farrell RL: Enzymatic “combustion”: the microbial degradation of lignin. Annu Rev Microbiol 1987, 41:465-501.
• [66]Omori S, Dence CW: The reactions of alkaline hydrogen-peroxide with lignin model dimers. 2. Guaiacylglycerol-beta-guaiacyl ether. Wood Sci Technol 1981, 15:113-123.
• [67]Mansfield SD, Kim H, Lu F, Ralph J: Whole plant cell wall characterization using solution-state 2D NMR. Nat Protoc 2012, 7:1579-1589.
• [68]Marttila S, Santén K: Practical aspects of immunomicroscopy on plant material. In Modern research and educational topics in microscopy. Edited by Méndez-Vilas A, Díaz D. Formatex, Badajoz; 2007:1015-1021.
• [69]Stoklosa RJ, Hodge DB: Extraction, recovery, and characterization of hardwood and grass hemicelluloses for integration into biorefining processes. Ind Eng Chem Res 2012, 51:11045-11053.
• [70]Kim H, Ralph J, Akiyama T: Solution-state 2D NMR of ball-milled plant cell wall gels in DMSO-d 6. Bioenergy Res 2008, 1:56-66.
• [71]Kupče E, Freeman R: Compensated adiabatic inversion pulses: broadband INEPT and HSQC. J Magn Reson 2007, 187:258-265.
• [72]Kim H, Ralph J: Solution-state 2D NMR of ball-milled plant cell wall gels in DMSO-d 6 /pyridine-d 5. Org Biomol Chem 2010, 8:576-591.