Enzymatic hydrolysis of loblolly pine: effects of cellulose crystallinity and delignification

Umesh P. Agarwal; J.Y. Zhu; Sally A. Ralph

doi:10.1515/hf-2012-0116

Article

Enzymatic hydrolysis of loblolly pine: effects of cellulose crystallinity and delignification

, and

Published/Copyright: November 17, 2012

Published by

Become an author with De Gruyter Brill

Submit Manuscript Author Information Explore this Subject

From the journal Holzforschung Volume 67 Issue 4

Abstract

Hydrolysis experiments with commercial cellulases have been performed to understand the effects of cell wall crystallinity and lignin on the process. In the focus of the paper are loblolly pine wood samples, which were systematically delignified and partly ball-milled, and, for comparison, Whatman CC31 cellulose samples with different crystallinities. In pure cellulose samples, the percentage of cellulose hydrolysis was inversely proportional to the degree of crystallinity. For the loblolly pine samples, the extent of hydrolysis was low for the fraction with 74- to 149-μm particle size, but the ball-milled fraction was hydrolyzed easily. The impact of lignin removal was also influential as demonstrated on progressively delignified wood, i.e., the degree of saccharification increased with lignin removal. On the basis of data of 72 h hydrolysis time on materials with similar crystallinity, the cell wall was found to be eight times less hydrolyzable than Whatman CC31 cellulose. Taken together, cellulose crystallinity and composition are not as important as the ultrastructural changes caused by the disruption of the tightly packed regions of the cell wall that ensued upon acid chlorite delignification.

Keywords: ball milling; cellulase; cellulose; crystallinity; enzymatic hydrolysis; hydrolysis; lignin; loblolly pine; wood

Corresponding author: Umesh P. Agarwal, Forest Products Laboratory, USDA Forest Service, Madison, WI 53726, USA, Phone: +1-608-231-9441, Fax: +1-608-231-9538

The authors thank Fred Matt and Tom Kuster (Analytical Chemistry and Microscopy Laboratory, Forest Products Laboratory) for the composition and SEM analyses, respectively. The authors are grateful to Dr. Oskar Faix for the comprehensive review of the manuscript. The authors state that they have no conflict of interest to declare.

References

Agarwal, U.P., Reiner, R.S., Ralph, S.A. (2010) Cellulose I crystallinity determination using FT-Raman spectroscopy: univariate and multivariate methods. Cellulose 17:721–733.10.1007/s10570-010-9420-zSearch in Google Scholar

Agarwal, U.P., Reiner, R.S., Ralph, S.A. (2011) Cellulose crystallinity of woods, wood pulps, and agriculture fibers by FT-Raman spectroscopy. In: Proceedings 16th International Symposium on Wood, Fiber and Pulping Chemistry, June 8–10. Tianjin, China. China Light Industry Press: Beijing, China. pp. 69–74.Search in Google Scholar

Ahlgren, P.A., Goring, D.A.I. (1971) Removal of wood components during chlorite delignification of black spruce. Can. J. Chem. 49:1272–1275.Search in Google Scholar

Cheng, G., Varanasi, P., Li, C., Liu, H., Melnichenko, Y.B., Simmons, B.A., Kent, M.S., Singh, S. (2011) Transition of cellulose crystalline structure and surface morphology of biomass as a function of ionic liquid pretreatment and its relation to enzymatic hydrolysis. Biomacromolecules 12:933–941.10.1021/bm101240zSearch in Google Scholar PubMed

Dasari, R.K., Berson, E.R. (2007) The effect of particle size on hydrolysis reaction rates and rheological properties in cellulosic slurries. Appl. Biochem. Biotechnol. 136–140:289–299.10.1007/978-1-60327-181-3_26Search in Google Scholar

Davis, M.W. (1998) A rapid method for compositional carbohydrate analysis of lignocellulosics by high pH anion exchange chromatography with pulsed amperometric detection (HPAEC/PAD). J. Wood Chem. Technol. 18:235–252.10.1080/02773819809349579Search in Google Scholar

Díaz, M.J., Huijgen, W.J.J., van der Laan, R.R., Reith, J.H., Cara, C., Castro, E. (2011) Organosolv pretreatment of olive tree biomass for fermentable sugars. Holzforschung 65:177–183.10.1515/hf.2011.030Search in Google Scholar

Fan, L.T., Lee, Y.-H., Beardmore, D.H. (1980) Mechanism of the enzymatic hydrolysis of cellulose: effects of major structural features of cellulose on enzymatic hydrolysis. Biotechnol. Bioeng. 22:177–199.10.1002/bit.260220113Search in Google Scholar

Fukazawa, K., Revol, J.-F., Jurasek, L., Goring, D.A.I. (1982) Relationship between ball milling and the susceptibility of wood to digestion by cellulase. Wood Sci. Technol. 16:279–285.Search in Google Scholar

Guerra, A., Filpponen, I., Lucia, L., Saquing, C., Baumberger, S., Argyropoulos, D.S. (2006) Toward a better understanding of the lignin isolation process from wood. J. Agric. Food Chem. 54:5939–5947.10.1021/jf060722vSearch in Google Scholar PubMed

Jeoh, T., Ishizawa, C.I., Davis, M.F., Himmel, M.E., Adney, W.S., Johnson, D.K. (2007) Cellulase digestibility of pretreated biomass is limited by cellulose accessibility. Biotechnol. Bioeng. 98:112–122.10.1002/bit.21408Search in Google Scholar PubMed

Kirsch, C., Zetzl, C., Smirnova, I. (2011) Development of an integrated thermal and enzymatic hydrolysis for lignocellulosic biomass in fixed-bed reactors. Holzforschung 65:438–489.10.1515/hf.2011.061Search in Google Scholar

Kojiro, K., Miki, T., Sugimoto, H., Nakajima, M., Kanayama, K. (2010) Micropores and mesopores in the cell wall of dry wood. J. Wood Sci. 56:107–111.10.1007/s10086-009-1063-zSearch in Google Scholar

Luo, X., Zhu, J. (2011) Effects of drying-induced fiber hornification on enzymatic saccharification of lignocelluloses. Enzyme Microb. Technol. 48:92–99.Search in Google Scholar

Luo, X., Zhu, J.Y., Gleisner, R., Zhan, H.Y. (2011) Effect of wet pressing-induced fiber hornification on enzymatic saccharification of lignocelluloses. Cellulose 18:1055–1062.10.1007/s10570-011-9541-zSearch in Google Scholar

Maurer, A., Fengel, D. (1992) On the origin of milled wood lignin. Part 1. The influence of ball-milling on the ultrastructure of wood cell walls and the solubility of lignin. Holzforschung 46:417–423.10.1515/hfsg.1992.46.5.417Search in Google Scholar

Mooney, C.A., Mansfield, S.D., Touhy, M.G., Saddler, J.N. (1998) The effect of initial pore volume and lignin content on the enzymatic hydrolysis of softwoods. Bioresour. Technol. 64:113–119.Search in Google Scholar

Ragauskas, A.J., Williams, C.K., Davison, B.H., Britovsek, G., Cairney, J., Eckert, C.A., Frederick, W.J. Jr., Hallett, J.P., Leak, D.J., Liotta, C.L., Mielenz, J.R., Murphy, R., Templer, R., Tschaplinski, T. (2006) The path forward for biofuels and biomaterials. Science 311:484–489.10.1126/science.1114736Search in Google Scholar PubMed

Rahikainen, J., Mikander, S., Marjamaa, K., Tamminen, T., Lappas, A., Viikari, L., Kruus, K. (2011) Inhibition of enzymatic hydrolysis by residual lignins from softwood – study of enzyme binding and inactivation on lignin-rich surface. Biotechnol. Bioeng. 108:2823–2834.10.1002/bit.23242Search in Google Scholar PubMed

Rollin, J.A., Zhu, Z., Sathitsuksanoh, N., Zhang, Y.-H.P. (2010) Increasing cellulose accessibility is more important than removing lignin: a comparison of cellulose solvent-based lignocellulose fractionation and soaking in aqueous ammonia. Biotechnol. Bioeng. 108:22–30.10.1002/bit.22919Search in Google Scholar PubMed

Salmén, L., Burgert, I. (2009) Cell wall features with regard to mechanical performance. A review. COST Action E35 2004–2008: wood machining – micromechanics and fracture. Holzforschung 63:121–129.10.1515/HF.2009.011Search in Google Scholar

Schütt, F., Puls, J., Saake, B. (2011) Optimization of steam pretreatment conditions for enzymatic hydrolysis of poplar wood. Holzforschung 65:453–459.10.1515/hf.2011.066Search in Google Scholar

Stevanic, J.S., Salmén, L. (2009) Orientation of the wood polymers in the cell wall of spruce wood fibres. Holzforschung. 63:497–503.10.1515/HF.2009.094Search in Google Scholar

Stone, J.E., Scallan, A.M. (1965) Effect of component removal upon the porous structure of the cell wall of wood. J. Poly. Sci., Part C: Polym. Symp. 11:13–25.Search in Google Scholar

Sugimoto, T., Magara, K., Hosoya, S., Oosawa, S., Shimoda, T., Nishibori, K. (2009) Ozone pretreatment of lignocellulosic materials for ethanol production: improvement of enzymatic susceptibility of softwood. Holzforschung 63:537–543.10.1515/HF.2009.091Search in Google Scholar

TAPPI standard (1983) Acid insoluble lignin in wood and pulp. Official test method T 222 (Om).Search in Google Scholar

Terashima, N., Kitano, K., Kojima, M., Yoshida, M., Yamamoto, H., Westermark, U. (2009) Nanostructural assembly of cellulose, hemicellulose, and lignin in the middle layer of secondary wall of ginkgo tracheid. J. Wood Sci. 55:409–416.10.1007/s10086-009-1049-xSearch in Google Scholar

Walker, L.P., Wilson, D.B. (1991) Enzymatic hydrolysis of cellulose: an overview. Bioresour. Technol. 36:3–14.Search in Google Scholar

Wang, Q.Q., He, Z.B., Zhu, Z., Zhang, Y.-H.P., Ni, Y.H., Luo, X.L., Zhu, J.Y. (2012) Evaluations of cellulose accessibility to cellulase (CAC) of lignocelluloses by solute exclusion and protein adsorption techniques. Biotechnol. Bioeng. 109:381–389.10.1002/bit.23330Search in Google Scholar PubMed

Zhu, J.Y., Pan, X.J., Wang, G.S., Gleisner, R. (2009a) Sulfite pretreatment (SPORL) for robust enzymatic saccharification of spruce and red pine. Bioresour. Technol. 100:2411–2418.10.1016/j.biortech.2008.10.057Search in Google Scholar PubMed

Zhu, J.Y., Wang, G.S., Gleisner, R., Pan, X. (2009b) Specific surface to evaluate the efficiencies of milling and pretreatment of wood for enzymatic saccharification. Chem. Eng. Sci. 64:474–485.10.1016/j.ces.2008.09.026Search in Google Scholar

Received: 2012-7-11

Accepted: 2012-10-16

Published Online: 2012-11-17

Published in Print: 2013-05-01

You are currently not able to access this content.

Articles in the same Issue

https://doi.org/10.1515/hf-2012-0116

Keywords for this article

ball milling; cellulase; cellulose; crystallinity; enzymatic hydrolysis; hydrolysis; lignin; loblolly pine; wood