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Title: Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis

Abstract

A comprehensive picture of structural changes of cellulosic biomass during enzymatic hydrolysis is essential for a better understanding of enzymatic actions and development of more efficient enzymes. In this study, a suite of analytical techniques including sum frequency generation (SFG) spectroscopy, infrared (IR) spectroscopy, x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) were employed for lignin-free model biomass samples—Avicel, bleached softwood, and bacterial cellulose—to find correlations between the decrease in hydrolysis rate over time and the structural or chemical changes of biomass during the hydrolysis reaction. The results showed that the decrease in hydrolysis rate over time appears to correlate with the irreversible deposition of non-cellulosic species (either reaction side products or denatured enzymes, or both) on the cellulosic substrate surface. The crystallinity, degree of polymerization, and meso-scale packing of cellulose do not seem to positively correlate with the decrease in hydrolysis rate observed for all three substrates tested in this study. Moreover, it was also found that the cellulose Iα component of the bacterial cellulose is preferentially hydrolyzed by the enzyme than the cellulose Iβ component.

Authors:
 [1];  [2];  [1];  [2];  [1]
  1. Pennsylvania State Univ., University Park, PA (United States)
  2. North Carolina State Univ., Raleigh, NC (United States)
Publication Date:
Research Org.:
Pennsylvania State Univ., University Park, PA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Lignocellulose Structure and Formation (CLSF)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1239291
Grant/Contract Number:  
SC0001090
Resource Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 5; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; biofuels; optical spectroscopy

Citation Formats

Kafle, Kabindra, Shin, Heenae, Lee, Christopher M., Park, Sunkyu, and Kim, Seong H. Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis. United States: N. p., 2015. Web. doi:10.1038/srep15102.
Kafle, Kabindra, Shin, Heenae, Lee, Christopher M., Park, Sunkyu, & Kim, Seong H. Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis. United States. doi:10.1038/srep15102.
Kafle, Kabindra, Shin, Heenae, Lee, Christopher M., Park, Sunkyu, and Kim, Seong H. Wed . "Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis". United States. doi:10.1038/srep15102. https://www.osti.gov/servlets/purl/1239291.
@article{osti_1239291,
title = {Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis},
author = {Kafle, Kabindra and Shin, Heenae and Lee, Christopher M. and Park, Sunkyu and Kim, Seong H.},
abstractNote = {A comprehensive picture of structural changes of cellulosic biomass during enzymatic hydrolysis is essential for a better understanding of enzymatic actions and development of more efficient enzymes. In this study, a suite of analytical techniques including sum frequency generation (SFG) spectroscopy, infrared (IR) spectroscopy, x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) were employed for lignin-free model biomass samples—Avicel, bleached softwood, and bacterial cellulose—to find correlations between the decrease in hydrolysis rate over time and the structural or chemical changes of biomass during the hydrolysis reaction. The results showed that the decrease in hydrolysis rate over time appears to correlate with the irreversible deposition of non-cellulosic species (either reaction side products or denatured enzymes, or both) on the cellulosic substrate surface. The crystallinity, degree of polymerization, and meso-scale packing of cellulose do not seem to positively correlate with the decrease in hydrolysis rate observed for all three substrates tested in this study. Moreover, it was also found that the cellulose Iα component of the bacterial cellulose is preferentially hydrolyzed by the enzyme than the cellulose Iβ component.},
doi = {10.1038/srep15102},
journal = {Scientific Reports},
number = ,
volume = 5,
place = {United States},
year = {2015},
month = {10}
}

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Works referenced in this record:

Fuel Ethanol from Cellulosic Biomass
journal, March 1991


Toward an aggregated understanding of enzymatic hydrolysis of cellulose: Noncomplexed cellulase systems
journal, November 2004

  • Zhang, Yi-Heng Percival; Lynd, Lee R.
  • Biotechnology and Bioengineering, Vol. 88, Issue 7, p. 797-824
  • DOI: 10.1002/bit.20282

Substrate and Enzyme Characteristics that Limit Cellulose Hydrolysis
journal, October 1999

  • Mansfield, S. D.; Mooney, C.; Saddler, J. N.
  • Biotechnology Progress, Vol. 15, Issue 5
  • DOI: 10.1021/bp9900864

Correlation between X-ray diffraction measurements of cellulose crystalline structure and the susceptibility to microbial cellulase
journal, June 1979

  • Sasaki, Takashi; Tanaka, Takashi; Nanbu, Noriko
  • Biotechnology and Bioengineering, Vol. 21, Issue 6
  • DOI: 10.1002/bit.260210608

Effect of structural and physico-chemical features of cellulosic substrates on the efficiency of enzymatic hydrolysis
journal, July 1991

  • Sinitsyn, A. P.; Gusakov, A. V.; Vlasenko, E. Yu.
  • Applied Biochemistry and Biotechnology, Vol. 30, Issue 1
  • DOI: 10.1007/BF02922023

Effect of enzymatic hydrolysis on the morphology and fine structure of pretreated cellulosic residues
journal, October 1993


Effect of crystallinity and degree of polymerization of cellulose on enzymatic saccharification
journal, October 1984


Comparison of pretreatment methods on the basis of available surface area
journal, January 1992

  • Thompson, David N.; Chen, Hsin-Chih; Grethlein, Hans E.
  • Bioresource Technology, Vol. 39, Issue 2, p. 155-163
  • DOI: 10.1016/0960-8524(92)90135-K

Pretreatment for enhanced hydrolysis of cellulosic biomass
journal, January 1984


Common processes drive the thermochemical pretreatment of lignocellulosic biomass
journal, January 2014

  • Langan, Paul; Petridis, Loukas; O'Neill, Hugh M.
  • Green Chem., Vol. 16, Issue 1
  • DOI: 10.1039/C3GC41962B

Cellulase digestibility of pretreated biomass is limited by cellulose accessibility
journal, January 2007

  • Jeoh, Tina; Ishizawa, Claudia I.; Davis, Mark F.
  • Biotechnology and Bioengineering, Vol. 98, Issue 1, p. 112-122
  • DOI: 10.1002/bit.21408

Effects of hemicellulose removal on cellulose fiber structure and recycling characteristics of eucalyptus pulp
journal, June 2010


Characterization of crystalline cellulose in biomass: Basic principles, applications, and limitations of XRD, NMR, IR, Raman, and SFG
journal, October 2013

  • Kim, Seong H.; Lee, Christopher M.; Kafle, Kabindra
  • Korean Journal of Chemical Engineering, Vol. 30, Issue 12
  • DOI: 10.1007/s11814-013-0162-0

Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance
journal, January 2010

  • Park, Sunkyu; Baker, John O.; Himmel, Michael E.
  • Biotechnology for Biofuels, Vol. 3, Issue 1
  • DOI: 10.1186/1754-6834-3-10

Cellulose polymorphy, crystallite size, and the Segal Crystallinity Index
journal, February 2013


Nanodomains of I α and I β Cellulose in Algal Microfibrils
journal, September 1998

  • Imai, Tomoya; Sugiyama, Junji
  • Macromolecules, Vol. 31, Issue 18
  • DOI: 10.1021/ma980664h

Monitoring Meso-Scale Ordering of Cellulose in Intact Plant Cell Walls Using Sum Frequency Generation Spectroscopy
journal, August 2013


Selective Detection of Crystalline Cellulose in Plant Cell Walls with Sum-Frequency-Generation (SFG) Vibration Spectroscopy
journal, July 2011

  • Barnette, Anna L.; Bradley, Laura C.; Veres, Brandon D.
  • Biomacromolecules, Vol. 12, Issue 7
  • DOI: 10.1021/bm200518n

Cellulose polymorphs and physical properties of cotton fabrics processed with commercial textile mills for mercerization and liquid ammonia treatments
journal, March 2014

  • Kafle, Kabindra; Greeson, Kenneth; Lee, Christopher
  • Textile Research Journal, Vol. 84, Issue 16
  • DOI: 10.1177/0040517514527379

An Empirical Method for Estimating the Degree of Crystallinity of Native Cellulose Using the X-Ray Diffractometer
journal, October 1959


Analyzing cellulose degree of polymerization and its relevancy to cellulosic ethanol
journal, January 2011

  • Hallac, Bassem B.; Ragauskas, Arthur J.
  • Biofuels, Bioproducts and Biorefining, Vol. 5, Issue 2
  • DOI: 10.1002/bbb.269

Evaluation of several microcrystalline celluloses obtained from agricultural by-products
journal, January 2011

  • Rojas, John; Lopez, Alvin; Guisao, Santiago
  • Journal of Advanced Pharmaceutical Technology & Research, Vol. 2, Issue 3
  • DOI: 10.4103/2231-4040.85527

Study on crystal structures of enzyme-hydrolyzed cellulosic materials by X-ray diffraction
journal, February 2005


Cellulose crystallinity - a key predictor of the enzymatic hydrolysis rate: Cellulose crystallinity
journal, February 2010


Helically agitated mixing in dry dilute acid pretreatment enhances the bioconversion of corn stover into ethanol
journal, January 2014

  • He, Yanqing; Zhang, Longping; Zhang, Jian
  • Biotechnology for Biofuels, Vol. 7, Issue 1
  • DOI: 10.1186/1754-6834-7-1

Changes in Submicrometer Structure of Enzymatically Hydrolyzed Microcrystalline Cellulose
journal, April 2010

  • Penttilä, Paavo A.; Várnai, Anikó; Leppänen, Kirsi
  • Biomacromolecules, Vol. 11, Issue 4
  • DOI: 10.1021/bm1001119

Molecular-Scale Investigations of Cellulose Microstructure during Enzymatic Hydrolysis
journal, August 2010

  • Santa-Maria, Monica; Jeoh, Tina
  • Biomacromolecules, Vol. 11, Issue 8
  • DOI: 10.1021/bm100366h

Visualizing cellulase activity
journal, March 2013

  • Bubner, Patricia; Plank, Harald; Nidetzky, Bernd
  • Biotechnology and Bioengineering, Vol. 110, Issue 6
  • DOI: 10.1002/bit.24884

Changes in pore size distribution during the drying of cellulose fibers as measured by differential scanning calorimetry
journal, October 2006


Effect of pore size in substrate and diffusion of enzyme on hydrolysis of cellulosic materials with cellulases
journal, August 1988

  • Tanaka, Mitsuo; Ikesaka, Makoto; Matsuno, Ryuichi
  • Biotechnology and Bioengineering, Vol. 32, Issue 5
  • DOI: 10.1002/bit.260320515

Sum-Frequency-Generation Vibration Spectroscopy and Density Functional Theory Calculations with Dispersion Corrections (DFT-D2) for Cellulose Iα and Iβ
journal, May 2013

  • Lee, Christopher M.; Mohamed, Naseer M. A.; Watts, Heath D.
  • The Journal of Physical Chemistry B, Vol. 117, Issue 22
  • DOI: 10.1021/jp402998s

Nanostructure of cellulose microfibrils in spruce wood
journal, November 2011

  • Fernandes, A. N.; Thomas, L. H.; Altaner, C. M.
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 47
  • DOI: 10.1073/pnas.1108942108

Reproducible XPS on biopolymers: cellulose studies
journal, August 2004

  • Johansson, Leena-Sisko; Campbell, J. M.
  • Surface and Interface Analysis, Vol. 36, Issue 8
  • DOI: 10.1002/sia.1827

XPS characterization of naturally aged wood
journal, December 2009

  • Popescu, Carmen-Mihaela; Tibirna, Carmen-Mihaela; Vasile, Cornelia
  • Applied Surface Science, Vol. 256, Issue 5
  • DOI: 10.1016/j.apsusc.2009.08.087

Changes in the enzymatic hydrolysis rate of Avicel cellulose with conversion
journal, January 2006

  • Yang, Bin; Willies, Deidre M.; Wyman, Charles E.
  • Biotechnology and Bioengineering, Vol. 94, Issue 6
  • DOI: 10.1002/bit.20942

Evaluation of the factors affecting avicel reactivity using multi-stage enzymatic hydrolysis
journal, December 2011

  • Yu, Zhiying; Jameel, Hasan; Chang, Hou-min
  • Biotechnology and Bioengineering, Vol. 109, Issue 5
  • DOI: 10.1002/bit.24386

Mineral components of plant cell walls
journal, October 1978


Effects of alkaline or liquid-ammonia treatment on crystalline cellulose: changes in crystalline structure and effects on enzymatic digestibility
journal, January 2011

  • Mittal, Ashutosh; Katahira, Rui; Himmel, Michael E.
  • Biotechnology for Biofuels, Vol. 4, Issue 1
  • DOI: 10.1186/1754-6834-4-41

Molecular-Level Origins of Biomass Recalcitrance: Decrystallization Free Energies for Four Common Cellulose Polymorphs
journal, April 2011

  • Beckham, Gregg T.; Matthews, James F.; Peters, Baron
  • The Journal of Physical Chemistry B, Vol. 115, Issue 14
  • DOI: 10.1021/jp1106394

The enzymatic susceptibility of cellulose microfibrils of the algal-bacterial type and the cotton-ramie type
journal, December 1997


Enzymatic hydrolysis of different allomorphic forms of microcrystalline cellulose
journal, October 2011


Allomorphs of native crystalline cellulose I evaluated by two equatoriald-spacings
journal, April 2001

  • Wada, Masahisa; Okano, Takeshi; Sugiyama, Junji
  • Journal of Wood Science, Vol. 47, Issue 2
  • DOI: 10.1007/BF00780560

Idealized powder diffraction patterns for cellulose polymorphs
journal, August 2013


Varietal difference in cellulose microfibril dimensions observed by infrared spectroscopy
journal, September 2008