Transition of Cellulose Crystalline Structure and Surface Morphology of Biomass as a Function of Ionic Liquid Pretreatment and Its Relation to Enzymatic Hydrolysis
Abstract
Cellulose is inherently resistant to breakdown, and the native crystalline structure (cellulose I) of cellulose is considered to be one of the major factors limiting its potential in terms of cost-competitive lignocellulosic biofuel production. Here we report the impact of ionic liquid pretreatment on the cellulose crystalline structure in different feedstocks, including microcrystalline cellulose (Avicel), switchgrass (Panicum virgatum), pine ( Pinus radiata ), and eucalyptus ( Eucalyptus globulus ), and its influence on cellulose hydrolysis kinetics of the resultant biomass. These feedstocks were pretreated using 1-ethyl-3-methyl imidazolium acetate ([C2mim][OAc]) at 120 and 160 °C for 1, 3, 6, and 12 h. The influence of the pretreatment conditions on the cellulose crystalline structure was analyzed by X-ray diffraction (XRD). On a larger length scale, the impact of ionic liquid pretreatment on the surface roughness of the biomass was determined by small-angle neutron scattering (SANS). Pretreatment resulted in a loss of native cellulose crystalline structure. However, the transformation processes were distinctly different for Avicel and for the biomass samples. For Avicel, a transformation to cellulose II occurred for all processing conditions. For the biomass samples, the data suggest that pretreatment for most conditions resulted in an expanded cellulose I lattice. For switchgrass, first evidence of cellulose II only occurred after 12 h of pretreatment at 120 °C. For eucalyptus, first evidence of cellulose II required more intense pretreatment (3 h at 160 °C). For pine, no clear evidence of cellulose II content was detected for the most intense pretreatment conditions of this study (12 h at 160 °C). Interestingly, the rate of enzymatic hydrolysis of Avicel was slightly lower for pretreatment at 160 °C compared with pretreatment at 120 °C. For the biomass samples, the hydrolysis rate was much greater for pretreatment at 160 °C compared with pretreatment at 120 °C. The result for Avicel can be explained by more complete conversion to cellulose II upon precipitation after pretreatment at 160 °C. By comparison, the result for the biomass samples suggests that another factor, likely lignin-carbohydrate complexes, also impacts the rate of cellulose hydrolysis in addition to cellulose crystallinity.
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Several empirical and semi-empirical polarity scales have been used to explain and predict solubility of biomolecules and biopolymers in solvents, for example Hansen solubility parameters, COSMO-RS and Kamlet-Taft polarity parameters.
“Several empirical and semi-empirical polarity scales have been used to explain and predict solubility of biomolecules and biopolymers in solvents, for example the Hansen solubility parameters, 21,85 COSMO-RS 86 and the Kamlet-Taft polarity parameters.87”
From Deconstruction of lignocellulosic biomass with ionic liquids (2013) · cites this paper as [86]
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- Authors
- Cheng, G., Varanasi, P., Li, C., Liu, H., Melnichenko, Y. B., Simmons, B. A., Kent, M. S., & Singh, S.
- Affiliations
- Sandia National Laboratories California (US)
- Oak Ridge National Laboratory (US)
- Corresponding author
- Singh, Seema
- Venue
- Biomacromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2011-02-25
- Volume
- 12
- Issue
- 4
- Pages
- 933-941
- ISSN
- 1525-7797 (ISSN-L)
- 1526-4602
- OpenAlex
- W2064639345
- Cited by
- 437
- References
- 44
- Citations by year
- 2026: 11 · 2025: 17 · 2024: 15 · 2023: 24 · 2022: 31 · 2021: 23 · 2020: 25 · 2019: 21 · 2018: 28 · 2017: 48 · 2016: 38 · 2015: 36 · 2014: 39 · 2013: 44 · 2012: 27
- FWCI
- 22.72
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Biomacromolecules (publishedVersion)
- PubMed (publishedVersion)
- Lincoln (University of Nebraska) (submittedVersion)
- Topics
- Physical Sciences › Engineering › Biomedical Engineering › Biofuel production and bioconversion
- Physical Sciences › Materials Science › Biomaterials › Advanced Cellulose Research Studies
- Physical Sciences › Engineering › Biomedical Engineering › Catalysis for Biomass Conversion
- Keywords
- ionic liquid pretreatment, cellulose crystalline structure, cellulose I, cellulose II, enzymatic hydrolysis, hydrolysis kinetics, surface roughness, biomass pretreatment, 1-ethyl-3-methylimidazolium acetate, switchgrass, pine, Eucalyptus, microcrystalline cellulose, lignocellulosic biofuels
- MeSH terms
- Carbohydrate Conformation, Cellulose, Enzymes, Hydrolysis, Surface Properties, Crystallography, X-Ray, Biomass
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