Vibrational Spectral Signatures of Crystalline Cellulose Using High Resolution Broadband Sum Frequency Generation Vibrational Spectroscopy (HR-BB-SFG-VS)
Abstract
Here we reported the first sub-wavenumber high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) study on both the C-H and O-H region spectra of crystalline cellulose. HR-BB-SFG-VS has about 10 times better resolution than the conventional scanning SFG-VS and is known to be able to measure the intrinsic spectral lineshape and to resolve much more spectral details. With HR-BB-SFG-VS, we found that in cellulose from different sources, including Avicel and cellulose crystals isolated from algae Valonia (Iα) and tunicates (Iβ), the spectral signatures in the OH regions were unique for different allomorphs, i.e. Iα and Iβ, while the spectral signatures in the C-H regions varied in all samples examined. Even though the origin of the different behaviors of the crystalline cellulose in the O-H and C-H vibrational frequency regions is yet to be correlated to the structure of cellulose, these results provided new spectroscopic methods and opportunities to classify and understand the basic crystalline structure, as well as variations, in polymorphism of the crystalline cellulose structure.
- Authors:
- Publication Date:
- Research Org.:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1182941
- Report Number(s):
- PNNL-SA-105805
47913; 47760; 46208; KP1704020
- DOE Contract Number:
- AC05-76RL01830
- Resource Type:
- Journal Article
- Journal Name:
- Cellulose, 22(3):1469-1484
- Additional Journal Information:
- Journal Name: Cellulose, 22(3):1469-1484
- Country of Publication:
- United States
- Language:
- English
- Subject:
- Vibrational; spectral; signatures; crystalline; cellulose; high resolution; broadband; vibrational; spectroscopy; Environmental Molecular Sciences Laboratory
Citation Formats
Zhang, Libing, Lu, Zhou, Velarde Ruiz Esparza, Luis A., Fu, Li, Pu, Yunqiao, Ding, Shi-You, Ragauskas, Art J., Wang, Hongfei, and Yang, Bin. Vibrational Spectral Signatures of Crystalline Cellulose Using High Resolution Broadband Sum Frequency Generation Vibrational Spectroscopy (HR-BB-SFG-VS). United States: N. p., 2015.
Web. doi:10.1007/s10570-015-0588-0.
Zhang, Libing, Lu, Zhou, Velarde Ruiz Esparza, Luis A., Fu, Li, Pu, Yunqiao, Ding, Shi-You, Ragauskas, Art J., Wang, Hongfei, & Yang, Bin. Vibrational Spectral Signatures of Crystalline Cellulose Using High Resolution Broadband Sum Frequency Generation Vibrational Spectroscopy (HR-BB-SFG-VS). United States. https://doi.org/10.1007/s10570-015-0588-0
Zhang, Libing, Lu, Zhou, Velarde Ruiz Esparza, Luis A., Fu, Li, Pu, Yunqiao, Ding, Shi-You, Ragauskas, Art J., Wang, Hongfei, and Yang, Bin. 2015.
"Vibrational Spectral Signatures of Crystalline Cellulose Using High Resolution Broadband Sum Frequency Generation Vibrational Spectroscopy (HR-BB-SFG-VS)". United States. https://doi.org/10.1007/s10570-015-0588-0.
@article{osti_1182941,
title = {Vibrational Spectral Signatures of Crystalline Cellulose Using High Resolution Broadband Sum Frequency Generation Vibrational Spectroscopy (HR-BB-SFG-VS)},
author = {Zhang, Libing and Lu, Zhou and Velarde Ruiz Esparza, Luis A. and Fu, Li and Pu, Yunqiao and Ding, Shi-You and Ragauskas, Art J. and Wang, Hongfei and Yang, Bin},
abstractNote = {Here we reported the first sub-wavenumber high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) study on both the C-H and O-H region spectra of crystalline cellulose. HR-BB-SFG-VS has about 10 times better resolution than the conventional scanning SFG-VS and is known to be able to measure the intrinsic spectral lineshape and to resolve much more spectral details. With HR-BB-SFG-VS, we found that in cellulose from different sources, including Avicel and cellulose crystals isolated from algae Valonia (Iα) and tunicates (Iβ), the spectral signatures in the OH regions were unique for different allomorphs, i.e. Iα and Iβ, while the spectral signatures in the C-H regions varied in all samples examined. Even though the origin of the different behaviors of the crystalline cellulose in the O-H and C-H vibrational frequency regions is yet to be correlated to the structure of cellulose, these results provided new spectroscopic methods and opportunities to classify and understand the basic crystalline structure, as well as variations, in polymorphism of the crystalline cellulose structure.},
doi = {10.1007/s10570-015-0588-0},
url = {https://www.osti.gov/biblio/1182941},
journal = {Cellulose, 22(3):1469-1484},
number = ,
volume = ,
place = {United States},
year = {Tue Mar 03 00:00:00 EST 2015},
month = {Tue Mar 03 00:00:00 EST 2015}
}
Works referenced in this record:
Vibrational Sum-Frequency Spectroscopy for Trace Chemical Detection on Surfaces at Stand-Off Distances
journal, March 2013
- Asher, William E.; Willard-Schmoe, Ella
- Applied Spectroscopy, Vol. 67, Issue 3
Native Cellulose: A Composite of Two Distinct Crystalline Forms
journal, January 1984
- Atalla, R. H.; Vanderhart, D. L.
- Science, Vol. 223, Issue 4633
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
Quantification of crystalline cellulose in lignocellulosic biomass using sum frequency generation (SFG) vibration spectroscopy and comparison with other analytical methods
journal, July 2012
- Barnette, Anna L.; Lee, Christopher; Bradley, Laura C.
- Carbohydrate Polymers, Vol. 89, Issue 3
Structure and Interactions of Plant Cell-Wall Polysaccharides by Two- and Three-Dimensional Magic-Angle-Spinning Solid-State NMR
journal, February 2011
- Dick-Pérez, Marilú; Zhang, Yuan; Hayes, Jennifer
- Biochemistry, Vol. 50, Issue 6
Imaging Cellulose Using Atomic Force Microscopy
book, January 2012
- Ding, Shi-You; Liu, Yu-San
- Methods in Molecular Biology
Versatile derivatives of carbohydrate-binding modules for imaging of complex carbohydrates approaching the molecular level of resolution
journal, October 2006
- Ding, Shi-You; Xu, Qi; Ali, Mursheda K.
- BioTechniques, Vol. 41, Issue 4
Size, shape, and arrangement of native cellulose fibrils in maize cell walls
journal, December 2013
- Ding, Shi-You; Zhao, Shuai; Zeng, Yining
- Cellulose, Vol. 21, Issue 2
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
Cellulose Nanocrystals: Chemistry, Self-Assembly, and Applications
journal, June 2010
- Habibi, Youssef; Lucia, Lucian A.; Rojas, Orlando J.
- Chemical Reviews, Vol. 110, Issue 6
The confirmation of existences of cellulose IIII, IIIII, IVI, and IVII by the X-ray method
journal, January 1975
- Hayashi, Jisuke; Sufoka, Akinori; Ohkita, Junji
- Journal of Polymer Science: Polymer Letters Edition, Vol. 13, Issue 1
Undirectional degradation of valonia cellulose microcrystals subjected to cellulase action
journal, May 1985
- Chanzy, Henri; Henrissat, Bernard
- FEBS Letters, Vol. 184, Issue 2
Biomass Recalcitrance: Engineering Plants and Enzymes for Biofuels Production
journal, February 2007
- Himmel, M. E.; Ding, S.-Y.; Johnson, D. K.
- Science, Vol. 315, Issue 5813, p. 804-807
Almost Pure Iα Cellulose in the Cell Wall of Glaucocystis
journal, October 1999
- Imai, Tomoya; Sugiyama, Junji; Itoh, Takao
- Journal of Structural Biology, Vol. 127, Issue 3
Solid-state CP/MAS carbon-13 NMR study of cellulose polymorphs
journal, July 1989
- Isogai, Akira; Usuda, Makoto; Kato, Takashi
- Macromolecules, Vol. 22, Issue 7
Cellulose microfibril orientation in onion (Allium cepa L.) epidermis studied by atomic force microscopy (AFM) and vibrational sum frequency generation (SFG) spectroscopy
journal, December 2013
- Kafle, Kabindra; Xi, Xiaoning; Lee, Christopher M.
- Cellulose, Vol. 21, Issue 2
Vibrational sum-frequency-generation (SFG) spectroscopy study of the structural assembly of cellulose microfibrils in reaction woods
journal, June 2014
- Kafle, Kabindra; Shi, Rui; Lee, Christopher M.
- Cellulose, Vol. 21, Issue 4
Surface and Interface Spectroscopy of High Explosives and Binders: HMX and Estane
journal, April 2006
- Kim, Hackjin; Lagutchev, Alexei; Dlott, Dana D.
- Propellants, Explosives, Pyrotechnics, Vol. 31, Issue 2
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
Crystalline cellulose: structure and hydrogen bonds
journal, May 2010
- Kovalenko, Valeri I.
- Russian Chemical Reviews, Vol. 79, Issue 3
Atomic Force Microscopy Characterization of Cellulose Nanocrystals
journal, March 2010
- Lahiji, Roya R.; Xu, Xin; Reifenberger, Ronald
- Langmuir, Vol. 26, Issue 6
CP/MAS -NMR spectroscopy applied to structure and interaction studies on cellulose I
journal, October 1999
- Larsson, Per Tomas; Hult, Eva-Lena; Wickholm, Kristina
- Solid State Nuclear Magnetic Resonance, Vol. 15, Issue 1
Cellulose polymorphism study with sum-frequency-generation (SFG) vibration spectroscopy: identification of exocyclic CH2OH conformation and chain orientation
journal, April 2013
- Lee, Christopher M.; Mittal, Ashutosh; Barnette, Anna L.
- Cellulose, Vol. 20, Issue 3
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
Probing crystal structure and mesoscale assembly of cellulose microfibrils in plant cell walls, tunicate tests, and bacterial films using vibrational Sum Frequency Generation (SFG) spectroscopy
journal, January 2014
- Lee, Christopher M.; Kafle, Kabindra; Park, Yong Bum
- Physical Chemistry Chemical Physics, Vol. 16, Issue 22
Infrared spectra of crystalline polysaccharides. II. Native celluloses in the region from 640 to 1700 cm.1
journal, September 1959
- Liang, C. Y.; Marchessault, R. H.
- Journal of Polymer Science, Vol. 39, Issue 135
Vibrational Polarization Spectroscopy of CH Stretching Modes of the Methylene Group at the Vapor/Liquid Interfaces with Sum Frequency Generation
journal, June 2004
- Lu, Rong; Gan, Wei; Wu, Bao-hua
- The Journal of Physical Chemistry B, Vol. 108, Issue 22
C−H Stretching Vibrations of Methyl, Methylene and Methine Groups at the Vapor/Alcohol ( n = 1−8) Interfaces
journal, July 2005
- Lu, Rong; Gan, Wei; Wu, Bao-hua
- The Journal of Physical Chemistry B, Vol. 109, Issue 29
Molecular ordering of cellulose after extraction of polysaccharides from primary cell walls of Arabidopsisthaliana: a solid-state CP/MAS 13C NMR study
journal, April 2002
- Davies, Lynette M.; Harris, Philip J.; Newman, Roger H.
- Carbohydrate Research, Vol. 337, Issue 7
Surface Studies of Aqueous Methanol Solutions by Vibrational Broad Bandwidth Sum Frequency Generation Spectroscopy
journal, July 2003
- Ma, Gang; Allen, Heather C.
- The Journal of Physical Chemistry B, Vol. 107, Issue 26
Crystalline modifications of cellulose. Part II. A study with plane-polarized infrared radiation
journal, November 1958
- Mann, J.; Marrinan, H. J.
- Journal of Polymer Science, Vol. 32, Issue 125
Infrared spectra of the crystalline modifications of cellulose
journal, August 1956
- Marrinan, H. J.; Mann, J.
- Journal of Polymer Science, Vol. 21, Issue 98
Relation of certain infrared bands to cellulose crystallinity and crystal latticed type. Part I. Spectra of lattice types I, II, III and of amorphous cellulose
journal, May 1964
- Nelson, Mary L.; O'Connor, Robert T.
- Journal of Applied Polymer Science, Vol. 8, Issue 3
Solid-State 13C NMR Investigation of Molecular Ordering in the Cellulose of Apple Cell Walls
journal, July 1994
- Newman, Roger H.; Ha, Marie-Ann; Melton, Laurence D.
- Journal of Agricultural and Food Chemistry, Vol. 42, Issue 7
Crystal Structure and Hydrogen-Bonding System in Cellulose Iβ from Synchrotron X-ray and Neutron Fiber Diffraction
journal, August 2002
- Nishiyama, Yoshiharu; Langan, Paul; Chanzy, Henri
- Journal of the American Chemical Society, Vol. 124, Issue 31
Crystal Structure and Hydrogen Bonding System in Cellulose I α from Synchrotron X-ray and Neutron Fiber Diffraction
journal, November 2003
- Nishiyama, Yoshiharu; Sugiyama, Junji; Chanzy, Henri
- Journal of the American Chemical Society, Vol. 125, Issue 47
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
Monitoring Meso-Scale Ordering of Cellulose in Intact Plant Cell Walls Using Sum Frequency Generation Spectroscopy
journal, August 2013
- Park, Y. B.; Lee, C. M.; Koo, B. -W.
- PLANT PHYSIOLOGY, Vol. 163, Issue 2
Effects of Plant Cell Wall Matrix Polysaccharides on Bacterial Cellulose Structure Studied with Vibrational Sum Frequency Generation Spectroscopy and X-ray Diffraction
journal, May 2014
- Park, Yong Bum; Lee, Christopher M.; Kafle, Kabindra
- Biomacromolecules, Vol. 15, Issue 7
Ring current enhanced vibrational circular dichroism in the carbon-hydrogen bond stretching motions of sugars
journal, April 1986
- Paterlini, M. Germana.; Freedman, Teresa B.; Nafie, Laurence A.
- Journal of the American Chemical Society, Vol. 108, Issue 7
Plant Biomass Characterization: Application of Solution- and Solid-State NMR Spectroscopy
book, April 2013
- Pu, Yunqiao; Hallac, Bassem; Ragauskas, Arthur J.
- Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion to Fuels and Chemicals
Solid-state NMR characterization of switchgrass cellulose after dilute acid pretreatment
journal, January 2010
- Samuel, Reichel; Pu, Yunqiao; Foston, Marcus
- Biofuels, Vol. 1, Issue 1
New Method for Determining the Degree of Cellulose I Crystallinity by Means of FT Raman Spectroscopy
journal, June 2005
- Schenzel, Karla; Fischer, Steffen; Brendler, Erica
- Cellulose, Vol. 12, Issue 3
Surface properties probed by second-harmonic and sum-frequency generation
journal, February 1989
- Shen, Y. R.
- Nature, Vol. 337, Issue 6207
Toward a Systems Approach to Understanding Plant Cell Walls
journal, December 2004
- Somerville, C.
- Science, Vol. 306, Issue 5705
Orientation of cellulose microcrystals by strong magnetic fields
journal, August 1992
- Sugiyama, J.; Chanzy, H.; Maret, G.
- Macromolecules, Vol. 25, Issue 16
Surface Nonlinear Vibrational Spectroscopy of Energetic Materials: HMX
journal, February 2007
- Surber, Eric; Lozano, Aaron; Lagutchev, Alexei
- The Journal of Physical Chemistry C, Vol. 111, Issue 5
Vibrational circular dichroism (VCD) studies on disaccharides in the CH region: toward discrimination of the glycosidic linkage position
journal, January 2007
- Taniguchi, Tohru; Monde, Kenji
- Organic & Biomolecular Chemistry, Vol. 5, Issue 7
Structure of Cellulose Microfibrils in Primary Cell Walls from Collenchyma
journal, November 2012
- Thomas, Lynne H.; Forsyth, V. Trevor; Šturcová, Adriana
- Plant Physiology, Vol. 161, Issue 1
Infrared spectrum and crystal structure of cellulose
journal, July 1957
- Tsuboi, Masamichi
- Journal of Polymer Science, Vol. 25, Issue 109
Capturing inhomogeneous broadening of the –CN stretch vibration in a Langmuir monolayer with high-resolution spectra and ultrafast vibrational dynamics in sum-frequency generation vibrational spectroscopy (SFG-VS)
journal, August 2013
- Velarde, Luis; Wang, Hong-fei
- The Journal of Chemical Physics, Vol. 139, Issue 8
Unique determination of the –CN group tilt angle in Langmuir monolayers using sum-frequency polarization null angle and phase
journal, October 2013
- Velarde, Luis; Wang, Hong-fei
- Chemical Physics Letters, Vol. 585
Communication: Spectroscopic phase and lineshapes in high-resolution broadband sum frequency vibrational spectroscopy: Resolving interfacial inhomogeneities of “identical” molecular groups
journal, December 2011
- Velarde, Luis; Zhang, Xian-yi; Lu, Zhou
- The Journal of Chemical Physics, Vol. 135, Issue 24
Quantitative spectral and orientational analysis in surface sum frequency generation vibrational spectroscopy (SFG-VS)
journal, April 2005
- Wang *, Hong-Fei; Gan † ‡, Wei; Lu † ‡ §, Rong
- International Reviews in Physical Chemistry, Vol. 24, Issue 2
Enzymatic hydrolysis of cellulosic biomass
journal, July 2011
- Yang, Bin; Dai, Ziyu; Ding, Shi-You
- Biofuels, Vol. 2, Issue 4
Cellulose Microcrystal Film of High Uniaxial Orientation
journal, October 1997
- Yoshiharu, Nishiyama; Shigenori, Kuga; Masahisa, Wada
- Macromolecules, Vol. 30, Issue 20
Mapping molecular orientation and conformation at interfaces by surface nonlinear optics
journal, May 1999
- Zhuang, X.; Miranda, P. B.; Kim, D.
- Physical Review B, Vol. 59, Issue 19
Structural Models for Some Liquid Crystalline Cellulose Derivatives
journal, November 1985
- Vogt, U.; Zugenmaier, P.
- Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 89, Issue 11
Works referencing / citing this record:
Strengths, challenges, and opportunities for hydrothermal pretreatment in lignocellulosic biorefineries
journal, October 2017
- Yang, Bin; Tao, Ling; Wyman, Charles E.
- Biofuels, Bioproducts and Biorefining, Vol. 12, Issue 1
Amorphous cellulose thin films
journal, February 2020
- Lu, Rui; Zhang, Xin; Fu, Li
- Cellulose, Vol. 27, Issue 6
High-resolution broadband sum frequency generation vibrational spectroscopy using intrapulse interference
journal, January 2018
- Wang, Yang; Ma, Xiangyun; Wang, Huijie
- Physical Chemistry Chemical Physics, Vol. 20, Issue 32
Flexible pulse shaping for sum frequency microspectroscopies
journal, December 2019
- Müller, Niklas; Buckup, Tiago; Motzkus, Marcus
- Journal of the Optical Society of America B, Vol. 37, Issue 1