, Volume 22, Issue 3, pp 1469–1484 | Cite as

Vibrational spectral signatures of crystalline cellulose using high resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS)

  • Libing Zhang
  • Zhou Lu
  • Luis Velarde
  • Li Fu
  • Yunqiao Pu
  • Shi-You Ding
  • Arthur J. Ragauskas
  • Hong-Fei Wang
  • Bin Yang
Original Paper


Both the C–H and O–H region spectra of crystalline cellulose were studied using the sub-wavenumber high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) for the first time. The resolution of HR-BB-SFG-VS is about 10-times better than conventional scanning SFG-VS and has the capability of measuring the intrinsic spectral lineshape and revealing many more spectral details. With HR-BB-SFG-VS, we found that in cellulose samples from different sources, including Avicel and cellulose crystals isolated from algae Valonia (Iα) and tunicates (Iβ), the spectral signatures in the O–H region were unique for the two 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 spectral signatures of the crystalline cellulose in the O–H and C–H vibrational frequency regions are yet to be correlated to the structure of cellulose, these results lead to new spectroscopic methods and opportunities to classify and to understand the basic crystalline structures, as well as variations in polymorphism of the crystalline cellulose.


Cellulose Iα Cellulose Iβ Avicel High resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) 



This work was made possible through the support of the DARPA Young Faculty Award Contract # N66001-11-1-414. Authors also acknowledge the support of Bioproducts, Sciences and Engineering Laboratory, Department of Biosystems Engineering at Washington State University. L. Zhang was partially supported by the grant from the Chinese Scholarship Council (CSC). S.Y. Ding was supported by the BioEnergy Science Center, a DOE Bioenergy Research Center, and the Genomic Science Program (ER65258), both supported by the Office of Biological and Environmental Research in the DOE Office of Science. Part of this work was conducted at the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility located at the Pacific Northwest National Laboratory (PNNL) and sponsored by the Department of Energy’s Office of Biological and Environmental Research (BER). We also thank Dr. Seong Kim (Penn State University) for insightful discussions.

Supplementary material

10570_2015_588_MOESM1_ESM.docx (156 kb)
Table S1 Peak position and relative peak intensity parameters from curve fitting using Lorentzian lineshape profiles (as in Eq. 3 in the main text) of (a) Avicel, (b) cellulose Iα from alga Valonia ventricosa (Glaucocystis (nostochinearum)), and (c) cellulose Iβs from red reef tunicate and (d) Halocynthiaroretzi tunicate within wavelength of 2700–3050 cm−1 and 3200 cm−1–3450 cm−1. (DOCX 156 kb)
10570_2015_588_MOESM2_ESM.docx (277 kb)
Figure S1 (a) Raman spectra of cellulose Iα from alga Valonia ventricosa (Glaucocystis (nostochinearum)) and (b) cellulose Iβ from Halocynthiaroretzi tunicate in the frequency regions of 300 to 1600 cm−1 and 2500 to 3700 cm−1. (DOCX 277 kb)


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Copyright information

© Springer Science+Business Media Dordrecht 2015

Authors and Affiliations

  • Libing Zhang
    • 1
  • Zhou Lu
    • 2
    • 5
  • Luis Velarde
    • 2
    • 6
  • Li Fu
    • 2
  • Yunqiao Pu
    • 3
    • 7
  • Shi-You Ding
    • 4
    • 8
  • Arthur J. Ragauskas
    • 3
    • 7
  • Hong-Fei Wang
    • 2
  • Bin Yang
    • 1
  1. 1.Bioproduct Sciences and Engineering Laboratory, Department of Biological Systems EngineeringWashington State UniversityRichlandUSA
  2. 2.William R. Wiley Environmental Molecular Sciences LaboratoryPacific Northwest National LaboratoryRichlandUSA
  3. 3.School of Chemistry and BiochemistryGeorgia Institute of TechnologyAtlantaUSA
  4. 4.Biosciences CenterNational Renewable Energy LaboratoryGoldenUSA
  5. 5.Beijing National Laboratory for Molecular Sciences, Institute of ChemistryThe Chinese Academy of SciencesBeijingChina
  6. 6.Department of ChemistryUniversity at Buffalo, The State University of New YorkBuffaloUSA
  7. 7.Department of Chemical and Biomolecular EngineeringThe University of TennesseeKnoxvilleUSA
  8. 8.Department of Plant BiologyMichigan State UniversityEast LansingUSA

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