Probing cellulose structures with vibrational spectroscopy

Abstract

This paper reviews principles, data interpretations, and applications of vibrational spectroscopic methods used for analysis of cellulose in the isolated state and in plant cell walls or lignocellulose biomass. The paper begins with reviewing the crystalline structures of crystalline cellulose polymorphs and the principles of three different vibrational spectroscopy methods—infrared (IR), Raman, and sum frequency generation (SFG)—complemented with density functional theory calculations. Then, it discusses the vibrational modes of crystalline celluloses, how the chain orientation in crystalline domain is analyzed in each method, and how the concentration and spatial distribution of crystalline cellulose domains interspersed in amorphous matrices are manifested or analyzed differently in these three methods. Lastly, the paper discusses examples of analyzing crystalline cellulose in plant cell walls or lignocellulose biomass with IR, Raman, and SFG including spectroscopic imaging. One review cannot cover all vibrational spectroscopy literatures on cellulose; this review aims at providing tutorial information, using selected literatures and experimental data, needed to interpret nano-, meso-, and micro-scale structures of cellulose in plant cell walls and lignocellulose biomass.

Graphical abstract

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Acknowledgments

This work was supported by The Center for Lignocellulose Structure and Formation, Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award Number DE-SC0001090. TD-DFT calculations of theoretical SFG spectra were from the work supported by the Air Force Office of Scientific Research (AFOSR) (Grant No. FA9550-16-1-0062).

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10570_2018_2199_MOESM2_ESM.avi

Movie S7A corresponding to 3410 cm−1 vibration mode (AVI 248 kb)

10570_2018_2199_MOESM3_ESM.avi

Movie S7B corresponding to 3370 cm−1 vibration mode (AVI 260 kb)

10570_2018_2199_MOESM4_ESM.avi

Movie S7C corresponding to 3330 cm−1 vibration mode (AVI 248 kb)

10570_2018_2199_MOESM5_ESM.avi

Movie S7D corresponding to 3270 cm−1 vibration mode (AVI 307 kb)

10570_2018_2199_MOESM6_ESM.avi

Movie S7E corresponding to 2944 cm−1 vibration mode (AVI 2505 kb)

Movie S7F corresponding to 2867 cm−1 vibration mode (AVI 5097 kb)

Movie S7G corresponding to 1477 cm−1 vibration mode (AVI 5146 kb)

Movie S7H corresponding to 1160 cm−1 vibration mode (AVI 2587 kb)

Movie S7I corresponding to 1098 cm−1 vibration mode (AVI 5232 kb)

Movie S7J corresponding to 710 cm−1 vibration mode (AVI 5220 kb)

Movie S7K corresponding to 380 cm−1 vibration mode (AVI 5193 kb)

Movie S7L corresponding to 93 cm−1 vibration mode (AVI 5222 kb)

Supplementary material 1 (DOCX 90 kb)

Movie S7A corresponding to 3410 cm−1 vibration mode (AVI 248 kb)

Movie S7B corresponding to 3370 cm−1 vibration mode (AVI 260 kb)

Movie S7C corresponding to 3330 cm−1 vibration mode (AVI 248 kb)

Movie S7D corresponding to 3270 cm−1 vibration mode (AVI 307 kb)

Movie S7E corresponding to 2944 cm−1 vibration mode (AVI 2505 kb)

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Makarem, M., Lee, C.M., Kafle, K. et al. Probing cellulose structures with vibrational spectroscopy. Cellulose 26, 35–79 (2019). https://doi.org/10.1007/s10570-018-2199-z

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Keywords

  • Cellulose structures
  • Infrared spectroscopy
  • Raman spectroscopy
  • Sum frequency generation (SFG) spectroscopy
  • Plant cell walls
  • Lignocellulose
  • Biomass