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Cellulose polymorphism study with sum-frequency-generation (SFG) vibration spectroscopy: identification of exocyclic CH2OH conformation and chain orientation

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Abstract

Sum-frequency-generation (SFG) vibration spectroscopy is a technique only sensitive to functional groups arranged without centrosymmetry. For crystalline cellulose, SFG can detect the C6H2 and intra-chain hydrogen-bonded OH groups in the crystal. The geometries of these groups are sensitive to the hydrogen bonding network that stabilizes each cellulose polymorph. Therefore, SFG can distinguish cellulose polymorphs (Iβ, II, IIII and IIIII) which have different conformations of the exocyclic hydroxymethylene group or directionalities of glucan chains. The C6H2 asymmetric stretching peaks at 2,944 cm−1 for cellulose Iβ and 2,960 cm−1 for cellulose II, IIII and IIIII corresponds to the trans-gauche (tg) and gauche-trans (gt) conformation, respectively. The SFG intensity of the stretch peak of intra-chain hydrogen-bonded O–H group implies that the chain arrangement in cellulose crystal is parallel in Iβ and IIII, and antiparallel in II and IIIII.

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Acknowledgments

This work was supported by Subcontract No. XGB-1-11444-01 with the National Renewable Energy Laboratory, under Contract No. DE-AC36-08-GO28308 with the US Department of Energy.

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Authors and Affiliations

  1. Department of Chemical Engineering and Materials Research Institute, Pennsylvania State University, University Park, PA, 16802, USA

    Christopher M. Lee, Anna L. Barnette, Kabindra Kafle & Seong H. Kim

  2. National Renewable Energy Laboratory, Biosciences Center, Golden, CO, 80401, USA

    Ashutosh Mittal & David K. Johnson

  3. Department of Biology, Pennsylvania State University, University Park, PA, 16802, USA

    Yong Bum Park

  4. Department of Forest Biomaterials, North Carolina State University, Raleigh, NC, 27695, USA

    Heenae Shin & Sunkyu Park

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  1. Christopher M. Lee
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  2. Ashutosh Mittal
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Correspondence to Seong H. Kim.

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Lee, C.M., Mittal, A., Barnette, A.L. et al. Cellulose polymorphism study with sum-frequency-generation (SFG) vibration spectroscopy: identification of exocyclic CH2OH conformation and chain orientation. Cellulose 20, 991–1000 (2013). https://doi.org/10.1007/s10570-013-9917-3

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