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Measuring the crystallinity index of cellulose by solid state 13C nuclear magnetic resonance

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Abstract

The crystallinity index of cellulose is an important parameter to establish because of the effect this property has on the utilization of cellulose as a material and as a feedstock for biofuels production. However, it has been found that the crystallinity index varies significantly depending on the choice of instrument and data analysis technique applied to the measurement. We introduce in this study a simple and straightforward method to evaluate the crystallinity index of cellulose. This novel method was developed using solid state 13C NMR and subtraction of the spectrum of a standard amorphous cellulose. The crystallinity indexes of twelve different celluloses were measured and the values from this method were compared with the values obtained by other existing methods, including methods based on X-ray diffraction. An interesting observation was that the hydration of the celluloses increased their crystallinity indexes by about 5%, suggesting that addition of water increased cellulose order for all the cellulose samples studied.

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References

  • Evans R, Newman RH, Roick UC, Suckling ID, Wallis AFA (1995) Changes in cellulose crystallinity during kraft pulping. Comparison of infrared, X-ray diffraction and solid state NMR results. Holzforschung 49:498–504

    Article  CAS  Google Scholar 

  • Garvey CJ, Parker IH, Simon GP (2005) On the interpretation of X-ray diffraction powder patterns in terms of the nanostructure of cellulose I fibers. Macromol Chem Phys 206:1568–1575. doi:10.1002/macp.200500008

    Article  CAS  Google Scholar 

  • Helbert W, Chanzy H, Husum TL, Schülein M, Ernst S (2003) Fluorescent cellulose microfibrils as substrate for the detection of cellulase activity. Biomacromolecules 4:481–487. doi:10.1021/bm020076i

    Article  CAS  Google Scholar 

  • Jeoh T, Ishizawa C, Davis MF, Himmel ME, Adney WS, Johnson DK (2007) Cellulase digestibility of pretreated biomass is limited by cellulose accessibility. Biotechnol Bioeng 98:112–122. doi:10.1002/bit.21408

    Article  CAS  Google Scholar 

  • Lahaye M, Rondeau-Mouro C, Deniaud E, Buléon A (2003) Solid-state 13C NMR spectroscopy studies of xylans in the cell wall of Palmaria palmate (L. Kuntze, Rhodophyta). Carbohydr Res 338:1559–1569. doi:10.1016/S0008-6215(03)00241-6

    Article  CAS  Google Scholar 

  • Newman RH (1999) Estimation of the lateral dimensions of cellulose crystallites using 13C NMR signal strengths. Solid State Nucl Magn Reson 15:21–29. doi:10.1016/S0926-2040(99)00043-0

    Article  CAS  Google Scholar 

  • Newman RH (2004) Carbon-13 NMR evidence for cocrystallization of cellulose as a mechanism for hornification of bleached kraft pulp. Cellulose 11:45–52. doi:10.1023/B:CELL.0000014768.28924.0c

    Article  CAS  Google Scholar 

  • Newman RH, Hemmingson JA (1994) Carbon 13 NMR distinction between categories of molecular order and disorder in cellulose. Cellulose 2:95–110. doi:10.1007/BF00816383

    Article  Google Scholar 

  • Park S, Baker JO, Himmel ME, Johnson DK (2009) Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance. Biotechnol Biofuels (in press)

  • Schroeder LR, Gentile VM, Atalla RH (1986) Nondegradative preparation of amorphous cellulose. J Wood Chem Technol 6:1–14. doi:10.1080/02773818608085213

    Article  CAS  Google Scholar 

  • Smith SO, Kustanovich I, Wu X, Peersen OB (1994) Variable-amplitude cross-polarization MAS NMR. J Magn Reson 104:334–339

    Google Scholar 

  • Teeäär R, Serimaa R, Paakkari T (1987) Crystallinity of cellulose, as determined by CP/MAS NMR and XRD methods. Polym Bull 17:231–237. doi:10.1007/BF00285355

    Article  Google Scholar 

  • Thygesen A, Oddershede J, Lilholt H, Thomsen AB, Ståhl K (2005) On the determination of crystallinity and cellulose content in plant fibres. Cellulose 12:563–576. doi:10.1007/s10570-005-9001-8

    Article  CAS  Google Scholar 

  • Wood T (1988) Preparation of crystalline, amorphous, and dyed cellulase substrates. Methods Enzymol 160:19–25. doi:10.1016/0076-6879(88)60103-0

    Article  CAS  Google Scholar 

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Correspondence to Mark F. Davis.

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Park, S., Johnson, D.K., Ishizawa, C.I. et al. Measuring the crystallinity index of cellulose by solid state 13C nuclear magnetic resonance. Cellulose 16, 641–647 (2009). https://doi.org/10.1007/s10570-009-9321-1

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  • DOI: https://doi.org/10.1007/s10570-009-9321-1

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