Home A CP/MAS 13C NMR investigation of cellulose ultrastructure in traditional Chinese handmade papers
Article
Licensed
Unlicensed Requires Authentication

A CP/MAS 13C NMR investigation of cellulose ultrastructure in traditional Chinese handmade papers

  • Peng Liu ORCID logo , Chao Jin , Kai Zhang , Yu Xue , Boxu Gao , Yingshuai Jia , Yueer Yan EMAIL logo , Hongbin Zhang ORCID logo EMAIL logo , Sinong Wang and Yi Tang EMAIL logo
Published/Copyright: July 13, 2022
Become an author with De Gruyter Brill
Submit Manuscript Author Information
Holzforschung
From the journal Holzforschung Volume 76 Issue 9

Abstract

Cellulose-based handmade paper records a substantial amount of historical data and promotes human civilization. Due to the complexity of its structure and external factors, the deterioration of paper in the restoration of ancient books cannot be completely stopped. Nonetheless, the lack of microstructure analysis of handmade paper limits the understanding of its aging mechanism and storage life-span. Herein, CP/MAS 13C NMR method was used to estimate the cellulose types, crystallinity, average lateral fibril dimension (LFD), and the average lateral fibril aggregate dimension (LFAD), relying on integrated spectral fitting from C1, C4, and C6 regions, respectively. Consequently, cellulose I β crystals were predominant in all handmade paper samples. Based on the results of C4 and C6 regions by peak separation method, bast paper (Kaihua paper and Yingchun paper) demonstrated a higher crystallinity than bamboo paper (Yuanshu paper). Additional analysis of the C4 data revealed that bast papers exhibit larger cellulose microfibrils, and their LFDs and LFADs were greater than bamboo papers. Moreover, external stress of Wiley milling reduced the LFAD from the original 9 elementary fibrils to 4 elementary fibrils with unchanged LFDs.

Keywords: CP/MAS 13C NMR; lateral fibril dimension; pulverization; traditional Chinese handmade paper; ultrastructure
Corresponding authors: Yueer Yan and Hongbin Zhang, Institute for Preservation and Conservation of Chinese Ancient Books, Fudan University Library, Fudan University, Shanghai 200433, China, E-mail: (Y. Yan), . Yi Tang, Department of Chemistry, Fudan University, Shanghai 200433, China, E-mail: (Y. Tang)

Funding source: National Natural Science Foundation of China

Award Identifier / Grant number: 21805042

Award Identifier / Grant number: 22175040

Funding source: Natural Science Foundation of Shanghai

Award Identifier / Grant number: 21ZR1405100

Award Identifier / Grant number: 22ZR1407200

Funding source: Foundation of State Key Laboratory of Biobased Material and Green Papermaking, Qilu University of Technology, Shandong Academy of Sciences

Award Identifier / Grant number: KF201930

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: This work was supported by the National Natural Science Foundation of China (21805042; 22175040), the Natural Science Foundation of Shanghai (21ZR1405100; 22ZR1407200), the Foundation of State Key Laboratory of Biobased Material and Green Papermaking, Qilu University of Technology, Shandong Academy of Sciences (KF201930).

  3. Conflict of interest statement: The authors declare that they have no conflicts of interest regarding this article.

References

Amaral, H.R., Cipriano, D.F., Santos, M.S., Schettino, M.A., Ferreti, J.V.T., Meirelles, C.S., Pereira, V.S., Cunha, A.G., Emmerich, F.G., and Freitas, J.C.C. (2019). Production of high-purity cellulose, cellulose acetate and cellulose-silica composite from babassu coconut shells. Carbohydr. Polym. 210: 127–134, https://doi.org/10.1016/j.carbpol.2019.01.061.Search in Google Scholar PubMed

Baccile, N., Falco, C., and Titirici, M.-M. (2014). Characterization of biomass and its derived char using 13C-solid state nuclear magnetic resonance. Green Chem. 16: 4839–4869, https://doi.org/10.1039/c3gc42570c.Search in Google Scholar

Baty, J.W., Maitland, C.L., Minter, W., Hubbe, M.A., and Jordan-Mowery, S.K. (2010). Deacidification for the conservation and preservation of paper-based works: a review. Bioresources 5: 1955–2023, https://doi.org/10.15376/biores.5.3.1955-2023.Search in Google Scholar

Bernardinelli, O.D., Lima, M.A., Rezende, C.A., Polikarpov, I., and de Azevedo, E.R. (2015). Quantitative 13C MultiCP solid-state NMR as a tool for evaluation of cellulose crystallinity index measured directly inside sugarcane biomass. Biotechnol. Biofuels 8: 110, https://doi.org/10.1186/s13068-015-0292-1.Search in Google Scholar PubMed PubMed Central

Brinkmann, A., Chen, M., Couillard, M., Jakubek, Z.J., Leng, T., and Johnston, L.J. (2016). Correlating cellulose nanocrystal particle size and surface area. Langmuir 32: 6105–6114, https://doi.org/10.1021/acs.langmuir.6b01376.Search in Google Scholar PubMed

Cipriano, D.F., Chinelatto, L.S., Nascimento, S.A., Rezende, C.A., de Menezes, S.M.C., and Freitas, J.C.C. (2020). Potential and limitations of 13C CP/MAS NMR spectroscopy to determine the lignin content of lignocellulosic feedstock. Biomass Bioenergy 142: 105792, https://doi.org/10.1016/j.biombioe.2020.105792.Search in Google Scholar

Daicho, K., Saito, T., Fujisawa, S., and Isogai, A. (2018). The crystallinity of nanocellulose: dispersion-induced disordering of the grain boundary in biologically structured cellulose. ACS Appl. Nano Mater. 1: 5774–5785, https://doi.org/10.1021/acsanm.8b01438.Search in Google Scholar

Daicho, K., Fujisawa, S., Kobayashi, K., Saito, T., and Ashida, J. (2020). Cross-polarization dynamics and conformational study of variously sized cellulose crystallites using solid-state 13C NMR. J. Wood Sci. 66: 62, https://doi.org/10.1186/s10086-020-01909-9.Search in Google Scholar

Dassanayake, R.S., Dissanayake, N., Fierro, J.S., Abidi, N., Quitevis, E.L., Boggavarappu, K., and Thalangamaarachchige, V.D. (2021). Characterization of cellulose nanocrystals by current spectroscopic techniques. Appl. Spectrosc. Rev.: 1–26, https://doi.org/10.1080/05704928.2021.1951283.Search in Google Scholar

Fernandes, A.N., Thomas, L.H., Altaner, C.M., Callow, P., Forsyth, V.T., Apperley, D.C., Kennedy, C.J., and Jarvis, M.C. (2011). Nanostructure of cellulose microfibrils in spruce wood. Proc. Natl. Acad. Sci. U.S.A. 108: 1195–1203, https://doi.org/10.1073/pnas.1108942108.Search in Google Scholar PubMed PubMed Central

Foston, M. (2014). Advances in solid-state NMR of cellulose. Curr. Opin. Biotechnol. 27: 176–184, https://doi.org/10.1016/j.copbio.2014.02.002.Search in Google Scholar

Frey-Wyssling, A. (1954). The fine structure of cellulose microfibrils. Science 119: 80–82, https://doi.org/10.1126/science.119.3081.80.Search in Google Scholar

Ghassemi, N., Poulhazan, A., Deligey, F., Mentink-Vigier, F., Marcotte, I., and Wang, T. (2021). Solid-state NMR investigations of extracellular matrixes and cell walls of algae, bacteria, fungi, and plants. Chem. Rev. 122: 10036–10086, https://doi.org/10.1021/acs.chemrev.1c00669.Search in Google Scholar

Ghosha, M., Prajapati, B.P., Suryawanshi, R.K., Dey, K.K., and Kango, N. (2019). Study of the effect of enzymatic deconstruction on natural cellulose by NMR measurements. Chem. Phys. Lett. 727: 105–115, https://doi.org/10.1016/j.cplett.2019.04.063.Search in Google Scholar

Heux, L., Dinand, E., and Vignon, M.R. (1999). Structural aspects in ultrathin cellulose microfibrils followed by 13C CP-MAS NMR. Carbohydr. Polym. 40: 115–124, https://doi.org/10.1016/s0144-8617(99)00051-x.Search in Google Scholar

Hubbe, M., Venditti, R., and Rojas, O. (2007). What happens to cellulosic fibers during papermaking and recycling? A review. Bioresources 2: 739–388.10.15376/biores.2.4.739-788Search in Google Scholar

Hult, E.-L., Larsson, P.T., and Iversen, T. (2000). A comparative CP/MAS 13C-NMR study of cellulose structure in spruce wood and kraft pulp. Cellulose 7: 35–55, https://doi.org/10.1023/a:1009236932134.10.1023/A:1009236932134Search in Google Scholar

Idström, A., Brelid, H., Nydén, M., and Nordstierna, L. (2013). CP/MAS 13C NMR study of pulp hornification using nanocrystalline cellulose as a model system. Carbohydr. Polym. 92: 881–884, https://doi.org/10.1016/j.carbpol.2012.09.097.Search in Google Scholar

Karimi, K. and Taherzadeh, M.J. (2016). A critical review of analytical methods in pretreatment of lignocelluloses: composition, imaging, and crystallinity. Bioresour. Technol. 200: 1008–1018, https://doi.org/10.1016/j.biortech.2015.11.022.Search in Google Scholar

Larsson, P.T., Wickholm, K., and Iversen, T. (1997). A CP/MAS 13C NMR investigation of molecular ordering in celluloses. Carbohydr. Res. 302: 19–25, https://doi.org/10.1016/s0008-6215(97)00130-4.Search in Google Scholar

Larsson, P.T., Hult, E.-L., Wickholm, K., Pettersson, E., and Iversen, T. (1999). CP/MAS 13C-NMR spectroscopy applied to structure and interaction studies on cellulose I. Solid State Nucl. Magn. Reson. 15: 31–40, https://doi.org/10.1016/s0926-2040(99)00044-2.Search in Google Scholar

Larsson, P.T., Svensson, A., and Wågberg, L. (2013). A new, robust method for measuring average fibre wall pore sizes in cellulose I rich plant fibre walls. Cellulose 20: 623–631, https://doi.org/10.1007/s10570-012-9850-x.Search in Google Scholar

Ling, Z., Wang, T., Makarem, M., Santiago Cintrón, M., Cheng, H.N., Kang, X., Bacher, M., Potthast, A., Rosenau, T., King, H., et al.. (2019). Effects of ball milling on the structure of cotton cellulose. Cellulose 26: 305–328, https://doi.org/10.1007/s10570-018-02230-x.Search in Google Scholar

Liu, P., Zhang, H., Wang, S., Yu, H., Lu, B., Li, X., Wang, C., Yan, Y., and Tang, Y. (2020). Determination of crystallinity of Chinese handmade papers by means of X-ray diffraction. Restaurator Int. J. Preserv. Libr. Arch. Mater. 41: 69–86, https://doi.org/10.1515/res-2019-0009.Search in Google Scholar

Łojewski, T., Zięba, K., Kołodziej, A., and Łojewska, J. (2011). Following cellulose depolymerization in paper: comparison of size exclusion chromatography techniques. Cellulose 18: 1349–1363, https://doi.org/10.1007/s10570-011-9562-7.Search in Google Scholar

Lu, Y., Lu, Y.-C., Hu, H.-Q., Xie, F.-J., Wei, X.-Y., and Fan, X. (2017). Structural characterization of lignin and its degradation products with spectroscopic methods. J. Spectrosc. 2017: 8951658, https://doi.org/10.1155/2017/8951658.Search in Google Scholar

Madhu, P., Sanjay, M.R., Senthamaraikannan, P., Pradeep, S., Saravanakumar, S.S., and Yogesha, B. (2019). A review on synthesis and characterization of commercially available natural fibers: Part II. J. Nat. Fibers 16: 25–36, https://doi.org/10.1080/15440478.2017.1379045.Search in Google Scholar

Malucelli, L.C., Lacerda, L.G., Dziedzic, M., and da Silva Carvalho Filho, M.A. (2017). Preparation, properties and future perspectives of nanocrystals from agro-industrial residues: a review of recent research. Rev. Environ. Sci. Biotechnol. 16: 131–145, https://doi.org/10.1007/s11157-017-9423-4.Search in Google Scholar

Maunu, S., Liitiä, T., Kauliomäki, S., Hortling, B., and Sundquist, J. (2000). 13C CPMAS NMR investigations of cellulose polymorphs in different pulps. Cellulose 7: 147–159, https://doi.org/10.1023/a:1009200609482.10.1023/A:1009200609482Search in Google Scholar

Maunu, S.L. (2002). NMR studies of wood and wood products. Prog. Nucl. Magn. Reson. Spectrosc. 40: 151–174, https://doi.org/10.1016/s0079-6565(01)00041-3.Search in Google Scholar

Meng, Q., Wan, J., Ma, Y., and Wang, Y. (2013). Effects of different deinking processes on fiber morphology, hydrogen bond models, and cellulose supramolecular structure. Bioresources 8: 2398–2416, https://doi.org/10.15376/biores.8.2.2398-2416.Search in Google Scholar

Newman, R.H. (1999). Estimation of the lateral dimensions of cellulose crystallites using 13C NMR signal strengths. Solid State Nucl. Magn. Reson. 15: 21–29, https://doi.org/10.1016/s0926-2040(99)00043-0.Search in Google Scholar

Paci, M., Federici, C., Capitani, D., Perenze, N., and Segre, A.L. (1995). NMR study of paper. Carbohydr. Polym. 26: 289–297, https://doi.org/10.1016/0144-8617(95)00011-u.Search in Google Scholar

Park, S., Baker, J.O., Himmel, M.E., Parilla, P.A., and Johnson, D.K. (2010). Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance. Biotechnol. Biofuels 3: 10, https://doi.org/10.1186/1754-6834-3-10.Search in Google Scholar

Pedersoli, Júnior, J.L. (2000). Effect of cellulose crystallinity on the progress of thermal oxidative degradation of paper. J. Appl. Polym. Sci. 78: 61–66, https://doi.org/10.1002/1097-4628(20001003)78:1<61::aid-app90>3.0.co;2-k.10.1002/1097-4628(20001003)78:1<61::AID-APP90>3.0.CO;2-KSearch in Google Scholar

Peter, Z. (2021). Order in cellulosics: historical review of crystal structure research on cellulose. Carbohydr. Polym. 254: 117417, https://doi.org/10.1016/j.carbpol.2020.117417.Search in Google Scholar

Pu, Y., Ziemer, C., and Ragauskas, A.J. (2006). CP/MAS 13C NMR analysis of cellulase treated bleached softwood kraft pulp. Carbohydr. Res. 341: 591–597, https://doi.org/10.1016/j.carres.2005.12.012.Search in Google Scholar

Roger, H.N. and Hemmingson, J.A. (1990). Determination of the degree of cellulose crystallinity in wood by carbon-13 nuclear magnetic resonance spectroscopy. Holzforschung 44: 351–356, https://doi.org/10.1515/hfsg.1990.44.5.351.Search in Google Scholar

Rongpipi, S., Ye, D., Gomez, E.D., and Gomez, E.W. (2018). Progress and opportunities in the characterization of cellulose – an important regulator of cell wall growth and mechanics. Front. Plant Sci. 9: 1894, https://doi.org/10.3389/fpls.2018.01894.Search in Google Scholar

Siuda, J., Perdoch, W., Mazela, B., and Zborowska, M. (2019). Catalyzed reaction of cellulose and lignin with methyltrimethoxysilane – FT-IR, 13C NMR and 29Si NMR studies. Materials 12: 2006, https://doi.org/10.3390/ma12122006.Search in Google Scholar

Sugiyama, J., Persson, J., and Chanzy, H. (1991). Combined infrared and electron diffraction study of the polymorphism of native celluloses. Macromolecules 24: 2461–2466, https://doi.org/10.1021/ma00009a050.Search in Google Scholar

Sun, Y., Lin, L., Deng, H., Li, J., He, B., Sun, R., and Ouyang, P. (2008). Structural changes of bamboo cellulose in formic acid. Bioresources 3: 297–315.10.1007/s11461-008-0072-1Search in Google Scholar

Terrett, O.M., Lyczakowski, J.J., Yu, L., Iuga, D., Franks, W.T., Brown, S.P., Dupree, R., and Dupree, P. (2019). Molecular architecture of softwood revealed by solid-state NMR. Nat. Commun. 10: 4978, https://doi.org/10.1038/s41467-019-12979-9.Search in Google Scholar

Viren, C., Bush, T., Larsson, P.T., Iversen, T., and Kindness, A. (2010). A CP/MAS 13C-NMR study of cellulose fibril aggregation in eucalyptus dissolving pulps during drying and the correlation between aggregate dimensions and chemical reactivity. Holzforschung 64: 693–698.10.1515/hf.2010.097Search in Google Scholar

Walker, T.W., Kuch, N., Vander Meulen, K.A., Clewett, C.F.M., Huber, G.W., Fox, B.G., and Dumesic, J.A. (2020). Solid-state NMR studies of solvent-mediated, acid-catalyzed woody biomass pre-treatment for enzymatic conversion of residual cellulose. ACS Sustain. Chem. Eng. 8: 6551–6563, https://doi.org/10.1021/acssuschemeng.0c01538.Search in Google Scholar

Wan, J., Wang, Y., and Xiao, Q. (2010). Effects of hemicellulose removal on cellulose fiber structure and recycling characteristics of eucalyptus pulp. Bioresour. Technol. 101: 4577–4583, https://doi.org/10.1016/j.biortech.2010.01.026.Search in Google Scholar

Wickholm, K., Larsson, P.T., and Iversen, T. (1998). Assignment of non-crystalline forms in cellulose I by CP/MAS 13C NMR spectroscopy. Carbohydr. Res. 312: 123–129, https://doi.org/10.1016/s0008-6215(98)00236-5.Search in Google Scholar

Yamamoto, H. and Horii, F. (1993). CP/MAS 13C NMR analysis of the crystal transformation induced for Valonia cellulose by annealing at high temperatures. Macromolecules 26: 1313–1317, https://doi.org/10.1021/ma00058a020.Search in Google Scholar

Yao, J., Zhang, R., Luo, C., Yan, Y., Bi, N., and Tang, Y. (2022). Deterioration of Kaihua handmade paper: evolution of molecular, supermolecular and macroscopic structures. Polym. Degrad. Stabil. 195: 109773, https://doi.org/10.1016/j.polymdegradstab.2021.109773.Search in Google Scholar

Yuan, L., Wan, J., Ma, Y., Wang, Y., Huang, M., and Chen, Y. (2013). The content of different hydrogen bond models and crystal structure of eucalyptus fibers during beating. Bioresources 8: 717–734, https://doi.org/10.15376/biores.8.1.717-734.Search in Google Scholar

Zervos, S. and Alexopoulou, I. (2015). Paper conservation methods: a literature review. Cellulose 22: 2859–2897, https://doi.org/10.1007/s10570-015-0699-7.Search in Google Scholar

Zhao, W., Kirui, A., Deligey, F., Mentink-Vigier, F., Zhou, Y., Zhang, B., and Wang, T. (2021). Solid-state NMR of unlabeled plant cell walls: high-resolution structural analysis without isotopic enrichment. Biotechnol. Biofuels 14: 14, https://doi.org/10.1186/s13068-020-01858-x.Search in Google Scholar PubMed PubMed Central

Supplementary Material

The online version of this article offers supplementary material (https://doi.org/10.1515/hf-2022-0048).

Received: 2022-03-16
Accepted: 2022-06-29
Published Online: 2022-07-13
Published in Print: 2022-09-27

© 2022 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Original Articles
  3. Variation analyses of extractive contents by NIR-spectroscopy bring out the differences between agroforestry and forestry walnut (Juglans regia × nigra) trees
  4. Correlation between lignin content and syringyl-to-guaiacyl (S/G) ratio of Eucalyptus globulus wood
  5. Accelerated relaxation behavior during water desorption in the mechano-sorptive creep of wood: modeling and analysis based on the free volume concept and Kohlausch–Williams–Watts function
  6. Degradation of beech wood by Kretzschmaria deusta: its heterogeneity and influence on dynamic and static bending properties
  7. Performance improvement of poplar wood based on the synergies of furfurylation and polyethylene glycol impregnation
  8. Artificial lignification of a cellulose microfibril-based hydrogel and resulting effect on tensile properties
  9. Depolymerisation of kraft lignin to obtain high value-added products: antioxidants and UV absorbers
  10. A CP/MAS 13C NMR investigation of cellulose ultrastructure in traditional Chinese handmade papers
  11. Quality control of natural cork stoppers by image analysis and oxygen transmission rate
https://doi.org/10.1515/hf-2022-0048
Keywords for this article
CP/MAS 13C NMR; lateral fibril dimension; pulverization; traditional Chinese handmade paper; ultrastructure

Articles in the same Issue

  1. Frontmatter
  2. Original Articles
  3. Variation analyses of extractive contents by NIR-spectroscopy bring out the differences between agroforestry and forestry walnut (Juglans regia × nigra) trees
  4. Correlation between lignin content and syringyl-to-guaiacyl (S/G) ratio of Eucalyptus globulus wood
  5. Accelerated relaxation behavior during water desorption in the mechano-sorptive creep of wood: modeling and analysis based on the free volume concept and Kohlausch–Williams–Watts function
  6. Degradation of beech wood by Kretzschmaria deusta: its heterogeneity and influence on dynamic and static bending properties
  7. Performance improvement of poplar wood based on the synergies of furfurylation and polyethylene glycol impregnation
  8. Artificial lignification of a cellulose microfibril-based hydrogel and resulting effect on tensile properties
  9. Depolymerisation of kraft lignin to obtain high value-added products: antioxidants and UV absorbers
  10. A CP/MAS 13C NMR investigation of cellulose ultrastructure in traditional Chinese handmade papers
  11. Quality control of natural cork stoppers by image analysis and oxygen transmission rate
Sign up now to receive a 20% welcome discount
Institutional Access
How does access work?
Have an idea on how to improve our website?
Please write us.
© 2025 De Gruyter Brill
Downloaded on 13.9.2025 from https://www.degruyterbrill.com/document/doi/10.1515/hf-2022-0048/html
Scroll to top button