Home Evaluation of changes in cellulose micro/nanofibrils structure under chemical and enzymatic pre-treatments
Article
Licensed
Unlicensed Requires Authentication

Evaluation of changes in cellulose micro/nanofibrils structure under chemical and enzymatic pre-treatments

  • Jordão Cabral Moulin ORCID logo EMAIL logo , Alisson Farley Soares Durães ORCID logo , Matheus Cordazzo Dias ORCID logo , Luiz Eduardo Silva , Allan de Amorim dos Santos , Renato Augusto Pereira Damásio , Júlio César Ugucioni and Gustavo Henrique Denzin Tonoli
Published/Copyright: July 19, 2021
Become an author with De Gruyter Brill
Submit Manuscript Author Information
Holzforschung
From the journal Holzforschung Volume 75 Issue 11

Abstract

The objective of the present work was to evaluate the use of Raman microspectroscopy analysis to assess changes in cellulose micro/nanofibril structure from fibers subjected to different pre-treatments. Pulp fibers were pre-treated with 5 wt% NaOH for 2 h, 10 wt% NaOH for 1 h, and endoglucanase-type enzymes to improve nanofibrilation. After the pre-treatments, the fibers were mechanically fibrillated to produce cellulose micro/nanofibrils, which were made into films to be analyzed. Fibers pre-treated with 5 wt% NaOH produced 59% micro/nanofibrils with average diameter less than 30 nm, for Eucalyptus, and 46% of micro/nanofibrils, with the same diameter, for Pinus. However, the enzymatic pre-treatment was the most efficient, resulting in 83% of micro/nanofibrils for Eucalyptus and 78% for Pinus. This corroborates with the lowest values of the 1.096/2.896 ratio and degree of polymerization, indicating chain shortening in cellulose. X-ray diffraction and Raman microspectroscopy crystallinity results presented similar tendencies, with increased crystallinity caused by all pre-treatments, being 5 wt% NaOH for 2 h the highest, with 70%, for Eucalyptus and Pinus. Enzymatic pre-treatment has produced the best fibrillation and greater crystallinity. The present work has shown a reliable way of assessing cellulose structure using Raman microspectroscopy.

Keywords: cellulose structure; chemical characterization; enzymes; nanofibrillated cellulose; pre-treatments
Corresponding author: Jordão Cabral Moulin, Forest and Wood Sciences Department, Federal University of Espírito Santo, Av. Gov. Lindemberg, n° 316 – Centro, 29550-000 Jerônimo Monteiro, ES, Brazil, E-mail:

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

  2. Research funding: None declared.

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

References

Agarwal, U.P. (2019). Analysis of cellulose and lignocellulose materials by Raman spectroscopy: a review of the current status. Molecules 24: 1659–1675, https://doi.org/10.3390/molecules24091659.Search in Google Scholar PubMed PubMed Central

Agarwal, U.P., Atalla, R.H., and Forsskahl, I. (1995). Sequential treatment of mechanical and chemime chanical pulps with light and heat: a Raman spectroscopic study. Holzforschung 49: 300–312, https://doi.org/10.1515/hfsg.1995.49.4.300.Search in Google Scholar

Agarwal, U.P., Reiner, R.R., and Ralph, S.A. (2010). Cellulose I crystallinity determination using FT–Raman spectroscopy: univariate and multivariate methods. Cellulose 17: 721–733, https://doi.org/10.1007/s10570-010-9420-z.Search in Google Scholar

Agarwal, U.P., Reiner, R.R., and Ralph, S.A. (2013). Estimation of cellulose crystallinity of lignocelluloses using near-IR FT-Raman spectroscopy and comparison of the Raman and Segal-WAXS methods. J. Agric. Food Chem. 61: 103–113, https://doi.org/10.1007/s00226-014-0667-7.Search in Google Scholar

Agarwal, U.P., Ralph, S.A., Reiner, R.S., Moore, R.K., and Baez, C. (2014). Impacts of fiber orientation and milling on observed crystallinity in jack pine. Wood Sci. Technol. 48: 1213–1227, https://doi.org/10.1007/s00226-014-0667-7.Search in Google Scholar

Alexander, W.J., Goldschmid, O., and Mitchell, R.L. (1957). Relation of intrinsic viscosity to cellulose chain length. Degree of polymerization range below 400. Ind. Eng. Chem. 49: 1303–1306, https://doi.org/10.1021/ie50572a039.Search in Google Scholar

Alves, A.P.P., Oliveira, L.P.Z., Castro, A.A.N., Neumann, R., Oliveira, L.F.C., Edwards, H.G.M., and Sant’Ana, A.C. (2016). The structure of different cellulosic fibres characterized by Raman spectroscopy. Vib. Spectrosc. 86: 324–330, https://doi.org/10.1016/j.vibspec.2016.08.007.Search in Google Scholar

Bettaieb, F., Khiari, R., Dufresne, A., Mhenni, M.F., and Belgacem, M.N. (2015). Mechanical and thermal properties of Posidonia oceanica cellulose nanocrystal reinforced polymer. Carbohydr. Polym. 123: 99–104, https://doi.org/10.1016/j.carbpol.2015.01.026.Search in Google Scholar PubMed

Bufalino, L., SenaNeto, A.R., Tonoli, G.H.D., Souza, A.F., Costa, T.G., Marconcini, J.M., Colodette, J.L., Labory, C.R.G., and Mendes, L.M. (2015). How the chemical nature of Brazilian hardwoods affects nanofibrillation of cellulose fibers and film optical quality. Cellulose 22: 3657–3672, https://doi.org/10.1007/s10570-015-0771-3.Search in Google Scholar

Chen, Y., He, Y., Fan, D., Han, Y., Li, G., and Wang, S. (2017). An efficient method for cellulose nanofibrils length shearing via environmentally friendly mixed cellulose pretreatment. J. Nanomater. 2017: 1–12, https://doi.org/10.1155/2017/1591504.Search in Google Scholar

Chirayil, C.J., Joy, J., Mathew, L., Mozetic, M., Koetz, J., and Thomas, S. (2014). Isolation and characterization of cellulose nanofibrils from Helicteres isora plant. Ind. Crop. Prod. 59: 27–34, https://doi.org/10.1016/j.indcrop.2014.04.020.Search in Google Scholar

Choi, K., Kim, R., and Cho, B. (2016). Effects of alkali swelling and beating treatments on properties of kraft pulp fibers. BioResources 11: 3769–3782, https://doi.org/10.15376/biores.11.2.3769-3782.Search in Google Scholar

Dias, M.C., Mendonça, M.C., Damásio, R.A.P., Zidanes, U.L., Mori, F.A., Ferreira, S.R., and Tonoli, G.H.D. (2019). Influence of hemicellulose content of Eucalyptus and Pinus fibers on the grinding process for obtaining cellulose micro/nanofibrils. Holzforschung 73: 1035–1046, https://doi.org/10.1515/hf-2018-0230.Search in Google Scholar

Edwards, H.G.M., Farwell, D.W., and Webste, D. (1997). Raman microscopy of untreated natural plant fibres. Spectrochim. Acta, Part A 53: 2383–2392, https://doi.org/10.1016/S1386-1425(97)00178-9.Search in Google Scholar

Espinosa, E., Domínguez-Robles, J., Sánchez, R., Tarrés, Q., and Rodríguez, A. (2017). The effect of pre-treatment on the production of lignocellulosic nanofibers and their application as a reinforcing agent in paper. Cellulose 24: 2605–2618, https://doi.org/10.1007/s10570-017-1281-2.Search in Google Scholar

Félix, F.T., Marinho, J.P.N., Silva, S.N., and Azevedo, D.M.F.S. (2017). Síntese e caracterização de compósitos de fosfato de cálcio e nanofibras de celulose visando aplicação no reparo de tecidos ósseos. The Journal of Engineering and Exact Sciences 3: 1209–1226, https://doi.org/10.18540/jcecvl3iss8pp1209-1226.Search in Google Scholar

Fonseca, C.S., Silva, T.F., Silva, M.F., Oliveira, I.R.C., Mendes, R.F., Hein, P.R.G., Mendes, L.M., and Tonoli, G.H.D. (2016). Micro/nanofibrilas celulósicas de eucalyptus em fibrocimentos extrudados. Cerne 22: 59–68, https://doi.org/10.1590/01047760201622012084.Search in Google Scholar

Guimarães, M.Jr, Botaro, V.R., Novack, K.M., Neto, F., Pires, W., Mendes, L.M., and Tonoli, G.H.D. (2015). Preparation of cellulose nanofibrils from bamboo pulp by mechanical defibrillation for their applications in biodegradable composites. J. Nanosci. Nanotechnol. 15: 6551–6768, https://doi.org/10.1166/jnn.2015.10854.Search in Google Scholar PubMed

Gupta, A. and Verma, J.P. (2015). Sustainable bioethanol production from agro-residues: a review. Renew. Sustain. Energy Rev. 41: 550–567, https://doi.org/10.1016/j.rser.2014.08.032.Search in Google Scholar

He, M., Yang, G., Chen, J., Ji, X., and Wang, Q. (2018). Production and characterization of cellulose nanofibrils from different chemical and mechanical pulps. J. Wood Chem. Technol. 38: 149–158, https://doi.org/10.1080/02773813.2017.1411368.Search in Google Scholar

Jähn, A., Schröder, M.W., Füting, M., Schenzel, K., and Diepenbrock, W. (2002). Characterization of alkali treated flax fibres by means of FT Raman spectroscopy and environmental scanning electron microscopy. Spectrochim. Acta, Part A 58: 2271–2279, https://doi.org/10.1016/S1386-1425(01)00697-7.Search in Google Scholar

Jones, R.R., Hooper, D.C., Zhang, L., Wolverson, D., and Valev, V.K. (2019). Raman techniques: fundamentals and frontiers. Nanoscale Res. Lett. 14: 231, https://doi.org/10.1186/s11671-019-3039-2.Search in Google Scholar PubMed PubMed Central

Kafle, K., Greeson, K., Lee, C., and Kim, S.H. (2014). Cellulose polymorphs and physical properties of cotton fabrics processed with commercial textile mills for mercerization and liquid ammonia treatments. Textil. Res. J. 84: 1692–1699, https://doi.org/10.1177/0040517514527379.Search in Google Scholar

Kanmani, P., Aravind, J., Kamaraj, M., Sureshbabu, P., and Karthikeyan, S. (2017). Environmental applications of chitosan and cellulosic biopolymers: a comprehensive outlook. Bioresour. Technol. 242: 295–303, https://doi.org/10.1016/j.biortech.2017.03.119.Search in Google Scholar PubMed

Kihlman, M., Medronho, B.F., Romano, A.L., Germgård, U., and Lindman, B. (2013). Cellulose dissolution in an alkali based solvent: influence of additives and pretreatments. J. Braz. Chem. Soc. 24: 295–303, https://doi.org/10.5935/0103-5053.20130038.Search in Google Scholar

Lago, R.C., Oliveira, A.L.M., Dias, M.C., Carvalho, E.E.N., Tonoli, G.H.D., and Boas, E.V.B.V. (2020). Obtaining cellulosic nanofibrils from oat straw for biocomposite reinforcement: mechanical and barrier properties. Ind. Crop. Prod. 148: 112264, https://doi.org/10.1016/j.indcrop.2020.112264.Search in Google Scholar

Lakhundi, S., Siddiqui, R., and Khan, N.A. (2015). Cellulose degradation: a therapeutic strategy in the improved treatment of Acanthamoeba infections. Parasites Vectors 8: 1–16, https://doi.org/10.1186/s13071-015-0642-7.Search in Google Scholar PubMed PubMed Central

Lengowski, E.C., De Muniz, G.B, Nisgosk, D., and Magalhães, W.L.E. (2013). Cellulose acquirement evaluation methods with different degrees of crystallinity. Sci. Forestalis 41: 185–194, https://doi.org/10.1016/j.tca.2016.06.010.Search in Google Scholar

Michelin, M., Gomes, D.G., Romani, A., Polizeli, M.L.T.M., and Teixeira, J.A. (2020). Nanocellulose production: exploring the enzymatic route and residues of pulp and paper industry. Molecules 25: 3411, https://doi.org/10.3390/molecules25153411.Search in Google Scholar PubMed PubMed Central

Mishra, R.K., Sabu, A., and Tiwari, S.K. (2018). Materials chemistry and the futurist eco-friendly applications of nanocellulose: status and prospect. Journal of Saudi Chemical Society 22: 949–978, https://doi.org/10.1016/j.jscs.2018.02.005.Search in Google Scholar

Nam, S., French, A., Condon, B., and Concha, M. (2016). Segal crystallinity index revisited by the simulation of X-ray diffraction patterns of cotton cellulose Iβ and cellulose II. Carbohydr. Polym. 135: 1–9, https://doi.org/10.1016/j.carbpol.2015.08.035.Search in Google Scholar PubMed

Ng, H.M., Sin, L.T., Tee, T.T., Bee, S.T., Huj, D., Low, C.Y., and Rahmat, A.R. (2015). Extraction of cellulose nanocrystals from plant sources for application as reinforcing agent in polymers. Compos. B Eng. 75: 176–200, https://doi.org/10.1016/j.compositesb.2015.01.008.Search in Google Scholar

Nie, S., Zhang, C., Zhang, Q., Zhang, K., Zhang, Y., Tao, P., and Wang, S. (2018). Enzymatic and cold alkaline pretreatments of sugarcane bagasse pulp to produce cellulose nanofibrils using a mechanical method. Ind. Crop. Prod. 124: 435–441, https://doi.org/10.1016/j.indcrop.2018.08.033.Search in Google Scholar

Novy, V., Aïssa, K., Nielsen, F., Straus, S.K., Ciesielski, P., Hunt, C.G., and Saddler, J. (2019). Quantifying cellulose accessibility during enzyme-mediated deconstruction using 2 fluorescence-tagged carbohydrate-binding modules. Proc. Natl. Acad. Sci. Unit. States Am. 116: 22545–22551, https://doi.org/10.1073/pnas.1912354116.Search in Google Scholar PubMed PubMed Central

Oushabi, A., Sair, S., Hassani, F.O, Abboud, Y., Tanane, O., and El Bouari, A. (2017). The effect of alkali treatment on mechanical, morphological and thermal properties of date palm fibers (DPFs): study of the interface of DPF–Polyurethane composite. S. Afr. J. Chem. Eng. 23: 116–123, https://doi.org/10.1016/j.sajce.2017.04.005.Search in Google Scholar

Peng, T., Yuehua, Z., Zhengmei, W., Xiaoping, L., and Shuangxi, N. (2019). Enzymatic pretreatment for cellulose nanofibrils isolation from bagasse pulp: transition of cellulose crystal structure. Carbohydr. Polym. 214: 1–7, https://doi.org/10.1016/j.carbpol.2019.03.012.Search in Google Scholar PubMed

Potulski, D.C., Viana, L.C., Muniz, G.I.B, Andrade, A.S., and Klock, U. (2016). Characterization of fibrillated cellulose nanofilms obtained at different consistencies. Sci. Forestalis 44: 361–372, https://doi.org/10.18671/scifor.v44n110.09.Search in Google Scholar

Potulski, D.C., Lopes, M.S., de Muniz, G.I.B, Carneiro, M.E., and Andrade, A.S. (2018). Influência da adição de celulose nanofibrilada (cnf) nas propriedades ópticas e físicas do papel. Biofix Scientific Journal 3: 122–129, https://doi.org/10.5380/biofix.v3i1.57860.Search in Google Scholar

Rol, F., Belgacem, M.N., Gandini, A., and Bras, J. (2019). Recent advances in surface-modified cellulose nanofibrils. Prog. Polym. Sci. 88: 241–264, https://doi.org/10.1016/j.progpolymsci.2018.09.002.Search in Google Scholar

Sá, R.M., Miranda, C.S., and José, N.M. (2015). Preparation and characterization of Nanowhiskers cellulose from fiber arrowroot (Maranta arundinacea). Mater. Res. 18: 225–229, https://doi.org/10.1590/1516-1439.366214.Search in Google Scholar

Saelee, K., Yingkamhaeng, N., Nimchua, T., and Sukyai, P. (2016). An environmentally friendly xylanase-assisted pretreatment for cellulose nanofibrils isolation from sugarcane bagasse by high-pressure homogenization. Ind. Crop. Prod. 82: 149–160, https://doi.org/10.1016/j.indcrop.2015.11.064.Search in Google Scholar

SaifulAzry, S.O.A., Chuah, T.G., Paridah, M.T., Aung, M.M., and Edi, S.Z. (2017). Effects of Polymorph transformation via mercerisation on microcrystalline cellulose fibres and isolation of nanocrystalline cellulose fibres. Pertanika Journal of Science and Technology 25: 1275–1290.Search in Google Scholar

Schindelin, J., Arganda-Carreras, I., Frise, E., Kaynig, V., Longair, M., Pietzsch, T., Preibisch, S., Rueden, C., Saalfeld, S., Schmid, B., et al.. (2012). Fiji: an open-source platform for biological-image analysis. Nat. Methods 9: 676–682, https://doi.org/10.1038/nmeth.2019.Search in Google Scholar PubMed PubMed Central

Segal, L., Creely, J.J., Martin, A.E., and Conrad, C.M. (1959). An empirical method for estimating the degree of crystallinity of native cellulose using the x-ray diffractometer. Textil. Res. J. 29: 786–794, https://doi.org/10.1177/004051755902901003.Search in Google Scholar

Svenningsson, L., Lin, Y., Karlsson, M., Martinelli, A., Nordstierna, L. (2019). Molecular orientation distribution of regenerated cellulose fibers investigated with polarized Raman spectroscopy. Macromolecules 52: 3918−3924. https://doi.org/10.1021/acs.macromol.9b00520.Search in Google Scholar

Tarrés, Q., Saguer, E., Pèlach, M.A., Alcalà, M., Delgado-Aguilar, M., and Mutjé, P. (2016). The feasibility of incorporating cellulose micro/nanofibers in papermaking processes: the relevance of enzymatic hydrolysis. Cellulose 23: 1433–1445, https://doi.org/10.1007/s10570-016-0889-y.Search in Google Scholar

Tonoli, G.H.D., Holtman, K.M., Glenn, G., Fonseca, A.S., Wood, D., Williams, T., Sa, V.A., Torres, L., Klamczynski, A., and Orts, W.J. (2016). Properties of cellulose micro/nanofibers obtained from eucalyptus pulp fiber treated with anaerobic digestate and high shear mixing. Cellulose 23: 1239–1256, https://doi.org/10.1007/s10570-016-0890-5.Search in Google Scholar

Vítek, P., Klem, K., and Urban, O. (2017). Application of Raman spectroscopy to analyse lignin/cellulose ratio in Norway spruce tree rings. Beskydy 10: 41–48, https://doi.org/10.11118/beskyd201710010041.Search in Google Scholar

Wallis, A.F.A., Wearne, R.H., and Wright, P.J. (1996). Chemical analysis of polysaccharides in plantation eucalypt woods and pulps. Appita J. 49: 258–262.Search in Google Scholar
Received: 2020-10-27
Accepted: 2021-06-08
Published Online: 2021-07-19
Published in Print: 2021-11-25

© 2021 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Original Articles
  3. Variations in heartwood formation and wood density as a function of age and plant spacing in a fast-growing eucalyptus plantation
  4. On-line characterization of wood chip brightness and chemical composition by means of visible and near-infrared spectroscopy
  5. Extractives in Betula celtiberica stemwood and isolation and identification of diarylheptanoids in the hydrophilic extract
  6. High recovery of stilbene glucosides by acetone extraction of fresh inner bark of Norway spruce
  7. Natural cork and its agglomerates as substitutes for high-density expanded polystyrene foams in sandwich cores
  8. Understanding the thermal durability of wood-based composites (WBCs) using crack propagation fracture toughness
  9. Evaluation of changes in cellulose micro/nanofibrils structure under chemical and enzymatic pre-treatments
  10. Multi-scale evaluation of the effect of saturated steam on the micromechanical properties of Moso bamboo
  11. Short Note
  12. Wood modification with N-methylol and N-methyl compounds: a case study on how non-fixated chemicals in modified wood may affect the classification of their durability
https://doi.org/10.1515/hf-2020-0231
Keywords for this article
cellulose structure; chemical characterization; enzymes; nanofibrillated cellulose; pre-treatments

Articles in the same Issue

  1. Frontmatter
  2. Original Articles
  3. Variations in heartwood formation and wood density as a function of age and plant spacing in a fast-growing eucalyptus plantation
  4. On-line characterization of wood chip brightness and chemical composition by means of visible and near-infrared spectroscopy
  5. Extractives in Betula celtiberica stemwood and isolation and identification of diarylheptanoids in the hydrophilic extract
  6. High recovery of stilbene glucosides by acetone extraction of fresh inner bark of Norway spruce
  7. Natural cork and its agglomerates as substitutes for high-density expanded polystyrene foams in sandwich cores
  8. Understanding the thermal durability of wood-based composites (WBCs) using crack propagation fracture toughness
  9. Evaluation of changes in cellulose micro/nanofibrils structure under chemical and enzymatic pre-treatments
  10. Multi-scale evaluation of the effect of saturated steam on the micromechanical properties of Moso bamboo
  11. Short Note
  12. Wood modification with N-methylol and N-methyl compounds: a case study on how non-fixated chemicals in modified wood may affect the classification of their durability
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 19.9.2025 from https://www.degruyterbrill.com/document/doi/10.1515/hf-2020-0231/html
Scroll to top button