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Structural variations of cotton cellulose nanocrystals from deep eutectic solvent treatment: micro and nano scale

  • Zhe Ling
  • J. Vincent EdwardsEmail author
  • Zongwei Guo
  • Nicolette T. Prevost
  • Sunghyun Nam
  • Qinglin Wu
  • Alfred D. French
  • Feng XuEmail author
Original Paper


Solvents that produce cellulose nanocrystals (CNCs) and promote cellulose fibrillation are of current interest. In this work, CNCs were fabricated from cotton at 80 and 100 °C using deep eutectic solvents (DESs) having choline chloride/oxalic acid dihydrate (OA) ratios of 1:1, 1:2 and 1:3. To investigate the side effects of the fabrication, the crystal structure and morphology of micro-sized treated cellulose together with nano-sized CNCs were analyzed by X-ray diffraction, field emission scanning electron microscopy and atomic force microscopy. OA promoted the formation of carboxyl groups on the C6 positions of molecules on the hydrophilic (1–10) lattice planes, causing extensive fibrillation of cellulose and disruption of surface layers on (110) and (200) planes. Lower crystallinity and lamellar structures for CNCs with mild treatment were observed after mechanical disintegration and subsequent lyophilization, which was ascribed to van der Waals forces and hydrogen bonding between adjacent crystalline cellulose chains, accelerating the self-assembly into cellulose macrofibrils. This work is discussed in light of cellulose supramolecular structures that are modified from CNC fabrication via DES treatment, with a view to enhancing the efficacy of treatment by understanding the variations that arise in cellulose structure from a green solvent.

Graphical abstract


Cotton Cellulose nanocrystals Deep eutectic solvent Crystal structure 



The authors gratefully acknowledge financial support by National Key Research and Development Program of China (2017YFD0601004) and Chinese Scholarship Council (CSC No. 201706510045). We also appreciate Dr. Mohammad Saghayezhian of LSU Shared Instrument Facility for technical assistance with the XRD experiments.

Supplementary material

10570_2018_2092_MOESM1_ESM.docx (973 kb)
Supplementary material 1 (DOCX 972 kb)


  1. Cael JJ, Koenig JL, Blackwell J (1974) Infrared and raman spectroscopy of carbohydrates: part IV. identification of configuration-and conformation-sensitive modes for d-glucose by normal coordinate analysis. Carbohydr Res 32:79–91CrossRefGoogle Scholar
  2. Chen L, Zhu JY, Baez C, Kitin P, Elder T (2016) Highly thermal-stable and functional cellulose nanocrystals and nanofibrils produced using fully recyclable organic acids. Green Chem 18:3835–3843. CrossRefGoogle Scholar
  3. Cuba-Chiem LT, Huynh L, Ralston J, Beattie DA (2008) In situ particle film ATR FTIR spectroscopy of carboxymethyl cellulose adsorption on talc: binding mechanism, pH effects, and adsorption kinetics. Langmuir 24:8036–8044CrossRefGoogle Scholar
  4. Deng M, Zhou Q, Du A, van Kasteren J, Wang Y (2009) Preparation of nanoporous cellulose foams from cellulose-ionic liquid solutions. Mater Lett 63:1851–1854CrossRefGoogle Scholar
  5. Deville S, Saiz E, Nalla RK, Tomsia AP (2006) Freezing as a path to build complex composites. Science 311:515–518CrossRefGoogle Scholar
  6. Ding S-Y, Himmel ME (2006) The maize primary cell wall microfibril: a new model derived from direct visualization. J Agric Food Chem 54:597–606. CrossRefPubMedGoogle Scholar
  7. Fang W, Arola S, Malho JM, Kontturi E, Linder MB, Laaksonen P (2016) Noncovalent dispersion and functionalization of cellulose nanocrystals with proteins and polysaccharides. Biomacromolecules 17:1458–1465. CrossRefPubMedGoogle Scholar
  8. French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896. CrossRefGoogle Scholar
  9. Han J, Zhou C, Wu Y, Liu F, Wu Q (2013) Self-assembling behavior of cellulose nanoparticles during freeze-drying: effect of suspension concentration, particle size, crystal structure, and surface charge. Biomacromolecules 14:1529–1540CrossRefGoogle Scholar
  10. Hebeish A, Hashem M, Shaker N, Ramadan M, El-Sadek B, Hady MA (2009) New development for combined bioscouring and bleaching of cotton-based fabrics. Carbohydr Polym 78:961–972CrossRefGoogle Scholar
  11. Holzwarth U, Gibson N (2011) The Scherrer equation versus the ‘Debye-Scherrer equation’. Nat Nanotechnol 6:534CrossRefGoogle Scholar
  12. Hori R, Wada M (2005) The thermal expansion of wood cellulose crystals. Cellulose 12:479CrossRefGoogle Scholar
  13. Idström A, Brelid H, Nydén M, Nordstierna L (2013) CP/MAS 13C NMR study of pulp hornification using nanocrystalline cellulose as a model system. Carbohydr Polym 92:881–884. CrossRefPubMedGoogle Scholar
  14. Ilharco LM, Garcia AR, Lopes da Silva J, Vieira Ferreira LF (1997) Infrared approach to the study of adsorption on cellulose: influence of cellulose crystallinity on the adsorption of benzophenone. Langmuir 13:4126–4132CrossRefGoogle Scholar
  15. Isogai A (2013) Wood nanocelluloses: fundamentals and applications as new bio-based nanomaterials. J wood Sci 59:449–459CrossRefGoogle Scholar
  16. Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cellulose nanofibers. Nanoscale 3:71–85CrossRefGoogle Scholar
  17. Iwamoto S, Nakagaito AN, Yano H (2007) Nano-fibrillation of pulp fibers for the processing of transparent nanocomposites. Appl Phys A 89:461–466CrossRefGoogle Scholar
  18. Kettering J, Conrad C (1942) Quantitative determination of cellulose in raw cotton fiber. Simple and rapid semimicro method. Ind Eng Chem Anal Ed 14:432–434CrossRefGoogle Scholar
  19. Kim D-Y, Nishiyama Y, Wada M, Kuga S, Okano T (2001) Thermal decomposition of cellulose crystallites in wood. Holzforschung 55:521–524CrossRefGoogle Scholar
  20. Klemm D, Kramer F, Moritz S, Lindström T, Ankerfors M, Gray D, Dorris A (2011) Nanocelluloses: a new family of nature-based materials. Angew Chem Int Ed 50:5438–5466CrossRefGoogle Scholar
  21. Kuribayashi T, Ogawa Y, Rochas C, Matsumoto Y, Heux L, Nishiyama Y (2016) Hydrothermal transformation of wood cellulose crystals into pseudo-orthorhombic structure by cocrystallization. ACS Macro Lett. pp 730–734. CrossRefGoogle Scholar
  22. Laitinen O, Ojala J, Sirviö JA, Liimatainen H (2017) Sustainable stabilization of oil in water emulsions by cellulose nanocrystals synthesized from deep eutectic solvents. Cellulose 24:1679–1689. CrossRefGoogle Scholar
  23. Lee CM, Chen X, Weiss PA, Jensen L, Kim SH (2016) Quantum mechanical calculations of vibrational sum-frequency-generation (SFG) spectra of cellulose: dependence of the CH and OH peak intensity on the polarity of cellulose chains within the SFG coherence domain. J Phys Chem Lett 8:55–60CrossRefGoogle Scholar
  24. Li D, Henschen J, Ek M (2017) Esterification and hydrolysis of cellulose using oxalic acid dihydrate in a solvent-free reaction suitable for preparation of surface-functionalised cellulose nanocrystals with high yield. Green Chem 19:5564–5567. CrossRefGoogle Scholar
  25. Ling Z, Zhang X, Yang G, Takabe K, Xu F (2018) Nanocrystals of cellulose allomorphs have different adsorption of cellulase and subsequent degradation. Ind Crops Prod 112:541–549CrossRefGoogle Scholar
  26. Liu Y, Chen W, Xia Q, Guo B, Wang Q, Liu S, Liu Y, Li J, Yu H (2017) Efficient cleavage of lignin-carbohydrate complexes and ultrafast extraction of lignin oligomers from wood biomass by microwave-assisted treatment with deep eutectic solvent. Chemsuschem 10:1692–1700. CrossRefPubMedPubMedCentralGoogle Scholar
  27. Martínez-Sanz M, Lopez-Rubio A, Lagaron JM (2011) Optimization of the nanofabrication by acid hydrolysis of bacterial cellulose nanowhiskers. Carbohydr Polym 85:228–236CrossRefGoogle Scholar
  28. Matthews JF, Skopec CE, Mason PE, Zuccato P, Torget RW, Sugiyama J, Himmel ME, Brady JW (2006) Computer simulation studies of microcrystalline cellulose Iβ. Carbohydr Res 341:138–152CrossRefGoogle Scholar
  29. Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev. 40:3941–3994CrossRefGoogle Scholar
  30. Morais JPS, de Freitas Rosa M, Nascimento LD, do Nascimento DM, Cassales AR (2013) Extraction and characterization of nanocellulose structures from raw cotton linter. Carbohydr Polym 91:229–235CrossRefGoogle Scholar
  31. Nam S, French AD, Condon BD, 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. CrossRefGoogle Scholar
  32. Nechyporchuk O, Belgacem MN, Bras J (2016) Production of cellulose nanofibrils: a review of recent advances. Ind Crops Prod 93:2–25. CrossRefGoogle Scholar
  33. Nishiyama Y, Langan P, Chanzy H (2002) Crystal structure and hydrogen-bonding system in cellulose Iβ from synchrotron X-ray and neutron fiber diffraction. J Am Chem Soc 124:9074–9082CrossRefGoogle Scholar
  34. Reddy N, Yang Y (2009) Properties and potential applications of natural cellulose fibers from the bark of cotton stalks. Bioresour Technol 100:3563–3569CrossRefGoogle Scholar
  35. Rosa MF, Medeiros ES, Malmonge JA, Gregorski KS, Wood DF, Mattoso LHC, Glenn G, Orts WJ, Imam SH (2010) Cellulose nanowhiskers from coconut husk fibers: effect of preparation conditions on their thermal and morphological behavior. Carbohydr Polym 81:83–92CrossRefGoogle Scholar
  36. Saito T, Nishiyama Y, Putaux J-L, Vignon M, Isogai A (2006) Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed oxidation of native cellulose. Biomacromolecules 7:1687–1691CrossRefGoogle Scholar
  37. Salminen R, Baccile N, Reza M, Kontturi E (2017) Surface-induced frustration in solid state polymorphic transition of native cellulose nanocrystals. Biomacromolecules. CrossRefGoogle Scholar
  38. Selkälä T, Sirviö JA, Lorite GS, Liimatainen H (2016) Anionically stabilized cellulose nanofibrils through succinylation pretreatment in urea–lithium chloride deep eutectic solvent. ChemSusChem. pp 3074–3083. CrossRefGoogle Scholar
  39. Sirviö JA, Visanko M, Liimatainen H (2015) Deep eutectic solvent system based on choline chloride-urea as a pre-treatment for nanofibrillation of wood cellulose. Green Chem 17:3401–3406. CrossRefGoogle Scholar
  40. Sirviö JA, Visanko M, Liimatainen H (2016) Acidic deep eutectic solvents as hydrolytic media for cellulose nanocrystal production. Biomacromolecules 17:3025–3032. CrossRefPubMedGoogle Scholar
  41. Sugiyama J, Okano T, Yamamoto H, Horii F (1990) Transformation of Valonia cellulose crystals by an alkaline hydrothermal treatment. Macromolecules 23:3196–3198CrossRefGoogle Scholar
  42. Tang X, Zuo M, Li Z, Liu H, Xiong C, Zeng X, Sun Y, Hu L, Liu S, Lei T, Lin L (2017) Green processing of lignocellulosic biomass and its derivatives in deep eutectic solvents. Chemsuschem 10:2695. CrossRefGoogle Scholar
  43. Zhbankov RG, Firsov SP, Buslov DK, Nikonenko NA, Marchewka MK, Ratajczak H (2002) Structural physico-chemistry of cellulose macromolecules. Vibrational spectra and structure of cellulose. J Mol Struct 614:117–125CrossRefGoogle Scholar

Copyright information

© This is a U.S. Government work and not under copyright protection in the US; foreign copyright protection may apply  2018

Authors and Affiliations

  1. 1.Beijing Key Laboratory of Lignocellulosic ChemistryBeijing Forestry UniversityBeijingChina
  2. 2.Southern Regional Research Center, Agricultural Research Service, USDANew OrleansUSA
  3. 3.School of Renewable Natural ResourcesLouisiana State University Agricultural CenterBaton RougeUSA

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