, Volume 19, Issue 3, pp 671–678 | Cite as

Interaction between –OH groups of methylcellulose and solvent in NaOH/urea aqueous system at low temperature

  • Zhiwei Jiang
  • Ang Lu
  • Jinping Zhou
  • Lina Zhang


To clarify the interaction between the –OH groups of cellulose and NaOH/urea in aqueous solutions, methylcellulose (MC) was used as solute to study its solution properties at low temperature. Dynamic light scattering, 13C NMR spectroscopy, differential scanning calorimetry, and transmission electron microscopy (TEM) were used to characterize the MC macromolecular size and intermolecular interactions between MC and solvent molecules. The results revealed that MC existed mainly as individual molecules in the NaOH/urea aqueous solution prepared by freeze-thawing process, whereas aggregates occurred in the MC solution prepared at room temperature. DLS further confirmed that MC existed mainly as individual flexible chains in the solution treated at low temperature. TEM images showed the sphere-like coil appearance of the MC macromolecules in the solution prepared at low temperature. Therefore, the strong interaction between –OH groups of MC and solvent occurred at low temperature, leading to the formation of the imperfect inclusion complex through hydrogen bonding network between MC, NaOH, urea and water.


Interaction of the –OH groups Methylcellulose Imperfect inclusion complex Low temperature Hydrogen bond 



This work was supported by National Basic Research Program of China (973 Program, 2010CB32203) and the National Natural Science Foundation of China (20874079).


  1. Asbury JB, Steinel T, Fayer M (2004) Hydrogen bond networks: structure and evolution after hydrogen bond breaking. J Phys Chem B 108(21):6544–6554CrossRefGoogle Scholar
  2. Cai J, Zhang L (2005) Rapid dissolution of cellulose in LiOH/urea and NaOH/urea aqueous solutions. Macromol Biosci 5(6):539–548CrossRefGoogle Scholar
  3. Cai J, Zhang L (2006) Unique gelation behavior of cellulose in NaOH/urea aqueous solution. Biomacromolecules 7(1):183–189CrossRefGoogle Scholar
  4. Cai J, Liu Y, Zhang L (2006) Dilute solution properties of cellulose in LiOH/urea aqueous system. J Polym Sci Part B Polym 44(21):3093–3101CrossRefGoogle Scholar
  5. Cai J, Zhang L, Chang C, Cheng G, Chen X, Chu B (2007) Hydrogen bond induced inclusion complex in aqueous cellulose/LiOH/urea solution at low temperature. ChemPhysChem 8(10):1572–1579CrossRefGoogle Scholar
  6. Cai J, Zhang L, Liu S, Liu Y, Xu X, Chen X, Chu B, Guo X, Xu J, Cheng H (2008) Dynamic self-assembly induced rapid dissolution of cellulose at low temperatures. Macromolecules 41(23):9345–9351CrossRefGoogle Scholar
  7. Chu B (ed) (1991) Laser light scattering, 2nd edn. Academic Press, New YorkGoogle Scholar
  8. Egal M, Budtova T, Navard P (2008) The dissolution of microcrystalline cellulose in sodium hydroxide-urea aqueous solutions. Cellulose 15(3):361–370CrossRefGoogle Scholar
  9. Heinze T, Liebert T (2001) Unconventional methods in cellulose functionalization. Prog Polym Sci 26(9):1689–1762CrossRefGoogle Scholar
  10. Ke H, Zhou J, Zhang L (2006) Structure and physical properties of methylcellulose synthesized in NaOH/urea solution. Polym Bull 56(4):349–357CrossRefGoogle Scholar
  11. Klemm D, Heublein B, Fink HP, Bohn A (2005) Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem Int Ed 44(22):3358–3393CrossRefGoogle Scholar
  12. Kondo T (1997) The relationship between intramolecular hydrogen bonds and certain physical properties of regioselectively substituted cellulose derivatives. J Polym Sci Part B Polym 35(4):717–723CrossRefGoogle Scholar
  13. Lu A, Liu Y, Zhang L, Potthast A (2011) Investigation on metastable solution of cellulose dissolved in NaOH/urea aqueous system at low temperature. J Phys Chem B 115(44):12801–12808CrossRefGoogle Scholar
  14. Lue A, Zhang L (2010) Effects of carbon nanotubes on rheological behavior in cellulose solution dissolved at low temperature. Polymer 51(12):2748–2754CrossRefGoogle Scholar
  15. Lue A, Zhang L, Ruan D (2007) Inclusion complex formation of cellulose in NaOH–thiourea aqueous system at low temperature. Macromol Chem Phys 208(21):2359–2366CrossRefGoogle Scholar
  16. Malsam J, Aksan A (2009) Hydrogen bonding and kinetic/thermodynamic transitions of aqueous trehalose solutions at cryogenic temperatures. J Phys Chem B 113(19):6792–6799CrossRefGoogle Scholar
  17. Miyazaki M, Fujii A, Ebata T, Mikami N (2004) Infrared spectroscopic evidence for protonated water clusters forming nanoscale cages. Science 304(5674):1134–1137CrossRefGoogle Scholar
  18. Niu A, Liaw DJ, Sang HC, Wu C (2000) Light-scattering study of a zwitterionic polycarboxybetaine in aqueous solution. Macromolecules 33(9):3492–3494CrossRefGoogle Scholar
  19. Qi H, Yang Q, Zhang L, Liebert T, Heinze T (2011) The dissolution of cellulose in NaOH-based aqueous system by two-step process. Cellulose 18(2):1–9CrossRefGoogle Scholar
  20. Ruan D, Zhang L, Lue A, Zhou J, Chen H, Chen X, Chu B, Kondo T (2006) A rapid process for producing cellulose multi filament fibers from a NaOH/thiourea solvent system. Macromol Rapid Commun 27(17):1495–1500CrossRefGoogle Scholar
  21. Schriver L, Abdelaoui O, Schriver A (1992) Atmospheric cryochemistry: oxygen atom reaction with the fluorocarbon freon 11 in matrixes: FTIR spectra of isolated COFCl and COFCl: Cl2 complex in solid argon. J Phys Chem 96(20):8069–8073CrossRefGoogle Scholar
  22. Sekiguchi Y, Sawatari C, Kondo T (2003) A gelation mechanism depending on hydrogen bond formation in regioselectively substituted O-methylcelluloses. Carbohydr Polym 53(2):145–153CrossRefGoogle Scholar
  23. Specht A, Ursby T, Weik M, Peng L, Kroon J, Bourgeois D, Goeldner M (2001) Cryophotolysis of ortho nitrobenzyl derivatives of enzyme ligands for the potential kinetic crystallography of macromolecules. Chembiochem 2(11):845–848CrossRefGoogle Scholar
  24. Szajdzinska-Pietek E, Bednarek J, Plonka A, Hallbrucker A, Mayer E (2001) Radiation cryochemistry of frozen dilute aqueous solutions: influence of the extent of solute segregation on the radiolysis pathway. Res Chem Intermed 27(9):937–943CrossRefGoogle Scholar
  25. Tezuka Y, Imai K, Oshima M, Chiba T (1987) Determination of substituent distribution in cellulose ethers by means of a carbon-13 NMR study on their acetylated derivatives. 1. Methylcellulose. Macromolecules 20(10):2413–2418CrossRefGoogle Scholar
  26. Vajda T, Szókán G, Hollósi M (1998) Cryochemistry: freezing effect on peptide coupling in different organic solutions. J Pept Sci 4(4):300–304CrossRefGoogle Scholar
  27. Wang X, Xu X, Zhang L (2008) Thermally induced conformation transition of triple-helical lentinan in NaCl aqueous solution. J Phys Chem B 112(33):10343–10351CrossRefGoogle Scholar
  28. Yan L, Chen J, Bangal PR (2007) Dissolving cellulose in a NaOH/thiourea aqueous solution: a topochemical investigation. Macromol Biosci 7(9/10):1139–1148CrossRefGoogle Scholar
  29. Yoshida Y, Isogai A (2007) Preparation and characterization of cellulose β-ketoesters prepared by homogeneous reaction with alkylketene dimers: comparison with cellulose/fatty acid esters. Cellulose 14(5):481–488CrossRefGoogle Scholar
  30. Zhou J, Xu Y, Wang X, Qin Y, Zhang L (2008) Microstructure and aggregation behavior of methylcelluloses prepared in NaOH/urea aqueous solutions. Carbohydr Polym 74(4):901–906CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2012

Authors and Affiliations

  1. 1.Department of ChemistryWuhan UniversityWuhanChina

Personalised recommendations