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Swelling-assisted reduction of chitosan molecular weight in the solid state using hydrogen peroxide

Abstract

Chitosan in the solid state has been degraded in a controlled way by treatment with hydrogen peroxide at room temperature. Chitosan was swollen in diluted NaOH, making it more susceptible to the peroxide treatment. The product has been characterized by intrinsic viscosity, FTIR infrared spectroscopy and roentgen diffraction. The molecular weight and the intrinsic viscosity were reduced significantly (about tenfold). The degree of deacetylation did not change. The chitosan product has a low viscosity (about 100 cP), a lower molecular weight (1.4 × 102 kDa), a high purity and a high crystallinity. It can be used in many potential applications. This method is easy and suitable for a large-scale process.

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References

  1. 1.

    Rinaudo M (2006) Chitin and chitosan: properties and applications. J Prog Polym Sci 31:603–632

    CAS  Article  Google Scholar 

  2. 2.

    Domard A (2011) A perspective on 30 years research on chitin and chitosan. Carbohydr Polym 84:696–703

    CAS  Article  Google Scholar 

  3. 3.

    Goosen MFA (1996) Applications of chitin and chitosan. CRC Press, USA

    Google Scholar 

  4. 4.

    Mishra M (2015) Handbook of encapsulation and controlled release. CRC Press, London

    Book  Google Scholar 

  5. 5.

    Zamani A, Taherzadeh MJ (2010) Production of low molecular weight chitosan by hot dilute sulfuric acid. Bioresources 5:1554–1564

    CAS  Google Scholar 

  6. 6.

    Rojas-Reyna R, Schwarz S, Heinrich G, Petzold G, Schütze S, Bohrisch J (2010) Flocculation efficiency of modified water soluble chitosan versus commonly used commercial polyelectrolytes. Carbohydr Polym 81:317–322

    CAS  Article  Google Scholar 

  7. 7.

    Schwarz S, Bratskaya S, Jaeger W, Paulke BR (2006) Effect of charge density, molecular weight and hydrophobicity on polycations adsorption and flocculation of polystyrene latices and silica. J Appl Polym Sci 101:3422–3429

    CAS  Article  Google Scholar 

  8. 8.

    Park PJ, Je JY, Byun HG, Moon SH, Kim SK (2004) Antimicrobial activity of hetero-chitosans and their oligosaccharides with different molecular weights. J Microbiol Biotechnol 14:317–323

    CAS  Google Scholar 

  9. 9.

    Chung YC, Su YP, Chen CC, Jia G, Wang HL, Wu JC (2004) Relationship between antibacterial activity of chitosan and surface characteristics of cell wall. Act pharmacol Sin 25:932–936

    CAS  Google Scholar 

  10. 10.

    Tsai GJ, Su WH, Chen HC, Pan CL (2002) Antimicrobial activity of shrimp chitin and chitosan from different treatments and applications of fish preservation. J Fish Sci 68:170–177

    CAS  Article  Google Scholar 

  11. 11.

    Russell GS (2013) A review of the applications of chitin and its derivatives in agriculture to modify plant-microbial interactions and improve crop yields. J Agron 3:757–793

    Article  Google Scholar 

  12. 12.

    No HK, Park NY, Lee SH, Meyers SP (2002) Antibacterial activity of chitosans and chitosan oligomers with different molecular weights. Inter J Food Microbiol 74:65–72

    CAS  Article  Google Scholar 

  13. 13.

    Liu H, Du Y, Wang X, Sun L (2004) Chitosan kills bacterial through cell membrane damage. Int J Food Microbiol 95:147–155

    CAS  Article  Google Scholar 

  14. 14.

    Osorio MA, David L, Trombotto S, Lucas JM, Peniche-Covas C, Domard A (2010) Kinetics study of the solid-state acid hydrolysis of chitosan: evolution of the crystallinity and macromolecular structure. J Biomacromol 11:1376–1386

    Article  Google Scholar 

  15. 15.

    Emmanuel B, Alain D, Marie M, Giraud G (1997) Study of the solid-state hydrolysis of chitosan in presence of HCl. J Polym Sci 35:3181–3191

    Article  Google Scholar 

  16. 16.

    Kulicke WM, Kull AH, Kull W, Thielking H, Engelhardt J, Pannek JB (1996) Characterization of aqueous carboxymethylcellulose solutions in terms of their molecular structure and its influence on rheological behaviour. Polymer 37:2723–2731

    CAS  Article  Google Scholar 

  17. 17.

    Garcia MA, Paz N, Castro C, Rodriguez JL, Rapado M, Zuluaga R, Ganan P, Casariego A (2015) Effect of molecular weight reduction by gamma irradiation on the antioxidant capacity of chitosan from lobster shells. J Radiat Res Appl Sci 8:190–200

    CAS  Article  Google Scholar 

  18. 18.

    Savitri E, Juliastuti SR, Handaratri A, Roesyadi A (2014) Degradation of chitosan by sonication in very-low-concentration acetic acid. J Polym Degrad Stab 110:344–352

    CAS  Article  Google Scholar 

  19. 19.

    Tian F, Liu Y, Hu K, Zhao B (2003) The depolymerization mechanism of chitosan by hydrogen peroxide. J Mater Sci 38:4709–4712

    CAS  Article  Google Scholar 

  20. 20.

    Tanioka S, Matsui Y, Irie T, Tanigawa T, Tanaka Y, Shibata H, Sawa Y, Kono Y (2014) Oxidative depolymerization of chitosan by hydroxyl radical. J Biosci Biotechnol Biochem 60:2001–2004

    Article  Google Scholar 

  21. 21.

    Chang KLB, Tai MC, Cheng FH (2001) Kinetics and products of the degradation of chitosan by hydrogen peroxide. J Agric Food Chem 49:4845–4851

    CAS  Article  Google Scholar 

  22. 22.

    AOAC (1990) Official methods of analysis. Association of Official Analytical Chemists, Washington, DC

    Google Scholar 

  23. 23.

    Boyer RF (1993) Modern experimental biochemistry, 2nd edn. Benjamin-Cummings, Redwood City, California

  24. 24.

    No HK, Meyers SP (1995) Preparation and characterization of chitin and chitosan—a review. J Aquat Food Prod Technol 4:27–52

    CAS  Article  Google Scholar 

  25. 25.

    Tang H, Chen H, Duan B, Lu A, Zhang L (2014) Swelling behaviors of superabsorbent chitin/carboxymethylcellulose hydrogels. J Mater Sci 49:2235–2242

    CAS  Article  Google Scholar 

  26. 26.

    Tao W, Svetlana Z (2008) Determination of the degree of acetylation (DA) of chitin and chitosan by an improved first derivative UV method. Carbohydr Polym 73:248–253

    Article  Google Scholar 

  27. 27.

    Brugnerotto J, Lizardi J, Goycoolea FM, Arguelles-Monal W, Desbrie J, Rinaudo M (2001) An infrared investigation in relation with chitin and chitosan characterization. Polymer 42:3569–3580

    CAS  Article  Google Scholar 

  28. 28.

    Takara EA, Marchese J, Ochoa NA (2015) NaOH treatment of chitosan films: impact on macromolecular structure and film properties. Carbohydr Polym 132:25–30

    CAS  Article  Google Scholar 

  29. 29.

    Eroğlu M, Irmak S, Acar A, Denkbaş EB (2002) Design and evaluation of a mucoadhesive therapeutic agent delivery system for postoperative chemotherapy in superficial bladder cancer. Int J Pharm 235:51–59

    Article  Google Scholar 

  30. 30.

    Soleimani F, Sadeghi M, Shahsavari H (2012) Preparation and swelling behavior of carrageenan-graft-polymethacrylamide superabsorbent hydrogel as a releasing drug system. Indian J Sci Technol 5:2143–2147

    CAS  Google Scholar 

  31. 31.

    Nguyen QH, Dang VP, Nguyen ND, Nguyen TKL (2012) Degradation of chitosan in solution by gamma irradiation in the presence of hydrogen peroxide. Carbohydr Polym 87:935–938

    CAS  Article  Google Scholar 

  32. 32.

    Qin C, Du Y, Xiao L (2002) Effect of hydrogen peroxide treatment on the molecular weight and structure of chitosan. J Polym Degrad Stab 76:211–218

    CAS  Article  Google Scholar 

  33. 33.

    Feng T, Yu L, Keao H, Binyuan Z (2004) Study of the depolymerization behavior of chitosan by hydrogen peroxide. Carbohydr Polym 57:31–37

    Article  Google Scholar 

  34. 34.

    Ioelovich M (2014) Crystallinity and hydrophilicity of chitin and chitosan. J Chem 3:7–14

    Google Scholar 

Download references

Acknowledgements

The authors thank the Ministry of Science and Technology, Vietnam who have funded this research and Leibniz-Institute of Polymer Research Dresden, Germany for analytical supports.

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Correspondence to Trang Si Trung.

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Minh, N.C., Cuong, H.N., Phuong, P.T.D. et al. Swelling-assisted reduction of chitosan molecular weight in the solid state using hydrogen peroxide. Polym. Bull. 74, 3077–3087 (2017). https://doi.org/10.1007/s00289-016-1880-3

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Keywords

  • Swelling
  • Solid-state degradation
  • Chitosan