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Hydration and drying of various polysaccharides studied using DSC

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Abstract

The hydration of cellulose, chitosan, schizophyllan, hyaluronan, and carboxymethyl cellulose was studied using differential scanning calorimetry (DSC). In the first part, the classical freezing/thawing approach was used to determine the amount of non-freezing water. The inconsistency in enthalpies obtained during crystallization and melting of freezable water was discussed with respect to the DSC experimental conditions. Our interpretation questions the recent conclusions about competitive processes occurring during melting which are hypothesized to influence the determined melting enthalpy. In the second part, the hydration and drying were studied using the evaporation enthalpy of water. The dry mass normalized dependency of vaporization enthalpy on water content confirmed an abrupt break at low water content in hyaluronan sample which was attributed to the sudden appearance of a parallel process taking part during the drying. The rest of polysaccharide samples showed only a linear decrease in evaporation enthalpy. The renormalization of enthalpies by the water content revealed the increase in evaporation enthalpy with decreasing water content in most samples which was ascribed to the strong interaction between polysaccharide and water. The exceptions were carboxymethyl cellulose which showed a decrease in evaporation enthalpy. This indicates the existence of a simultaneous process occurring during drying, but unlike in hyaluronan, the processes do not appear abruptly but accompany the evaporation in the wide concentration range. Comparison of determined hydration numbers showed that part of non-freezing water in hyaluronan is not bound to sorption sites but occurs presumably in small temporary pores. In contrast, water-soluble schizophyllan forms temporary pores as well but presumably with higher dimension and the non-freezing water is formed mostly by water molecules interacting with sorption sites.

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References

  1. Cavallaro G, Donato DI, Lazzara G, Milioto S. Films of halloysite nanotubes sandwiched between two layers of biopolymer: from the morphology to the dielectric, thermal, transparency, and wettability properties. J Phys Chem C. 2011;115:20491–8.

    Article  CAS  Google Scholar 

  2. Cavallaro G, Lazzara G, Milioto S. Dispersions of nanoclays of different shapes into aqueous and solid biopolymeric matrices. Extended physicochemical study. Langmuir. 2011;27:1158–67.

    Article  CAS  Google Scholar 

  3. Dammström S, Salmén L, Gatenholm P. The effect of moisture on the dynamical mechanical properties of bacterial cellulose/glucuronoxylan nanocomposites. Polymer. 2005;46:10364–71.

    Article  Google Scholar 

  4. Gocho H, Shimizu H, Tanioka A, Chou TJ, Nakajima T. Effect of polymer chain end on sorption isotherm of water by chitosan. Carbohydr Polym. 2000;41:87–90.

    Article  CAS  Google Scholar 

  5. Blicharska B, Peemoeller H, Witek M. Hydration water dynamics in biopolymers from NMR relaxation in the rotating frame. J Magn Reson. 2010;207:287–93.

    Article  CAS  Google Scholar 

  6. Mracek A, Benesova K, Minarik A, Urban P, Lapcik L. The diffusion process of sodium hyaluronate (Na-HA) and Na-HA-n-alkyl derivatives films swelling. J Biomed Mater Res Part A. 2007;83A(1):184–90.

    Article  CAS  Google Scholar 

  7. Hatakeyama T, Nakamura K, Hatakeyama H. Vaporization of bound water associated with cellulose fibers. Thermochim Acta. 2000;352–353:233–9.

    Article  Google Scholar 

  8. Hatakeyama H, Hatakeyama T. Interaction between water and hydrophilic polymers. Thermochim Acta. 1998;308:3–22.

    Article  CAS  Google Scholar 

  9. Hatakeyama T, Hatakeyama H, Nakamura K. Non-freezing water content of mono- and divalent cation salts of polyelectrolyte–water systems studied by DSC. Thermochim Acta. 1995;253:137–48.

    Article  CAS  Google Scholar 

  10. Takahashi M, Hatakeyama T, Hatakeyama H. Phenomenological theory describing the behaviour of non-freezing water in structure formation process of polysaccharide aqueous solutions. Carbohydr Polym. 2000;41:91–5.

    Article  CAS  Google Scholar 

  11. Průšová A, Conte P, Kučerík J, Alonzo G. Dynamics of hyaluronan aqueous solutions as assessed by fast field cycling NMR relaxometry. Anal Bioanal Chem. 2010;397:3023–8.

    Article  Google Scholar 

  12. Hunger J, Bernecker A, Bakker HJ, Bonn M, Richter R. Hydration dynamics of hyaluronan and dextran. Biophys J. 2012;103:L10–L12.

    Google Scholar 

  13. Maréchal Y, Milas M, Rinaudo M. Hydration of hyaluronan polysaccharide observed by IR spectrometry. III. Structure and mechanism of hydration. Biopolymers. 2003;72:162–73.

    Article  Google Scholar 

  14. Mracek A, Varhanikova J, Lehocky M, Grundelova L, Pokopcova A, Velebny V. The influence of Hofmeister series ions on hyaluronan swelling and viscosity. Molecules. 2008;13(5):1025–34.

    Article  CAS  Google Scholar 

  15. Mazeau K, Rinaudo M. The prediction of the characteristics of some polysaccharides from molecular modeling. Comparison with effective behavior. Food Hydrocolloid. 2004;18:885–98.

    Article  CAS  Google Scholar 

  16. Takigami S, Takigami M, Phillips GO. Hydration characteristics of the cross-linked hyaluronan derivative hylan. Carbohydr Polym. 1993;22:153–60.

    Article  CAS  Google Scholar 

  17. Takigami S, Takigami M, Phillips GO. Effect of preparation method on the hydration characteristics of hylan and comparison with another highly cross-linked polysaccharide, gum arabic. Carbohydr Polym. 1995;26:11–8.

    Article  CAS  Google Scholar 

  18. Kučerík J, Průšová A, Rotaru A, Flimel K, Janeček J, Conte P. DSC study on hyaluronan drying and hydration. Thermochim Acta. 2011;523(1–2):245–9.

    Article  Google Scholar 

  19. Belton PS. NMR and the mobility of water in polysaccharide gels. Int J Biol Macromol. 1997;21:81–8.

    Article  CAS  Google Scholar 

  20. Gemmei-Ide M, Ohya A, Kitano H. Thermally latent water in a polymer matrix. J Phys Chem B. 2010;114:4310–2.

    Article  CAS  Google Scholar 

  21. Prusova A, Smejkalova D, Chytil M, Velebny V, Kucerik J. An alternative DSC approach to study hydration of hyaluronan. Carbohydr Polym. 2010;82(2):498–503.

    Article  CAS  Google Scholar 

  22. Park S, Venditti RA, Jameel H, Pawlak JJ. Changes in pore size distribution during the drying of cellulose fibers as measured by differential scanning calorimetry. Carbohydr Polym. 2006;66(1):97–103.

    Article  CAS  Google Scholar 

  23. Prado JR, Vyazovkin S. Activation energies of water vaporization from the bulk and from laponite, montmorillonite, and chitosan powders. Thermochim Acta. 2011;524(1–2):197–201.

    CAS  Google Scholar 

  24. Park S, Venditti RA, Jameel H, Pawlak JJ. Studies of the heat of vaporization of water associated with cellulose fibers characterized by thermal analysis. Cellulose. 2007;14(3):195–204.

    Article  CAS  Google Scholar 

  25. Ghosh A, Ali MA, Walls R. Modification of microstructural morphology and physical performance of chitosan films. Int J Biol Macromol. 2010;46:179–86.

    Article  CAS  Google Scholar 

  26. Nishinari K, Takahashi R. Interaction in polysaccharide solutions and gels. Curr Opin Colloid Interface Sci. 2003;8:396–400.

    Article  CAS  Google Scholar 

  27. Kony DB, Damm W, Stoll S, van Gunsteren WF, Hűnenberger PH. Explicit-solvent molecular dynamics simulations of the polysaccharide schizophyllan in water. Biophys J. 2007;93:442–55.

    Article  CAS  Google Scholar 

  28. Robert L, Robert A-M, Renard G. Biological effects of hyaluronan in connective tissues, eye, skin, venous wall. Role in aging. Pathol Biol. 2010;58:187–98.

    Article  CAS  Google Scholar 

  29. Nikolakakis I, Tsarvouli K, Malamataris S. Water retention and drainage in different brands of microcrystalline cellulose: effect of measuring conditions. Eur J Pharm Biopharm. 2006;63:278–87.

    Article  CAS  Google Scholar 

  30. Liu P, Zhai M, Li J, Peng J, Wu J. Radiation preparation and swelling behavior of sodium carboxymethyl cellulose hydrogels. Radiat Phys Chem. 2002;63:525–8.

    Article  CAS  Google Scholar 

  31. Liu J, Cowman MK. Thermal analysis of semi-dilute hyaluronan solutions. J Therm Anal Calorim. 2000;59:547–57.

    Article  CAS  Google Scholar 

  32. Della Gatta G, Richardson MJ, Sarge SM, Stolen S. Standards, calibration, and guidelines in microcalorimetry—Part 2 calibration standards for differential scanning calorimetry—(IUPAC Technical Report). Pure Appl Chem. 2006;78:1455–76.

    Article  CAS  Google Scholar 

  33. Faroongsarng D, Sukonrat P. Thermal behavior of water in the selected starch- and cellulose-based polymeric hydrogels. Int J Pharm. 2008;352:152–8.

    Article  CAS  Google Scholar 

  34. Qu X, Wirsén A, Albertsson AC. Novel pH-sensitive chitosan hydrogels: swelling behavior and states of water. Polymer. 2000;41:4589–98.

    Article  CAS  Google Scholar 

  35. Kučerík J, Bursáková P, Průšová A, Grebíková L, Schaumann GE. Hydration of humic and fulvic acids studied by DSC. J Therm Anal Calorim. 2012;110:451–9.

    Article  Google Scholar 

  36. Cowman MK, Matsuoka S. Experimental approaches to hyaluronan structure. Carbohydr Res. 2005;340:791–809.

    Article  CAS  Google Scholar 

  37. Hargittai I, Hargittai M. Molecular structure of hyaluronan: an introduction. Struct Chem. 2008;19:697–717.

    Article  CAS  Google Scholar 

  38. Marsh KN. Recommended reference materials for the realization of physicochemical properties. Oxford: Blackwell; 1987.

    Google Scholar 

  39. Kohl I, Mayer E, Hallbrucker A. The glassy water-cubic ice system: a comparative study by X-ray diffraction and differential scanning calorimetry. Phys Chem Chem Phys. 2000;2:1579–86.

    Article  CAS  Google Scholar 

  40. Kerch G, Glonin A, Zicans J, Meri RM. A DSC study of the effect of ascorbic acid on bound water content and distribution in chitosan-enriched bread rolls during storage. J Therm Anal Calorim. 2012;108:73–8.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the Ministry of Education, Youth and Sport of the Czech Republic project no. 0021630501. Authors would like to thank Dr. Vladimir Velebný from CPN Company, Dolní Dobrouč, Czech Republic for providing hyaluronan and schizophyllan samples and to Ms. Alena Prusova for the help with evaporation experiments.

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Correspondence to Jiří Kučerík.

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Mlčoch, T., Kučerík, J. Hydration and drying of various polysaccharides studied using DSC. J Therm Anal Calorim 113, 1177–1185 (2013). https://doi.org/10.1007/s10973-013-2946-1

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  • DOI: https://doi.org/10.1007/s10973-013-2946-1

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