Skip to main content
SpringerLink
Log in

Detailed investigation of gel–sol transition temperature of κ-carrageenan studied by DSC, TMA and FBM

  • Published:
Journal of Thermal Analysis and Calorimetry Aims and scope Submit manuscript

Abstract

A broad temperature range of the gel–sol transition of κ-carrageenan was precisely examined by differential scanning calorimetry (DSC), thermomechanical analysis (TMA) and the falling ball method (FBM). κ-Carrageenan the transition temperature of which ranged from 290 to 350 K was used as a representative sample of a thermo-reversible hydrogel. The starting of transition attributed to dissociation of the weak cross-linking zone of aggregated double helices was detected as a change of expansion coefficient by TMA and as an endothermic deviation by DSC. Peak temperature of endotherm by DSC agreed well with the temperature where expansion changed from positive to negative value and this temperature was attributed to gel–sol transition caused by dissociation of double helices’ assembly. Transition temperature measured by FBM was observed at a temperature higher than those obtained by DSC and TMA, which was attributed to decomposition of double helices.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. Desbrières J, Hirrien M, Rinaudo M. A calorimetric study of methylcellulose gelation. Carbohydr Polym. 1998;37:145–52.

    Article  Google Scholar 

  2. Nishinari K, Hofmann KE, Moritaka H, Kohyama K, Nishinari N. Gel–sol transition of methylcellulose. Macromol Chem Phys. 1997;198:1217–26.

    Article  CAS  Google Scholar 

  3. Iijima M, Hatakeyama T, Takahashi M, Hatakeyama H. Effect of thermal history on kappa-carrageenan hydrogelation by differential scanning calorimetry. Thermochim Acta. 2007;452:53–8.

    Article  CAS  Google Scholar 

  4. Hatakeyama T, Dohjima M, Onishi T, Hatakeyama H. AFM and DSC studies on gelation of methyl cellulose mixed with sodium cellulose sulphate. In: Williams PA, Phillips GO, editors. Gums and stabilisers for the food industry 14. Cambridge: Royal Soc Chem; 2008. p. 446–53.

    Google Scholar 

  5. Iijima M, Hatakeyama T, Takahashi M, Hatakeyama H. Thermomechanical analysis of polysaccharide hydrogels in water. J Therm Anal Calorim. 2001;64:617–27.

    Article  CAS  Google Scholar 

  6. Iijima M, Hatakeyama T, Nakamura K, Hatakeyama H. Thermomechanical analysis of calcium alginate hydrogels in water. J Therml Anal Calorim. 2002;70:807–14.

    Article  CAS  Google Scholar 

  7. Iijima M, Hatakeyama T, Nakamura K, Hatakeyama H. Effect of annealing on calcium pectin gel formation by thermomechanical analysis. J Therm Anal Calorim. 2002;70:815–24.

    Article  CAS  Google Scholar 

  8. Iijima M, Hatakeyama T, Hatakeyama H. Swelling behaviour of calcium pectin hydrogels by thermomechanical analysis in water. Thermochim Acta. 2005;431:68–72.

    Article  CAS  Google Scholar 

  9. Watase M, Nishinari K. Dynamic viscoelasticity and anomalous thermal behaviour of concentrated agarose gels. Makromol Chem. 1987;188:1177–86.

    Article  Google Scholar 

  10. Watase M, Nishinari K. Rheological and thermal properties of carrageenan gels. Effect of sulfate content. Makromol Chem. 1987;188:2213–21.

    Article  CAS  Google Scholar 

  11. Nishinari K, Watase M, William PA, Phillips GO. κ-Carrageenan gels: effect of sucrose, glucose, urea, and guanidine hydrochloride on the rheological and thermal properties. J Agr Food Chem. 1990;38:1188–93.

    Article  CAS  Google Scholar 

  12. te Nijenhuis K. Thermoreversible networks: viscoelastic properties and structure of gels. Adv Polym Sci. 1997;130:5–252.

    Google Scholar 

  13. Park J-S, Ruckenstein E. Viscoelastic properties of plasticized methylcellulose and chemically crosslinked methylcellulose. Carbohydr Polym. 2001;46:373–81.

    Article  CAS  Google Scholar 

  14. Pelletier E, Viebke C, Meadows J, Williams PA. Solution rheology of κ-carrageenan in the ordered and disordered conformations. Biomacromol. 2001;2:946–51.

    Article  CAS  Google Scholar 

  15. Anderson NS, Campbell JW, Harding MM, Rees DA, Samuel JWB. X-ray diffraction studies of polysaccharide sulphates: double helix models for κ- and ι-carrageenans. J Mol Bio. 1969;45:85–8.

    Article  CAS  Google Scholar 

  16. Thành TTT, Yuguchi Y, Mimura M, Yasunaga H, Takano R, Urakawa H, Kajiwara K. Molecular characteristics and gelling properties of the carrageenan family, 1. Preparation of novel carrageenans and their dilute solution properties. Macromol. Chem Phys. 2002;203:15–23.

    Google Scholar 

  17. Berth G, Vukovic J, Lechner MD. Physicochemical characterization of carrageenans—A critical reinvestigation. J Appl Polym Sci. 2008;110:3508–24.

    Article  CAS  Google Scholar 

  18. Mangione MR, Giacomazza D, Bulonea D, Martorana V, San Biagio PL. Thermoreversible gelation of κ-carrageenan: relation between conformational transition and aggregation. Biophys Chem. 2003;104:95–105.

    Article  CAS  Google Scholar 

  19. Kara S, Tamerler C, Bermek H, Pekcan Ö. Hysteresis during sol–gel and gel–sol phase transitions of κ-carrageenan: a photon transmission study. J Bioactive Compat Polym. 2003;18:33–44.

    Article  CAS  Google Scholar 

  20. Mahmood SJ, Bi F, Taj N, Farhan M, Shahid M, Azmat R, Uddin F. Physica-chimical characterization of carrageenan ad different tempertures, isolated from Hypnea musciformis from Karach coast Pakistan. J Appl Sci. 2007;7:3506–77.

    Article  CAS  Google Scholar 

  21. Tanaka R, Hatakeyama T, Hatakeyama H, Phillips GO. Differential scanning calorimetric studies of Philippines natural grade κ-carrageenan. Food Hydrocoll. 1996;10:441–4.

    Article  CAS  Google Scholar 

  22. Hilliou L, Larotonda FDS, Sereno AM, Goncüalves MP. Thermal and viscoelastic properties of κ/□-hybrid carrageenan gels obtained from the Portuguese seaweed mastocarpusstellatus. J Agric Food Chem. 2006;54:7870–8.

    Article  CAS  Google Scholar 

  23. Piculell L. Gelling carrageenans. Food Sci Technol. 1995;67:205–44.

    CAS  Google Scholar 

  24. Hoare TR, Kohane DS. Hydrogels in drug delivery: progress and challenges. Polymer. 2008;49:1993–2007.

    Article  CAS  Google Scholar 

  25. Kara S, Tamerle C, Bermek H, Pekcan Ö. Cation effects on sol–gel and gel–sol phase transitions of k-carrageenan-water system. Inter J Biol Macromol. 2003;31:177–85.

    Article  CAS  Google Scholar 

  26. Kara S, Arda E, Kavzak B, Pekcan Ö. Phase transitions of κ-carrageenan gels in various types of salts. J Appl Polym Sci. 2006;102:3008–16.

    Article  CAS  Google Scholar 

  27. Smidsrød O, Grasdalen H. Some physical properties of carrageenan in solution and gel state. Carbohydr Polym. 1982;2:270–2.

    Article  Google Scholar 

Download references

Acknowledgements

The authors are grateful to Professor Clive S. Langham, Nihon University, for his helpful comments and advice. This work was supported by a Grant from the Otsuma Kotaka Foundation and a Grant-in-Aid for Scientific Research (Young Scientists (B)).

Author information

Author notes

  1. Hyoe Hatakeyama

    Present address: Lignocel Research, 73-8, Yatsumata, Fukui, 910-3558, Japan

Authors and Affiliations

  1. Nagasaki University, 1-14, Bunkyo, Nagasaki, 852-8521, Japan

    Mika Iijima

  2. Shinshu University, 3-15-1, Tokida, Ueda, Nagano, 386-8567, Japan

    Masato Takahashi

  3. Lignocel Research, 73-8, Yatsumata, Fukui, 910-3558, Japan

    Tatsuko Hatakeyama

  4. Fukui University of Technology, Gakuen, Fukui, 910-8505, Japan

    Hyoe Hatakeyama

Authors
  1. Mika Iijima
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Masato Takahashi
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Tatsuko Hatakeyama
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Hyoe Hatakeyama
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Tatsuko Hatakeyama.

Appendix

Appendix

In order to obtain reliable results by FBM, preliminary experiments were carried out using 1 % κ-carrageenan hydrogel. Figure 10 shows the relationship between the height of the steel ball and temperature. Steel balls having various sizes as described in the experimental section were used. As shown in Fig. 10, when the size of the steel ball is in a range from 0.8 to 1.5 mm, the height of the steel ball sharply decreases at about 316 K. When the steel ball size was 0.5 mm, the ball moved gradually, indicating the mass of the ball was too light.

Fig. 10
figure 10

Relationship between the height of the steel ball having various diameters and temperature, open circle steel ball size = 0.5 mm, open diamond 0.8 mm, open rectangular 1.0 mm, open triangle 1.2 mm, open inverse triangle 1.5 mm Sample; 1 % κ-carrageenan hydrogel

Full size image

Figure 11 shows the relationship between gel–sol transition temperature of 1 % κ-carrageenan hydrogel and size of the steel ball. T g−s of 1 % κ-carrageenan hydrogel maintains a constant value, regardless of the size of the steel ball. From the above results, FBM measurements were carried out using a 0.8-mm steel ball.

Fig. 11
figure 11

Relationship between gel–sol transition temperature (T g−s) of 1 % κ-carrageenan hydrogel and size of steel ball

Full size image

Rights and permissions

Reprints and permissions

About this article

Cite this article

Iijima, M., Takahashi, M., Hatakeyama, T. et al. Detailed investigation of gel–sol transition temperature of κ-carrageenan studied by DSC, TMA and FBM. J Therm Anal Calorim 114, 895–901 (2013). https://doi.org/10.1007/s10973-013-2953-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10973-013-2953-2

Keywords

Search

Navigation