Studies of Reaction Kinetics in Relation to the Tg′ of Polymers in Frozen Model Systems

  • Miang Hoong Lim
  • David S. Reid
Part of the Advances in Experimental Medicine and Biology book series (AEMB, volume 302)


The rates of diffusion-controlled processes in a frozen system can be influenced by the presence of glassy states. One characteristic of cryostabilization by this mechanism is a change in the temperature dependence of reaction rates at the Tg′ of the system. The cryostabilization behavior of solutes such as maltodextrin, carboxymethylcellulose (CMC), and sucrose was studied. Three different model reaction systems (enzyme hydrolysis, protein aggregation, and non-enzymatic oxidation) were used. Maltodextrin had a consistent pattern of cryostabilization behavior at temperatures ranging from −3°C to −20°C for all three model systems. Significant retardation effects were evident in the temperature range corresponding to its glassy states. Sucrose did not show a stabilizing effect in the non-proteinaceous model system (the non-enzymatic oxidation reaction). This could partly be due to the absence of the glassy state, since the storage temperatures were above its Tg′. However, in the protein aggregation model system, sucrose was an excellent stabilizer in protecting actomyosin from aggregation. This may be explained by a “solute exclusion” mechanism. CMC did not show any stabilizing effect in the protein aggregation and non-enzymatic oxidation model systems studied, even though it has a Tg′ as high as that of maltodextrin. These results demonstrated that although the presence of a glassy state may well have a retarding effect on the rates of diffusion processes, just knowing the Tg′ of a polymer is not sufficient for prediction of its stabilization effect in a frozen system.


Glassy State State Diagram Freeze Storage Ascorbic Acid Solution Freeze System 
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  1. 1.
    F. Franks, Complex aqueous systems at subzero temperatures, in: “Properties of Water in Foods in Relation to Quality and Stability,” D. Simatos and J.L. Multon, eds., Martinus Nijhoff, Dordrecht (1985).Google Scholar
  2. 2.
    O.R. Fennema, Reaction kinetics in partially frozen aqueous systems, in: “Water Relations of Foods,” R.B. Duckworth, ed., Academic Press, N.Y. (1974).Google Scholar
  3. 3.
    H. Levine and L. Slade, Principles of “cryostabilization” technology from structure/property relationships of carbohydrate/water systems — A review, Cryo-Lett. 9:21 (1988).Google Scholar
  4. 4.
    H. Levine and L. Slade, A polymer physico-chemical approach to the study of commercial starch hydrolysis products (SHPs), Carbohydr. Polym. 6:213 (1986).CrossRefGoogle Scholar
  5. 5.
    H. Levine and L. Slade, Water as a plasticizer: physico-chemical aspects of low-moisture polymeric systems, in: “Water Science Reviews,” Vol. 3, F. Franks, ed., Cambridge Univ. Press, Cambridge (1988).Google Scholar
  6. 6.
    H. Levine and L. Slade, A food polymer science approach to the practice of cryostabilization technology, Comments Agric. Food Chem. 1:315 (1989).Google Scholar
  7. 7.
    M. Karel and I.M. Saguy, Effect of glass transitions in food materials on diffusion properties, presented at AIChE Meeting, Washington, D.C., Nov. (1988).Google Scholar
  8. 8.
    F. Franks, The properties of aqueous solutions at subzero temperatures, in: “Water — A Comprehensive Treatise,” Vol. 7, F. Franks, ed., Plenum Press, N.Y. (1982).Google Scholar
  9. 9.
    R. Zallen, “The Physics of Amorphous Solids,” John Wiley & Sons, N.Y. (1983).CrossRefGoogle Scholar
  10. 10.
    P. Molyneux, The interface between the chemistry of aqueous polymer solutions and their application technology, in: “Chemistry and Technology of Water-Soluble Polymers,” C.A. Finch, ed., Plenum Press, N.Y. (1983).Google Scholar
  11. 11.
    R.T. Bailley, A.M. North, and B. Pethrick, “Molecular Motion in High Polymers,” Clarendon Press, Oxford (1981).Google Scholar
  12. 12.
    J.W. Park, T.C. Lanier, H.E. Swaisgood, D.D. Hamann, and J.T. Keeton, Effect of cryoprotectants in minimizing physicochemical changes of bovine natural actomyosin during frozen storage, J. Food Biochem. 11:143 (1987).CrossRefGoogle Scholar
  13. 13.
    J.J. Matsumoto, Chemical deterioration of muscle proteins during frozen storage, In: “Chemical Deterioration of Proteins,” J.R. Whitaker and M. Fujimaki, eds., ACS, Washington, D.C. (1980).Google Scholar
  14. 14.
    S.R. Tannenbaum, Vitamins and minerals, in: “Principles of Food Science,” O.R. Fennema, ed., Marcel Dekker, N.Y. (1976).Google Scholar
  15. 15.
    M.H. Lim, Studies of reation kinetics in frozen systems in relation to thermal behavior of solutes, Ph.D. dissertation, University of California, Davis (1989).Google Scholar
  16. 16.
    O.A. Bessey, O.H. Lowry, and M.J. Brock, A method for the rapid determination of alkaline phosphatase with five cubic millimeters of serum, J. Biol. Chem. 164:321 (1946).Google Scholar
  17. 17.
    R. Aschaffenburg and J.E.C. Mullen, A rapid and simple phosphatase test for milk, J. Dairy Res. 16:58 (1949).CrossRefGoogle Scholar
  18. 18.
    E.J. Briskey and T. Fukazawa, Myofibrillar proteins of skeletal muscle, in: “Advances in Food Research,” C.O. Chichester, E.M. Mark, and G.F. Stewart, eds., Academic Press, N.Y. (1971).Google Scholar
  19. 19.
    D. Simatos, DSC studies of mobility and solute-water interactions, in: this book.Google Scholar
  20. 20.
    A.P. MacKenzie, Complementary thermal and electrical studies on aqueous macromolecular solutions during freezing and thawing, presented at ACS meeting, Dallas, April (1989).Google Scholar
  21. 21.
    H. Levine and L. Slade, Cryostabilization technology: thermoanalytical evaluation of food ingredients and systems, in: “Thermal Analysis of Foods,” C.Y. Ma and V.R. Harwalker, eds., Elsevier Applied Science, London (1989).Google Scholar
  22. 22.
    O.R. Fennema, W.D. Powrie, and E.H. Marth, “Low. Temperature Preservation of Foods and Living Matter,” Marcel Dekker, N.Y. (1973).Google Scholar
  23. 23.
    F.W. Billmeyer, “Textbook of Polymer Science,” 3rd edn., Wiley-Inter-science, N.Y. (1984).Google Scholar
  24. 24.
    J.D. Ferry, “Viscoelastic Properties of Polymers,” 3rd edn., John Wiley and Sons, N.Y. (1980).Google Scholar
  25. 25.
    J.F. Carpenter and J.H. Crowe, The mechanism of cryoprotection of proteins by solutes, Cryobiology 25:244 (1988).CrossRefGoogle Scholar
  26. 26.
    T. Arakawa and S.N. Timasheff, Stabilization of protein structure by sugars, Biochemistry 21:6536 (1982).CrossRefGoogle Scholar
  27. 27.
    M.H. Lim, M.S.B.A. Alviar, and D.S. Reid, The effect of polymers on the kinetics of ice recrystallization, AIChE Meeting, Denver, microfiche #10549, Aug. (1988).Google Scholar
  28. 28.
    L.U. Thompson and O.R. Fennema, Effect of freezing on oxidation of L-ascorbic acid, J. Agric. Food Chem. 19:121 (1971).CrossRefGoogle Scholar
  29. 29.
    R.H.M. Hatley, F. Franks, and H. Day, Subzero temperature preservation of reactive fluids in the undercooled state. II. The effect on the oxidation of ascorbic acid of freeze concentration and undercooling, Biophvs. Chem. 24:1887 (1986).Google Scholar
  30. 30.
    M. Glicksman, Sodium carboxymethylcellulose, in: “Gum Technology in the Food Industry,” M. Glicksman, ed., Academic Press, N.Y. (1969).Google Scholar
  31. 31.
    S.L. Rosen, “Fundamental Principles of Polymeric Materials,” Wiley-Interscience, N.Y. (1982).Google Scholar
  32. 32.
    J.D. Keller, Sodium carboxymethylcellulose (CMC), in: “Food Hydrocolloids,” M. Glicksman, ed., CRC Press, Boca Raton (1986).Google Scholar
  33. 33.
    T.A. Nickerson, Lactose crystallization in ice cream. IV. Factors responsible for reduced incidence of sandiness, J. Dairy Sci. 45:354 (1962).CrossRefGoogle Scholar
  34. 34.
    A.J. Ganz, Some effects of gums derived from cellulose on the texture of foods, Cereal Sci. Today 18:398 (1973).Google Scholar
  35. 35.
    A.S. Szczesniak and E. Farkas, Objective characterization of the mouth-feel of gum solutions, J. Food Sci. 27:381 (1962).CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 1991

Authors and Affiliations

  • Miang Hoong Lim
    • 1
  • David S. Reid
    • 1
  1. 1.Department of Food Science and TechnologyUniversity of CaliforniaDavisUSA

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