Thermodynamic and kinetic features of vitrification and phase transformations of proteins and other constituents of dry and hydrated soybean, a high protein cereal

  • G. P. Johari
  • G. Sartor


To understand the features of molecular motions in mixtures of structurally complex native proteins in which both intermolecular and intramolecular interactions occur, the nature of the glass transition and structural relaxation of vitrified soybean constituents have been studied by differential scanning calorimetry (DSC), as has the phase transformation in its dry and hydrated states. Experiments done during both cooling and heating and with samples of different thermal histories show a broad endothermic feature beginning at about 160 K which is interrupted by a partial crystallization exotherm at about 230 K. The endothermic features resembled those observed for several simpler hydrated proteins (Sartor, Mayer and Johari, 1994a; Green, Fan and Angell, 1994), a hydrated cross-linked polymer (Hofer, Mayer and Johari, 1990) and a dry interpenetrating network polymer blend (Sartor, Mayer and Johari, 1992b). Their broadness is a result of the closely spaced multiplicity of small but sharp miniendotherms and has its origin in the onset of different configurational substates that become available to the protein’s structure as the temperature is increased. The remarkable similarity of these features amongst a broad class of materials is a reflection of the predominant role of the intermolecular energy barriers in determining the structural relaxation kinetics. On heating the vitrified constituents of the soybean two exotherms appear in the 180–220 K range, which correspond to the crystallization of its constituents, and two corresponding endotherms of their melting, both below 273 K. Ice and freeze-concentrated solution coexist at a thermodynamic equilibrium at T < 273 K, for which a formalism based on equilibrium thermodynamics has been developed, and the DSC scans for cooling simulated. The interpretation in terms of the role of protein dynamics in the crystallization of water and the formalism developed are general and useful for studies of other complex biomaterials.


Differential Scanning Calorimetry Structural Relaxation Soybean Protein Interpenetrate Network Polymer Differential Scanning Calorimetry Scan 
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  1. Angell, C.A. (1995) Formation of glasses from liquids and biopolymers. Science 267: 1924 - 1935.CrossRefGoogle Scholar
  2. Atkins, P.W. (1986) Physical Chemistry, Oxford University Press, 3rd edition, p. 702.Google Scholar
  3. Avrami, M.J. (1939) Kinetics of phase change I. J. Chem. Phys 7: 1103 - 1112.CrossRefGoogle Scholar
  4. Avrami, M.J. (1940) Kinetics of phase change II. J. Chem. Phys 8: 212 - 224.CrossRefGoogle Scholar
  5. Avrami, M.J. (1941) Granulation, phase change and microstructure. Kinetics of phase change III. J. Chem. Phys. 9: 177 - 184.CrossRefGoogle Scholar
  6. Cavaille, J.Y., Perez, J. and Johari. G.P. (1989) Molecular theory for the rheology of glasses and polymers. Phys. Rev. B. 39: 2411 - 2422.CrossRefGoogle Scholar
  7. Christian, J.W. (1975) The Theory of Transformation in Metals and Alloys, Pergambn Press, 2nd edition, pp. 525-548.Google Scholar
  8. Doster, W., Bachleitner, A., Dunau, R. et al(1986) Thermal properties of water in myoglobin crystals and solutions at subzero temperatures. Biophys. J.50: 213 - 219.CrossRefGoogle Scholar
  9. Doster, W., Cusack, S. and Petry. W. (1990) Structure dynamics of proteins, scahng behavior and liquid gas transition. J. Noncryst. Solids 131: 357 - 361.CrossRefGoogle Scholar
  10. Doster, W., Post, F. and Settles, M. (1994) Origin of nonexponential relaxations in proteins. In Disorder Effects on Relaxational Processes, eds Richert, R. and Blumen, A., Springer Verlag, Berlin, pp. 615 - 625.Google Scholar
  11. Frauenfelder, H., Parak, F. and Young, R.D. (1988) Conformational substates in proteins. Annu. Rev. Biophys. Biophys. Chem 17: 451 - 479.CrossRefGoogle Scholar
  12. Fraunfelder, H., Nienhaus, G.U. and Young, R.D. (1994) Relaxation and disorder in proteins. In Disorder Effects on Relaxational Processes, eds Richert, R. and Blumen, A., Springer Verlag, Berlin.Google Scholar
  13. Frick, B. and Richter, D. (1995) The microscopic basis of the glass transition in polymers from neutron scattering studies. Science267: 1939 - 1945.CrossRefGoogle Scholar
  14. Green, J.L., Fan, J. and Angell, C.A. (1994) The protein-glass analogy: some insights from homopeptide comparisons. J. Phys. Chem 98: 13780 - 13790.CrossRefGoogle Scholar
  15. Hage, W., Hallbrucker. A., Mayer, E. and Johari. G.P. (1995) Kinetics of crystallizing D20 water near 150 K by Fourier transform infrared spectroscopy and a comparison with the corresponding calorimetric studies on H?0 water in amorphous materials. J. Chem. Phys103: 545 - 550.CrossRefGoogle Scholar
  16. Hodge, I.M. (1994) Enthalpy relaxation and recovery in amorphous materials. J. Noncryst. Solids 169: 211 - 266.CrossRefGoogle Scholar
  17. Hodge, I.M. and Berens, A. (1982) Effects of annealing and prior history on enthalpy relaxation in glassy polymers. 2. Mathematical modelling. Macromolecules 15: 762 - 770.CrossRefGoogle Scholar
  18. Hofer, K., Mayer, E, and Johari, G.P. (1990) Glass-liquid transition of water and ethylene glycol solution in poly(2-hydroxyethyl methacrylate) hydrogel. J. Phys. Chem 94: 2689 - 2696.CrossRefGoogle Scholar
  19. Johari, G.P. (1973) Intrinsic mobility of molecular glasses. J. Chem. Phys 58: 1766 - 1770.CrossRefGoogle Scholar
  20. Johari, G.P. (1976) Glass transition and secondary relaxations in molecular liquids and crystals. Ann. N.Y. Acad. Sci 279: 117 - 140.CrossRefGoogle Scholar
  21. Johari, G.P. (1982a) Glass transition and molecular mobility in glasses. In Plastic Deformation of Amorphous and Semicry tailint Materials, eds Escaig, B. and G’sell, C., Les Editions de Physique, Paris, 1982, pp. 109–141.Google Scholar
  22. Johari. G.P. (1982b) Effect of annealing on ec ndary relaxations in glasses. J. Chem. Phys77: 4619 - 4626.CrossRefGoogle Scholar
  23. Johari. G.P. (1993) A defect theory of glass transition and residual entropy of hyperquenched glassy water. J. Chem. Phys 98: 7324 - 7329.CrossRefGoogle Scholar
  24. Johari, G.P. and Goldstein, M.J. (1970) Viscous liquids and the glass transition. II. Secondary relaxations in glasses of rigid molecules. J. Chem. Phys 53: 2372 - 2388.CrossRefGoogle Scholar
  25. Johari. G.P., Pascheto, W. and Jones, S.J. (1994) lotergranular liquid in solids and premelting of ice. J. Chem. Phys 100:4548-4553.Google Scholar
  26. Mai, C. and Johari, G.P. (1987) Dielectric relaxation and aging effect in interpenetrating network polymers of poly(urethane)-polv(methyl methacrylate). J. Polym. Sci. B. Polym. Phys 25: 1903 - 1911.CrossRefGoogle Scholar
  27. Mivazaki, Y., Matsuo, T. and Suga, H. (1993) Glass transition of myoglobin crystal. Chem. Google Scholar
  28. Phys. Lett. 213:303-308.Google Scholar
  29. Moynihan, CT., Macedo, P.B., Montrose, C.J. et al(1976) Structural relaxation in vitreous materials. Ann. N.Y. Acad. ScL 279: 15 - 36.CrossRefGoogle Scholar
  30. Orädd, G. Lindblom G., Fontell K. And Ljusberg-Waren, H. (1995) Phase diagram of soybean phosphatidylcholine-diacylglycerol-water studied by X-ray diffraction and 31P- and pulse field gradient 1H-NMR: Evidence for reversed micelles in the cubic phase. Biophys. J 68: 1856.CrossRefGoogle Scholar
  31. Pascheto, W., Parthun, M.G.. Hallbrucker. A. and Johari, G.P. (1994) Calorimetric studies of structural relaxation in AgI-AgP03 glasses. J. Non Cryst. Solids 171: 182 - 190.CrossRefGoogle Scholar
  32. Ram, S. and Johari, G.P. (1990) Glass-liquid transition in hyperquenched metal alloys. Philos. Mag 61: 299 - 310.CrossRefGoogle Scholar
  33. Riidisser, S. and Mayer, E. (1996) probing DNA’s dynamics and conformational substates by enthalpy relaxation and its recovery. J. Phys. Chem 100:458-461.Google Scholar
  34. Rüdisser, S., Mayer, E. and Johari G.P. (1997) Enthalpy, entropy and structural relaxation behavior of a A- and B-DNAIn their vitrified states, and the effect of water on the dynamics of B-DNA. J. Phys. Chem. 101: 266 - 277.Google Scholar
  35. Salvetti. G., Tombari, E and Johari, G.P. (1995) Calorimetric effects of intergranular water in ice. J. Chem Phys 102: 4987 - 4990.CrossRefGoogle Scholar
  36. Sartor, G. and Johari, G.P. (1996) Structural relaxation of a vitrified high protein food, beef, and the phase transformations of its water content. J. Phys. Chem 100: 10450 - 10463.CrossRefGoogle Scholar
  37. Sartor, G. and Mayer E. (1995) Calorimetric study of crystal growth of ice in hydrated methemoglobin and redistribution of the water clusters formed on melting the ice. Biophys. J 67: 1724 - 1732.CrossRefGoogle Scholar
  38. Sartor, G., Hallbrucker, A., Hofer, K. and Mayer, E. (1992) Calorimetric glass-liquid transition and crystallization behavior of a vitreous, but freezable, water fraction in hydrated methemoglobin. J. Phys. Chem96: 5133 - 5138.CrossRefGoogle Scholar
  39. Sartor, G., Hallbrucker, A, Hofer, K. and Mayer, E. (1993) Glass-liquid transition and crystallization of a vitreous, but freezable, water fraction in hydrated methemoglobin. Ital. Phys. Soc., Conf. Proc. 43: 143 - 146.Google Scholar
  40. Sartor, G., Mayer, E. and Johari, G.P. (1994a) Calorimetric studies of the kinetic unfreezing of molecular motions in hydrated iysozyme, hemoglobin and myoglobin. Biophys. J66: 249 - 258.CrossRefGoogle Scholar
  41. Sartor, G., Mayer, E. and Johari, G.P. (1994b) Thermal history and enthalpy relaxation of an interpenetrating network polymer with an exceptionally broad relaxation time distribution. J. Polym. ScL B. Polym. Phys 32: 683 - 689.CrossRefGoogle Scholar
  42. Sartor, G., Hofer, K. and Johari, G.P. (1996) Structural relaxation and H-bonding in isometric octanols and their LiCl-solutions by calorimetry. J. Phys. Chem 100: 6801 - 6807.CrossRefGoogle Scholar

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© Thomson Science 1998

Authors and Affiliations

  • G. P. Johari
  • G. Sartor

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