Abstract
Descriptions of the functional significance of carbohydrates based on the familiar equilibrium thermodynamics of very dilute solutions fail for pragmatical time scales and conditions, which are far from equilibrium. This is not too surprising, since limiting partial-molar properties reflect the independent behavior of solute in the limit of infinite dilution where free volume is maximum at a given temperature, while Tg′-Wg′ properties reflect the cooperative behavior of solute-plasticizer blends at the limiting minimum value of free volume to observe relaxation within experimental time scales. Carbohydrate-water systems, with well-characterized structure and MW above and below the entanglement limit, provide a unique framework for the investigation of non-equilibrium behavior. Thermal analysis by DSC reveals the central role of water as a plasticizer for carbohydrates and of the glass transition as a physicochemical parameter that governs their properties, processing, and stability. A classical polymer science approach is used to study structure-property relationships of carbohydrates as water-compatible food polymers, which are treated as homologous systems of polymers, oligomers, and monomers with their plasticizers and solvents. Mechanical relaxation behavior is described by a “transformation map” of the critical variables of moisture content, temperature, and time. The glass curve is a reference contour, which represents the limiting isogram for free volume, local viscosity, relaxation rates, and rotational and translational mobility. Map domains are discussed as aspects of “water dynamics,” to dispel the myth of “bound water,” and “glass dynamics,” to relate to macroscopic structure and collapse phenomena. A particular glass with invariant composition and Tg (prepared by freeze-concentration) is identified as a pivotal and practical reference state. The Tg observed during DSC analysis is often an effective Tg, resulting from instantaneous relative relaxation rates and non-uniform distribution of total sample moisture. Non-equilibrium melting, annealing, and gelation/recrystallization of kinetically metastable, partially crystalline carbohydrate systems exhibit non-Arrhenius kinetics which depend on the magnitude of ΔT above the appropriate Tg, as defined by WLF relaxation transformations. Thermally reversible aqueous gels (crystallized from an under-cooled, rubbery melt) are described by a “fringed micelle” structural model for a three-dimensional polymer network, composed of microcrystalline junction zones crosslinking plasticized amorphous regions of flexible-coiled, entangled chain segments.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
F. Franks, M.H. Asquith, C.C. Hammond, H.B. Skaer, and P. Echlin, Polymeric cryoprotectants in the preservation of biological ultrastructure. I., J. Microsc. 110:223 (1977).
F. Franks, The properties of aqueous solutions at subzero temperatures, in: “Water: A Comprehensive Treatise,” Vol. 7, F. Franks, ed., Plenum Press, New York (1982).
F. Franks, “Biophysics and Biochemistry at Low Temperatures,” Cambridge University Press, Cambridge (1985).
F. Franks, Complex aqueous systems at subzero temperatures, in: “Properties of Water in Foods,” D. Simatos and J.L. Multon, eds., Martinus Nijhoff, Dordrecht (1985).
F. Franks, Metastable water at subzero temperatures. J. Microsc. 141:243 (1986).
F. Franks, Improved freeze-drying: an analysis of the basic scientific principles, Process Biochem. 24 (1):R3 (1989).
L. Finegold, F. Franks, and R.H.M. Hatley, Glass/rubber transitions and heat capacities of binary sugar blends, J. Chem. Soc. Faraday Trans. I 85:2945 (1989).
L. SladeandH. Levine, Thermal analysis of starch and gelatin, in: “Proceedings 13th NATAS Conference,” A.R. McGhie, ed., NATAS, Philadelphia (1984).
L. Slade, Starch properties in processed foods: staling of starch-based products, presented at AACC 69th Ann. Meet., Minneapolis, abs. 112 (1984).
T.J. Maurice, L. Slade, C. Page, and R. Sirett, Polysaccharide-water interactions — thermal behavior of rice starch, in: “Properties of Water in Foods,” D. Simatos and J.L. Multon, eds., Martinus Nijhoff, Dordrecht, (1985).
C.G. Biliaderis, C.M. Page, L. Slade, and R.R. Sirett, Thermal behavior of amylose-lipid complexes, Carbohvdr. Polym. 5:367 (1985).
L. Slade, R. Altomare, R. Oltzik, and D.G. Medcalf, Accelerated staling of starch-based food products, U.S. patent 4,657,770 (1987).
L. Slade and H. Levine, Non-equilibrium melting of native granular starch. Part I. Temperature location of the glass transition associated with gelatinization of A-type cereal starches, Carbohydr. Polym. 8:183 (1988).
L. Slade and H. Levine, Intermediate moisture systems; concentrated and supersaturated solutions; pastes and dispersions; water as plasticizer; the mystique of “bound” water; thermodynamics versus kinetics, presented at Faraday Divion, Royal Society of Chemistry Discussion Conference — Water Activity: A Credible Measure of Technological Performance and Physiological Viability?, Cambridge (1985).
L. Slade and H. Levine, Non-equilibrium behavior of small carbohydrate-water systems, Pure Appl. Chem. 60:1841 (1988).
L. Slade and H. Levine, Polymer-chemical properties of gelatin in foods, in: “Advances in Meat Research, Vol. 4 — Collagen as a Food,” A.M. Pearson, T.R. Dutson, and A. Bailey, eds., AVI, Westport (1987).
B.A. Cole, H.I. Levine, M.T. McGuire, K.J. Nelson, and L. Slade, Soft, frozen dessert formulation, U.S. patent 4,374,154 (1983).
B.A. Cole, H.I. Levine, M.T. McGuire, K.J. Nelson, and L. Slade, Soft, frozen dessert formulation, U.S. patent 4,452,824 (1984).
T.W. Schenz, M.A. Rosolen, H. Levine, and L. Slade, DMA of frozen aqueous solutions, in: “Proceedings 13th NATAS Conference,” A.R. McGhie, ed., NATAS, Philadelphia (1984).
H. Levine and L. Slade, A polymer physico-chemical approach to the study of commercial starch hydrolysis products (SHPs), Carbohydr. Polym. 6:213 (1986).
H. Levine and L. Slade, Collapse phenomena — a unifying concept for interpreting the behavior of low-moisture foods, in: “Food Structure — Its Creation and Evaluation,” J.R. Mitchell and J.M.V. Blanshard, eds., Butterworths, London (1988).
H. Levine and L. Slade, Principles of cryostabilization technology from structure/property relationships of water-soluble food carbohydrates — review, Cryo-Lett. 9:21 (1988).
H. Levine and L. Slade, Thermomechanical properties of small carbohydrate-water glasses and “rubbers”: kinetically-metastable systems at subzero temperatures, J. Chem. Soc. Faraday Trans. I 84:2619 (1988).
H. Levine and L. Slade, A food polymer science approach to the practice of cryostabilization technology, Comments Agric. Food Chem. 1:315 (1989).
H. Levine and L. Slade, Response to the letter by Simatos, Blond, and Le Meste on the relation between glass transition and stability of a frozen product, Cryo-Lett. 10:347 (1989).
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 University Press, Cambridge (1988).
L. Slade, H. Levine, and J.W. Finley, Protein-water interactions: water as a plasticizer of gluten and other protein polymers, in: “Protein Quality and the Effects of Processing,” D. Phillips and J.W. Finley, eds., Marcel Dekker, New York (1989).
H. Levine and L. Slade, Influences of the glassy and rubbery states on the thermal, mechanical, and structural properties of doughs and baked products, in: “Dough Rheology and Baked Product Texture: Theory and Practice,” H. Faridi and J.M. Faubion, eds., Van Nostrand Rein-hold/AVI, New York (1989).
L. Slade and H. Levine, Beyond water activity: recent advances based on an alternative approach to the assessment of food quality and safety, CRC Crit. Revs. Food Sci. Nutr.: in press (1990).
L. Slade and H. Levine, Structural stability of intermediate moisture foods — a new understanding?, in: “Food Structure — Its Creation and Evaluation,” J.R. Mitchell and J.M.V. Blanshard, eds., Butter-worths, London (1988).
H. Levine and L. Slade, Interpreting the behavior of low-moisture foods, in: “Water and Food Quality,” T.M. Hardman, ed., Elsevier, London (1989).
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. Harwalkar, eds., Elsevier Applied Science, London (1990).
L. Slade and H. Levine, Recent advances in starch retrogradation, in: “Industrial Polysaccharides — The Impact of Biotechnology and Advanced Methodologies,” S.S. Stivala, V. Crescenzi, and I.C.M. Dea, eds., Gordon and Breach Science, New York (1987).
L. Slade and H. Levine, Thermal analysis of starch, in: “1988 CRA Scientific Conference,” Corn Refiners Assoc., Washington, D.C. (1988).
L. Slade and H. Levine, A food polymer science approach to selected aspects of starch gelatinization and retrogradation, in: “Frontiers in Carbohydrate Research-1: Food Applications,” R.P. Millane, J.N. Be-Miller, and R. Chandrasekaran, eds., Elsevier Applied Science, London (1989).
G.W. White and S.H. Cakebread, The glassy state in certain sugar-containing food products, J. Food Technol. 1:73 (1966).
C. van den Berg, Vapour sorption equilibria and other water-starch interactions; a physico-chemical approach, Doctoral Thesis, Agricultural Univ., Wageningen (1981).
C. van den Berg, On the significance of water activity in low moisture systems; water vapor sorption equilibrium and hysteresis; the starch/water system as a model, presented at Faraday Divion, Royal Society of Chemistry Discussion Conference — Water Activity: A Credible Measure of Technological Performance and Physiological Viability?, Cambridge (1985).
C. van den Berg, Water activity, in: “Concentration and Drying of Foods,” D. MacCarthy, ed., Elsevier Applied Science, London (1986).
C.G. Biliaderis, C.M. Page, T.J. Maurice, and B.O. Juliano, Thermal characterization of rice starches: a polymeric approach to phase transitions of granular starch, J. Agric. Food Chem. 34:6 (1986).
J.M.V. Blanshard, The significance of the structure and function of the starch granule in baked products, in: “Chemistry and Physics of Baking,” J.M.V. Blanshard, P.J. Frazier, and T. Galliard, eds., Royal Society of Chemistry, London (1986).
J.M.V. Blanshard, Starch granule structure and function: physicochemical approach, in: “Starch: Properties and Potential,” T. Galliard, ed., John Wiley & Sons, New York (1987).
J.M.V. Blanshard, Elements of cereal product structure, in: “Food Structure — Its Creation and Evaluation,” J.M.V. Blanshard and J.R. Mitchell, eds., Butterworths, London (1988).
J.M.V. Blanshard and F. Franks, Ice crystallization and its control in frozen food systems, in: “Food Structure and Behaviour,” J.M.V. Blanshard and P. Lillford, eds., Academic Press, London (1987).
R.D.L. Marsh and J.M.V. Blanshard, The application of polymer crystal growth theory to the kinetics of formation of the B-amylose polymorph in a 50% wheat starch gel, Carbohvdr. Polym. 9:301 (1988).
S.F. Edwards, P.J. Lillford, and J.M.V. Blanshard, Gels and networks in practice and theory, in: “Food Structure and Behaviour,” J.M.V. Blanshard and P. Lillford, eds., Academic Press, London (1987).
S. Ablett, G.E. Attenburrow, and P.J. Lillford, The significance of water in the baking process, in: “Chemistry and Physics of Baking,” J.M.V. Blanshard, P.J. Frazier, and T. Galliard, eds., Royal Society of Chemistry, London (1986).
G.E. Attenburrow, R.M. Goodband, L.J. Taylor, and P.J. Lillford, Structure, mechanics, and texture of a food sponge, J. Cereal Sci. 9:61 (1989).
P.J. Lillford, The polymer/water relationship — its importance for food structure, In: “Food Structure — Its Creation and Evaluation,” J.M.V. Blanshard and J.R. Mitchell, eds., Butterworths, London (1988).
M. Karel, Effects of water activity and water content on mobility of food components, and their effects on phase transitions in food systems, In: “Properties of Water in Foods,” D. Simatos and J.L. Multon, eds., Martinus Nijhoff, Dordrecht (1985).
M. Karel, Control of lipid oxidation in dried foods, in: “Concentration and Drying of Foods,” D. MacCarthy, ed., Elsevier Applied Science, London (1986).
M. Karel and R. Langer, Controlled release of food additives, in: “Flavor Encapsulation,” ACS Symp. Ser. 370, S.J. Risch and G.A. Reineccius, eds., American Chemical Society, Washington, D.C. (1988).
D. Simatos and M. Karel, Characterizing condition of water in foods: physico-chemical aspects, in: “Food Preservation by Moisture Control,” C.C. Seow, ed., Elsevier Applied Science, London (1988).
D. Simatos, G. Blond, and M. Le Meste, Relation between glass transition and stability of a frozen product, Cryo-Lett. 10:77 (1989).
R.C. Hoseney, K. Zeleznak, and C.S. Lai, Wheat gluten: a glassy polymer, Cereal Chem. 63:285 (1986).
D.A. Yost and R.C. Hoseney, Annealing and glass transition of starch, Starke 38:289 (1986).
K.J. Zeleznak and R.C. Hoseney, The glass transition in starch, Cereal Chem. 64:121 (1987).
K.J. Zeleznak and R.C. Hoseney, Characterization of starch from bread aged at different temperatures, Starke 39:231 (1987).
L.C. Doescher, R.C. Hoseney, and G.A. Milliken, Mechanism for cookie dough setting, Cereal Chem. 64:158 (1987).
S.G. Ring, P. Colonna, K.J. l’Anson, M.T. Kalichevsky, M.J. Miles, V.J. Morris, and P.D. Orford, Gelation and crystallization of amylopectin, Carbohydr. Res. 162:277 (1987).
P.D. Orford, R. Parker, S.G. Ring, and A.C. Smith, The effect of water as a diluent on the glass transition behavior of malto-oligosaccharides, amylose and amylopectin, Int. J. Biol. Macromol. 11:91 (1989).
P.L. Russell, Gelatinization of starches of different amylose/amylopectin content — DSC study, J. Cereal Sci. 6:133 (1987).
H.F. Zobel, Starch crystal transformations and their industrial importance, Starke 40:1 (1988).
H.F. Zobel, S.N. Young, and L.A. Rocca, Starch gelatinization: an X-ray diffraction study, Cereal Chem. 65:443 (1988).
T. Soesanto and M.C. Williams, Volumetric interpretation of viscosity for concentrated and dilute sugar solutions, J. Phys. Chem. 85:3338 (1981).
A.G. Atkins, Basic principles of mechanical failure in biological systems, in: “Food Structure and Behaviour,” J.M.V. Blanshard and P. Lillford, eds., Academic Press, London (1987).
S. Quinquenet, C. Grabielle-Madelmont, M. Ollivon, and M. Serpelloni, Influence of water on pure sorbitol polymorphism, J. Chem. Soc. Faraday Trans. I 84:2609 (1988).
Y. Fujio and J.K. Lim, Correlation between the glass-transition point and color change of heat-treated gluten, Cereal Chem. 66:268 (1989).
E.A. Niediek, Effect of processing on the physical state and aroma sorption properties of carbohydrates, Food Technol. 42(11):81 (1988).
S. Bone and R. Pethig, Dielectric studies of the binding of water to lysozyme, J. Mol. Biol. 157:571 (1982).
P.J. Flory, “Principles of Polymer Chemistry,” Cornell University Press, Ithaca (1953).
P.J. Flory, Introductory lecture — gels and gelling processes, Faraday Disc. Chem. Soc. 57:7 (1974).
M.L. Williams, R.F. Landel, and J.D. Ferry, Temperature dependence of relaxation mechanisms in amorphous polymers and other glass-forming liquids, J. Amer. Chem. Soc. 77:3701 (1955).
J.A. Brydson, The glass transition, melting point and structure, in: “Polymer Science,” A.D. Jenkins, ed., North Holland, Amsterdam (1972).
B. Wunderlich, “Macromolecular Physics, Vol. 1 — Crystal Structure, Morphology, Defects,” Academic Press, New York (1973).
B. Wunderlich, “Macromolecular Physics, Vol. 2 — Crystal Nucleation, Growth, Annealing,” Academic Press, New York (1976).
B. Wunderlich, “Macromolecular Physics, Vol. 3 — Crystal Melting,” Academic Press, New York (1980).
B. Wunderlich, The basis of thermal analysis, in: “Thermal Characterization of Polymeric Materials,” E.A. Turi, ed., Academic Press, Orlando (1981).
J.D. Ferry, “Viscoelastic Properties of Polymers,” 3rd edn., John Wiley & Sons, New York (1980).
S.P. Rowland, ed., “Water in Polymers,” ACS Symp. Ser. 127, American Chemical Society, Washington, D.C. (1980).
J.K. Sears and J.R. Darby, “The Technology of Plasticizers,” Wiley-Interscience, New York (1982).
A. Eisenberg, The glassy state and the glass transition, in: “Physical Properties of Polymers,” J.E. Mark, A. Eisenberg, W.W. Graessley, L. Mandelkern, and J.L. Koenig, eds., American Chemical Society, Washington, D.C. (1984).
T.S. Ellis, Moisture-induced plasticization of amorphous polyamides and their blends, J. Appl. Polym. Sci. 36:451 (1988).
W.W. Graessley, Viscoelasticity and flow in polymer melts and concentrated solutions, in: “Physical Properties of Polymers,” J.E. Mark, A. Eisenberg, W.W. Graessley, L. Mandelkern, and J.L. Koenig, eds., American Chemical Society, Washington, D.C. (1984).
F.W. Billmeyer, “Textbook of Polymer Science,” 3rd edn., Wiley-Interscience, New York (1984).
L.H. Sperling, “Introduction to Physical Polymer Science,” Wiley-Interscience, New York (1986).
A.G. Walton, Nucleation in liquids and solutions, in: “Nucleation,” A.C. Zettlemoyer, ed., Marcel Dekker, New York (1969).
J.M.G. Cowie, “Polymers: Chemistry and Physics of Modern Materials,” Intertext, New York (1973).
E.A. Turi, ed., “Thermal Characterization of Polymeric Materials,” Academic Press, Orlando (1981).
R.N. Haward, ed., “The Physics of Glassy Polymers,” Applied Science, London (1973).
W. Kauzmann, Nature of the glassy state and behavior of liquids at low temperatures. Chem. Rev. 43:219 (1948).
S.E.B. Petrie, The problem of thermodynamic equilibrium in glassy polymers, in: “Polymeric Materials: Relationships Between Structure and Mechanical behavior,” E. Baer and S.V. Radcliffe, eds., American Society Metals, Metals Park, Ohio (1975).
D.R. Buchanan and J.P. Walters, Glass-transition temperatures of polyamide textile fibers. Part I: effect of water, Textile Res. J. 47:398 (1977).
A. Sharpies, Crystallinity, in: “Polymer Science,” A.D. Jenkins, ed., North Holland, Amsterdam (1972).
J.F. Fuzek, Glass transition temperature of wet fibers: its measurement and significance, in: “Water in Polymers,” S.P. Rowland, ed., ACS Symp. Ser. 127, American Chemical Society, Washington, D.C. (1980).
P. Moy and F.E. Karasz, The interactions of water with epoxy resins, in: “Water in Polymers,” S.P. Rowland, ed., ACS Symp. Ser. 127, American Chemical Society, Washington, D.C. (1980).
J.N. BeMiller, as reported by M.A. Hill, Carbohvdr. Polym. 10:64 (1989).
C.Y. Ma and V.R. Harwalkar, eds., “Thermal Analysis of Foods,” Elsevier Applied Science, London (1989).
S.S. Kelley, T.G. Rials, and W.G. Glasser, Relaxation behavior of the amorphous components of wood, J. Materials Sci. 22:617 (1987).
C.A.J. Hoeve and M.B.J.A. Hoeve, The glass point of elastin as a function of diluent concentration, Organ. Coat. Plast. Chem. 39:441 (1978).
A.P. MacKenzie, Non-equilibrium freezing behavior of aqueous systems, Phil. Trans. Royal Soc. London B. 278:167 (1977).
W.J. Sichina, Predicting mechanical performance and lifetime of polymeric materials, Amer. Lab. 20(1):42 (1988).
A.P. MacKenzie, Collapse during freeze drying — qualitative and quantitative aspects, in: “Freeze Drying and Advanced Food Technology,” S.A. Goldlith, L. Rey, and W.W. Rothmayr, eds., Academic Press, New York (1975).
E.C. To and J.M. Flink, “Collapse”, a structural transition in freeze dried carbohydrates. I.-III., J. Food Technol. 13:551 (1978).
J.M. Flink, Structure and structure transitions in dried carbohydrate materials, in: “Physical Properties of Foods,” M. Peleg and E.B. Bagley, eds., AVI, Westport (1983).
M. Karel and J.M. Flink, Some recent developments in food dehydration research, In: “Advances in Drying,” A.S. Mujumdar, ed., Vol. 2, Hemisphere, Washington (1983).
M. Scandola, G. Ceccorulli, and M. Pizzoli, Water clusters in elastin, Int. J. Biol. Macromol. 3:147 (1981).
J.E. Jolley, The microstructure of photographic gelatin binders, Photogr. Sci. Eng. 14:169 (1970).
J.R. Mitchell, The rheology of gels, J. Text. Stud. 11:315 (1980).
S.W. Shalaby, Thermoplastic polymers, in: “Thermal Characterization of Polymeric Materials,” E.A. Turi, ed., Academic Press, Orlando (1981).
M. Richter, F. Schierbaum, S. Augustat, and K.D. Knoch, Method of producing starch hydrolysis products for use as food additives, U.S. patent 3,962,465 (1976).
M. Richter, F. Schierbaum, S. Augustat, and K.D. Knoch, Method of producing starch hydrolysis products for use as food additives, U.S. patent 3,986,890 (1976).
E.E. Braudo, E.M. Belavtseva, E.F. Titova, I.G. Plashchina, V.L. Krylov, V.B. Tolstoguzov, F.R. Schierbaum, and M. Richter, Struktur und eigenschaften von maltodextrin-hydrogelen, Starke 31:188 (1979).
E.E. Braudo, I.G. Plashchina, and V.B. Tolstoguzov, Structural characterization of thermoreversible anionic polysaccharide gels by their elastoviscous properties, Carbohvdr. Polym, 4:23 (1984).
P.V. Bulpin, A.N. Cutler, and I.C.M. Dea, Thermally-reversible gels from low DE maltodextrins, in: “Gums and Stabilizers for the Food Industry 2,” G.O. Phillips, D.J. Wedlock, and P.A. Williams, eds., Pergamon Press, Oxford (1984).
F. Reuther, G. Damaschun, C. Gernat, F. Schierbaum, B. Kettlitz, S. Radosta, and A. Nothnagel, Molecular gelation mechanism of maltodextrins investigated by wide-angle X-ray scattering, Coll. Polym. Sci. 262:643 (1984).
J.M. Lenchin, P.C. Trubiano, and S. Hoffman, Converted starches for use as a fat-or oil-replacement in foodstuffs, U.S. patent 4,510,166 (1985).
M.J. Miles, V.J. Morris, and S.G. Ring, Gelation of amylose, Carbohydr. Res. 135:257 (1985).
H.S. Ellis and S.G. Ring, A study of some factors influencing amylose gelation, Carbohydr. Polvm. 5:201 (1985).
M.L. German, A.L. Blumenfeld, V.P. Yuryev, and V.B. Tolstoguzov, An NMR study of structure formation in maltodextrin systems, Carbohydr. Polym. 11:139 (1989).
E. Mayer, Hyperquenching of water and dilute aqueous solutions into their glassy states: an approach to cryofixation. Cryo-Lett. 9:66 (1988).
T.S. Ellis, X. Jin, and F.E. Karasz, The water-induced plasticization behavior of semi-crystalline polyamides. Polym. Prepr. 25(2):197 (1984).
X. Jin, T.S. Ellis, and F.E. Karasz, The effect of crystallinity and crosslinking on the depression of the glass transition temperature in nylon 6 by water, J. Polym. Sci.: Polvm. Phys. Edn. 22:1701 (1984).
R.F. Boyer, E. Baer, and A. Hiltner, Concerning gelation effects in atactic polystyrene solutions, Macromolecules 18:427 (1985).
H.E. Bair, Thermal analysis of additives in polymers, in: “Thermal Characterization of Polymeric Materials,” E.A. Turi, ed., Academic Press, Orlando (1981).
F. Franks, Solute-water interactions: do polyhydroxy compounds alter the properties of water?. Cryobiol. 20:335 (1983).
F. Franks, Bound water: fact and fiction. Cryo-Lett. 4:73 (1983).
T.P. Labuza, Water binding of humectants, in: “Properties of Water in Foods,” D. Simatos and J.L. Multon, eds., Martinus Nijhoff, Dordrecht (1985).
S. Wynne-Jones and J.M.V. Blanshard, Hydration studies of wheat starch, amylopectin, amylose gels and bread by proton magnetic resonance, Carbohydr. Polym. 6:289 (1986).
D. French, Organization of starch granules, in: “Starch: Chemistry and Technology,” R.L. whistler, J.N. Bemiller, and E.F. Paschall, eds., 2nd edn., Academic Press, Orlando (1984).
A. Imberty and S. Perez, A revisit to the three-dimensional structure of B-type starch, Biopolymers 27:1205 (1988).
H.W. Starkweather, Water in nylon, in: “Water in Polymers,” S.P. Rowland, ed., ACS Symp. Ser. 127, American Chemical Society, Washington, DC (1980).
S. Gaeta, A. Apicella, and H.B. Hopfenberg, Kinetics and equilibria associated with the absorption and desorption of water and lithium chloride in an ethylene-vinyl alcohol copolymer, J. Membrane Sci. 12:195 (1982).
N.S. Murthy, M. Stamm, J.P. Sibilia, and S. Krimm, Structural changes accompanying hydration in nylon 6, Macromolecules 22:1261 (1989).
T. Kuge and S. Kitamura, Annealing of starch granules warm water treatment and heat-moisture treatment, J. Jap. Soc. Starch Sci. 32:65 (1985).
R.J. Aguerre, C. Suarez, and P.E. Viollaz, Swelling and pore structure in starchy materials, J. Food Engn. 9:71 (1989).
B.O. Juliano, Properties of rice starch in relation to varietal differences in processing characteristics of rice grain, J. Jap. Soc. Starch Sci. 29:305 (1982).
J. Lelievre, Theory of gelatinization in a starch-water-solute system. Polymer 17:854 (1976).
F. Franks, Nucleation: a maligned and misunderstood concept. Cryo-Lett. 8:53 (1987).
J. Kuprianoff, Fundamental aspects of the dehydration of foodstuffs, in: “Conference on Fundamental Aspects of the Dehydration of Foodstuffs,” Society of Chemical Industry, Aberdeen (1958).
J. Biros, R.L. Madan, and J. Pouchly, Heat capacity of water-swollen polymers above and below 0°C, Collect. Czech. Chem. Commun. 44:3566 (1979).
J. Pouchly, J. Biros, and S. Benes, Heat capacities of water-swollen hydrophilic polymers above and below 0°C, Makromol. Chem. 180:745 (1979).
J. Pouchly, S. Benes, Z. Masa, and J. Biros, Sorption of water in hydrophilic polymers, Makromol. Chem. 183:1565 (1982).
J. Pouchly and J. Biros, Comments on the interpretation of thermodynamic data on swollen hydrogels, Polym. Bull. 19:513 (1988).
W. Derbyshire, Dynamics of water in heterogeneous systems with emphasis on subzero temperatures, In: “Water: A Comprehensive Treatise,” F. Franks, ed., Vol. 7, Plenum Press, New York (1982).
C.A.J. Hoeve, The structure of water in polymers, in: “Water in Polymers,” S.P. Rowland, ed., ACS Symp. Ser. 127, American Chemical Society, Washington, DC (1980).
H.G. Burghoff and W. Pusch, Thermodynamic state of water in cellulose acetate membranes, Polym. Engn. Sci. 20:305 (1980).
S. Mashimo, S. Kuwabara, S. Yagihara, and K. Higasi, Dielectric relaxation time and structure of bound water in biological materials, J. Phvs. Chem. 91:6337 (1987).
T.P. Labuza, Fiber’s water binding capacity, Cereal Foods World 34:566 (1989).
C.A. Angell, Perspective on the glass transition, J. Phys. Chem. Solids 49:863 (1988).
G.E. Roberts and E.F.T. White, Relaxation processes in amorphous polymers, in: “The Physics of Glassy Polymers,” R.N. Haward, ed., Applied Science, London (1973).
G.P. Johari, A. Hallbrucker, and E. Mayer, Thermal behavior of several hyperquenched organic glasses, J. Phys. Chem. 93:2648 (1989).
V.N. Morozov and S.G. Gevorkian, Low-temperature glass transition in proteins, Biopolymers 24:1785 (1985).
R.K. Chan, K. Pathmanathan, and G.P. Johari, Dielectric relaxations in the liquid and glassy states of glucose and its water mixtures, J. Phvs. Chem. 90:6358 (1986).
S. Matsuoka, G. Williams, G.E. Johnson, E.W. Anderson, and T. Furukawa, Phenomenological relationship between dielectric relaxation and thermodynamic recovery processes near the glass transition, Macromolecules 18:2652 (1985).
W. Borchard, W. Bremer, and A. Keese, State diagram of the water-gelatin system, Colloid Polym. Sci. 258:516 (1980).
I. Tomka, J. Bohonek, A. Spuhler, and M. Ribeaud, Structure and formation of the gelatin gel, J. Photogr. Sci. 23:97 (1975).
I.V. Yannas, Collagen and gelatin in the solid state, J. Macromol. Sci. — Revs. Macromol. Chem. C7:49 (1972).
J.A. Wesson, H. Takezoe, H. Yu, and S.P. Chen, Dye diffusion in swollen gels by forced Rayleigh scattering, J. Appl. Phys. 53:6513 (1982).
R.E. Robertson, Segmental mobility in the equilibrium liquid below the glass transition, Macromolecules 18:953 (1985).
S.Z.D. Cheng, Thermal characterization of macromolecules, J. Appl. Polym. Sci.: Appl. Polym. Symp. 43:315 (1989).
G.E. Johnson, H.E. Bair, S. Matsuoka, E.W. Anderson, and J.E. Scott, Water sorption and its effects on a polymer’s dielectric behavior, in: “Water in Polymers,” S.P. Rowland, ed., ACS Symp. Ser. 127, American Chemical Society, Washington, DC (1980).
F. Franks, Biophysics and biochemistry of low temperatures and freezing, in: “Effects of Low Temperatures on Biological Membranes,” G.J. Morris and A. Clarke, eds., Academic Press, London (1981).
U. Bengtzelius and A. Sjolander, Glass transitions in hard sphere and Lennard-Jones fluids, Conference on Dynamic Aspects of Structural Change in Liquids and Glasses, New York Acad. Sci., New York (1986).
C.R. Cantor and P.R. Schimmel, “Biophysical Chemistry: Part I The Conformation of Biological Macromolecules.” W.H. Freeman, San Francisco (1980).
K.E. Van Holde, “Physical Biochemistry,” Prentice-Hall, Englewood Cliffs, New Jersey (1971).
K. Hofer, A. Hallbrucker, E. Mayer, and G.P. Johari, Vitrified dilute aqueous solutions. 3. Plasticization of water’s H-bonded network and the glass transition temperature’s minimum, J. Phys. Chem. 93:4674 (1989).
M.J. Pikal and S. Shah, The collapse temperature in freeze drying: dependence on measurement methodology and rate of water removal from the glassy phase, Int. J. Pharm. in press (1990).
C.A. Angell, Supercooled water, Ann. Rev. Phys. Chem. 34:593 (1983).
M.D. Baro, N. Clavaguera, S. Bordas, M.T. Clavaguera-Mora, and J. Casa-Vazquez, Evaluation of crystallization kinetics by DTA, J. Thermal Anal. 11:271 (1977).
A.J. Phillips, R.J. Yarwood, and J.H. Collett, Thermal analysis of freeze-dried products, Anal. Proceed. 23:394 (1986).
A. Hiltner and E. Baer, Reversible gelation of macromolecular systems, Polym. Prepr. 27(1):207 (1986).
R.C. Domszy, R. Alamo, C.O. Edwards, and L. Mandelkern, Thermoreversible gelation and crystallization of homopolymers and copolymers, Macromolecules 19:310 (1986).
L. Mandelkern, Thermoreversible gelation and crystallization from solution, Polvm. Prepr. 27(1): 206 (1986).
W. Burchard, Entanglement and reversible gelation for polymers of different architectures. Progr. Colloid Polym. Sci. 78:63 (1988).
F.D. Blum and B. Nagara, Solvent mobility in gels of atactic polystyrene, Polym. Prepr. 27(1):211 (1986).
M.J. Tait, A. Suggett, F. Franks, S. Ablett, and P.A. Quiekenden, Hydration of monosaccharides: study by dielectric and NMR, J. Solution Chem. 1:131 (1972).
F. Franks, D.S. Reid, and A. Suggett, Conformation and hydration of sugars and related compounds in dilute aqueous solution. J. Solution Chem. 2:99 (1973).
A. Suggett and A.H. Clark, Molecular motion and interactions in aqueous carbohydrate solutions. I. dielectric relaxation studies, J. Solution Chem. 5:1 (1976).
A. Suggett, S. Ablett, and P.J. Lillford, Molecular motion and interactions in aqueous carbohydrate solutions. II. NMR studies, J. Solution Chem. 5:17 (1976).
A. Suggett, Molecular motion and interactions in aqueous carbohydrate solutions. III. a combined NMR and dielectric relaxation strategy. J. Solution Chem. 5:33 (1976).
S.E. Keinath and R.F. Boyer, Thermomechanical analysis of Tg and T > Tg transitions in polystyrene, J. Appl. Polym. Sci. 26:2077 (1981).
A.S. Marshall and S.E.B. Petrie, Thermal transitions in gelatin and aqueous gelatin solutions, J. Photogr. Sci. 28:128 (1980).
W.A. Atwell, L.F. Hood, D.R. Lineback, E. Varriano-Marston, and H.F. Zobel, Terminology and methodology associated with basic starch phenomena, Cereal Foods World 33:306 (1988).
A.H. Bloksma, Rheological aspects of structural changes during baking, in: “Chemistry and Physics of Baking,” J.M.V. Blanshard, P.J. Frazier, and T. Galliard, eds., Royal Society of Chemistry, London (1986).
A.H. Bloksma and W. Bushuk, Rheology and chemistry of dough, in: “Wheat Science and Technology,” 3rd edn., Y. Pomeranz, ed., Vol. II, American Association of Cereal Chemists, St. Paul, Minn. (1988).
R.C. Hoseney, Component interaction during heating and storage of baked products, in: “Chemistry and Physics of Baking,” J.M.V. Blanshard, P.J. Frazier, and T. Galliard, eds., Royal Society of Chemistry, London (1986).
S.G. Ring, Observations on crystallization of amylopectin from aqueous solution, Int. J. Biol. Macromol. 7:253 (1985).
S.G. Ring, Studies on starch gelation, Starke 37:80 (1985).
S.G. Ring and P.D. Orford, Recent observations on retrogradation of amylopectin, in: “Gums and Stabilizers for the Food Industry 3,” G.O. Phillips, D.J. Wedlock, and P.A. Williams, eds., Elsevier Applied Science, London (1986).
P.L. Russell, Aging of gels from starches of different amylose/amylopectin content studied by DSC, J. Cereal Sci. 6:147 (1987).
K.J. l’Anson, M.J. Miles, V.J. Morris, S.G. Ring, and C. Nave, Study of amylose gelation using synchrotron X-Ray source, Carbohydr. Polym. 8:45 (1988).
C. Mestres, P. Colonna, and A. Buleon, Gelation and crystallization of maize starch after pasting, drum-drying, or extrusion cooking, J. Cereal Sci. 7:123 (1988).
M.J. Gidley and P.V. Bulpin, Aggregation of amylose in aqueous systems: the effect of chain length on phase behavior and aggregation kinetics, Macromolecules 22:341 (1989).
A.H. Clark, M.J. Gidley, R.K. Richardson, and S.B. Ross-Murphy, Rheological studies of aqueous amylose gels: the effect of chain length and concentration on gel modulus, Macromolecules 22:346 (1989).
M.J. Gidley, Molecular mechanisms underlying amylose aggregation and gelation, Macromolecules 22:351 (1989).
M.J. Miles, V.J. Morris, P.D. Orford, and S.G. Ring, Roles of amylose and amylopectin in gelation and retrogradation of starch, Carbohydr. Res. 135:271 (1985).
D.S. Reid and S. Charoenrein, DSC studies of starch-water interaction in gelatinization process, in: “Proceedings 14th NATAS Conference,” NATAS, San Francisco (1985).
A. Chungcharoen and D.B. Lund, Influence of solutes and water on rice starch gelatinization, Cereal Chem. 64:240 (1987).
B.C. Burros, L.A. Young, and P.A. Carroad, Kinetics of corn meal gelatinization at high temperature and low moisture, J. Food Sci. 52:1372 (1987).
D. Paton, DSC of oat starch pastes. Cereal Chem. 64:394 (1987).
J.W. Donovan, Phase transitions of the starch-water system, Biopolymers 18:263 (1979).
C.G. Biliaderis, T.J. Maurice, and J.R. Vose, Starch gelatinization phenomena studied by DSC, J. Food Sci. 45:1669 (1980).
S.Z.D. Cheng and B. Wunderlich, Glass transition and melting behavior of poly(oxy-2,6-dimethyl-l,4-phenylene), Macromolecules 20:1630 (1987).
J.M.V. Blanshard, Physicochemical aspects of starch gelatinization, in: “Polysaccharides in Food,” J.M.V. Blanshard and J.R. Mitchell, eds., Butterworths, London (1979).
D.B. Lund, Influence of time, temperature, moisture, ingredients, and processing conditions on starch gelatinization, CRC Crit. Rev. Food Sci. Nutr. 20:249 (1984).
G.C. Alfonso and T.P. Russell, Kinetics of crystallization in semi-crystalline/amorphous polymer mixtures, Macromolecules 19:1143 (1986).
T. Jankowski and C.K. Rha, Retrogradation of starch in cooked wheat, Starke 38:6 (1986).
K. Kulp and J.G. Ponte, Staling of white pan bread: fundamental causes, CRC Crit. Revs. Food Sci. Nutr. 15:1 (1981).
P.J. Flory and E.S. Weaver, Phase transitions in collagen and gelatin systems, J. Amer. Chem. Soc. 82:4518 (1960).
F. Nakazawa, S. Noguchi, J. Takahashi, and M. Takada, Retrogradation of gelatinized potato starch studied by DSC, Agric. Biol. Chem. 49:953 (1985).
M.J. Gidley, Factors affecting crystalline type of native starches and model materials, Carbohvdr. Res. 161:301 (1987).
M.J. Gidley and P.V. Bulpin, Crystallization of maltaoses as models of the crystalline forms of starch, Carbohvdr. Res. 161:291 (1987).
A. Guilbot and B. Godon, Le pain rassis, Cah. Nut. Diet. 19:171 (1984).
J.D. Ferry, Mechanical properties of substances of high molecular weight, J. Amer. Chem. Soc. 70:2244 (1948).
W.M. Nicol, Sucrose and food technology, in: “Sugar: Science and Technology,” G.G. Birch and K.J. Parker, eds., Applied Science, London (1979).
T.G. Cooper, “The Tools of Biochemistry,” Wiley-Interscience, New York (1977).
K.J. Parker, The role of sucrose syrups in food manufacture, in: “Glucose Syrups and Related Carbohydrates,” G.G. Birch, L.F. Green, and C.B. Coulson, eds., Elsevier, Amsterdam (1970).
H. Weisser, Influence of temperature on sorption equilibria, in: “Properties of Water in Foods,” D. Simatos and J.L. Multon, eds., Martinus Nijhoff, Dordrecht (1985).
F. Franks, Physical chemistry of small carbohydrates equilibrium solution properties. Pure Appl. Chem. 59:1189 (1987).
U. Matsukura, A. Matsunaga, and K. Kainuma, Contribution of amylose to starch retrogradation, J. Jpn. Soc. Starch Sci. 30:106 (1983).
E.J. Welsh, J. Bailey, R. Chandarana, and W.E. Norris, Physical characterization of interchain association in starch systems, Prog. Fd. Nutr. Sci. 6:45 (1982).
P.A.M. Steeneken, Rheological properties of aqueous suspensions of swollen starch granules, Carbohvdr. Polym. 11:23 (1989).
M.J. Gidley, P.V. Bulpin, and S. Kay, Effect of chain length on amylose retrogradation, In: “Gums and Stabilizers for the Food Industry 3,” G.O. Phillips, D.J. Wedlock, and P.A. Williams, eds., Elsevier Applied Science, London (1986).
R.L. Whistler and J.R. Daniel, Molecular structure of starch, in: “Starch: Chemistry and Technology,” 2nd edn., R.L. Whistler, J.N. BeMiller, and E.F. Paschall, eds., Academic Press, Orlando (1984).
A. Buleon, F. Duprat, F.P. Booy, and H. Chanzy, Single crystals of amylose with a low degree of polymerization, Carbohydr. Polym. 4:161 (1984).
S. Hizukuri, Polymodal distribution of chain lengths of amylopectins and its significance. Carbohydr. Res. 147:342 (1986).
H. Krusi and H. Neukom, Untersuchungen uber die retrogradation der starke in konzentrierten weizenstarkegelen, Starke 36:300 (1984).
C.J. Durning and M. Tabor, Mutual diffusion in concentrated polymer solutions under small driving force, Macromolecules 19:2220 (1986).
A.H. Muhr and J.M.V. Blanshard, Effect of polysaccharide stabilizers on the rate of growth of ice, J. Food Technol. 21:683 (1986).
H. Bizot, A. Buleon, N. Mouhoud-Riou, and J.L. Multon, Water vapor sorption hysteresis on potato starch, in: “Properties of Water in Foods,” D. Simatos and J.L. Multon, eds., Martinus Nijhoff, Dordrecht (1985).
F. Franks, Freeze drying: from empiricism to predictability. Cryo-Lett. 11:93 (1990).
P.L. Russell and G. Oliver, The effect of pH and NaCl content on starch gel aging. A study by DSC and rheology, J. Cereal Sci. 10:123 (1989).
M. Karel, Role of water activity, in: “Food Properties and Computer-Aided Engineering of Food Processing Systems,” R.P. Singh and A.G. Medina, eds., Kluwer, Dordrecht (1989).
D.B. Lund, Starch gelatinization, in: “Food Properties and Computer-Aided Engineering of Food Processing Systems,” R.P. Singh and A.G. Medina, eds., Kluwer, Dordrecht (1989).
S. Radosta, F. Schierbaum, F. Reuther, and H. Anger, Polymer-water interaction of maltodextrins. Part I: water vapor sorption and desorption of maltodextrin powders, Starke 41:395 (1989).
J.L. Doublier and L. Choplin, A rheological description of amylose gelation, Carbohydr. Res. 193:215 (1989).
Y. Roos and M. Karel, Plasticizing effect of water on thermal behavior and crystallization of amorphous food models, J. Food Sci., in press (1990).
Y. Roos, Effect of moisture on the thermal behavior of strawberries studied using DSC. J. Food Sci. 52:146 (1987).
K. Paakkonen and Y.H. Roos, Effects of drying conditions on water sorption and phase transitions of freeze-dried horseradish roots, J. Food Sci. 55:206 (1990).
F. Franks and J.R. Grigera, Solution properties of low molecular weight polyhydroxy compounds, In: “Water Science Reviews-5: The Molecules of Life,” F. Franks, ed., Cambridge University Press, Cambridge (1990).
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1991 Springer Science+Business Media New York
About this chapter
Cite this chapter
Slade, L., Levine, H. (1991). A Food Polymer Science Approach to Structure-Property Relationships in Aqueous Food Systems: Non-Equilibrium Behavior of Carbohydrate-Water Systems. In: Levine, H., Slade, L. (eds) Water Relationships in Foods. Advances in Experimental Medicine and Biology, vol 302. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-0664-9_3
Download citation
DOI: https://doi.org/10.1007/978-1-4899-0664-9_3
Publisher Name: Springer, Boston, MA
Print ISBN: 978-1-4899-0666-3
Online ISBN: 978-1-4899-0664-9
eBook Packages: Springer Book Archive