Biopolymer co solute systems theory and applications

BIOPOLYMER CO-SOLUTE SYSTEMS – THEORY AND APPLICATIONS JIANG BIN NATIONAL UNIVERSITY OF SINGAPORE 2011 I BIOPOLYMER CO-SOLUTE SYSTEMS – THEORY AND APPLICATIONS JIANG BIN (B. Appl. Sc. (Hons.), NUS) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY DEPARTMENT OF CHEMISTRY NATIONAL UNIVERSITY OF SINGAPORE 2011 II ACKNOWLEDGEMENTS This thesis would not have been possible without the technical and financial support from Food Science and Technology programme of the National University of Singapore as well as Nestlé R&D Center Singapore Pte. Ltd. I owe my deepest gratitude to the following supervisors for their encouragement, guidance, and support throughout the years. I would never be able to complete my studies without any of them. Assistant Professor Huang Dejian for providing generous help and guidance both scientifically and financially. Professor Stefan Kasapis for his supervision and help in the area of biopolymers and journal publications. Mr. Foo Check Woo for his advices in relation to the food industry. I’m also grateful to the following people for their various contributions. Miss Ang Jia Xi, Mr Guo Ren, Miss Tan Si Wei from the National University of Singapore for their help in experiments. Mdm Lee Chooi Lan, Miss Lew Huey Lee, Miss Jiang Xiao Hui, and Mr Abdul Rahman bin Mohd Noor for the patient help in the laboratories. Mr Teh Wai Keen, Dr Allan Lim, and Mr Vinod Krishnan from Nestlé R&D Center Singapore Pte. Ltd. for their technical support in the pilot plant. I must also extend my appreciation to my colleagues, Miss Koh Lee Wah, Miss Preeti Shrinivas, Miss Lilia Bruno, Mr Wong Shen Siung, and Mr Yao Wei for their various help and moral supports. I Last but not least, I would like to thank my parents and grandparents from the bottom of my heart, I would not be able to reach the current stage of my life without them. II TABLE OF CONTENTS ACKNOWLEDGEMENTS I VIII SUMMARY LIST OF TABLES X LIST OF FIGURES XI LIST OF ABBREVIATIONS LIST OF PUBLICATIONS AND PRESENTATIONS XVIII XIX PART I: BEHAVIOR OF HIGHLY HYDRATED GLUTEN NETWORK AT SUBZERO TEMPERATURES Chapter 1: Rheological Investigation and Molecular Architecture of Highly Hydrated Gluten Networks at Subzero Temperatures 1.1 Abstract 1.2 Introduction 1.3 Literature Review 1.4 1.3.1 Gluten 1.3.2 Glass Transition 1.3.3 Modulated Differential Scanning Calorimetry 1.3.4 Rheology 1.3.5 Transmission Electron Microscopy Materials and Methods 1.4.1 Materials and sample preparation 12 14 14 III 1.4.2 Modulated differential scanning calorimetry 14 1.4.3 Small deformation dynamic oscillation 15 1.4.4 Transmission electron microscopy 17 1.5 Results and Discussion 19 1.5.1 MDSC measurements 19 1.5.2 Small deformation dynamic oscillatory measurements 22 1.5.3 TEM observations of hydrated gluten networks at 30 ambient and subzero temperatures 1.6 Conclusions and Suggestions for Future Work 36 37 References PART II: HIGH SOLID HYDROCOLLOID / CO-SOLUTE SYSTEMS Chapter 2: Outline of Conducted Studies 45 Chapter 3: Literature Review 47 3.1 Hydrocolloids 47 3.2 Method of Reduced Variables 54 3.3 Williams, Landel, and Ferry (WLF) Equation and Free 56 Volume Theory 3.4 Kohlrausch, Williams and Watts (KWW) Function and 58 Coupling Theory 3.5 Textural Profile Analysis and Tensile Test 60 3.6 Scanning Electron Microscopy (SEM) 61 3.7 Fourier Transform Infrared (FT-IR) Spectroscopy 62 Chapter 4: Effect of Molecular Weight on the Glass Transition 64 Phenomenon of Gelatin/co-Solute Systems IV 4.1 Abstract 64 4.2 Introduction 65 4.3 Materials and Methods 67 4.4 4.3.1 Materials and sample preparation 67 4.3.2 Experimental protocol 68 Results and Discussion 4.4.1 Experimental observations of the viscoelastic behavior 69 69 of molecular gelatin fractions in the rubber to glass dispersion 4.4.2 The use of shift factor for modeling the relaxation 79 dynamics of the molecular gelatin fractions in the glass transition region 4.4.3 Correlation between the coupling modeling of 84 cooperativity and the molecular weight of gelatin fractions in glass related structural relaxations Chapter 5: Glass Transition Phenomenon of Polysaccharide/co- 91 Solute Systems 5.1 Abstract 91 5.2 Introduction 92 5.3 Materials and Methods 94 5.4 5.3.1 Materials and sample preparation 94 5.3.2 Experimental protocol 96 Results and Discussion 5.4.1 Molecular relaxations in polysaccharide/co-solute 98 98 systems as a function of temperature V 5.4.2 Utilizing the method of reduced variables to model the relaxation behavior of 102 polysaccharide/co-solute systems 5.4.3 Parameterization of the stress relaxation master curves 108 of the systems with the WLF and KWW equations Chapter 6: Diffusional Mobility of Caffeine in High Solid Matrix in 118 the Vicinity of Glass Transition Temperature 6.1 Abstract 118 6.2 Introduction 119 6.3 Materials and Methods 120 6.3.1 Materials and sample preparation 120 6.3.2 Differential scanning calorimetry 121 6.3.3 Small deformation dynamic oscillation 122 6.3.4 Diffusion kinetics using UV spectroscopy 122 6.4 Results and Discussion 6.4.1 Calorimetric glass transition temperature measurement 124 124 of the systems 6.4.2 Following the mechanical relaxation of the systems 125 using the concept of free volume 6.4.3 Diffusion kinetics of caffeine in the high solid matrix Chapter 7: Effect of Biopolymer Incorporation in an Instant Rice 134 141 Noodle System 7.1 Abstract 141 7.2 Introduction 142 7.3 Materials and Methods 143 VI 7.3.1 Materials and sample preparation 143 7.3.2 Rheological measurement on shear 144 7.3.3 Determination of cooking yield and cooking loss 144 7.3.4 Tensile test and textural profile analysis 145 7.3.5 Swelling power and solubility 147 7.3.6 Differential Scanning Calorimetry 148 7.3.7 Fourier transform infrared spectroscopy 148 7.3.8 Scanning electron microscopy 149 7.4 Results and Discussion 149 7.4.1 Breaking strain of rice flour and tapioca starch 149 7.4.2 Determination of cooking yield and cooking loss 151 7.4.3 Tensile test and textural profile analysis 154 7.4.4 Swelling power and solubility 157 7.4.5 Gelatinization temperature and enthalpy 158 7.4.6 Fourier transform infrared spectroscopy 159 7.4.7 Scanning electron microscopy 161 Chapter 8: Conclusions and Suggestions for Future Work 164 References 166 APPENDIX 182 VII SUMMARY The thesis aims to study the physicochemical properties of various biopolymers. It contains two parts, progressing from intermediate to high solid biopolymer systems. The first part of the thesis attempts to reveal the relaxation mechanism and molecular architecture of intermediate solid gluten system at subzero temperatures. In doing so, techniques of modulated differential scanning calorimetry, small-deformation dynamic oscillation on shear, and transmission electron microscopy were employed. The shallow and broad relaxation observed calorimetrically due to the polydispersity of the material was not seen in mechanical response of the material; instead, ice melting was the most important factor controlling the mechanical stability. In the absence of a distinct glass transition region, ice melting was proposed to be a valid indicator of molecular mobility and quality control for frozen hydrated gluten. The supramolecular morphology of the protein is made of cohesive sheets or thin films, and the molecular interactions of the gluten network are severely affected by ice formation as well as recrystallization. The second part of the thesis deals with characterization of high solid systems, and three different types of systems were studied. First type of system consists of gelatin and co-solute (glucose syrup), and the effect of molecular weight difference of gelatin on the vitrification of the system was studied. Vitrification behavior of the systems was characterized using small-deformation dynamic oscillation and transient stress relaxation experiments, and was further modeled according to the scheme of Williams, Landel, and Ferry (WLF) equation in conjunction with the concept of free volume, as well as the coupling model in the form of the Kohlrausch, Williams and Watts (KWW) VIII Garti, N.; Madar, Z.; Aserin, A.; Sternheim, B., 1997. Fenugreek galactomannans as food emulsifiers. Lebensmittel-Wissenschaft und Technologie, http://www.sciencedirect.com.libproxy1.nus.edu.sg/science/journal/00236438, 30, 305 – 311. Gunning, Y. M.; Parker, R.; Ring, S. G., 2000. Diffusion of short chain alcohols from amorphous maltose-water mixtures above and below their glass transition temperature. Carbohydrate Research, 329, 377-385. Günzler, H.; Gremlich, H-U., 2002. Qualitative spectral interpretation, in IR Spectroscopy: An Introduction, Günzler, H.; Gremlich, H-U. Ed., Wiley VCH, Weinheim, p 171-278. Guo, R., 2008. Honors Thesis: Evaluation of structural-function relationships of biopolymers for propylene glycol alginate replacement in instant rice noodles, work performed in the National University of Singapore. Hahn, S. F.; Hillmyer, M. A., 2003. High glass transition temperature polyolefins obtained by the catalytic hydrogenation of polyindene. Macromolecules, 36, 7176. Hawkins, K.; Lawrence, M.; Williams, P. R.; Williams, R. L., 2008. A study of gelatin gelation by Fourier transform mechanical spectroscopy. Journal of Non-Newtonian Fluid Mechanism, 148, 127-133. Heneen, W. K.; Brismar, K., 2003. Structure of cooked spaghetti of durum and bread wheats. Starch, 55, 546-557. Hoefler, A. C., 2004a. Introduction to food hydrocolloids. In Hydrocolloids, Hoefler, A. C. Ed., Eagan Press, St. Paul, p 1-6. 170 Hoefler, A. C., 2004b. Hydrocolloid sources, processing, and characterization. In Hydrocolloids, Hoefler, A. C. Ed., Eagan Press, St. Paul, p 7-26. Hrma, P., 2008. Arrhenius model for high-temperature glass-viscosity with a constant pre-exponential factor. Journal of Non-Crystalline Solids, 354, 1962-1968. Hu, X, Z.; Wei, Y. M.; Wang, C.; Kovacs, M. I. P., 2007. Quantitative assessment of protein fractions of Chinese wheat flours and their contribution to white salted noodle quality. Food Research International, 40, 1-6. Huang, Y.; Paul, D. R., 2004. Physical aging of thin glassy polymer films monitored by gas permeability. Polymer, 45, 8377-8393. Hung, P. V.; Maeda, T.; Miskelly, D.; Tsumori, R.; Morita, N., 2008. Physicochemical characteristics and fine structure of high-amylose wheat starches isolated from Australian wheat cultivars. Carbohydrate Polymers, 71, 656-663. Hutchinson, J. M., 1995. Physical aging of polymers. Progress in Polymer Science, 20, 703-760. Jazouli, S.; Luo, W.; Bremand, F.; Vu-Khanh, T., 2005. Application of time–stress equivalence to nonlinear creep of polycarbonate. Polymer Testing, 24, 463-467. Jiang, B.; Kasapis, S.; Kontogiorgos, V., 2011. Combined use of the free volume and coupling theories in the glass transition of polysaccharide/co-solute systems. Carbohydrate Polymers, 83, 926-933. Juliano, B. O.; Albano, E. L.; Cagampang, G. B., 1965. Variability in protein content, amylose content and alkali digestibility of rice varieties in Asia. Philippine Agriculturalist, 48, 234-241. 171 Karmas, R.; Buera, M. P.; Karel M., 1992. Effect of glass transition on the rates of nonenzymatic browning in food systems. Journal of Agricultural and Food Chemistry, 40, 873-879. Kasapis, S., 2006. Building on the WLF/free volume framework: utilization of the coupling model in the relaxation dynamics of the gelatin/cosolute system. Biomacromolecules, 7, 1671-1678. Kasapis, S., 2008. Recent advances and future challenges in the explanation and exploitation of the network glass transition of high sugar/biopolymer mixtures. Critical Reviews in Food Science and Nutrition, 48, 185-203. Kasapis, S., 2001. The use of Arrhenius and WLF kinetics to rationalize the rubberto-glass transition in high sugar/κ-carrageenan systems. Food Hydrocolloids, 15, 239-245. Kasapis, S.; Al-Marhoobi, I. M., 2005. Bridging the divide between the high- and low-solid analysis in the gelatin/κ-carrageenan mixture. Biomacromolecules, 6, 14-23. Kasapis, S.; Al-Marhoobi, I. M.; Deszczynski, M.; Mitchell, J. R.; Abeysekera, R., 2003. Gelatin vs polysaccharide in mixture with sugar. Biomacromolecules, 4, 1142-1149. Kasapis, S.; Al-Marhoobi, I. M.; Mitchell, J. R., 2003. Testing the validity of comparisons between the rheological and the calorimetric glass transition temperatures. Carbohydrate Research, 338, 787-794. 172 Kasapis, S.; Sablani, S. S.; Rahman, M. S.; Al-Marhoobi, I. M.; Al-Amri, I. S., 2007. Porosity and the effect of structural changes on the mechanical glass transition temperature. Journal of Agricultural and Food Chemistry, 55, 2459-2466. Kasapis, S.; Al-Marhoobi, I. M.; Mitchell, J. R., 2003. Molecular weight effects on the glass transition of gelatin / co-solute mixtures. Biopolymers, 70, 169-185. Kasapis, S.; Desbrières, J.; Al-Marhoobi, I. M.; and Rinaudo, M., 2002. Disentangling α from β mechanical relaxations in the rubber-to-glass transition of high-sugar-chitosan mixtures. Carbohydrate Research, 337, 595-605. Kasapis, S.; Sworn, G., 2000. Separation of the variables of time and temperature in the mechanical properties of high sugar/polysaccharide mixtures. Biopolymers, 53, 40-45. Kasapis, S.; Shrinivas, P., 2010. Combined use of thermomechanics and UV spectroscopy to rationalize the kinetics of bioactive compound (caffeine) mobility in a high solid matrix. Journal of Agricultural and Food Chemistry, 58, 38253832. Kasapis, S.; Mitchell, J.; Abeysekera, R.; MacNaughtan, W., 2004. Rubber-to-glass transitions in high sugar/biopolymer mixtures. Trends in Food Science & Technology, 15, 298-304. Kasapis, S., 2006. Composition and structure-function relationships in gums. In Handbook of Food Science, Technology, and Engineering, Volume 2. Hui, Y. H. Ed., Taylor & Francis, Boca Raton, p 92(1)-92(19). 173 Kennedy, J. F.; Griffiths, A. J.; Philip, K.; Stevenson, D. L.; Kambanis, O.; Gray, C. J., 1989. Characteristics and distributions of ester groups in propylene glycol alginates. Carbohydrate Polymers, 11, 1-22. Kongseree, N.; Juliano, B. O., 1972. Physicochemical properties of rice grain and starch from lines differing in amylose content and gelatinization temperature. Journal of Agricultural and Food Chemistry, 20, 714-718. Ledward, D. A., 2000. Gelatin. In Handbook of Hydrocolloids, Williams, P. A.; Phillips, G. O. Ed., Woodhead Publishing Limited, Cambridge, p 67-86. Levine, H.; Slade, L., 1986. A polymer physicochemical approach to the study of commercial starch hydrolysis products (SHPs). Carbohydrate Polymer, 6, 213244. Li, X.; Yee, A. F., 2003. Design of mechanically robust high-Tg polymers: synthesis and dynamic mechanical relaxation behavior of glassy poly(ester carbonate)s with cyclohexylene rings in the backbone. Macromolecules, 36, 9411-9420. Li, J. Y., 2003. Noodle dough rheology and quality of instant fried noodles. MS thesis. McGill University Montreal, Quebec, Canada. Lievonen, S. M.; Laaksonen, T. J.; Roos, Y. H., 1998. Glass transition and reaction rates: nonenzymatic browning in glassy and liquid systems. Journal of Agricultural and Food Chemistry, 46, 2778-2784. Lii, C. Y.; Shao, Y. Y.; Tseng, K. H., 1995. Gelation mechanism and rheological properties of rice starch. Cereal Chemistry, 72, 393-400. 174 Liu, Y. T.; Bhandari, B.; Zhou, W. B., 2006. Glass transition and enthalpy relaxation of amorphous food saccharides: a review. Journal of Agricultural and Food Chemistry, 54, 5701-5717. Malkin, A. Ya.; Isayev, A. I., 2006. Viscoelasticity. In Rheology – Concepts, Methods & Applications, Malkin, A. Ya.; Isayev, A. I. Ed., ChemTec Publishing, Toronto, p 43-120. Mandala, I. G.; Bayas, E., 2004. Xanthan effect on swelling, solubility and viscosity of wheat starch dispersions. Food Hydrocolloids, 18, 191-201. Mestres, C.; Colonna, P.; Buleon, A., 1988. Characteristics of starch networks within rice flour noodles and mungbean starch vermicelli. Journal of Food Science, 53, 1809-1812. Momany, F. A.; Willett, J. L., 2002. Molecular dynamics calculations on amylose fragments. I. Glass transition temperatures of maltodecaose at 1, 5, 10, and 15.8% hydration. Biopolymers, 63, 99-110. Montserrat, S.; Roman, F.; Colomer, P., 2003. Vitrification and dielectric relaxation during the isothermal curing of an epoxy-amine resin. Polymer, 44, 101-114. Nandan, B.; Kandpal, L. D.; Mathur, G. N., 2003. Glass transition behavior of poly(ether ether ketone)/poly(aryl ether sulphone) blends: dynamic mechanical and dielectric relaxation studies. Polymer, 44, 1267-1279. Ngai, K. L., 2000a. Short-time and long-time relaxation dynamics of glass-forming substances: a coupling model perspective. Journal of Physics: Condensed Matter, 12, 6437-6451. 175 Ngai, K. L., 2000b. Dynamic and thermodynamic properties of glass-forming substances. Journal of Non-Crystalline Solids, 275, 7-51. Ngai, K. L.; Magill, J. H.; Plazek, D. J., 2000. Flow, diffusion and crystallization of supercooled liquids: Revisited. Journal of Chemical Physics, 112, 1887-1892. Ngai, K. L.; Plazek, D. J., 1995. Identification of different modes of molecular motion in polymers that cause thermorheological complexity. Rubber Chemistry and Technology, 68, 376-434. Ngai, K. L.; Yee, A. F., 1991. Some connections between viscoelastic properties of PVC and plasticized PVC and molecular kinetics. Journal of Polymer Science: Part B: Polymer Physics, 29, 1493-1501. Ngai, K. L.; Roland, C. M., 2000. Development of coorperativity in the local segmental dynamics of poly(vinylacetate): synergy of thermal dynamics and intermolecular coupling. Polymer, 43, 567-573. Parker, R.; Ring, S. G., 1995. Diffusion in maltose-water mixtures at temperatures close to the glass transition. Carbohydrate Research, 273, 147-155. Parks, G. S.; Huffman, H. M., 1926. Glass as a fourth state of matter. Science, 64, 363-364. Pennapa, D., 2001. Instant noodle war looms. Market report in Thailand. Feb 27, 2001. Perry, P. A.; Donald, A. M., 2002. The effect of sugars on the gelatinization of starch. Carbohydrate Polymers, 49, 155-165. Phillips, G. O.; Williams, P. A., 2000. Introduction to food hydrocolloids, In Handbook of hydrocolloids, Phillips, G. O.; Williams, P. A. Ed., CRC Press, Boca Raton, p 1-19. 176 Plazek, D. J.; Chay, I. C.; Ngai, K. L.; Roland, C. M., 1995. Viscoelastic properties of polymers. 4. Thermorheological complexity of the softening dispersion in polyisobutylene. Macromolecules, 28, 6432-6436. Plazek, D. J; Ngai, K. L., 1990. Correlation of polymer segmental chain dynamics with temperature-dependent time-scale shifts. Macromolecules, 24, 1222-1224. Raghavendra Rao, S. N.; Juliano, B. O., 1970. Effect of parboiling on some physicochemical properties of rice. Journal of Agricultural and Food Chemistry, 18, 289-294. Rahman, M. S.; Al-Marhubi, I. M.; Al-Mahroqi, A., 2007. Measurements of glass transition temperature by mechanical (DMTA), thermal (DSC and MDSC), water diffusion and density methods: a comparison study. Chemical Physics Letters, 440, 372-377. Rahman, M. S., 2006. State diagram of foods: Its potential use in food processing and product stability. Trends in Food Science & Technology, 17, 129-141. Raina, C. S.; Singh S.; Bawa, A. S.; Saxena, D. C.; 2005. Effect of vital gluten and gum arabic on the textural properties of pasta made from pre-gelatinized broken rice flour. Food Science and Technology International, 11, 433-442. Ramazan, K.; Joseph, I.; Koushik, S., 2002. Characterization of Irradiated Starches by Using FT-Raman and FTIR Spectroscopy. Journal of Agricultural and Food Chemistry, 50, 3912-3918. Reyes, A. C.; Albano, E. L.; Broines, V. P.; Juliano, B. O., 1965. Genetic variation, varietal differences in physicochemical properties of rice starch and its fractions. Journal of Agricultural and Food Chemistry, 13, 438-441. 177 Rieger, J., 2001. The glass transition temperature Tg of polymers – comparison of the values from differential thermal analysis (DTA, DSC) and dynamic mechanical measurements (torsion pendulum). Polymer Testing, 20, 199-204. Ring, S. G.; Colonna, P.; Panson, K. J.; Kalicheagainstky, M. T.; Miles, M. J.; Morris, V. J.; Orford, P. D., 1987. The gelation and crystallization of amylopectin. Carbohydrate Research, 162, 277-293. Robertson, C. G.; Palade, L. I., 2006. Unified application of the coupling model to segmental, Rouse, and terminal dynamics of entangled polymers. Journal of NonCrystalline Solids, 352, 342-348. Robertson, C. G.; Rademacher, C. M., 2004. Coupling model interpretation of thermorheological complexity in polybutadienes with varied microstructure. Macromolecules, 37, 10009-10017. Rojas, J. A.; Rosell, C. M.; Benedito de Barber, C., 1999. Pasting properties of different wheat flour-hydrocolloid systems. Food Hydrocolloids, 13, 27-33. Roland, C. M.; Ngai, K. L., 1991. Segmental relaxation and molecular structure in polybutadienes and polyisoprene. Macromolecules, 24, 5315-5319. Schmidt, S. J., 2004. Water and solids mobility in foods. Advances in Food and Nutrition Research, 48, 1-101. Schmidt, S. J.; 1999. Probing the physical and sensory properties of food systems using NMR spectroscopy. In Advances in Magnetic Resonance in Food Science, Belton, P. S.; Hills, B. P.; Webb, G. A. Ed., Royal Society of Chemistry, Cambridge, p 79-94. 178 Shivakumar, E.; Das, C. K.; Segal, E.; Narkis, M., 2005. Viscoelastic properties of ternary in situ elastomer composites based on fluorocarbon, acrylic elastomers and thermotropic liquid crystalline polymer blends. Polymer, 46, 3363-3371. Shrinivas, P.; Kasapis, S.; Tongdang, T., 2009. Morphology and mechanical properties of bicontinuous gels of agarose and gelatin and the effect of added lipid phase. Langmuir, 25, 8763-8773. Shrinivas, P.; Kasapis, S., 2010. Unexpected phase behavior of amylose in a high solids environment. Biomacromolecules, 11, 421-429. Slade, L.; Franks, F., 2002. Appendix I: Summary report of the discussion symposium on chemistry and application technology of amorphous carbohydrates. In Amorphous Food and Pharmaceutical Systems, H. Levine, Eds., The Royal Society of Chemistry, Cambridge, pp x-xxvi. Slade, L.; Levine, H., 1991. Beyond water activity: recent advances based on alternative approach to the assessment of food quality and safety. Critical Review of Food Science and Nutrition, 30, 115-360. Sporns, P., 2005. Texture / Rheology, In Handbook of food analytical chemistry: pigments, colorants, flavors, texture, and bioactive food components, Wrolstad, R. E.; Acree, T. E.; Decker, E. A.; Penner, M. H.; Reid, D. S.; Schwartz, S. J.; Shoemaker, C. F.; Sporns, P. Ed., John Wiley & Sons, Inc., Hoboken, p 365-437. Sworn, G., 2000. Xanthan gum. In Handbook of Hydrocolloids, Williams, P. A.; Phillips, G. O. Ed., Woodhead Publishing Limited, Cambridge, p 103-115. 179 Tan, S. W., 2009, Honors Thesis: Investigation of propylene glycol alginate – starch interaction in rice noodle system, work performed in the National University of Singapore. Tchesskaya, T. Yu., 2005. Kinetics of semidilute and dense polymer solution: the time dependence of single-chain dynamics. Journal of Molecular Liquids, 120, 143-146. Terefe, N. S.; Hendrickx, M., 2002. Kinetics of the pectin methylesterase catalyzed de-esterification of pectin in frozen food model systems. Biotechnology Progress, 18, 221-228. Terefe, N. S.; Nhan, M. T.; Vallejo, D.; Loey, A. V.; Hendrickx, M., 2004. Modeling the kinetics of the pectin methylesterase catalyzed de-esterification of pectin in frozen systems. Biotechnology Progress, 20, 480-490. Thomas, D. J.; Atwell, W. A., 1999. Starches. American Association of Cereal Chemists, Inc., St. Paul. Tsoga, A.; Kasapis, S.; Richardson, R. K., 1999. The rubber-to-glass transition in high sugar agarose systems. Biopolymers, 49, 267-275. Tsui, N. T.; Paraskos, A. J.; Torun, L.; Swager, T. M.; Thomas, E. L., 2006. Minimization of internal molecular free volume: A mechanism for the simultaneous enhancement of polymer stiffness, strength, and ductility. Macromolecules, 39, 3350-3358. Wang, B.; Gong, W.; Liu, W. H.; Wang, Z. F.; Qi, N.; Li, X. W.; Liu, M. J.; Li, S. J., 2003. Influence of physical aging and side group on the free volume of epoxy resins probed by positron. Polymer, 44, 4047-4052. 180 Ward, I. M.; Hadley, D. W., 1993. Experimental studies of linear viscoelastic behavior as a function of frequency and temperature: time-temperature equivalence. In An Introduction to the Mechanical Properties of Solid Polymers. Ward, I. M.; Sweeney, J. Ed., John Wiley & Sons, Chichester, p 84-108. Weiss, G. H.; Dishon, M.; Long, A. M.; Bendler, J. T.; Jones, A. A.; Inglefield, P. T.; Bandis, A., 1994. Improved computational methods for the calculation of KohlrauschWilliams-Watts (KWW) decay functions. Polymer, 35, 1880-1883. Williams, M. L.; Landel, R. F.; Ferry, J. D., 1955. The temperature dependence of relaxation mechanisms in amorphous polymers and other glass-forming liquids. Journal of American Chemical Society, 77, 3701-3707. Yano, T.; Nagano, T.; Lee, J.; Shibata, S.; Yamane, M., 2002. Ionic conduction and dielectric relaxation in Ag+/Na+ ion-exchanged aluminosilicate glasses: mixed mobile ion effect and KWW relaxation. Solid State Ionics, 150, 281-290. 181 APPENDIX 1. Time sweep of hydrated gluten at 20°C 182 APPENDIX 2. Noodle formulations Rice Tapioca Palm Water Hydrocolloid flour starch oil Salt (mM) (%) (%) (%) (%) (%) Blank 58.8 11.2 2.1 – – 27.9 PGA 58.3 11.1 2.1 0.7 – 27.8 Fenugreek 59.5 11.2 2.1 0.7 – 26.5 Ghatti 59.5 11.2 2.1 0.7 – 26.5 Arabic 58.5 10.9 2.1 2.0 – 26.5 Agar 57.9 11.0 2.1 1.0 – 28.0 Carrageenan 57.9 11.0 2.1 1.0 50 (KCl) 28.0 Gellan 57.9 11.0 2.1 1.0 (CaCl2) 28.0 Xanthan 57.9 11.0 2.1 1.0 10 (CaCl2) 28.0 183 APPENDIX 3. Assignment of IR absorption bands for PGA Wave number (cm-1) Intensity-shape Assignment of bonds 3700-3000 very strong-broad O-H stretching 2970-2930 weak-sharp C-H stretching 1739 weak-sharp C=O stretching 1614 strong-sharp COO-1 stretching (asymmetric) 1420 medium-sharp COO-1 stretching (symmetric) 1328 weak-broad C-O stretching 1252 weak- shoulder C-O stretching 1200-1030 very strong-sharp C-O & C-C stretching 893 weak- shoulder C-C stretching, C-C-H & C-O bending 815 weak- shoulder C-C-H & C-O bending 184 APPENDIX 4. Assignment of IR absorption bands for gelatinized tapioca / rice starches Wave number (cm-1) Intensity-shape Assignment of bonds 3600-3000 very strong-broad O-H stretching 2929 medium-shoulder C-H stretching (asymmetric) 1652 strong-sharp O-H stretching 1420 weak- shoulder C-H bending 1159 weak-sharp C-O stretching (asymmetric) 1100-900 weak- shoulder C-O, C-C, C-O-H stretching 857 weak-sharp C-H deformation 762 weak-sharp C-C stretching 185 [...]... polysaccharide /co- solute systems were found to be stronger compared to those of gelatin /co- solute systems, due to their distinct microstructures Building on the understanding of polysaccharide /co- solute system, the translational mobility of a small molecular compound in high solid glucose syrup system with/without κ-carrageenan at the vicinity of Tg was examined using UV spectroscopy and correlated with... frequency, and temperature are kept constant, and viscoelastic properties are measured as a function of time; strain sweep, in which frequency and temperature are kept constant, and viscoelastic properties are measured as a function of strain; frequency sweep, in which strain and temperature are kept constant, and viscoelastic properties are measured as a function of frequency of oscillation; and temperature... time (τ), and coupling constant (n) Finally, molecular weight of gelatin was related to the coupling constant of the system Second type of system utilizes gelling polysaccharides instead of gelatin, together with glucose syrup The same techniques were used to evaluate the relaxation dynamics of the systems, and the data obtained were modeled with WLF and KWW equations to find out the Tg, f, τ, and n Molecular... provide as much as a thousand fold increase in resolving power compare to light microscope ((Flegler, Heckman, & Klomparens, 1993), and it is widely used in biology, medicine, and material sciences Two basic types of electron microscopes are transmission electron microscope (TEM) and scanning electron microscope (SEM) Transmission electron microscope (TEM) is similar to light microscope, except that electrons... is called gluten, and it accounts for approximately 80% of total wheat protein Wheat gluten proteins are mainly comprised of gliadins and glutenins Gliadins are monomeric protein molecules which contribute to the viscosity of the hydrated gluten network Glutenins, on the other hand, contain different subunits connected by intermolecular disulfide bonds, upon hydration, glutenins contribute to the elasticity... instruments currently, heat flux DSC and power compensation DSC In heat flux DSC, the sample and reference pans are placed in the same furnace and heated by the same source The temperature difference between sample and reference is measured, and converted back to heat flow In power compensation DSC, the sample and reference pans are placed in two isolated furnace and heated by separate sources The temperature... formation behaviour and network structure of non-aqueous ethylcellulose gel In 2007 AAPS National Biotechnology Conference, San Diego, CA, United States, June 24-27 XIX Jiang, B and Kasapis, S (2009) Application of the coupling model to the relaxation dynamics of polysaccharide /co- solute systems In 2009 15th Gums & Stabilisers for the Food Industry Conference, Wrexham, UK, June 22-25 Conference Presentations... 22-25 Conference Presentations Jiang, B and Kasapis, S Effects of matrix vitrification on the diffusional mobility of a bioactive compound Oral presentation at the 10th International Hydrocolloids Conference, Shanghai, China (June 20th – 24th, 2010) Jiang, B and Kasapis, S Application of the coupling model to the relaxation dynamics of polysaccharide /co- solute systems Oral presentation at the 15th Gums... respective Tg, and becomes minimal at Tg In addition, for both systems, translational mobility can be directly related to mechanical Tg of the systems Furthermore, the diffusing compound was found to have a much higher translational mobility compared to the molecules composing the matrices In the last type of system, eight different polysaccharides, both gelling and non-gelling, were incorporated into... transition and second order phase transition, based on the observed discontinuities at transition temperatures (Roos, 1995) First-order phase transition exhibits discontinuity in the primary variables of thermodynamics including volume, enthalpy, and free energy; whereas second-order phase transition records discontinuity in the first derivative of these variables, such as heat capacity and thermal . I BIOPOLYMER CO- SOLUTE SYSTEMS – THEORY AND APPLICATIONS JIANG BIN NATIONAL UNIVERSITY OF SINGAPORE 2011 II BIOPOLYMER CO- SOLUTE SYSTEMS – THEORY AND APPLICATIONS. polysaccharide /co- solute systems were found to be stronger compared to those of gelatin /co- solute systems, due to their distinct microstructures. Building on the understanding of polysaccharide /co- solute. characterization of high solid systems, and three different types of systems were studied. First type of system consists of gelatin and co- solute (glucose syrup), and the effect of molecular weight