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Structure and Dynamics of Wheat Starch in Breads Fortified with Polyphenols and Pectin: an ESEM and Solid-State CP/MAS 13C NMR Spectroscopic Study

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Abstract

Two sets of breads formulated with a 20% difference in water quantity in the absence (control bread), or presence (fortified bread) of high methoxyl pectin (HM) and an apple, kiwifruit, or blackcurrant polyphenol (PP) extract (APE, KPE or BPE) were examined by Environmental Scanning Electron Microscopy (ESEM) and Cross Polarization/Magic Angle Spinning 13C NMR Spectroscopy. ESEM revealed that all the bread doughs had similar microstructures, comprising starch granules and yeast cells embedded in a continuous gluten matrix. However, the microstructure of the finished breads differed. NMR studies revealed differences in amylopectin-related crystalline domains and the amylose-related amorphous domains among the breads. All the breads showed V-type or amorphous starch structures by NMR, and the control bread may also contain some A-type starch. Breads formulated with 20% extra water showed a greater degree of starch gelatinization, a smoother crumb microstructure, and a lower amorphous starch content. It is feasible to incorporate PPs and pectin in breads at reasonably high concentrations.

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References

  • Arts, I. C. W., & Hollman, P. C. H. (2005). Polyphenols and disease risk in epidemiologic studies. American Journal of Clinical Nutrition, 81(1), 317S–325S.

    CAS  Google Scholar 

  • Atichokudomchai, N., Varavinit, S., & Chinachoti, P. (2004). A study of ordered structure in acid-modified tapioca starch by 13C CP/MAS solid-state NMR. Carbohydrate Polymers, 58, 383–389.

    Article  CAS  Google Scholar 

  • Atwell WA (2001) Composition of commercial flour. In: Wheat Flour, pp 27–45. American Association of Cereal Chemists, Minnesota, USA.

  • Baik, M.-Y., Dickinson, L. C., & Chinachoti, P. (2003). Solid-state 13C CP/MAS NMR studies on aging of starch in white bread. Journal of Agricultural and Food Chemistry, 51, 1242–1248.

    Article  CAS  Google Scholar 

  • BeMiller, J. N., & Whistler, R. L. (1996). Carbohydrates. In O. R. Fennema (Ed.), Food chemistry (3rd ed., pp. 157–160). New York, USA: Marcel Dekker, Inc.

    Google Scholar 

  • Ben Aissa, M. F., Monteau, J. Y., Perronnet, A., Roelens, G., & Le Bail, A. (2010). Volume change of bread and bread crumb during cooling, chilling and freezing, and the impact of baking. Journal of Cereal Science, 51, 115–119.

    Article  Google Scholar 

  • Bogracheva, T. Y., Wang, Y. L., & Hedley, C. L. (2001). The effect of water content on the ordered/disordered structures in starches. Biopolymers, 58, 247–259.

    Article  CAS  Google Scholar 

  • Boyer, J., & Liu, R. H. (2004). Apple phytochemicals and their health benefits. Nutrition Journal, 3(5), 1–15.

    Google Scholar 

  • Bravo, L. (1998). Polyphenols: chemistry, dietary sources, metabolism, and nutritional significance. Nutrition Reviews, 56(11), 317–333.

    Article  CAS  Google Scholar 

  • Chanzy, H., Henrissat, B., Vincendon, M., Tanner, S. F., & Belton, P. S. (1987). Carbohydrate Research, 160, 1–11.

    Article  CAS  Google Scholar 

  • Cheetham, N. W. H., & Tao, L. (1998). Variation in crystalline type with amylose content in maize starch granules: an X-ray powder diffraction study. Carbohydrate Polymers, 36, 277–284.

    Article  CAS  Google Scholar 

  • Collins TH (1994) Mixing, moulding and processing of bread doughs in the UK. In: Breeding to Baking, pp77–83, Proceedings of an International Conference at FMBRA (15–16 June). Chorleywood, Chipping Campden, UK.

  • Colquhoun, I. J., De Ruiter, G. A., Schols, H. A., & Voragen, A. G. (1990). Identification by n.m.r. spectroscopy of oligosaccharides obtained by treatment of the hairy regions of apple pectin with rhamnogalacturonase. Carbohydrate Research, 206, 131–144.

    Article  CAS  Google Scholar 

  • Cooke, D., & Gidley, M. J. (1992). Loss of crystalline and molecular order during starch gelatinisation: origin of the enthalpic transition. Carbohydrate Research, 227, 103–112.

    Article  CAS  Google Scholar 

  • Dudley, R. L., Fyfe, C. A., Stephenson, P. J., Deslandes, Y., Hamer, G. K., & Marchessault, R. H. (1983). High-resolution 13C CP/MAS NMR spectra of solid cellulose oligomers and the structure of cellulose II. Journal of the American Chemical Society, 105, 2469–2472.

    Article  CAS  Google Scholar 

  • Farrera-Rebollo, R. R., de la Paz, Salgado-Cruz M., Chanona-Pérez, J., Gutiérrez-López, G. F., Alamilla-Beltrán, L., & Calderón-Domínguez, G. (2011). Evaluation of image analysis tools for characterization of sweet bread crumb structure. Food and Bioprocess Technology. doi:10.1007/s11947-011-0513-y.

  • Garbow, J. R., & Schaefert, J. (1991). Magic-angle 13C NMR study of wheat flours and doughs. Journal of Agricultural and Food Chemistry, 39, 877–880.

    Article  CAS  Google Scholar 

  • Georgé, S., Brat, P., Alter, P., & Amiot, M. J. (2005). Rapid determination of polyphenols and vitamin C in plant derived products. Journal of Agriculture and Food Chemistry, 53, 1370–1373.

    Article  Google Scholar 

  • Gidley, G., & Bociek, S. M. (1985). Molecular organization of starches: a 13C CP MAS NMR study. Journal of American Society, 107, 7040–7044.

    Article  CAS  Google Scholar 

  • Gidley, M. J., & Bociek, S. M. (1988). 13C CP/MAS NMR studies of amylose inclusion complexes, cyclodextrins, and the amorphous phase of starch granules. Relationships between glycosidic linkage conformation and solid-state C-13 chemical shifts. Journal of the American Chemical Society, 110, 3820–3829.

    Article  CAS  Google Scholar 

  • Ha, M. A., Apperley, D. C., & Jarvis, M. C. (1997). Molecular rigidity in dry and hydrated onion cell walls. Plant Physiology, 115, 593–598.

    CAS  Google Scholar 

  • Harris, R. K. (1993). State of the art for solids. Chemistry in Britain, 29, 601–604.

    CAS  Google Scholar 

  • Hediger, S., Emsley, L., & Fischer, M. (1999). Solid-state NMR characterization of hydration effects on polymer mobility in onion cell-wall material. Carbohydrate Research, 322, 102–112.

    Article  CAS  Google Scholar 

  • Horn, F., Yamamoto, H., Hirai, A., & Kitamaru, R. (1987). Structural study of amylose polymorphs by cross-polarization-magic-angle spinning, 13C-N.M.R. spectroscopy. Carbohydrate Research, 160, 29–40.

    Article  Google Scholar 

  • Hoseney RC (1994) Starch. In: Principles of Cereal Science and Technology, pp 29–63, 2nd ed. American Association of Cereal Chemists, Inc., USA.

  • Imberty, A., & Perez, S. (1988). A revisit to the three-dimensional structure of B-type starch. Biopolymers, 27, 1205–1221.

    Article  CAS  Google Scholar 

  • Imberty, A., Chanzy, H., & Perez, S. (1988). The double-helical nature of crytalline part of A-starch. Journal of Molecular Biology, 201, 365–378.

    Article  CAS  Google Scholar 

  • Inagaki, T., & Seib, P. A. (1992). Firming of bread crumb with cross-linked waxy barley starch substituted for wheat starch. Cereal Chemistry, 69(3), 321–325.

    CAS  Google Scholar 

  • Jenkins, D. J. A., Kendall, C. W. C., & Ransom, T. P. P. (1998). Dietary fiber, the evolution of the human diet and coronary heart disease. Nutrition Research, 18, 633–652.

    Article  CAS  Google Scholar 

  • Khondkar, D., Tester, R. F., & Karkalas, J. (2009). Effect of cross-linking on the resistance to enzymatic hydrolysis of waxy maize starch and low-methoxy pectin. Food Hydrocolloids, 23, 387–393.

    Article  CAS  Google Scholar 

  • Kim, H. J., Morita, N., Lee, S. H., & Moon, K. D. (2003). Scanning electron microscopic observations of dough and bread supplemented with Gastrodia elata Blume powder. Food Research International, 36, 387–397.

    Article  Google Scholar 

  • Kim, W., Choi, S. G., Kerr, W. L., Johnson, J. W., & Gaines, C. S. (2004). Effect of heating temperature on particle size distribution in hard and soft wheat flour. Journal of Cereal Science, 40, 9–16.

    Article  CAS  Google Scholar 

  • Kuakpetoon, D., & Wang, Y. J. (2007). Internal structure and physicochemical properties of corn ctarches as revealed by chemical surface gelatinization. Carbohydrate Research, 342, 2253–2263.

    Article  CAS  Google Scholar 

  • Lauren, D. R., Smith, W. A., Adaim, A., Cooney, J. M., Wibisono, R., Jensen, D. J., et al. (2009). Chemical composition and in vitro anti-inflammatory activity of apple phenolic extracts and of their sub-fractions. International Journal of Food Sciences and Nutrition, 60(S7), 188–205.

    Article  CAS  Google Scholar 

  • Le Bail, P., Rondeau, C., & Buléon, A. (2005). Structural investigation of amylose complexes with small ligands: helical conformation, crystalline structure and thermostability. International Journal of Biological Macromolecules, 35, 1–7.

    Article  Google Scholar 

  • Lujan, A., & Moreira, R. G. (1997). Effects of different drying processes on oil absorption and microstructure of tortillas chips. Cereal Chemistry, 74, 216–223.

    Article  Google Scholar 

  • Lyall, K. A., Hurst, S. M., Cooney, J., Jensen, D., Lo, K., Hurst, R. D., et al. (2009). Short-term blackcurrant extract consumption modulates exercise-induced oxidative stress and lipopolysaccharide-stimulated inflammatory responses. American Journal of Physiology—Regulatory, Integrative and Comparative Physiology, 297(1), R70–R81.

    Article  CAS  Google Scholar 

  • McDonough, C. M., & Rooney, L. W. (1999). Use of the environmental scanning electron microscope in the study of cereal-based foods. Cereal Foods World, 44, 342–348.

    Google Scholar 

  • Morgan, K. R., Furneaux, R. H., & Stanley, R. A. (1992). Observation by solid-state 3C CP MAS NMR spectroscopy of the transformations of wheat starch associated with the making and staling of bread. Carbohydrate Research, 235, 15–22.

    Article  CAS  Google Scholar 

  • Ozge Ozkoc, S., Sumnu, G., & Sahin, S. (2009). The effects of gums on macro and micro-structure of breads baked in different ovens. Food Hydrocolloids, 23, 2182–2189.

    Article  CAS  Google Scholar 

  • Paris, M., Bizot, H., Emery, J., Buzaré, J. Y., & Buléon, A. (1999). Crystallinity and structuring role of water in native and recrystallized starches by 13C CP-MAS NMR spectroscopy: 1: spectral decomposition. Carbohydrate Polymers, 39, 327–339.

    Article  CAS  Google Scholar 

  • Parkkonen, T., Hakaen, H., & Autio, K. (1994). Effect of baking on the microstructure of ryecell walls and protein. Cereal Chemistry, 71, 58–63.

    CAS  Google Scholar 

  • Polaki, A., Xasapis, P., Fasseas, C., Yanniotis, S., & Mandala, I. (2010). Fiber and hydrocolloid content affect the microstructural and sensory characteristics of fresh and frozen stored bread. Journal of Food Engineering, 97, 1–7.

    Article  Google Scholar 

  • Pomeranz, Y., Shogren, M., Finney, K., & Bechtel, D. (1977). Fibre in breadmaking-effects on functional properties. Cereal Chemistry, 54, 25–41.

    Google Scholar 

  • Primo-Martín, C., van Nieuwenhuijzen, N. H., Hamer, R. J., & van Vliet, T. (2007). Crystallinity changes in wheat starch during the bread-making process: starch crystallinity in the bread crust. Journal of Cereal Science, 45, 219–226.

    Article  Google Scholar 

  • Rice-Evans, C. A., Miller, N. J., & Paganga, G. (1996). Structure–antioxidant activity relationships of flavonoids and phenolic acids. Free Radical Biology & Medicine, 20, 933–956.

    Article  CAS  Google Scholar 

  • Ritota, M., Gianferri, R., Bucci, R., & Brosio, E. (2008). Proton NMR relaxation study of swelling and gelatinisation process in rice starch–water samples. Food Chemistry, 110, 14–22.

    Article  CAS  Google Scholar 

  • Roman-Gutierrez, A. D., Guilbert, S. P., & Cuq, B. (2002). Frozen and unfrozen water contents of wheat flours and their components. Cereal Chemistry, 79, 471–475.

    Article  CAS  Google Scholar 

  • Rosales-Juárez, M., González-Mendoza, B., López-Guel, E. C., Lozano-Bautista, F., Chanona-Pérez, J., Gutiérrez-López, G., et al. (2008). Changes on dough rheological characteristics and bread quality as a result of the addition of germinated and non-germinated soybean flour. Food and Bioprocess Technology, 1, 152–160.

    Article  Google Scholar 

  • Ryden, P., Colquhoun, I. J., & Selvendran, R. R. (1989). Investigation of structural features of the pectic polysaccharides of onion by 13C-N.M.R. spectroscopy. Carbohydrate Research, 185, 233–237.

    Article  CAS  Google Scholar 

  • Salmeenkallio-Marttila, M., Autio, R., & Lahteenmaki, L. (2004). Effects of gluten and transglutaminase on microstructure, sensory characteristics and instrumental texture of oat bread. Agricultural and Food Science, 13, 138–150.

    Article  Google Scholar 

  • Santos, E., Rosell, C. M., & Collar, C. (2008). Retrogradation kinetics of high fibre-wheat flour blends: a calorimetric approach. Cereal Chemistry, 85, 455–463.

    Article  CAS  Google Scholar 

  • Saulnier, L., Brillouet, J.-M., & Joseleau, J.-P. (1988). Structural studies of pectic substances from the pulp of grape berries. Carbohydrate Research, 182, 63–78.

    Article  CAS  Google Scholar 

  • Seymour, G. B., Colquhoun, I. J., DuPont, M. S., Parsley, K. R., & Selvendran, R. R. (1990). Composition and structural features of cell wall polysaccharides from tomato fruits. Phytochemistry, 29, 725–731.

    Article  CAS  Google Scholar 

  • Sivam, A. S., Sun-Waterhouse, D., Perera, C. O., & Waterhouse, G. I. N. (2011). Application of FT-IR and Raman spectroscopy for the study of biopolymers in breads fortified with fibre and polyphenols. Food Research International. doi:10.1016/j.foodres.2011.03.039.

  • Sivam, A. S., Sun-Waterhouse, D., Waterhouse, G. I. N., Quek, S., & Perera, C. O. (2011). Physicochemical properties of bread dough and finished bread with added pectin fiber and phenolic antioxidants. Journal of Food Science, 76, H97–H107.

    Article  CAS  Google Scholar 

  • Snape, C. E., Morrison, W. R., MarotoValer, M. M., Karkalas, J., & Pethrick, R. A. (1998). Solid state 13C NMR investigation of lipid ligands in V-amylose inclusion complexes. Carbohydrate Polymers, 36(2), 225–237.

    Article  CAS  Google Scholar 

  • Stauffer, C. E. (2007). Principles of dough formation. In S. P. Cauvain & L. S. Young (Eds.), Technology of breadmaking (pp. 299–329). New York, USA: Springer.

    Chapter  Google Scholar 

  • Sun, D. (2004). Interactions between plant cell wall materials and natural antioxidants (pp. 139–151). Auckland, New Zealand: The University of Auckland.

    Google Scholar 

  • Sun-Waterhouse, D., Sivam, A. S., Cooney, J., Zhou, J., Perera, C. O., & Waterhouse, G. I. N. (2011). Effects of added fruit polyphenols and pectin on the properties of finished breads revealed by HPLC/LC-MS and size exclusion-HPLC. Food Research International. doi:10.1016/j.foodres.2011.07.022.

  • Tan, I., Flanagan, B. M., Halley, P. J., Whittaker, A. K., & Gidley, M. J. (2007). A method for estimating the nature and relative proportions of amorphous, single, and double-helical components in starch granules by 13C CP/MAS NMR. Biomacromolecules, 8, 885–891.

    Article  CAS  Google Scholar 

  • Tang, H., & Hills, B. P. (2003). Use of 13C MAS NMR to study domain structure and dynamics of polysaccharides in the native starch granules. Biomacromolecules, 4, 1269–1276.

    Article  CAS  Google Scholar 

  • Tang, H.-R., Belton, P. S., Ng, A., & Ryden, P. (1999). 13C MAS NMR studies of the effects of hydration on the cell walls of potatoes and Chinese water chestnuts. Journal of Agricultural and Food Chemistry, 47, 510–517.

    Article  CAS  Google Scholar 

  • Thérien-Aubin, H., & Zhu, X. X. (2009). NMR spectroscopy and imaging studies of pharmaceutical tablets made of starch. Carbohydrate Polymers, 75, 369–379.

    Article  Google Scholar 

  • Veregin, R. P., Fyfe, C. A., Marchessault, R. H., & Taylor, M. G. (1986). Characterization of the crystalline A and B starch polymorphs and investigation of starch crystallization by high-resolution carbon-13 CP/MAS NMR. Macromolecules, 19, 1030–1034.

    Article  CAS  Google Scholar 

  • Waterhouse, G. I. N., Metson, J. B., Idriss, H., & Sun-Waterhouse, D. (2008). Physical and optical properties of inverse opal CeO2. Chemistry of Materials, 20(3), 1183–1190.

    Article  CAS  Google Scholar 

  • Wiggins, C., & Cauvain, S. P. (2007). Proving, baking and cooling. In S. P. Cauvain & L. S. Young (Eds.), Technology of breadmaking, pp 141–170 (2nd ed.). New York, USA: Spinger.

    Google Scholar 

  • Yan, B., & Stark, R. E. (2000). Biosynthesis, molecular structure, and domain architecture of potato suberin: a 13C NMR study using isotopically labeled precursors. Journal of Agricultural and Food Chemistry, 48, 3298–3304.

    Article  CAS  Google Scholar 

  • York, W., Harvey, L., Guillen, R., Albersheim, P., & Darvill, A. (1993). Structural analysis of tamarind seed xyloglucan oligosaccharide using β-galactosidase digestion and spectroscopic methods. Carbohydrate Research, 248, 285–301.

    Article  CAS  Google Scholar 

  • Yoshimizu, H., Mimura, H., & Ando, I. (1991). 13C CP/MAS NMR study of the conformation of stretched or heated low-sulfur keratin protein films. Macromolecules, 24, 862–866.

    Article  CAS  Google Scholar 

  • Yu, S., Ma, Y., Menager, L., & Sun, D.-W. (2011a). Physicochemical properties of starch and flour from different rice cultivars. Food and Bioprocess Technology. doi:10.1007/s11947-010-0330-8.

  • Yu, S., Ma, Y., Zheng, X., Liu, X., & Sun, D.-W. (2011b). Impacts of low and ultra-low temperature freezing on retrogradation properties of rice amylopectin during storage. Food and Bioprocess Technology. doi:10.1007/s11947-011-0526-6.

  • Zabar, S., Lesmes, U., Katz, I., Shimoni, E., & Bianco-Peled, H. (2010). Structural characterization of amylose-long chain fatty acid complexes produced via the acidification method. Food Hydrocolloids, 24, 347–357.

    Article  CAS  Google Scholar 

  • Zhang, X., Do, M. D., Hoobin, P., & Burgar, I. (2006). The phase composition and molecular motions of plasticized wheat gluten-based biodegradable polymer materials studied by solid-state NMR spectroscopy. Polymer, 47, 5888–5896.

    Article  CAS  Google Scholar 

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Sivam, A.S., Waterhouse, G.I.N., Zujovic, Z.D. et al. Structure and Dynamics of Wheat Starch in Breads Fortified with Polyphenols and Pectin: an ESEM and Solid-State CP/MAS 13C NMR Spectroscopic Study. Food Bioprocess Technol 6, 110–123 (2013). https://doi.org/10.1007/s11947-011-0699-z

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