Electron Paramagnetic Resonance as a tool for detection changes in the starch polymer occurring upon phosphorylation and high pressure treatment. A review.
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Abstract
Abstract: Modification by chemical and physical methods is widely used to improve features of the starch polymer important for industrial applications. In this review it was shown, that thermally generated radicals studied by Electron Paramagnetic Resonance (EPR) spectroscopy may serve as sensitive detectors of the changes occurring in the polymer structure and properties upon modification. Results obtained by using two types of radicals, relatively stable and short-lived ones, and two methods of modification, phosphorylation and high pressure treatment, were presented. Significance of the following experimental factors: optimal heating parameters, correctly prepared reference samples, sufficient amount of modifying agent, controlled moisture on the effectiveness of this method was evidenced. The proposed approach enables distinction between two types of phosphorus bonded as terminating or bridging polymer chains. Moreover, EPR data of the short-lived radicals reflect correctly the starch granule architecture and its changes caused by applied treatment.
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References
[1] Perez S., Bertoft E.The molecular structures of starch components and their contribution to the architecture of starch granules: A comprehensive review. Starch/Stärke, 2010; 62: 398-420.
[2] Tomasik P., Schilling C. H. Chemical modification of starch. Advances in Carbohydrate Chemistry and Biochemistry 2004; 59: 176-322.
[3] Ciesielski W., Tomasik P. Starch radicals. Part I. Thermolysis of plain starch. Carbohydrate Polymers 1996; 31: 205-210.
[4] Błaszczak W., Bidzińska E., Dyrek K.et al. Effect of high hydrostatic pressure on the formation of radicals in maize starches with different amylose content. Carbohydrate Polymers 2008; 74: 914-921.
[5] Bidzińska E., Błaszczak W., Dyrek K. et al. Effect of phosphorylation of the maize starch on thermal generation of stable and short-living radicals. Starch/Stärke 2012; 64: 729-739.
[6] Bidzińska E., Dyrek K., Kruczała K. et al. Electron paramagnetic resonance (EPR) study of the short-living radicals generated thermally in phosphorylated maize starch with different amounts of amylose. Nukleonika 2013; 58 (3): 429-433.
[7] Dyrek K., Madej A., Mazur E. et al. Standards for EPR measurements of spin concentration. Colloids and Surfaces 1990; 45: 135-144.
[8] Dyrek K., Rokosz A., Madej A. Spin Dosimetry in Catalysis Research. Appl. Magn. Reson. 1994; 6: 309-332.
[9] Bidzińska E. Thermally Generated Radicals as Indicators of the Starch Modification Studied by EPR Spectroscopy: A Review. Carbohydrate Polymers 2015; 124: 139-149.
[10] Blennow A., Engelsen S. B., Nielsen T. H. et al. Starch phosphorylation: a new front line in starch research. TRENDS in Plant Science 2002; 7: 445-450.
[11] Hemar Y., Hardacre A., Hedderley D. I. et al. Relationship between the pasting behavior and the phosphorus content of different potato starches. Starch/Stärke 2007; 59: 149-155.
[12] Sang Y., Prakash O., Seib P.A. Characterization of phosphorylated cross-linked resistant starch by 31P nuclear magnetic resonance (31P NMR) spectroscopy. Carbohydrate Polymers 2007; 67: 201-212.
[13] Błaszczak W., Valverde S., Fornal J. Effect of high pressure on the structure of potato starch. Carbohydrate Polymers 2005; 59: 377-383.
[14] Błaszczak W., Fornal J., Valverde S. et al. Pressure-induced changes in the structure of corn starches with different amylose content. Carbohydrate Polymers 2005; 61: 132-140.
[15] Lim S., Seib P. A. Preparation and pasting properties of wheat and corn starch phosphates.
Cereal Chem. 1992; 70: 137-144.
[16] Sang Y., Seib P.A. Resistant starches from amylose mutants of corn by simultaneous heat-moisture treatment and phosphorylation. Carbohydrate Polymers 2006; 63: 167-175.
[17] Spałek T., Pietrzyk P., Sojka Z. Application of genetic algorithm joint with Powell method to non-linear least-squares fitting of powder EPR spectra. Journal of Chemical Information and Modeling 2005; 45: 18-29.
[18] Bidzińska E., Michalec M., Pawcenis D. Effect of thermal treatment on potato starch evidenced by EPR, XRD and molecular weight distribution. Magnetic Resonance in Chemistry 2015; 53: 1051-1056.
[19] Dyrek K., Bidzińska E., Łabanowska M. et al. EPR study of radicals generated in starch by microwaves or by conventional heating. Starch/Stärke 2007; 59: 318-325.
[20] Krupska A., Więckowski A. B., Słonimska L. et al. Influence of heating time and pressure treatment of potato starch on the generation of radicals: EPR studies. Carbohydrate Polymers 2012; 89: 54-60.
[21] Łabanowska M., Wesełucha-Birczyńska A., Kurdziel M. et al. Thermal effects on the structure of cereal starches. EPR and Raman spectroscopy studies. Carbohydrate Polymers
2013; 92: 842-848.
[22] Yordanov N. D., Lubenova S. Effect of dielectric constants, sample container dimensions and frequency of magnetic field modulation on the quantitative EPR response. Analytica Chimica Acta 2000; 403: 305 – 313.
[23] Kruczała K., Varghese B., Bokria J. G. et al. Thermal aging of heterophasic propylene-ethylene copolymers: Morphological aspects, based on ESR, FTIR and DSC. Macromolecules 2003; 36: 1899-1908.
[24] Schlick S. (Editor) Advanced ESR methods in polymer research. New Jersey, USA: Wiley, 2006.
[25] Błaszczak W., Bidzińska E., Dyrek K. et al. EPR study of the influence of high hydrostatic pressure on the formation of radicals in phosphorylated potato starch. Carbohydrate Polymers 2010; 82: 1256-1263.
[26] Błaszczak W., Bidzińska E., Dyrek K. et al. Effect of phosphorylation and pretreatment with high hydrostatic pressure on radical processes in maize starches with different amylose contents. Carbohydrate Polymers 2011; 85: 86-96.
[27] Wenda E., Bidzińska E., Dyrek K. et al. Role of reference samples in studying of the modified starches. Recent Advances in Biopolymer Science and Technology, Chapter 8.pp. 103-112. Editors: Fiedorowicz M., Bertoft E., Nova Science Publishers, New York, 2010.
[28] Bertolini A. C., Mestres C., Colonna P. et al. Free radical formation in UV- and gamma-irradiated cassava starch. Carbohydrate Polymers 2001; 44: 269-271.