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Hydration level significantly impacts the freezable - and unfreezable -water contents of native and modified starches

Abstract

The freezable- and unfreezable-water contents of corn and waxy corn starches (native, pregelatinized and retrograded) were analyzed at various hydration levels (25, 35, 45, 55, 65, 75, 85%) using Differential Scanning Calorimetry (DSC). The unfreezable water contents and also the temperature of onset (To), peak (Tp) and endset (Te) of the peaks' in all samples were increased with increasing hydration level. Water absorption index (WAI) and water solubility index (WSI) values of the pregelatinized and retrograded starch samples were significantly higher (p<0.05) than their native counterparts. RVA profiles revealed that modified starches had higher viscosity values than natural starches.

Keywords:
corn-waxy corn starch; DSC; physical modifications; RVA; unfreezable water

1 Introduction

Starch is not only being widely used in the production of many food substances (soups, salad dressings, bakery products, milk puddings, snacks, coatings, meat products) but it is also sought by the pharmaceutical industry, textile, paper industry, alcohol-based fuels and adhesives (Kaur et al., 2012Kaur, B., Ariffin, F., Bhat, R., & Karim, A. A. (2012). Progress in starch modification in the last decade. Food Hydrocolloids, 26(2), 398-404. http://dx.doi.org/10.1016/j.foodhyd.2011.02.016.
http://dx.doi.org/10.1016/j.foodhyd.2011...
; Fu et al., 2014Fu, Z. Q., Wang, L. J., Zou, H., Li, D., & Adhikari, B. (2014). Studies on the starch-water ınteractions between partially gelatinized corn starch and water during gelatinization. Carbohydrate Polymers, 101, 727-732. http://dx.doi.org/10.1016/j.carbpol.2013.09.098. PMid:24299832.
http://dx.doi.org/10.1016/j.carbpol.2013...
). The chemical and physical features of starches affect the texture, viscosity, gel structure, stickiness, binding ability, water holding capacity and homogeneity of the products where they are used. These functional properties of the starch vary with the amylose-amylopectin content.

Amylose-amylopectin content in starches varies depending on the botanic source. In general, amylose and amylopectin content of native starches varies between 20-30% and 70-80%, respectively, while in waxy starches, which are mutant genotypes, the amylose amount is less than 1% (Kamal et al., 2007Kamal, H., Sabry, G. M., Lotfy, S., Abdallah, N. M., Ulanski, P., Rosiak, J., & Hegazy, E. S. A. (2007). Controlling of degradation effects in radiation processing of starch. Journal of Macromolecular Science. Part A, 44(8), 865-875. http://dx.doi.org/10.1080/10601320701407961.
http://dx.doi.org/10.1080/10601320701407...
; Klaochanpong et al., 2015Klaochanpong, N., Puttanlek, C., Rungsardthong, V., Puncha-Arnon, S., & Uttapap, D. (2015). Physicochemical and structural properties of debranched waxy rice, waxy corn and waxy potato starches. Food Hydrocolloids, 45, 218-226. http://dx.doi.org/10.1016/j.foodhyd.2014.11.010.
http://dx.doi.org/10.1016/j.foodhyd.2014...
). Amylose/amylopectin ratio as well as branching density of starch impact its functional properties. High levels of chain branching improve of the solubility of starch while delay gel formation (Kohyama et al., 2004Kohyama, K., Matsuki, J., Yasui, T., & Sasaki, T. (2004). A differential thermal analysis of the gelatinization and retrogradation of wheat starches with different amylopectin chain lengths. Carbohydrate Polymers, 58(1), 71-77. http://dx.doi.org/10.1016/j.carbpol.2004.06.032.
http://dx.doi.org/10.1016/j.carbpol.2004...
; Sasaki, 2005Sasaki, T. (2005). Effect of wheat starch characteristics on the gelatinization, retrogradation, and gelation properties. Japan Agricultural Research Quarterly, 39(4), 253-260. http://dx.doi.org/10.6090/jarq.39.253.
http://dx.doi.org/10.6090/jarq.39.253...
; Sajilata et al., 2006Sajilata, M. G., Singhal, R. S., & Kulkarni, P. R. (2006). Resistant starch - a review. Comprehensive Reviews in Food Science and Food Safety, 5(1), 1-17. http://dx.doi.org/10.1111/j.1541-4337.2006.tb00076.x.
http://dx.doi.org/10.1111/j.1541-4337.20...
; Kaur et al., 2012Kaur, B., Ariffin, F., Bhat, R., & Karim, A. A. (2012). Progress in starch modification in the last decade. Food Hydrocolloids, 26(2), 398-404. http://dx.doi.org/10.1016/j.foodhyd.2011.02.016.
http://dx.doi.org/10.1016/j.foodhyd.2011...
). The granule type of starch also significantly impacts its functional properties such as water solubility, hydration temperature and swelling indexes.

Native starch granules do not dissolve in cold water but they absorb water and swell slowly. Also, native starch is a good texture stabilizator and regulator of food systems. However, due to low tensile strength, thermal strength, thermal decomposition and high retrogradation tendencies, the use of native starch is limited in some industrial food applications (Singh et al., 2007Singh, J., Kaur, L., & McCarthy, O. J. (2007). Factors ınfluencing the physico-chemical, morphological, thermal and rheological properties of some chemically modified starches for food applications: A review. Food Hydrocolloids, 21(1), 1-22. http://dx.doi.org/10.1016/j.foodhyd.2006.02.006.
http://dx.doi.org/10.1016/j.foodhyd.2006...
). Therefore, there is a need to perform certain modifications to increase the functional properties of starch (BeMiller, 1997BeMiller, J. N. (1997). Starch modification: challenges and prospects. Stärke, 49(4), 127-131. http://dx.doi.org/10.1002/star.19970490402.
http://dx.doi.org/10.1002/star.199704904...
). Through these modifications, the structure of starch molecule is changed. The cooking characteristics, paste’s freezing-thawing stability, gel clarity and brightness, gel texture, film formation, adhesion, emulsion stabilization increase, while retrogradation, paste’s gelling tendency and syneresis reduce (BeMiller, 1997BeMiller, J. N. (1997). Starch modification: challenges and prospects. Stärke, 49(4), 127-131. http://dx.doi.org/10.1002/star.19970490402.
http://dx.doi.org/10.1002/star.199704904...
). Starch modifications may be achieved in three different types, namely chemical (derivatization, acid thinning, dextrinization, oxidation, hydrolysis), physical (pregelatinized and granular cold-water swelling starches) and genetic (waxy, starch with high amylose) (BeMiller, 1997BeMiller, J. N. (1997). Starch modification: challenges and prospects. Stärke, 49(4), 127-131. http://dx.doi.org/10.1002/star.19970490402.
http://dx.doi.org/10.1002/star.199704904...
; Kaur & Singh, 2016Kaur, L., & Singh, J. (2016). Starch: Modified starches. In B. Caballero, P. M. Finglas & F. Toldrá (Eds.), Encyclopedia of food and health (p. 152-159). Oxford, United Kingdom: Academic Press. http://dx.doi.org/10.1016/B978-0-12-384947-2.00659-0.
http://dx.doi.org/10.1016/B978-0-12-3849...
). Physical modification techniques do not require chemical agents. Therefore, they are safer for human consumption and preferred more (Kaur et al., 2012Kaur, B., Ariffin, F., Bhat, R., & Karim, A. A. (2012). Progress in starch modification in the last decade. Food Hydrocolloids, 26(2), 398-404. http://dx.doi.org/10.1016/j.foodhyd.2011.02.016.
http://dx.doi.org/10.1016/j.foodhyd.2011...
; Majzoobi et al., 2015Majzoobi, M., Kaveh, Z., Blanchard, C. L., & Farahnaky, A. (2015). Physical properties of pregelatinized and granular cold water swelling maize starches in presence of acetic acid. Food Hydrocolloids, 51, 375-382. http://dx.doi.org/10.1016/j.foodhyd.2015.06.002.
http://dx.doi.org/10.1016/j.foodhyd.2015...
).

Physicochemical properties of the starch can be affected with the interactions between water and starch molecules. Starch-water interactions can be determined by the changes in the physical state of water. The physical state of the water in starch may be described as freezable (free) and unfreezable (bound) water. Water bonded tightly to the starch molecule is defined as unfreezable water, and it does not assume the role of a solvent, unlike free water. This water cannot be frozen even at very low temperatures subzero, and it can significantly affect the stability of starch-based products. Determining the unfreezable water content in starch-rich foods provides important information to establishing appropriate processing and storage conditions (Suzuki & Kitamura, 2008Suzuki, S., & Kitamura, S. (2008). Unfrozen water in amylosic molecules is dependent on the molecular structures—a differential scanning calorimetric study. Food Hydrocolloids, 22(5), 862-867. http://dx.doi.org/10.1016/j.foodhyd.2007.04.011.
http://dx.doi.org/10.1016/j.foodhyd.2007...
; Fu et al., 2014Fu, Z. Q., Wang, L. J., Zou, H., Li, D., & Adhikari, B. (2014). Studies on the starch-water ınteractions between partially gelatinized corn starch and water during gelatinization. Carbohydrate Polymers, 101, 727-732. http://dx.doi.org/10.1016/j.carbpol.2013.09.098. PMid:24299832.
http://dx.doi.org/10.1016/j.carbpol.2013...
). Even though several studies have been performed on starch gelatinization (Fredriksson et al., 1998Fredriksson, H., Silverio, J., Andersson, R., Eliasson, A. C., & Aman, P. (1998). The ınfluence of amylose and amylopectin characteristics on gelatinization and retrogradation properties of different starches. Carbohydrate Polymers, 35(3-4), 119-134. http://dx.doi.org/10.1016/S0144-8617(97)00247-6.
http://dx.doi.org/10.1016/S0144-8617(97)...
; Liu et al., 2006Liu, H. S., Yu, L., Xie, F. W., & Chen, L. (2006). Gelatinization of cornstarch with different amylose/amylopectin content. Carbohydrate Polymers, 65(3), 357-363. http://dx.doi.org/10.1016/j.carbpol.2006.01.026.
http://dx.doi.org/10.1016/j.carbpol.2006...
; Ratnayake & Jackson, 2006Ratnayake, W. S., & Jackson, D. S. (2006). Gelatinization and solubility of corn starch during heating in excess water: new insights. Journal of Agricultural and Food Chemistry, 54(10), 3712-3716. http://dx.doi.org/10.1021/jf0529114. PMid:19127749.
http://dx.doi.org/10.1021/jf0529114...
; Wang et al., 2014Wang, S., Li, C., Yu, J., Copeland, L., & Wang, S. (2014). Phase transition and swelling behaviour of different starch granules over a wide range of water content. Lebensmittel-Wissenschaft + Technologie, 59(2), 597-604. http://dx.doi.org/10.1016/j.lwt.2014.06.028.
http://dx.doi.org/10.1016/j.lwt.2014.06....
; Li et al., 2015Li, Z. F., Liu, W. J., Gu, Z. B., Li, C. M., Hong, Y., & Cheng, L. (2015). The effect of starch concentration on the gelatinization and liquefaction of corn starch. Food Hydrocolloids, 48, 189-196. http://dx.doi.org/10.1016/j.foodhyd.2015.02.030.
http://dx.doi.org/10.1016/j.foodhyd.2015...
) the number of studies on modified starch-water interactions is limited. Thus, the objectives of this study were: (1) to determine the freezable and unfreezable water contents of corn and waxy corn starches both native and physically modified (pregelatinized and retrograded) at different hydration levels by using DSC, (2) to determine water absorption – water solubility indexes and (3) to reveal the RVA properties.

2 Materials and methods

2.1 Materials

Corn and waxy corn starches used as material were obtained from Sunar Mısır Company (Adana, Turkey). Amylose/amylopectin ratios of corn and waxy corn starches were determined by spectrophotometric method (Garg & Jana, 2011Garg, S., & Jana, A. K. (2011). Characterization and evaluation of acylated starch with different acyl groups and degrees of substitution. Carbohydrate Polymers, 83(4), 1623-1630. http://dx.doi.org/10.1016/j.carbpol.2010.10.015.
http://dx.doi.org/10.1016/j.carbpol.2010...
) and found 27.6±0.3/72.4±0.3 and 0.8±0.2/99.2±0.2, respectively. Pregelatinized and retrograded starches were obtained from these starch samples by using the physical modification techniques described in the method section.

2.2 Methods

Preparation of physically modified starches and determination of pasting properties

The 12.28% suspension (w/w) of corn and waxy corn starch samples (3.5 g, dry basis) were prepared in RVA vessels with 25 ml distilled water, and the samples were loaded into RVA (RVA 4500, Perten, Sweden). Following RVA procedure was applied to obtain the RVA viscogram. The suspension was stirred in RVA at 400 rpm for 10 seconds and then held for 10 min at 30°C. At the end of this period, the temperature was risen to 95 °C at 10.83°C/min and held for at this temperature for 5 min. The samples were cooled from 95 °C to 50 °C in 4 min and kept at this temperature for 10 min. Pregelatinized starch samples were obtained at viscosity peak from the RVA viscogram, while retrograde starch samples were obtained after being stored for 120h at 4 °C of the completed RVA samples. After the mentioned periods, the samples were frozen by adding liquid nitrogen, and then freeze drying were carried out (Operon FDU-8612, Korea) was performed. The dried samples were powdered for the analysis by using a 1 mm mesh screened cyclone mill (Retsch ZM 200, Germany). The moisture content of the starch samples was determined by the oven drying method in an oven at 105 °C for 24 h. Starch concentration of the slurry used in pasting analyses was adjusted to 12.28%, and the pasting properties of starch samples (native, pregelatinized and retrograded) were determined by applying the above-mentioned RVA procedure. The RVA parameters were obtained from the RVA viscogram data according to Ragaee & Abdel-Aal (2006)Ragaee, S., & Abdel-Aal, E. S. M. (2006). Pasting properties of starch and protein in selected cereals and quality of their food products. Food Chemistry, 95(1), 9-18. http://dx.doi.org/10.1016/j.foodchem.2004.12.012.
http://dx.doi.org/10.1016/j.foodchem.200...
.

Water absorption and water solubility index

Water absorption index (WAI) in corn, pregelatinized corn, retrograded corn, waxy corn, pregelatinized waxy corn and retrograded waxy corn samples were determined based on the method described by Anderson (1969)Anderson, R. (1969). Gelatinization of corn grits by roll-and extrusion-cooking. Cereal Science Today, 14, 4-12.. For this purpose, 2.5 g sample was weighed into 50 ml tared centrifuge tubes and 30 ml distilled water was added to form suspension. The prepared samples were centrifuged (Hanil Combi 514R, Korea) at 3000 x g for 10 min. After the centrifuging process, the supernatant was carefully transferred into tared drying vessels and dried at 105 °C for 12 h in a drying cabinet. Water Solubility Index (WSI) was calculated in dried samples accordance with Equation 1. The pellet in centrifuge tubes was weighed and WAI was calculated accordance with Equation 2.

WSI = weight after drying g dry weight of original starch g (1)
WAI = pellet weight g dry weight of original starch g (2)

Freezable and unfreezable water contents by using Differential Scanning Calorimetry

DSC studies were conducted on samples at various hydration levels (25, 35, 45, 55, 65, 75, 85%). For this purpose, accurately 10 mg samples were weighed into the hermetic DSC pans (product number 03190029, Perkin Elmer, USA), and distilled water was added with a micro syringe to obtain the desired hydration-level samples. Pans were sealed and weighed (BEL M214Ai, Italy). The sealed pans were kept for 24 h at room temperature to ensure homogenous distribution of water. The freezable and unfreezable water contents of the samples were determined by using DSC (DSC 6000, Perkin Elmer, USA) with an intercooler system. The temperature and heat flow calibration of the DSC were performed by using indium (melting point: 156.6 °C, ΔH=28.47 J/g) and water (melting point: 0 °C, ΔH=333.20 J/g). An empty pan was used as reference. The following temperature program was used to determine freezable and unfreezable water contents of samples: (1) cooling from 20 °C to -80 °C at 5 °C/min; (2) holding at -80 °C for 5 min; (3) heating from -80 °C to 50 °C at 5 °C/min. To determine the freezable and unfreezable water contents of the samples at the end of the DSC analyses, the method used described by Fu et al. (2014)Fu, Z. Q., Wang, L. J., Zou, H., Li, D., & Adhikari, B. (2014). Studies on the starch-water ınteractions between partially gelatinized corn starch and water during gelatinization. Carbohydrate Polymers, 101, 727-732. http://dx.doi.org/10.1016/j.carbpol.2013.09.098. PMid:24299832.
http://dx.doi.org/10.1016/j.carbpol.2013...
. The method contains the ratio of the area corresponding to the melting enthalpy of the ice in the material to the pure water melting enthalpy (333.20 J/g). The exact moisture content of each sample was confirmed after collecting the calorimetric data. The sealed DSC pans were punctured and dried in an oven at 105 °C for 24 h and the reweighed to determine the exact water content in the sample. Unfreezable water content was defined by using Equation 3.

U n f r e e z a b l e w a t e r c o n t e n t = m w m s Δ H s Δ H w (3)

Unfreezable water content: (g water/ g dry starch); mw: water content in samples (g); ms: dry starch in samples (g); ΔHs: the ice melting enthalpies of moisture in starch samples (J/g); ΔHw: the ice melting enthalpy pure water (J/g).

2.3 Statistical analysis

All the tests in the study were carried out in triplicate and the results were reported with mean values and standard deviation values. The acquired data were subjected to analysis of variance by using SPSS 22.0 (IBM Corp., Armonk, NY, USA) package program, and the average values of meaningful main variance sources were compared with Duncan’s multiple comparison test (p<0.05).

3 Results and discussion

3.1 Rapid Visco Analyser

RVA results of corn, waxy corn and their physically modified forms were given in Table 1. The physically modified types of corn and waxy corn had higher initial viscosity values (the viscosity value at the starting point of gelation) when compared to their native forms. The highest initial viscosity value was observed in the retrograded waxy corn, followed by pregelatinized waxy corn. Obtaining higher initial viscosity values in physically modified waxy corn starches is due to the fact that amylopectin in the starch molecule is the main component responsible for swelling of starch and the physical modifications promote this swelling. The waxy corn starch granules exclusively consist of amylopectin, and thus swelled more readily than normal corn starch resulting in higher initial viscosity. It was also found that each form of the corn starch (native, pregelatinized, retrograded) had higher (p<0.05) peak, trough, breakdown, final and setback viscosity values than the waxy corn starches. This situation indicates that amylose plays an important role in providing the effects of physical modification on pasting viscosity. The heat treatment allowed water to diffuse inside granules causing granule swelling and amylose leaching (BeMiller & Huber, 2015BeMiller, J. N., & Huber, K. C. (2015). Physical modification of food starch functionalities. Annual Review of Food Science and Technology, 6(1), 19-69. http://dx.doi.org/10.1146/annurev-food-022814-015552. PMid:25884280.
http://dx.doi.org/10.1146/annurev-food-0...
). The released amylose has a strong tendency to aggregation. Zhang et al. (2018)Zhang, C., Han, J. A., & Lim, S. T. (2018). Characteristics of some physically modified starches using mild heating and freeze-thawing. Food Hydrocolloids, 77, 894-901. http://dx.doi.org/10.1016/j.foodhyd.2017.11.035.
http://dx.doi.org/10.1016/j.foodhyd.2017...
reported that the starch matrix formed by amylose aggregation on the granule surface eventually increased the rigidity of starch granules.

Table 1
The viscosity values of starch samples.

Peak viscosity is an important characteristic to distinguish properties of starches, an indication of water holding capacity (Thakur et al., 2015Thakur, S., Kaur, A., Singh, N., & Virdi, A. S. (2015). Successive reduction dry milling of normal and waxy corn: grain, grit, and flour properties. Journal of Food Science, 80(6), 1144-1155. http://dx.doi.org/10.1111/1750-3841.12895. PMid:25943010.
http://dx.doi.org/10.1111/1750-3841.1289...
). Similar to our results, Sun et al. (2014)Sun, Q., Xu, Y. C., & Xiong, L. (2014). Effect of microwave-assisted dry heating with xanthan on normal and waxy corn starches. International Journal of Biological Macromolecules, 68, 86-91. http://dx.doi.org/10.1016/j.ijbiomac.2014.04.032. PMid:24769087.
http://dx.doi.org/10.1016/j.ijbiomac.201...
reported that normal corn starch had higher peak viscosity value than waxy corn starch. High crystallinity in waxy corn may have been responsible for its lower peak viscosity than normal corn forms as observed earlier (Thakur et al., 2015Thakur, S., Kaur, A., Singh, N., & Virdi, A. S. (2015). Successive reduction dry milling of normal and waxy corn: grain, grit, and flour properties. Journal of Food Science, 80(6), 1144-1155. http://dx.doi.org/10.1111/1750-3841.12895. PMid:25943010.
http://dx.doi.org/10.1111/1750-3841.1289...
). As the starch granules swell, the viscosity of the system increases, and when the amount of swollen granules reaches the highest level, the viscosity reaches the peak (BeMiller, 2019BeMiller, J. N. (2019). Corn Starch Modification. In S. O. Serna-Saldivar (Ed.), Corn: Chemistry and technology (3rd ed. 537 p.). Duxford, United Kingdom: Elsevier Ltd, Woodhead Publishing. https://doi.org/10.1016/B978-0-12-811971-6.00019-X.
https://doi.org/10.1016/B978-0-12-811971...
). As shown in Table 1, modified forms of starch samples have higher peak viscosity values than native forms. This indicates that physical modification significantly increases the swelling ability of the starch granules.

Significant differences were determined in the setback viscosity values of corn and waxy corn starch (p<0.05). Waxy corn starch forms showed much less setback viscosity values than does normal corn starch forms. This finding is attributable to an absence of amylose, because amylose interacts with amylopectin in the swelling (Kurakake et al., 2009Kurakake, M., Akiyama, Y., Hagiwara, H., & Komaki, T. (2009). Effects of cross-linking and low molecular amylose on pasting characteristics of waxy corn starch. Food Chemistry, 116(1), 66-70. http://dx.doi.org/10.1016/j.foodchem.2009.02.006.
http://dx.doi.org/10.1016/j.foodchem.200...
). The increase in viscosity during cooling is called setback. Setback viscosity occurs as a result of rearranged amylose molecules in solution during cooling and it is considered to be the measure of starch gelation ability or retrogradation tendency of the starch (Alamri et al., 2013Alamri, M. S., Mohamed, A. A., & Hussain, S. (2013). Effects of alkaline-soluble okra gum on rheological and thermal properties of systems with wheat or corn starch. Food Hydrocolloids, 30(2), 541-551. http://dx.doi.org/10.1016/j.foodhyd.2012.07.003.
http://dx.doi.org/10.1016/j.foodhyd.2012...
). It is being emphasized that the amylose content in starch is responsible for the higher setback values (Blazek & Copeland, 2009Blazek, J., & Copeland, L. (2009). Effect of monopalmitin on pasting properties of wheat starches with varying amylose content. Carbohydrate Polymers, 78(1), 131-136. http://dx.doi.org/10.1016/j.carbpol.2009.03.023.
http://dx.doi.org/10.1016/j.carbpol.2009...
). This is probably due to cooling and the fact that it is linked to amylose, which leads to the lowering of the energy system.

3.2 Water absorption and water solubility indexes

The water absorption and solubility indexes of the starch samples were given in Table 2. Physically modified starches had higher water absorption and solubility indexes, compared to native starches. Both water absorption and water solubility indexes were determined to be at the highest level in pregelatinized starches. This is an indicator of higher water holding and better levels by swollen granules. Obtaining the highest water solubility index in pregelatinized starch samples may be associated with destruction of the regular structure, while obtaining lower values in retrograded samples may be attributed to retrogradation. The crystal structure re-appears with retrogradation and this lowers the solubility of starch. In addition, when waxy corn and its modifications are compared to corn starch and its modifications, it can be seen that waxy corn varieties have much higher absorption indexes (Table 2). The higher absorption index of waxy corn starch may be attributed to the high amylopectin content. This is due to the fact that much more water is absorbed in the three-dimensional branched structure of amylopectin (Wang et al., 2011Wang, S., Sharp, P., & Copeland, L. (2011). Structural and functional properties of starches from field peas. Food Chemistry, 126(4), 1546-1552. http://dx.doi.org/10.1016/j.foodchem.2010.11.154. PMid:25213925.
http://dx.doi.org/10.1016/j.foodchem.201...
; Wang et al., 2014Wang, S., Li, C., Yu, J., Copeland, L., & Wang, S. (2014). Phase transition and swelling behaviour of different starch granules over a wide range of water content. Lebensmittel-Wissenschaft + Technologie, 59(2), 597-604. http://dx.doi.org/10.1016/j.lwt.2014.06.028.
http://dx.doi.org/10.1016/j.lwt.2014.06....
).

Table 2
The water absorption and water solubility index of starch samples.

3.3 Unfreezable water contents by DSC

A single endotherm was obtained in all studied starch samples, and increasing hydration level resulted in an increase in the sizes of the obtained endotherms. Similarly, To, Tp and Te values of the endotherms were shifted towards higher temperatures with increase in hydration level (Table 3). To, Tp and Te values of the endotherms were significantly different from each other (p<0.05, Table 3). These shifts are reflected to the increase in the size of the ice melting peak. In higher hydration level conditions, adequate amounts of water are present in the medium to form ice crystals, while in limited water conditions most of the water is bound to starch with a small freezable fraction. A similar situation was reported by Suzuki & Kitamura (2008)Suzuki, S., & Kitamura, S. (2008). Unfrozen water in amylosic molecules is dependent on the molecular structures—a differential scanning calorimetric study. Food Hydrocolloids, 22(5), 862-867. http://dx.doi.org/10.1016/j.foodhyd.2007.04.011.
http://dx.doi.org/10.1016/j.foodhyd.2007...
, Tananuwong & Reid (2004)Tananuwong, K., & Reid, D. S. (2004). DSC and NMR relaxation studies of starch-water interactions during gelatinization. Carbohydrate Polymers, 58(3), 345-358. http://dx.doi.org/10.1016/j.carbpol.2004.08.003.
http://dx.doi.org/10.1016/j.carbpol.2004...
, Tran et al. (2008)Tran, T., Thitipraphunkul, K., Piyachomkwan, K., & Sriroth, K. (2008). Effect of starch modifications and hydrocolloids on freezable water in cassava starch systems. Stärke, 60(2), 61-69. http://dx.doi.org/10.1002/star.200700684.
http://dx.doi.org/10.1002/star.200700684...
and Grunina et al. (2015)Grunina, N. A., Tsereteli, G. I., Belopolskaya, T. V., & Smirnova, O. I. (2015). Thermal properties of frozen water in the native and amorphous starches with various hydration degrees. Carbohydrate Polymers, 132, 499-508. http://dx.doi.org/10.1016/j.carbpol.2015.05.086. PMid:26256375.
http://dx.doi.org/10.1016/j.carbpol.2015...
.

Table 3
To, Tp and Te values of the endotherms of starch samples with various hydration levels.

The unfreezable water contents of the physically modified and unmodified starch samples in different hydration levels were given in Table 4. The obtained values were statistically significantly different from each other (p<0.05). This may be attributed to the different water binding sites present in the starch samples. These binding sites are hydroxyl groups and inter-glucose oxygen atoms in the starches. The interaction of these sites with water varies depending on the structural and compositional properties of the starches (Fu et al., 2014Fu, Z. Q., Wang, L. J., Zou, H., Li, D., & Adhikari, B. (2014). Studies on the starch-water ınteractions between partially gelatinized corn starch and water during gelatinization. Carbohydrate Polymers, 101, 727-732. http://dx.doi.org/10.1016/j.carbpol.2013.09.098. PMid:24299832.
http://dx.doi.org/10.1016/j.carbpol.2013...
). The unfreezable water contents of corn starches were higher than those of the pregelatinized corn starches in all hydration levels. Retrograded corn starches had higher unfreezable water content than corn starches up to 45% hydration level. In general, pregelatinized and retrograded waxy corn starches were higher unfreezable water contents than that waxy corn starches up to 65% hydration level (Table 4). These results indicate that physical modifications may be effective in improving starch-water interaction. Fu et al. (2014)Fu, Z. Q., Wang, L. J., Zou, H., Li, D., & Adhikari, B. (2014). Studies on the starch-water ınteractions between partially gelatinized corn starch and water during gelatinization. Carbohydrate Polymers, 101, 727-732. http://dx.doi.org/10.1016/j.carbpol.2013.09.098. PMid:24299832.
http://dx.doi.org/10.1016/j.carbpol.2013...
and Wootton & Bamunuarachchi (1978)Wootton, M., & Bamunuarachchi, A. (1978). Water binding capacity of commercial produced native and modified starches. Stärke, 30(9), 306-309. http://dx.doi.org/10.1002/star.19780300905.
http://dx.doi.org/10.1002/star.197803009...
reported that gelatinization process breaks the weaker bonds in the amorph zone of the granule, hence increasing the hydration capacity of the starch molecule. Similarly, Tananuwong and Reid (2004)Tananuwong, K., & Reid, D. S. (2004). DSC and NMR relaxation studies of starch-water interactions during gelatinization. Carbohydrate Polymers, 58(3), 345-358. http://dx.doi.org/10.1016/j.carbpol.2004.08.003.
http://dx.doi.org/10.1016/j.carbpol.2004...
emphasized that heating of native starch increases the unfreezable water content, and they have observed that the completely gelatinized starch samples contain more unfreezable water than that of partially gelatinized samples. The researchers emphasized that higher temperatures induce more damage to the structure of starch granule, leading to the emergence of more hydroxyl groups to interaction with water. Fu et al. (2014)Fu, Z. Q., Wang, L. J., Zou, H., Li, D., & Adhikari, B. (2014). Studies on the starch-water ınteractions between partially gelatinized corn starch and water during gelatinization. Carbohydrate Polymers, 101, 727-732. http://dx.doi.org/10.1016/j.carbpol.2013.09.098. PMid:24299832.
http://dx.doi.org/10.1016/j.carbpol.2013...
, on the other hand, determined lower unfreezable water content in fully gelatinized starch samples. The unfreezable water contents of all physically modified waxy corn starch samples were higher than all physically modified corn starch samples (Table 4). This indicates that amylopectin plays an important role in starch-water interaction. A similar situation was also emphasized by Tananuwong & Reid (2004)Tananuwong, K., & Reid, D. S. (2004). DSC and NMR relaxation studies of starch-water interactions during gelatinization. Carbohydrate Polymers, 58(3), 345-358. http://dx.doi.org/10.1016/j.carbpol.2004.08.003.
http://dx.doi.org/10.1016/j.carbpol.2004...
. Furthermore, as a result of this study, much higher unfreezable water content was obtained in waxy corn starch above 55% hydration levels. When hydration level is increased from 55% to 85% in native corn starch, the increase in the unfreezable water content for corn starch was 227.73%, while for corn starch was 304.06%.

Table 4
The unfreezable water contents of the starch samples with various hydration levels (g water/ g dry starch x100).

4 Conclusion

The highest WAI and WSI were obtained in the pregelatinized waxy corn starch samples. The To, Tp and Te values of the DSC endotherms obtained from the starch samples were increased with increase in hydration level. Unfreezable water contents of starch samples were depended on hydration level. The highest unfreezable water content was determined in retrograded waxy corn starch samples (up to 65% hydration level), whereas the lowest unfreezable water content was determined in native waxy corn starch samples (up to 55% hydration level). Therefore, it is possible to state that much more stable products may be obtained if retrograded waxy corn starch is present in starch-rich foods.

  • Practical Application: Starch is one of the most important vegetable polysaccharides and is used in many areas of the industry. Various modification techniques have been developed to improve the technological properties of native starches. Physical modification techniques are more preferred because there is no chemical application.

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Publication Dates

  • Publication in this collection
    06 July 2020
  • Date of issue
    Apr-Jun 2021

History

  • Received
    05 Feb 2020
  • Accepted
    15 Apr 2020
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