Pressure-Induced Gelatinization of Starch in Excess Water

High pressure processing is a promising non-thermal technology for the development of fresh-like, shelf-stable foods. The effect of high pressure on starch has been explored by many researchers using a wide range of techniques. In general, heat and pressure have similar effects: if sufficiently high, they both induce gelatinization of starch in excess water, resulting in a transition of the native granular structure to a starch paste or gel. However, there are significant differences in the structural and rheological properties between heated and pressurized starches. These differences offer benefits with respect to new product development. However, in order to implement high-pressure technology to starch and starch-containing products, a good understanding of the mechanism of pressure-induced gelatinization is necessary. Studies that are published in this area are reviewed, and the similarities and differences between starches gelatinized by pressure and by temperature are summarized.     

Gelatinization of Starch in Aqueous Alkaline Solutions

The effect of kind and concentration of alkali on the gelatinization of maize, rice and wheat starches were thoroughly investigated. No gelatinization could be observed on using the carbonate and/or bicarbonate of sodium and potassium even on using their saturated solutions, while both sodium and potassium hydroxides undergo gelatinization. Gelatinization of starch occurs immediately at a concentration of sodium hydroxide of 1.2%, while clear gelatinized pastes could be obtained at 4% or more. Infra-red spectra of maize and rice starches before and after alkali treatment reveal that treatment of starch with sodium hydroxide is accompanied by some physicochemical changes in the structure of starch. The rheological properties as well as the apparent viscosity of the gelatinized starch pastes depend on the kind of starch as well as the nature and concentration of alkali used.     

RHEOLOGICAL AND CALORIMETRIC INVESTIGATIONS OF STARCH-FISH PROTEIN SYSTEMS DURING THERMAL PROCESSING2,,3

During the thermal processing of starch-surimi systems, significant rheological changes due to the sol-gel transformation of fish proteins and the gelatinization of starch were observed by rigidity scanning. Differential scanning calorimetry (DSC), produced results which corresponded well with rheological changes. Starch gelatinization in cooked fish-starch gels was studied by DSC. The effects of starches on the textural properties of cooked gels were dependent on their gelatinization characteristics, such as gelatinization temperature, degree of swelling and water uptake of the granules. Gels producing higher failure stress values were obtained after starch gelatinized; however, no significant effect on failure strain was observed by the addition of starch. Pregelatinized starch had detrimental effects on the gelation of fish protein, and more water was absorbed by this starch compared to non-pregelatinized starches. Resulting gels were weaker and less deformable.     

Chemical Composition and Structure of Granule Periphery and Envelope Remnant of Rice Starches as Revealed by Chemical Surface Gelatinization

In this work the contribution of molecular structures to the swelling behavior of rice starches was investigated. Rice starches with different amylose contents (0 ‐ 23.4 %) were gelatinized to various degrees (approximately 10, 20, and 50 %) with 13 M aqueous LiCl, and the surface‐gelatinized starch and ungelatinized remaining granules were separated and characterized. The native starches were heated at 85 or 95°C for 30 min in excess water, and the granule envelope remnants were recovered by centrifugation for further characterization. The remaining granules after surface removal exhibited a lower gelatinization temperature and enthalpy, and swelled to a greater extent upon heating than the native counterpart. The amylopectin molecules in granule envelope remnants obtained at 95°C had larger M_w (weight‐average molar mass) and R_z (z‐average gyration radius) than those in remnants obtained at 85°C. The chemical composition and structure of granule envelope remnants obtained at 85°C were different from those obtained at 95°C for the same rice starch cultivar. The results imply that starch periphery may not be responsible for maintaining starch granule integrity during gelatinization and swelling. It is proposed that the composition and structure of the granule envelope remnant that maintains granule integrity are not constant but dynamic. The formation of a semi‐permeable membrane‐like surface structure during gelatinization and swelling is proposed to be a result of molecule entanglement after gelatinization.     

Rheological Properties of Mixed Gels using Waxy and Non‐waxy Wheat Starch

Mixed starches with an amylose content of 5, 10, 18, 20, 23, and 25% were prepared by blending starches isolated from waxy and non‐waxy wheat at different ratios. The dynamic viscoelasticity of mixed 30% and 40% starch gels was measured using a rheometer with parallel plate geometry. The change in storage shear modulus (G′) over time at 5 °C was measured, and the rate constant of G′ development was estimated. As the proportion of waxy starch in the mixture increased, starch gels showed lower G′ and higher frequency dependence during 48 h storage at 5 °C. Since the amylopectin of waxy starch granules was solubilized more easily in hot water than that of non‐waxy starch granules, mixed starch containing more waxy starch was more highly solubilized and formed weaker gels. G′ of 30% and 40% starch gels increased steadily during 48 h. 30% starch gel of waxy, non‐waxy and mixed starches showed a slow increase in G′. For 40% starch gels, mixed starch containing more waxy starch showed rapidly developed G′ and had a higher rate constant of starch retrogradation. Waxy starch greatly influenced the rheological properties of mixed starch gels and its proportion in the mixture played a major role in starch gel properties.     

Comparison of Endosperm Starch Granule Development and Physicochemical Properties of Starches from Waxy and Non-Waxy Wheat

Starch granule development and physicochemical properties of starches in waxy wheat and non-waxy wheat were investigated in this article. Starch granules in waxy wheat endosperm showed an early developmental process. Compared with non-waxy wheat starch granules (round-shaped), waxy wheat starch granules (ellipse-shaped) were larger and contained more B-type granules. According to the granule size, starch granules were divided into two groups in waxy wheat, but were divided into three groups in non-waxy wheat. Compared with non-waxy wheat starch, waxy wheat starch had higher swelling power, gelatinization temperatures (To, Tp, Tc), and relative degree of crystallinity. They showed similar ordered structures on external regions of starch granules. Additionally, waxy wheat starch had a higher proportion of double-helical components and a lower proportion of single-helical components than non-waxy wheat starch. Based on the previous results, it was concluded: (1) waxy wheat and non-waxy wheat not only differed in starch granule development, but also in physicochemical properties of starches; (2) waxy wheat had more potential value for producing traditional products than non-waxy wheat.     

糊化条件对淀粉溶解度及性能的影响

考察了原淀粉和变性淀粉的取代度、糊化温度与时间和添加NaOH等糊化条件对淀粉溶解度的影响。并解析了溶解度与淀粉作用效果的关系。研究结果表明，糊化温度越高，淀粉的溶解度越大，糊化温度应在90~C以上。淀粉才能充分溶解；添加NaOH加速淀粉的糊化速度；变性淀粉的取代度和制备条件对其溶解度均有较大影响；延长糊化时间可提高阳离子淀粉的作用效果，而加碱糊化会降低阳离子淀粉的作用效果。     

Effect of cooking time and ingredients on the performance of different starches in white sauces

The effect of white sauce ingredients and increased cooking time at 90 °C on the degree of gelatinization of corn, waxy corn, rice, potato and modified waxy corn starches was studied. The changes in pasting properties, linear viscoelastic properties, and microstructure were determined. In all the native starches in water, a longer cooking time at 90 °C caused greater starch granule swelling and more leaching of solubilized starch polymers into the intergranular space. These effects were more noticeable in the waxy corn and potato starches. The potato starch was the most affected, with complete disruption of the starch granules after 300 s at 90 °C. The microstructural changes which transformed a system characterized by starch granules dispersed in a continuous phase (amylose/amylopectin matrix) into a system with an increase in the continuous phase and a decrease in starch granules were associated with a decrease in system viscoelasticity. The elastic moduli were higher in the sauce than in the starch in water system. However, with the exception of potato starch, the white sauce showed lower viscoelasticity than the starch in water system. The white sauce ingredients decreased the effect of cooking time on the starch gelatinization process, particularly in potato starch.     

Properties of Korean Amaranth Starch Compared to Waxy Millet and Waxy Sorghum Starches

Characteristics of waxy type starches isolated from amaranth, waxy millet and waxy sorghum harvested in Korea were evaluated. Shapes of all starch granules were polygonal or slightly round and the surfaces of waxy millet and waxy sorghum starch granules showed visible pores. Amylose contents of the three starches were between 3.2–6.0% and amaranth starch showed the highest water binding capacity (WBC) (130.7%). The swelling power and solubility of amaranth starch studied at 65.0–95.0°C increased about 13.7‐ and 14.0‐fold, respectively, with increase in temperature. Swelling power of waxy sorghum starch was the highest (72.6 at 95°C) among the starches studied, while amaranth starch had a constant swelling power and its rate of solubility increasely only slowly at temperatures higher than 75°C. From RVA data, initial pasting temperatures of amaranth, waxy sorghum and waxy millet starches were 75.7, 73.3 and 75.2°C, respectively. Peak viscosity, breakdown, and setback from trough of amaranth starch were 68.3, 16.7 and 7.5 RVU, respectively, which were the lowest values among the starches investigated. Using DSC, onset temperature of gelatinization of amaranth starch was 1.5–4.0°C higher than those of waxy sorghum and millet starches, corresponding to the RVA result. The enthalpies of gelatinization of the starches studied in our laboratory were in the range of 8.5–12.7 J/g with decreasing order of waxy sorghum > amaranth > waxy millet starch.     

Retrogradation properties of rice starch gelatinized by heat and high hydrostatic pressure (HHP)

Retrogradation process of pressure-gelatinized rice starches was investigated and compared with the heat-gelatinized ones in this study. Our results showed that the retrogradation rate of normal rice starch gelatinized by high hydrostatic pressure (HHP) was slower than that by heat. Nevertheless, there was no difference in retrogradation rate for waxy rice starch gelatinized by the two treatments (P > 0.05). The DSC data were further analyzed using the Avrami equation. The result indicated that the pressure-gelatinized normal rice starch had a lower recrystallization rate (k) and a higher Avrami exponent (n) than the heat-gelatinized one, but the two treatments did not affect the k and n for waxy rice starch. Furthermore, the intact starch granules and lower amylose leaching were observed only in the pressure-gelatinized normal rice starch. These findings suggest that the retardation mechanism of HHP on starch retrogradation is probably attributed to less broken granules and lower leached amylose.     

冻融循环处理对玉米淀粉凝胶结构及颗粒理化特性的影响

本文研究了不同次数(0、1、2、3、4、5和6次)的冻融处理对糊化后的普通玉米和糯玉米淀粉凝胶理化性的影响。采用扫描电子显微镜对淀粉凝胶的微观结构进行分析,测定了凝胶化淀粉的碘蓝值、碘结合力、最大吸收波长、透明度、持水性、溶解度与膨胀力、水解特性和体外消化性。普通玉米淀粉凝胶呈孔状结构,糯玉米淀粉凝胶冻融2次后出现层状结构,二者孔径和层距都随冻融次数增加而减小。冻融循环处理对两种凝胶化玉米淀粉的碘蓝值、碘结合力、最大吸收波长和直链淀粉含量均无显著性影响。随冻融次数增加,普通玉米淀粉的透明度、持水性、RDS与SDS含量逐渐减小,而溶解度、膨胀力、水解率和RS含量逐渐升高;而糯玉米淀粉的透明度、持水性、溶解度和膨胀力逐渐减小,RDS、SDS和RS含量及水解率均无显著性变化。     

RELATIONSHIP BETWEEN PHYSICOCHEMICAL PROPERTIES OF STARCHES AND EXPANSION OF FISH CRACKER 'KEROPOK'

The influence of physicochemical properties of starches on expansion of‘keropok’was studied. Swelling power, solubility, and amylose leaching of a starch were dependent on the lipid and protein contents of the starch. The morphology of different starch granules used in‘keropok’gel was observed using scanning electron microscopy. The sizes of swollen starch granules in the gel were quantitatively measured by image analysis. The average length and width of swollen gelatinized sago and tapioca starch granules were significantly higher than that of wheat starch, and consequently, the linear expansion of‘keropok’with wheat starch was lower than those of‘keropok’made with tapioca or sago starches. Linear expansion was positively correlated to swelling power and solubility of the starch. Textural properties of‘keropok’gels with different starches were also measured and found to have correlation with linear expansion of the final products.     

Effects of Annealing on ultra-high pressure induced gelatinization of corn starch

Ultra-high pressure (UHP) can induce starch gelatinization at the room temperature, while the change of starch architecture could affect the gelatinization process. This work evaluated the effects of annealing on UHP induced starch gelatinization. Native and annealed corn starches were subjected to UHP treatment (300–600 MPa) for 15 min at room temperature. The scanning electron microscopy, confocal laser scanning microscopy, differential scanning calorimetry and X-ray diffraction analysis showed that UHP treatment partially disrupted the ordered structures of native and annealed starches, which made starch gelatinized gradually and a transformation in crystal type from type A to type B. However, compared with native starch, annealing (C3 and C24) delayed the internal and external structure destruction of starch granules, as well as induced a slower decrease in ΔH and relative crystallinity as increasing pressure. Therefore, the suitable UHP treatment can increase the pressure resistance of starch, or delay the UHP gelatinization process.     

A Differential Scanning Calorimetry Study on the Effect of Annealing on Gelatinization Behavior of Corn Starch

Gelatinization characteristics of laboratory-isolated and commercial corn starch were compared by differential scanning calorimetry (DSC) before and after being annealed at subgelatinization temperatures in excess water. Prior to annealing, commercial corn starch has a relatively narrow gelatinization range, with a peak temperature at 71°C. Starches isolated in the laboratory have wide gelatinization ranges and lower peak temperatures. After annealing, commercial starch showed little change in gelatinization characteristics, whereas laboratory starches all had narrowed gelatinization ranges, higher peak temperatures, and increased gelatinization enthalpy, indicating changes in the internal structure of the starch granules. This demonstrates that the wet-milling process anneals corn starch during the isolation procedure.     

Effect of hydroxypropyl β-cyclodextrin on physical properties and transition parameters of amylose–lipid complexes of native and acetylated starches

The effect of hydroxpropyl β-cyclodextrin (HPβ-CD) on physical properties and digestibility of wheat, potato, waxy maize and high-amylose maize starches before and after acetylation was studied. Effect of HPβ-CD on amylose–lipid complexes in native and acetylated potato starches synthesized using α-lysophosphatidylcholine was also studied. Acetylation increased swelling factor, amylose leaching, peak viscosity and susceptibility to α-amylase hydrolysis, but decreased gelatinization temperature and enthalpy and gel hardness in all starches. HPβ-CD markedly increased swelling factor and amylose leaching in native and acetylated wheat starches but had little or no impact on other starches. Wheat starch gelatinization enthalpy decreased in the presence of HPβ-CD but gelatinization temperature of all the starches was slightly increased. HPβ-CD had no influence on enzymatic hydrolysis. Melting enthalpy of amylose–lipid complex in both native and acetylated wheat starches was decreased by HPβ-CD. Acetylation also decreased the melting enthalpy of amylose–lipid complex in wheat starch. Similar trend of thermal transitions was observed in the presence of HPβ-CD for the amylose–lipid complexes synthesized in potato starch. Acetylation reduces the complex formation ability of the amylose polymer. Similar to gelatinization, acetylation widened the melting temperature range of amylose–lipid complexes while shifting it to a lower temperature. Higher swelling and amylose leaching, and decreased gelatinization temperature and enthalpy resulting from acetylation of wheat starch is consistent with its influence on starch hydration. Similar effects resulting from the inclusion of HPβ-CD were consistent with the disruption of amylose–lipid complex by HPβ-CD which promotes granular hydration.     

Gelatinization Properties of Navy Bean Starch

Gelatinization properties of navy bean (Phaseolus vulgaris) starch under different combinations of concentration (6, 8, 10 and 12%) and cooking temperature (75, 85 and 95°C) were studied using a rotational viscometer. The torque response due to swelling and/or breakdown of starch granules approached equilibrium after either a gradual increase or a relatively rapid increase to a peak followed by a decline during cooking. For every condition, the difference between the final torque values obtained for the rapid and the slow heating processes was not significant. In general, the viscosity of the paste increased as the starch concentration and/or cooking temperature increased. However, cooking temperature of 75°C did not cause a significant gelatinization or swelling of starch granules in pastes of 6 or 8% concentration. Maximum final viscosity values were obtained at 85°C for all starch concentrations except for a maxium at 95°C for 6%. Thixotropic breakdown was observed at 10 and 12% concentrations during initial shearing at 85 and 95°C. The threshold concentration for singnificant viscosity effects in this study was in the range of about 8 to 10% or 95°C. The calculated activation energy (14.5 Kcal.g⁻¹ mole⁻¹) of navy bean starch gelatinization was similar to values reported for rough rice and rice starches.     

Partial Leaching of Granule‐Associated Proteins from Rice Starch during Alkaline Extraction and Subsequent Gelatinization

Starch granule‐associated proteins, including granule‐bound starch synthase (GBSS), were found to be partially lost during alkaline extraction of rice starch. Variability in amount of loss of GBSS and other granule proteins was found among different rice lines. Also, part of the GBSS and other granule proteins leached out during gelatinization of the alkali‐extracted rice starch. Confocal laser scanning microscopy revealed that some protein still existed in gelatinized starch granules prepared from starch isolated using alkaline extraction. The starch that retained more GBSS and other granule proteins after alkaline extraction tended to have more protein in the isolated gelatinized starch granules, indicating that proteins resistant to alkaline extraction also tended to resist leaching during gelatinization. The study suggests that leaching of granule‐associated proteins may contribute to variations in paste properties of alkali‐extracted starches.     

Starch Properties of a Waxy Mutant Line of Hull‐less Barley (Hordeum vulgare L.)

Endosperm starch isolated from an amylose‐free waxy mutant hull‐less barley line, Shikoku Hadaka 97, had an amylose content of 0.3% and higher swelling power than ordinary waxy barley cultivars/lines with amylose contents of 2.2—6.5%. A highly significant correlation was observed between amylose content and swelling power among waxy barley starches. No clear differences were detected in the chain‐length distribution profiles or thermal properties between the amylose‐free starch and ordinary waxy starch. The chain‐length distribution profile of waxy barley starch was slightly different from that of normal barley starch. Gelatinization temperatures and gelatinization enthalpy of waxy barley starch were higher than those of normal barley starch. Significant correlations were observed between amylose content and thermal properties of starch samples analyzed. Waxy barley starch stained with a concentrated iodine‐potassium iodide solution showed a ghost‐like appearance.     

Structure-viscosity relationships for starches from different rice varieties during heating

The effects of starch particle size and leached amylose on the viscosity of rice starch dispersions and changes of short-range structure and amylose content in starch granules of different rice varieties during heating were investigated. It was found that starch granule swelling increased rice starch dispersion viscosity during heating. The viscosities of the starch dispersions during heating were principally dependent on granular volume fraction and independent of starch variety. A distinct correlation between the amount of leached amylose and swelling of starch granules was also found. High initial amylose concentrations in starch granules reduced swelling during heating, thereby reducing rice dispersion viscosities. Fourier-transform IR spectroscopy indicated that the loss of short-range order was significant when the temperature reached the pasting onset temperature. The short-range order of waxy and medium grain rice starches was higher than that of long grain rice starches before gelatinization. The loss of order of waxy and medium grain rice starches was greater than that of long grain rice starches during heating, which was due to the presence of amylose, restraining the swelling and disruption of starch granules during heating.     

Viscoelastic Changes of Rice Starch Suspensions During Gelatinization

Dynamic rheometry was utilized to characterize viscoelastic changes during heat-induced gelatinization of 2 domestic rice starch suspensions, 1 from waxy and the other from indica rice. Gelatinization included 4 stages: suspension into sol, sol transition to gel, network destruction, and network strengthening. Increase in storage modulus (G') was observed as early as about 47°C. For indica rice, the maximum value (G'_max) was higher, and the decrease afterwards was slower, owing to its higher amylose content. The effects of heating time and temperature were found additive. Sealing samples with oil affected the accuracy of measurement. Finally, the network of starch gels had a larger fractal dimension than that of soy protein isolates previously investigated, suggesting firmer food texture.