Studies on Rye Starch Properties and Modification. Part II: Swelling and Solubility Behaviour of Rye Starch Granules

Rye starch shows the typical inhibited swelling behaviour of triticeae starches with an onset of swelling at rather low temperature (50–55°C). Swollen rye starch granules exist as individuals even after swelling at 100°C. The total dispersion of rye starch needs temperatures above 120°C with pressure cooking. On heating of the rye starch suspension preferentially amylose is leached. Defatting of rye starch exhibits no influence on swelling power but results in higher solubility and in increased amylose leaching. The drying procedures applied here resulted in stronger assoziation of the polymer molecules in the starch granule leading to higher swelling temperatures and a reduced solubility. Shiftings of the crystalline/ amorphous-ratio of the starch granules as caused by different drying procedures, had no influence on the results of swelling power investigation but the highest swelling enthalpy as well as Brabender viscosity were exhibited by a sample dried at room temperature. It is proved to be possible to change the swelling behaviour of rye starch to “potato starch type” by slight chemical modification like succination.     

韧化处理对板栗淀粉特性的影响

以燕山板栗淀粉为材料,在30、40和50℃分别进行韧化处理。采用扫描电子显微镜(SEM)、X-射线衍射分析(XRD)、差示扫描量热分析(DSC)及体外消化法等方法,研究了韧化处理对板栗淀粉颗粒结构、理化特性和体外消化性的影响。研究表明:与原淀粉相比,韧化处理后2种板栗淀粉的直链淀粉含量降低,淀粉颗粒破损率增大,但淀粉仍为C型晶体。随着韧化温度的升高,淀粉颗粒表面出现凹坑和损伤越显著,膨胀度随着处理温度的升高而降低。DSC分析表明,韧化处理使淀粉的糊化温度升高,热焓变化不大。不同的韧化处理温度对板栗淀粉体外消化性有不同的影响,韧化处理使淀粉的快消化淀粉(RDS)含量减少,慢消化淀粉(SDS)含量增大。     

Starch characteristics of black bean,chick pea,lentil, navy bean and pinto bean cultivars grown in Canada

The physicochemical properties of starches from different cultivars of black bean, chick pea, lentil, navy bean, smooth pea and pinto bean were examined. Starch granule size ranged from 8 to 35 μm. The starch granules were round to elliptical with smooth surfaces. The total amylose content ranged from 23.0 to 29.5%, of which 6.0–14.9% was complexed by native lipid. All starches showed a ‘C’ type X-ray pattern. The peak at 2θ=5.54 (characteristic of B type starches) was most pronounced in pinto bean and black bean starches. Relative crystallinity followed the order: pinto bean>lentil∼smooth pea∼chick pea∼black bean∼navy bean. The swelling factor (at 80 °C) followed the order: black bean>smooth pea∼chick pea>lentil>navy bean>pinto bean, whereas, amylose leaching (at 80 °C) followed the order: lentil>smooth pea>chick pea>black bean>navy bean>pinto bean. Pinto bean starches showed the highest gelatinization transition temperatures and enthalpies of gelatinization, whereas, the highest gelatinization temperature range was exhibited by black bean starches. All legume starches exhibited high thermal stability during the holding cycle (at 95 °C) in the Brabender viscoamylogram. However, they differed significantly with respect to the viscosity at 95 °C and the degree of set-back. These differences were more pronounced in pinto bean starches. The extent of syneresis followed the order: black bean>chick pea∼lentil>smooth pea>navy bean>pinto bean. Differences in physicochemical properties were more marked among cultivars of black bean, and between cultivars of chick pea and smooth pea starches. This study showed that black bean and pinto bean starches differed significantly from each other, and from the other starches, with respect to the magnitude of interaction between starch chains within the amorphous and crystalline domains.     

Physico-chemical Characteristics of Starches from Chick Pea,Cow Pea and Horse Gram

Starches were isolated in 36, 37 and 28% yields, from chick pea, cow pea and horse gram, respectively. Study of their properties revealed mixed granule population; single stage swelling with high solubility in water for cow pea and horse gram starches in comparison to chick pea starch; slightly higher solubility in DMSO for chick pea starch followed by cow pea and horse gram starches; a relatively high viscosity in alkaline solution of cow pea starch; and Brabender amylograms indicating a low slurry viscosity and low set back in the case of chick pea starch compared to the other two starches which exhibited considerable peak viscosity as well as retrogradation. All the starches contained amylose in the range of 32 – 34%. X-ray powder patterns showed chick pea and horse gram starches to be of B-type, whereas cow pea starch was of A-type.     

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.     

Effects of sodium dodecyl sulphate and sonication treatment on physicochemical properties of starch

Effects of sodium dodecyl sulphate (SDS) and sonication treatment on physicochemical properties of starch were studied on four types of starch, namely, corn, potato, mung bean, and sago. The SDS and sonication treatments caused a significant reduction of protein content for all the starches. The SDS treatment did not cause apparent damage on granular structure but sonication appeared to induce changes such as rough surface and fine fissures on starch granules. The combination of SDS and sonication increased amylose content for all starches. This could be attributed to the removal of surface protein by SDS and structural weakening by sonication which facilitated amylose leaching from swollen starch granule. The X-ray pattern for all starches remained unchanged after SDS treatment, suggesting no complexation of amylose–SDS had occurred. Combined SDS-sonication treatment increased swelling and solubility of corn, mung bean, and potato starch. The treated starches showed significant increase in peak viscosity with reduction in pasting temperature, except for potato starch. Results of the present study indicate the possibilities of exploring SDS and sonication treatments for starch modifications.     

Effect of single and dual hydrothermal treatments on the crystalline structure,thermal properties,and nutritional fractions of pea,lentil, and navy bean starches

Pea, lentil and navy bean starches were annealed at 50 °C (70% moisture) for 24 h and heat-moisture treated at 120 °C (30% moisture) for 24 h. These starches were also modified by a combination of annealing (ANN) and heat-moisture treatment (HMT). The impact of single and dual modifications (ANN–HMT and HMT–ANN) on the crystalline structure, thermal properties, and the amounts of rapidly digestible starch (RDS), slowly digestible starch (SDS), and resistant starch (RS) were investigated. Birefringence remained unchanged on ANN but decreased on HMT. Granular swelling and amylose leaching decreased on ANN and HMT. Relative crystallinity, gelatinization enthalpy, and short-range order on the granule surface increased on ANN but decreased on HMT. Gelatinization transition temperatures increased on ANN and HMT. Gelatinization temperature range decreased and increased on ANN and HMT, respectively. ANN and HMT increased SDS and decreased RS levels in all starches. However, RDS levels increased on ANN and HMT in pea and lentil starches but decreased in navy bean starch. In gelatinized starches, ANN and HMT decreased RDS level and increased SDS and RS levels. Changes to crystalline structure, thermal properties and amounts of RDS, SDS, and RS were modified further on ANN–HMT and HMT–ANN.     

Effect of heat-moisture treatment on the structure and physicochemical properties of legume starches

Native green arrow pea (GAP), eston lentil (EL), othello pinto bean (PB), black bean (BB) and express field pea (FP) starches were heat-treated at 100 °C for 16 h at a moisture content of 30%. The heat treatment did not change granule size and shape. The surfaces of GAP and EL were modified after heat treatment. Heat treatment decreased amylose leaching (GAP > FP˜EL > BB˜PB) and the swelling factor (EL ˜ FP > GAP > BB ˜ PB). The X-ray diffraction intensities increased in GAP starch, but decreased in the other starches (FP > BB > PB > EL). However, the X-ray pattern of all starches remained unchanged after heat treatment. Differential scanning calorimetry of the heat-treated samples showed a broadening of the gelatinization temperature range and a shifting of the endothermal transition towards a higher temperature (EL-EP>BB-PB). However, the gelatinization enthalpy (ΔH) of all starches remained unchanged. The susceptibility towards hydrolysis by porcine pancreatic -amylase increased on heat treatment (BB > EL > FP > PB > GAP). The action of -amylase on the starches decreased ΔH in EL and FP. However, ΔH decreased only marginally in PB and BB. Acid hydrolysis (2.2 N HCl) increased on heat treatment (BB>FP˜EL˜PB>GAP). The results showed that bonding forces within the amorphous regions of the granule, crystallite orientation and the granule surface (in GAP and EL) are altered during heat treatment, the magnitude of these changes being dependent upon the starch source.     

EFFECT OF SUGARS ON THE THERMAL AND RETROGRADATION PROPERTIES OF OAT STARCHES

The thermal and retrogradation properties of oat starches from two cultivars (NO 753-2 and AC Stewart) were characterized in the presence of glucose, fructose and sucrose at a concentration of 36% w/v. In both oat starches, amylose leaching (AML) and swelling factor (SF) decreased in the presence of sugars (sucrose > glucose > fructose). These decreases were more pronounced in AC Stewart starch. The decrease in AML showed that sugars interact with amylose chains within the amorphous regions of the starch granule. The gelatinization transition temperature and the enthalpy of gelatinization increased in the presence of sugars (sucrose > glucose > fructose). The above increase was also more pronounced in AC Stewart starch. The decrease in SF and the increase in gelatinization parameters indicated that these changes were influenced by the interplay of factors such as starch-sugar interaction, changes in water structure in the presence of sugars, and the antiplastizing properties of sugars relative to water. The retrogradation enthalpy and the X-ray diffraction intensities of NO 753-2 and AC Stewart starch gels (stored at 4C) increased in the presence of sugars (glucose > fructose > sucrose). These changes were more pronounced in NO 753-2 starch. The results showed that interaction (during storage) between leached amylopectin and sugar molecules was the main causative factor influencing oat starch retrogradation.     

Effect of Aqueous Ethanol Cationization on Functional Properties of Normal and Waxy Starches

Cationic starch ethers of normal and waxy corn, normal and waxy barley and normal pea starch were prepared by an aqueous alcoholic process for evaluation of their functional properties as compared to the native starch controls. The native starches exhibited a wide range in average granule size (10–21 μm diameter), amylose content (0–34%) and swelling power (13–31). Cationization to degrees of substitution (DS) of 0.030–0.035 with 3-chloro-2-hydroxypropyltrimethylammonium chloride resulted in marked increases in swelling power of all starches, with little corresponding increases in starch solubility. Cationization also decreased the onset of endothermic transitions and pasting temperatures quite substantially, and promoted the development of sharp peak viscosities in the amylographs of all normal and waxy starches, including that of pea starch. Final cold viscosities of the cationic starches exhibited positive setbacks, and the cooked starch gels, after storage for 7 days at 4°C and −15°C, showed no syneresis. All cationic starches except for waxy corn were more susceptible to α-amylase hydrolysis than native control starches. The general improvement in functional properties, especially in the waxy corn, waxy barley and pea starches, due to the aqueous alcoholic-alkaline cationization process would greatly enhance their industrial applications.     

Functional Properties and Retrogradation of Heat‐Moisture Treated Wheat and Potato Starches in the Presence of Hydroxypropyl β‐cyclodextrin

Some functional and retrogradation properties of native and heat‐moisture treated potato and wheat starches were examined in the presence of hydroxypropyl β‐cyclodextrin (HPβ‐CD). HPβ‐CD increased swelling factor, amylose leaching, and solubility of both native and heat‐moisture treated wheat starches but it had less impact on corresponding potato starches. Gelatinization enthalpy of native wheat starch was decreased in the presence of HPβ‐CD but was increased in potato starch with increasing concentration. Reduction of amylose‐lipid complex endotherm in both native and heat‐moisture treated wheat starch was observed in the presence of HPβ‐CD. Heat‐moisture treatment did not change the transition parameters of amylose‐lipid complex showing its resistance to hydrothermal treatment. HPβ‐CD greatly decreased the pasting temperature of wheat starch. Cold paste viscosity of both native and heat‐moisture treated wheat starch was increased by HPβ‐CD to a greater extent than corresponding potato starch. Amylopectin retrogradation of all the starches was unaffected in the presence of HPβ‐CD but heat‐moisture treatment slightly decreased retrogradation of potato starch. These results suggest that HPβ‐CD can disrupt the amylose‐lipid complex within the starch granule in both native and heat‐moisture treated wheat starch but has no influence on amylopectin retrogradation. However, greatly increased wheat starch setback with HPβ‐CD indicates its greater effect on wheat starch amylose retrogradation.     

Physicochemical Properties of Field Pea, Pinto and Navy Bean Starches

Legume starches were compared for physicochemical properties that may explain differences in functional properties. Field pea starch had higher amylose, greater swelling power and solubility, and lower pasting temperatures than pinto and navy bean starches. Scanning electron microscopy (SEM) showed that field pea starch had larger, more irregularly shaped granules and more broken large granules than pinto or navy starches. The most starch damage was observed for field pea. Pinto and navy bean starches had greater resistance to swelling at 60°C than field pea indicating a more strongly bonded micellar network. Higher cold paste viscosity was observed for navy bean and field pea.     

Effect of Cross-Linking on Functional Properties of Legume Starches

Refined starches from lentil, fababean and field pea contained 38.5, 32.0 and 34.2% amylose, respectively, where the water binding capacities, swelling powers, susceptibilities to amylase digestibility and amylograph viscosities were in the order: lentil > fababean > field pea. This evidence and the X-ray diffraction data suggested that the degrees of molecular association between starch chains, especially amylopectin, followed the order: field pea > fababean > lentil. Cross linking with phosphorus oxychloride decreased water binding capacity, swelling power, α-amylase digestibility and 95°C viscosity in the amylograph but increased the degree of set-back. X-ray diffraction patterns indicated that cross linking occurred mainly in the amorphous regions of the starch granule. Scanning electron microscopy showed that cross linking hindered amylose exudation. The stable hot paste viscosities of cross-linked starches would be of value where low pH and high temperature are employed during pressure cooking or sterilization while the low degree of set-back of field pea starch should improve the freeze-thaw stability and textural quality of frozen foods.     

The impact of heat-moisture treatment on molecular structures and properties of starches isolated from different botanical sources

Heat-moisture treatment is a hydrothermal treatment that changes the physicochemical properties of starches by facilitating starch chain interactions within the amorphous and crystalline domains and/or by disrupting starch crystallites. The extent of these changes is influenced by starch composition, moisture content and temperature during treatment, and by the organization of amylose and amylopectin chains within native starch granules. During heat-moisture treatment starch granules at low moisture levels [(<35% water (w/w)] are heated at a temperature above the glass transition temperature (T(g)) but below the gelatinization temperature for a fixed period of time. Significant progress in heat-moisture treatment has been made during the last 15 years, as reflected by numerous publications on this subject. Therefore, this review summarizes the current knowledge on the impact of heat-moisture treatment on the composition, granule morphology, crystallinity, X-ray pattern, granular swelling, amylose leaching, pasting properties, gelatinization and retrogradation parameters, and susceptibility towards α-amylase and acid hydrolysis. The application of heat-moisture treatment in the food industry is also reviewed. Recommendations for future research are outlined.     

韧化温度和时间对不同直链淀粉质量分数玉米淀粉物化性质的影响

为进一步探讨韧化处理对淀粉性质的作用机理,通过测定糊化性质、热特性、膨胀力、结晶特性及观察偏光十字现象和微观结构,研究了不同韧化温度和时间对不同直链淀粉质量分数玉米淀粉（普通玉米淀粉（normal corn starch,NCS）和蜡质玉米淀粉（waxy corn starch,WCS））物化性质的影响。结果表明,韧化处理主要作用于NCS和WCS淀粉颗粒的无定形区,对淀粉结晶类型没有影响;但韧化处理能够明显增强NCS和WCS的热稳定性和抗剪切能力,抑制淀粉老化和糊化,显著降低峰值黏度和膨胀力（P＜0.05）。韧化温度升高至60 ℃时韧化效果更加明显,糊化焓和相对结晶度明显降低,颗粒表面被明显破坏。但延长韧化时间对NCS和WCS老化的抑制效果和对糊化焓、膨胀力、颗粒形貌等的影响不明显。     

Changes in Starch Granules Trapped and Heated Using Optical Tweezers

A microscopic method to investigate the swelling process of individual starch granules heated in excess water is proposed. A starch granule focused under a light microscope is adjustably trapped using the optical tweezing of a near-infrared laser beam, which simultaneously heats the granule. Using this method, morphological changes in starch granules during heating were continuously recorded and quantitatively analyzed by image-processing techniques. The changes in granules of domestic wheat starches with differing amylose content were investigated under irradiation by the laser beam at constant optical power. The shapes of swollen granules of waxy wheat starches were observed to be distinctly different from those of non-waxy starches. Numerical indicators, specifically the time constant of swelling for the granule and its swelling magnification, were also obtained. These showed little relation to the pasting profiles of the same starches, obtained with a Rapid Visco Analyser.     

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.     

Effect of annealing on the semicrystalline structure of normal and waxy corn starches

The influence of amylose and amylopectin on structural reorganization occurred during annealing was studied for normal and waxy corn starches. Annealing caused an increase in crystallinity in the waxy corn starch, whereas the number of pores on the granule surface, observed by SEM, increased especially for normal corn starch. Amylose and amylopectin chains of the annealed normal corn starch were degraded to greater extension during enzymatic hydrolysis than those of the native starch. On contrary, the annealing caused a protective effect on waxy corn starch amylopectin toward the enzymatic reaction suggesting that this treatment promoted a better interaction between amylopectin chains of waxy corn starch. The amylose molecules of normal corn starch may have impaired the mobility of amylopectin molecules and restricted the reorganization of the crystalline structure during the annealing. The major increase in pores number on the granule surface of annealed normal corn starch, resulted of the endogenous amylase action during annealing, could facilitate the exogenous enzymes’ role in the degradation of the starch granules’ amorphous area.     

Starch retrogradation

Abstract

Starch granules heated in excess water undergo an order‐disorder phase transition called gelatinization (1) over a temperature range characteristic of the starch source. This phase transition is a non‐equilibrium process associated with the diffusion of water into the granule, hydration and swelling of the starch granules, uptake of heat, loss of crystallinity, and amylose leaching (1–3). On cooling, the starch chains (amylose and amylopectin) in the gelatinized paste associate, leading to the formation of a more ordered structure. These molecular interactions are termed collectively “retrogradation” and have important textural and dietary implications (not covered in this review). This review summarizes the present knowledge on amylose gelation and amylopectin crystallization, and on the factors that influence starch retrogradation.     

THE EFFECT OF ANNEALING ON THE PHYSICOCHEMICAL PROPERTIES OF WHEAT, OAT, POTATO AND LENTIL STARCHES

Native wheat, oat, potato and lentil starches were annealed at various starch/water ratios at 50C for time intervals ranging from 0.5 to 72 h. Annealing did not change granule size and shape. Oat starch granules were less compactly packed after annealing. X-ray diffraction patterns remained unchanged and X-ray intensities changed only marginally in all starches. The swelling factor (SF), amylose leaching (AML) and the gelatinization temperature range (GTR) decreased on annealing. The extent of decrease in SF and AML followed the order: lentil > wheat > potato > oat, while the corresponding order for GTR was: wheat > lentil > oat > potato. The gelatinization transition temperatures (GTT) and enthalpy (ΔH) increased on annealing. However, the increases in GTT and ΔH did not begin concurrently during the time course of annealing. Increases in ΔH were slower and were evident only after 1, 2, 6 and 48 h, respectively, in lentil, potato, oat and wheat starches. The extent and rate of increase in GTT and ΔH followed the order: potato > lentil > wheat > oat. The magnitude of changes in GTT and ΔH increased with increase in annealing moisture content. The susceptibility of oat starch to enzyme and acid hydrolysis increased on annealing. However, decreases occurred in the other starches (lentil > wheat > potato). Thermal and shear stability of starch granules increased on annealing (potato > lentil > wheat > oat). The results showed that the above changes in physicochemical properties were due to increased interaction between starch components during annealing.