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.     

辛烯基琥珀酸淀粉酯在速冻水饺中的应用

采用黏度速测仪和分光光度计测定糯玉米淀粉和大米淀粉辛烯基琥珀酸酐改性前后糊的性质,并将其按照不同比例分别添加到面粉中,研究其对速冻水饺品质的影响。结果表明：辛烯基琥珀酸酐改性使糯玉米淀粉和大米淀粉糊的透明度提高、凝沉性降低、冻融稳定性得到改善。添加不同比例的糯玉米辛烯基琥珀酸淀粉酯和大米辛烯基琥珀酸淀粉酯可增大面粉的黏度,提高饺子皮的硬度、弹性和咀嚼性(P ＜ 0.05);其中添加5% 预糊化糯玉米辛烯基琥珀酸淀粉酯的饺子冻裂率最低,并且饺子的色泽、透明度、韧性和细腻度最好。     

Preparation of Amphoteric Starches During Aqueous Alcoholic Cationization

Use of an aqueous alcoholic-alkaline solvent allowed cationization and phosphorylation to be combined in simultaneous or sequential processes in the production of amphoteric starch. Degrees of substitution required by the paper industry were obtained in normal corn, pea and barley starches, and in waxy corn and barley starches without the need for drying and heating the cationic starches to complete the phosphorylation reaction. The amphoteric starches had increased welling power, lower gelatinization temperatures, improved paste consistency and stability, and increased α-amylase digestibility than native controls, while gel syneresis after cold storage was eliminated.     

The Reactivity of Native and Autoclaved Starches from Different Origins Towards Acetylation and Cationization

Native potato, waxy corn, corn, wheat, filed pea and lentil starches were autoclaved at 15 psi, 121°C for 1min. Scanning electron micrographs of the native and autoclaved starches showed no changes in granular surfaces and shapes. In all starches, the X-ray intensities at most of the d-spacings between 3-18 Å increased upon autoclaving, being more pronounced in potato. The X-ray patterns of cereals and legumes remained unchanged, while that of tuber (potato) became more cereal-like. Differential scanning calorimetry of the starch samples revealed that autoclaving increased the gelatinization transition temperatures of wheat but decreased that of potato; the changes observed in waxy corn, corn, field pea and lentil starches were very small. The gelatinization enthalpy of all native starches decreased upon autoclaving while the percentage decrease was highly marked in potato. Image analysis of the native and autoclaved starches revealed changes in the granule size distribution patterns. Also, the population mean area of all native starch granules considerably increased upon autoclaving. Acetyl binding capacity, measured at 5% and 10% acetic anhydride addition levels, was higher in autoclaved than in native starches. Furthermore, autoclaving had no influence on starch cationization, studied at 3% and 6% reagent addition levels. The results indicated that the changes in starch molecular organization caused by autoclaving enhanced its reactivity towards acetylation but not cationization.     

不同分子量辛烯基琥珀酸蜡质玉米淀粉酯的制备及其性能

以蜡质玉米淀粉为原料,辛烯基琥珀酸酐(OSA)为酯化剂,β-淀粉酶为酶解剂,制备了不同分子量辛烯基琥珀酸蜡质玉米淀粉酯(OSAS),并测定了其理化特性。结果表明:不同分子量(1.0×104~2.0×105 Da) OSAS的黏度在0.0035~0.0010 Pa·s范围内随分子量下降显著(P<0.05)降低,糊透明度自28.6%降低至23.1%,凝沉性和膨胀度也均随分子量降低而下降;辛烯基琥珀酸酐对蜡质玉米淀粉的酯化作用主要发生在蜡质玉米淀粉颗粒表面,酶解处理不会引入新基团。本研究初步揭示了OSAS分子量与其理化性质间的相互关系。     

乙酰化辛烯基琥珀酸蜡质玉米淀粉酯的制备及性质研究

以蜡质玉米淀粉为原料,选取乙酸酐和辛烯基琥珀酸酐对其进行双重酯化改性,以取代度为衡量标准,确定了蜡质玉米双重酯化淀粉的制备顺序是先进行乙酸酐的乙酰化再进行辛烯基琥珀酸酐的酯化,得到产物乙酰化辛烯基琥珀酸蜡质玉米淀粉酯。按照确定好的酯化顺序,以实验室自制取代度为0.0768的乙酰化淀粉为原料,采用单因素和正交实验的方法研究湿法工艺制备乙酰化辛烯基琥珀酸蜡质玉米淀粉酯,得出最佳工艺条件为:在辛烯基琥珀酸酐加入量为3%的情况下,淀粉乳初始浓度30%,反应体系pH8.5,反应温度35℃,反应时间4h。采用最佳工艺条件所得产品辛烯基琥珀酸酐酯化取代度为0.0197,利用红外光谱分析方法对乙酰化辛烯基琥珀酸蜡质玉米淀粉酯的结构进行了初步表征,并对产品的乳化性及乳化稳定性、透明度、表观黏度等性质做了测定和分析。     

Characteristics and application of octenyl succinic anhydride modified waxy corn starch in sausage

Native and acid‐hydrolyzed wx corn starches were modified by octenyl succinic anhydride (OSA) in aqueous slurry systems. The characteristics of the modified wx corn starches and their effects on chicken meat sausages were evaluated by means of FT‐IR, rapid visco analyser, SEM, and texture profile analysis. FT‐IR spectroscopy indicated that the ester carbonyl groups in the OSA modified native and acid‐hydrolyzed starches were characterized at 1725 cm⁻¹. The process of OSA modification could achieve starch derivatives, which had higher viscosities, better paste clarity and freeze–thaw stability than the native counterparts. Texture results showed that the hardness, springiness, cohesiveness, and chewiness of the sausage increased as OSA‐H0 was added (p < 0.05). SEM revealed that the sausages with native wx corn starch had larger and uneven pores, while it was comparatively compact for the sausages with OSA starches. The OSA modified wx corn starch offered a great potential to be used in meat products to enhance textural quality.     

Production and characterization of digestion‐resistant starch by the reaction of Neisseria polysaccharea amylosucrase

Recombinant amylosucrase (200 U/mL) from Neisseria polysaccharea was used to produce digestion‐resistant starch (RS) using 1–3% (w/v) corn starches and 0.1–0.5 M sucrose incubated at 35°C for 24 h. Characterization of the obtained enzyme‐modified starches was investigated. Results show that the yields of the enzyme‐modified starches were inversely proportional to the original amylose contents of corn starches. After enzymatic reaction, insoluble RS contents increased by 22.3 and 20.7% from 6.9% of waxy and 7.7% of normal corn starches, respectively, using 3.0% starch as acceptor and 0.3 M sucrose as donor, while amylomaize VII showed the lowest increase (8.5%) in RS content. The crystalline polymorph of these enzyme‐modified starches resulted in the B‐type immediately after enzymatic reaction. The enzyme‐modified starches displayed higher melting peak temperatures (85.6–100.6°C) compared to their native starch counterparts (70.1–78.4°C). After enzymatic reaction, pasting temperature increased in waxy (71.9 → 77.6°C) and normal corn starches (75.3 → 80.6°C), and the peak viscosity of waxy corn starches increased from 264 to 349 RVU, whereas that of normal corn starches decreased from 235 to 66 RVU.     

Physical Stability of Octenyl Succinate–Modified Polysaccharides and Whey Proteins for Potential Use as Bioactive Carriers in Food Systems

The high cost and potential toxicity of biodegradable polymers like poly(lactic‐co‐glycolic)acid (PLGA) has increased the interest in natural and modified biopolymers as bioactive carriers. This study characterized the physical stability (water sorption and state transition behavior) of selected starch and proteins: octenyl succinate–modified depolymerized waxy corn starch (DWxCn), waxy rice starch (DWxRc), phytoglycogen, whey protein concentrate (80%, WPC), whey protein isolate (WPI), and α‐lactalbumin (α‐L) to determine their potential as carriers of bioactive compounds under different environmental conditions. After enzyme modification and particle size characterization, glass transition temperature and moisture isotherms were used to characterize the systems. DWxCn and DWxRc had increased water sorption compared to native starch. The level of octenyl succinate anhydrate (OSA) modification (3% and 7%) did not reduce the water sorption of the DWxCn and phytoglycogen samples. The Guggenheim–Andersen–de Boer model indicated that native waxy corn had significantly (P < 0.05) higher water monolayer capacity followed by 3%‐OSA‐modified DWxCn, WPI, 3%‐OSA‐modified DWxRc, α‐L, and native phytoglycogen. WPC had significantly lower water monolayer capacity. All Tg values matched with the solid‐like appearance of the biopolymers. Native polysaccharides and whey proteins had higher glass transition temperature (Tg) values. On the other hand, depolymerized waxy starches at 7%‐OSA modification had a “melted” appearance when exposed to environments with high relative humidity (above 70%) after 10 days at 23 °C. The use of depolymerized and OSA‐modified polysaccharides blended with proteins created more stable blends of biopolymers. Hence, this biopolymer would be suitable for materials exposed to high humidity environments in food applications.     

Starch as a potential fat replacer for application in cheese: Behaviour of different starches in casein/starch mixtures and in the casein matrix

The behaviour of different types of native starch (regular, waxy, and high-amylose maize starch) and modified starch (acetylated/adipate maize starch with regular basis and hydroxypropylated/phosphate maize starch with waxy basis) in mixtures with calcium caseinate (CN) and embedded in casein matrix were studied to understand the potential use of starch as a fat replacer in fresh cheese. In mixtures with CN, the modified starches showed high viscosities (peak and final), indicating high potential for water retention in cheese, as well as low peak temperature and low variation of enthalpy (ΔH), requiring thereby low gelatinisation temperatures. They also showed low tendency for retrogradation, high swelling power, and good thermomechanical resistance. Furthermore, due to the very low loss in whey of both modified starches and their presence embedded in the protein matrix acting as inert fillers, they can be considered as promising fat replacers in cheese.     

酸解对不同链/支比含量玉米淀粉特性的影响

以4种不同链/支比含量的玉米淀粉为原料,酸解处理不同时间,以酸解玉米淀粉的形貌特性、冻融稳定性、膨胀度、溶解度、晶体性质为指标衡量不同酸解时间对玉米淀粉结构性质的影响。结果表明:4种玉米淀粉酸水解程度的顺序为:蜡质玉米普通玉米淀粉G50G80。酸解后,同品种的4种玉米淀粉的析水率随着酸解天数的增加而增加;溶解度增加,膨胀度降低。酸解并未改变淀粉的晶型,随着酸解时间的延长,蜡质玉米淀粉和普通玉米的相对结晶度先增大后保持不变,G50和G80的相对结晶度随着酸解时间的增加而增大。表明酸解对低直链淀粉(蜡质玉米淀粉和普通玉米淀粉)的结构、性能影响最大。     

A comparison of native and acid thinned normal and waxy corn starches: Physicochemical, thermal, morphological and pasting properties

The starches isolated from normal and waxy corn varieties were hydrolyzed with hydrochloric acid (0.14 mol equivalent/L) and evaluated for physicochemical and functional properties. Acid thinning decreased the amylose content and swelling power but increased the solubility. The light transmittance of acid thinned (AT) starch pastes was higher than those of their native starches after similar storage intervals. The scanning electron microscopic observation demonstrated that the acid thinning did not cause any disruption of the granular crystalline structure. Native normal corn starches showed lower onset temperature (T_o) and peak temperature (T_p) as compared to their counterpart AT starches, whereas the reverse was observed for waxy corn starch. Enthalpy of gelatinization (ΔH_gel) was lower in AT normal and waxy starches as compared to their native starches. The percentage of retrogradation (%R) was significantly higher for native corn starches as compared to their AT starches. A significant reduction in peak—(P_V), trough—(T_V), breakdown—(B_V), final—(F_V), and setback viscosity (S_V) was observed by acid thinning, and the reduction was more pronounced in AT waxy starches. Among AT starches, AT waxy starch showed the lowest values of P_V, T_V, B_V, F_V and S_V.     

Microstructural and physicochemical properties of heat-moisture treated waxy and normal starches

Starches from normal rice (21.72% amylose), waxy rice (1.64% amylose), normal corn (25.19% amylose), waxy corn (2.06% amylose), normal potato (28.97% amylose) and waxy potato (3.92% amylose) were heat-treated at 100 °C for 16 h at a moisture content of 25%. The effect of heat-moisture treatment (HMT) on morphology, structure, and physicochemical properties of those starches was investigated. The HMT did not change the size, shape, and surface characteristics of corn and potato starch granules, while surface change/partial gelatinization was found on the granules of rice starches. The X-ray diffraction pattern of normal and waxy potato starches was shifted from B- to C-type by HMT. The crystallinity of the starch samples, except waxy potato starch decreased on HMT. The viscosity profiles changed significantly with HMT. The treated starches, except the waxy potato starch, had higher pasting temperature and lower viscosity. The differences in viscosity values before and after HMT were more pronounced in normal starches than in waxy starches, whereas changes in the pasting temperature showed the reverse (waxy > normal). Shifts of the gelatinization temperature to higher values and gelatinization enthalpy to lower values as well as biphasic endotherms were found in treated starches. HMT increased enzyme digestibility of treated starches (except waxy corn starch); i.e., rapidly and slowly digestible starches increased, but resistant starch decreased. Although there was no absolute consistency on the data obtained from the three pairs of waxy and normal starches, in most cases the effects of HMT on normal starches were more pronounced than the corresponding waxy starches.     

不同蜡制玉米淀粉对肌原纤维蛋白凝胶特性的影响

将蜡制玉米淀粉、酯化蜡制玉米淀粉和交联酯化蜡制玉米淀粉以添加量分别为0%、2%、4%、6%、8%、10%添加到肌原纤维蛋白中,形成蛋白淀粉复合物,研究3?种淀粉对肌原纤维蛋白凝胶保水性、质构特性、白度值、表面疏水性、流变特性和微观结构的影响。结果表明,相比纯肌原纤维蛋白,淀粉均能显著提高复合凝胶的保水性、硬度和弹性（P＜0.05）,且随添加量的增加而显著增加（P＜0.05）,但在添加量为10%时,各指标上升不显著（P＞0.05）,其中交联酯化蜡制玉米淀粉效果最好;3?种淀粉均能增加复合凝胶的白度值,但交联酯化蜡制玉米淀粉的添加会使复合凝胶的白度值过大（P＜0.05）,对色泽不利;同时,淀粉能显著提高复合蛋白的表面疏水性和凝胶的弹性模量（P＜0.05）,且随着添加量的增加而显著增加（P＜0.05）,与肌原纤维蛋白凝胶相比,复合凝胶结构趋于致密均匀。在实验的3?种淀粉中,除色泽因素外,交联酯化蜡制玉米淀粉提高凝胶性能的效果要优于其他两种淀粉。?     

Substitution of wheat starch with non-wheat starches and cross-linked waxy barley starch affects sensory properties and staling of Arabic bread

Substitution of starch from barley, corn, oat, potato, rice or sorghum for prime wheat starch in the formulation of Arabic bread resulted in breads with significantly (P < 0.05) different textural attributes from regular wheat bread except for barley starch. Substitution of waxy barley starch (957 g kg⁻¹ amylopectin) for wheat starch (279 g kg⁻¹ amylopectin) resulted in bread that was not significantly different from regular wheat bread when assessed in the fresh state. However, upon aging, the waxy barley starch-containing bread staled at a significantly (P < 0.05) faster rate than regular wheat bread. Breads made with waxy barley starch cross-linked with 50, 200 or 500 ppm phosphorus oxychloride showed higher enthalpy of melting (ΔH) upon aging and staled faster than the bread formulated with waxy barley starch. These findings suggest that amylopectin retrogradation is one of the determinants of Arabic bread staling and that cross-linking promotes recrystallisation of amylopectin, possibly by keeping the polymer chains in close proximity. The rate of staling in breads formulated with cross-linked waxy barley starch decreased with increasing levels of cross-linking, possibly owing to restrictions in the degree of starch swelling. © 1999 Society of Chemical Industry     

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.     

Development and Physicochemical Characterization of New Resistant Citrate Starch from Different Corn Starches

Resistant starch has drawn broad interest for both potential health benefits and functional properties. In this study, a technology was developed to increase resistant starch content of corn starch using esterification with citric acid at elevated temperature. Waxy corn, normal corn and high‐amylose corn starches were used as model starches. Citric acid (40% of starch dry weight) was reacted with corn starch at different temperatures (120–150°C) for different reaction times (3–9 h). The effect of reaction conditions on resistant starch content in the citrate corn starch was investigated. When conducting the reaction at 140°C for 7 h, the highest resistant starch content was found in waxy corn citrate starch (87.5%) with the highest degree of substitution (DS, 0.16) of all starches. High‐amylose corn starch had 86.4% resistant starch content and 0.14 DS, and normal corn starch had 78.8% resistant starch and 0.12 DS. The physicochemical properties of these citrate starches were characterized using various analytical techniques. In the presence of excess water upon heating, citrate starch made from waxy corn starch had no peak in the DSC thermogram, and small peaks were found for normal corn starch (0.4 J/g) and Hylon VII starch (3.0 J/g) in the thermograms. This indicates that citrate substitution changes granule properties. There are no retrogradation peaks in the thermograms when starch was reheated after 2 weeks storage at 5°C. All the citrate starches showed no peaks in RVA pasting curves, indicating citrate substitution changes the pasting properties of corn starch as well. Moreover, citrate starch from waxy corn is more thermally stable than the other citrate starches.     

Influence of moisture content on the degradation of waxy and normal corn starches acid-treated in methanol

Waxy and normal corn starches with different moisture contents, 5.1-16.9% and 4.8-15.9%, respectively, were prepared and treated in methanol containing 0.36% HCl at 45 °C for 1 h. Recovery of all the treated starches was found to be above 90%. Peak viscosity, gelatinization temperature and enthalpy change of gelatinization of waxy and normal corn starches decreased after treatment and this decrement was found to be more in treated starches having lower initial moisture content. The weight-average degree of polymerization and chain length (CL) of waxy and normal corn starches decreased upon acid-methanol treatment. The decrement ratio of molecular weight of modified starches was found to be negatively correlated with the initial moisture content of the starches. The decrement ratio of normal corn starch was higher than waxy corn starch with similar moisture content of starch. The content and CL of long chain fraction of amylopectin for waxy corn starch slightly decreased after treatment, while no obvious trend was found among starches with different moisture contents. CL of amylose for acid-methanol-treated normal corn starch decreased and this change was found to be higher in starches with lower initial moisture contents. Results demonstrated that the initial moisture content of starch granules strongly influenced the functional properties and degradation of starch treated by acid in methanol.     

Amylopectin structure of heat–moisture treated starches

The effects of heat–moisture treatment (HMT; moisture content of 25%, at 100°C for 24 h) on starch chain distribution and unit chain distribution of amylopectin in normal rice, waxy rice, normal corn, waxy corn, normal potato, and waxy potato starches were investigated. After HMT, starch chain distribution (amylose and amylopectin responses) of waxy corn and potato starches were identical to those of untreated starches, whereas the chromatographic response of waxy rice starch showed a slight decrease, but with a slight increase in peak tailing. This result indicated that HMT had no (or very limited) effect on the degradation of amylopectins. Analysis of unit chain distribution of amylopectins revealed that waxy characteristics affected the molecular structure of amylopectin in untreated starches, i.e., the CL of normal‐type starches was greater than that of waxy‐type starches. After HMT, the CL and unit chain distribution of all starches were no different than those of untreated starches. The results implied that changes in the physico‐chemical properties of HMT starches would be due to other phenomena rather than the degradation of amylopectin molecular structure. However, the thermal degradation of amylopectin molecules of waxy starches could occur by HMT at higher treatment temperatures (120 and 140°C).     

Digestibility and Pasting Properties of Rice Starch Heat‐Moisture Treated at the Melting Temperature (Tm )

Non‐waxy and waxy rice starches adjusted to 20% moisture (wet based, w.b.) were heated in a differential scanning calorimeter to determine the optimum parameters for producing slowly digestible starch (SDS). Starches heated to the temperature of melting (T_m) and held for 60 min in the calorimeter showed a slow digestibility compared to unheated samples. Digestibility decreased by 25 and 10%, respectively, for non‐waxy and waxy rice starches relative to non‐treated starches. Heat‐moisture treatment of waxy corn, non‐waxy corn and wheat starches at the T_m determined for non‐waxy rice starch did not result in significant decreases in digestibility. For waxy rice starches heat‐treated in microwave or conventional ovens at the T_m , there were slight but significant increases in digestibility of the treated starches compared to non‐treated starches at all incubation times. Digestibility was higher for starches heated for 30 min than for 60 min. Non‐waxy rice starches did not show any significant changes in digestibility. Heat‐moisture treatment at the T_m and the holding time of sample at that temperature in a differential scanning calorimeter were found to be significant to the formation of slowly digestible heat‐moisture treated starch.