The effect of acid and glucoamylase hydrolysis on partial physicochemical properties and characteristics of Dioscorea alata Linn. starch

Dioscorea alata Linn. (D. AL) rich in starch was widely used as food and medicine. This work aimed to compare the effect of acid and glucoamylase on the starch of different reaction time. The physicochemical properties of the native and hydrolyzed starches, such as swelling power (SP), starch solubility (SOL), and paste clarity were also determined in this study. The native and modified starches by acid and glucoamylase were compared and characterized by scanning electron microscope (SEM) and secondary derivative FT‐IR spectroscopy. The morphological characteristics of native D. AL starch granules revealed by SEM varied from round to oval or elliptic with smooth surface. SEM showed that glucoamylase primarily attacked the exterior of starch granules and permeate into the interior by the cracks formed on the surface. Owing to acid hydrolysis, the starch granules were depressed and transformed to bread‐like in shape and then broke into irregular lumps with particles adhered. From secondary derivative FT‐IR spectrum, the intensities of the two peaks from acid and enzyme hydrolysis starches at 1137 and 1066/cm were stronger than native starch. Some new peaks appeared due to hydrolysis. The digested starches exhibited a lower SOL and SP than native starch in water as the temperature increasing. The light transmittance of the digested starches was significantly higher than that of native starch paste and decreased with increase in storage period.     

Zur genaueren Kenntnis durch Temperatureinfluß modifizierter Wachsmais- und Amylosestärke

Contribution on Waxy Maize Starch and High Amylose Starch Modified under the Influence of Temperature. The starches of the two genetic varieties of the corn grain, waxy maize starch and high amylose starch, were subjected to the influence of different temperatures. Subsequently, the physico-chemical properties of the modified starches were examined. Waxy maize starch which mainly consists of amylopectin, and high amylose starch which contains a high portion of linear chains of polymerized glucose units are interesting test materials because of their properties which are different by nature. Waxy maize starch with its high viscosity values, great swelling power and good solubility in hot water shows no tendency to settle or retrograde. While the process of freezing the starch granules hardly changes the properties mentioned, the influence of a temperature of 100°C causes morphological changes of a small proportion of grains, including the loss of birefringence. These changes are particularly pronounced after treatment of native starch at 120°C. The properties of the starch pastes were also strongly changed. The native high amylose starch characterized by unusual, oblong starch granules without birefringence, a low viscosity, low swelling power and low solubility showed only minor changes after freezing, whereas a temperature of 100°C resulted in reduced values of solubility and aggregation of the starch granules. A temperature treatment at 120°C and at 125°C brought about changes in the swelling properties, the viscosity and limiting viscosity, settling, swelling power, and solubility of the starch pastes. Attempts were made to conform the changes in the different properties observed with the expected influence of temperature treatment on the intermolecular forces (hydrogen bonds, crossbonding).     

Effect of phosphoric acid treatment on physicochemical,functional, and structural properties of starch extracted from yam (Dioscorea rotundata)

This work was designed to elucidate selected physicochemical, functional, and structural properties of native and modified yam (Dioscorea rotundata) starch. The isolated starch was chemically modified using 5, 10, 15, 20, and 25% phosphoric acid solution at 50°C for 1 h, and yield, swelling power, gelation, water holding capacity, paste clarity, blue value, and amylose and amylopectin content of the native and modified yam starch were determined. Structural changes in the native and starch modified with 25% phosphoric acid were evaluated using Fourier transform infrared spectroscopy and optical microscopy. The result showed that the yield, swelling power, water holding capacity, paste clarity, blue value and amylose and amylopectin content of native yam starch was 33.38% (217 g), 3.84 g/g, 1.0 v/g, 10%, 0.52 and 25.96, respectively, whereas gelation study of the native and modified starch indicated that native starch was viscous and modified starch firm. However, yield, swelling power, water holding capacity, paste clarity, blue value, and amylose content of modified yam starch reduced in a dose dependent manner with phosphoric acid. The reduction in the values of the various functional properties could be associated with the effect of phosphoric acid on the starch granular structure. The result of Fourier transform infrared spectroscopy and optical microscopy revealed that the yam starch was modified by phosphoric acid with changes in functional groups spectra such as –OH stretch (3177 cm^?1), H₂O absorbed (1644 cm^?1) (amorphous region), C-H stretch (2923 cm^?1), CH₂O (1253 cm^?1), and C-O-C (1078 cm^?1) when compared to native starch. The morphology of native and modified yam starch granules ranged from oval to eliptical. However, modified starch granules were rough in surface. In conclusion, the characterized physicochemical and functional properties and structure exhibited by native and modified yam starch indicated that, yam could be a cheap and valuable source of starch for industrial application.     

Physicochemical,crystalline, and thermal properties of native,oxidized, acid,and enzyme hydrolyzed Chinese yam (Dioscorea opposite Thunb) starch

Native yam starch was modified by oxidation (with sodium hypochlorite), acid, and enzyme (with gluco‐amylase), respectively. Ash content, fat content, protein, and AM contents were reduced following modifications. All the modifications reduced swelling capacity whereas improved the solubility. The SEM of the native starch showed the presence of large oval or spherical to small irregular‐shaped granules, however, oxidation and hydrolysis caused collapse of the granules. From the XRD, the typical C‐type XRD pattern of the native starch changed to the typical A‐type XRD pattern of the three modified starches. The above results also demonstrated that amorphous region of yam starch granules was preferentially degraded than crystalline region of granules. DSC showed that oxidation and acid/enzyme hydrolysis reduced peak temperature of gelatinization (T_p) of native starch significantly. Enthalpy of gelatinization (ΔH) of oxidation and enzyme starch was reduced but it has no obviously change following acid modification.     

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。     

发芽对黑糯玉米淀粉特性的影响

将黑糯玉米进行发芽处理后，采用湿法提取工艺制得淀粉。比较发芽黑糯玉米淀粉与未发芽黑糯玉米淀粉的特性。结果表明：发芽处理后淀粉的颗粒保持原有的偏光十字结构；发芽处理后淀粉的溶解度和膨胀度变小；酸水解过程的前6d，发芽处理淀粉水解率比原淀粉大，之后水解率小于原淀粉；发芽处理淀粉糊的透明度高，抗凝沉性强，冻融稳定性好。淀粉性质的变化说明发芽处理使淀粉内部结构发生变化，特别是无定形区的直链淀粉的结合产生了不同稳定性的新的结晶。     

Granule Sizes of Canna (Canna edulis) Starches and their Reactivity Toward Hydration,Enzyme Hydrolysis and Chemical Substitution

Small and large granule fractions were isolated from canna starch (Canna edulis, green leaf cultivar), and their morphology, physicochemical properties, susceptibility towards granular starch hydrolyzing enzymes and chemical reaction with propylene oxide were investigated. Canna starch consisted of a mixed population of large, medium and small granules; the mean of granule diameter was 47.4 μm. The small granules presented round and polygonal shapes, whereas the large granules had oval and elliptical shapes. Significant variations in digestibility of the various granules size by granular starch hydrolyzing enzymes were observed. During the first 24 h, the hydrolysis rate of small granules was higher than that of native and large granule starches. After 72 h, however, the degree of hydrolysis of small granule, large granule and native starches had reached the extent of 19.6%, 32.0% and 27.2%, respectively. The larger the granule size, the higher the MS obtained when modified with propylene oxide, which was due to the higher swelling power of the large granules. The results obtained from this study suggest that small granules had lower water and chemical affinity when compared with the bigger ones. The difference in the reactivity of small and large granules could be presumably attributed to the starch components (amylose and amylopectin) and their organization of glucan chains in ordered and/or less ordered structure of these two fractions.     

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.     

Isolation and physicochemical characterisation of starch from cocoyam (Colocasia esculenta) grown in Malawi

BACKGROUND: The aim of this study was to determine the physicochemical properties of starches isolated from Malawian cocoyams and compare them with those of cassava and corn starches. RESULTS: The purity of the isolated starches varied from 851 to 947 g kg^?1 and pH from 4.93 to 6.95. Moisture, ash, protein, fat and amylose contents ranged from 104 to 132, 0.3 to 1.5, 3.5 to 8.4, 0.9 to 1.6, and 111 to 237 g kg^?1, respectively. Cocoyam starches gave higher potassium and phosphorus but lower calcium levels than the other starches. The shape of starch granules varied from spherical to polygonal with cocoyam starches displaying smaller‐sized granules than cassava and corn starches. Cocoyam starches gave a higher wavelength of maximum iodine absorption and blue value but lower reducing capacity values than cassava and corn starches. The extent of acid hydrolysis of the starches also differed. Cocoyam starches exhibited amylopectin molecules of higher molecular weights but amylose molecules of lower molecular weights than cassava and corn starches. Cocoyam starches exhibited lower water absorption capacity and swelling power, paste clarity and viscosity but higher solubility, gelatinisation temperatures and retrogradation tendencies than cassava and corn starches. CONCLUSIONS: The physicochemical properties of native Malawian cocoyam starches vary among the different accessions and differ from those of cassava and corn starches. Copyright © 2010 Society of Chemical Industry     

Physico-chemical Properties of Black Pepper Starch

Unusually small-sized (2 - 2.5 μ) starch granules were isolated from black pepper (Piper nigrum) in 25 – 38% yield. The granules having an amylose content of 18% were non-ionic in nature and exhibited low solubility and low swelling power in water, but high solubility in DMSO. The amylogram peak viscosity of the starch was about 530 B. U. with a very little set back (∼ 550 B. U.) on cooling, indicating a stable linear molecule very strongly associated with amylopectin. X-ray power pattern revealed the starch granules to be of A-type.     

玉米淀粉退火处理及其性质变化

采用扫描电子显微镜(SEM)、激光粒度分析仪(LPA)、X射线粉末衍射仪(XRD)和差示扫描量热仪(DSC)研究退火处理对玉米淀粉颗粒形貌、粒径大小、晶体结构和热力学性质的影响。结果显示:退火处理会改变玉米淀粉颗粒的外貌,使其微孔增多,孔径增大;退火处理会增加玉米淀粉颗粒粒径;退火处理不涉及玉米淀粉晶体结构的变化;退火处理会使玉米淀粉糊化温度显著增高,糊化温度范围变窄;原玉米淀粉(NC)和退火处理玉米淀粉(AC)的溶解度和膨胀率都随着温度的升高而增大,在相同温度条件下,退火处理玉米淀粉(AC)溶解度和膨胀率均小于原玉米淀粉(NC)。     

Chemical and Physical Characterisation of Grain Tef [Eragrostis tef (Zucc.) Trotter] Starch Granule Composition

Chemical and physical properties of starch granules isolated from five grain tef (Eragrostis tef) varieties were characterised and compared with those of maize starch. Endogenous starch lipids extracted with hot water‐saturated n‐butanol and total starch lipids extracted with n‐hexane after HCl hydrolysis were 7.8 mg/g (mean) and 8.9 mg/g (mean), respectively, slightly lower than in the maize starch granules. The starch phosphorus content (0.65 mg/g) was higher than that of maize starch but virtually the same as reported for rice starch. The starch granule‐swelling factor was lower than that of maize starch and extent of amylose leaching was higher. The starch X‐ray diffraction pattern was characteristic of A type starch with a mean crystallinity of 37%, apparently lower than the crystallinity of maize starch and more similar to that reported for rice and sorghum starches. The starch DSC gelatinisation temperature was high, like for other tropical cereals; T_o, T_p, T_c and ΔH were in the range 63.8—65.4, 70.2—71.3, 81.3—81.5 °C and 2.28—7.22 J/g, respectively. The lower swelling, apparently lower percentage crystallinity and lower DSC gelatinisation endotherms than maize starch suggest that the proportion of long amylopectin A chains in tef starch is smaller than in maize starch.     

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.     

高直链玉米III型抗性淀粉制备及其结构和特性

以高直链玉米淀粉G50和G70为原料,经酸解、糊化、脱支和重结晶步骤获得III型抗性淀粉,通过退火与压热处理以进一步提升淀粉的抗性比例。采用扫描电子显微镜、X射线衍射、差示扫描量热、快速黏度分析等方法,研究淀粉颗粒形貌、结晶结构、热特性及糊化特性,利用Englyst法测试淀粉消化特性。结果表明：高直链玉米淀粉G50和G70酸解后的得率分别为77.9%和84.5%,重结晶后的得率降为54.4%和70.2%。原G50和G70改性后,淀粉颗粒形貌被破坏,形成大小不等、颗粒形貌不规则的团聚体;淀粉结晶型由B＋V型转变为A＋V型,且结晶度升高;淀粉糊化温度升高,且加热过程中黏度几乎消失。溶解与膨胀特性结果表明,经酸解、糊化、脱支和老化处理后原G50和G70的溶解性显著升高,退火和压热处理后降低了III型抗性淀粉的溶解性和膨胀度。体外消化特性分析表明,改性后的G50和G70具备更强的抗消化性能,抗性淀粉含量最高可达80.5%（G70-RS3-压热20%）。本研究的改性处理能有效提高高直链玉米淀粉G50和G70中抗性淀粉含量,同时抗性淀粉含量与结晶度和糊化温度呈显著正相关。     

Properties of Low‐substituted Cationic Starch Derivatives Prepared by Different Derivatisation Processes

Cationic starch ethers prepared by the chemical reaction of starch with a quaternary ammonium reagent are commercially important derivatives. Cationic potato starch derivatives were produced under pilot‐scale conditions, employing four different principles. Wet cationisation was carried out by the slurry and paste processes, in which the cationic reagent and catalyst are added to the starch. Besides being prepared by these more commonly used processes, cationic starches were also produced by dry cationisation and by adding the cationic reagent during extrusion of starch. The cationic reagent used was 2,3‐epoxypropyltrimethylammonium chloride. Derivatives with three graded degrees of substitution (DS) between 0.03 and 0.12 were prepared by each process. The physical properties of the derivatives were analysed by the following methods: polarised light microscopy, X‐ray scattering, differential scanning calorimetry (DSC), solubility and swelling behaviour, and High‐Performance Size‐Exclusion Chromatography‐Multiangle Laser Light Scattering (HPSEC‐MALLS). The degree of substitution was determined by high resolution ¹³C‐NMR spectroscopy after hydrolysis with trifluoroacetic acid. The properties of the cationic starch derivatives were highly dependent on the derivatisation method. The granular structure of the starch was not visibly affected by the slurry process. Products from the semi‐dry reaction showed some granular damage, which was particularly evident after suspension of the granules in water. In the paste and extrusion processes, the starch granules were completely destroyed. Swelling temperatures and enthalpies can be determined only for starch derivatives that still retain a granular structure. As a result, samples from the paste and extrusion reactions exhibited no swelling endotherm in DSC. The samples from the slurry process showed a shift in the swelling temperature range towards lower temperature and a decrease in swelling enthalpy both as compared to native potato starch and also with increasing DS. Similar behaviour was found for the samples from the semi‐dry process. The swelling temperature region was comparable to that of the slurry samples for the same DS but the swelling enthalpy was distinctly lower, indicating that the granular structure of the starch was altered far more by the semi‐dry than the slurry process. Swelling in excess water and solubility were affected primarily by the cationisation process, while the influence of DS was of minor importance. The extrusion products had pronounced cold‐water solubility, the semi‐dry products showed increasing cold‐water solubility with increasing DS, the paste products were highly swollen in cold water and the slurry products were insoluble in cold water. All products were soluble in hot water but the state of dissolution was different. The molar mass distributions of the samples were determined after dissolution by pressure cooking. The different derivatisation methods resulted in characteristic molar mass distributions. The average molar mass decreased in the order slurry, semi‐dry‐, paste and extrusion process.     

无水有机醇介质中盐酸对小麦淀粉性质的影响

研究了小麦淀粉在有机醇溶液中酸变性前后的物化性质。采用无水甲辞、无水乙醇、异丙醇及正丁醇为溶剂,用盐酸对小麦淀粉进行改性。结果表明:经酸处理的小麦淀粉与原淀粉相比,随有机醇介质(从甲醇到正丁醇)碳原子数量的增加,颗粒表面出现的形变逐渐明显、冻溶稳定性依次减弱、透光率依次增强,在不同温度下溶解度逐渐增加,膨胀度逐渐降低,但改性后淀粉的黏度很小,几乎检测不出。说明酸在不同有机醇介质中对淀粉的作用程度不同,从甲醇到丁醇依次增强。     

Structural and Physicochemical Characteristics of Lintnerized Native and Sour Cassava Starches

The comprehension of the structure of starch granules is important for the understanding of its physicochemical properties. Native and sour cassava starches after being analyzed with respect to their pasting properties and baking expansion capacity, were treated with 2.2 N HCl at 38 °C for a maximum of nine days. The starch granules remaining after lintnerization were analyzed for amylose content and intrinsic viscosity, by X‐ray diffraction, scanning electron microscopy and chromatographic analysis. The results indicated that the acid hydrolysis on all starches occurred in two steps. The first one, with high hydrolysis rate, was characterized by a quick degradation of the amorphous part of the granules whereas the second step, with lower hydrolysis rate, was characterized by a higher resistance of the organized areas of the granules to acid treatment. Most of the amylose chains were found in the amorphous areas of starch granules only a small percentage was involved in the crystalline regions. The microscopic and chromatographic analysis demonstrated that the acid hydrolysis was not able to disrupt the entire granular crystalline structure. Fermented starch showed amylose and/or amylopectin chain fractions resistant to pullulanase, probably due to structural alterations during fermentation.     

Characterization of Potato Starch and Its Monoglyceride Complexes

Native potato starch granules and those complexed below the gelatinization temperature with 1-(C₈ to C₁₈)-monoglycerides were compared for solubility, swelling power (SP), viscosity, heat stability and water binding capacity (WBC). X-ray diffraction analysis proved that complexes were true clathrates (inclusion) compounds. Clathrate stability was a function of monoglyceride chain length. The presence of clathrates in granules decreased solubility by up to 90% and SP up to 10-times, while WBC dropped from 0.39 to as low as 0.25 g water/g starch. Endotherm characteristics were given for gelatinization, most perfect crystallite, and clathrate fusions. Enthalpies per mole glucose units of 15.4 kcal/mole for native starch and 27.5 for clathrate were obtained irrespective of monoglyceride chain length.     

湿热处理玉米淀粉的溶胀和水解性质初探

对三种不同链淀粉含量的玉米淀粉(高链玉米淀粉、普通玉米淀粉和蜡质玉米淀粉)经湿热处理前后的溶胀及酸、酶水解性质进行研究,探索湿热处理对淀粉微观性质的影响。研究结果表明:湿热处理后淀粉的膨胀度和溶解度较原淀粉减小;湿热处理淀粉在酸、酶作用初期水解率比原淀粉大,后期由于经湿热处理后淀粉链之间的重新结合,形成了新的双螺旋结构,结合更为紧密,酸、酶难于作用,水解率较原淀粉降低。     

Preparation of granular cold‐water‐soluble corn starch by surface modification with poly(ethylene glycol)

The main target of this study is to synthesize one kind of granular cold‐water‐soluble (GCWS) starch by grafting poly(ethylene glycol) (PEG) segments onto the surface of native starch granules. It is found that the grafting process could introduce long PEG chains onto the granule surface, resulting in the presence of special micropits on the granule surface, as characterized by SEM. The cold water solution test verified that the resultant PEG‐grafted corn starches exhibited excellent cold‐water‐solubility. The XRD analysis and further polar optical micrograph (POM) observation indicated that the crystallites structure inside the PEG‐grafted corn starches was fully preserved, since no gelatinization process was involved. The present study provides a new train of thought that we can adjust the physiochemical properties of starch granules with proper surface modification.