A Study of Some Physicochemical Properties of High‐Crystalline Tapioca Starch

Tapioca starch was partially hydrolyzed in hydrochloric acid solution at room temperature for various lengths of time to obtain high‐crystalline starches. RVA viscoamylograms of acid‐modified starches demonstrated a very low viscosity as compared to that of native tapioca starch. The relative crystallinity of native and acid‐modified tapioca starches were measured by X‐ray diffraction ranging from 39.53% to 57.75%. The native and acid‐modified tapioca starches were compressed into tablets using various compression forces. The % relative crystallinity of starch increased with the increase in hydrolysis time and the crushing strength of the tablet was also increased in line with the crystallinity while the amylose content decreased when the crystallinity increased. These results suggested that the erosion of amylose might cause the rearrangement of starch structure into a new more tightly packed form, which provided the higher crushing strength for the tablets.     

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 Study of Annealing and Freeze‐Thaw Stability of Acid‐Modified Tapioca Starches by Differential Scanning Calorimetry (DSC)

Tapioca starch was partially hydrolyzed by 6% (w/v) hydrochloric acid at room temperature for various lengths of time. Annealing and freeze‐thaw stability of the acid‐modified starches were studied using Differential Scanning Calorimetry (DSC). In the annealing study, as the hydrolysis time increased, the effect of annealing on narrowing and shifting the endothermic peak to a higher temperature was decreased. The endothermic transition of annealed 48‐h acid‐modified tapioca starch showed a narrow peak and a broad shoulder, corresponding to the melting of the amylopectin double helices (crystalline regions) and the retrograded partially hydrolyzed amylose, respectively. This effect of annealing on the sharpening of the endotherm was less pronounced on acid‐modified tapioca starches annealed for 192 h and 768 h, respectively. These results indicated that annealing leads to more homogeneous crystallites and this effect is enhanced when the material contains more amorphous and homogeneous domains. In the case of the freeze‐thaw stability study, the melting endotherm of recrystallized amylopectin became larger with increasing hydrolysis time. The first detectable endotherm of native tapioca retrograded gel was observed after five cycles, while all acid‐modified retrograded gels showed the melting endotherm after only one cycle. Increasing hydrolysis time may increase the proportion of short chain amylose and amylopectin molecules, which are able to form double helices, resulting in an increase in the enthalpy and a higher retrogradation rate of the gel.     

Preparation and Characterization of Annealed‐Enzymatically Hydrolyzed Tapioca Starch and the Utilization in Tableting

Tapioca starch was annealed at 60°C for 90 min followed by hydrolysis with α‐amylase at 60°C at various lengths of time (30, 60 and 120 min) to obtain high‐crystalline starches. The reaction products were subjected to spray drying to obtain annealed–enzymatically hydrolyzed–spray dried tapioca starch (SANET) in the form of spherical agglomerated granules. The properties of SANET were compared with those of annealed–spray dried tapioca starch without enzymatic treatment (SANT) and native–spray dried tapioca starch (SNT). Scanning electron micrographs of the starch samples were used to study the morphological changes and to suggest the mode of enzyme attack during hydrolysis. The á‐amylase preferentially attacked the interior of the starch granules, leaving a deep round hole on the starch granule surface. It was found by X‐ray diffraction that both annealing and amylolysis did not alter the A type diffraction pattern. The% relative crystallinity of SANET was raised with increasing hydrolysis time and with decreasing amylose content. High performance size exclusion chromatography (HPSEC) demonstrated the decrease of the degree of polymerization (DP) of the amylose fraction of SANET after prolonged hydrolysis. For the utilization of SANET as tablet filler, it was directly compressed by a tablet compression machine at 4 kN to obtain tablets. The increased relative crystallinity of starch resulted in increased crushing strength and disintegration time, but in a decreased tablet friability.     

Physicochemical Properties of Starch Isolated from Bracken (Pteridium aquilinim) Rhizome

Bracken (Pteridium aquilinum) is an important wild plant starch resource worldwide. In this work, starch was separated from bracken rhizome, and the physicochemical properties of this starch were systematically investigated and compared with 2 other common starches, that is, starches from waxy maize and potato. There were significant differences in shape, birefringence patterns, size distribution, and amylose content between bracken and the 2 other starches. X‐ray diffraction analysis revealed that bracken starch exhibited a typical C‐type crystalline structure. Bracken starch presented, respectively, lower and higher relative degree of crystallinity than waxy maize and potato starches. Ordered structures in particle surface differed among these 3 starches. The swelling power tendency of bracken starch in different temperature intervals was very similar to that of potato starch. The viscosity parameters during gelatinization were the lowest in waxy maize, followed by bracken and potato starches. The contents of 3 nutritional components, that is, rapidly digestible, slowly digestible, and resistant starches in native, gelatinized, and retrograded starch from bracken rhizome presented more similarities with potato starch than waxy maize starch. These finding indicated that physicochemical properties of bracken starch showed more similarities with potato starch than waxy maize starch.     

微细化处理对大米淀粉物化特性及血糖指数的影响

本实验采用扫描电镜、X-射线衍射、差示量热扫描仪及体外消化法,对微细化大米淀粉的凝聚态结构、颗粒大小、晶体特性、热特性和消化特性、淀粉水解率、水解动力学常数和血糖指数的变化进行了分析。实验结果表明:干法球磨微细化处理对大米淀粉的凝聚态结构和消化性影响显著。经球磨的微细化大米淀粉颗粒分布均匀,粒度减小;有序的微晶区结构被破坏,但亚微晶区结构增加;焓变曲线吸热峰消失,淀粉在常温下开始糊化;抗性淀粉含量显著降低,可消化淀粉含量增加,微细化处理12h可提高血糖指数,但延长球磨时间,淀粉水解率增加不显著。     

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.     

Characterisation of low‐digestible starch fractions isolated from amylosucrase‐modified waxy corn starch

Amylosucrase (AS) modification of starch increases the slowly digestible (SDS) and resistant starch (RS) fractions. However, the characteristics and formation mechanism of each fraction of AS‐modified starch have not been determined yet. Therefore, this study isolated SDS and/or RS from AS‐modified waxy corn starches and investigated their structural characteristics. The amount of SDS+RS and RS had a positive correlation with the proportion of the medium length (13–24 of degree of polymerisation) branched chains of amylopectin. The relative crystallinity increased in the order of AS‐modified starch < SDS+RS < RS, while maintaining the B‐type crystalline structure. The thermal transition temperature ranges of the isolated fractions were also higher than those of undigested starches. The medium branched chains of amylopectin were presumably the clincher for the SDS and/or RS formation in AS‐modified starches. The principal causes of SDS and RS formation were the chain length elongation and the subsequent retrogradation‐like process, respectively.     

Effect of acid treatment on the physicochemical and structural characteristics of starches from different botanical sources

Starch and starch derivatives (maltodextrins) are used as encapsulating materials. Starch for use as encapsulating material could be subjected to mild acid treatment. However, the granule size and organization of starch components (AM and AP) play an important role in the acid treatment. The aim of this research was to produce modified starch that might be used as encapsulate material, applying moderate acid‐treatment with 3 N sulphuric acid in a ratio 1:5 w/v for 3 h at 60°C, in starches from different granule size, evaluating their morphological, physicochemical, and structural features. Acid treatment has an effect in the AM content and the outcome was higher in starch with larger granule size. Bimodal granule size distribution was found in acid‐treated rice and maize starches. Erosion and exo‐corrosion were observed in acid‐treated starches with SEM. The XRD pattern did not change with the acid treatment, the native and acid‐treated samples showed similar crystallinity values, except rice starch. The branching degree was higher for modified potato starch, showing higher branching points, modified starches had shorter chains with increased A‐chains, and decreased B3+ chains, and the effect was higher in cereal starches; modified starches had a higher degree of retrogradation and they did not show pasting properties. The internal organization given by the granule size is an important parameter in the acid treatment of starches as it affected their physicochemical and structural features, and in the end, their functionality as encapsulate agent.     

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).     

Structures and Physicochemical Properties of Acid‐Thinned Corn,Potato and Rice Starches

The structures and physicochemical properties of acid‐thinned corn, potato, and rice starches were investigated. Corn, potato, and rice starches were hydrolyzed with 0.14 N hydrochloric acid at 50 °C until reaching a target pasting peak of 200—300 Brabender Units (BU) at 10% solids in the Brabender Visco Amylograph. After acid modification the amylose content decreased slightly and all starches retained their native crystallinity pattern. Acid primarily attacked the amorphous regions within the starch granule and both amylose and amylopectin were hydrolyzed simultaneously by acid. Acid modification decreased the longer chain fraction and increased the shorter chain fraction of corn and rice starches but increased the longer chain fraction and decreased the shorter chain fraction of potato starch, as measured by high‐performance size‐exclusion chromatography. Acid‐thinned potato starches produced much firmer gels than did acid‐thinned corn and rice starches, possibly due to potato starch's relatively higher percentage of long branch chains (degree of polymerization 13—24) in amylopectin. The short‐term development of gel structure by acid‐thinned starches was dependent on amylose content, whereas the long‐term gel strength appeared dependend on the long branch chains in amylopectin.     

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.     

Effects of Cooking Methods and Starch Structures on Starch Hydrolysis Rates of Rice

This study aimed to understand effects of different cooking methods, including steamed, pilaf, and traditional stir‐fried, on starch hydrolysis rates of rice. Rice grains of 3 varieties, japonica, indica, and waxy, were used for the study. Rice starch was isolated from the grain and characterized. Amylose contents of starches from japonica, indica, and waxy rice were 13.5%, 18.0%, and 0.9%, respectively. The onset gelatinization temperature of indica starch (71.6 °C) was higher than that of the japonica and waxy starch (56.0 and 56.8 °C, respectively). The difference was attributed to longer amylopectin branch chains of the indica starch. Starch hydrolysis rates and resistant starch (RS) contents of the rice varieties differed after they were cooked using different methods. Stir‐fried rice displayed the least starch hydrolysis rate followed by pilaf rice and steamed rice for each rice variety. RS contents of freshly steamed japonica, indica, and waxy rice were 0.7%, 6.6%, and 1.3%, respectively; those of rice pilaf were 12.1%, 13.2%, and 3.4%, respectively; and the stir‐fried rice displayed the largest RS contents of 15.8%, 16.6%, and 12.1%, respectively. Mechanisms of the large RS contents of the stir‐fried rice were studied. With the least starch hydrolysis rate and the largest RS content, stir‐fried rice would be a desirable way of preparing rice for food to reduce postprandial blood glucose and insulin responses and to improve colon health of humans.     

酸解时间对大米淀粉结构性质的影响

以4种不同直链淀粉含量的大米淀粉(0%的优糯3号、10.90%的稻花灿、21.03%的聚两优、28.46%的华优香占)为原料,酸解处理不同时间,以酸解大米淀粉的酸解率、颗粒形貌、结晶性质、溶解度的变化为指标衡量不同酸解时间对大米淀粉结构及性质的影响。结果表明,不同直链淀粉含量的大米淀粉具有不同的耐酸性,酸解时间对不同直链淀粉含量大米淀粉的结构和性质有着不同的影响。大米淀粉酸解率与直链淀粉含量成反比,优糯3号为50%而华优香占仅为30%;所有淀粉颗粒在酸解后均产生一定程度的破碎,偏光十字变形直至消失,酸解相同时间,直链淀粉含量高的大米淀粉破碎率低;酸解未改变淀粉的晶型,仍为A晶型;随着酸解时间的延长相对结晶度增加;淀粉的溶解度随着酸解时间的增加而增大。     

Effect of Acid Hydrolysis and Ball Milling on Porous Corn Starch

Porous corn starch from glucoamylase hydrolysis of native corn starch was examined before and after cross-linking, acid hydrolysis and dry ball milling. Cross-linking does not significantly change the crystallinity, water absorption or gelatinisation properties but acid hydrolysis at 60°C increases, proportionately, crystallinity and water absorption capacity and decreases moisture adsorption at humidities less than 80%, in comparison to untreated porous corn starch. Highly crystalline porous starch has a fragile granule structure. Ball milling destroys crystallinity in both normal, porous, and cross-linked or partially hydrolyzed starches. Particle sizes of 1–2m are obtained by milling dry starches for 48 h. Water absorption for milled starches is more than 200% (weight water/weight starch d.b.). Viscosities of these products were significantly reduced at high temperatures. Products formed stable gels in 25–30% dispersions in cold water.     

In vitro Digestibility of Hydroxypropylated and Cross-linked Waxy and Non-waxy Rice Starches

In vitro digestibility of hydroxypropylated and cross-linked waxy and non-waxy rice starches was investigated to find the proper resistant starch (RS) assaying method for chemically modified starches. RS and total dietary fiber (TDF) content of hydroxypropylated and cross-linked waxy and non-waxy rice starches were measured using the approved AOAC RS assay procedure (AOAC method 2002.02) and the AOAC TDF assay procedure (AOAC method 985.29). Hydroxypropylation did not alter the RS content of waxy and non-waxy rice starches (less than 1% of RS). Cross-linking also did not change the RS content of waxy and non-waxy rice starches (less than 1% of RS). It is interesting to note that non-RS content decreased with increasing hydroxypropylation (97-80%) and cross-linking (99-95%) in both waxy and non-waxy rice starches. This indicates that some fraction of RS in hydroxypropylated and cross-linked waxy and non-waxy rice starches cannot be measured using approved AOAC RS and TDF assay procedures. Therefore, the RS and TDF assay procedures performed in this study are not appropriate to determine the RS content of chemically modified starch. Further investigation is needed to develop a method to determine the RS content of chemically modified starch.     

Influence of prior acid treatment on physicochemical and structural properties of acetylated sorghum starch

Influence of prior acid treatment on acetylation of starch isolated from an Indian sorghum cultivar was investigated. The starch was acid thinned (AT) using 0.1, 0.5, and 1 M HCl for 1.5 h and then acetylated (Ac) with acetic anhydride (8% w/w). The acid thinning and subsequent acetylation appeared to reduce the percentage acetylation as indicated by degree of substitution. Ac‐AT starches exhibited significantly different physicochemical, thermal, pasting, and gel textural properties from those of AT and Ac starches. Starches after dual modification showed higher solubility, lower AM content, gelatinization temperatures, retrogradation, peak viscosity, and gel hardness than native starch. Enthalpy and range of gelatinization were observed to be higher in dual modified starches than native starch. However, no significant changes in granule morphology or crystalline pattern of Ac‐AT starches were observed compared with native starch.     

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.     

Comparative Acid Modification of Various Starches

Eight starches (maize, sorghum, finger millet, waxy and nonwaxy rice, chick pea, tapioca and potato) were acid modified with 0.5N HCl at 50°C. Alkali fluidity number (AFN) increased progressively with time of modification, and was highest in cereal followed by root, legume, and tuber starches. However, reduction in the number average molecular weight (M̄_n) was in the reverse order. Potato starch had the highest M̄_n, among the nonwaxy native starches and showed the greatest fall upon modification, whereas cereal starches had the least M̄_n in native form and showed the least fall. In fact, there was a clear proportionality between the M̄_n, of native starch and the extent of its hydrolysis under any given set of conditions. This relationship could be expressed by two intersecting lines, one for grains and one for root and tuber starches. When acid modified starches were recovered and dried without neutralization, hydrolysis still continued strongly in potato starch and slightly in tapioca, finger millet and sorghum starches. Other starches showed no change.     

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。