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).     

Characterization of Residues from Partially Hydrolyzed Potato and High Amylose Corn Starches by Pancreatic α‐Amylase

High amylose corn starch (HACS) and potato starch were hydrolyzed by pancreatic α‐amylase in vitro. Residues after hydrolysis were collected and characterized for their physicochemical properties and molecular structure. Compared with raw starches, residues had lower apparent amylose contents and higher resistant starch contents. The gelatinization enthalpy of residues from HACS increased while enthalpy of residues from potato starch decreased from 15.4 to 11.3 J/g. Peak viscosity and breakdown values of the residues from potato starch were markedly decreased but final viscosity values did not show much change. Chain length distribution of debranched amylopectin from the residues indicated that the relative portion of short chain in the residue decreased for both starches. More molecules with intermediate chain length (DP 16—31) were found in residue after 48‐h hydrolysis of potato starch.     

Characterization of Different Starches Oxidized by Hypochlorite

The effects of starch origin (potato, corn, and rice starches) and hypochlorite level (NaOCl, 0.8% and 2% w/w) on the structures and physicochemical properties of oxidized starches were investigated. Carboxyl and carbonyl group contents of oxidized starches increased with increasing NaOCl level, with potato starch having the highest and corn starch having the lowest carboxyl groups content at both NaOCl levels. Oxidation generally reduced the pasting temperature and viscosity of native starches as demonstrated by using a Rapid Visco Analyser. The peak viscosities of oxidized rice and corn starches were higher than those of their native counterparts at 0.8% NaOCl. The morphology of starches was not altered and X‐ray diffraction patterns of all the starches remained unchanged after oxidation. Oxidized starch batters exhibited greater adhesions than did native starch batters, with rice starch batter exhibiting the greatest adhesion. Carbohydrate profiles by high‐performance size‐exclusion chromatography indicated that both amylopectin and amylose were degraded during oxidation. The level of oxidation was largely dependent on the degree of crystallinity of starch and the degree of polymerization of amylose, whereas the adhesion property of oxidized starch was mainly attributed to its granular size and shape.     

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。     

Molecular Fractionation of Starch in Nycodenz‐Dimethyl Sulfoxide by Density‐Gradient Ultracentrifugation

Starches from various origins (normal corn, waxy corn, high‐amylose corn, normal rice, waxy rice, potato and tapioca) were fractionated by density‐gradient ultracentrifugation at 124,000×g, using a gradient of Nycodenz (0–40%, w/w) in 90% dimethyl sulfoxide (DMSO). The fractions of different densities were collected from a centrifuge tube, and then analyzed by the phenol‐sulfuric acid method and iodine‐binding test. Amylose and amylopectin were clearly separated by the density‐gradient centrifugation within 6 h of centrifugation in the total carbohydrate vs. density profile. The amylose content in the starches, measured from the centrifugation for 6 h, agreed with the values reported in the literature, and the content of intermediate fraction (5–13%) was also measured. Amylopectin quickly reached a density region (1.22–1.23 g/mL) with a sharp and stable peak, whereas amylose showed a band in a broad density range, moving toward higher density as the centrifugation continued. The buoyant density of amylose became similar to that of amylopectin after extensive centrifugation. Because the sedimentation rate of amylose was much lower than that of amylopectin, both starch chains are effectively fractionated in the gradient medium, and the iodine‐binding property of the fractionated starches provides valuable information on the chain conformation of starch.     

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.     

不同提取方法对粳米淀粉结构的影响

本实验从淀粉形态学、直链淀粉含量、支链淀粉分子量和支链淀粉侧链分布等方面研究碱法、酶法、SDS结合超声波法提取对粳米淀粉结构的影响.得到以下结论:碱法提取对粳米淀粉结构影响最大,其次是SDS结合超声波法,酶法提取影响最小;与酶法提取的支链淀粉相比,碱法和SDS结合超声波法提取的支链淀粉分子量有所下降,并且侧链中长B链含量下降,而中B链、短B链和A链的含量增加.     

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.     

Structure‐Functionality Changes in Starch Following Rough Rice Storage

The molecular‐level features of starch in relation to the changes in rice functionality during storage are not yet fully elucidated. This work investigated the effects of rough rice storage conditions on starch fine structures and physicochemical properties. Dried rough rice samples (medium‐grain Bengal and long‐grain Cypress) were stored at 4, 21, and 38°C in temperature‐controlled chambers and then periodically removed and evaluated after 1, 3, 5, 7, and 9 months. Flour (powdered head rice) and starch (extracted from head rice by alkali steeping) samples were evaluated for pasting and thermal properties. High‐performance size‐exclusion chromatography and high‐performance anion exchange chromatography were used to characterize starch molecular size and amylopectin chain‐length distribution, respectively. Significant changes in starch fine structure were observed primarily on the 38°C lots, and to some extent on the 21°C lots. The decreased amylose: amylopectin ratio, shortened amylopectin average chain length, and the shift in chain‐length distribution to shorter branch chains were implicative of molecular‐level starch degradation. The flour and starch samples showed inconsistent trends in pasting and thermal properties, thus suggesting the role of not only starch but also its interaction with non‐starch components in rice aging.     

Characterization of Dextrins obtained by Enzymatic Treatment of Cationic Potato Starch

The substitution pattern of cationic potato starches was studied using starch hydrolyzing enzymes and a characterization of the hydrolysis products. Native and cationic starch samples were hydrolyzed with pullulanase, isoamylase, and α‐amylase and the molecular‐weight distributions of the resulting dextrins were studied using gel permeation chromatography. Isoamylase hydrolyzed the native potato starch sample readily, whereas hydrolysis with pullulanase was incomplete. Pullulanase hydrolyzed, however, cationic starch with higher DS (degree of substitution) more efficiently than isoamylase. The hydrolysis products obtained with pullulanase were separated according to charge using cation‐exchange chromatography into one unbound and two bound fractions. The unbound fraction possessed an increasing number of short chains from amylopectin with increasing DS of the starch sample. The bound material contained amylose and dextrins with sizes corresponding to the long B‐chains. The high portion of uncharged dextrins after α‐amylolysis suggested that the substitution pattern, on the molecular level, was non‐random. The composition of the unbound and bound material, obtained by ion‐exchange chromatography of α‐amylase treated starches, suggested a more intense fragmentation with increasing DS of the sample. Possibly, the substituents influence substrate conformation and thereby alter the hydrolysis patterns. It is concluded that a thorough understanding of the enzymatic hydrolysis patterns is of ultimate importance in structural studies of modified starch.     

Chemical composition,digestibility and emulsification properties of octenyl succinic esters of various starches

Octenyl succinate starches are commonly used as emulsifiers and texturizing agents in many food-systems. Rice, tapioca, corn, wheat and potato starches were modified with octenyl succinic anhydride (OSA) at 3% level. Structural characterization, molecular weight, starch digestibility and physical properties of starch granule stabilized emulsions were studied for modified starches. Modified potato (0.022) and wheat (0.018) starches had the highest and lowest degrees of OSA substitution, respectively. For all starches, amylose and amylopectin molecular mass was significantly (P < 0.05) lower for OSA starches. OSA modification may have hydrolyzed the small amylose and amylopectin chains, or caused rearrangement of the starch molecules. Although the starch modification improved emulsification properties, botanical source showed more influence on this parameter. Overall, botanical source had more influence on functional properties than degree of substitution. Further studies on OSA group distribution and fine molecular structure of amylopectin and relationship with functional properties will be important.     

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。     

Morphological,Physicochemical and Structural Characteristics of Oxidized Barley and Corn Starches

Barley starch was oxidized to different levels and the morphological, physicochemical and structural of the resultant oxidized barley starch were determined and compared with oxidized corn starch at the same oxidation level. The amylose content in oxidized starches decreased with increasing oxidation level, and the extent of decrease was similar for both starch types. No evidences of alteration in morphology and X‐ray diffraction pattern were noted after oxidation. The crystallinity of barley starch increased with increasing oxidation but corn starch displayed a reduced crystallinity at 5% NaOCl. The onset and peak gelatinization temperatures of oxidized starches as measured by differential scanning calorimetry showed a slight increase up to 3% NaOCl and then decreased at 5% NaOCl, whereas gelatinization enthalpy gradually decreased with increasing oxidation level. The melting temperature of retrograded oxidized starches increased with increasing oxidation. Both amylose and amylopectin were degraded during oxidation, but a higher degradation in both components as determined by high‐performance size‐exclusion chromatography (HPSEC) was noted for barley starch than for corn starch. Results of amylopectin chain‐length distribution showed that the proportions of A and B1 chains significantly increased while that of B2+ chains significantly decreased. These results suggest that differences in the structure of barley and corn starches affected their responses to oxidation. Barley starch seemed to be more susceptible to oxidation with more significant reduction in pasting temperature, viscosity, and molecular size than corn starch.     

Physicochemical Properties of Sweetpotato Starches with Different Gelatinization Temperatures

Physicochemical properties of five sweetpotato starches differing in gelatinization temperature were examined. The gelatinization temperature of Koganesengan starch, an ordinary cultivar of sweetpotato in Japan, was 73.6°C, whereas those of the other starches were measured to be 71.6°C for Kyukei 96162–1, 65.8°C for Kyushu No.127, 63.9°C for Kyukei 240, and 54.9°C for Quick Sweet. Some relationships of the primary structural properties with the gelatinization temperature have been found. As the gelatinization temperature decreased: i) the content of phosphate groups attached to the glucosyl residues decreased, ii) the amylose content, which was determined as difference in long chains of debranched original starch and of its amylopectin, decreased, iii) the proportion of unit chains with DP > 100 in the amylopectin fraction increased, iv) the proportion of unit chains with DP 6 to 10 in the amylopectin fraction increased, whereas that of unit chains with DP 12 to 24 decreased, v) the B‐type crystallinity of the starch granules was enhanced, and vi) the proportion of longer chains constituting each Nägeli amylodextrin increased. Moreover, it was found that thin pastes of the low temperature‐gelatinizing starches retrograded slower during cold storage than the ordinary starch. Among the starches, Quick Sweet starch granules, having the lowest gelatinization temperature, were digested rapidly by pancreatin.     

6种不同种类直支链淀粉相互混合对其回生的影响

目的 研究6种不同种类直支链淀粉相互混合对其回生的影响。方法 将玉米淀粉、甘薯淀粉、木薯淀粉、马铃薯淀粉、糯米淀粉、小麦淀粉等6种不同种类直支链淀粉分离出来, 然后两两混合, 研究不同直支链混合对其回生率的影响。 结果 马铃薯支链淀粉与甘薯支链淀粉以2:8(m:m)混合回生率最低, 为60.0%, 玉米支链淀粉与木薯支链淀粉以8:2(m:m)混合回生率最低为52.6%, 小麦支链淀粉与糯米支链淀粉以8:2(m:m)混合回生率最低为51.2%, 甘薯支链淀粉与小麦支链淀粉以1:1(m:m)混合回生率最低为53.7%。木薯支链淀粉与小麦直链淀粉以1:1(m:m)混合时所得淀粉回生率最大, 达到了92.0%, 混合淀粉回生后X射线晶型为B型。结论 不同种类直支链淀粉混合对其回生率影响很大, 食品加工中尽量不要混合使用木薯支链淀粉与小麦直链淀粉。     

Sensory and rheological properties of transgenically and chemically modified starch ingredients as evaluated in a food product model

Starches derived from five genetically modified potato lines, two chemically modified potato starches and two native starches from potato and maize were subjected to physical and chemical analyses and their functionality evaluated in a milk-based food product model. The transgenic starches were specifically modified with respect to amylopectin chain length and phosphorous content by suppression of the starch branching enzyme and overexpression of glycogen branching enzyme. Transgenic starches with long amylopectin chains and high phosphorous content had increased gelatinisation temperatures, produced gels with a higher tendency to retrograde and a low freeze/thaw stability as compared to starches with shorter amylopectin chains and lower phosphorous content. The textural properties of the food product model prepared from genetically and chemically modified starches were characterised by sensory and rheological analyses. To clearly visualise the effects of the modifications, data was evaluated by radar plots and multiple regression analysis (chemometrics). Genetically modified potato starches with longer amylopectin chains and increased phosphorous content gave a more gelled and a shorter texture as compared to starches with shorter amylopectin chains and decreased phosphorous content. Acetylated and hydroxypropylated potato starches gave sticky and stringy textures. Correlations between rheology parameters and sensory parameters were found. The sensory parameter stringy/long could be predicted from the rheological data.     

Effects of the Barley amo1 and wax Genes on Starch Structure and Physicochemical Properties

Starch structural mutants showing abnormal endosperm characteristics have been used for investigating the effects of the mutation on structure and physicochemical properties of starches. Inbred lines of barley cultivars ‘Shikoku Hadaka 97’ and ‘Glacier AC38’ were used to investigate the impact of amo1 and waxy genes on starch properties. The amo1 type starch had high apparent amylose content and low starch content. The amo1+waxy type starch contained very little amylose. The content of long chains of amylopectin as detected with high‐performance size‐exclusion chromatography (HPSEC) was decreased, and that of amylopectin chains with the degree of polymerization (DP) of 12‐36 was increased in amo1 and amo1+waxy type starches. The amo1 and amo1+waxy type starches exhibited high gelatinization temperatures and low gelatinization enthalpies.     

Retrogradation of Sweetpotato Starch

Hardness and the percentage of leaked water of sweetpotato starch gels after storage were investigated as indexes of starch retrogradation. Starches of some varieties of sweetpotato were retrograded rapidly, but those of others were not retrograded during storage for one week. After one month of storage, starches of all varieties were highly retrograded, but the varietal order of hardness and the percentage of leaked water were almost the same as that after storage for one week. The study of chain length distribution by gel permeation chromatography after debranching by isoamylase showed that the hardness and the percentage of leaked water from the gel were positively correlated with amylose content and the proportion of Fr 1, the fraction of the highest molecular weight, containing amylose and extremely long chains of amylopectin, and negatively correlated with the proportion of Fr 3, the fraction with the lowest molecular weight, containing shorter chains of amylopectin. In addition, it was demonstrated by high performance anion exchange chromatography that the proportion of extra‐short chains (around DP 10) of amylopectin after isoamylase treatment was negatively correlated with the retrogradation index of starch. These results suggest that retrogradation of sweetpotato starch was promoted by amylose and extremely long chains of amylopectin and was inhibited by extra‐short chains (around DP 10) of amylopectin.     

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.     

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.