Characterization and Utilization of Acid‐modified Rice Starches for Use in Pharmaceutical Tablet Compression

Acid modified, agglomerated starches offer specific advantages as fillers in production of pharmaceutical tablets. Spray drying can improve processing of tablet mixtures significantly. In order to investigate prerequisites in utilization of rice starch, non‐waxy and waxy types were partially hydrolyzed in 6% (w/v) HCl solution at room temperature for varied length of time to obtain rice starches with increased crystallinity (so‐called crystalline rice starches). Scanning electron micrographs of native and highly crystalline starches were used to study the morphological changes and to suggest the mode of acid attack during hydrolysis. Exo‐corrosion distributed over the surface of acid‐modified waxy rice starch (AWRS) was observed after 192 h of hydrolysis. In contrast, the surface of acid‐modified rice starch (ARS) remained unchanged at 192 h of acid hydrolysis. The amylose content and the median particle size (diameter) were reduced with increasing hydrolysis time. It was found by X‐ray diffraction that the relative crystallinity of acid‐modified starches at >95% relative humidity was clearly increased with prolonged hydrolysis time. For studying tablet properties spherical agglomerates of the native and acid modified starches were directly compressed at 4 kN to obtain tablets. Crushing strength and disintegration time of tablets increased with relative crystallinity. In contrast, tablet friability was reduced. Concerning tablet functionality, the crystalline starches were positioned in overlapping ranges between the common commercial tablet fillers (microcrystalline cellulose, pregelatinized starch and lactose, respectively).     

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.     

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.     

Gelatinization Transitions of Acid‐modified Tapioca Starches by Differential Scanning Calorimetry (DSC)

Tapioca starch was partially hydrolyzed by 6 % and 12 % hydrochloric acid (w/v) at room temperature for various length of time. The gelatinization transitions of the acid‐modified tapioca starches were studied using Differential Scanning Calorimetry. Starch suspensions (67 % moisture) were heated at 5 °C/min to follow melting transition of amylopectin. As the hydrolysis time increased, onset (T_o), peak (T_p) and conclusion (T_c) temperatures of gelatinization have been observed to increase, in the same order of relative crystallinity, until reaching some critical values, then decreased with the large broadening of the endotherms. The increasing of the transition temperatures corresponded to the retrogradation of the remaining partially hydrolyzed amylose followed by a decrease of these parameters corresponding to the reduction of the length of the chains of double helices amylopectin.     

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.     

Crystallinity and Pasting Properties of Freeze‐Thawed High Amylose Maize Starch

Native and defatted high amylose (about 70%) maize starch gels were freeze‐dried or repeatedly freeze‐thawed, and the effects of the treatments on the crystallinity, pasting viscosity, and resistance to digestive enzymes of the dried starch were examined. Both native and defatted starches showed a B‐type crystal structure in the X‐ray diffractogram, but the crystallinity was decreased by repeating the freeze‐thawing cycle. In the DSC thermogram, the freeze‐thawed starches exhibited two endothermic transitions in the temperature ranges of 90—110 °C and 130—160 °C, representing amyloselipid complexes and amylose‐amylose double helix crystals, respectively. By defatting, the melting enthalpy for the amylose double helices was increased, indicating that the residual lipids inhibited the amylose crystal formation. Ice crystals in the starch gel matrix became smaller and the ice cell membrane became thinner as freeze‐thawing was repeated. The freeze‐dried or freeze‐thawed starch powders swelled to a paste by heating in water as did typical granular starch, but the setback by cooling was significantly high due to the rapid retrogradation of leached amylose. By the treatments, the resistance of the starch to digestive enzymes was also raised. The defatted starches displayed greater paste viscosity and resistance to digestive enzymes than the native starches. But the overall viscosity was decreased as the number of freeze‐thawing cycles increased.     

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。     

Physicochemical,structural, and digestibility properties of enzymatic modified plantain and mango starches

The effect of two enzymatic treatments (increasing the branch density of starch and shortening of AP and amylose chains) on the fraction of slowly digestible starch (SDS) and resistant starch (RS) of plantain (Musa paradisiaca L.) and mango (Mangifera indica L.) starches was investigated. The enzymatic modifications were carried out using β‐amylase (β‐AMY) and β‐amylase‐transglucosidase (β‐AMY‐TGs), in gelatinized starches. Plantain starch showed an increase from 10.9 to 18.5% of SDS, when it was modified by β‐AMY‐TGs, while the treatment with β‐AMY alone showed reduction from 10.9 to 7.1% in SDS. RS content increased with both treatments. On the other hand, mango starch showed an increase in SDS from 6.3 to 22.3% using β‐AMY treatment and from 6.3 to 11.7% using β‐AMY‐TGs treatment. The latter treatment also increased RS content. The enzyme modified starches showed a reduction in the values of molar mass and gyration radius compared with the native starch. The content of short chains of AP, particularly in the DP range 5–12, increased, the percentage of crystallinity decreased in treated starches, and ¹H NMR spectra showed a significant increase of α‐(1 → 6) linkages in the starches modified with β‐AMY‐TGs. These characteristics were related to an increase in the slow and resistant digestion properties of plantain and mango starches.     

Thermal properties of new varieties of yam starches

Starches isolated from yam varieties of Dioscorea alata and Dioscorea cayenensis‐rotundata species were prepared at different time–temperature conditions and characterised by DSC, amperometric iodine titration, light microscopy and rheology and compared to native and chemical modified tapioca starches. The observation by light microscopy showed different morphologies of the granules when heated above 100°C and the tendency for disintegration decreased in the order native tapioca starch > yam starch > modified tapioca starch. Differences between yam and tapioca starches were also revealed by DSC. Yam starch enthalpy is higher than tapioca starch, but the peak temperature is low. However, the significant differences between yam and the other tested starches were found in terms of their rheological behaviour. The viscosity of yam starch was very stable at high temperatures on the viscograph. With this property, yam starch can be used as thickening and gelling agent in food.     

Influence of heat–moisture treatment and annealing on functional properties of sorghum starch

Sorghum starch was annealed in excess water at 50 °C for 24 h. Starch was also modified under heat–moisture treatment at 110 °C after adjusting various moisture contents (20, 30 and 40%) for 8 h. Significant decrease in chain lengths of amylose fraction in HMT starches was observed. Heat moisture treated (HMT) and annealed (ANN) starches showed lower granule sizes, swelling power, peak and setback viscosity but higher retrogradation as compared to native starch. HMT starch with addition of 40% moisture showed a decrease in relative crystallinity. HMT and ANN starch gels were observed to be harder than native starch gel.     

底物浓度对三种不同来源的脱支重结晶淀粉的影响

以三种不同来源淀粉（普通玉米淀粉、木薯淀粉、豌豆淀粉）为研究对象,对样品进行脱支重结晶处理,分析底物浓度对三类脱支重结晶淀粉的形态、大小、结晶结构、热性质和凝胶性质等功能特性的影响。结果表明,原淀粉表面光滑无孔洞,脱支重结晶淀粉完整性均被破坏且受浓度影响不明显;粒径随底物浓度增加而增大;相对结晶度随底物浓度增加呈先减小后增大的趋势;与原淀粉相比,三种改性淀粉的储能模量（G'）高于损耗模量（G"）,凝胶强度增强,热稳定性和有序度（DO）均下降而双螺旋度（DD）均上升。改性玉米淀粉和木薯淀粉在较低底物浓度（6%、10%）表现出较弱的粘弹性,而豌豆淀粉在中等底物浓度（10%、14%）表现为较高的粘弹性;DD值随底物浓度增加而减小（底物浓度为18%样品除外）;热稳定性随底物浓度增大有所改善,但仍低于原淀粉。由此可见,调节底物浓度可以选择性地获取理想的脱支重结晶淀粉,这将为不同品种淀粉的综合利用提供思路。     

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。     

淀粉类对低温乳化香肠品质的影响

以鸡肉和猪肉为主要原料,采用肥瘦肉分离斩拌法制备低温乳化香肠,研究原淀粉及其变性淀粉对低温乳化香肠保水保油性、质构和感官品质的影响。结果表明:在7种淀粉中,添加原淀粉如玉米淀粉和木薯淀粉的乳化肠保水保油性最差,而添加玉米交联酯化淀粉和木薯交联淀粉(SH50)的乳化香肠的保水保油性最好;对低温乳化香肠质构改善作用最优的为木薯交联淀粉(SH50),其次为玉米交联酯化淀粉、马铃薯醋酸酯化淀粉(P0170)、木薯醋酸酯化淀粉(T0170)、木薯淀粉、玉米淀粉、复合变性淀粉(DURAT010)。添加木薯交联淀粉(SH50)的乳化香肠感官评分最高。     

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.     

Bread quality of frozen dough substituted with modified tapioca starches

Rheological properties of dough and bread quality of frozen dough-bread containing 18.4% of hydroxypropylated (HTS), acetylated (ATS), and phosphorylated cross-linked (PTS) tapioca starch with different degrees of modification and 1.6% of dried powdered gluten were compared to the same amount of native tapioca starch (NTS) or wheat flour-bread. Doughs substituted with native or modified tapioca starches had the same mixing tolerance as 100% wheat flour. The dough was frozen and stored for 1 week at −18°C, and thawed (one freeze-cycle). The amount of freezable water in the dough substituted with native or modified tapioca starches was not significantly different from that of wheat flour. Frozen dough-bread substituted with highly modified HTS (degree of substitution; DS 0.09–0.11) retarded bread staling, while lowly modified HTS (DS 0.06–0.07) or ATS (DS 0.02–0.04), and PTS (0.004–0.020% phosphoryl content) substitution fastened bread staling as compared with frozen dough-bread baked from wheat flour. The breadcrumbs containing HTS and ATS felt tacky, whereas the bread containing PTS was dry feel. HTS and ATS swelled and collapsed easily during heating, while PTS was difficult to swell and disperse as compared with NTS, therefore the gelatinization properties seemed to affect the texture of bread. Breadcrumb containing HTS showed small firmness during storage, and highly modified HTS-h (DS 0.1) was the smallest. This means highly hydroxypropylated tapioca starch significantly retards bread staling. Staling properties and texture of frozen dough-bread with various tapioca starches were the same as conventional bread baked with the same amount of tapioca starches. These results suggest that a one freeze–thaw cycle and a 1-week frozen period do not change characteristics of starch, gelatinization and retrogradation properties as compared with the conventional method, and the highly modified HTS-h is prominent anti-staling food-stuff in frozen dough.     

Effect of acid‐ethanol treatment followed by ball milling on structural and physicochemical characteristics of cassava starch

Structural and physicochemical characteristics of cassava starch treated with 0.36% HCl in anhydrous ethanol during 1 and 12 h at 30, 40, and 50°C followed by ball milling for 1 h were analyzed. Average yield of acid‐ethanol starches reached 98% independent of the treatment conditions. Solubility of acid‐ethanol starches increased with reaction temperature and time, but it did not change after ball milling. Granule average size reduced with chemical treatment from 25.2 to 20.0 µm after 12 h at 50°C. Ball milling decreased the granule average diameter of the native starch and those chemically treated at 30°C/1 h or 40°C/1 h, but it did not alter the starches treated for 12 h, independent of temperature. From scanning electron microscopy (SEM), starch granules presented round shape and after modification at 50°C/12 h, before and after ball milling, showed a rough and exfoliated surface. Some granules were deformed, suggesting partial gelatinization that was more intense after milling. Starch crystallinity increased as temperature and time of chemical treatment were increased, while amylose content, intrinsic, and pasting viscosities decreased. Gelatinization temperatures increased for all chemical starches. The findings can be related to the preferential destruction of amorphous areas in the granules, which are composed of amylose and amylopectin. After ball milling, the starch crystallinity decreased, amylose content, intrinsic, and pasting viscosities kept unchanged and gelatinization temperatures and enthalpy reduced. Ball milling on native and chemical starches caused the increase of amorphous areas with consequent weakening and decreasing of crystalline areas by breaking of hydrogen bonds within the granules.     

微波对板栗淀粉结构和理化性质的影响

为探讨微波辐照对板栗淀粉颗粒结构和理化性质的影响,采用微波辐照板栗淀粉,通过扫描电镜(SEM)、X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)、差示扫描量热仪(DSC)等研究微波处理不同时间后板栗淀粉的颗粒结构和理化特性。研究表明:与原淀粉相比,微波处理后板栗淀粉的微观形貌发生明显变化,但淀粉颗粒仍为C型晶体。随着微波处理时间的增加,直链淀粉含量增大,淀粉颗粒表面出现裂纹、孔洞和黏结越显著,淀粉颗粒的相对结晶度降低、红外光谱(1 047/1 022)cm~(-1)峰强度比值降低;淀粉膨胀度和透光率也随微波处理时间的增加而降低。DSC分析表明,微波处理80 s的淀粉相转变温度(T_o和T_p)降低、糊化焓(ΔH)减少。表明微波辐照对板栗淀粉的颗粒结构和理化特征均有显著影响。     

Properties of Cassava Starch Modified by Amylomaltase from Corynebacterium glutamicum

Amylomaltase (α‐1,4‐glucanotransferase, AM; EC 2.4.1.25) from Corynebacterium glutamicum expressed in Escherichia coli was used to prepare the enzyme‐modified cassava starch for food application. About 5% to 15% (w/v) of cassava starch slurries were incubated with 1, 3, or 5 units of amylomaltase/g starch. Apparent amylose, amylopectin chain length distribution, thermal properties, freeze–thaw stability, thermo‐reversibility, and gel strength of the obtained modified starches were measured. The apparent amylose content and retrogradation enthalpy were lower, whereas the retrogradation temperatures, freeze–thaw stability, and thermo‐reversibility were higher than those of the native cassava starch. However, when amylomaltase content was increased to 20 units of amylomaltase/g starch and for 24 h, the modified starch showed an improvement in the thermo‐reversibility property. When used in panna cotta, the gel strength of the sample using the 20 units/24 h modified cassava starch was similar to that of using gelatin.     

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.     

Gelatinization and Retrogradation Properties of Native and Hydroxypropylated Crosslinked Tapioca Starches with Added Sucrose and Sodium Chloride

The effects of sucrose and sodium chloride on the gelatinization and retrogradation of native and hydroxypropylated crosslinked tapioca starches were investigated by using Differential Scanning Calorimetry (DSC). Hydroxypropylated crosslinked tapioca starches showed low gelatinization temperature and enthalpy compared to the native tapioca starch. Sucrose and sodium chloride increased the gelatinization temperatures of all starch samples. The enthalpy to melt retrograded amylopectin of hydroxypropylated crosslinked tapioca starches were low, compared to that of the native starch. Sucrose did not have much effect on retrogradation of the starch, while sodium chloride decreased retrogradation of all starch samples.