Thermoplastic starch blends with a poly(ethylene-co-vinyl alcohol): Processability and physical properties

We investigated the effect of poly(ethylene-co-vinyl alcohol) (EVOH) concentration on the processability and physical properties of thermoplastic starch plasticized with glycerine and water. Waxy maize starch (Amioca), native corn starch (Melogel), and a treated high amylose corn starch (Hylon VII) were employed to explore the effect of starch type on blend properties. All the starches exhibited similar changes in properties with increasing EVOH content. The minimum injection pressure required for filling a standard test specimen (a measure of processability) decreased with increasing EVOH concentration and provided an indication of improved processability. Blends with high amylose corn exhibited higher injection pressures than the corresponding waxy maize or native corn starch blends. The ductility of all the thermoplastic starches was significantly increased upon the addition of EVOH. The waxy maize blends were stiffer and the high amylose corn blends exhibited higher elongation at low EVOH concentrations, but all the starch/EVOH blends exhibited similar physical properties when the EVOH concentration was ≥ 50 wt%. An investigation of physical properties of this blend series after long term aging from 10% to 90% relative humidity is in progress. Future studies include rheology, electron microscopy, and thermal analysis to more fully elucidate phase behavior in these binary blends.     

Effect of minor addition of xanthan on cross‐linking of rice starches by dry heating with phosphate salts

Effects of xanthan on the crosslinking of normal and waxy rice starches using a mixture of phosphate salts (sodium trimetaphosphate and sodium tripolyphosphate, 99 : 1, dry solid basis) were investigated. The starch (158.4 g, dry solids) was dispersed in an aqueous solution containing xanthan and phosphate salts (1.6 and 0.6 g in 280 mL water, respectively), and the slurry was dried overnight at 45°C until the moisture content was less than 10%. The dry cake was then ground into powders and heated for 2 h at 130°C in a convection oven. The pasting viscosity, paste clarity, melting and in vitro digestion behaviors of the starches with modifying agents (xanthan and phosphate salts) were investigated. The heat treated starches displayed enhanced shear stability and reduced breakdown, as evidences of crosslinking. Xanthan (1.0% based on starch solids) enhanced the crosslinking effects in the viscosity profile. Waxy rice starch evidenced more profound viscosity changes than did normal rice starch, indicating it was more susceptible to the heat treatment. The waxy rice starch heated with the mixture of phosphate salts and xanthan exhibited a continuous increase in pasting viscosity without any breakdown. Under a DSC analysis, melting enthalpy decreased but melting temperature increased somewhat as results of the heat treatment with xanthan. In an in vitro digestion analysis, the starches treated with xanthan exhibited decreases in the maximum digestion level, and increases in the resistant starch (RS) content. Dry heating, however, increased the digestion rate and glycemic index (GI) regardless of the presence of phosphate salts or xanthan indicating that the starches were thermally degraded. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

不同直链含量热塑性淀粉的制备及性能研究

利用转矩流变仪,以丙三醇为增塑剂对不同来源的淀粉进行改性制备热塑性淀粉（TPS）。采用X射线衍射仪（XRD）、热重分析仪（TG）、水接触角测量仪、傅里叶变换红外光谱仪（FTIR）和扫描电子显微镜（SEM）等对获得的热塑性淀粉进行了表征。结果表明,4种热塑性淀粉均含有颗粒状和颗粒状碎片,并且在热塑性木薯淀粉中所含比例更高;淀粉在增塑过程中达到稳态的扭矩依次为木薯淀粉（23 N·m）>玉米淀粉（21 N·m）>马铃薯淀粉（17.8 N·m）>蜡质玉米淀粉（15.2 N·m）,这与不同种类来源淀粉的直链淀粉比例差异直接相关;不同类型的淀粉与增塑剂形成氢键的能力存在差异,蜡质玉米淀粉的能力最强;4种热塑性淀粉的亲水性依次为热塑性木薯淀粉（75.9 °）>热塑性玉米淀粉（69.2 °）>热塑性马铃薯淀粉（67.9 °）>蜡质玉米淀粉（64.9 °）。     

Effects of drying process for amorphous waxy maize starch on theophylline release from starch‐based tablets

Physical properties and theophylline‐release profiles of compressed tablets prepared with amorphous waxy maize starches dried using different methods were examined. A gelatinized waxy maize starch paste (10% solids in water) was either freeze‐dried or oven‐dried (40 or 105°C) until the moisture content reached to <5%. To form the tablets, the dried amorphous starch powders, either with or without theophylline (3 : 10, w/w), were remoistened to a water content of (17 ± 0.2)%, and compressed into tablets. The drying process applied to the amorphous starch powders affected both the compactness and swelling behavior of the tablets. Although no crystallinity was detected in all the starches tested, X‐ray diffraction patterns indicated that starch chains dried at the lower temperature (40°C) are allowed more time to re‐associate during the drying process than those dried at the higher temperature (105°C). The freeze‐dried starch powders formed tablets characterized by greater compactness and rigidity than was observed in the oven‐dried starch samples. The drug release of the tablets prepared with the starch dried at the higher temperature (105°C) occurred at a much slower rate than that of the tablets made with the starch dried at the lower temperature (40°C). The drug release characteristics of the freeze‐dried starch tablets were nearly identical to those of the tablets prepared with the starch dried at 105°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

The effect of temperature on the observed flow-induced structure in semidilute solutions of gently solubilized starches

The effect of temperature on the unexpected shear-thickening behavior exhibited by semidilute solutions of waxy maize starch during a repeated shear-loop experiment was evaluated. Shear-thickening behavior, characterized using power law models, was observed for waxy maize starch, but not for normal maize starch at the same concentration. The shear-thickening region was observed for waxy maize starch at temperatures ranging from 25°C to 80°C and shear rates from 2–100 s^?1 during the initial part of the shear-loop experiment. For waxy maize starch, the power law exponent, n, was found to be 0.539 ± 0.017 in the shear-thinning region. For normal maize starch, the value of n was found to be equal to 0.751 ± 0.015 and only shear-thinning behavior was observed. The values of n for both waxy maize and normal maize starch were found to be temperature independent within the precision of the experimental measurements. The differences in n indicate the differences in the conformational dynamics of waxy maize and normal maize starches in solution.     

Effects of jet-cooking conditions upon intrinsic viscosity and flow properties of starches

This work examined the sensitivity of intrinsic viscosity values of jet-cooked waxy maize starch to initial pH conditions and the effects of jet-cooker steam pressure parameters upon the intrinsic viscosity and flow viscosity values of four jet-cooked starches. Flow viscosities of the 10 wt % cooked starches and intrinsic viscosities in 90% DMSO-H₂O were the lowest when mixing and turbulence during steam jet-cooking was increased (i.e., by adjusting steam line pressure vs. pressure within the cooking chamber to allow greater amounts of steam to flow through the apparatus). The percent decreases of the intrinsic viscosity caused by the most severe cooking conditions compared to gentle cooking conditions were 52, 45, 32, and 12, respectively, for waxy maize, waxy rice, normal maize, and 70% high amylose maize starches. Initial pH values, from 3 to 10.5, of waxy maize starch had minor effects upon the intrinsic viscosity of the jet-cooked material. © 1996 John Wiley & Sons, Inc.

1 This is a U.S. Government work and, as such, is in the public domain in the United States of America.

     

Optimum Production and Characterization of Thermostable Amylolytic Enzymes from B. stearothermophilus GRE1

Optimum production of extracellular, thermostable amylolytic enzymes (α and β‐amylase) by a newly isolated bacterium, Bacillus stearothermophilus, was investigated in a batch bioreactor. Starch and lactose at 1.0% and 3.0% (w/v) respectively were found to be optimum for maximum enzyme production. Optimization of cultural conditions (pH 7.0 and temperature 45°C) resulted in high bacterial specific growth rate (0.64 h^?1), yielding 2.20 gL^?1 biomass, 11.43 UmL^?1 α‐amylase and 10.04 UmL^?1 of β‐amylase. Hydrolysis of native starches from wheat, cassava, corn and potato at 60°C using the crude enzyme showed 60‐80% saccharification with potato starch showing the least and wheat starch showing the greatest hydrolysis. The K_m and V_max values of the crude α‐amylase for starch were 4.78 mg starch/mL and 6.67 mg/mL.min respectively.     

Ingestion of gelatinized potato starch containing a high level of phosphorus decreases serum and liver lipids in rats

Potato starch is known to have a higher concentration of phosphate than other starches. The presence of phosphate groups in amylopectin results in resistance to digestion by amylase. Therefore, there is a possibility that potato starch is slowly digested, inducing a physiological effect similar to that of resistant starch and indigestible oligosaccharides. The amount of phosphate group in starch differs with potato cultivar. In the present study, we investigated the effects of gelatinized potato starch containing a high level of phosphorus on lipid metabolism in rats. For this purpose, we determined lipid levels in the serum and liver in rats fed two kinds of gelatinized potato starches with different phosphorus contents. Four groups of male Sprague-Dawley rats were fed a 60% sucrose diet (control) or one of three diets containing cornstarch (CS), Benimaru (BM) potato starch or Hokkaikogane (HK) potato starch. Fat pad weight was slightly decreased in the HK diet group compared with that in the other groups. Free fatty acids in serum were significantly lowered by dietary HK starch compared with control, and serum triglyceride in rats fed the HK diet was also decreased. In the BM and HK diet groups, triglyceride levels in the liver were decreased compared with that in the control and CS groups. As for hepatic total cholesterol level, there were no significant differences among three starch diet groups. Fecal bile acid excretion was greater in the two potato starch groups than in the control group. On the other hand, there were no significant differences in cecal short-chain fatty acid content or pH. Thus, we conclude that dietary gelatinized potato starch reduces free fatty acid and triglyceride in serum and hepatic triglyceride, but does not affect cecal fermentation.     

Cold enzyme hydrolysis of wheat starch granules

Three α-amylase enzymes were used to hydrolyze wheat starch granules suspended in water below the gelatinization temperature. The rates of hydrolysis were determined at various temperatures, pH, enzyme and starch concentrations. Barley amylase was found to be the “best” enzyme when used at pH 4.5, 45°C and starch and enzyme concentrations of 30 and 8 mg/mL respectively. It was found that under these conditions, 98% of the starch granules were hydrolyzed in 3 hours, the same amount of time used in the industrial cooking process of soluble starch. Starch particles were observed to be attacked at specific points on the surface and then hydrolyzed from the inside-out. Some granules were hydrolyzed at a very fast rate with a first order rate constant estimated to be 40 h^?1; but most granules were hydrolyzed slowly according to the Michaelis-Menten model and the best fit parameters were found to depend on enzyme type, pH and temperature.     

Immobilisation of α-amylase from Aspergillus niger onto polyaniline

α-Amylase from Aspergillus niger culture medium was immobilised on glutaraldehyde-modified polyaniline (PANIG-AMY) in a yield of 42% activity retention. Compared with the free enzyme, PANIG-AMY was less sensitive to inhibition by Zn²⁺, Cu²⁺ and Fe²⁺. The catalytic efficiencies of hydrolysis of starch (potato, cassava, wheat, maize and rice/maize) were similar for free and PANIG-AMY. Oligosaccharides were formed following the hydrolysis of potato starch by PANIG-AMY whereas the free enzyme produced oligosaccharides and glucose. PANIG-AMY retained 50% of its activity after repeated assay and storage at 5 °C and pH 7.0. The thermal stability of PANIG-AMY was increased by the presence of CaCl₂. The repeated batch-wise hydrolysis of potato starch using 5.0 mg of PANIG-AMY (0.8 U α-amylase) produced 1.7 μmol of reducing sugar per cycle, yielding a total of 25.5 μmol of reducing sugar after 15 cycles. The same yield would require 12.5 U of free α-amylase.     

不同淀粉的酸解历程及性质研究

将玉米淀粉和马铃薯淀粉分别在35℃条件下用浓度为2 4mol/L的HCl处理不同时间,采用碘量法、X射线衍射(X ray)分析和差热分析(DTA)等对酸解后的淀粉颗粒进行了结构和性能表征。结果表明,马铃薯淀粉的酸解过程可分为3个阶段,酸解速率常数分别为2 78(t<24h),0 94(24h96h)。在比较分析了玉米和马铃薯淀粉酸解前后的一些物理化学性质及结构变化与酸解时间的相互联系后,认为酸首先水解淀粉的无定型区,提高淀粉颗粒结晶度、热稳定性和酶解速率;而后随着酸解时间的延长,淀粉结晶结构遭到侵蚀,热稳定性降低。酸解时间为4d时,玉米淀粉和马铃薯淀粉颗粒的结晶最完美,热稳定性最佳,结晶转变温度分别为87 0℃和93 5℃。     

Structure and properties of compression-molded thermoplastic starch materials from normal and high-amylose maize starches

The structural and mechanical properties of compression-molded normal and high-amylose maize starches were studied as a function of processing water content and ageing time. Rubbery thermoplastic starches were produced by compression molding of four maize starches with differences in amylose content and amylopectin structure. Glycerol (30% on the basis of dry starch) and water (between 10 and 35% on the basis of total mass) were used as plasticizers. After processing, the amorphous thermoplastic starch materials crystallized during ageing. The semicrystalline materials contained both E-type and V-type, as well as B-type crystallinity. The properties of the thermoplastic starch materials are dependent on water content during processing, starch source, and ageing time. The normal maize starch materials are highly flexible with elongations between 56 and 104%. The elongations of the high-amylose maize starch materials were between 5–35%. The tensile stress and E-modulus of the normal maize starch materials were in the range of 3.9–6.7 and 27–131 MPa, respectively. The tensile stress and E-modulus of the high-amylose maize starch materials increased from approximately 0.5 to 23 and 5 to 700 MPa, respectively, with increasing water content during processing from 10 to 35%. The differences in mechanical properties of the normal and high-amylose materials were explained by differences in the structure of the amylose and amylopectin structure. It was concluded that both lead to differences in the starch network. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 631–644, 1997     

Comparative study of maize cultivars 30 days after pollination (30 DAP): characterization of starch

Characterization of starch was comparatively studied in five maize cultivars, i.e., Maya Normal, Nutrimaiz, two hybrids (L90 x L78, L90 x L41) and Supersweet (SRR "Duro"), 30 days after pollination (30 DAP). Amylose content was found to be higher in the Maya Normal starch (31.3%) and lower (23 to 27%) in the genetically-modified cultivars. The absolute density of the isolated starches did not show significant differences among cultivars. Solubility and swelling studies suggested the presence of more homogenous forces maintaining the granular matrix on the starch from Maya Normal in relation to the other maize cultivars. The starch from the genetically-modified cultivars had a reduced solubility in dimethylsulfoxide and lower values for the gelatinization temperature range, in comparison to the Maya Normal. Information from the Brabender amylogram indicated greater resistance of the gelatinized maize starches to granule breakdown by mechanical stirring, in the new genotypes, resembling those starches modified by cross-linking.     

Structural changes of injection molded starch during heat treatment in water atmosphere: Simultaneous wide and small‐angle X‐ray scattering study

Native starches with wide varying amylose content were processed by injection molding. The injection‐molded materials were conditioned in water for 20 days and sealed in glass capillaries. Simultaneous wide‐ and small‐angle X‐ray scattering (WAXS and SAXS, respectively) were recorded during thermal heating using a synchrotron source. Crystallinity, SAXS invariant, Q, and long period, L, were measured as a function of heating temperature. The injection‐molding process provokes a destruction of the crystal forms A (cereal starch) and B (tubercle starch) but favors a development of the crystal form V_h. After wet conditioning, WAXS of the injection‐molded samples shows again the appearance of the crystal forms A or B, and crystallinity reaches values similar or larger than those of native starch. A constant heating rate (5°C/min) was particularly used for a comparison of potato and corn starch with a similar amylose content. While the crystallinity associated to forms A and B slowly decreases below 55°C and then rapidly decreases until its disappearance at 85–90°C, the invariant shows a maximum around 40°C and rapidly decreases thereafter. The total nanostructure disappearance occurs at temperatures about 10°C higher for the case of potato starch. In addition, a recovery of the WAXS and SAXS maxima during the subsequent cooling process before reaching room temperature was observed only for potato starch. Analysis of WAXS and SAXS for the rest of the starch materials reveals clear differences in the structural parameters of the samples that cannot be easily explained solely on the basis of the amylose content. Thus, for Cerestar and Roquette, it is noteworthy that there was a continuous decrease of L until its total disappearance as well as the persistence of crystallinity (form B), presumably stabilized by the presence of the V_h structure (12–15%). Real‐time crystallization experiments on two amorphous injection molded samples, waxy maize (free amylose starch) and potato starch, are also discussed. It is shown that the absence of amylose delays the recrystallization of amylopectine during the experiment. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 301–309, 2004     

改性蜡质玉米淀粉稳定Pickering乳液的制备及应用

采用辛烯基琥珀酸酐(OSA)对蜡质玉米淀粉(WS)疏水改性制得辛烯基琥珀酸酐改性蜡质玉米淀粉(OSA-WS),以不同取代度OSA-WS制备了稳定的Pickering乳液。测定了OSA-WS取代度(DS)、反应效率(RE)及三相接触角,对其进行了FT-IR、XRD和SEM表征。结果表明,OSA通过与淀粉表面羟基反应对其进行改性并未改变淀粉颗粒结构;随着取代度的增大,淀粉颗粒乳化性增加,制得Pickering乳液稳定性增强;以OSA-WS为乳化剂制得包埋辅酶Q10的Pickering乳液,通过透皮运输实验可知,与辅酶Q10的油溶液相比,包埋辅酶Q10的Pickering乳液更有利于辅酶Q10的透皮运输。     

Fermentative production of L(+)‐lactic acid from starch hydrolyzate and corn steep liquor as inexpensive nutrients by batch culture of Enterococcus faecalis RKY1

BACKGROUND: Attempts were made to determine the lactic acid production efficiency of novel isolate, Enterococcus faecalis RKY1 using four different starches (corn, tapioca, potato, and wheat starch) with different concentrations (50, 75, 100, and 125 g L^?1) and corn steep liquor as an inexpensive nitrogen source. RESULTS: The yield of lactic acid from each starch was higher than 95% based on initial starch concentrations. High lactic acid concentration (129.9 g L^?1) and yield (1.04 g‐lactic acid g^?1‐starch) were achieved faster (84 h) from 125 g L^?1 of corn starch. Among the starches used, tapioca starch fermentation usually completed in a shorter incubation period. The final dry cell weight was highest (7.0 g L^?1) for the medium containing 75 g L^?1 of corn starch, which resulted in maximum volumetric productivity of lactic acid (3.6 g L^?1 h^?1). The addition of 30 g L^?1 corn steep liquor supplemented with a minimal amount of yeast extract supported both cell growth and lactic acid fermentation. CONCLUSION: Enterococcus faecalis RKY1 was found to be capable of growing well on inexpensive nutrients and producing maximum lactic acid from starches and corn steep liquor as lower‐cost raw materials than conventionally‐used refined sugars such as glucose, and yeast extract as an organic nitrogen source in laboratory‐scale studies. These fermentation characteristics are prerequisites for the industrial scale production of lactic acid. Copyright © 2008 Society of Chemical Industry     

蜡质玉米羧甲基淀粉的合成与表征

以蜡质玉米淀粉为原料,用乙醇溶剂法制备了蜡质玉米羧甲基淀粉(CMS)。考察了碱化时间、醚化反应温度、醚化反应时间、n(NaOH)/n(淀粉)、n(ClCH2COONa)/n(淀粉)对CMS粘度的影响。结果表明,在醚化反应时间2.5 h,n(NaOH)/n(淀粉)为0.4,n(ClCH2COONa)/n(淀粉)为1.2,醚化反应温度65℃,碱化时间为50 min的最佳反应条件下制得的CMS粘度为1 490 mPa.s。同时发现,随着n(ClCH2COONa)/n(淀粉)的增大,CMS粘度表现出先增大后减小再增大,最后减小的趋势,对其进行了分析。     

抗消化乙酰酯淀粉结构和结肠靶向性能研究

采用扫描电镜、X射线衍射和生物体外(In-V itro)降解等方法,对不同取代度DS的抗消化乙酰酯淀粉的颗粒形貌、结晶结构和生物降解性能进行了研究。结果表明:乙酰酯淀粉的颗粒表面变得粗糙并发生破损;随着乙酰基团取代度的增大,淀粉的抗消化性能不断提高,当DS>2时,淀粉中抗消化淀粉质量分数达到90%以上,其结晶结构也由A型向V型转变。生物体外降解试验表明,抗消化乙酰酯淀粉薄膜在模拟人体上消化道环境中的降解程度低于2.5%,在人工模拟结肠环境中的微生物降解程度为30%—50%,显示出潜在的结肠靶向性和微生物降解性。由此可见,抗消化乙酰酯淀粉适合作为菌群触发型口服结肠靶向药物控释载体材料。     

Preparation and properties of biodegradable thermoplastic starch/poly(hydroxy butyrate) blends

The vital differences using three types of thermoplastic starches (TPS), including potato starch, corn starch, and soluble potato starch, with two different gelatinization degrees to blend with poly(hydroxy butyrate) (PHB) are thoroughly discussed in this study. For blends containing a certain amount of PHB, thermal stability remains in a certain degree. In all cases of this study, mechanical properties of TPS blended with PHB confer higher performance than those of pristine TPS. In particular, a significant increase on tensile strength and tear strength is observed for TPS (potato starch) blended with PHB at low gelatinization degree. A suitable degree of gelatinization of starch is critical to achieve optimum performance. The investigation on the morphological observation partly features the supporting evidence of the above findings. The assessment of biodegradability indicates that the values of water absorption and weight loss increase with increasing treatment period and glycerol content, but decrease with increasing amount of PHB content. Among three types of starches investigated, the TPS (soluble starch)/PHB blend gives the highest level of water absorption and weight loss. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2371–2379, 2006     

Immobilization of malto‐oligosaccharide forming α‐amylase from Bacillus subtilis KCC103: properties and application in starch hydrolysis

BACKGROUND: A malto‐oligosaccharide forming α‐amylase from Bacillus subtilis KCC103 immobilized in calcium alginate beads was repeatedly used in batch processes of starch hydrolysis. The degree of starch degradation and operational stability of the immobilized system were optimized by varying the physical characteristics and composition of the beads. The products formed from hydrolysis of various starches by α‐amylase immobilized in different supports were analyzed. RESULTS: Immobilized beads prepared from 3% (w/v) alginate and 4% (w/v) CaCl₂ were suitable for up to 10 repeated uses, losing only 25% of their efficiency. On addition of 1% silica gel to alginate prior to gelation, the operational stability of the immobilized enzyme was enhanced to 20 cycles of operation, retaining > 90% of the initial efficiency. Distribution of malto‐oligosaccharides in the starch hydrolyzate depended on the type of starch, reaction time and mode of immobilization. Soluble starch and potato starch formed a wide range of malto‐oligosaccharides (G1–G5). Starches from wheat, rice and corn formed a narrow range of smaller oligosaccharides (G1–G3) as the major products. CONCLUSION: The immobilized beads of α‐amylase from KCC103 prepared from alginate plus silica gel showed high efficiency and operational stability for hydrolysis of starch. This immobilized system is useful for production of malto‐oligosaccharides applied in the food and pharmaceutical industries. Since this KCC103 amylase can be produced at low cost utilizing agro‐residues in a short time and immobilized enzyme can be recycled, the overall cost of malto‐oligosaccharide production would be economical for industrial application. Copyright © 2008 Society of Chemical Industry