Influence of extrusion and digestion on the nanostructure of high-amylose maize starch

An in-depth characterization of the structural changes undergone by high-amylose starch after extrusion and digestion with a pancreatic alpha-amylase has been carried out. The combination of USAXS, SAXS, XRD, and SEM techniques has provided a wide "picture" of the morphological transformations of starch, covering a length scale from approximately 0.3 nm to approximately 230 microm. Depending on the extrusion conditions, either gelatinization was attained ("mild" conditions) or single-amylose helix formation was induced ("extreme" conditions). SAXS experiments demonstrated that upon contacting the extruded materials with water, retrogradation took place. A new type of molecular organization with a characteristic repeat length of 5 nm was observed in the dry resistant starch fractions from the extruded high-amylose starch. The crystalline morphology of the resistant starch fractions, as observed by XRD, varied from B-type crystallinity for the "mild" extruded starch to a mixture of C- and V-type crystallinity in the case of "extreme" extrusion.     

Extruding foams from corn starch acetate and native corn starch

Because of the hydrophilic characteristics of native starch foams and the cost of modifying starch, the uses of starch and modified starch foams are hindered. To decrease hydrophilicity and cost of starch foams, native corn starch was blended with starch acetate and extruded. A twin-screw mixing extruder was used to produce the foams. Native starch content, screw speed, and barrel temperature had significant effects on molecular degradation of starches during extrusion. The melting temperature of extruded starch acetate/native starch foam was higher (216 degrees C) than that for starch acetate (193.4 degrees C). Strong peaks in the X-ray diffractograms of extruded starch acetate/native starch foam suggested new crystalline regions were formed. Optimum conditions for high radial expansion ratio, high compressibility, low specific mechanical energy requirement, and low water absorption index were 46.0% native starch content, 163 rpm screw speed, and 148 degrees C barrel temperature.     

Extrusion processing of high amylose potato starch materials

Thermoplastic starch was prepared by mixing native high amylose potato starch and normal potato starch in a Buss co-kneading extruder at starch to glycerol ratios of 100:45 and 100:30. The materials were also conditioned to different moisture contents at different relative humidities at 23 °C. After the mixing, the compounds were extruded into sheets with a Brabender laboratory extruder. The thermoplastic high amylose materials exhibited a higher melt viscosity than the normal potato starch materials when conditioned at 53% relative humidity. Increasing the moisture content in HAP from 27% to 30% (by weight) lowered the melt viscosity to the same level as that of normal potato starch with a moisture content of 28%. In general, the high amylose materials were more difficult to extrude than the thermoplastic material based on normal starch. The main extrusion problems encountered with the high amylose starch were unstable flow, insufficient melt tenacity and clogging of the die. By increasing the moisture content, increasing the compression ratio of the screw and increasing the rotation rate of the screw, the problems were reduced or eliminated. However, only with a starch to glycerol ratio of 100:45 was an acceptable extrusion result obtained. Extruded sheets of such high amylose materials had a stress at break of about 5 MPa at room temperature and 53% relative humidity, whereas the corresponding value for normal potato (thermoplastic) starch was 3 MPa. The elongation at break was also higher in the case of the high amylose material. The results are discussed in terms of residual crystallinity of the starch materials.     

Physicochemical changes to starch granules during micronisation and extrusion processing of wheat, and their implications for starch digestibility in the newly weaned piglet

Two trials were performed to assess changes in the physicochemical properties of precisely processed (micronised v. extruded) wheats, prior to inclusion in piglet diets. The in vitro data obtained were subsequently related to biological responses of newly weaned piglets over 14 days. The effects of the severity of micronisation (Trial 1) or extrusion (Trial 2) on the nutritional value of two wheats (varying in endosperm texture) were examined. Extrusion, in contrast to micronisation, drastically disrupted the structural properties of wheat starch granules through melting of crystallites and macromolecular degradation of starch polysaccharides. These structural changes strongly improved the hydration characteristics of starch and its digestibility. The amount of starch digested in vitro was approximately 0.20, 0.70 and 0.90 for the unprocessed, micronised and extruded samples, respectively. This enhanced in vitro digestibility correlated well with, and helped to explain, the significant improvement in the apparent digestibility of starch at both the 0.5 region (mean coefficients for extruded wheat were 0.869 and 0.959 v. raw 0.392; P = 0.017) and 0.75 region (extruded 0.973 v. raw 0.809; P = 0.009) of the small intestine, when compared with piglets fed an unprocessed wheat diet. Extrusion and, to a lesser extent, micronisation lessened the reduction in apparent starch digestibility on day 4 post-weaning, typically seen at the 0.5 intestinal region in piglets fed an unprocessed wheat diet. Processing variables influenced both in vitro and in vivo data, with for instance, a positive relationship between specific mechanical energy (SME) input during extrusion and starch digestibility at the 0.5 region. The higher digestibility coefficient observed at the 0.5 region for the high SME diet suggests enhanced digestion and more rapid release of starch. However, it remains to be seen whether a diet containing rapidly digestible, as opposed to slowly digestible, starch is more beneficial for piglets. This rate of starch breakdown in the piglet is an important finding, which may have implications in helping to alleviate the post-weaning growth check, particularly in the absence of in-feed antibiotic growth promoters. Processing did not appear to offer any benefit over unprocessed wheat with regard to daily live-weight gain or the apparent digestibility of nitrogen in the small intestine over the 14-day period. Based on the enhanced in vivo starch digestibility, performance might be improved over a longer period, although future studies are required to confirm this. Precise processing variables for raw materials must be stated in all animal trials.     

Production of ethanol from extruded corn starch by a nonconvencional fermentation method

Summary In single-step 48-hour fermentations of extruded, liquefied and raw corn starch, the yields of ethanol from extruded starch were similar to those from liquefied starch, whereas the yields of ethanol from raw starch were lower.     

Extrusion of pectin and glycerol with various combinations of orange albedo and starch

Microstructural and mechanical properties of extruded pectin and glycerol films with various combinations of orange albedo and starch were determined by universal mechanical testing (UMT), dynamic mechanical analysis (DMA), optical microscopy (OM) and scanning electron microscopy (SEM). A glass transition and a second order transition attributed to the onset of translational motion of the pectin molecules was observed in all films. Observation by OM suggested that extrusion in the presence of dilute HCl was more effective in disintegrating albedo than either water or dilute citric acid. UMT, DMA and SEM analysis revealed that extruded pectin/albedo/starch/glycerol films provided better mechanical properties than pectin/albedo/glycerol films and were comparable in mechanical properties to extruded pectin/starch/glycerol films.     

Cross-linking starch at various moisture contents by phosphate substitution in an extruder

Starch was extruded with sodium trimetaphosphate and sodium hydroxide in a single-screw extruder with barrel and die temperature of 130 °C at three screw speeds of 40, 90, and 140 rpm and three moisture contents of 40, 55, and 70%. Time required for phosphorylation of starch in an extruder was found to be less than 2 min, and cross-linking of starch by phosphorus, which was incorporated into starch, was confirmed by paste viscosity of extruded starch. Cross-linking starch with 2.5% sodium trimetaphosphate did not significantly affect water absorption index, but reduced water solubility index so replacement of the process including mixing of starch with synthetic polymer in the extruder with another process including cross-linking of starch and then mixing with synthetic polymer can result in composite with lower solubility of starch. On the other hand, increasing moisture content of starch reduced both water absorption and solubility index of extrudates.     

Extrusion of pectin/starch blends plasticized with glycerol

The microstructural and thermal dynamic mechanical properties of extruded pectin/starch/glycerol (PSG) edible and biodegradable films were measured by scanning electron microscopy (SEM) and thermal dynamic mechanical analysis (TDMA). SEM revealed that the temperature profile (TP) in the extruder and the amount of water present during extrusion could be used to control the degree to which the starch was gelatinized. TDMA revealed that moisture and TP during extrusion and by inference the amount of starch gelatinization had little effect on the mechanical properties of PSG films. Furthermore, TDMA revealed that PSG films underwent a glass transition commencing at about −50°C and two other thermal transitions above room temperature. Finally, it was concluded that the properties of extruded PSG films were comparable to those cast from solution.     

Amylose content and chemical modification effects on thermoplastic starch from maize – Processing and characterisation using conventional polymer equipment

A design of experiments was performed on extruded starch based materials studied in a recently published article [Chaudhary, A. L., Miler, M., Torley, P. J., Sopade, P. A., & Halley, P. J. (2008). Amylose content and chemical modification effects on the extrusion of thermoplastic starch from maize. Carbohydrate Polymers, 74(4), 907–913] highlighting the effects of amylose content, chemical modification and extrusion on a range of maize starches. An investigation into the effects of starch type (unmodified 0–80% amylose starch; hydroxypropylated 80% amylose starch), screw speed and ageing after moulding on final product properties such as mechanical properties (Young’s modulus, maximum stress and strain at break), moisture absorption, morphology and retrogradation are included. A full factorial design was used to study these starch type, processing and final product property relationships. Microscopy was used to observe any morphological difference between the various starch types in thermoplastic starch (TPS) blends and X-ray diffraction (XRD) was used to observe changes in crystallinity over time (retrogradation). The results show that 0% amylose (waxy maize) and hydroxypropylated 80% amylose thermoplastic starches have mechanical properties comparable to that of low density polyethylene (LDPE) and high density polyethylene (HDPE), therefore these materials have the potential to be an environmentally friendly alternative to current polymer resins.     

Biodegradable films made from low density polyethylene (LDPE), wheat starch and soluble starch for food packaging applications. Part 2

Blends of LDPE and wheat or soluble starch were extruded, hot pressed and studied, after conditioning at various relative humidities, with regard to their mechanical properties and gas/water permeabilities before and after storage. Several theoretical and semiempirical calculations for mechanical properties and gas permeability are applied and possible interpretations are provided for occasionally observed deviations between the experimental and the theoretical values. Some of the semiempirical models predicted reasonably well the mechanical behaviour of the films. The presence of starch, at contents >30%, had an adverse effect on the mechanical properties of LDPE/starch blends. The degradability of several LDPE/starch blends and the accompanying changes in their mechanical properties are also assessed. Gas permeability and water vapour transmission rate increased proportionally with the starch content in the blend.     

Laboratory composting of extruded starch acetate and poly lactic acid blended foams

Composting of extruded foams made of starch acetate and poly lactic acid (PLA) with pre-conditioned yard waste was studied using a laboratory composting system. Extruded foams of high amylose starch were used as the control. Degradation was measured by analyzing the exhaust gases for carbon dioxide. There were significant differences in the amounts of carbon dioxide produced in the vessels containing foams of high amylose starch and foams of starch acetate blended with 20% or 30% PLA. The high amylose starch foams completely degraded within 15 days. The starch acetate foams with 0% PLA took longer, with evolution of carbon dioxide still measurable after 55 days. The rate of degradation was faster for foams with higher PLA contents. The starch acetate foams took even longer to degrade. The maximum time was found to be 130 days for the starch acetate foams.     

Film blowing of thermoplastic starch

Thermoplastic starch materials are often based on a combination of starch, glycerol and water. In the present study, two potato starch grades were employed; a native (natural) grade and an oxidised and hydroxypropylated grade of the native material, in order to produce the thermoplastic material. The primary aim of the study was to identify possible routes for film blowing thermoplastic starch on a laboratory scale by a suitable choice of processing conditions, amount of glycerol and moisture content. With an appropriate combination of these parameters, the thermoplastic material based on the modified starch could be film blown in a satisfactory manner. Film blowing of material based on the natural starch was significantly more difficult. The difficulties encountered were mainly related to a sticky surface of the film, insufficient tenacity and foaming. The processing window for thermoplastic starch (related to film blowing) is briefly outlined and discussed.     

The starch granule associated proteomes of commercially purified starch reference materials from rice and maize

Commercially available reference materials are integral components of many experimental protocols, as it is critical to compare one's results to those derived from well-characterized standards. Most reference materials are well defined, with all their components being cataloged. However, certain reference materials, such as commercially prepared starch samples, can have undefined components, potentially limiting their usefulness as standards. The proteome of commercially prepared starch has not been documented, and to that end, we initiated a mass spectrometry-based survey of the proteins associated with starch granules in commercially prepared rice and maize starch samples. We performed direct trypsin treatments of starch samples and sequenced both the water-soluble peptides liberated into the aqueous supernatant and the peptides released from the starch granule surface by isopropanol solvent washing. We discovered that the majority of proteins, in both rice and maize samples, were involved in either carbohydrate metabolism or storage. We also documented proteins that are markers for seed maturity and for starch mobilization.     

A novel in situ atomic force microscopy imaging technique to probe surface morphological features of starch granules

The application of atomic force microscopy (AFM) for observing iodine complexes in starch has been limited due to limitations including granular sample fixation techniques and possible unintended reactions with embedding materials such as epoxy resins or adhesives. In this paper, a new method is described that employs an optical microscopic technique to ensure that the tip of the AFM is scanning a specified granule without any probe-induced particle movement by the AFM probe motion. The direct sprinkling of samples on a two-sided adhesive tape allows investigations in an in situ environment of the un-embedded starch granule surface and thus provides high-resolution images of granule morphology and phase changes of starches in the presence of humidity and with iodine vapor. These observations demonstrate that this novel in situ AFM imaging technique allows us to visualize the hair-like structures on the surface of granular starches when starches are exposed to iodine vapor under humid environments. This study reveals that the hair-like extensions on the starch granule surfaces are strongly dependent on the organization of the glucan polymers within corn or potato starch.     

Small grains for starch production

Wheat, sorghum, rice, barley, oat and rye grains are actual or potential raw materials for the industrial production of starch, but only the first three are so used. All six contain about 60% to 70% starch, and yield oil and protein as valuable byproducts of starch manufacture. Successful competition of these grains with the present major industrial sources of starch— corn, potatoes and cassava— depends on a number of factors, including comparative costs of the raw materials, efficiency of processing methods, and value of the byproducts.     

Influence of amylose content on starch films and foams

After extraction of smooth pea starch and waxy maize starch from pure amylose and amylopectin fractions, films with various amylose contents were prepared by casting in the presence of water or water with glycerol. For unplasticized films, a continuous increase in tensile strength (40–70 MPa) and elongation (4–6%) was observed as amylose increased from 0 to 100%. Discrepancies with values obtained for native starches with variable amylose content and different botanical origins were attributable to variations in the molecular weights of components. Taking cell wall properties into account, the values obtained in the laboratory were used to improve the relation between the flexural behavior of extruded foams and the model of cellular solids with open cavities.

The properties of plasticized films were not improved by the presence of glycerol and remained constant when amylose content was higher than 40%. Results are interpreted on the basis of topological differences between amylose and amylopectin.     

Compression molding and tensile properties of thermoplastic potato starch materials

The mechanical and melt flow properties of two thermoplastic potato starch materials with different amylose contents were evaluated. The materials were prepared by mixing starch, glycerol, and water, mainly in the weight proportions of 10:3:4.5. Compression molding was used to produce sheets/films with a thickness in the range of 0.3-1 mm. After conditioning at 53% relative humidity (RH) and 23 C, the glycerol-plasticized sheets with a higher amylose content (HAP) were stronger and stiffer than the normal thermoplastic starch (NPS) with an amylose content typical for common potato starch. The tensile modulus at 53% RH was about 160 MPa for the high-amylose material and about 120 MPa for the plasticized NPS. The strain at break was about 50% for both materials. The stress at break was substantially higher for the HAP materials than for the NPS materials, 9.8 and 4.7 MPa, respectively. Capillary viscometry at 140 C showed that the high-amylose material had a higher melt viscosity and was more shear-thinning than the NPS. Dynamic mechanical measurements indicated a broad transition temperature range for both types of starch material. The main transition peaks for glycerol-plasticized starch were located at about room temperature with the transition for the HAP material being at a somewhat higher temperature than that of the NPS material with a lower amylose content. It was also noted that the processing conditions used during the compression molding markedly affected the mechanical properties of the starch material.     

Films of starch and poly(butylene adipate co-terephthalate) added of soybean oil (SO) and Tween 80

Starch extruded in the presence of a plasticizer results in a material called thermoplastic starch (TPS). TPS mixed with poly(butylene adipate co-terephthalate) (PBAT), soybean oil (SO), and surfactant may result in films with improved mechanical properties due to greater hydrophobicity and compatibility among the polymers. This study characterized films produced from blends containing 65% TPS and 35% PBAT with SO added as compatibilizer. The Tween 80 was added to prevention of phase separation. The elongation and resistance were greater in the films with SO. The infrared spectra confirmed an increase in ester groups bonded to the PBAT and the presence of groups bonded to the starch ring, indicating TPS-SO and PBAT-SO interactions. The micrographs suggest that the films with SO were more homogenous. Thus, SO is considered to be a good compatibilizer for blends of TPS and PBAT.     

复合淀粉凝胶电泳同工酶分析

为了克服水解马铃薯淀粉不易获得的困难,并使“水平切片淀粉凝胶电泳同工酶分析”更容易开展,普通的化学试剂马铃薯淀粉(或精制食用马铃薯淀粉)和可溶性淀粉混合物加入适当的添加剂被用来代替水解马铃薯淀粉制作凝胶。试验结果表明：用8～10％的上述混合淀粉(5∶3),添加1％的琼脂粉和2～4％的蔗糖,所制成的“复合淀粉凝胶”可以很好地被切片,并成功地对许多不同类群的植物材料的PGM、PGI、MDH、AAT、SKDH、6PGD、IDH和ME等酶进行染色。     

高水分、富含淀粉植物组织的扫描电镜制备技术优化

应用常规高真空扫描电子显微镜观察生物样品必须经过脱水和干燥处理,但无论采用临界点干燥还是冷冻干燥方法,都存在样品表面不同程度失真的问题。植物高水分、富含淀粉组织样品经处理后,容易出现淀粉流失、细胞壁变形等现象,从而造成扫描图像粗糙,无法获得真实的细胞内部结构。本文通过对CO_2临界点干燥、化学固定样品冷冻干燥和新鲜样品冷冻干燥3种扫描电镜样品制备技术中后期制样进行机械断裂和液氮脆断改进,优化出两种植物高水分、富含淀粉组织的扫描电镜样品制备方法:(1)样品首先进行FAA化学固定,经冷冻干燥后用液氮脆断,对断面喷金镀膜和扫描电镜观察。利用该方法所得细胞结构完整,细胞壁整齐,淀粉粒和蛋白轮廓明确,可用于分析淀粉粒和蛋白颗粒在细胞内的分布。(2)新鲜样品直接进行冷冻干燥,经液氮脆断后对断面喷金镀膜和扫描电镜观察。利用该方法所得细胞壁整齐,淀粉粒轮廓更清晰,并且无蛋白颗粒干扰,用于分析淀粉粒在细胞内的分布更加理想。