Engineering starch for increased quantity and quality

The characterization and production of starch variants from mutation studies and transgene technology has been invaluable for our understanding of the synthesis of the starch granule. The knowledge gained has allowed for genetic manipulation of the starch biosynthetic pathway in plants. This in vivo approach can be used to generate novel starches and diminishes the need for post-harvest chemically and enzymatically treated starches. Thus, the modification of the starch biosynthetic pathway is a plausible means by which starches with novel properties and applications can be created.     

Starch modification by iterated syneresis

Potato, tapioca, corn and wheat starches were solubilised in water and isolated from the solution by iterated syneresis and the effect of this physical modification on the physicochemical properties and structure was studied. The experimental starches were examined by chemical analysis, the Brabender rheological method, scanning electron or light microscopy, X-ray diffractometry, infrared spectroscopy, and differential scanning calorimetry. Physical modification was evidenced to the change starch–water interaction and the structure of starches. Pasting temperature shifted to lower values and the gelatinisation mechanism changed. All modified starches had a B-type of X-ray diffraction pattern. The melting temperature of starch crystallites was typical of retrograded starch, but the enthalpy change was higher. The correlation between the resistant starch content of modified starches and their crystal structure was discussed together with the thermal properties.     

Applications of nonthermal plasma technology on safety and quality of dried food ingredients

Cold plasma technology is an efficient, environmental-friendly, economic and noninvasive technology; and in recent years these advantages placed this novel technology at the centre of diverse studies for food industry applications. Dried food ingredients including spices, herbs, powders and seeds are an important part of the human diet; and the growing demands of consumers for higher quality and safe food products have led to increased research into alternative decontamination methods. Numerous studies have investigated the effect of nonthermal plasma on dried food ingredients for food safety and quality purposes. This review provides critical review on potential of cold plasma for disinfection of dried food surfaces (spices, herbs and seeds), improvement of functional and rheological properties of dried ingredients (powders, proteins and starches). The review further highlights the benefits of plasma treatment for enhancement of seeds performance and germination yield which could be applied in agricultural sector in near future. Different studies applying plasma technology for control of pathogens and spoilage micro-organisms and modification of food quality and germination of dried food products followed by benefits and current challenges are presented. However, more systemic research needs to be addressed for successful adoption of this technology in food industry.     

Effect of acid–alcohol treatment on the molecular structure and physicochemical properties of maize and potato starches

The molecular structure and physicochemical properties of acid–alcohol treated maize and potato starches (0.36% HCl in methanol at 25 °C for 1–15 days) were investigated. The yields of the modified starches were ranging from 91 to 100%. The average granule size of modified starches decreased slightly. The solubility of starches increased with the increase of treatment time, and the pasting properties confirmed the high solubility of modified starches. The gelatinization temperatures and range of gelatinization increased with the increase of treatment time except T_o (onset temperature) of maize starch. Molecular structures of modified starches suggested the degradation of starches occurred mostly within the first 5 days of treatment, and degradation rate of potato starch was higher than maize starch both in amylopectin and in amylose. Maize starch was found less susceptible to acid–alcohol degradation than potato starch.     

Process optimization for the synthesis of octenyl succinyl derivative of waxy corn and amaranth starches

Modification of starch by dicarboxylic acid anhydrides to starch esters, containing both hydrophilic and hydrophobic groups are known to improve its emulsification properties, and can also be used for encapsulation after hydrolysis. Reports on the effect of process conditions on the extent of modification of starches by using n-octenyl succinic anhydride (n-OSA) are not readily available. In the present study, the process of manufacturing of OSA starches from waxy corn and amaranth starch were studied with respect to the OSA/starch ratio, pH, temperature and time of the reaction. The effects of these parameters were evaluated on the basis of degree of substitution (DS). The concluding conditions for amaranth-OSA starches was a reaction time of 6 h at 3% OSA/starch ratio at 30 °C and pH 8.0 at 25% starch concentration. For waxy corn-OSA starch, all parameters were identical except for the reaction time of 24 h. The maximum DS achieved for both the starches was 0.02. Emulsification capacity and oil absorption capacity of the OSA-modified starches were more or less similar within the parameter chosen and also independent of starch type.     

Effects of structure and modification on sustained release properties of starches

Starches of different sources and compositions were investigated to determine the effect of structure and chemical modification on the sustained release properties of the resultant modified starches. Starches were cross-linked with epichlorohydrin and substituted with carboxymethyl or aminoethyl groups at different levels. Substitution efficiency was overall higher for waxy corn and potato starches than for Hylon VII, and was higher for starches at low cross-linking levels than those at high cross-linking ones. Waxy corn starch displayed better sustained release properties when cross-linked to a lower level, whereas Hylon VII showed better performances when cross-linked to a higher level. Matrices substituted with carboxymethyl and aminoethyl groups at the high level showed better sustained release properties than those substituted at the low level. The proportion and structure of amylose and amylopectin in starches from different botanical sources strongly influenced the level of modification required to produce a satisfactory sustained release matrix.     

Effects of hydrogen, oxygen, and ammonia low-pressure glow plasma on granular starches

Cassava, corn, high amylose corn, potato, rice Indica, rice Japonica, sweet potato, waxy corn, and wheat starches were exposed to low-pressure ammonia, hydrogen, and oxygen plasma. In every case, depolymerization of the starch polysaccharides was noted. The extent of the depolymerization depended on the nature of the starch as well as the type of plasma applied. Among three fractions of polysaccharides distinguished by their molecular weight average, the fraction of the highest molecular weight suffered the most efficient depolymerization. The relative depolymerization for the middle- and low-molecular fractions of polysaccharides was found to be starch and plasma specific. The chemical character of the plasma had very little influence on the starch polysaccharides. Only subtle oxidation effects were observed in oxygen plasma. Low-pressure glow plasma treatment appeared to be a convenient tool for a waste-less dextrinization of starch. Manipulation of the plasma variety and the time of exposure resulted in a wide spectrum of dextrins of various molecular weights and paste-forming properties.     

Physicochemical characteristics and fine structure of high-amylose wheat starches isolated from Australian wheat cultivars

High-amylose starch is a source of resistant starch (RS) which have great impact on human health like dietary fiber. Nowadays, high-amylose wheat has been produced by genetic backcrossing, which enhances apparent amylose content and generates altered amylopectin. In this study, the high-amylose wheat starches isolated from various high-amylose wheat cultivars grown in Australia were characterized for understanding their physicochemical properties and fine structure of starch. The physicochemical characteristics of the high-amylose wheat starches are significantly different among the cultivars. Amylose contents of these cultivars were in a range of 28.0–36.9%, which is significantly higher than that of the normal wheat starch (25.6%). The high-amylose wheat starches also had higher blue value but lower λ_max than the normal wheat starch. Gelatinization temperature of the high-amylose wheat starches is higher than that of the normal wheat starch but transition enthalpy is lower. X-ray diffraction showed that the high-amylose wheat starch had C-type crystals close to A-type crystal. Pasting properties of the high-amylose wheat starches were varying depending on the cultivars. However, almost high-amylose wheat starches had lower peak and final viscosities and higher setback viscosity than did the normal wheat starch. Fine structure of amylose and amylopectin was different among the high-amylose wheat cultivars and related to the physicochemical properties of starch. These results help to understand well the characteristics of the high-amylose wheat starches before application for food processing.     

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.     

Preparation and characterization of soluble starches having different molecular sizes and composition,by acid hydrolysis in different alcohols

Potato and waxy-maize starches were separately modified for 1 h at 65° with 0.36% hydrochloric acid in methanol, ethanol, 2-propanol, and 1-butanol. All of the modified starches were readily soluble in hot water, to give crystal-clear solutions up to a concentration of at least 20% (w/v). The modified granules were studied by light-microscopy and iodine-iodide staining. All of the modified starches retained their granule appearance, although with various degrees of damage that progressively increased from methanol to 1-butanol. Both hydrolysis and alcoholysis occurred, but to different extents in the different alcohols. The highest proportion of alcoholysis occurred in methanol where 50% of the resulting molecules were glycosides, the lowest in 1-butanol where 6% were glycosides. The number-average molecular weights of the modified starches also progressively decreased from 126,670 for the methanol-modified waxy-maize starch to 4,750 for the 1-butanol-modified potato starch. The methanol- and ethanol-modified potato starches were fractionated into amylose and amylopectin components. The 2-propanol- and 1-butanol-modified potato starches gave only an amylopectin component. The amylose components were characterized by gel-permeation chromatography on Bio-Gel A-5m, and the amylopectin components, on Bio-Gels A-150m and A-0.5m. The molecular sizes of the amylose and amylopectin components progressively decreased from methanol- to 1-butanol-modified starches. Furthermore, the polymodal composition of the amylopectin component was decreased to give a more homogeneous product. Waxy-maize starch was modified in methanol and 2-propanol and gave products that were of lower molecular size and more homogeneous than the polymodal native starch. It is shown that the differential effect of the different alcohols on the modification of the starch granules is produced by effecting different concentrations of acid inside the granule, where hydrolysis occurs in the 10–12% of water contained in the granule. It is postulated that 2-propanol and 1-butanol dissolve the double-helical, crystalline regions in the starch granule to give different types of products under otherwise identical conditions of modification.     

Composition, structure, functionality, and chemical modification of legume starches: a review

The major carbohydrate of the legume seed is starch, which represents up to 45% of the total seed weight. In recent years, substantial progress has been made in understanding the relationship between starch structure and functionality. However, these studies have been mainly on cereal and tuber starches. The present status of knowledge on the composition, structure, functionality, digestibility, and chemical modification of legume starches is reviewed. In addition present concepts of granule structure, gelatinization, retrogradation, and rheology are also reviewed. Future research needs in the area of legume starch chemistry are discussed.     

Improving starch for food and industrial applications

Progress in understanding starch biosynthesis, and the isolation of many of the genes involved in this process, has enabled the genetic modification of crops in a rational manner to produce novel starches with improved functionality. For example, potato starches have been created that contain unprecedented levels of amylose and phosphate. Amylose-free short-chain amylopectin starches have also been developed; these starches have excellent freeze-thaw stability without the need for chemical modification. These developments highlight the potential to create even more modified starches in the future.     

Resistant glutarate starch from adlay: Preparation and properties

Reaction conditions were optimized to increase the content of resistant starch in adlay starch using esterification with glutaric acid, and the physicochemical properties of the prepared glutarate starches were investigated. Different amounts of glutaric acid (0.1–0.5 g/g starch, dry weight basis) were reacted with adlay starch at various temperatures (70–130 °C) and reaction times (3–9 h). The resistant starch levels increased with increased glutaric acid content, reaction temperature, and reaction time. The color difference was mainly affected by reaction time. The highest resistant starch content (RS 66%) was obtained using conditions of 0.4 g glutaric acid/g starch, 115 °C, and 7.5 h, with a color difference of 10.24. After digestion with α-amylase and amyloglucosidase, the water-soluble fraction of glutarate starch had more oligosaccharides than high-amylose maize starch (RS 43%). FT-IR and solid-state NMR detected carbonyl groups in the glutarate starch, indicating the formation of cross-linkages through esterification. The granular structure of the glutarate starches was not destroyed and they retained birefringence. After heating with an excess of water, the granules kept their shape but lost their birefringence. The glutarate starches had low solubility in both cold and hot water, and the resistant starch contents were unchanged after heating due to the restriction of swelling by cross-linking. The glutarate starches had a similar chain-length distribution to raw starch, indicating that acid hydrolysis took place at branching points in the amorphous region. Furthermore, the glutarate starches possessed a weaker crystalline region, more diverse double helical chains, and lower enthalpy than raw starch.     

An investigation of the action of porcine pancreatic alpha-amylase on native and gelatinised starches

The action of pancreatic alpha-amylase (EC 3.2.1.1) on various starches has been studied in order to achieve better understanding of how starch structural properties influence enzyme kinetic parameters. Such studies are important in seeking explanations for the wide differences reported in postprandial glycaemic and insulinaemic indices associated with different starchy foodstuffs. Using starches from a number of different sources, in both native and gelatinised forms, as substrates for porcine alpha-amylase, we showed by enzyme kinetic studies that adsorption of amylase to starch is of kinetic importance in the reaction mechanism, so that the relationship between reaction velocity and enzyme concentration [E0] is logarithmic and described by the Freundlich equation. Estimations of catalytic efficiencies were derived from measurements of kcat/Km performed with constant enzyme concentration so that comparisons between different starches were not complicated by the logarithmic relationship between E0 and reaction velocity. Such studies reveal that native starches from normal and waxy rice are slightly better substrates than those from wheat and potato. After gelatinisation at 100 degrees C, kcat/Km values increased by 13-fold (waxy rice) to 239-fold (potato). Phosphate present in potato starch may aid the swelling process during heating of suspensions; this seems to produce a very favourable substrate for the enzyme. Investigation of pre-heat treatment effects on wheat starch shows that the relationship between treatment and kcat/Km is not a simple one. The value of kcat/Km rises to reach a maximum at a pre-treatment temperature of 75 degrees C and then falls sharply if the treatment is conducted at higher temperatures. It is known that amylose is leached from starch granules during heating and dissolves. On cooling, the dissolved starch is likely to retrograde and become resistant to amylolysis. Thus the catalytic efficiency tends to fall. In addition, we find that the catalytic efficiency on the different starches varies inversely with their solubility and we interpret this finding on the assumption that the greater the solubility, the greater is the likelihood of retrogradation. We conclude that although alpha-amylase is present in high activity in digestive fluid, the enzymic hydrolysis of starch may be a limiting factor in carbohydrate digestion because of factors related to the physico-chemical properties of starchy foods.     

Production of very-high-amylose potato starch by inhibition of SBE A and B

High-amylose starch is in great demand by the starch industry for its unique functional properties. However, very few high-amylose crop varieties are commercially available. In this paper we describe the generation of very-high-amylose potato starch by genetic modification. We achieved this by simultaneously inhibiting two isoforms of starch branching enzyme to below 1% of the wild-type activities. Starch granule morphology and composition were noticeably altered. Normal, high-molecular-weight amylopectin was absent, whereas the amylose content was increased to levels comparable to the highest commercially available maize starches. In addition, the phosphorus content of the starch was increased more than fivefold. This unique starch, with its high amylose, low amylopectin, and high phosphorus levels, offers novel properties for food and industrial applications.     

Physicochemical and functional properties of starches from sorghum cultivated in the Sahara of Algeria

Pure starches were isolated from white and red sorghum cultivated in Tidikelt, a hyper arid region situated in south Algeria. Amylose content, X-ray pattern and rheological properties of starches were examined. The amylose content in white sorghum starch (27.1%) was slightly higher than that in red sorghum (24.8%). The swelling power and the solubility behavior of both starches were nearly similar below 65 °C. At higher temperatures, starch isolated from the white sorghum cultivar showed higher swelling power and lower solubility index than pigmented sorghum starch. The pasting properties of starches determined by RVA, Rapid Visco Analyser showed different viscosity peaks. Red sorghum starch had a higher value (4731 cP) than white sorghum starch (4093 cP). For both sorghum, X-ray diffractograms exhibit an A-type diffraction pattern, typical of cereal starches and the relative degrees of crystallinity were estimated at 22.72% and 28.91%, respectively, for local white and red sorghum starch. DSC analysis revealed that sorghum starches present higher temperatures at the peak (70.60 and 72.28 °C for white and red sorghum starches, respectively) and lower gelatinization enthalpies (9.087 and 8.270 J/g for white and red sorghum starches, respectively) than other cereal starches.The results showed that physicochemical and functional properties of sorghum cultivar starches were influenced by the genotype and the environment.     

Origins of B-type crystallinity in glycerol-plasticised, compression-moulded potato starches

The amount of B-type crystallinity in compression-moulded, glycerol-plasticised potato starches was strongly dependent on both the properties of the potato starch used and the applied processing conditions. The presence of amylose and the morphology of the potato starch used, but also processing parameters such as moulding temperature and water content during moulding affected the amount of B-type crystallinity in the materials and thus the ultimate mechanical properties of the plasticised starches. This indicated that the direct relation between composition and physical properties of processed starches is not always valid; processing parameters are important tools for controlling the physical properties of processed starches as they influence the amount of B-type crystallinity in the material. It was shown that the total amount of B-type crystallinity in the glycerol-plasticised potato starches should be considered as a summation of residual amylopectin crystallinity and recrystallisation of both amylose and amylopectin, being strongly dependent on the applied processing conditions. In order to explain the observed amount of B-type crystallinity in these starches, partial (co-)crystallisation of both amylose and amylopectin should occur at high moulding temperatures. The measured mechanical properties of the plasticised potato starches correlated well with the amount of B-type crystallinity observed in the materials.     

Production of a freeze-thaw-stable potato starch by antisense inhibition of three starch synthase genes

The use of unmodified starches in frozen foods is severely limited by the undesirable textural changes that occur after freezing and thawing. Retrogradation of glucan chains leads to syneresis, a separation of the starch gel and water phases. Stabilization of the starch structure is normally achieved by chemical modification to prevent these changes from occurring. We have now created a freeze-thaw-stable potato starch by alteration of starch composition and structure by genetic modification. An amylose-free starch with short-chain amylopectin was produced by simultaneous antisense downregulation of three starch synthase genes. This starch is extremely freeze-thaw-stable and shows no syneresis even after five freeze-thaw cycles. The use of this starch has potential for environmental and consumer benefits because its production requires no chemical modification.     

Change of granular and molecular structures of waxy maize and potato starches after treated in alcohols with or without hydrochloric acid

Starches from waxy maize and potato were treated in methanol and 2-propanol either with or without 0.36% hydrochloric acid at 65 °C for 1 h. The granule morphology, molecular structure and pasting properties of the starches were determined and the effects of treatments on the granule and molecular structures of starch were investigated. Starch treated in alcohols without acid showed loss of native order through the hilum of granules, and no obvious molecular degradation was found. However, acid–alcohol treated starch showed many cracks inside granules, and both waxy maize and potato starches showed obvious molecular degradation after treated. Furthermore, the amylose chains and long chains of amylopectin of starch were more easily degraded with acid–alcohol treatment. The pasting viscosity of acid–alcohol treated starches were also obviously less than that of their counterpart native starch and starch after alcohol treatment. The extent of degradation of molecules and the decrease of pasting viscosity on potato starch after acid–alcohol treated were more obvious than that of waxy maize starch. The result indicates that the degradation preferentially occur in the amorphous region when starch treated by acid–alcohol, and the degradation of starch molecules enhances the amorphous excretion and the occurrence of cracks inside the granules.     

Behaviour of granular starches in low-pressure glow plasma

Granular starches of nine botanical origins were exposed to low-pressure glow plasma generated in the air from either a high voltage DC supply or an AC inductor. Experiments with low energy air-plasma (10⁻² Torr) and starches provided insight into some details of their surface structure. Starches were partly oxidized to carboxylic starches and partly depolymerized. Their affinity to plasma depended on their botanical origin. The structure of starch granules seemed to be a crucial factor, which determined the behaviour of starches in plasma. Lipids and/or proteins stabilized polysaccharides to plasma being preferentially decomposed.