New insights on the mechanism of acid degradation of pea starch

The degradation of pea starch granules by acid hydrolysis has been investigated using a range of chemical and structural methods, namely through measuring changes in amylose content by both the iodine binding and concanavalin A precipitation methods, along with small angle X-ray scattering (SAXS), wide angle X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). The relative crystallinity, intensity of the lamellar peak and the low-q scattering increased during the initial stages of acid hydrolysis, indicating early degradation of the amorphous regions (growth rings and lamellae). In the first 2 days of hydrolysis, there was a rapid decline in amylose content, a concomitant loss of precipitability of amylopectin by concanavalin A, and damage to the surface and internal granular structures was evident. These observations are consistent with both amylose and amylopectin being located on the surface of the granules and attacked simultaneously in the early stages of acid hydrolysis. The results are also consistent with amylose being more concentrated at the core of the granules. More extensive hydrolysis resulted in the simultaneous disruption of amorphous and crystalline regions, which was indicated by a decrease in lamellar peak intensity, decrease in interhelix peak intensity and no further increase in crystallinity. These results provide new insights into the organization of starch granules.     

Effects of amylose/amylopectin ratio on starch-based superabsorbent polymers

Biodegradable superabsorbent polymers (SAPs) were prepared by grafting acrylamide onto starches then crosslinking with N,N′-methylene-bisacrylamide. This work focused on the effects of the amylose/amylopectin ratio of starches from the same source (corn) on the grafting reactions and performance of the resultant starch-based SAPs. To characterise each SAP, the acrylamide groups grafted onto the starch were detected by FTIR; grafting ratio and grafting efficiency were evaluated by a gravimetric method; and graft position and the length of the grafted segment were investigated by NMR. The relationships between the microstructures of the starches, and the graft reactions and performance of the SAPs were studied based on the amylose content in the starches. It was found that under the same reaction conditions, the grafting ratio and efficiency increased with increasing amylose content, which corresponds with water absorption ratio. NMR results indicated that the acrylamide group mainly grafted onto C6, and that the length of the grafted segment decreased with increasing amylopectin content in general, and in particular for waxy starch. The high molecular weight and branched structure of amylopectin reduced the mobility of the polymer chains and increased viscosity, which could explain the graft reactions and performance of the starch-based SAPs.     

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.     

Properties of a plasticised starch blend. Part 1: Influence of moisture content on fracture properties

The effect of moisture content on tensile and fracture properties of a plasticised starch/high molecular weight polyol blend was investigated. A wide range of mechanical behaviour was achieved by varying slightly the water uptake of this material. At low moisture content, the Young’s modulus was 3800 MPa and the yield stress, 54 MPa. When the moisture content reached 15 wt%, their values dropped, respectively, to around 1500 MPa and 21 MPa. As the material behaviour varies greatly over the moisture content range, two fracture mechanics techniques were employed: the linear elastic fracture mechanics approach to characterise brittle behaviour and the essential work of fracture method to investigate a more ductile material. At low moisture content, the measured strain energy release rate at fracture, J_Q was very low and showed little dependency on the moisture content. As the moisture content increases, the material becomes increasingly ductile and displayed a brittle-to-ductile transition at 12% of moisture content, which corresponded to the glass transition temperature of the added polyol.     

Effect of high hydrostatic pressure on the formation of radicals in maize starches with different amylose content

Native and high pressure-treated (water suspensions, 650 MPa) waxy maize starch, containing mainly amylopectin, and Hylon VII, rich in amylose, were studied for their ability to generate free radicals upon thermal treatment at 180–230 °C. The electron paramagnetic resonance (EPR) spectroscopy was used to characterize the nature, number and stability of radicals. Various stable and short living (stabilized by N-tert-butyl-α-phenylnitrone (PBN) spin trap) radical species were formed. It was found, that at given conditions the waxy maize starch reveals higher ability to generate radicals, than Hylon VII. The presence of water and high pressure pretreatment of starches, both resulted in the reduction of the amount of thermally generated radicals. The decrease in crystallinity of waxy maize starch and of Hylon VII, occurring upon high pressure treatment, leads to the increase of the relative amount of fast rotating component in the EPR spectrum of both types of starches.     

Starch analysis using hydrodynamic chromatography with a mixed-bed particle column

Columns packed with commercial glass beads 5 and 19 μm average size and a mixture of both (0.7 volume fraction of large particles) were used to analyse starch composition by hydrodynamic chromatography (HDC), applying water as mobile phase. To obviate retrogradation, experiments were carried out at column temperatures of 15 and 3 °C and several types of starch were assayed. In what concerns amylopectin and amylose separation, a better resolution and a lower pressure drop were obtained for the mixed binary packing when compared with the packing containing uniform 5 μm glass beads. A more efficient cooling of the mobile phase was also obtained with the mixed packing, which was determinant for improving resolution. For the Hylon VII starch the relative retention times (RRT) were 0.777 and 0.964 for amylopectin and amylose, respectively, while for the Tapioca starch the obtained RRTs were 0.799 and 0.923. Application of unbound glass beads as column packing not only might reduce equipment and running costs in preparative scale separations, but also proved to be useful as a fast and reliable method to monitor the amylose and amylopectin content of starch samples of different sources.     

Molecular regulation of sink–source transition in rice leaf sheaths during the heading period

The upper leaf sheath of rice (Oryza sativa L.) serves as a temporary starch sink before heading, subsequently becoming a carbon source tissue to the growing panicle at the post-heading stage. The time of sink–source transition in upper leaf sheaths is highly correlated to the panicle exsertion. Here, we found that the expression profiles of starch synthesis genes such as ADP-glucose pyrophosphorylase large subunit 2, granule-bound starch synthase II, soluble starch synthase I, starch branching enzyme (SBE) I, SBEIII, and SBEIV were highly correlated with starch content changes during the heading period in the second leaf sheath below the flag leaf. In addition, the α-amylase2A and β-amylase were considered as major genes that were in charge of starch degradation at the post-heading period. Of the five sucrose transporter (OsSUT) genes, OsSUT1 and OsSUT4 appeared to play an important role in sucrose loading into the phloem of source leaf sheaths. Moreover, the microarray-based data implied that the dominant processes associated with functional leaf sheath transition from sink to source were carbohydrate metabolism and the translocation of the carbon and nitrogen sources and inorganic phosphate.     

Substitution patterns in methylated potato starch as revealed from the structure and composition of fragments in enzymatic digests

The effect of the granule structure on the methylation of starch was investigated by comparing the substitution patterns of potato starch methylated in granular suspension and in solution to DS 0.3. Substitution patterns were analyzed by successive digestion with alpha-amylase and amyloglucosidase, fractionation of the resulting malto-oligosaccharide mixture by GPC on a preparative scale, and characterization of the fractions by GLC and MALDI-MS. The mass composition of fractions with intermediate and higher degree of polymerization was indicative of enhanced clustering of substituents in granular methyl starch. On the contrary, the composition of the smaller saccharides was governed by enzyme specificity, which was also reflected in strong deviations in their monomer composition. A sequencing study on selected 'pure' small saccharides confirmed and complemented previous conclusions on enzyme specificity.     

Microwave-accelerated methylation of starch

A novel microwave-accelerated method for methylating soluble starch is described. Soluble starch could be fully methylated in 72% yield within 4.66 min using iodomethane and 30% potassium hydroxide under microwave irradiation. The completely methylated starch thus obtained was hydrolyzed with 60% HCO(2)H for 1.5 min under 80% MW power, followed by 0.05 M H(2)SO(4) for 2.0 min under 100% MW power. The partially methylated monosaccharides were separated by preparative paper chromatography and identified by their melting points and optical rotations.