Aggregate and emulsion properties of enzymatically-modified octenylsuccinylated waxy starches

Sorghum and maize waxy starches were hydrophobically modified with octenylsuccinic anhydride (OSA) and treated with enzymes before being used to emulsify β-carotene (beta,beta-carotene) and oil in water. Enzyme treatment with β-amylase resulted in emulsions that were broken (separated) earlier and suffered increased degradation of β-carotene, whereas treatment with pullulanase had little effect on emulsions. Combinations of surfactants with high and low hydrodynamic volume (V) indicated that there is a relationship between V and emulsion stability. Degree of branching (DB) had little direct influence on emulsions, though surfactants with the highest DB were poor emulsifiers due to their reduced molecular size. Results indicate that V and branch length (including linear components) are the primary influences on octenylsuccinylated starches forming stable emulsions, due to the increased steric hindrance from short amphiphilic branches, consistent with current understanding of electrosteric stabilization. The success of OSA-modified sorghum starch points to possible new products of interest in arid climates

Structures of octenylsuccinylated starches: Effects on emulsions containing β-Carotene

Starches with different amylopectin contents and different molecular sizes prepared using acid hydrolysis were hydrophobically modified using octenylsuccinic anhydride (OSA). The OSA-modified starches were used as surfactants to stabilize emulsions of β-Carotene and canola oil dispersed in water. The objective of this study is to investigate the relationship between starch molecular structure and the chemical stability of the emulsified β-Carotene, as well as the colloidal stability of emulsion droplets during storage. The oil droplet size in emulsions was smaller when starch had (a) lower hydrodynamic volume (Vh) and (b) higher amylopectin content. The oxidative stability of β-Carotene was similar across samples, with higher results at increased amylopectin content but higher Vh. Steric hindrance to coalescence provided by adsorbed OSA-modified starches appears to be improved by more rigid molecules of higher degree of branching

The influence of macromolecular architecture on the critical aggregation concentration of large amphiphilic starch derivatives

A range of hyperbranched emulsifiers were prepared by reaction between starch and 2-octen-1-yl succinic anhydride (OSA, commonly used in the food industry), under slightly basic conditions in water, leading to starches bearing hydrophobic OSA groups randomly distributed along the chains. By using different starch backbones and varying the amount of OSA during the synthesis, amphiphilic OSA-modified starches were obtained that formed aggregates in water and having controlled structural parameters. These parameters were characterized using H NMR, multiple-angle laser light scattering and size-exclusion chromatography. The critical aggregation concentration (CAC) was measured for samples with different levels of OSA modification, of macromolecular size and degree of starch branching. Increasing the dispersity in macromolecular size and/or degree of OSA substitution noticeably decreased the CAC. The results are interpreted in terms of the branching structure and conformation of the modified starches: all findings can be understood in terms of the various influences of molecular size, composition and flexibility. The structural factors affecting the CAC of large hyperbranched surfactants are found to be similar to those seen with smaller and simpler branched synthetic surfactants

Structure and physicochemical properties of octenyl succinic anhydride modified starches: a review

Starches modified with octenyl succinic anhydride (OSA) have been used in a range of industrial applications, particularly as a food additive, for more than half a century. Interest in these products has grown in recent years as a result of new methods and applications becoming available. Due to a combination of OSA's hydrophobic and steric contribution and starch's peculiar highly branched macromolecular structure, these starch derivatives display useful stabilizing, encapsulating, interfacial, thermal, nutritional and rheological properties. We review the synthesis procedures, structural characterization methods and physico-chemical properties, and the influences of the botanical origins and structural parameters of OSA starches on physico-chemical properties. A better understanding of these features has the potential to lead to products with targeted macromolecular structures and optimized properties for specific applications

Effect of octenylsuccinic anhydride modification on beta-amylolysis of starch

The effects of octenylsuccinic anhydride (OSA) modification of waxy maize and sorghum starches on subsequent β-amylolysis are examined. Hydrolysis with β-amylase is a method by which OSA starches may be structurally modified for industrial purposes. The hydrolysis of both granular and gelatinised forms of both starches follows first-order kinetics regardless of the OSA used as a percent of starch mass (0-24%). The highest hydrolysis rate coefficients for granular starches are at modification with 6% OSA/starch. The largest molecular sizes of β-amylase hydrolysed OSA-modified gelatinised starches are found at modification with 24% OSA/starch. The results suggest that octenylsuccinyl groups have an action-blocking effect on β-amylolysis of gelatinised starch, but the effect of semi-crystalline granular structure is more pronounced than that of OSA modification. Hence β-amylolysis can be used under appropriate conditions to modify the structure of gelatinised OSA-modified starches

New H-1 NMR procedure for the characterization of native and modified food-grade starches

A novel, fast, and straightforward procedure is presented for the characterization of starch (the largest energy component in food) and modified starches (such as octenyl succinic anhydride (OSA)-modified starches used as a dispersing agent in the food industry). The method uses H-1 NMR to measure the degree of branching and also, for modified starches, the degree of chemical substitution. The substrate is dissolved in dimethyl-d(6) sulfoxide; addition of a very low amount of deuterated trifluoroacetic acid (d(1)-TFA) to the medium gives rise to a shift to high frequency of the exchangeable protons of the starch hydroxyl groups, leading to a clear and well-defined H-1 NMR spectrum, which provides an improved way to determine the degrees of both branching and chemical substitution. Measurements of the size and molecular weight distributions by multiple-detector size exclusion chromatography show that degradation by TFA does not affect the accuracy of the method

Extraction, isolation and characterisation of phytoglycogen from su-1 maize leaves and grain

Phytoglycogen is a highly branched soluble α-glucan found in plants, particularly those with decreased activity of isoamylase-type starch debranching enzyme, such as sugary-1 (su-1) maize. An improved technique has been designed to extract and isolate phytoglycogen from the grain and leaves of su-1 maize with minimal degradation for structural characterisation. The structures of extracted phytoglycogen samples were analysed using size-exclusion chromatography (SEC, also termed GPC) and transmission electron microscopy (TEM) and compared with the structure of pig liver glycogen. The SEC weight molecular size distributions indicate that the extraction procedure with protease is most effective in obtaining pure phytoglycogen from grain, whereas that without protease at cold temperature followed by purification using a sucrose gradient is more effective for leaf material. The extracted and purified phytoglycogen samples from both grain and leaf contain wide distributions of molecular sizes (analysed by SEC and TEM), with the smallest being "individual" β particles, which collectively form larger α particles; the latter are dominant in the phytoglycogen samples examined here. The results show that phytoglycogen is similar to liver glycogen in both the range of molecular size distribution and in the presence of α particles. Abbreviations* AUC*area under the curve*C*ice-cold tricine buffer treatment at 0-4 C*DAP*days after pollination*DBE*debranching enzyme*DMSO/LiBr*dimethyl sulfoxide containing 0.5% (w/w) lithium bromide*SG*sucrose gradient*IUPAC*International Union of Pure and Applied Chemistry*NMR*nuclear magnetic resonance*P*treatment using protease in tricine buffer at 37 C*R*hydrodynamic radius*SEC*size-exclusion chromatography*sh-2*shrunken-2 genetic mutation*su- 1*sugary-1 genetic mutation*TEM*transmission electron microscopy*V*hydrodynamic volume*W*warm tricine buffer treatment at 37 C