Ali Marefati

Chemical composition, digestibility and emulsification properties of octenyl succinic esters of various starches

Octenyl succinate starches are commonly used as emulsifiers and texturizing agents in many food-systems. Rice, tapioca, corn, wheat and potato starches were modified with octenyl succinic anhydride (OSA) at 3% level. Structural characterization, molecular weight, starch digestibility and physical properties of starch granule stabilized emulsions were studied for modified starches. Modified potato (0.022) and wheat (0.018) starches had the highest and lowest degrees of OSA substitution, respectively. For all starches, amylose and amylopectin molecular mass was significantly (P<0.05) lower for OSA starches. OSA modification may have hydrolyzed the small amylose and amylopectin chains, or caused rearrangement of the starch molecules. Although the starch modification improved emulsification properties, botanical source showed more influence on this parameter. Overall, botanical source had more influence on functional properties than degree of substitution. Further studies on OSA group distribution and fine molecular structure of amylopectin and relationship with functional properties will be important.

Pickering emulsifiers based on hydrophobically modified small granular starches – Part I: Manufacturing and physico-chemical characterization

Small granular starches from rice, quinoa and amaranth were hydrophobized by esterification with octenyl succinic anhydride (OSA) in an aqueous alkaline slurry to obtain series of modified starches at defined intervals (i.e. 0.6, 1.2, 1.8, 2.4, 3.0%). The physical and the physico-chemical properties of the starch particles were characterized by proximate analysis including protein level, amylose level and dry matter. The shape and size of the starch granules were characterized by scanning electron microscopy and light scattering. The gelatinization properties were characterized by differential scanning calorimetry. The degree of modification was determined by titration with NaOH. With regard to the emulsion formulation and in order to assess the emulsifying capacity of the small granular starches, the effect of starch type, degree of modification and starch concentration on the resulting emulsion droplet size were evaluated by light scattering and optical microscopy. Emulsifying properties were found to depend on the degree of substitution, size of the granules and the starch to oil ratio of the formulation. Quinoa starch granules, in general, had the best emulsifying capacity followed by amaranth and rice. However, in higher starch concentrations (>400mg/mL oil) and adequate levels of OSA (3.0%) amaranth performed best, having the smallest size of starches studied.

Comparative Emulsifying Properties of Octenyl Succinic Anhydride (OSA)-Modified Starch: Granular Form vs Dissolved State

The emulsifying ability of OSA-modified and native starch in the granular form, in the dissolved state and a combination of both was compared. This study aims to understand mixed systems of particles and dissolved starch with respect to what species dominates at droplet interfaces and how stability is affected by addition of one of the species to already formed emulsions. It was possible to create emulsions with OSA-modified starch isolated from Quinoa as sole emulsifier. Similar droplet sizes were obtained with emulsions prepared at 7% (w/w) oil content using OSA-modified starch in the granular form or molecularly dissolved but large differences were observed regarding stability. Pickering emulsions kept their droplet size constant after one month while emulsions formulated with OSA-modified starch dissolved exhibited coalescence. All emulsions stabilized combining OSA-modified starch in granular form and in solution showed larger mean droplet sizes with no significant differences with respect to the order of addition. These emulsions were unstable due to coalescence regarding presence of free oil. Similar results were obtained when emulsions were prepared by combining OSA-modified granules with native starch in solution. The degree of surface coverage of starch granules was much lower in presence of starch in solution which indicates that OSA-starch is more surface active in the dissolved state than in granular form, although it led to unstable systems compared to starch granule stabilized Pickering emulsions, which demonstrated to be extremely stable.

Combined emulsifying capacity of polysaccharide particles of different size and shape

The aim of this study is to understand mixed systems of two types of particles with different size and shape, quinoa starch granules (NQ) and cellulose nanocrystals (CNC), to stabilize oil-in-water (O/W) emulsions. This study considers the extent of Pickering stabilization with respect to which particle type dominates at droplet interfaces and how stability is affected by the addition of one particle type to already formed emulsions, or combining both, simultaneously. Results demonstrate that the order of addition has an influence allowing to predominantly have NQ particles at the interface when both types are added simultaneously. However when CNC is added first, both types are responsible for emulsion stabilization leading to a system with an intermediate droplet size yet with a higher stability compared to single particle formulations. A dual stabilization mechanism is observed, large particles prevent coalescence and small particles regulate the curvature of the interface and govern the droplet size.

Rice Starch Particle Interactions at Air/Aqueous Interfaces - Effect of Particle Hydrophobicity and Solution Ionic Strength

Starch particles modified by esterification with dicarboxylic acids to give octenyl succinic anhydride (OSA) starch is an approved food additive that can be used to stabilize oil in water emulsions used in foods and drinks. However, the effects of the OSA modification of the starch particle on the interfacial interactions are not fully understood. Here, we directly measured the packing of films of rice starch granules, i.e., the natural particle found inside the plant, at air/aqueous interfaces, and the interaction forces in that system as a function of the particle hydrophobicity and ionic strength, in order to gain insight on how starch particles can stabilize emulsions. This was achieved by using a combined Langmuir trough and optical microscope system, and the Monolayer Interaction Particle Apparatus. Native rice starch particles were seen to form large aggregates at air/water interfaces, causing films with large voids to be formed at the interface. The OSA modification of the rice starches particles decreased this aggregation. Increasing the degree of modification improved the particle packing within the film of particles at the air/water interface, due to the introduction of inter-particle electrostatic interactions within the film. The introduction of salt to the water phase caused the particles to aggregate and form holes within the film, due to the screening of the charged groups on the starch particles by the salt. The presence of these holes in the film decreased the stiffness of the films. The effect of the OSA modification was concluded to decrease the aggregation of the particles at an air/water interface. The presence of salts, however, caused the particles to aggregate, thereby reducing the strength of the interfacial film.

Pickering emulsifiers based on hydrophobically modified small granular starches Part II – Effects of modification on emulsifying capacity

Small granular starches from rice, quinoa, and amaranth were modified with octenyl succinic anhydride (OSA) at 5 defined intervals (0-3.0%) and investigated with respect to emulsifying capacity and stability. Starch granule surfaces were characterized by Brunauer-Emmett-Teller and contact angle measurements. Emulsifying capacity was characterized by multiple light scattering (MLS) and particle size analysis. Stability towards environmental stress was characterized by centrifugation and MLS. Surface hydrophobicity and emulsifying capacity correlated with starch type and modification level. Quinoa stabilized emulsions had the smallest droplet size (e.g. 59.2 μm at 3.0% OSA) and superior stability, both before and after centrifugation, especially at the lowest modification levels. Rice and amaranth had larger droplets (99.8 and 84.1 μm at 3.0% OSA respectively). Amaranth, despite its small size showed poorer performance than quinoa, especially at lower modification levels. The higher emulsifying efficiency of quinoa starch granules attributed to the higher protein content.