Octenyl Succinic Anhydride Esterification Research Articles

Effects of the degree of substitution of octenyl succinic anhydride on the physicochemical characteristics of adlay starch

Impact of octenyl succinic anhydride (OSA) esterification on the structural, thermal, pasting, and emulsifying characteristics of adlay starch was investigated. The degree of substitution (DS) increased significantly from 0.008 to 0.025 with increasing OSA quantity, and the bands intensity at 1724 cm−1 and 1572 cm−1 in Fourier transform infrared spectroscopy increased with increasing DS. OSA modified starch showed unaltered orthorhombic diffraction pattern and morphological structure in native adlay starch, but gelatinization temperatures and enthalpy decreased significantly. Higher DS values lowered iodine binding capacity (from 1.37 to 0.77) and a shift in the maximum absorbance wavelength toward the shortwave direction was observed (from 530 nm to 510 nm). Significant increases were observed in peak, through, breakdown and final viscosities upon OSA esterification, while the pasting temperature decreased. Furthermore, contact angles increased significantly from 27.4° to 73.4° with increasing DS, and OSA-starch exhibited superior emulsion stability. Therefore, esterification with OSA effectively modified adlay starch to meet industrial demands and enhance its functional properties.

Fabrication and characterization of O/W emulsion stabilized by Octenyl Succinic Anhydride (OSA) modified resistant starch

Reducing fat content without compromising its sensory qualities is a major technological challenge to the food industry in manufacturing healthy tasty food. Based on the fact that Octenyl Succinic Anhydride (OSA) starch emulsifiers have been successfully applied in food applications for stabilizing oil-in-water (O/W) emulsions, further converting native starch to resistant starch is an attractive alternative which does not require fat reduction but can protect fat droplets against enzymatic digestion. The main purpose of this study was to determine the feasibility of a combined process of debranching and OSA esterification to prepare resistant starch emulsifier for food applications. Following debranching, the resistant starch content of the modified starches markedly increased in comparison with the native starch and reached 43.09% when the enzyme concentration was set at 80 NPUN/g. In contrast, the degree of substitution (DS) of resistant starch was significantly decreased compared with native starch. The resulting resistant starch emulsifier exhibited weaker emulsifying capacity compared to native counterparts, this is caused probably by their lower DS. The environmental stability of resistant starch emulsions has also been investigated and it was observed that these emulsions remained stable after a storage period of 21 days at 4 and 25 °C, respectively however, they showed reduced stability at low pH, increased ionic strength and heat treatment. The overall research study provides useful insights into the utilization of resistant starch emulsifiers in novel food formulations for reduced fat digestion.

Effects of octenyl succinylation on the properties of starches with distinct crystalline types and their Pickering emulsions

Effects of octenylsuccinic anhydride (OSA) esterification on the morphology, crystalline structure, and emulsifying properties of three representative starches with different crystalline types, namely waxy corn starch (A-type), potato starch (B-type), and pea starch (C-type) were investigated. XRD patterns testified OSA substitution occurred principally in the amorphous region without affecting the crystalline patterns, whereas SEM verified esterification was mainly a surface phenomenon. However, OSA esterification caused a decrease in the peak intensity and area of small-angle X-ray scattering profiles, indicating the semi-crystalline lamellae ordering was impeded to a certain extent. Compared with A- and C-type starches, B-type starch had a stronger affinity for OSA, as manifested by its higher degree of substitution (DS), graver surface detriment, and depressed order of semi-crystalline lamellae. The emulsifying properties of all starches were pronouncedly improved by OSA modification, especially for A-type starch even with comparatively lower DS. Pickering emulsion stabilized by OSA-modified A-type starch (A-OSAS) with smaller droplet size and more uniform droplet size distribution exhibited more splendiferous stability relative to the other two modified starches. Moreover, rheological tests revealed A-OSAS possessed the highest apparent viscosity and storage modulus (G′), insinuating strong intermolecular interactions between starch granules at the interface and/or in the continuous phase.

Hydrophobic surface modification of citrus fiber using octenyl succinic anhydride (OSA): Preparation, characterization and emulsifying properties

We reported herein the modification of fiber acquired from citrus processing residue via the esterification with octenyl succinic anhydride. OSA-CF with degree of substitution (DS) of 0.904–0.103 were obtained. The chemical compositions of fiber were changed in pectin content. The hydration properties of the fiber increased significantly with the esterification reaction, especially the water holding capacity (WHC) increased from 12.42 g/g to 17.23 g/g. OSA-CF has more negative charge than CF since the exposure of hydrophilic group and addition of carboxyl (-COO - ). FT-IR spectrum of the OSA-CF at 1734 cm −1 revealed characteristic absorption peaks of the ester carbonyl groups (C O). Compared to original fiber, OSA-CF showed higher crystallinity and slightly lower thermal stability from the XRD, TG and DTG patterns. It can be seen from the scanning electron microscope (SEM) image that the surface of OSA-CF has more fold and porous structure. Meanwhile, emulsion prepared by OSA-CF showed superior emulsifying abilities such as higher emulsifying activity index (EAI) and emulsifying stability (ES) and smaller particle size. In conclusion, OSA esterification did improve the physicochemical properties and change chemical composition of fiber. The purposed mechanism and characterization for surface modification of citrus fiber using octenyl succinic anhydride (OSA). • The original water holding capacity of citrus fiber was retained. • Octenyl succinate citrus fiber ester (OSA-CF) displayed higher emulsifying capacities. • OSA-CF has more surface negative charge. • The carbonyl group (C O) decreased first and then increased. • OSA-CF has more folds and deeper pore structure.

OSA improved the stability and applicability of emulsions prepared with enzymatically hydrolyzed pomelo peel insoluble fiber

Insoluble fibers are not commonly used as emulsion stabilizers because of their compact physical structure and strong hydrophilicity. In this study, pomelo insoluble fibers (PISFs) prepared via cellulase hydrolysis and cellulase hydrolysis followed by octenyl succinic anhydride esterification were used as emulsifiers. The fabricated fibers are denoted as MPISF and OMPISFs, respectively. Unlike MPISF, the OMPISFs with different degrees of substitution (i.e., OMPISF(I) and (II)) increased in the ζ-potentials and contact angles but decreased in the oil-water interfacial tensions to different degrees. Furthermore, an 0.5 wt% OMPISF(II) content was required to prepare a stable non-creaming emulsion, whereas the corresponding MPISF and OMPISF(I) contents were 0.75 wt%. The OMPISF(II)-stabilized emulsions did not undergo creaming after three freeze-thaw treatment cycles. Therefore, the properties of the OMPISF(II)-stabilized emulsions were superior to those of the MPISF- and OMPISF(I)-stabilized emulsions. Additionally, the final amount of free fatty acids released by the OMPISF(II)-stabilized emulsion was 13.3% lower than that released by the MPISF-stabilized emulsion during simulated gastrointestinal digestion. During lipid oxidation processes, the amounts of lipid hydroperoxide and thiobarbituric acid reactive substance produced in the OMPISF(II)-stabilized emulsion were 41.3% and 40.0% lower, respectively, than those in the MPISF-stabilized emulsion. OMPISFs improved the emulsion properties by increasing the oil–water interface stability, forming more solid three-dimensional structures, and promoting electrostatic repulsion between emulsion droplets. These findings indicate that pomelo peel dietary fiber is a promising emulsifier with excellent application potential for the preparation of emulsion stabilizers. • Dual modification of OSA and cellulase endowed PISF an excellent emulsibility. • Freeze-thaw, digestion and oxidative stability of emulsions were improved by OSA. • Higher DS provide emulsions with higher stabilization and application properties. • Improved network, interface layer and electrostatic value were the main mechanism. • This study facilitates the development of utilization of pomelo peel as emulsifier.

Effect of ultrasonic pre‐treatments on the octenyl succinic anhydride substitution of potato starch and its physicochemical and emulsifying properties

SummaryTo investigate whether the ultrasonic pre‐treatments of starch will affect the octenyl succinic anhydride (OSA) esterification, different power ultrasonic pre‐treatments (150, 300, 450 and 600 W) were performed on potato starch, then the OSA esterification was performed and the physicochemical as well as the emulsifying properties of the OSA starch were analysed. Results indicated that ultrasonic pre‐treatments decreased the degree of substitution and reaction efficiency by 30%, regardless of the pre‐treatments condition, while little differences were observed in the crystalline type and the long‐range ordered structure. DSC results demonstrated that low‐power ultrasound decreased the values of To and Tp, but increased ΔH, while high‐power ultrasound had the opposite effect. In addition, high‐power sonication improved the emulsifying capacity of OSA starch, which ranged from 189.08 ± 0.23 m2/g to 334.70 ± 0.35 m2/g, while emulsion stability decreased from 277.02 ± 10.83 min to 42.75 ± 0.08 min. Overall, the result of the present work implied that OSA starch exhibited varied thermal and emulsifying properties under different ultrasonic pre‐treatments, and our work might provide basic theory for the preparation of OSA starch.

Effect of gelatinization degree on emulsification capacity of corn starch esterified with octenyl succinic acid

Normal corn starch (∼26% amylose content) was subjected to different degrees of extrusion-based pregelatinization (55, 75, and 95%) to improve the efficiency of octenyl succinic anhydride (OSA) esterification. The partial disruption of the native semi-crystalline structure was verified with X-ray diffraction and Fourier transform infrared analysis. It was found that partial gelatinization (pregelatinization) reduced the relative crystallinity, which is an effect that was magnified by OSA esterification. Polarized and scanning electron microscopies revealed gradual destruction of the starch granules, yielding a fraction of insoluble remnants for high gelatinization degrees. The emulsification index showed a marked increase of about 18% by single extrusion treatment. However, fully stable emulsions (emulsification index = 1.0) were obtained by dual extrusion-esterification treatment. The hardness of hydrogels was reduced by pregelatinization. Principal component analysis revealed that most starch characteristics were mutually interdependent and that the impact of gelatinization degree was independent of the impact of OSA esterification.

Influence of gelatinization degree and octenyl succinic anhydride esterification on the water sorption characteristics of corn starch

The effects of gelatinization degree (GD) and octenyl succinic anhydride (OSA) esterification in the sorption-desorption characteristics of normal corn starch (NCS) were studied. NCS was subjected to different GD (53, 70, and 96%) with an extruder and lyophilized. FTIR analysis revealed that GD increased the hydrated (995/1022 ratio) and decreased the short-range ordered (1022/1047 ratio). The equilibrium sorption-desorption curve of starches was obtained for water activities up to 0.95 and fitted with the Guggenheim-Anderson-de Boer (GAB) model. Gelatinization of corn starch decreased its water sorption capacity, increased its sorption hysteresis and decreased its monolayer moisture content. OSA treatment of NCS reduced the water sorption capacity, hysteresis, and monolayer moisture content as reflected by slight variations of these parameters with the GD. A principal component analysis showed that GD and OSA esterification are mutually independent treatments, which can provide different effects on the water sorption characteristics of NCS.

Effects of the degree of substitution of OSA on the properties of starch microparticle-stabilized emulsions

An amphiphilic polymer of octenyl succinic anhydride (OSA)-modified starch microparticles (SMPs) was synthesized and used to stabilize emulsions. The effects of the degree of substitution (DS) on the physicochemical properties of OSA-modified SMPs and the stability of OSA-modified SMP-stabilized emulsions during a three-step in vitro digestion model were studied. The results showed that OSA esterification acted on the surface of SMPs and that the hydrophobicity of SMPs improved with increasing DS. In addition, the emulsion stability during storage and the changes in ionic strength were enhanced by increasing DS. Moreover, a higher DS also led to smaller oil droplets and more OSA-modified SMPs retained during intestinal digestion. Most importantly, the encapsulation efficiency and the bioaccessibility of curcumin in the emulsion during intestinal digestion were both enhanced significantly with the increase of DS.

Effect of the OSA Esterification of Oxalis tuberosa Starch on the Physicochemical, Molecular, and Emulsification Properties

AbstractThis work studies the physicochemical, molecular, and emulsification properties of Oxalis tuberosa (oca) starch modified with octenyl succinic anhydride (OSA). Freshly harvested oca tubers are washed and selected, and starch is extracted by tuber size reductions and successive washes. Modifications are performed with OSA for 6 h at pH 8.5–9. Mean particle size increases, while temperature and enthalpy of gelatinization decrease with OSA modification. In addition, peak, breakdown, and final viscosities increase as caused by partial disorganization of starch components during chemical modifications, an effect that is exhibited by variations of X‐ray diffraction type and crystallinity. Oca‐OSA starch produces pastes with pseudoplastic behavior and emulsions with higher emulsification properties in comparison with the native starch. These results indicate that esterification of oca starch with OSA can be used to produce starches with desired physicochemical and emulsification properties.

Properties and Digestibility of Octenyl Succinic Anhydride-Modified Japonica-Type Waxy and Non-Waxy Rice Starches.

Waxy and non-waxy rice starches from japonica type Korean rice varieties were esterified with different levels of octenyl succinic anhydride (OSA), and the molecular structure of amylopectin (AP), digestibility, and emulsion stability were investigated. As OSA levels increased, the degree of substitution, granule size, peak and final viscosities, emulsion stability, and short chain of AP increased. However, the gelatinization temperature and enthalpy, and digestibility decreased. All OSA esterified starches showed a new band at 1723 cm−1, but maintained A-type crystallinity. The DP6-12 of AP in waxy rice starch (WRS) was higher than that in non-waxy rice starch (NRS) with increasing OSA levels. Because the amylose and long chain of AP accessed easily with OSA groups, the digestibility of NRS was lower than that of WRS. The emulsion stability was higher in WRS than in NRS. From the above results, it is suggested that amylose should have a higher affinity with OSA esterification than AP and that the emulsion stability should increase in WRS, but the digestibility should decrease in NRS after OSA modification.

Starch-based Janus particles: Proof-of-concept heterogeneous design via a spin-coating spray approach

The asymmetric nature of Janus particles made from synthetic polymers gives them intriguing properties that have found applications in a wide variety of fields, such as drug delivery, emulsion stabilization, and environmental decontamination. The potential of using natural biopolymers as base materials for Janus particles in the food industry, however, has not yet been fully explored. Here we demonstrate for the first time the design of a starch-only-based Janus particle. Using a spin-coating spray approach, we produced both large (12.2 μm) half-porous, waxy cornstarch Janus granules by alpha-amylase treatment and small (1.2 μm) half-hydrophobic, amaranth starch Janus granules by octenyl succinic anhydride esterification. Optical microscopy, scanning electron microscopy, super resolution-structured illumination spectroscopy, and infrared spectroscopy were used to confirm the binary nature of these particles. A methylene blue adsorption test further showed that the untreated (non-porous), half-porous Janus, and fully porous waxy cornstarch granules had five-hour adsorption rates of 20.5, 72.1, and 100%, respectively, and adsorption capacities of 0.82, 2.88, and 3.96 mg/g. Meanwhile, untreated amaranth starch granules were shown not to interact with each other in water, while >68% of the half-hydrophobic granules self-assembled into wormlike strings and micelles, and >66% of the fully hydrophobic granules aggregated into spherical, complex supermicelles. While the low yield typical of Janus particle formation prevents a more detailed characterization of these starch-based Janus particles, the unique properties they displayed here may open exciting, future applications in the food industry as texturants or surface-active agents, as well as in other fields requiring such uncanny materials.

Effects of concurrent ball milling and octenyl succinylation on structure and physicochemical properties of starch

This work concerns the effects of concurrent ball milling (BM) and octenyl succinic anhydride (OSA) modification on the starch microstructure and physicochemical properties (swelling, emulsifying, and rheological). Unlike normal OSA-modified starches, the BM/OSA-modified starch displayed new features such as reduced viscosity and rigidity but increased paste stability during shearing, heating and cooling, regardless of the substitution degree. More interestingly, while the physicochemical properties could be regulated by simply altering the BM treatment time, BM/OSA was more efficient and effective at modulating starch properties during the initial period (approx. 10h), as seen by the rapid evolutions in starch structural disruption and OSA esterification. Thus, the BM/OSA modification can serve as a viable and cost-effective approach for producing octenyl succinate starches where low viscosity (at relatively high concentrations) and high paste stability are desired.

Physicochemical Properties of Octenyl Succinic Esters of Cereal, Tuber and Root Starches

Changing the physicochemical properties of starch by chemical modification is a common process. Starches can be modified to alter their hydrophobicity by treatment with octenyl succinic anhydride (OSA). The physicochemical properties of OSA starches from corn, tapioca, rice, potato and wheat were studied. The increase of swelling volume and pasting properties in OSA starches was observed and attributed to the introduction of OSA groups into the starch. However, the botanical source also played a key role in starch swelling and pasting properties. The OSA modification improved the textural properties, while not significantly (P < 0.05) affecting the thermal properties. Therefore, it was found that the level of OSA substitution and the botanical sources affected the physicochemical properties. However, it will be important to investigate the chemical properties and starch backbone structure of the modified starches, factors that play an important role in the physicochemical properties. Practical Applications Modified starches are important in development of new food products with regards to both processing properties and end-product properties. Esterification of starch with octenyl succinic anhydride (OSA) alters the swelling power, paste viscosity, gel texture and retrogradation of starches. OSA starches also have emulsification capacity which makes them useful as emulsion stabilizers, texturizers and fat-replacers in food systems. However, the botanical source of the starch plays a key role in the functionality of both native and modified starches. It is important to ascertain the properties of OSA modified starches prepared from various botanical sources to determine how the interaction of OSA esterification and botanical source will affect the functionality of the starches.

Impact of octenyl succinylation on rheological, pasting, thermal and physicochemical properties of pearl millet (Pennisetum typhoides) starch

The impact of octenyl succinic anhydride (OSA) esterification was investigated on rheological, pasting, thermal and physicochemical properties of pearl millet (Pennisetum typhoides) starch. Starch was esterified with 3% OSA at four reaction times viz. 2 (OSA-2H), 3 (OSA-3H), 4 (OSA-4H), and 5 h (OSA-5H). Degree of substitution (DS) increased significantly (p < h.05) from 0.018 to 0.022 with increasing reaction time and peak height at 1724 cm−1 in fourier transform infrared spectroscopy increased with increase in DS. Resistant starch and oil absorption capacity increased significantly (p < 0.05) from 2.41 to 13.72% and 1.31–2.67 g/g, respectively with increasing DS. Significant increase was observed in peak, hot paste, cold paste and breakdown viscosity upon OSA esterification while, pasting temperature and setback ratio decreased. Storage modulus, loss modulus and strain increased upon OSA esterification. Herschel Bulkley model was found best fitted with R2 values 0.997 and 0.995 for native and OSA-3H (DS 0.0208) gels, respectively. Consistency index decreased from 13.57 to 2.25 and 27.30 to 1.84 for native and OSA-3H, respectively with increase in temperature from 5 to 85 °C. Gelatinization temperature and enthalpy of gelatinization decreased significantly. OSA-starch gels exhibited good proportioning, homogeneous mixing and self leveling characteristics making them potential fat replacers.

Analysis of octenylsuccinate rice and tapioca starches: Distribution of octenylsuccinic anhydride groups in starch granules

Characterization of the fine structure of octenylsuccinic anhydride (OSA) starch would lead to a better understanding of functional properties. OSA rice and tapioca starches were analyzed using microscopy, liquid chromatography and nuclear magnetic resonance. Chain length distribution of amylopectin changed significantly (P<0.05) after OSA esterification. Weight averaged degree of polymerization (DPw) decreased significantly (P<0.05) from 16.47 to 13.29 and from 14.87 to 12.47 in native and OSA rice and tapioca starches, respectively. The chain length distribution of pure amylopectin fractions suggested that OSA groups were not present in the amylopectin portion of the starch. 1H NMR analysis of pure amylose and amylopectin fractions indicated that OSA substitution was present only in amylose fractions of rice and tapioca starches. Esterification with 3% OSA results in starch that has OSA substituted mainly on amylose chains or possibly on amylopectin chains that have been hydrolyzed from the amylopectin molecules during esterification.

Structure and physicochemical properties of octenyl succinic esters of sugary maize soluble starch and waxy maize starch

The structure and physicochemical properties of octenyl succinic anhydride (OSA) starches prepared from sugary maize (SMSS) and waxy maize (WMS) were studied and compared. The degree of substitution (DS) increased linearly with the amount of OSA, while the DS of OSA-SMSS was higher than that of OSA-WMS using equivalent modification conditions. FT-IR analysis indicated that two characteristic peaks, at 1725 and 1570cm−1, were observed for OSA-starch. The weight-average of the molar mass (Mw) and z-root mean square radius of gyration (Rz) of SMSS increased with increased OSA esterification substitutions, whereas Mw was reduced and Rz was nearly constant for WMS. The zeta-potential and emulsifying activity increased with DS for starch modified with OSA. OSA-SMSS (DS of 0.0192) was the best material for stable oil-in-water emulsion preparation. The increase of DS in OSA-starch resulted in a substantial reduction of RDS content with an accompanying increase of SDS and RS. This study revealed the potential application of OSA-SMSS as a particle stabilizer of oil-in-water emulsion, which would allow encapsulate and protect functional food components.

Slowly Digestible Waxy Maize Starch Prepared by Octenyl Succinic Anhydride Esterification and Heat−Moisture Treatment: Glycemic Response and Mechanism

The mechanism and molecular structure of the slowly digestible waxy maize starch prepared by octenyl succinic anhydride (OSA) esterification and heat-moisture treatment were investigated. The in vitro Englyst test showed a proportion of 28.3% slowly digestible starch (SDS) when waxy maize starch was esterified with 3% OSA (starch weight based, and it is named OSA-starch), and a highest SDS content of 42.8% was obtained after OSA-starch (10% moisture) was further heated at 120 degrees C for 4 h (named HOSA-starch). The in vivo glycemic response of HOSA-starch, which showed a delayed appearance of blood glucose peak and a significant reduction (32.2%) of the peak glucose concentration, further confirmed its slow digestion property. Amylopectin debranching analysis revealed HOSA-starch had the highest resistance to debranching enzymes of isoamylase and pullulanase, and a simultaneous decrease of K m and V m (enzyme kinetics) was also shown when HOSA-starch was digested by either alpha-amylase or amyloglucosidase, indicating that the slow digestion of HOSA-starch resulted from an uncompetitive inhibition of enzyme activity during digestion. Size exclusion chromatography analysis of HOSA-starch showed fragmented amylopectin molecules with more nonreducing ends that are favorable for RS conversion to SDS by the action of amyloglucosidase in the Englyst test. Further solubility analysis indicates that the water-insolubility of HOSA-starch is caused by OSA-mediated cross-linking of amylopectin and the hydrophobic interaction between OSA-modified starch molecules. The water-insolubility of HOSA-starch would decrease its enzyme accessibility, and the digestion products with attached OSA molecules might also directly act as the uncompetitive inhibitor to reduce the enzyme activity leading to a slow digestion of HOSA-starch.