Octenylsuccinic Groups Research Articles

Octenylsuccinylation strategy to construct high-amylose maize starch–myristic acid complexes with high thermal stability, complexation efficiency and anti-retrogradation ability

Gelatinizing high-amylose maize starch (HAMSt) requires high temperatures to allow complexation with lipids, making it a challenging process. An octenylsuccinylation method was examined as a part of a strategy to decrease the gelatinization temperature of HAMSt, thereby promoting the complexation between HAMSt and myristic acid (MAc). Octenyl succinic anhydride (OSA) modification of HAMSt reduces the onset gelatinization temperature of HAMSt from 71.63 °C to 66.97 °C. Moreover, as the OSA concentration increased from 2 % to 11 %, the degree of substitution and molecular weights of the esterified HAMSt gradually increased from 0.0069 to 0.0184 and from 0.97 × 106 to 1.17 × 106 g/mol, respectively. Fourier transform infrared analysis indicated that the octenyl-succinate groups were grafted onto the HAMSt chains. The formation of HAMSt–MAc complexes improved the thermal stability of OSA-treated HAMSt (peak temperature increased by 0.11 °C–13.95 °C). Moreover, the diffraction intensity of the V-type peak of the 11 % sample was greater than that of other samples. Finally, the anti-retrogradation ability was in the order of OSA–HAMSt–MAc complexes > HAMSt–MAc complexes > HAMSt. Overall, our results indicate that octenylsuccinylation can be an effective strategy to promote the formation of OSA–HAMSt–MAc complexes and delay starch retrogradation.

In Vitro Bioaccessibility of Bioactive Compounds of Freeze-Dried Orange Juice Co-Product Formulated with Gum Arabic and Modified Starch

The large amount of waste generated by the orange juice industry has sparked the interest of many researchers in incorporating recycling systems and following a much more sustainable circular economy model. This work proposes the valorization of the co-product generated in the orange juice extraction industry after freeze-drying for its subsequent reuse as a natural ingredient in the food industry. In addition, the possible protective effect of gum Arabic and corn starch esterified with octenyl succinic groups, in proportions optimised in previous studies 0.25 and 0.45 g/g orange co-product dry solutes, on the main bioactive compounds of orange peel during the freeze-drying process has been studied. The samples were characterised for their content of vitamin C (ascorbic and dehydroascorbic acids), flavonoids (hesperidin and narirutin), total phenols and total carotenoids, as well as their antioxidant capacity (DPPH and FRAP assays). In addition, samples were digested, mimicking the human enzymatic oral gastro-intestinal digestion process, and the bioaccessibility of the bioactive compounds was evaluated. It was observed that the addition of both biopolymers improved the stability of the hydrophilic compounds during freeze-drying. This conservative effect was more remarkable for higher biopolymer concentrations. However, no protective effect on carotenoid compounds was observed. This trend was reflected in the antioxidant activity of the different samples. In addition, the incorporation of biopolymers improved the bioaccessibility of the bioactive compounds studied. In conclusion, the results supported the feasibility of the freeze-dried orange juice co-product as a natural, sustainable source of health-promoting compounds.

Revealing substitution priority and pattern of octenylsuccinic groups along the starch chain under a continuous mode

Octenylsuccinic (OS) groups distribution was considered random under traditional batch mode (BM) process due to excessive available octenyl succinic anhydride (OSA) at early stage, making the functionality optimization of OSA starch under restricted substitution degree (DS) difficult. To reveal the priority rule of substituent position at starch molecular level, a continuous mode (CM, dropwise OSA addition) was applied for OSA starch preparation. Initial OSA substitution was predominately at the branching points of amylopectin backbone, then successive at the branching points of shorter and longer chains with increasing DS. As DS increased over 1.49%, substitution started occurring along the chains and moved towards the non-reducing ends until DS reached 6.65%. At similar DS, more branching point substitutions occurred at CM starch, showing superior emulsifying property over BM starch. OSA substitution priority rule does exist under controlled OSA supply, which would facilitate OSA starch design with specific substitution pattern and favored functionality.

Protective capacity of gum Arabic, maltodextrin, different starches, and fibers on the bioactive compounds and antioxidant activity of an orange puree (Citrus sinensis (L.) Osbeck) against freeze-drying and in vitro digestion

Dehydrated fruit puree may be a convenient way to promote the healthy consumption of fruit based foods. Drying carriers, highly used by the food industry to stabilize dried fruit products, may show a potential encapsulating capacity of the biocompounds, that could also limit their bioaccesibility. This study analyzed the impact of gum Arabic (GA), bamboo fiber (BF), native corn starch, starch substituted with octenylsuccinic groups, pea fiber, and maltodextrin on the in vitro bioaccessibility of vitamin C (VC), total phenols (TP), and β-carotene, as well as on the antioxidant capacity during the freeze-drying and in vitro digestion of an orange puree. Amongst the formulations studied, GA + BF was the most effective for phytochemicals protection of the freeze-dried orange puree during the intestinal stage of digestion, resulting in a higher TP and VC bioaccessibility (59% and 36%, respectively).

Impact of Maltodextrin, Gum Arabic, Different Fibres and Starches on the Properties of Freeze-Dried Orange Puree Powder

Fruits are essential components of a healthy diet contributing to the prevention of different diseases. Nevertheless, their consumption is limited among the population for reasons of convenience, among others. High-quality products are obtained by freeze-drying; however, dehydrated fruit presents a physical stability problem associated with the glass transition of its amorphous matrix. A common technique to prevent the rubbery state is the incorporation of biopolymers that contribute to increasing the glass transition temperature or that may exert a steric role. Nevertheless, the chemical composition and physical properties of these biopolymers may affect the quality of the dehydrated product which could compromise its use for specific applications. This work studies the impact of gum Arabic, bamboo fibre, maltodextrin, pea fibre, starch substituted with octenyl succinic groups and native corn starch added to an orange puree, on powder flowability and rehydration behaviour of the freeze-dried fruit powder. As regards the flowability, according to the angle of repose values (37–42°), all powder formulations were considered in the range of ‘acceptable’ powders. However, both samples containing maltodextrin showed significantly the lowest angle of repose value (37–38°), and therefore a better flowability. Samples containing gum Arabic, bamboo fibre and maltodextrin showed the lower wetting time (175–570 s), which is desired for rehydration, compared to those formulated with OSA (914–1887 s). Moreover, sample with gum Arabic showed the lowest viscosity after rehydration (0.199 Pas), desired to be consumed as a juice. According to the obtained results, if to get an orange puree powder with a good flowability is desired, the use of maltodextrin may be recommended. However, if rehydration is preferred, the use of gum Arabic is more recommended.

The effect of thermal and irradiation treatments on structural and physicochemical properties of octenyl succinate maize starches.

The aim of this paper was to evaluate the effect of thermal treatment and UV irradiation on structural and physicochemical properties of octenyl succinate (OS) maize starches differing in content of OS groups (0.76%-2.38%). X-ray diffraction (XRD), gel permeation chromatography (GPC), and electron paramagnetic resonance (EPR) spectroscopy were used to estimate structural characteristics of octenyl succinate starches and their physically treated counterparts. Starch functional properties were also determined. XRD spectra and hydrodynamic volume distribution revealed that growth of octenyl succinate groups' content resulted in stabilization of starch structure, which was confirmed by processes of radical formation, stimulated by thermal and UV treatments. It was found, on the basis of measurements of water binding capacity, water solubility and intrinsic viscosity, that OSA addition changed physicochemical properties of starch and influenced the course of physical modifications. It was established that temperature affected starch properties to a greater extent than UV.

Distribution of octenylsuccinic groups in modified waxy maize starch: An analysis at granular level

This study aimed to report the distribution of octenylsuccinic (OS) groups in waxy maize starch granules. A series of octenylsuccinic anhydride (OSA) substituted starch with degree of substitution (DS) ranging from 0.018 to 0.068 were prepared. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) showed an integrated granular structure of OSA starch were maintained, and the crystal regions, likewise, were not modified. Fourier transform infrared spectroscopy (FTIR) results suggested that OS groups could be grafted on surface of starch granules. However, Confocal 2D Raman microscopy confirmed that OS groups are located unevenly throughout the starch granule, with an increased intensity in the center. A refined lamellar model was proposed, which indicated that OS groups occurred on each layer of amorphous regions, and further modified the center of the cavity, probably due to the OSA reagent accessibility to hilum by the presence of a large number of channels in each granule.

Effect of acid hydrolysis and OSA esterification of waxy cassava starch on emulsifying properties in Pickering-type emulsions

The emulsifying properties of waxy cassava starch modified by acid hydrolysis and esterification with octenyl succinic groups in Pickering-type emulsions were evaluated using zeta potential, emulsification index, light microscopy and rheology behavior. The optimal conditions of acid hydrolysis to achieve the highest emulsification index were determined to be a hydrochloric acid concentration of 4 mol/L for 5.20 h. After that, the starch was esterified to obtain a double modification. The emulsification index values were acid treated/succinated starch > optimal acid treated starch > native starch. The acid treated/succinated starch emulsion presented higher storage modulus (G′) values, without G’ and loss modulus (G”) crossing point in the evaluated frequency range. Acid hydrolysis modified the emulsifying properties of waxy cassava starch improving its interaction at the oil/water interface. According to observations by light microscopy and rheology behavior, the double modification formed a more uniform and stable network over time through granule-granule and granule-interface interactions.

Interfacial Activity of Starch-Based Nanoparticles at the Oil-Water Interface.

Understanding the interfacial activity of polysaccharide nanoparticles adsorbed at oil-water interfaces is essential and important for the application of these nanoparticles as Pickering stabilizers. The interfacial properties of starch-based nanospheres (SNPs) at the interface of an n-hexane-water system were investigated by monitoring the interfacial tension at different bulk concentrations. The three-phase contact angle (θ) and the adsorption energy (ΔE) increased with increasing size and degree of substitution with octenyl succinic groups (OSA) in the particles. Compared with the OSA-modified starch (OSA-S) macromolecule, the SNPs effectively reduced the interfacial tension of the n-hexane-water system at a relatively higher concentration. These results and the method reported herein are useful for selecting and preparing polysaccharide nanoparticles as Pickering stabilizers for oil-water emulsions.

Substituent distribution changes the pasting and emulsion properties of octenylsuccinate starch

An improved preparation method of octenylsuccinate (OS) starch under high shear condition was described in this study. The distribution of OS substituents at the granular and molecular levels was assessed by confocal laser scanning microscopy (CLSM), β-amylase hydrolysis, chromatographic and 1H NMR techniques. We found that the OS group distribution could change the pasting and emulsion properties of OS starches. Specifically, more uniform OS group distribution was identified in the central region of OS starch granules prepared under high shear condition (H–OS–starch), and OS groups were located both near the branching points and the non-reducing ends. More OS groups exposed outside of non-reducing ends would access the interface between oil and water and give more stabilized emulsion.

Elucidation of substituted ester group position in octenylsuccinic anhydride modified sugary maize soluble starch.

The octenylsuccinic groups in esterification-modified sugary maize soluble starches with a low (0.0191) or high (0.0504) degree of substitution (DS) were investigated by amyloglucosidase hydrolysis followed by a combination of chemical and physical analysis. The results showed the zeta-potential remained at approximately the same value regardless of excessive hydrolysis. The weight-average molecular weight decreased rapidly and reached 1.22 × 10(7) and 1.60 × 10(7) g/mol after 120 min for low-DS and high-DS octenylsuccinic anhydride (OSA) modified starch, respectively. The pattern of z-average radius of gyration as well as particle size change was similar to that of Mw, and z-average radius of gyration decreased much more slowly, especially for high-DS OSA starch. Compared to native starch, two characteristic absorption peaks at 1726.76 and 1571.83 cm(-1) were observed in FT-IR spectra, and the intensity of absorption peaks increased with increasing DS. The NMR results showed that OSA starch had several additional peaks at 0.8-3.0 ppm and a shoulder at 5.56 ppm for OSA substituents, which were grafted at O-2 and O-3 positions in soluble starch. The even distribution of OSA groups in the center area of soluble starch particle has been directly shown under CLSM. Most substitutions were located near branching points of soluble starch particles for a low-DS modified starch, whereas the substituted ester groups were located near branching points as well as at the nonreducing ends in OSA starch with a high DS.

Synthesis, Characterization, and Aqueous Self-Assembly of Octenylsuccinate Oat β-Glucan

Amphiphilic oat β-glucan derivatives carrying octenylsuccinic groups as hydrophobic moieties have been synthesized. Materials with a different degree of substitution (DS) and weight-average molecular weight (Mw) for oat β-glucan were prepared and characterized using elemental analysis, infrared (IR) spectroscopy, and high performance size exclusion chromatography (HPSEC). Dynamic light scattering (DLS), fluorescence spectroscopy, and transmission electron microscopy (TEM) revealed that octenylsuccinate oat β-glucan (OSG) can self-assemble into spherical micelles in water with an average size ranging from 175 to 600 nm. OSG micelles were negatively charged as indicated by ζ-potential measurement. The critical micelle concentration (CMC) of OSGs varied from 0.206 to 0.039 mg/mL, depending on the DS and Mw of the oat β-glucan. It was found that the presence of OSG micelles in aqueous solution could significantly enhance the solubility of curcumin by 880 fold. Thus, OSG might have great potential in applications as hydrophobic nutrient delivery carriers.

Distribution of Octenylsuccinic Substituents in Modified A and B Polymorph Starch Granules

The octenylsuccinic (OS) substituent distribution in octenylsuccinic anhydride (OSA)-modified normal maize and potato starches with different degrees of subsititution (DS) was studied using confocal laser scanning microscopy (CLSM) and surface gelatinization. The remaining non-gelatinized portions of starch granules after removal of surface-gelatinized starch (remaining granules) were studied with light microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy (FTIR), and the level of succinylation. Results showed that greater proportions of the OS groups were present at the periphery than at the core of the granules. However, the granular interior of OS maize starch has higher fluorescent intensity than that of OS potato starch, as shown by CLSM. The DS of OS maize starch degraded less than that of OS potato starch under the same degree of gelatinization. In addition, the characteristic peaks of the remaining OS maize granules in the FTIR were more protruding than that of the OS potato granules after 50% chemical surface gelatinization. The results implied that maize starch displayed much more homogeneous OSA reaction pattern when compared to potato starch. With the special architectures (pinholes and channels) of maize, it is easier to change the location of OS groups than with potato starch by changing reaction conditions or starch pretreatments.

Effects of octenylsuccinylation on the structure and properties of high-amylose maize starch

Structural changes from the octenylsuccinylation of high-amylose maize starch were investigated by FT-IR and differential scanning calorimetry (DSC), with observations made on the distribution of octenyl succinate (OS) groups using confocal laser scanning microscopy (CLSM). Results of the octenylsuccinylation on in vitro digestion property (uncooked and cooked) were also determined. DSC data revealed a broad gelatinization endothermic peak ranged from 72.5°C to 96.4°C for the native starch, and a downward trend for products of increasing degree of substitution (DS). The OS groups appeared to be distributed throughout the OS-starch granules, especially on the surface. Octenylsuccinylation decreased the slowly digestible starch content of low DS OS-starch after cooking, while increased the resistant starch (RS) level in uncooked OS-starch. Even though uncooked OS-starch (DS≈0.04) has 86.3% RS content, its RS content was reduced to 7.5% after cooking.

EFFECT OF OCTENYLSUCCINYLATION ON FUNCTIONAL PROPERTIES OF LIMA BEAN (PHASEOLUS LUNATUS) STARCH

ABSTRACT The functional properties of lima bean (Phaseolus lunatus) starch modified with octenyl succinic anhydride (OSA) were evaluated and compared with native starch. The OSA starch was produced from a starch aqueous suspension at 40% (w/w) with 3% OSA at pH 7 for 30 min. The modified starch had 0.51% succinyl groups and a 0.008 degree of substitution. Succinylation increased emulsifying capacity from 0.47 mL oil/mL sample in the native starch to 0.53 mL oil/mL sample in the OSA starch. Starch gel clarity (transmittance percentage) increased from 23.8 to 37.3%. Viscosity increased from 700 to 1,000 BU. Gel firmness decreased from 0.3401 kgf for gel rupture in the native starch to 0.0314 kgf for rupture in the OSA starch. Gelatinization temperature decreased from 75.3 to 64.6C and gel enthalpy decreased from 10.7 to 9.7 J/g. Succinylation caused not significant changes in solubility, swelling power and water absorption capacity. OSA starch stability was lower under refrigeration conditions.PRACTICAL APPLICATIONSThe incorporation of octenylsuccinate groups into lima bean starch produce a derivative with more versatility as a food additive providing new and improved functional properties. The octenylsuccinylation allows the use of the lima bean starch in products such as beverages, salad dressings and soups where the use of this starch is limited because lack of diversity in their functional properties necessaries in the alimentary industry. Therefore, the improved properties of the Phaseolus lunatus octenyl succinic anhydride starch make it potentially useful in processes requiring a thickening agent that must gel at lower temperatures; it can also serve to reduce energy consumption during cooking processes or like thickening or emulsifying agent or make it potentially useful as an additive in jellies and candies to provide brightness. However, the election of this derived as additive in food, should take into account the functional properties that it presents, the ingredients and the process conditions.

The effect of enzymatic pretreatments on subsequent octenyl succinic anhydride modifications of cornstarch

Cornstarch granules were allowed to react with α-amylase and then esterified with octenyl succinic anhydride (OSA). The paste properties and the distribution of octenyl succinate (OS) groups of OS-starch granule were studied. Results show that the α-amylase pretreatments significantly decreased the degree of substitution (DS) of OS-starch compare with a non-pretreated control group, while the retrogradation properties, freeze-thaw stability and shearing resistant stability of α-amylase pretreated OS-starch didn't change markedly. Enzymatic pretreatment appears to influence the distribution of the OS groups from being mostly on the surface and amorphous part of the starch granules to being in the inner amorphous and crystalline regions of the granules, as shown by X-ray photoelectron spectroscopy (XPS) and lintnerisation studies.

Surface properties of enzymatic hydrolysis products of octenylsuccinate starch derivatives

Octenylscuccinate derivatives of starch are attracting growing attention of food technologist as potential additives as emulsifying agents. The functional properties of sodium starch octenylsuccinate E 1450 depends on many structural conditions mainly to the degree of substitution of octenylsuccinate groups and degree of hydrolysis of starch macromolecules. The application of the UF membrane bioreactor to enzymatic hydrolysis could be the way of intensification of the production process, however, knowledge is needed on how it affects the functionality of the products. The aim of the work was to examine the effect of the ultrafiltration process on the surface activity of products of enzymatic hydrolysis of octenylsuccinate starch derivatives. It was found that all investigated oligosaccharides decrease interfacial tension both in air/water and toluene/water systems. The contents of filtrate, i.e., the products of higher DE values lowered the surface tension surprisingly poorly although their effectiveness of adsorption is relatively high. These hydrolysates formed very densely populated adsorption layers, but the saturation at the interface required a high bulk concentration.

Distribution of Octenyl Succinate Groups in Octenyl Succinic Anhydride Modified Waxy Maize Starch

The location of octenyl succinate groups within octenyl succinic anhydride (OSA)-modified waxy maize (WM) starch granules was studied in order to better understand the relationship between the structure and physical properties of OSA starches. OSA starches of D.S. 0.03—0.11 were prepared by reaction between starch, OSA and NaOH in aqueous suspension; the native granular structure of starch was retained after reaction. Backscattered electron imaging of osmium-stained, sectioned OSA starch granules showed a uniform distribution of OSA groups over the cross-section of the granules. Anion-exchange chromatography of OSA starches solubilized in water showed that most of the amylopectin molecules contain some negative charge, suggesting that most of the starch granule is accessible to and reacts with OSA. However, after partial debranching with pullulanase, more of the resulting chains were neutral than would be expected on statistical grounds, suggesting heterogeneity in OSA substitution at the branch level. X-ray photoelectron spectroscopy suggested that the concentration of OSAgroups on the immediate surface of the OSA starch granules was about 3—4 times that of the bulk.