Influence of acetylation on physicochemical, functional and thermal properties of potato and cassava starches

Starches were isolated from cassava (Manihot esculenta) and potato (Solanum tuberosum) tubers. They were further modified by acetylation. The physicochemical, functional and thermal properties of native and modified starches, prepared using acetic anhydride at different times (10 and 20 min) were compared. Potato starch (Sipiera/20) showed higher acetyl percentage and degree of substitution values than cassava (2425/20) starch when acetylated for 20 min. Proximate analysis revealed that the acetylated starches retained more moisture than the native ones. Above 75 °C, acetylation improved the water binding capacity of the native cassava starch; the same trend was observed for potato starch from 60 to 90 °C after acetylation. The X-ray powder diffraction patterns derived from acetylated potato starches were similar to its native form, which was expected as B-type pattern; the same trend was observed for modified cassava starch. However the modified starches showed increased crystalline index.     

Analysis of water binding in starch plasticized films

The water-binding properties of wheat starch films were studied through the determination of water vapour adsorption isotherms at 20 °C. Starch films were obtained by casting after mixing native starch at 95 °C for 15 min with different ratios of plasticizer (glycerol).     

Paste viscosity of rice starches of different amylose content and carboxymethylcellulose formed by dry heating and the physical properties of their films

Starch modified by combination with sodium carboxymethylcellulose (CMC) has been reported to have improved film properties. In this study, rice starches with different amylose content were heat-treated in a dry state after being impregnated with low or medium-viscosity CMC. Noticeable change was found in pasting properties of the starches after dry heat treatment with CMC. It indicated that crosslinkage occurred between the starch and CMC. The waxy starch showed significant change in viscosity throughout pasting after dry heating with CMC, suggesting that the ester bonds were mostly formed between the hydroxyl groups in amylopectin branches of rice starch and carboxylate acid groups of CMC. Particle size also increased after heat treatment with CMC. The modified starch-based films showed improvement in the tensile strength. Both water vapor and oxygen permeability reduced for the modified starch-based films. Dynamic mechanical analysis (DMA) study showed that the values of G′ of modified starch-based film were higher than those of native starch-based film over the temperature range −40 to 60 °C. The heating process with CMC could be used as a modification method for starch and provide desirable properties of starch-based films.     

Physicochemical characterization of chemically modified corn starches related to rheological behavior,retrogradation and film forming capacity

An integral approach of chemical modification effects on physicochemical and functional properties of corn starch was performed using different and complementary techniques. Acetylated, acetylated crosslinked, hydroxypropylated crosslinked, and acid modified corn starches were analyzed. Substitution and dual modification reduced significantly amylose concentration. Chemical modification decreased granules crystallinity degree. A significant increase in swelling power was observed in substituted and dual modified starches at 90 °C, besides these treatments decreased gelatinization temperature and enthalpy. Acid modified starch pastes showed a Newtonian behavior while substituted and dual modified ones exhibited a viscoelastic response. Dynamic rheological properties of modified starch pastes were not affected by post gelatinization time while native starch pastes developed a more rigid structure during storage. Retrogradation of substituted starch pastes after 12 days at 4 °C was reduced, since syneresis degree and hardness increase were significantly lower than those of native pastes. It was demonstrated that only substituted and native starches exhibited film forming capacity.     

Acetylated and native corn starch blend films produced by blown extrusion

Thermoplastic starch (TPS) materials were developed from mixtures of native and acetylated corn starches with glycerol. To optimize the formulations an experimental design for multicomponent mixtures was used and the assayed formulations were determined by statistical software. Blends and pellets humidity content increased with glycerol concentration. Starch destructuration during the extrusion process was studied by thermal analysis. Films presented homogenous structure, rough surfaces and certain stickiness. They presented different properties, related mainly to the differential characteristics of native and acetylated starches and to hydrophilic character of glycerol. Their mechanical behavior indicated that they are a good option as a food packaging materials since TPS films resulted enough resistant to protect the product and flexible to resist moderate deformations. Besides, the use of acetylated starch in the formulations enhanced film resistance and reduced their WVP, despite of its low modification degree. The storage of the films under controlled conditions increased their stiffness, while their flexibility and WVP were reduced. Plasticizer migration towards the matrix surface was observed in stored films. Films resulted stable till a_w = 0.7 and due to their selective gaseous permeability they are useful to package products susceptible to oxidation or to control vegetable respiration and senescence.     

Effect of gelatinisation on slowly digestible starch and resistant starch of heat-moisture treated and chemically modified canna starches

The effects of gelatinisation on slowly digestible (SDS) and resistant starch (RS) of native and modified canna starches were investigated. Starch slurries (10% w/w) were gelatinised at 100 °C for 5, 10, 20 and 40 min using a rapid visco analyzer (RVA). Significant change in the degree of gelatinisation (DG) values of all starch samples was observed during the initial 10 min of gelatinisation; after that the DG values increased gradually with gelatinisation time. The RS contents in all gelatinised starches decreased with increasing gelatinisation time, while the SDS values fluctuated. Chemical modification affected DG values as well as RS/SDS contents. The RS contents in 10% (w/w) acetylated, hydroxypropylated, octenyl succinylated and cross-linked canna starches gelatinised at 100 °C for 40 min were 26.6%, 32.0%, 45.3% and 19.8%, respectively, which were higher than that of the native starch (12.4%). Canna starch modified by crosslinking had the highest SDS content when gelatinised for 20-40 min. Modification of canna starch by heat-moisture treatment resulted in a lower content of RS for all treated samples. However, the Vt-HMT25 (canna starch containing moisture content of 25% during heat treatment) when gelatinised for 5-20 min contained a higher amount of SDS, compared to unmodified starch. The most effective modification method for RS and SDS formation was octenyl succinylation, where the sum of RS and SDS approached that of Novelose260.     

Migration of α-tocopherol and resveratrol from poly(L-lactic acid)/starch blends films into ethanol

Poly(L-lactic acid) (PLLA)/starch blends with various concentrations of two natural antioxidants, α-tocopherol (α-TOC) and resveratrol, were fabricated by a melt blending and compression molding processes. The effects of the two antioxidants on the optical (color), thermal and mechanical properties of PLLA/starch blends with antioxidants were assessed. PLLA/starch blend films with α-TOC and resveratrol showed a yellowish color influenced by the combined effect of white starch and the brown color of the antioxidants. The glass transition and melting temperatures were significantly reduced with the addition of antioxidants while enhanced thermal stability was observed, which could be a benefit and important for processing and production. The enhanced mechanical properties could be attributed to not only a compatibilization effect based on the chemical linkage between PLLA and starch chains, but also restriction of the chain mobility by antioxidants. The release of resveratrol from PLLA and PLLA/starch blend films into ethanol followed Fickian behavior. The D values of α-TOC were in the range of 0.47–3.95 × 10⁻¹¹ cm² s⁻¹ for PLLA films and 0.70–6.83 × 10⁻¹¹ cm² s⁻¹ for PLLA/starch blend films at 13 °C, 5.67–13.0 × 10⁻¹¹ cm² s⁻¹ for PLLA films and 4.10–24.2 × 10⁻¹¹ cm² s⁻¹ for PLLA/starch blend films at 23 °C, and 89.0–118.0 × 10⁻¹¹ cm² s⁻¹ for PLLA films and 123–282 × 10⁻¹¹ cm² s⁻¹ for PLLA/starch blend films at 43 °C. The D values of resveratrol were in the range of 0.073–0.54 × 10⁻¹⁰ cm² s⁻¹ for PLLA films and 1.42–6.93 × 10⁻¹⁰ cm² s⁻¹ for PLLA/starch blend films at 13 °C, 0.90–3.44 × 10⁻¹⁰ cm² s⁻¹ for PLLA films and 4.16–22.3 × 10⁻¹⁰ cm² s⁻¹ for PLLA/starch blend films at 23 °C, and 24.8–74.1 × 10⁻¹⁰ cm² s⁻¹ for PLLA films and 40.1–309 × 10⁻¹⁰ cm² s⁻¹ for PLLA/starch blend films at 43 °C.     

Enzymatic hydrolysis of granular native and mildly heat-treated tapioca and sweet potato starches at sub-gelatinization temperature

The effect of mild heat treatment (below gelatinization temperature) towards the susceptibility of granular starch to enzymatic hydrolysis was investigated. Tapioca and sweet potato starches were subjected to enzymatic hydrolysis with a mixture of fungal α-amylase and glucoamylase at 35 °C for 24 h. Starches were hydrolyzed in native (granular) state and after heat treatment below gelatinization temperature (60 °C for 30 min). The dextrose equivalent (DE) value of heat-treated starch increased significantly compared to native starch, i.e., 36–50% and 27–34% for tapioca and sweet potato starch, respectively. Scanning electron microscopy examination showed that enzymatic erosion occurred mainly at the surface of starch granules. Hydrolyzed heat-treated starch exhibited rougher surface and porous granules compared to native starch. X-ray analysis suggested that enzymatic erosion preferentially occurred in amorphous areas of the granules. The amylose content, swelling power and solubility showed insignificant increase for both starches. Evidently, heating treatment below gelatinization temperature was effective in enhancing the degree of hydrolysis of granular starch.     

Development and characterization of novel probiotic-residing pullulan/starch edible films

An innovative approach was performed to prepare novel pullulan/starch blended edible films by direct incorporation of multiple probiotic bacterial strains. Various starches different in origin were blended into the pullulan solutions with different ratios. The physical and mechanical properties of the films were investigated in the presence and absence of probiotic cells. An increase in the starch content of pullulan films resulted in a substantial decrease in relative cell viabilities and mechanical properties. Moreover, slight changes in the physical and mechanical properties of the films were observed with the addition of probiotic strains. Pullulan and pullulan/potato starch films were found to be the most suitable carrier matrices, with a maximum relative cell viability of 70–80% after 2 months of storage at 4 °C. The results suggest that pullulan and pullulan/starch films can be used as effective delivery and carrier systems for probiotics.     

Microstructure and rheology of phase-separated gels of gelatin + oxidized starch

We report on small-deformation rheology and confocal microscopy at 24 °C of high-sugar gel samples based on an aqueous mixture of gelatin + oxidized (non-gelling) starch exhibiting thermodynamic incompatibility. Using a standard protocol involving the heating of previously rapidly quenched samples at a fixed holding temperature (24–60 °C) for a fixed time (from 20 s to 30 min), gel samples of different storage modulus and degrees of spinodal-type phase separation were systematically generated. The developing time-dependent modulus of the gelatin gel was found to be sensitive to the extent of gelatin crosslinking as influenced by the nature of the thermal processing conditions. Under identical processing conditions, a gradual increase in starch content gave gels of lower elastic modulus and increased degree of microscopic phase separation. Taken all together, our results indicate that the gel rheology is determined by a subtle combination of overall system composition and temperature/time processing history. We conclude that the mechanical properties of this mixed biopolymer system are not directly deducible from the extent of phase separation observed microscopically without detailed additional information concerning sample preparation and treatment conditions.     

Citric acid cross-linking of starch films

This paper shows that citric acid can cross-link starch and improve the tensile strength, thermal stability and decrease the dissolution of starch films in water and formic acid. The poor mechanical properties and water stability of starch have restricted its industrial applications. Although cross-linking is a common approach to improve the properties of starch products, current starch cross-linking methods are either expensive, toxic or do not impart the desired properties to the cross-linked materials. In this research, the possibility of cross-linking starch films using citric acid to improve their strength and stability was examined. Citric acid cross-linked starch films show about 150% higher strength than non-cross-linked films and have strength better than most cross-linked starch and synthetic polymer blended films previously developed. Films cross-linked with 5% citric acid had only 35% loss in weight after being in formic acid for 5 h at 50 °C whereas the non-cross-linked films dissolved immediately.     

Microstructure and elastic modulus of mixed gels of gelatin + oxidized starch: Effect of pH

The microstructure and elastic shear modulus of cold-set gels formed from high-sugar aqueous mixtures of gelatin (7 wt%) + oxidized starch (0-6 wt%) were investigated as a function of pH. Samples prepared at 90 °C, with citric acid added to adjust the pH, were rapidly quenched to ∼1 °C, subjected to a standard thermal treatment (40 °C for 10 min), and then investigated by confocal microscopy and small-deformation rheology at 24 °C. Under ‘natural’ conditions of pH ≈ 5.2 (no citric acid addition), the samples exhibited phase separation with a characteristic spinodal-type morphology. The spatial extent of the structural heterogeneity, expressed by a single length-scale parameter, was found to increase with starch concentration. Gradual acidification led to a reduction in this length-scale parameter, leading to complete inhibition of phase separation below a certain characteristic pH value in the range 4.5-4.9 (depending on starch content). Over the investigated pH range, the effect of starch addition was to reduce the storage modulus of the resulting gel. This reduction was more pronounced for the phase-separated samples. The pH of maximum rigidity was found to decrease from pH_max ≈ 4.6 for 0 wt% starch to pH_max ≈ 4.2 for 6 wt% starch. Taken all together, these observations can be understood in terms of the effects of pH on the cross-linking behaviour of the gelatin and the nature of the gelatin-starch electrostatic interactions. The microscopy results are consistent with a transition in behaviour from thermodynamic incompatibility (segregative interactions) at high pH to soluble complexation (associative interactions) at low pH.     

Physical and mechanical properties of peanut protein films

The properties of peanut protein films were modified using physical and chemical treatments, and their effects on color, mechanical strength, water solubility and barrier to water vapor and oxygen of the films were investigated. Physical treatments consisted of heat denaturation of film-forming solution for 30 min at 60°C, 70°C, 80°C and 90°C, ultraviolet irradiation of films for up to 24 h, and three ultrasound processes of film-forming solution. Chemical treatments consisted of addition of aldehydes and anhydrides. Heat curing at 70°C, ultraviolet irradiation for 24 h, ultrasound for 10 min in a water-bath, and formaldehyde and glutaraldehyde addition caused a significant increase in the tensile strength of the films. The water vapor permeability (WVP) and oxygen permeability (OP) of the films decreased after heat denaturation and aldehyde treatment. OP also decreased with UV treatment. Heat curing was the most effective treatment, making the films stronger, more resistant to water and less permeable to water vapor and oxygen.     

Impact of γ-irradiation,CIPC treatment,and storage conditions on physicochemical and nutritional properties of potato starches

In the present study, three potato varieties were treated with chlorpropham (CIPC, 35 ppm), γ-irradiated (0.1 kGy) and stored for up to 5 months at 8 °C, and the physicochemical properties and in vitro starch digestibility of native and cooked starches were investigated. Sprouting was found to be satisfactorily suppressed by γ-irradiation and CIPC treatment. However, irradiation increased total free glucose content in two potato varieties, and decreased the thermal transition and pasting temperature of starch. The crystallinity of starch in irradiated potatoes decreased significantly (p ? 0.05) which may explain its decreased resistant starch content. Sprout inhibiting treatments and storage had no effect on in vitro starch digestibility in cooked starches, but cooling cooked starch significantly (p ? 0.05) increased its resistant starch content.     

DMA peaks in potato cork tissue of different mealiness

Dynamic mechanical analysis (DMA) was applied to potato cortex tissue of two cultivars (more waxy ‘Nicola’ and more mealy ‘Saturna’) in temperature scans in range the 30-90 °C and constant air humidity of 90%. The obtained scans indicate peaks in both storage and loss module of elasticity (SM and LM, respectively) at temperatures higher than 70 °C as was observed previously. The peak temperature as well as the peak value increase with increasing potato density. Higher peaks and higher peak temperatures was observed in the industrial cultivar ‘Saturna’ in comparison to more waxy salad cultivar ‘Nicola’. The source of the observed module peaks in the potato cooking process is discussed from the point of view of starch swelling.     

Viscoelastic behavior and microstructure of aqueous mixtures of cross-linked waxy maize starch,whey protein isolate and κ-carrageenan

The viscoelasticity and microstructure of mixtures of cross-linked waxy maize starch (CH10), whey protein isolate (WPI) and κ-carrageenan (κC) at pH 7.0 with 100 mM NaCl were investigated by oscillatory rheometry and confocal laser scanning microscopy (CLSM). Mixtures were heated to 90 °C (1.5 °C/min), held for 10 min at this temperature and cooled. Within the range of concentrations studied, CH10 swollen granules reinforced WPI and κC networks. The mechanical behavior of the three-component mixtures was modified by different WPI concentrations, but κC governed the overall response due to its gelling ability. CLSM images of three-component mixtures showed particulate systems in which swollen starch granules are surrounded by κC and WPI. CH10 granules were immersed in a single phase and a separate phase of κC and WPI, for low and high concentrations of these components, respectively. Therefore, it is possible to obtain two- and three-phase mixtures.     

Functional properties of square banana (Musa balbisiana) starch

Starch was isolated from unripe square banana (Musa balbisiana) fruit and its functional properties were determined. Square banana starch peak gelatinisation temperature was 79.8 °C and the transition enthalpy was 17.3 J/g. At 90 °C, the solubility was 16.8%, the swelling power was 17.1 g water/g starch and the water absorption capacity was 14.3 g water/g starch. The paste properties were: temperature, 81 °C; maximum viscosity, 326 BU; breakdown, 22 BU; setback, 40 BU and consistency, 18 BU. The clarity, expressed as transmittance, was 17.5%, and gel deformation was 32.4% with a 0.03 kgf maximum load. This starch had high syneresis and low stability in refrigeration and freezing cycles. Given its properties, square banana starch has potential applications in food systems requiring high temperature processing, such as jellies, sausages, bakery and canned products. It is inappropriate, however, for use in refrigerated or frozen foods.     

Development of fish gelatin edible films using extrusion and compression molding

Fish gelatin was plasticized with 20% and 25% glycerol (w/w of gelatin) and used to develop edible films by twin-screw extrusion at 110 and 120 °C followed by compression molding at 80 °C. Tensile and moisture barrier properties and glass transition temperature were then measured and compared with solution-cast films. The films extruded at 110 °C and with 25% glycerol had the highest percent elongation at break of 293 ± 27%. The water vapor permeability values of extruded films (the highest value being 2.9 ± 0.2 g mm h⁻¹ cm⁻² Pa⁻¹) were higher than those of solution-cast films while the glass transition temperatures (T_g) of the extruded films were generally lower than those of solution-cast films. Films with 25% glycerol that were extruded at 110 °C had the lowest T_g (2.10 ± 0.31 °C). This investigation showed that extrusion processing followed by compression molding is a feasible method to produce fish gelatin films for commercial applications in a wide range of food products.     

Effects of drying methods and plasticizer concentration on some physical and mechanical properties of edible chitosan films

In order to alleviate shortcomings of edible chitosan films, which are rigid and brittle in nature, an idea of using advanced drying methods, in combination with appropriate concentration of plasticizer, to improve the mechanical properties of the films was proposed and tested. Physical (thickness and color) and mechanical (tensile strength and percent elongation) properties of edible chitosan films plasticized at four glycerol concentrations (0%, 25%, 75% and 125% w/w chitosan) and prepared by three drying methods, namely, hot air drying (≈40 °C), vacuum drying and low-pressure superheated steam drying (LPSSD) (90 °C, 10 kPa) were investigated. Dynamic mechanical thermal analysis (DMTA) was used to determine the glass transition temperature to verify the compactness of edible chitosan films. It was found that the drying methods and plasticizer concentration significantly affected the drying time, tensile strength, percent elongation and glass transition temperature of the films. On the other hand, the drying methods and plasticizer concentration did not affect the thickness and final moisture content of the film samples at lower glycerol concentrations. In the cases of vacuum drying and LPSSD, there was a limiting value of plasticizer concentration (25% w/w) beyond which the effect of the plasticizer concentration on the mechanical properties was negligible. In all cases, the color of all tested films was not significantly different.     

Effect of heat treatment of film-forming solution on the properties of film from cuttlefish (Sepia pharaonis) skin gelatin

Effects of heat treatment at different temperatures (40–90 °C) of film-forming solution (FFS) containing 3% gelatin from cuttlefish (Sepia pharaonis) ventral skin and 25% glycerol (based on protein) on properties and molecular characteristics of resulting films were investigated. The film prepared from FFS heated at 60 and 70 °C showed the highest tensile strength (TS) with the highest melting transition temperature (T_max) (p < 0.05). Nevertheless, film from FFS heated at 90 °C had the highest elongation at break (EAB) with the highest glass transition temperature (T_g) (p < 0.05). With increasing heating temperatures, water vapor permeability (WVP) of films decreased (p < 0.05), but no differences in L*-value and transparency value were observed (p > 0.05). Based on FTIR spectra, the lower formation of hydrogen bonding was found in film prepared from FFS with heat treatment. Electrophoretic study revealed that degradation of gelatin was more pronounced in FFS and resulting film when heat treatment was conducted at temperature above 70 °C. Thus, heat treatment of FFS directly affected the properties of resulting films.