Partial Characterization of Tamarind (Tamarindus indica L.) Kernel Starch Oxidized at Different Levels of Sodium Hypochlorite

The effects of different levels of sodium hypochlorite (1–4 g/100 g dry solids active chlorine) on the physicochemical, pasting, and structural properties of tamarind kernel starches were investigated. The isolated starch had low traces of non-starch components, such as protein, fat, and ash, indicating its purity. Both the carboxyl and carbonyl contents in the oxidized starches increased significantly with the increase in chlorine concentration. The introduction of carboxyl and carbonyl groups resulted in significantly lower amylose content. The swelling power of oxidized starches was significantly lower than native starch and the solubility values increased when the chlorine concentration increased at all the measured temperatures. The percentage of light transmittance increased progressively after oxidation. Pasting properties showed that in treatments at high active chlorine concentrations, the peak viscosity decreased more drastically than in treatments at low chlorine concentration, indicating a greater degradation of starch. The morphology of the starches was not altered after oxidation. After oxidative treatment no change in the X-ray diffraction pattern was observed but intensity of the peaks increased. Therefore, tamarind kernel being underutilized raw material, has a great potential as a non-conventional source of starch and desirable properties of this starch can be enhanced by oxidation for applications in food industry.     

Physicochemical properties of acetylated starches from some Indian kidney bean (Phaseolus vulgaris L.) cultivars

Starches separated from four kidney bean cultivars were modified by acetylation to reduce retrogradation and increase gel stability and compared with respective native starches (data of native starch reported by Wani et al., 2010 ). Acetylation was carried out by treating starches with 0.04 and 0.08 g of acetic anhydride per gram of starch dry weight basis (dwb) at 25 °C and pH between 8.0 and 8.5. The extent of acetylation increased proportionally with the concentration of acetic anhydride used. The pasting curves of 10.7% starch determined by Rapid Visco Analyzer at 160 rpm showed that acetylation decreased the setback viscosity values by 0.64–34.58% and pasting temperature by 4.4–9.2 °C when compared with the native starch. Differential scanning calorimetry observations also revealed significant (P ≤ 0.05) decrease in gelatinisation temperature of acetylated starches than the corresponding native starches. Hardness of starch gels varied between 14.3 and 44.0 g, which was significantly (P ≤ 0.05) lower than the corresponding native starch gels.     

Technological Evaluation of Nitrogen Containing Starch Derivatives as Sizing Agents

The structural changes brought about by introducing different nitrogen containing groups via cyanoethylation, carbamoylethylation and carbamation in the molecules of rice and maize starches and oxidized starches derived thereof and the onset of these changes on the technical properties of yarns sized with such starch products were investigated. It was found that the apparent viscosity of pastes prepared from those products depends on the nature of starch, the degree of oxidation prior to chemical modification, the nature of modification as well as the measuring conditions, i. e. the rate of shear and temperature. Cotton yarns sized using these starch derivatives were measured for yarn number, tensile strength, C.V.%, elongation at break and C.V.% in elongation. Besides, the weavability test expressed as the minimum number of cycles due to abrasion (St₁) and average number of cycles due to abrasion (St₆) were investigated. A comparison among modified starches prepared from rice starch would reveral that the highest value of St₁ is obtained with yarns sized using carbamoylethylated sample derived from unoxidized starch. With maize starch, on the other hand, the highest value of St₁ is obtained with cotton yarns sized using carbamoylethylated starch derived from starch oxidized by 1 g/l active chlorine.     

Effects of cationization on DSC thermal profiles,pasting and emulsifying properties of sago starch

Cationic sago starches were prepared using an aqueous alkaline process with different levels of cationic reagent 3‐chloro‐2‐hydroxypropyltrimethylammonium chloride (0.01–0.10 M ), sodium hydroxide (0.03–0.86 M ) and reaction temperature (30–62 °C). The degree of substitution (DS), reaction efficiency, thermal and pasting properties of cationic sago starches were analysed. Emulsifying and fat binding properties of native sago starch, cationized sago starch and commercial chitosan were compared at two different pH values (4 and 7). Degree of substitution increased with an increase in concentration of cationic reagent or NaOH, or reaction temperature. The reaction efficiency was proportional to the concentration of NaOH and reaction temperature but inversely proportional to the cationic reagent concentration. The highest DS and reaction efficiency achieved was 0.06 and 79%, respectively. The pasting temperature and gelatinization enthalpy of cationic starch (DS 0.06) were lower compared with native sago starch. Cationization increased the peak viscosity and breakdown of the starch paste but decreased the setback. The presence of cationic groups significantly increased emulsion stability, emulsion viscosity and fat binding capacity of sago starch. However, the cationic sago starch was still inferior to chitosan, which showed the highest emulsion stability, emulsion viscosity and fat binding capacity. There was no significant difference between the surface tension values of native and cationic sago starch and chitosan. The influence of pH on emulsifying properties was not significant. The emulsion stability of the cationic sago starch improved due to an increase in viscosity and fat binding capacity but not its surface active property. Copyright © 2004 Society of Chemical Industry     

Effect of cross‐linking on some properties of potato (Solanum tuberosum L.) starches

Starches separated from different potato cultivars were modified using two different cross‐linking agents: epichlorohydrin (EPI) and phosphoryl chloride (POCl₃) at different concentrations (1.0 and 2.0 g kg^?1 POCl₃; 2.5, 5.0 and 10 g kg^?1 EPI). Differential scanning calorimetry, rheological and retrogradation measurements were performed to characterise the influence of cross‐linking on the properties of potato starches. Cross‐linking considerably reduced swelling power, solubility, water‐binding capacity and paste clarity. The decrease became greater as the reagent concentration increased. The starches treated with 1.0 g kg^?1 POCl₃ exhibited exceptionally higher swelling power than their counterpart native starches. Neither cross‐linking agent caused any change in morphology of the starch granules. Studies on the phase transitions associated with the gelatinisation showed significantly higher values for the onset temperature (T_o), peak temperature (T_p), conclusion temperature (T_c) and enthalpy of gelatinisation (ΔH_gel) for the cross‐linked starches than the native starches. Starches treated with both the reagents showed lower peak storage modulus (G′) and loss modulus (G″) than their native counterparts. The tendency of the starch pastes towards retrogradation increased considerably with increases in storage duration. However, the starches treated with 1 g kg^?1 POCl₃ exhibited much lower syneresis than the other cross‐linked starches. Copyright © 2006 Society of Chemical Industry     

Gelatinization and Thermal Properties of Modified Cassava Starches

The thermal properties of seven commercial modified cassava starches, including oxidized, acetylated, cross‐linked, and combined acetylated and cross‐linked starches were studied by differential scanning calorimetry (DSC) in the glassy and rubbery states. Increase in gel hardness in the rubbery state during storage was also monitored, as well as gelatinization behavior. The modified starches were prepared from granular starch and had a degree of substitution in the range 0–0.053. The glass transition temperatures (T_g) of the modified starches were 3–6°C significantly lower than that of the non‐modified starch. The physical aging peak temperatures were also significantly reduced by 2–3°C, compared to the non‐modified starch, while aging enthalpies increased. Starch modifications did not decrease amylopectin retrogradation significantly. During storage, the oxidized starch gel became significantly harder than the non‐modified starch gel, while the hardness of the acetylated and/or cross‐linked starch gels was significantly reduced, which confirmed that acetylation or cross‐linking can decrease hardness, even when the extent of modification is limited. Different modifications controlled different properties of the starch system, with cross‐linking and acetylation influencing the gelatinization behavior and the changes in starch gel texture during storage, respectively.     

Thermal properties of new varieties of yam starches

Starches isolated from yam varieties of Dioscorea alata and Dioscorea cayenensis‐rotundata species were prepared at different time–temperature conditions and characterised by DSC, amperometric iodine titration, light microscopy and rheology and compared to native and chemical modified tapioca starches. The observation by light microscopy showed different morphologies of the granules when heated above 100°C and the tendency for disintegration decreased in the order native tapioca starch > yam starch > modified tapioca starch. Differences between yam and tapioca starches were also revealed by DSC. Yam starch enthalpy is higher than tapioca starch, but the peak temperature is low. However, the significant differences between yam and the other tested starches were found in terms of their rheological behaviour. The viscosity of yam starch was very stable at high temperatures on the viscograph. With this property, yam starch can be used as thickening and gelling agent in food.     

Functional properties and retrogradation behaviour of native and chemically modified starch of mucuna bean (Mucuna pruriens)

Mucuna bean (Mucuna pruriens) starch was isolated and subjected to chemical modification by oxidation and acetylation. The proximate analysis of the non‐starch components of the native starch on a dry weight basis was 92 g kg^?1 moisture, 5 g kg^?1 ash, 2 g kg^?1 fat, 7 g kg^?1 crude fibre and 19 g kg^?1 protein. Chemical modification reduced the values for all the non‐starch components except the moisture level. For all the samples, swelling power and solubility increased as the temperature increased in the range 50–90 °C. The swelling power of mucuna native starch (MNS) and mucuna acetylated starch (MAS) increased with increasing acidity and alkalinity, while that of mucuna oxidised starch (MOS) only increased with increasing pH in the acidic range. The maximal solubility of all the starches was observed at pH 12. All the starch samples absorbed more oil than water. The lowest gelation concentration followed the trend MAS < MNS < MOS. Chemical modification reduced the gelatinisation temperature (Tp), while peak viscosity (Pv), hot paste viscosity (Hv) and cold paste viscosity (Cv) decreased after oxidation but increased following acetylation. The setback tendency of the native starch was reduced significantly after chemical modification. However, the breakdown value of MNS, 65 BU (Brabender units), was lower than that of MOS (78 BU) but higher than that of MAS (40 BU). Differential scanning calorimetry studies of gelatinisation and retrogradation revealed that chemical modification reduced the onset temperature (T_o), peak temperature (T_p) and conclusion temperature (T_c). Oxidation and acetylation reduced the gelatinisation and retrogradation enthalpies of the native starch. The enthalpy of retrogradation of the starches increased as the length of storage increased. Copyright © 2003 Society of Chemical Industry     

Influence of Heat‐Moisture Treatment and Acid Modifications on Physicochemical,Rheological, Thermal and Morphological Characteristics of Indian Water Chestnut (Trapa natans) Starch and its Application in Biodegradable Films

Water chestnut starch was subjected to acid modification and heat‐moisture treatment. Hydrochloric acid was used for acid modification at three different concentrations (0.25 M, 0.5 M and 1 M) for 2 h. Modifications did not alter the granule morphology. Heat‐moisture treatment (HMT) resulted in slight reduction in the granular size of the starch granules. Acid modification lowered the amylose content, swelling power, water‐ and oil‐binding capacity but improved the solubility of starch to a considerable level. Light transmittance of acid‐modified (AM) starches improved significantly. A significant reduction in peak, trough, final and setback viscosity was observed by acid‐thinning. In case of heat‐moisture treated starch the final viscosity (F_v) was found to be even higher than the peak viscosity (P_v). Native water chestnut starch exhibited a lower onset temperature (T_o) and peak temperature (T_p) of gelatinization than the corresponding acid‐treated starches. Starch films prepared from native starch exhibited excellent pliability, whereas those prepared from AM and HMT starches showed good tensile strength. Starch films prepared from acid‐treated starches provided better puncture and tensile strength.     

Characteristics of pores in native and hydrolyzed starch granules

Low‐temperature nitrogen adsorption and mercury porosimetry were applied for analyzing effect of α‐amylolysis upon the porosity of granules of native corn, wheat, rice, and potato starches. Specific surface area (S_BET), porosity, pore size distribution, total pore area, and mean pore radius were determined for native and digested granules. It was found that native starch granules are macroporous materials with a small participation of mesopores. In the case of native starches, the highest value of S_BET was obtained for rice starch (1.27 m²/g) and the lowest – for potato starch (0.14 m²/g). Pore size distribution curves obtained by nitrogen adsorption showed peaks in the range of diameters 2–3 nm (for all starches) and 100–200 nm (for corn and rice starches). After 60 min of enzyme action, surface area of all starches doubled in comparison to native ones. Arising of the new pores was also noted. The results of mercury porosimetry measurements showed that rice starch had the highest total area of pores and porosity but the lowest mean pore radius among all native starches. The pore size distribution curves for all starches exhibited solely one peak corresponding to the dominant group of pores of the radii in the range 0.5–8 µm, dependent on the starch source. There were also much smaller peaks situated within the range of 3–30 µm. After α‐amylolysis of corn and rice starches, the average radius of the dominant group of pores diminished. No substantial changes in the pore radii could be noted for potato starch.     

Physicochemical, crystallinity, pasting and morphological properties of bean starch oxidised by different concentrations of sodium hypochlorite

The effect of bean starch oxidation at different active chlorine concentrations (0.5%, 1.0% and 1.5%) on the physicochemical, crystallinity, pasting and morphological properties of starch was investigated. The carbonyl content, carboxyl content, starch colour, swelling power, solubility, gel hardness, X-ray crystallinity, pasting properties, gelatinisation characteristics and morphology of the starches were evaluated. The bean starch oxidised with 0.5% active chlorine had the characteristic of a slightly crosslinked starch. As compared to the native and 0.5% active chlorine-oxidised starches, active chlorine at 1.0% and 1.5% increased the carbonyl content, carboxyl content and solubility of the starches. Moreover, these concentrations of active chlorine decreased the swelling power, gel hardness, relative crystallinity, breakdown, peak viscosity and setback, as compared to the native and 0.5% active chlorine-oxidised starches. The starch granules oxidised with 1.5% active chlorine had imperfections in their structure, and its surface appears to be rougher than the other granules.     

Hypochlorite oxidation of field pea starch and its suitability for noodle making using an extrusion cooker

The effect of hypochlorite oxidation on the Brabendar pasting properties of field pea starch and the suitability of native and oxidized starch for noodle making by extrusion cooking were investigated. Field pea starch was oxidized with sodium hypochlorite at a level of active chlorine ranging from 0.89 to 3.28% (starch db). The degree of oxidation was determined and expressed in terms of percentage of carboxyl and carbonyl groups, which ranged from 0.02 to 0.38% and 0.06 to 0.19%, respectively. Starch recovery and peak viscosity, hot paste viscosity, cool paste viscosity, and setback of oxidized starches decreased with increasing degree of oxidation. The cooking quality attributes of noodles prepared from native field pea starches were acceptable but were negatively influenced by hypochlorite oxidation. Substitution of potato starch (40%, db) for field pea starch yielded more glossy noodles with better cooking quality. It was also observed that Brabendar pasting properties had high correlations with noodle quality characteristics.     

Studies on the properties of citrate derivatives of cassava (Manihot esculenta Crantz) starch synthesized by microwave technique

Cassava starch citrates with degree of substitution (DS) ranging from 0.005 to 0.063 were synthesized by the microwave‐assisted reaction of cassava starch with citric acid. A response surface small composite design was used to study the effect of different reaction conditions, viz. time, temperature and reagent concentration. All these variables significantly affected the substitution level in the modified starches. The DS increased with increase in the time of reaction and temperature. However, reagent concentration had a negative effect on the DS. The modified starches showed higher viscosity with lower breakdown, lower setback and higher final viscosities in comparison to native starch. Differential scanning calorimetry showed that the modified starches exhibited a decrease in gelatinization temperatures, T_o, T_p, T_e, in comparison to native starch. However, the heat of gelatinization was not significantly affected. The citrate derivatives exhibited reduced swelling volume and enhanced water binding capacities. They were found to be less susceptible to enzyme hydrolysis than native starch. Copyright © 2007 Society of Chemical Industry     

Fine structural characteristics related to digestion properties of acid‐treated fruit starches

Starches from unripe fruits (mango, banana, and plantain) were acid modified to form different degrees of lintners with the objective to increase the slowly digestible starch (SDS) and RS contents. Molecular, thermal, and structural characteristics were evaluated. Mango starch showed higher susceptibility to acid hydrolysis than banana and plantain starches. The peak temperature of gelatinization (T_p) showed a decrease at low hydrolysis percentage, but at higher hydrolysis percentage the T_p increased. However, the enthalpy of gelatinization presented an increase with the hydrolysis percentage, but was not higher than its native counterpart. In general, the peak temperature and enthalpy of retrogradation increased with hydrolysis percentage due to formation of linear chains during the modification that promoted retrogradation. High performance size exclusion chromatography (HPSEC) analysis demonstrated the presence of multiple‐branches (DP = 96–109), single branched (DP = 28–31), and linear (DP = 16–18) polymers in the fruit starch lintners. The acid treatment (lintnerization) of mango starch had no effect on the SDS fraction, while for plantain and banana starches, the SDS content increased (6.14–35.4%) at low hydrolysis percentage (0–50%) followed by a decrease at higher days of hydrolysis. At higher hydrolysis percentage (70–80%) the RS content increased for the three fruit lintners.     

Effect of Acidified Methanol Modification on Physico Chemical Properties of Black-Eyed Pea (Vigna unguiculata) Starch

Black-eyed pea starch was hydrolyzed using concentrated HCl (36% by weight) at different levels (10–60 mL) in the presence of methanol and the physico-chemical properties of native and acidified methanol modified black-eyed pea starches were compared. Results revealed high recovery (>93%) of acid-alcohol treated black-eyed pea starch upon modification. A drop in swelling power and increase in solubility was also observed during acidified methanol treatment. Acid hydrolysis increased paste clarity and the freeze–thaw stability; however, the trend was found to vary at a specific modification level. Acid thinning of starch revealed significant decrease in gel consistency, sediment volume, water, and oil binding capacity. Disruption of interactions between amylose chains resulted in increased amylose leaching on modification. The X-ray diffraction pattern of black-eyed pea starch was of C-type obtained and with increase in acid concentration the intensity of peak was found to be increased. Increased acid concentration showed significant increase in crystallinity; however, marked loss of crystallinity was observed at an acid level of 40 mL which further increased on acid concentrations of 50 and 60 mL. Also, acid concentration showed significantly improved post-reaction color difference (?E) of the modified starches.     

Effect of dual modification of banana starch and storage time on thermal and crystallinity characteristics of its films

Banana starch was oxidized at three different levels and subsequently acetylated. This double modified banana starch was used for film preparation with the addition of glycerol. Thermal and crystallinity properties were evaluated. Acetylation decreased the peak temperature and enthalpy of double modified banana starch. When the oxidation level and storage time increased in films elaborated with the double modified banana starch, both thermal parameters increased as well. The T_g showed slight changes in films prepared with the double modified banana starch compared to its oxidized counterpart, and similar patterns were found when oxidation levels increased in double modified films. However, a decrease in the T_g was determined with the storage time in films prepared with oxidized and double modified starches. Films prepared with the double modified banana starch presented lower percentage of crystallinity than its oxidized counterpart, nevertheless at higher storage periods, crystallinity levels increased. Thermal and crystallinity properties of films prepared with double modified banana starch could be used to understand the behavior during their application.     

Effect of Cross‐linking with Epichlorohydrin on the Properties of Cassava (Manihot esculenta Crantz) Starch

Cassava starch was cross‐linked with epichlorohydrin (EPI) at 45°C for 2 h in three different media which include water, water in the presence of a phase transfer catalyst (PTC) and N,N‐dimethylformamide (DMF). The products were characterized by determining their physicochemical, thermal and retrogradation properties. In aqueous medium, the use of a PTC, tetrabutylammonium bromide (TBAB) produced derivatives with higher degree of cross‐linking than those prepared without the use of the catalyst. The degree of cross‐linking was found to be higher using the same concentration of EPI when the reaction was carried out in DMF. At low levels of cross‐linking, the peak viscosity of the cross‐linked starches increased in comparison to that of the native starch. With increasing degree of cross‐linking, the peak viscosity showed a significant reduction. The swelling volume, solubility and light transmittance of the starch pastes were lower for the modified starches. The cross‐linked starches showed slightly reduced values for the gelatinization temperatures, T_onset, T_peak and T_end. The enthalpy of gelatinization of the modified starches increased with increase in the degree of cross‐linking. The modified starches exhibited higher water‐binding capacities (WBC) than the native starch; but with increase in the degree of cross‐linking, there was a gradual decrease in WBC. The in vitro alpha amylase digestibility of the modified starches decreased gradually with increase in the level of cross‐linking.     

Physico-chemical properties of flour and starch from jackfruit seeds (Artocarpus heterophyllus Lam.) compared with modified starches

Jackfruit (Artocarpus heterophyllus Lam.) is one of the most popular tropical fruits grown in Asia. The objective of this study was to compare physico‐chemical properties of native flour and starch from jackfruit seeds (A. heterophyllus) to commercially modified starches (Novation 2300 and Purity 4). The colour of jackfruit seed starch was lighter than the Novation 2300 starch but darker than the Purity 4 starch. The jackfruit seed starch had a narrower gelatinization temperature range than Purity 4 and required less gelatinization energy compared with modified starches. The peak viscosity of jackfruit seed starch was lower than commercially modified starches. Likewise, setback viscosity, swelling power and solubility of jackfruit seed starch showed similar trends. Results from this study suggest that native starch from jackfruit seed could be used as an alternative for modified starches in a system needing starch with a high thermal and/or mechanical shear stability.     

Production and characterization of oxidized cassava starch (Manihot esculenta Crantz) biodegradable films

Plastic is one of the most common pollutants in the environment. Therefore, the number of studies on the use of biodegradable packaging is increasing. Starch is the primary material used in the production of biodegradable plastics due to its natural abundance and high biodegradability. Yet, the strong hydrophilic character of starch presents a challenge. Therefore, the modification of its structure through oxidation may yield interesting results as the viscosity reduction. The objectives of this work were to obtain cassava (Manihot esculenta Crantz) starch oxidized with 0.8 and 2.0% active chlorine, to develop biodegradable films and characterize their mechanical properties, solubility in water, permeability to water vapor, degree of swelling, and sorption isotherms. Biodegradable films were produced with starch concentrations of 2, 3, 4, and 5% w/w and 25% glycerol (g/100 g starch) added as a plasticizer. Images of the films were obtained with an atomic force microscope and allow to observe a smooth surface and the absence of starch granules in the film produced with oxidized starches. The tensile strength of the biodegradable film produced with oxidized starch (0.8% active chlorine) was 80 MPa. The value of permeability to water vapor was 1.613 × 10⁻⁹ kg/day/m/Pa, and the average solubility was 41%. The sorption isotherms showed that biodegradable films made with oxidized starches cannot be used in environments with relative humidity below 35% or above 90%.     

Production and characterization of digestion‐resistant starch by the reaction of Neisseria polysaccharea amylosucrase

Recombinant amylosucrase (200 U/mL) from Neisseria polysaccharea was used to produce digestion‐resistant starch (RS) using 1–3% (w/v) corn starches and 0.1–0.5 M sucrose incubated at 35°C for 24 h. Characterization of the obtained enzyme‐modified starches was investigated. Results show that the yields of the enzyme‐modified starches were inversely proportional to the original amylose contents of corn starches. After enzymatic reaction, insoluble RS contents increased by 22.3 and 20.7% from 6.9% of waxy and 7.7% of normal corn starches, respectively, using 3.0% starch as acceptor and 0.3 M sucrose as donor, while amylomaize VII showed the lowest increase (8.5%) in RS content. The crystalline polymorph of these enzyme‐modified starches resulted in the B‐type immediately after enzymatic reaction. The enzyme‐modified starches displayed higher melting peak temperatures (85.6–100.6°C) compared to their native starch counterparts (70.1–78.4°C). After enzymatic reaction, pasting temperature increased in waxy (71.9 → 77.6°C) and normal corn starches (75.3 → 80.6°C), and the peak viscosity of waxy corn starches increased from 264 to 349 RVU, whereas that of normal corn starches decreased from 235 to 66 RVU.