Synthesis and characterization of highly acetylated sago starch

This study was carried out to understand and establish the changes in physicochemical parameters of sago starch after acetylation. Highly substituted starch acetate was prepared by reaction with native sago starch and acetic anhydride in organic solvent. Their formation was confirmed by the titrimetric analysis and FT‐IR. The presence of absorption band in FT‐IR at 1748 cm⁻¹ confirmed the carbonyl group attachment. The thermal behavior of native and acetyl substituted sago starch was investigated using thermo gravimetric analysis (TGA) and DSC. The results reveal that highly substituted starch acetate was more thermally stable as compared to native form. The XRD patterns showed loss of crystalline nature and its transformation into amorphous form. The SEM study suggested that the smooth surfaces of starch granules were changed into fibrous form after acetylation.     

A facile approach for controlled synthesis of hydrophilic starch‐based nanoparticles from native sago starch

A facile approach for the preparation of hydrophilic starch‐based spherical nanoparticles from native sago (Metroxylon sagu) starch using the drop‐wise solvent exchange method was reported. Starch‐maleate monoester (SM) was initially synthesized from native sago starch and maleic anhydride in an aqueous medium, and SM nanoparticles was subsequently precipitated in absolute ethanol under controlled conditions. The present study was focused mainly on modulating of the solvent and non‐solvent systems to prepare SM nanoparticles of different morphologies. The pH of the solvent system and the nature of surfactants being added into the solvent system could influence the morphology of regenerated SM nanoparticles. SM nanoparticles of discrete and spherical shape were regenerated from a basic SM sample solution, or an acidic sample solution in the presence of an appropriate surfactant. SM nanoparticles with mean diameter of about 250 nm was obtained by precipitation in absolute ethanol in the presence of Brij 35 as the surfactant.     

Synthesis and characterization of graft copolymers of Sago starch and acrylic acid

Sago starch has been graft copolymerized with acrylic acid (AAc) by mutual gamma radiation method. Reaction conditions such as total dose, monomer concentration and amount of methanol were optimized to obtain maximum grafting percentage. Maximum percentage of grafting, Pg (158.00%) was obtained at an optimum total dose of 62.64 kGy using 4.37 moles/L of AAc in 1 mL of methanol. Using optimum conditions, the effect of cross‐linker, glyoxal, on percent grafting was also studied and maximum grafting was obtained at [Glyoxal] = 54.70 moles/L. Characterization of the graft copolymer was carried out by FTIR, TGA, SEM, XRD analytical methods. The grafted Sago starch was found to have increased crystalline and improved thermal behavior. Swelling and solubility kinetics were measured for each of the samples and correlation between the effects of the reaction parameter on swelling‐solubility kinetics was evaluated. Maximum swelling (4192.3%) at 37°C in 8 h was observed for the sample with 59.9% graft level. Higher swelling percentage is indicative of the graft copolymer to have the properties of a hydro gels that can be utilized for use as drug delivery vehicle and purification of industrial effluents.     

Structural Transformation of Sago Starch by Heat‐Moisture and Osmotic‐Pressure Treatment

Sago starch was modified by osmotic‐pressure treatment (OPT) and heat‐moisture treatment (HMT) and physicochemical characteristics were compared. In OPT, sago starch was suspended in saturated sodium sulfate solution and heated for 1 h at 100, 110 and 120°C, corresponding to a calculated osmotic pressure of 32,728, 33,640 and 34,552 kPa (assuming sodium sulfate dissociates completely), respectively, and in HMT, sago starch with 20% moisture content was used. Change of X‐ray diffraction pattern from C‐type to A‐type was obtained for OPT and HMT starch at 110°C and 120 °C, respectively. RVA viscograms of both OPT and HMT starch exhibited a decrease of peak and breakdown viscosity but increase of final viscosity and pasting temperature. Onset (T_o), peak (T_p), and conclusion temperature (T_c) of gelatinization of both OPT and HMT starch increased significantly with increase of treatment temperature. Biphasic broadening of T_p was observed for HMT starch indicating an inhomogeneous heat transfer during HMT. The observed narrow peaks of DSC curves indicated better homogeneity of OPT. These properties suggest that OPT starch is more suitable for large‐scale production.     

Studies of Flavor Encapsulation by Agents Produced from Modified Sago and Tapioca Starches

The efficiency of sago and tapioca starch stearates for encapsulating lemon oil were studied and compared to the efficiency of gum arabic. The stearates were prepared by esterification of stearic acid with starch. To accomplish esterification, the stearic acid was first coated on the surface of the starch granules. Then the coated granules were heated at 150 °C for 2 h to obtain sago or tapioca starch stearate (SSS or TSS). SSS or TSS can be prepared as ready‐to‐use products in the form of pregelatinized‐hydrolyzed sago or tapioca starch stearate (PGHSSS or PGHTSS). The resulting modified starches were used for encapsulation of lemon oil. The lemon oil encapsulating efficiency for SSS with DS 0.009 and 0.014 were close to that of gum arabic, whereas the encapsulating efficiency for PGHSSS with DS 0.0052 and 0.016 were higher than that of the gum arabic. The TSS and PGHTSS provided encapsulating efficiencies lower than the gum arabic.     

Enzymic Extraction of Native Starch from Sago (Metroxylon sagu) Waste Residue

Residual native starch was extracted from sago pith residue using two types of commercial cell‐wall degrading enzymes, Pectinex Ultra SP‐L and Ultrazyme 100G. The first increased starch yield with a shorter incubation period than the second. The superior effect of Pectinex Ultra SP‐L was observed already at 0.5 h, where a wide granule size distribution (8—87 μm) was obtained. A slight increase in the release of granules ranging from 30—60 μm was noted within a 2 h incubation period. However, upon further incubation, the distribution pattern was similar to that of untreated samples. Samples treated with Ultrazyme 100G exhibited a unimodal distribution pattern, with larger granules, ranging from 40—70 μm, being released upon further incubation within a 2 h incubation period. However, all samples exhibited a bimodal distribution upon further incubation.     

Effect of Sago Starch Addition and Steaming Time on Making Cassava Cracker (Keropok)

This work was aimed at investigating the effects of steaming time and different fractions of sago starch (0, 6, 12, 18 and 24%) in mixtures with cassava starch on the properties of crackers as compared to cassava crackers. In the hydrothermal process, the steaming period was varied from 25 to 120 min. The properties of raw starches, half‐finished crackers (HFC) and puffed crackers (PC) were determined. Raw cassava starch had lower amylose content, smaller granule size, lower gelatinization and lower swelling power than sago starch. The properties of the raw starch mixtures varied according to the mixing proportions. Both sago starch content and steaming time influenced cracker quality, especially its expansion, which was related to the degree of gelatinization (DG). Increasing sago starch content caused decreased DG of HFC and hence decreased cracker expansion. Two groups of HFC were obtained; low DG (55–65%, 25‐45 min steaming time) and high DG (>80%, 60‐120 min steaming time) HFC. Generally the expansion increased as the DG increased – however, a too long steaming period (> 75 min) again reduced expansion, apparently the thinner starch gel allowed collapse of the air cells. No treatment gave complete gelatinization; which could be due to insufficient water for starch to gelatinize.     

Synthesis,characterization and swelling behaviour of superabsorbent polymers from cassava starch‐graft‐poly(acrylamide)

Superabsorbent polymers (SAPs) were prepared from cassava starch by graft copolymerization of acrylamide on to starch using ceric ammonium nitrate (CAN) as free radical initiator, followed by alkali saponification. The reaction parameters such as concentration of acrylamide, concentration of CAN, temperature, and duration of polymerization reaction were optimized for maximum water absorbency using a 4‐factor 3‐level Box‐Behnken design. The highest values of percentage grafting and absorbency obtained were 174.8% and 425.2 g/g, respectively. The polymers were characterized by determination of grafting efficiency, N‐content, acrylamide content, FTIR analysis, SEM and XRD analyses. Thermogravimetric analysis (TG) showed that the SAP has higher thermal stability. The rate of water absorbency and the swelling behaviour of the SAP under different conditions of pH, and different salts were determined. The de‐swelling pattern of the hydrogels over different time durations was also determined.     

Preparation,characterization, and water resistance of cationic acetylated starch‐g‐poly(styrene‐butyl acrylate) surfactant‐free emulsion

Cationic acetylated starch‐g‐poly(styrene‐butyl acrylate) surfactant‐free emulsion (CAS‐g‐poly(St‐BA)) was synthesized by graft copolymerization of styrene (St) and butyl acrylate (BA) onto CAS using FeSO₄–H₂O₂ redox initiator. The maximum graft of 55.68% was derived when H₂O₂ concentration, monomer concentration, and St/BA ratio were 9%, 130%, and 1:1, respectively. The results obtained from FTIR, NMR (H¹ NMR and C¹³ NMR), XRD, SEM, and thermogravimetric analysis (TGA‐DTG) confirmed graft copolymerization of St and BA onto CAS. And it was demonstrated that film‐forming properties of starch were greatly improved via grafting St and BA onto starch. It was also found that paper sized with CAS‐g‐poly(St‐BA) exhibited higher ring crush index and bursting strength than paper sized with cationic potato starch (CS) and CAS, as well as much lower water absorption, which is further verified by contact angles results.     

Effect of Temperature and Starch Concentration on the Intrinsic Viscosity and Critical Concentration of Sago Starch (Metroxylon sagu)

Intrinsic viscosity and critical concentration of sago starch dispersions were studied at different temperatures and presence of solutes (sodium chloride, glucose and sucrose). Ubbelohde capillary viscometer was used to measure relative viscosity. Intrinsic viscosity decreases with an increase in temperature but the critical concentration remained fairly constant over the range of temperature studied. Sodium chloride enhanced the intrinsic viscosity but sugars somehow reduced it. Critical concentration is defined as the point where the starch molecules start to entangle with each other and abruptly enhance viscosity. Sodium chloride enhanced the molecular entanglement and lowered the critical concentration.     

Water sorption kinetics of superabsorbent hydrogels of saponified cassava starch‐graft‐poly(acrylamide)

Superabsorbent polymers (SAPs) are hydrophilic polymeric networks that can absorb, swell and retain large quantity of water and other physiological fluids. In this paper, the water sorption pattern and kinetics of cassava starch based SAP hydrogels were studied under different conditions of swelling such as soaking duration, pH, presence of salts, and particle size of the hydrogel. The kinetics was studied using Voigt‐based viscoelastic model to determine the rate parameter and the swelling rate (SR). It was noted that under all conditions, the water sorption followed a second order kinetics. The absorbency was directly proportional to the rate of swelling. But when the sample was allowed to swell in aqueous solutions of CaCl₂ and AlCl₃, the absorbency as well as the SR was irregular. The particle size also had significant effect on water absorption by the SAP and the polymer with smaller particles showed more absorption than those with larger particle size. The solvent induced phase transition of the superabsorbent hydrogel was also studied.     

Effects of starch alkenylsuccinylation on the grafting efficiency,paste viscosity,and film properties of alkenylsuccinylated starch‐g‐poly(acrylic acid)

Commercial cornstarch was alkenylsuccinylated with alkenylsuccinic anhydride to different degrees of substitution (DS) and then the products were graft‐copolymerized with acrylic acid for investigating the effects of starch alkenylsuccinylation on the graft copolymerization with vinyl monomer, as well as on paste viscosity and film properties of alkenylsuccinylated starch‐g‐poly(acrylic acid) (ASS‐g‐PAA). The number of carbon atom of alkenyl in alkenylsuccinates considered was 8 and 12, corresponding to octenylsuccinylation and dodecenylsuccinylation of starch, respectively. The graft copolymerization was accessed by grafting efficiency, grafting ratio, and conversion of monomer to polymer, and the film properties of ASS‐g‐PAA considered included tensile strength, breaking elongation, and work‐to‐break. Experimental results demonstrated that the alkenylsuccinylation showed marked effects on the copolymerization, paste viscosity, and film properties. It resulted in increased grafting efficiency, stable paste viscosity, and strong starch film. Carbon‐chain length of the alkenyl and DS value of the alkenylsuccinates also exhibited evident effects on the copolymerization and film properties. Octenylsuccinylation of starch before the copolymerization was superior to dodecenylsuccinylation in improving the efficiency and film properties. Low levels of octenylsuccinylation could be utilized to increase the efficiency of the copolymerization and improve the properties of starch film.     

Effect of Pullulanase Debranching of Sago (Metroxylon sagu) Starch at Subgelatinization Temperature on the Yield of Resistant Starch

The effects of pullulanase debranching of sago (Metroxylon sagu) starch in the granular state and subsequent physical treatments on the formation and yield of type III resistant starch (RS 3) have been investigated. Sago starch was enzymatically debranched with pullulanase at 60°C and at pH 5.0 using different enzyme concentrations (24, 30, 40, 50 PUN/g dry starch) which was added to 20% (w/v) starch slurry and incubated for 0 to 48 h. Optimum enzyme concentration of 40 PUN/g dry starch and three debranching times (8, 16 and 24 h) have been selected for subsequent preparation of RS. Granule morphology and molecular weight distribution (MWD) of the debranched and resistant starch were examined. Debranched starch samples showed blurred birefringence patterns, a decrease in amylopectin fraction, an increase in low molecular weight fraction and a broadening of MWD. Debranched starch samples with a maximum RS yield of 7% were obtained at 8 h debranching time. Temperature cycling and incubation at certain temperature and storage time enhanced the formation of RS. Under the conditions used in this study, the optimum conditions to obtain the highest RS yield (11.6%) were 8 h of debranching time, followed by incubation at 80°C for seven days. The MWD analysis showed that RS consisted of material with relatively low degree of polymerization. This study showed that pullulanase treatment of starch in the granular state resulted in limited debranching of amylopectin but the subsequent physical treatments (incubation time/temperature) can be manipulated to promote crystallization and enhance formation of RS 3.     

Preparation of highly substituted carboxymethyl starch using a twin‐screw extruder

Carboxymethyl starch was prepared by reacting corn starch with sodium mono chloro acetate (SMCA) in a Brabender TSE‐20 co‐rotating twin screw extruder. The effects of the SMCA/starch ratio (theoretical degrees of substitutions 2.73, 3.62, and 4.53), aqueous ethanol/(starch + SMCA) ratio (0.13 and 0.25) and the screw configuration (0, 1, and 2 kneading blocks) on the degree of substitution (DS) and reaction efficiency were studied. A 3 × 2 factorial design with 3 levels of the starch/SMCA ratio and 2 levels of the aqueous ethanol/(starch + SMCA) ratio were used. This 3 × 2 factorial design was blocked, with the screw configuration as the blocking variable. The effects of the SMCA/starch ratio and the screw configuration were found to be significant. The carboxymethylated starches were characterized using FTIR, SEM, and XRD. The microstructure of the carboxymethylated starches, studied using SEM, revealed that the integrity of the starch granules was partially preserved at low aqueous ethanol levels when no kneading block was used. However, for all other reaction conditions either granule agglomeration or fusion was observed. XRD analysis indicated substantial loss of crystallinity in the carboxymethylated starches, irrespective of the damage to the granule structure. The highest DS and the highest reaction efficiency obtained were 1.54 and 0.42, respectively.     

Oxidized banana starch–polyvinyl alcohol film: Partial characterization

Composites of polyvinyl alcohol, native banana starch, oxidized banana starch using glycerol like plasticizer, were studied by mechanical tests (MT), scanning electronic microscopy (SEM), differential scanning calorimetry (DSC) and solubility in water. The oxidized banana starch showed higher level of carboxyl groups than of carbonyl groups. Composites of native banana starch/polyvinyl alcohol and oxidized banana starch/polyvinyl alcohol showed irregularities, indicating incomplete dispersion of the polymers. However, the film elaborated with the blend oxidized banana starch/polyvinyl alcohol showed the highest mechanical properties and the melting temperature of the first transition, as well as the lowest water vapor permeability, indicating higher interaction between both polymers. The composite oxidized banana starch/polyvinyl alcohol showed higher water solubility than the one of its counterpart with native banana starch at 25°C, and similar values were obtained for both films at 60°C. The oxidation of banana starch in order to elaborate a film blended with polyvinyl alcohol improved some mechanical and barrier properties, and this composite could be used for specific applications in the packing of food.     

Effect of acid concentration and treatment time on acid–alcohol modified jackfruit seed starch properties

The properties of starch extracted from jackfruit (Artocarpus heterophyllus Lam.) seeds, collected from west Assam after acid–alcohol modification by short term treatment (ST) for 15–30 min with concentrated hydrochloric acid and long term treatment (LT) for 1–15 days with 1 M hydrochloric acid, were investigated. Granule density, freeze thaw stability, solubility and light transmittance of the treated starches increased. A maximum decrease in the degree of polymerisation occurred in ST of 30 min (2607.6). Jackfruit starch had 27.1 ± 0.04% amylose content (db), which in ST initially decreased and then increased with the severity of treatment; in LT the effect was irregular. The pasting profile and granule morphology of the treated samples were severely modified. Native starch had the A-type crystalline pattern and crystalline structure increased on treatment. FTIR spectra revealed slight changes in bond stretching and bending. Colour measurement indicated that whiteness increased on treatment. Acid modified jackfruit seed starch can have applications in the food industry.     

Response Surface Methodology for the Optimization and Characterization of Cassava Starch‐graft‐Poly(acrylamide)

Response surface methodology (RSM) was employed for the synthesis of cassava starch‐graft‐poly(acrylamide) using ceric ammonium nitrate as free radical initiator. Concentration of acrylamide, concentration of ceric ammonium nitrate, reaction temperature and duration of reaction were optimized using a 4‐factor 3‐level Box‐Behnken design. The dependent variables were percentage grafting (%G) and grafting efficiency (GE). Second order polynomial relationships were obtained for %G and GE, which explained the main, quadratic and interaction effects of factors. The highest%G and GE obtained were 174.8% and 90.7%, respectively. The optimum values of parameters predicted through RSM were 20 g acrylamide/10 g dry starch, 3.3 g/L ceric ammonium nitrate, 180 min reaction duration and 45ºC temperature with a %G of 190.0. For GE, the predicted levels of factors for the optimum value of 90.8% were 17.5 g acrylamide/10 g dry starch, 4.1 g/L ceric ammonium nitrate, 180 min reaction duration and 55ºC temperature. The graft reaction was confirmed by FTIR analysis, where the absorption bands corresponding to the C=O stretching and N‐H bending of the –CONH₂ group were observed. Scanning electron microscopic studies on grafted starches revealed that the granular structure of the starch was affected by the reaction. X‐ray diffraction analysis showed that the crystallinity of starch was decreased as a result of grafting and the reduction was higher for the grafted starches with higher percentage grafting.