Characterization of the Reaction Products for Starch and Acrylonitrile

Rice starch was reacted with acrylonitrile in presence of sodium hydroxide under different conditions including liquor/starch ratio, sodium hydroxide concentration and acrylonitrile concentration as well as reaction time and temperature. The reaction products were analyzed for nitrogen and carboxylic contents and the results obtained were used for calculation of the degree of substitution (D. S.), reaction efficiency (R. E.) and total extent of etherification. Reaction products refered to mixed starch ethers, namely, cyanoethyl starch, carbamoyl ethyl starch, and carboxyethyl starch. Due to analytical difficulties to differentiate between the first two ethers, they were looked upon as cyanoethyl starch. The D. S. of the latter and the R. E. of cyanoethylation were greatly favoured at temperature not exceeding 40°C using lower liquor ratios for reaction time up to 4h provided that certain acrylonitrile and sodium hydroxide concentrations were used. Specifiably, the most appropriate conditions for preparation of cyanoethyl starch comprized:starch/acrylonitrile ratio 1 : 1, liquor/starch ratio 1:7.5 and sodium hydroxide 0.5N at 40°C for 4 h. Under these conditions a D. S. of 1.2 and R. E. of 40% could be achieved. Higher temperatures, i. e. 50 and 60°C, acted in favour of carboxyethyl starch formation particularly when the reaction was allowed to proceed for more than 3 h at 50°C and 0.5 h at 60°C.     

Chemical Modification of Jack Bean (Canavalia ensiformis) Starch by Succinylation

Canavalia ensiformis native starch was succinylated and the functional properties of the succinylated starch evaluated. Reaction conditions investigated included: pH (8.0—8.5 and 9.0—9.5), succinic anhydride concentration (3 and 4%), temperature (20 and 30 °C) and reaction time (1 and 3 h). When starch was succinylated with 4% succinic anhydride, at pH 8.0—8.5, at 30 °C for 1 h, 1.58% succinylation was obtained. Compared to native Canavalia starch, these succinylated products exhibited increasing paste and gel clarity, solubility (36%), swelling power (46.2 g water/g starch), and viscosity (86.5 mPas). Gelatinization temperature range was reduced to 67—73 °C and retrogradation was eliminated. The use of succinylated Canavalia starches as thickening and stabilizing agents in ice creams, fruit jellies, baked products, sauces and frozen foods is suggested.     

Development and Physicochemical Characterization of New Resistant Citrate Starch from Different Corn Starches

Resistant starch has drawn broad interest for both potential health benefits and functional properties. In this study, a technology was developed to increase resistant starch content of corn starch using esterification with citric acid at elevated temperature. Waxy corn, normal corn and high‐amylose corn starches were used as model starches. Citric acid (40% of starch dry weight) was reacted with corn starch at different temperatures (120–150°C) for different reaction times (3–9 h). The effect of reaction conditions on resistant starch content in the citrate corn starch was investigated. When conducting the reaction at 140°C for 7 h, the highest resistant starch content was found in waxy corn citrate starch (87.5%) with the highest degree of substitution (DS, 0.16) of all starches. High‐amylose corn starch had 86.4% resistant starch content and 0.14 DS, and normal corn starch had 78.8% resistant starch and 0.12 DS. The physicochemical properties of these citrate starches were characterized using various analytical techniques. In the presence of excess water upon heating, citrate starch made from waxy corn starch had no peak in the DSC thermogram, and small peaks were found for normal corn starch (0.4 J/g) and Hylon VII starch (3.0 J/g) in the thermograms. This indicates that citrate substitution changes granule properties. There are no retrogradation peaks in the thermograms when starch was reheated after 2 weeks storage at 5°C. All the citrate starches showed no peaks in RVA pasting curves, indicating citrate substitution changes the pasting properties of corn starch as well. Moreover, citrate starch from waxy corn is more thermally stable than the other citrate starches.     

Synthesis and Preparation of Crosslinked Allylglycidyl Ether‐Modified Starch‐Wood Fibre Composites

Native potato starch has been modified with allylglycidyl ether (AGE) under various reaction conditions including different sodium hydroxide and AGE concentrations, reaction temperatures and times. ¹H‐NMR and FT‐IR were used to analyze the products. AGE‐modified starch, with two degrees of substitution (DS), namely DS = 1.3 and DS = 2.3, was synthesized and used for preparation of a new family of crosslinked composites reinforced with various amounts of bleached softwood fibres. Composite premixes of modified starch, wood fibres and ethylene glycol dimethacrylate (EGDA) were cured in a hot press using 2% (w/w) of benzoyl peroxide at 150°C under high pressure for 10 min. The matrix with high degree of substitution exhibited good processability and was easily processed even for the highest fibre contents, up to 70% (w/w). In addition, scanning electron micrographs showed good dispersion and adhesion between the starch matrix with high degree of substitution and fibre. The original poor mechanical properties of the cured modified starch were markedly improved by the addition of wood fibres. In the extractions tests cured high‐DS and low‐DS composite samples showed weight losses in the range of 1 and 15% (w/w), respectively. No unreacted crosslinker ethylene glycol dimethacrylate was detected in the solutes as determined by NMR.     

Herstellung und thermische Eigenschaften hochsubstituierter Benzylstärken

Preparation and Thermal Properties of Highly Substituted Benzyl Starch. Starch reacts in alkaline medium with benzyl chloride yielding benzyl starch with various degrees of substitution. The resulting derivatives were characterized and the influence of the reaction conditions on the degree of substitution and the yield were determined. In aqueous-alkaline medium, benzyl starch with a maximum degree of substitution of 0.9 was obtained. Under water-free conditions higher degrees of substitution are possible. The highest substitution (2.9–3.0) is found by reaction of starch dissolved in dimethylsulfoxide with sodium hydroxide and benzyl chloride. Somewhat lower degrees of substitution (2.7–2.8) can be obtained in homogeneous medium with sodium hydride and benzyl chloride in dimethylsulfoxide. In dependence on the benzyl chloride concentration, also derivatives with lower degrees of substitution can be prepared. The glass transition temperatures of benzyl derivatives of starch with degrees of substitution above 2.5 are at about 45–55°C; with decreasing degree of substitution an increase of the glass transition temperature up to about 70°C is observed. The melting range of benzyl starch was found between 150 to 180°C; at these temperatures some decomposition starts.     

Degradability of Different Phosphorylated Starches and Thermoplastic Films Prepared from Corn Starch Phosphomonoesters

Different starch types (corn, rice, potato, corn amylose and corn amylopectin) were phosphorylated to varying degrees of substitution (DS) and tested both for acid hydrolysis during 3 h in a boiling bath and for enzymatic hydrolysis with a thermostable bacterial α‐amylase (Bacillus licheniformis) for 30 min at 95 °C. Generally, phosphorylated starches showed a reduced degree of acid hydrolysis during the entire time of hydrolysis (3 h) as well as reduced susceptibility to α‐amyIase hydrolysis. The enzyme action was inhibited by the presence of phosphate groups in the modified starch molecules and the extent of inhibition increased with increasing degree of phosphate substitution, regardless of the starch type. Thermoplastic films were fabricated by blending modified corn starches of different DS with polyacrylate, urea and water at a ratio of 4:5:1:50, heating for 30 min at 95 °C before casting and allowing to cool, stand and dry at room temperature. The plastic films prepared from phosphorylated corn starch showed both higher disintegration rate and a greater degradability by thermostable bacterial α‐amylase than the ones prepared from non‐phosphorylated starch. These new acquired properties can meet the increasing demand for biodegradable disposable plastic bags.     

Preparation of Long-chain Esters of Starch Using Fatty Acid Chlorides in the Absence of an Organic Solvent

An efficient method of synthesizing fatty acid esters of starch without organic solvents is described. The octanoate of starch was prepared by gelatinization of native starch with formic acid, followed by treatment with octanoyl chloride. Esterification was readily carried out under a stream of N₂ at a stirring rate of 500 min ^-1 at 25—130°C for a reaction duration of 20—120 min. Formic acid enabled esterification of starch by long-chain acyl chlorides with minimum degradation. The major factors affecting the esterification reaction were optimized. The results indicated that the octanoyl degree of substitution (DS₈) was increased with increase in fatty acid chloride concentration (from 3—12 eq. per anhydroglucose unit) and rise in temperature (25°C to 130°C). Higher octanoyl chloride concentrations and temperatures led to a reduction in yield due to acid hydrolysis of starch chains. A maximum DS₈ of 1.7 was reached after 40 min of reaction, and high concentrations of formic acid decreased the octanoyl substitution. On the other hand, higher concentration of octanoyl chloride, higher temperatures and longer reaction times increased the substitution of the long acyl chain into starch.     

Studies on the synthesis and properties of hydroxypropyl derivatives of cassava (Manihot esculenta Crantz) starch

Cassava starch was subjected to hydroxypropylation in three different media, which included water, water in the presence of a phase transfer catalyst, and 2‐propanol, all at 30 ± 2 °C for 24 h. Propylene oxide was used in four different concentrations (50, 100, 150 and 200 g kg^?1 of starch dry weight). The products were characterized by determining their molar substitution (MS), structural and functional properties. The analyses were done in triplicate and the data were analyzed using the statistical package 8.01. The MS of the products ranged from 0.26 to 1.41. The MS of the hydroxypropyl derivatives were found to be higher when the reaction was carried out in the aqueous medium in the presence of tetrabutylammonium bromide, a phase transfer catalyst, when compared to the reaction in 2‐propanol, which was found to be not very effective at 30 ± 2 °C. The etherification altered the granular properties of starch, as could be seen from scanning electron micrographs. Hydroxypropylation resulted in starch pastes which were stable and with higher swelling volume, solubility, light transmittance and water binding capacity as compared to native starch. The hydroxypropyl starches showed significantly lower pasting temperatures and setback viscosities. The enzyme digestibility of the derivatives was seen to decrease with increase in MS and there was a significant reduction in the syneresis of the starch pastes of hydroxypropyl derivatives. Texture profile analysis showed that hydroxypropylated starch gels exhibited higher hardness, springiness (elasticity) and gumminess and lower cohesiveness than the native starch. Copyright © 2007 Society of Chemical Industry     

Starch Modification,Destructuration and Hydrolysis during O‐Formylation

The mixing of dry starch with 40 or 99% (v/v) formic acid (FA) produces an O‐formylation reaction which causes a combination of acid hydrolysis and starch destructuration. Moreover, this esterification reaction is highly exothermic in the presence of pure FA. When O‐formylation is performed at temperatures higher than 20°C, starch formate content is high (degree of substitution, DS, of 2.15 after 60 min at 105°C) but then molecular weight decreases (η_red ≶ 10 mL/g). Under thermally‐controlled conditions at 20°C in formic acid, degrees of substitution reach 1.5–1.6 after 6 h reaction times and polymer degradation seems to be limited (η_red = 110 to 140 mL/g). The degrees of substitution obtained in water/formic acid mixtures are below those in formic acid alone. The level of destructuration of starch in formic acid and water/formic acid mixtures was also evidenced by dynamic rheological measurements and optical microscopy. Plots of storage modulus (G’) versus frequency (ω) was used to characterize both the gelatinization and the gel destruction processes as a function of reaction temperature (T_r) and FA concentration.     

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     

Binding of amino acids to hypochlorite‐oxidized potato starch

Novel starch derivatives were prepared by derivatization of oxidized potato starch with amino acids in aqueous suspension. Potato starch was oxidized using sodium hypochlorite and then reacted with amino acids under mildly alkaline conditions. By analysis of increased nitrogen content and by means of confocal laser scanning microscopy, efficient binding of positively charged amino acids to oxidized starch molecules was confirmed. A degree of substitution (DS) of up to 0.015 was obtained using oxidized starch (degree of oxidation (DO) of up to 1.0%) and positively charged amino acids (2–5%, dry starch basis) at reaction conditions of starch/water ratio of 1:2–2.5, pH 10, 40°C, 30–60 min. The DS was positively correlated with the DO of the starch. Derivatization of oxidized starch using amino acids generally enhanced the influence of oxidation on starch pasting characteristics, perhaps showing interesting functional properties and potential industrial application.     

Synthesis of high fatty acid starch esters with 1‐butyl‐3‐methylimidazolium chloride as a reaction medium

In this work, high fatty acid esters of corn starch were synthesized by reacting the starch with fatty acid methyl ester using 1‐butyl‐3‐methylimidazolium chloride (BMIMCl) ionic liquid (IL) as reaction media. The effect of reaction variables such as the catalyst amount, molar ratio of fatty acid methyl ester/anhydroglucose unit (AGU) in starch, pyridine/AGU molar ratio, reaction temperature, as well as reaction time on the degree of substitution (DS) of starch esters was investigated. The experimental results showed that the DS value of the obtained starch esters could be varied depending on the process conditions. In the optimum reaction condition, the achieved maximum DS of starch laurate and starch stearate was 0.37 and 0.28, respectively, at a reaction temperature of 110°C for starch laurate and 120°C for starch stearate for a reaction duration of 2 h. Furthermore, the starch esters were characterized by FTIR, SEM, and X‐ray diffractometry (XRD) techniques, respectively. Results from FT‐IR spectroscopy suggested that the hydroxyl groups in the starch molecules were converted into ester groups. SEM and XRD studies showed that the morphology and crystallinity of starch esters were disrupted largely in the IL medium under the reaction conditions.     

Thermal Stability of Some Metabolically Conjugated Potential Precursors of Flavor Components in Meat and Milk

The stability of selected metabolic conjugates (phenylphosphate, phenylglucuronide, naphthylglucuronide, and naphthylsulfate) was evaluated in model systems. Phenylphosphate was less stable than the glucuronides and the sulfate, especially under neutral (pH 6.8) and acidic conditions (pH 1.5). Phenylphosphate was completely degraded after 1.7 hr at 100°C, and after 0.3 hr at 150°C at pH 6.8. The glucuronide and sulfate conjugates were especially stable under neutral conditions (pH 6.8) requiring > 5 hr for complete hydrolysis at 100°C. All conjugates were quite stable to hydrolysis under alkaline conditions (pH 11). The presence of certain organic solvents (ethyl acetate or ethyl ether) caused rapid hydrolysis of conjugates under very mild conditions (40°C for 30 min). This information may improve under-standing of flavor production from animal products.     

Thermisches Dispergieren von nativen Stärken

Thermic Dispersing of Native Starches . Pastes of six native starches were prepared in a Brabender viscograph and then thermically treated at exactly defined conditions at 120°C in an autoclave for different periods of reaction time. The colloidal solutions, obtained in this way, were additionally treated with NaOH-solutions. It could be stated that at longer periods of reaction time at thermic dispersing the molecular weights and the pH values decreased much more than in the case of high amylose starch. Addition of alkali to the pastes and thermic dispersing caused further decrease of the molecular weights of the investigated starches. The results of our investigations indicate that in the first phase of heating in the autoclave to 120°C mainly a desaggregation of the associated molecules took place; at further thermic dispersing at 120°C a thermic degradation of the macromolecules and hydrolytic action of the formed products with acid properties – mainly in the amylopectin component of the starch – were stated.     

Synthesis and Application of Starch 3, 5‐Dinitrobenzoate

A novel starch ester was prepared by the reaction of starch and 3, 5‐dinitrobenzoyl chloride (DNBZ‐Cl). The product (starch 3, 5‐dinitrobenzoate, DNBZ‐ST) was characterized by means of elemental analysis, Fourier Transform Infrared (FTIR) and ¹³C NMR spectroscopy. The influences of molar ratio of DNBZ‐Cl to anhydroglucose (AGU), reaction temperature and time, and amount of pyridine on the degree of substitution (DS) were studied. The esterification reaction is essentially complete after 2 h. Increase in the molar ratio of DNBZ‐Cl to AGU leads to an increase in DS when the former varies from 2:1 to 5:1. DS increases with the reaction temperature when the latter is varied from 70 to 100 °C. DS first increases and then decreases with amount of pyridine, the highest DS was obtained when V(pyridine)/m(starch) was 53 mL/g. The thermal stability of DNBZ‐ST increases when the DS increases, and the degradation starts at 353 °C for the sample of DS 2.14. Creatinine is a toxin accumulated in the blood of chronic renal failure (CRF) patients and a special adsorbent for creatinine is not reported in literature. DNBZ‐ST displayed specific adsorption ability for creatinine, the adsorption equilibrium is reached after 4 h. The adsorption capacity increases with the DS of adsorbent and creatinine concentration. When the creatinine concentration is higher than 300 mg/L, concentration has no apparent effect on the adsorption capacity. As the temperature of the solution is varied from 19 to 49 °C, adsorption capacity first decreases and then increases, being lowest at 37 °C. The adsorption capacity first increases and then decreases as the pH value increases, and is highest at pH 8.The highest adsorption capacity obtained was 25 mg of creatinine per gram of adsorbent at 37 °C, pH 7 and a creatinine concentration of 100 mg/L. The study on the FTIR and UV‐VIS spectra suggested that some chemical reaction took place between the DNBZ‐ST and creatinine in buffer solution.     

Physicochemical Properties of Different Types of Starch Phosphate Monoesters

Different types of starch were phosphorylated to different degrees of substitution using monosodium and disodium hydrogen orthophosphate at 160 °C under vacuum. Generally, phosphation enhanced the physicochemical properties of the modified starches compared to their native counterparts. Solubility and swelling power greatly increase when phosphorylation was carried out to a low degree of substitution, while the solubility and swelling power decreased gradually by increasing the degree of substitution. However, the values of the monoesters were still higher than those of the corresponding native polysaccharides. Viscosities of different starch types except corn amylose showed the highest values at the lowest degree of substitution, when the degree of phosphation increased the viscosity values decreased. Native potato starch formed a clear paste (96% transmittance) due to the presence of phosphate groups while the paste clarity of potato starch decreased gradually by increasing the degree of phosphation. Generally, phosphorylation increased the light transmittance of the other starches investigated at the lowest degree of substitution but the clarity decreased by increasing the degree of substitution.     

Inverse Emulsion of Starch‐graft‐Polyacrylamide

An inverse emulsion of cationic starch‐graft‐polyacrylamide was prepared by inverse emulsion polymerization and a subsequent Mannich reaction. The copolymerization was carried out using potassium persulfate as initiator. The reaction conditions and factors affecting emulsion stability were studied. Experiments showed that a high solids content, a high cationic degree and a stable latex can be obtained under the following condition: A molar ratio starch/acrylamide/formaldehyde/dimethylamine of 0.11:1:1:1.2; a stable inverse emulsion system; graft copolymerization of starch and acrylamide for 2‐3 h at 50 °C; pre‐formation of an aldehyde‐amine adduct, which is subsequently dropped into an inverse emulsion of starch‐graft‐polyacrylamide. The reaction temperature was 45 °C, the reaction time was 3‐4 h, and the pH was 5.5.     

Synthesis of Octenyl Succinic Derivative of Mechanically Activated Indica Rice Starch

Indica rice starch was mechanically activated by ball milling and then esterified by octenyl succinic anhydride (OSA) in aqueous slurry systems. The process of esterification was studied with respect to the time of mechanical activation, OSA/starch ratio, temperature, pH, starch slurry concentration and reaction time. The effects of these reaction conditions were evaluated on the basis of degree of substitution (DS) and reaction efficiency (RE). The results indicated that mechanical activation could enhance the reaction of OSA and starch. The DS and RE of OSA starch increased sharply when the time of mechanical activation increased from 0 h to 10 h, after which it was not significantly affected until 50h. The suitable conditions for the synthesis of OSA starch from Indica rice starch that was mechanically activated for 10 h (MAIS10) were an OSA/starch ratio 3%, temperature 35°C, pH 8.5, starch slurry concentration 12.5% and reaction time 3h. For native Indica rice starch (NIS), all conditions were identical to MAIS10 except for the starch slurry concentration of 40% and reaction time of 4 h. The maximum DS and RE of OSA‐MAIS10 (0.02037, 88.03%) was higher than that of OSA‐NIS (0.01700, 73.46%) at OSA/starch ratio 3%. The esterification of MAIS10 with OSA showed a low sensitivity to pH and a higher stability than OSA‐NIS. Scanning electron microscopy (SEM) revealed that the modified OSA starches did not show any detectable change in the morphological structural characteristics. The esterification between OSA and starch was confirmed by Fourier transform infrared (FT‐IR) spectroscopy.     

Starch Phosphates Produced by Extrusion: Physical Properties and Influence on Yogurt Stability

Starch phosphorylation with sodium tripolyphosphate (STP) was performed using a single‐screw extrusion process. The extrusion variables studied were temperature (from 99.5°C to 200.4°C), water content (16.3% to 19.7%, w/w), and STP content (0.82% to 4.18%, w/w). The resulting phosphorylated starch was evaluated with respect to expansion, water solubility index (WSI), water absorption index (WAI), degree of substitution (DS), and viscosity. The phosphorylated starch was tested as a stabilizing additive in yogurt formulations, with respect to the syneresis index (SI) and the syneresis susceptibility coefficient (SSC). The results show that the expansion increases with increasing STP content, and decreases with increasing temperature and water content employed in the process. Increasing extrusion temperatures and decreasing water content resulted in increasing WSI and decreasing WAI. The DS was dependent on STP content, increasing as STP content increased, but appeared to be insensitive to changes in water content (between 16% and 20%, w/w). The highest level of yogurt stability, as measured by the syneresis index (SI) and the syneresis susceptibility coefficient (SSC), were obtained when the yogurt was formulated with the starch of the highest DS (0.018), which had been obtained at 150°C, 18% water content, and 4.12% (w/w) of STP.     

Preparation and Properties of Octenyl Succinic Anhydride Modified Early Indica Rice Starch

Octenyl succinic anhydride (OSA) modified early indica rice starch was prepared in aqueous slurry systems and the major factors affecting the esterification were investigated systematically. The physicochemical properties of the products were determined by means of Fourier transform infrared (FT‐IR) spectroscopy, scanning electron microscopy (SEM), X‐ray diffraction and Rapid Visco Analyser (RVA). The results indicated that the suitable parameters for the preparation of OSA starch from early indica rice starch in aqueous slurry systems were as follows: concentration of starch slurry 35% (in proportion to water, w/w), reaction period 4 h, pH of reaction system 8.5, reaction temperature 35°C, amount of OSA 3% (in proportion to starch, w/w). The degree of substitution (DS) was 0 018 and the reaction efficiency (RE) was 78%. FT‐IR spectroscopy showed characteristic absorption of the ester carbonyl groups in the OSA starch at 1724 cm^‐1. SEM and X‐ray diffraction revealed that OSA groups acted by first attacking the surface and some pores formed, but OSA modification caused no change in the crystalline pattern of rice starch up to DS 0.046. RVA results indicated that the starch derivatives gelatinized at shorter time to achieve higher viscosities with increased OSA modification.