Effect of Reaction Conditions and Alkyl Chain Lengths on the Properties of Hydroxyalkyl Starch Ethers

Starch applications in the plastics industry have been investigated intensively for many years. Unfortunately, native starch is unsuitable for most applications in polymers, because of its hydrophilic and brittle character. Modification of native starch can be a solution of this problem. In our research programme we developed an environmentally friendly process for the preparation of starch derivatives with long hydrophobic side chains based on natural products derived from vegetable fats and oils on the one hand and amylomaize starch on the other hand. In this process modification is carried out by the addition of longchain 1,2‐epoxyalkanes (chain lengths varying between 6—18 C atoms) to starch in an alkaline aqueous medium. Reaction yields and molar degrees of substitution depended on chain length, reaction time, temperature and catalyst concentration. Under optimised reaction conditions molar degrees of substitution of hydroxyalkyl starch ethers for theoretical molar substitution (MS) = 3.0 decreased from MS=1.8 (C₆ starch ether) to MS=0.2 (C₁₈ starch ether), respectively. Hydrophobic properties of starch products were measured in order to reveal structural effects obtained at different reaction conditions. Water solubility and water absorption properties of hydroxyalkyl starch ethers decreased with increasing chain length and number of hydroxyalkyl substituents. Thermal and thermoplastic properties of starch ethers were investigated in order to determine their potential use as biodegradable polymers in the plastics industry. As expected, thermoplasticity of starch ethers increased with increasing MS and increasing chain length of the hydroxyalkyl side groups.     

Starch Derivatives of High Degree of Functionalization. 7. Preparation of Cationic 2‐Hydroxypropyltrimethylammonium Chloride Starches

Water‐soluble starch derivatives containing quarternary ammonium groups of high degree of substitution are prepared by reacting starch with 2,3‐epoxypropyltrimethylammonium chloride in different reaction media. The reaction was carried out in aqueous sodium hydroxide under dissolution of the product, in dimethyl sulfoxide homogeneously, and completely heterogeneously in ethanol/water. The DS values of up to 1.1 in an one‐step synthesis of the samples can be controlled by adjusting the molar ratio of cationization agent to anhydroglucose unit and are only slightly dependent on the amylose content of the starting starch material. A two‐step reaction yields products of a DS of up to 1.5. The structure of the cationic starch derivatives was confirmed by means of elemental analysis, FTIR‐ and NMR spectroscopy as well as GC‐MS.     

The Role of Reaction Parameters on the Preparation and Properties of Carboxymethyl Cassava Starch

The role of reaction variables on carboxymethylation of cassava starch was investigated using a statistically experimental design approach. The reaction was carried out in an isopropanol‐water mixture at 40°C for 3 h. The reaction parameters under investigation included water fraction in the reaction medium, the ratio of sodium hydroxide to anhydroglucose unit (AGU) and the ratio of sodium monochloroacetate (SMCA) to AGU. The dependent responses were degree of substitution (DS) of CMS and the reaction efficiency (RE) of the carboxymethylation. Carboxymethyl cassava starches with DS in the range of 0.01 to 0.86 were prepared. The result from regression analysis indicated that the most important factors in controlling the DS of CMS were sodium hydroxide and SMCA contents followed by water content. Response surface plots suggested that the optimal levels of sodium hydroxide and water content to achieve CMS with high DS were at the intermediate values. Similar effects of sodium hydroxide and water content were also observed on the RE while SMCA content had a negative effect; increasing SMCA content resulted in lower RE. The optimal conditions to achieve the highest DS and RE were found to be at a water content of 17–19% with a molar ratio of sodium hydroxide to AGU of 1.8–1.9 and a molar ratio of SMCA to AGU between 1.1–1.5. Carboxymethyl cassava starch with various DS was also prepared. The properties of CMS as affected by the degree of modification were also discussed.     

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.     

Effects of Hydroxypropylation on Themal Properties,Starch Digestibility and Freeze-Thaw Stability of Field Pea (Pisum sativum cv Trapper) Starch

Field pea starch with an amylose content of 34.2% was hydroxypropylated with propylene oxide and sodium hydroxide to give products with molar substitutions (MS) ranging from 0.04 to 0.12. Increasing the degree of MS resulted in progressive decreases in enthalpy of gelatinization. gelatinization temperatures, pasting temperatures and syneresis. and increases in paste viscosities at 95 and 50°C. The digestibility with a-amylase decreased with increases in MS only up to the level of 0.08 and further increases in MS caused an increase in digestibility which was higher than that observed for native starch. These results were confirmed by scanning electron microscopy on hydrolyzed starch.     

Physicochemical and structural characteristics of cross‐linked banana starch using three cross‐linking reagents

Banana starch was cross‐linked using different cross‐linking reagents, phosphoryl chloride (POCl₃), sodium trimetaphosphate (STMP), and epichlorohydrin (ECH), under alkaline conditions. The reaction conditions were selected to produce similar pasting profiles. The effects of the different cross‐linking reagents on the physicochemical and structural characteristics of cross‐linked starches were evaluated. The microscopy study did not show difference on the surface of the granules. Slight decrease in the peak temperature and enthalpy were found in the cross‐linked banana starch. The chemical groups introduced in the starch molecules by the diverse reagents promoted the re‐association of starch chains during storage. The rheological analysis of all starch dispersion at 10% (flow curves) showed a non‐Newtonian shear‐thinning; pastes obtained were time‐independent, suggesting an important contribution of the continuous phase. Structural study showed that the cross‐linked STMP‐starch had the lowest level of amylose and the ratio short/long amylopectin chains. The three reagents used for cross‐linking presented different action mode on starch granule and its components.     

Phase and Gelation Behavior of 2‐Hydroxy‐3‐(N,N‐dimethyl‐N‐dodecylammonium)propyloxy Starches

Some starches containing quaternary dimethylalkylammonium groups exhibit an unique phase behavior. A solid phase or gel phase is formed upon cooling, i.e. they are temperature‐responsive polymers. The aim of this study was to investigate the phase and gelation behavior of hydrophobically modified quaternary ammonium starch ethers in aqueous solutions. The mechanisms behind the phase behavior and hydrophobic character were investigated by light scattering (turbidity) and rheological measurements. A relatively large increase in the complex viscosity at higher concentrations was observed when the solutions were cooled to room temperature. The phase angle decreased drastically at a certain critical temperature. The decrease in the phase angle depended on the concentration of starch in solution, higher concentrations showing the greatest decrease and lower concentrations showing no significant change. Turbidity measurements indicated that a solid‐like highly concentrated phase was precipitated. The starch with zero net charge showed a larger increase in turbidity than the starch with a positive net charge, which indicates that particular precipitation is favored by a zero net charge and that the formation of a gel network is favored by charged starch molecules.     

Determination of the mass‐specific distribution of the substituents in cationic starch derivatives

The mass‐specific charge distribution in molar mass fractions of cationic starch derivatives was investigated. The molar mass fractions were produced by semi‐preparative SEC (SP‐SEC). The derivatives were cut into an amylopectin‐rich fraction F1, an intermediate fraction F2, containing low molar mass amylopectin and high molar mass amylose, and an amylose‐rich fraction F3. The weight‐average molar mass (M_w) and molar mass distribution (MMD) of the fractions were determined by SEC with multi‐angle laser light scattering (SEC‐MALLS). The mass‐specific charge of each fraction was calculated from the consumption of anionic titrant solution using polyelectrolyte titration (PET) in combination with particle charge detection (PCD). The difference in substituent distribution between the fractions was tested by the Student's t‐test. The weight‐average molar mass of the starch derivatives was not dependent on the degree of substitution (DS) or the derivatization process. Depending on the DS value or derivatization process, different substituent distributions were observed. The results for the mass‐specific charge distribution in different molar mass fractions of cationic starch derivatives with graded DS between 0.015 and 0.130 from the slurry process were discussed. The heterogeneity of substituent distribution decreased with increasing DS of the starch derivative. This was the case for samples from both the slurry and semi‐dry processes. The heterogeneity of derivatization was highest for low DS samples up to DS 0.03, with the amylopectin‐rich fraction incorporating more charges than the amylose‐rich fraction. This was more pronounced for the sample from the slurry process than from the semi‐dry process.     

Synthesis and properties of carboxymethyl Pueraria thomsonii Benth. starch

As a source of starch, Pueraria thomsonii Benth. was selected to synthesize carboxymethyl starch (CMS) with monochloroacetic acid (MCA) in the presence of sodium hydroxide for the first time. The influence of the molar ratio of NaOH/AGU and MCA/AGU, reaction time, temperature, and water content of solvent on the degree of substitution and reaction efficiency were studied. IR spectrometry showed bands at 1609, 1420, and 1369 cm⁻¹ due to –COO⁻ symmetric and asymmetric stretching vibration when starch was successfully substituted. The SEM results displayed that the granules were agglomerate, and curly wrinkles appeared upon carboxymethylation. XRD revealed that the crystallinity reduced from 41.45 to 5.91%. Furthermore, the ¹³C NMR spectra of the CMS showed a broad band at d = 178.85 ppm, which was assigned to the –CO carbon (C‐8) of the carboxymethyl group.     

Characterisation of Dextrins Solubilised by α‐Amylase from Barley Starch Granules

Large granules from barley starch were packed into a column and hydrolysed with α‐amylase by pumping a diluted enzyme solution through the starch bed. The enzyme was then trapped onto an ion‐exchanger and the dextrins that solubilised from the granules were collected and characterised. The size‐distribution of the solubilished dextrins ranged from degree of polymerisation (DP) 2—500. The linear and branched products originated from both the amylose and the amylopectin components. The rate of solubilisation and the composition of the solubilised dextrins from barley starch were very similar to those found for large wheat starch granules.     

Chemical Modification of Starch via Reaction with Acrylamide

Reaction of starch with acrylamide was carried out under different conditions including reaction medium, catalyst, acrylamide concentration, reaction time and temperature as well as liquor ratio. Organic solvents, namely, isopropyl alcohol, dimethylformamide and cyclohexane alone and in admixture with water at different ratios were used as reaction medium. Catalysts used include sodium hydroxide, trisodium phosphate, sodium carbonate, sodium benzoate, sodium acetate and sodium formate. Acrylamide concentration ranged from 25% to 200%, based on weight of starch. The reaction was studied over a wide range of temperature and duration. Results obtained showed that the extent of reaction of starch with acrylamide is governed by each of these factors. Furthermore, this reaction yields mixed starch ethers, namely carbamoylethyl starch and carboxyethyl starch. Solubility, viscosity and moisture content of these starch ethers are determined by the sum of the amide and carboxyl contents.     

Isolation of a Recombinant Bacillus sp. TS‐23 α‐Amylase by Adsorption‐Elution on Raw Starch

A Bacillus sp. TS‐23 α‐amylase produced by recombinant Escherichia coli was adsorbed onto raw starch and the adsorbed enzyme was eluted with maltose or maltodextrin in 50 mM Tris/HCl buffer (pH 8.5). The adsorption‐elution procedure resulted in a yield of 53% α‐amylase activity and sodium dodecyl sulfate‐polyacrylamide gel electrophoresis (SDS/PAGE) analysis showed that the eluted α‐amylase had a molecular mass of approximately 64 kDa. Raw starch could be used repeatedly in the adsorption‐ elution cycle with good reproducibility. Scanning electron microscopy of the isolated corn starch exhibited a smooth appearance of the granules before adsorption and only a small change in appearance after three adsorption‐elution cycles. These results suggest that the raw starch adsorption‐elution technique has a great potential in the isolation of Bacillus sp. TS‐23 α‐amylase from the culture broth of recombinant E. coli.     

A Calorimetric Study of the Interaction between Waxy Maize Starch and Lipid

There is considerable debate on the definition and measurement of the amount of amylose in starch and whether hydrophobic ligands can form a complex with amylopectin. One method for amylose determination is through the measurement of amylose‐lipid complexation using differential scanning calorimetry (DSC), with the assumption that amylopectin cannot form such a complex. As the sensitivity and methodologies used for DSC improves, the validity of this assumption needs to be tested once again. For the experimental work, α‐L ‐lysophosphatidylcholine (LPC, 10% of starch dry weight) was used as the complexing agent and waxy maize starch. Optimisation of the DSC included changing the heating rate from 10ºC/min to 40ºC/min, which resulted in a higher sensitivity enabling the recording of an endotherm associated with the dissociation of a starch‐LPC complex. The observation of the endothermic formation of such complex could only be achieved when a microcalorimeter, which analyses a much larger sample than a standard calorimeter (190 mg of dry starch compared to 13 mg) was used. There are two possible interpretations for these observations: Either waxy maize starch contains traces of amylose (~ 0.5‐0.7%) and the DSC is sufficiently sensitive to detect these amounts or the α‐1,6 glucan long branches of waxy maize starch bind linear aliphatic compounds.     

Characterization of Residues from Partially Hydrolyzed Potato and High Amylose Corn Starches by Pancreatic α‐Amylase

High amylose corn starch (HACS) and potato starch were hydrolyzed by pancreatic α‐amylase in vitro. Residues after hydrolysis were collected and characterized for their physicochemical properties and molecular structure. Compared with raw starches, residues had lower apparent amylose contents and higher resistant starch contents. The gelatinization enthalpy of residues from HACS increased while enthalpy of residues from potato starch decreased from 15.4 to 11.3 J/g. Peak viscosity and breakdown values of the residues from potato starch were markedly decreased but final viscosity values did not show much change. Chain length distribution of debranched amylopectin from the residues indicated that the relative portion of short chain in the residue decreased for both starches. More molecules with intermediate chain length (DP 16—31) were found in residue after 48‐h hydrolysis of potato starch.     

Low‐ and Medium‐DE Maltodextrins From Waxy Wheat Starch: Preparation and Properties

The goal of the research was to prepare maltodextrins (MD) from waxy wheat starch and waxy corn starch (control). Waxy wheat starches with 0.2% protein, 0.2% lipid and ∼1% amylose were isolated from two flours by mixing a dough, dispersing the dough in excess water, and separating the starch and gluten from the resultant dispersion. The mean recoveries were 72% for the starches and 76% for the gluten fraction with 80% protein. Maltodextrins having low‐dextrose equivalence (DE) 1—2 and mid‐DE 9—10 were prepared by treatment of 15% slurries of waxy wheat starch and waxy corn starch at 95 °C for 5—10 min and 20—50 min, respectively, with a heat‐stable α‐amylase. Denaturing the enzyme and spray‐drying produced MD's with bulk densities of 0.3 g/cm ³. The powdery MD's were subjected to an accelerated‐rancidity development test at 60 °C, and an off‐odor was detected after 2 days storage for the low‐DE MD's from the two waxy wheat starches (WxWS₁‐MD 1.2 and WxWS₂‐MD 1.5), but not for the low‐DE waxy corn maltodextrin (WxCS‐MD 2.2) or a commercial waxy corn MD with DE 1. None of the mid‐DE 9—10 MD's developed off‐odor after 30 days storage at 60 °C. The experimental products WxWS₁‐MD 9.2, WxWS₂‐MD 9.9 and WxCS‐MD 9.1 showed high water‐solubility and gave 1—10% aqueous solutions of high clarity with no clouding upon cooling.     

小麦羟丙基淀粉的制备及其特性研究

以小麦淀粉为原料,在碱性条件下,通过淀粉与环氧丙烷之间的醚化反应制得羟丙基淀粉。应用正交试验的方法．探讨了醚化剂、碱、膨胀抑制剂的用量及反应时间等四个因素对分子取代度（MS）的影响。结果表明：在30％环氧丙烷、1．5％氢氧化钠、15％硫酸钠、反应时间为16h条件下制备的羟丙基淀粉MS最高可达0．055。对羟丙基淀粉的透光率、凝沉性、抗盐性、抗酸性等特性指标进行了测定和研究。     

Effect of Enzymatic Hydrolysis of Wheat Starch on Amylose‐Lipid Complexes Stability

In the process of enzymatic hydrolysis of wheat starch to glucose, the presence of amylose‐lipid complexes (AML's) decreases swelling and dissolving capacity and the water binding capacity of starch, thus impeding the access of amylolytic enzymes to the starch granules. The aim of the work was to define the relationship between the stability of AML's and the conditions of the enzymatic hydrolysis of wheat starch such as the kind of enzymatic preparation (only amylolytic or both amylolytic and lipolytic) and time of hydrolysis. Hydrolysates were produced from wheat starch liquefied with bacterial α‐amylase BAN 240L, subjected to further treatment with the enzymatic preparation Spezyme GA 300W, containing glucoamylase and lysophospholipase and, for comparison, only with a glucoamylase preparation (AMG 300L). The effect of amylolytic and lipolytic enzymes on the stability of AML's in the process of wheat starch hydrolysis was estimated. The amount of fatty acids released during hydrolysis was determined with gas‐liquid chromatography (GLC) and by differential scanning calorimetry (DSC) measuring the enthalpy of decomposition of AML's. The investigations revealed a differentiated effect of the individual enzymatic preparations on the degree of degradation of AML's. Amylose‐lipid complexes were more susceptible to the attack of preparation Spezyme GA 300W than to the digestion by α‐amylase BAN 240 L and glucoamylase AMG 300L.     

Comparison between Size Exclusion Chromatography and Micro‐Batch Analyses of Corn Starches in DMSO using Light Scattering Detector

The molecular structure of corn starches different in amylose content (waxy, normal, and high‐amylose) was analyzed in 90% dimethyl sulfoxide (DMSO) solution by refractive index (RI) and multi‐angle laser light scattering (MALLS) detectors. The starch sample solutions were measured either by medium‐pressure size exclusion chromatography (MPSEC) or by the micro‐batch mode. For waxy corn starch, the average molar mass (M_w) and radius of gyration (R_g) values were similar in both methods. However, for normal and high‐amylose corn starches, M_w measured by the micro‐batch mode was 2–4 times greater than that by the chromatographic method, although R_g values obtained from both methods were not very different. The M_w difference was the greater the higher the amylose content of starch.     

Preparation and Characterization of Annealed‐Enzymatically Hydrolyzed Tapioca Starch and the Utilization in Tableting

Tapioca starch was annealed at 60°C for 90 min followed by hydrolysis with α‐amylase at 60°C at various lengths of time (30, 60 and 120 min) to obtain high‐crystalline starches. The reaction products were subjected to spray drying to obtain annealed–enzymatically hydrolyzed–spray dried tapioca starch (SANET) in the form of spherical agglomerated granules. The properties of SANET were compared with those of annealed–spray dried tapioca starch without enzymatic treatment (SANT) and native–spray dried tapioca starch (SNT). Scanning electron micrographs of the starch samples were used to study the morphological changes and to suggest the mode of enzyme attack during hydrolysis. The á‐amylase preferentially attacked the interior of the starch granules, leaving a deep round hole on the starch granule surface. It was found by X‐ray diffraction that both annealing and amylolysis did not alter the A type diffraction pattern. The% relative crystallinity of SANET was raised with increasing hydrolysis time and with decreasing amylose content. High performance size exclusion chromatography (HPSEC) demonstrated the decrease of the degree of polymerization (DP) of the amylose fraction of SANET after prolonged hydrolysis. For the utilization of SANET as tablet filler, it was directly compressed by a tablet compression machine at 4 kN to obtain tablets. The increased relative crystallinity of starch resulted in increased crushing strength and disintegration time, but in a decreased tablet friability.     

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.