Chemical Characterization of Bromine Oxidized Potato Starch

Potato starch was oxidized with a neutral aqueous bromine solution at seven different levels of molar ratios of bromine/starch (1/40–5/1). The molecular weight distribution of the products obtained was analysed by gel permeation chromatography on two different agarose gels, Sepharose CL-2B and Superose 6. A gradually increased fragmentation of the molecules with increased oxidation level was noticed. Some of the modified samples were debranched and the products obtained were analysed by gel permeation chromatography. For comparison amylose and waxy maize starch were also treated at the 1/20 and 1/5 molar ratios. The results indicate that the amylose is more easily degraded to small fragments than amylopectin during the oxidation process. An enzymatic starch analysis method was applied on the oxidized samples. This method was found suitable for estimating the total content of introduced keto and carboxylic groups into the modified product.     

韧化处理对不同玉米淀粉理化特性的影响

以不同直/支链比例的普通玉米淀粉和蜡质玉米淀粉为材料,在40、50、60℃进行韧化处理,研究韧化处理对玉米淀粉理化特性的影响。结果表明：韧化处理的两种玉米淀粉颗粒形貌有较小变化。韧化处理后,两种淀粉的溶解度和膨胀度随着处理温度的升高而降低;所有韧化处理过的玉米淀粉黏度低于原淀粉,起糊温度高于原淀粉;韧化处理后淀粉的糊化温度升高,热焓变化不大。     

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.     

Localisation of Amylose and Amylopectin in Starch Granules Using Enzyme-Gold Labelling

The independent localisation of amylose and amylopectin in a range of dry and hydrated native starch granules with varying amylose content (0—70 %) has been indirectly visualised using enzyme-gold cytochemical markers. Increasing amylose content was clearly demonstrated to result in distinct changes in granule architecture. In the absence of amylose (waxy maize starch) a framework of closely packed concentric layers of amylopectin exists in the granules. Low amylose content (potato starch) results in alternating layers of densely packed amylopectin and amylose molecules. High amylose content (amylomaize starch) granules were shown to possess an amylopectin centre surrounded by an amylose periphery encapsulated by an amylopectin surface. Elongated granules without the amylopectin centre were also observed in high amylose starches suggesting a relationship between amylopectin, amylose and granule shape. A model of starch granule architecture is proposed where increased compartmentalisation of amylose and amylopectin is observed in granules containing increasing levels of amylose.     

Retrogradation of Potato Starch as Studied by Fourier Transform Infrared Spectroscopy

Retrogradation kinetics for a potato starch-water system (10% w/w gel) was monitored by Fourier Transform Infrared spectroscopy and compared with waxy maize starch. The spectra showed the C-C and C-O stretching region (1300-800 cm⁻¹) to be sensitive to the retrogradation process. A multi-stage process was observed during the retrogradation of potato starch and characterized as the formation of short- and long-range order. The first stage was characterized as the formation of helices and the fast formation of crystalline amylose regions. The second stage was described as the induction time for amylopectin helix aggregation. Stage three was described as the helix-helix aggregation and the crystallization of amylopectin. The overall-first order calculated rate constant of potato starch was (9.6±1.4) 10⁻ 3h⁻¹. The calculated rate constant were in agreement with the known difference in retrogradation kinetics of waxy maize and potato starch. The effects were explained by the differences in retrogradation rate of amylopectin and amylose. Potato starch consists of amylose as well as amylopectin. Whereas amylose crystallization occurs within a few hours, amylopectin crystallization is slow and takes a few weeks.     

Fine Structure of Mung Bean Starch: An Improved Method of Fractionation

Laboratory isolated mung bean starch was fractionated into its amylose and amylopectin components using a modified procedure. The resulting products were shown to be both homogeneous and more susceptible to the hydrolyzing enzymes commonly used for structural analysis. The fine structure of the fractions was investigated using hydrolytic enzymes, chemical analysis and gel filtration chromatography. Differences in amylose/amylopectin fractions isolated by the modified and conventional extraction procedures were apparent. The unit chain length of amylopectin, DP_n and limiting viscosity number of amylose were all lower for samples isolated by the modified method. In contrast the enzymatic hydrolysis of both the amylose and amylopectin fractions was improved for the material extracted by the modified method, low levels of branching and a unit chain distribution by gel filtration chromatography of the two overlapping populations with average degree of polymerization of 42 and 14 was obtained.     

Effect of retrogradation,pancreatin digestion and amylose/amylopectin ratio on the fermentation of starch by Clostridium butyricum (NCIMB 7423)

Using three different maize starches (maize, waxy maize and high amylose maize, containing 25%, 1% and 52% amylose, respectively) the influence of amylose/amylopectin content and of retrogradation on fermentation by the porcine caecal anaerobe Clostridium butyricum was assessed. Small intestine digestion was simulated using pancreatin before the starches were exposed to bacterial fermentation. It was found that retrogradation appeared to alter the extent of the fermentation and hence the amount of short-chain fatty acids produced, while pancreatin digestion appeared to alter the way in which the organism fermented the starch and hence the acetate/butyrate ratio. The amylose/amylopectin ratio seemed to have more influence on the way the starch was fermented by the bacteria after the starch had been subjected to digestion with pancreatic enzymes, but had less influence when the starch had been retrograded. © 1998 SCI.     

Pasting Properties of Potato Starch and Waxy Maize Starch Mixtures

The pasting viscosity, morphological properties, and swelling properties of potato starch and waxy maize starch mixtures at different ratios were investigated. Pasting analysis of the starch mixtures (7% solids in water, w/w) using a Rapid Visco Analyser showed linear changes in peak viscosity and pasting temperature according to the mixing ratios of both starches, but not in breakdown and setback. The pasting profile revealed that the starches rendered mutual effects during pasting, more significantly when the amounts of potato and waxy maize starches were similar. The volume fraction of swollen granules and the presence of amylose appeared to be important parameters in the mutual effects of both starched during pasting. Under a light microscope, the swelling of potato starch granules was delayed by the presence of waxy maize starch. Overall results indicate that new pasting properties can be generated by mixing starches of different botanical sources.     

Gel texture and chain structure of amylomaltase-modified starches compared to gelatin

Amylomaltase (AM) (4-α-d-glucanotransferase; E.C. 2.4.1.25) from Thermus thermophilus was used to modify starches from various botanical sources including potato, high amylose potato (HAP), maize, waxy maize, wheat and pea, as well as a chemical oxidized potato starch (Gelamyl 120). Amylopectin chain length distribution, textural properties of gels and molecular weight of 51 enzyme and 7 non-enzyme-modified starches (parent samples) were analyzed. Textural data were compared with the textural properties of gelatin gels. Modifying starch with AM caused broadening of the amylopectin chain length distribution, creating a unimodal distribution. The increase in longer chains was supposedly a combined effect of amylose to amylopectin chain transfer and transfer of cluster units within the amylopectin molecules.Exploratory principal component analysis (PCA) data analysis revealed that the data were composed of two components explaining 94.2% of the total variation. Parent starches formed a cluster separated from that of the AM-modified starches.Extended AM treatments reduced the apparent molecular weight and the gel texture without changing the amylopectin chain length distribution. However, the gel texture was typically increased as compared to the parent starch. AM-modified HAP gels were about twice as hard as gelatin gels at identical concentration, whereas gels of pea starch were comparable to gelatin gels. Modifying Gelamyl 120 and waxy maize with AM did not change the textural properties. Branching enzyme (BE) (1,4-α-d-glucan branching enzyme; EC 2.4.1.18) from Rhodothermus obamensis was used in just one modification and in combination with AM. The combined AM/BE modification of pea starch resulted in starches with shorter amylopectin chains and pastes unable to form gel network even at concentration as high as 12.0% (w/w). The PCA model of all gel texture data gave suggestive evidence for starch structural features being important for generating a gelatin-like texture.     

Starch/Sucrose Interactions by Organic Probe Analysis: An Inverse Gas Chromatography Study

The effect of freeze drying of high amylopectin starch was determined with samples of starch dispersed in water with or without solubilized sucrose. The X-ray diffraction data showed that this treatment disrupted crystalline structures of amylopectin and sucrose exposing additional sites for water sorption. This was shown also by sorption isotherms of the starch alone. The Hylon 7-sucrose freeze-dried samples produced a greater effect on sorption than did the corresponding Amioca freeze-dried mixtures. Organic probe analysis of the starch and starch-sucrose mixtures indicated that high amylose starches were more reactive with polar organic probes than high amylopectin starches when freeze-dried. Untreated high amylopectin starches were more reactive with probes in agreement with the water sorption data for a more branched polymer.     

复合酶法改性糯麦A-、B-型淀粉及对其结构和消化特性的影响

以从糯麦淀粉中分离所得的A-、B-型淀粉为研究对象,并以此作为受体,高直链玉米淀粉为供体,利用普鲁兰酶和分支酶协同处理对糯麦淀粉进行改性,测定其颗粒形态、结晶结构以及表观直链淀粉含量、溶解度、膨胀力等理化性质,并对其消化特性进行考察。结果表明：采用普鲁兰酶和分支酶两种复合酶法改性的糯麦A-、B-型淀粉,其预测血糖指数显著降低,表观直链淀粉含量显著增加、溶解度随着温度的增加而变大,膨胀力随着温度的增加基本保持不变。采用扫描电子显微镜观察到酶法改性后的淀粉颗粒形态出现孔洞结构,利用X射线衍射和傅里叶红外光谱分析相对结晶度和1 047 cm－1/1 022 cm－1处的比值可得,复合酶改性淀粉的长程有序结构和短程有序结构显著改善。通过普鲁兰酶预处理后再用分支酶改性,对糯麦A-型和B-型淀粉进行结构修饰,能够显著改善其消化特性。     

Gel Chromatography of Residue and Extract Obtained from Starch Granules by Hot Aqueous 1 -Butanol Solution Treatment

Starch granules of corn starches (normal, waxy, amylo and amylowaxy) and potato starch were treated with hot aqueous solution saturated with 1-butanol and fractionated. These fractionated starches were subjected to an advanced gel chromatography with a column system of Toyopearl HW 75 F. Amylose of normal maize and potato starches was perfectly leached out from the granules, but that of amylo maize was not perfectly extracted. Amylo and amylowaxy maize starches were proved to have large amount of low-molecular weight material. Normal and amylo maizes, and potato starches contained a high-molecular-weight material recognized as amylose type, and it is strongly suggested that amylopectin of normal maize is not same as that of waxy maize. It was found that the GPC analysis was a very important step to estimate an amylose content since a part of amylopectin made a precipitable complex with 1-butanol.     

Effect of pH on aqueous structure of maize starches analyzed by HPSEC-MALLS-RI system

Molecular conformation of maize starches (waxy, normal and high amylose) was examined at different pH values (5–10) using an aqueous medium-pressured size exclusion column chromatography (SEC) connected to multi-angle laser light scattering (MALLS) and refractive index (RI) detectors. The starch molecules were partially degraded at pH 5 and 10, resulting in lower values for molar size and radius of gyration than those in neutral condition. The specific volume data revealed that the structural changes under an alkaline condition such as pH 10 was more significant for amylose than that for amylopectin. Logarithmic ratios between molar size and radius of gyration were similar (0.2–0.3) for the amylopectins in waxy and normal maize starches, but higher (0.4–0.5) for the amylopectin in high amylose starch, indicating that the amylopectins in waxy or normal maize starches had sphere forms whereas that in high amylose starch had a random coil shape.     

The Interaction of the Amylose-Extender and Waxy Mutants of Maize (Zea Mays L.) Fine Structure of Amylose-Extender Waxy Starch

Investigations into the nature of the effect of the amylose-extender (ae) mutant of maize (Zea mays L.) on amylopectin structure were conducted by studying the fine structure of amylose-extender waxy (ae wx) starch. Approximately 59.6% of the starch from ae wx endosperms was converted to maltose by β-amylase. This starch contained 21% apparent amylose and had a λmax of 580 for the iodine-starch complex. Fractionation of ae wx starch on Sepharose 4B-200 gave an elution profile with a single peak characteristic of amylopectin. From these observations we concluded that ae wx starch consisted of an altered amylopectin, with iodine binding properties such that an apparent amylose content of 21% was measured. The fine structures of ae wx and waxy (wx) starches were determined. Pullulanase-debranched chains of whole starches and β-limit dextrins were fractionated by gel permeation. The amylopectin of ae wx was shown to be a loosely branched amylopectin with an average internal chain length of 52 glucose units compared with a length of 30 glucose units for wx. The ae wx outer chains were longer than those of wx and fewer in number per mg of starch. These characterizations demonstrate that ae wx starch has a unique structure which is similar to the anomalous amylopectin reported in ae starch.     

Rheology of Okenia hypogaea Starch Dispersions in Aqueous Solution of DMSO

The aim of this work was to study the rheological behavior of Okenia hypogea starch dispersions (OSD) in aqueous solution (90/10, v/v) of dimethyl sulfoxide (DMSO). Okenia starch dispersions with 3 and 7 % (w/v) total solids were prepared at 20 °C and rheological tests were undertaken at 20, 40 and 60 °C, using a shear rate controlled rotational viscometer. The data fitted better the power law than the Casson model. Flow curves and flow behavior index indicated shear‐thinning behavior. All rheological parameters were affected by the solids concentration and the measurement temperature. As regards amylose and amylopectin content okenia starch is grouped among “ordinary” (non‐waxy) starches. Overall, OSD behaved similarly to potato starch dispersions and corn starch dispersions used as controls.     

Structural,thermal and viscoelastic characteristics of starches separated from normal,sugary and waxy maize

Starches separated from five types of maize (two normal, one sugary and two waxy) were investigated for physicochemical, thermal, amylopectin structure and viscoelastic properties. Kisan and Paras were normal maize while Parbhat and LM-6 were waxy maize type. Apparent amylose content of normal and sugary maize was 29.5–32.6 and 41.0%, respectively. Swelling power of normal, sugary and waxy maize starches was 11.6–15.2, 7.8 and 30.2–39.2 (g/g), respectively. X-ray diffraction of maize starches indicated typical A-pattern. Maize starch showed a single broad peak at 2θ=23.2° and a dual peak 2θ=17°–18.1, respectively. Waxy maize starches showed the presence of greater crystallinity than other starches while sugary maize starch showed the presence of lower crystallinity and a large amount of amylose–lipid complex. Intrinsic viscosity [η] of starches in 90% DMSO at 25 °C was 79.7–119.5 ml g⁻¹ for normal, 70.5 ml g⁻¹ for sugary and 107.2–118.1 ml g⁻¹ for waxy starches. Branch chain–length distribution of amylopectin revealed that the apparent amylose, long side chain- and short side chain-amylopectin proportion ranged between 0.0–41%, 13.4–31.5% and 41.5–66.8%, respectively, among the various maize starches. Maize sugary showed the highest apparent amylose content and the least amount of short- and long-side chains of amylopectin. LM-6 and Parbhat showed higher proportion of both long- and short-chain amylopectin as compared to other starches. Distribution of α-1, 4-chains of amylopectin (short-/long-chain) ranged between 2.1 and 3.4, the least for LM-6 and the highest for Paras starch. The transition temperatures (T_o–T_c) ranged between 60.5 and 76.1 °C for sugary, 63.5–76.3 °C for normal and 64.4–81.3 °C for waxy maize starch. The enthalpy of gelatinization (ΔH_gel) of sugary, normal and waxy maize starches was 2.47, 3.7–4.75 and 4.15–5.4 J/g, respectively. Normal and sugary maize starches showed higher G′ and G″ than waxy type starches. The change in the moduli during cooling and reheating of pastes cooked at different temperatures revealed low disintegration of granular structure in starch with higher amylose and amylose–lipid complex as well as low crystallinity. The changes in moduli during 10 h at 10 °C revealed highest retrogradation in maize sugary followed by Paras and Kisan starch.     

Starch Derivatives of High Degree of Functionalization. 13. Novel Amphiphilic Starch Products

Amphiphilic starch derivatives of high degree of substitution (DS) were prepared by benzylation of pea, potato and waxy maize starch followed by the introduction of hydroxypropyltrimethylammonium and carboxymethyl moieties. The conversions were carried out under heterogeneous conditions leading to products with a total DS of up to 1.8. The starch composition regarding amylose and amylopectin influences the DS value. The structure of the products was characterized by means of elemental analysis, FTIR and NMR spectroscopy, and, in case of benzyl carboxymethyl starch by means of HPLC after complete chain degradation. The tensioactive properties depend on the DS values of hydrophilic and lipophilic groups and can be adjusted by controlling the molar ratio anhydroglucose unit to reagent during the synthesis. Surface tensions as low as 48.6 mN/m were found for benzyl hydroxypropyltrimethylammonium starch and 38.6 mN/m for benzyl carboxymethyl starch. The lowest critical micelle concentration determined is 2.1 mmol/L.     

Granular Properties of Different Starch Phosphate Monoesters

Different starch types (corn, rice, and potato starch, corn amylose and corn amylopectin) were phosphorylated by reaction with a mixture of mono and disodium phosphate at different molar ratios (mol phosphate/mol anhydrous glucose) under heat and vacuum. The starch granules of the modified and the native starches were microscopically examined for their sizes and morphology. The correlation between the variation in granular size of the modified starches with the extent of phosphorylation and some other physicochemical properties was studied. The granular size was generally increased while the iodine absorption capacity was decreased by phosphorylation. There were strong correlations between the variation in the starch granular size in dependence on phosphorylation and the corresponding changes in some physicochemical parameter of starch, e.g. solubility, swelling and paste clarity. This relationship was most evident in the case of phosphorylated corn amylopectin. Starch granular size can be taken as a quick indicator of the physicochemical properties of the native and modified starches.     

Amylose Chain Association Based On Differential Scanning Calorimetry

Amylose and lipid depleted starches from amylomaize, pea, maize, wheat, potato, and waxy maize were heated from 20°C to 180°C, cooled to 4°C, and then reheated to 180°C in a differential scanning calorimeter (DSC) in excess water. Cooling curves of the amylose and starch melts showed exothermic transitions (< 70°C) attributed to the mechanism of amylose chain association. Amylose/amylopectin mixtures covering the range 0–95% amylose were similarly heated and cooled. The association of linear amylose chains was restricted by amylopectin.     

Rheological Properties of Mixed Gels using Waxy and Non‐waxy Wheat Starch

Mixed starches with an amylose content of 5, 10, 18, 20, 23, and 25% were prepared by blending starches isolated from waxy and non‐waxy wheat at different ratios. The dynamic viscoelasticity of mixed 30% and 40% starch gels was measured using a rheometer with parallel plate geometry. The change in storage shear modulus (G′) over time at 5 °C was measured, and the rate constant of G′ development was estimated. As the proportion of waxy starch in the mixture increased, starch gels showed lower G′ and higher frequency dependence during 48 h storage at 5 °C. Since the amylopectin of waxy starch granules was solubilized more easily in hot water than that of non‐waxy starch granules, mixed starch containing more waxy starch was more highly solubilized and formed weaker gels. G′ of 30% and 40% starch gels increased steadily during 48 h. 30% starch gel of waxy, non‐waxy and mixed starches showed a slow increase in G′. For 40% starch gels, mixed starch containing more waxy starch showed rapidly developed G′ and had a higher rate constant of starch retrogradation. Waxy starch greatly influenced the rheological properties of mixed starch gels and its proportion in the mixture played a major role in starch gel properties.