The effect of microwave radiation on some thermal,rheological and structural properties of cassava starch

Three samples of native or untreated cassava starch were exposed to microwave radiation for periods of 5, 10 or 15 min. The temperature of each sample was measured immediately after each exposure time and the temperature of the samples was around 135 °C. The samples were cooled to room temperature and maintained in a desiccator with anhydrous calcium chloride. All the samples were analysed by thermogravimetry-derivative thermogravimetry, differential scanning calorimetry (DSC), rapid viscoamylographic analysis (RVA), X-ray diffraction powder patterns, non-contact atomic force microscopy and colour characteristics by reflectance spectrophotometry. The thermal behaviour, gelatinisation temperatures, enthalpy and pasting properties were determined. Relative to the time of microwave exposure, the peak viscosity and gelatinisation (RVA and DSC) increased slightly after 5 min, and, after 10 and 15 min, it decreased considerably. The degree of relative crystallinity (%) decreased, while the average roughness increased. The reflectance spectrophotometry showed that microwave action occured quickly and progressively, causing colour changes (mainly with trends to yellow) and very small differences to the starch samples that were heated at controlled temperature in a conventional oven.     

DSC study on the thermal properties of soybean protein isolates/corn starch mixture

The use of soybean protein isolates (SPI) and corn starch (CS) for the manufacturing of textured protein by thermo-mechanical means requires a characterization of their thermal properties. SPI and CS mixtures were examined at starch mass fractions from 0 (pure SPI) to 100 (pure CS). The blends were determined by means of differential scanning calorimetry, with water content of 30, 50, and 70 % and heating rate of 5 and 10 °C min^?1 over 20 to 130 °C. The results obtained showed that protein in the blend increased the onset (T _o) and peak (T _p) temperatures of the starch gelatinization, while starch in the blend decreased the ΔH and ΔT_1/2 of the protein. T _o , T _p, and ΔT_1/2 of SPI and CS decreased significantly with the increase of water content. T _p and ΔT_1/2 of SPI and CS had a marked increase with an increase of heating rate from 5 to 10 °C min^?1. These results suggested that there was no chemical reaction between SPI and CS when they were heated from 20 to 130 °C. SPI in the blend restricted the CS gelatinization, while the presence of CS protected the SPI from denaturation. The increasing water content did promote thermal transition of the mixture. Higher heating rate leads to higher transition temperature.     

Thermal analysis of the influence of water content on glass transitions

Starch is an important natural substance in which the water content has a significant influence on its structure and properties. In the present study, the effect of the water content on glass transition temperatures T _g and heat capacities C _p of wheat, maize and potato starches were investigated by high-sensitivity differential scanning calorimetry (temperature modulated TMDSC and conventional DSC). Thermal analysis measurements were performed on starch samples with different water contents. The exact water mass percentage of each sample was determined using the Karl-Fischer method. The obtained results show that the water content does influence the starch thermal properties in a systematic and measurable trend, the higher the water% the lower the glass transition temperature, and the higher the heat capacity jump during gelatinisation. At this stage possible interpretations of the results are just put forward and should be confirmed through complementary measurements.     

Effects of Preheating Temperature,Moisture and Sodium Metabisulfite Content on Property of Maize Flour Dough

Processing temperature,maze flour particle size,and level of water and sodium metabisulfite were varied during the preparation of maize noodles.Preheated to 90-95 ℃ a mixture of maize flour or meal,water(43%-45% moisture) and salt enabled the preparation of noodles using a pasta extruder.Maize flour with smaller particle size yielded better noodles than did maize meal.The addition of sodium metabisulfite enabled the production of noodles at lower processing temperatures; however,cooking losses increased.Processing maize flour with higher water absorption yielded noodles that required longer cooking time but with decreased losses.The functionalities of starch and protein in raw ingredients and in products were determined.Starch gelatinized and retorgraded during processing maize noodles,as indicated by changes in pasting viscosity curves.Maize proteins contributed to the increased viscosity of dough above 40 ℃.The increased integrity of cooked maize noodles,however,corresponded to the increased amounts of gelatinized and retrograded starch.     

Effect of Octenyl Succinic Anhydride (OSA) Modified Starches on the Rheological Properties of Dough and Characteristic of the Gluten-Free Bread

The study focused on the influence of starch modified by octenyl succinic anhydride (OSA) on the rheological and thermal properties of gluten-free dough containing corn and potato starch with the addition of pectin and guar gum as structure-forming substances. The starch blend used in the original dough recipe was partially (5% to 15%) replaced with OSA starch. The rheological properties of dough samples were determined, and the properties of the resulting bread were analyzed. It was found that the dough samples behaved as weak gels, and the values of storage and loss moduli (G′ and G″, respectively) significantly depended on angular frequency. Various shares of OSA starch in recipes modified dough in different ways, causing changes in its rheological characteristics. The introduction of OSA starch preparations resulted in changes in the bread volume and physical characteristics of the crumb. All the applied preparations caused an increase in bread porosity and the number of pores larger than 5 mm, and there was a parallel decrease in pore density. The presence of OSA starch preparations modified bread texture depending on the amount and type of the applied preparation. The introduction of OSA starches in gluten-free bread formulation caused a significant drop in the enthalpy of retrograded amylopectin decomposition, indicating a beneficial influence of such type of additive on staling retardation in gluten-free bread.     

Physical characterization of coupled poly(lactic acid)/starch/maleic anhydride blends plasticized by acetyl triethyl citrate

Acetyl triethyl citrate (ATC) was used as a plasticizer for poly(lactic acid) (PLA)/starch blends coupled with maleic anhydride and an initiator of 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane (L101). Elongation of the blend at break was markedly increased when the ATC content was above the 8% loading level, which is referred to as the percolation threshold. The extended elongation was achieved at the expense of tensile strength and elastic modulus. Thermal transitions of the blend, including the glass transition temperature (T(g)), cold crystallization temperature (T(c)) and melting temperature (T(m)), decreased with ATC content. Thermally induced ATC migration affected the thermal behavior of the plasticized blends and reduced elongation and tensile strength, whereas the elasticity modulus increased. ATC migration increased with ambient temperature, which was controlled by the activation energy of the blend system. Leaching of ATC was slow at room temperature in distilled water, but significant in boiling water. Additionally, the leaching rate was also directly proportional to the ATC content of the blend. Glass transition temperatures of PLA/starch/MA/L101 blends with various acetryl triethyl citrate contents.     

Effects of heat–moisture treatment on organic cassava starch

Organic foods and crops are produced throughout the world under strict controls on growing conditions, so that synthetic chemicals, irradiation or genetic modifications are avoided. Organic starch is extracted following the same rules. Heat–moisture treatment (HMT) on starch is a physical method considered to be natural: it consists of heating starch at a temperature above its gelatinisation point with insufficient moisture (<35 %) to cause gelatinisation. Samples of organic cassava starch (with 12.8 % moisture) were dried in an oven with forced air circulation at 50 °C for 48 h and, immediately, distilled water was added to each sample until it reached the ratios of 10, 20, and 30 %, respectively. The samples were transferred into 100 mL pressure flasks, sealed tightly with a cap, and maintained in an autoclave for 60 min at 120 °C. The flasks were opened and the samples were kept in a desiccator containing anhydrous calcium chloride up to constant mass. The effects of HMT were studied using the following techniques: thermogravimetry and derivative thermogravimetry (TG/DTG), differential scanning calorimetry (DSC), rapid viscoamylographic analysis (RVA), reflectance photocolorimetry, atomic force microscopy (NC-AFM) and X-ray diffractometry (XRD). Rheological properties such as the pasting temperature (RVA) and the peak temperature (DSC) increased, while gelatinisation enthalpy ?H (DSC) decreased. The average diameters of the granules showed no significant changes, while the degree of relative crystallinity decreased.     

Thermal analysis of food carbohydrates by determination of starch gelatinization phenomena

 A calorimetric (DSC) method for the analysis of starches and food-related compounds, based on the determination of onset and peak temperature (T_o, T_p) and the apparent enthalpy change (ΔH) of the starch gelatinization process is described. To set up the best experimental conditions to apply, the parameters that could affect the calorimetric response, such as temperature range of thermal analysis, water/starch ratio in the mixture, heating rate, size and weight of sample, time-temperature condition, were investigated. The method was applied to characterise starches, semolina and alimentary pasta. Received: 20 October 1995/Revised: 28 December 1995/Accepted: 8 January 1996     

Thermal analysis of food carbohydrates by determination of starch gelatinization phenomena

 A calorimetric (DSC) method for the analysis of starches and food-related compounds, based on the determination of onset and peak temperature (T_o, T_p) and the apparent enthalpy change (ΔH) of the starch gelatinization process is described. To set up the best experimental conditions to apply, the parameters that could affect the calorimetric response, such as temperature range of thermal analysis, water/starch ratio in the mixture, heating rate, size and weight of sample, time-temperature condition, were investigated. The method was applied to characterise starches, semolina and alimentary pasta. Received: 20 October 1995/Revised: 28 December 1995/Accepted: 8 January 1996     

Effect of SDS on the gelation of hydroxypropylmethylcellulose hydrogels

Thermal behavior of aqueous hydroxypropylmethylcellulose (HPMC)/surfactant mixtures was studied in the dilute concentration regime using micro-differential scanning calorimetry (DSC). The surfactant used was sodium n-dodecyl sulfate (SDS). The heat capacity of HPMC gel with various concentrations of SDS was much higher than that of the pure HPMC gel. The addition of SDS at different concentrations showed dissimilar influences on the gelation of HPMC; SDS at lower concentrations (≤6 mM) did not affect gelation temperature significantly except for enhancing the heat capacity whilst SDS at higher concentrations (≥6 mM) not only resulted in the gelation of HPMC at higher temperatures but also changed the pattern of the gelation thermograph from a single mode to a bimodal. On the basis of the observed thermal behavior of HPMC/SDS systems, the mechanism behind the sol-gel transition was discussed in terms of the properties of the surfactant and their influences on the extent of polymer/surfactant binding and polymer/polymer hydrophobic association. Gelation kinetics was analysed using the results from the DSC measurements. The kinetic parameters were determined.     

Thermal, structural and rheological behaviour of native and modified waxy corn starch with hydrochloric acid at different temperatures

In this study, samples of native waxy corn starch, waxy corn starch treated with HCl 0.15 mol L^?1 at 20 and 50 °C, respectively, were analysed. The thermogravimetric curves showed similar behaviour with three main mass losses and a decrease in the thermal stability. The acid hydrolysis in low HCl concentration performed for 4 h caused a decrease in peak temperature (DSC), viscosity peak (RVA), gelatinisation enthalpy (DSC) and relative crystallinity (XRD), and an increase in the average roughness (NC-AFM). The X-ray diffraction patterns displayed the ‘A’ type for all the starch granules.     

Effect of ingredients on the mass loss,pasting properties and thermal profile of semi-sweet biscuit dough

The drive to utilise different lipids, both for health benefits and for commercial reasons, in bakery goods has been extensive. However, the roles of the lipid plays in many products, let alone the influence of the level of saturation, are uncertain. The objective of work carried out is to understand how the typical ingredients in biscuit would impact on the thermal profile of semi-sweet biscuit dough. Three different techniques have been used namely gravimetric analysis (TGA), rapid visco analyser and differential scanning calorimetry (DSC). Wheat flour, sugar and fat/oil were the main ingredients used to produce basic dough of semi-sweet biscuit for this study. Semi-sweet biscuit dough formulations with varying types of oils namely palm oil, palm olein, palm stearine, sunflower oil and butterfat were developed. The final mass (i.e. the total amount of moisture lost) for the samples showed significant differences between the doughs; with the control dough, dough contained palm stearine and butter falling into one group and the butter, palm oil, palm olein and sunflower oil forming the second group that showed less mass loss. Doughs containing low levels of saturated fatty acids (palm olein, palm oil and sunflower oil) showed significant difference on the drying properties of samples compared to doughs containing high saturated fatty acids (palm stearine and butter) as revealed by TGA. Pasting properties result showed that oil with different saturation influenced peak viscosity obtained. The DSC results showed that sugar and oil increased the gelatinisation peak temperature up to 2 and 6 °C, respectively. Oils with low saturated fatty acids have more capability to make contact with starch granules during the mixing processing as compared to oil with a high level of saturated fat. It is suggested that the oil presence in the system was delaying the drying process by coating the wheat flour particles hence slowing the drying process as compared to a sample without oil.     

Preparation and investigation on tetradecanol and myristic acid/cellulose form-stable phase change material

In this paper, a novel form-stable phase change material (FS PCM) was prepared by incorporating the eutectic mixture of tetradecanol (TD) and myristic acid (MA) into the hydroxylpropyl methyl cellulose (HPMC). HPMC is used as support material, and the eutectic mixture is used as phase change material. The Fourier-transform infrared spectroscopy (FT-IR), X-ray diffractometer (XRD) and scanning electron microscopy (SEM) were used to study the chemical structure, crystallization behavior and morphology of the FS PCM, respectively. FT-IR, XRD and SEM showed that the TD–MA was distributed uniformly in HPMC by physical interaction. Specific surface area (BET) and pore size analysis determined the pore characteristics of the composite, and the results showed the porosity of HPMC. The thermal properties, thermal stability and thermal reliability were detected by differential scanning calorimetry (DSC), thermogravimetric analysis (TG), thermal cycling test and leakage test. The TG, DSC and leakage analysis results revealed that the absorption of eutectic mixture into HPMC is nearly 50% and without seepage from the composite. The peak temperatures of melting and solidifying were 34.61 and 31.09 °C, and latent heat was 102.11/84.58 J g^?1 by DSC. TG and cycling experiment detected that the FS PCM showed good thermal stability and reliability performance.     

Thermal behaviors of soy biodiesel

Biodiesel is a prospective and promising fuel for diesel engines. However, some aspects need improvement, to develop into an ideal fuel, such as flow properties at low temperatures and storage stability at high temperatures with exposure to the air. Thermal analysis is an efficient tool for measuring properties, such as crystallization temperature, and thermal and oxidative stabilities. In this study, the thermal behaviors of biodiesel at low and high temperatures were investigated by using thermogravimetric analyzer, differential scanning calorimetry, pressurized differential scanning calorimetry (PDSC), and sorption analyzer (SA). The soy biodiesel was obtained through a transesterification reaction with a homogeneous catalyst. The constituents of the soy biodiesel as determined by gas chromatography show that methyl esters content was 99?% and of these 84?% were unsaturated fatty acids. TG results illustrate that the total weight loss of the biodiesel was 99?% below 300?°C under nitrogen flow, indicating a high purity biodiesel. The onset decomposition temperature and the peak temperatrue of the soy biodiesel were 193 and 225?°C, respectively, implying the biodiesel has good thermal stability. PDSC results show that the oxidation onset temperature of the soy biodiesel was 152?°C, and the oxidative induction time was 24?min. DSC results demonstrate that the onset crystallization temperature of the soy biodiesel was 1.0?°C. The SA results point out that with increasing temperature and humidity, the soy biodiesel absorbed more water, and in which humidity was the dominant factor. The water absorption and desorption of the soy biodiesel is a non-reversible process. The preferable storage conditions for soy biodiesel occur when humidity is less than 30?% and the temperature is less than 30?°C. In summary, thermal analysis is a faster alternative for thermal behavior studies as compared with conventional standard methods.     

In situ thermal decomposition of starch with constant moisture in a sealed system

This paper reports a DSC study of the thermal decomposition of starch kept at constant moisture content (0-50%) in a sealed system comprising a high-pressure stainless steel pan with a gold-plated copper seal. The advantage of this technique is that it facilitates the detection and study of the processes of thermal decomposition of starch with constant moisture content, which is a common scenario in the processing of thermoplastic starches. It was found that the decomposition temperature decreased with increasing water content, and that the peak in decomposition temperature broadened, which is different to the case observed in open, unsealed systems.     

Effects of Physical and Chemical Factors on the Structure of Gluten,Gliadins and Glutenins as Studied with Spectroscopic Methods

This review presents applications of spectroscopic methods, infrared and Raman spectroscopies in the studies of the structure of gluten network and gluten proteins (gliadins and glutenins). Both methods provide complimentary information on the secondary and tertiary structure of the proteins including analysis of amide I and III bands, conformation of disulphide bridges, behaviour of tyrosine and tryptophan residues, and water populations. Changes in the gluten structure can be studied as an effect of dough mixing in different conditions (e.g., hydration level, temperature), dough freezing and frozen storage as well as addition of different compounds to the dough (e.g., dough improvers, dietary fibre preparations, polysaccharides and polyphenols). Additionally, effect of above mentioned factors can be determined in a common wheat dough, model dough (prepared from reconstituted flour containing only wheat starch and wheat gluten), gluten dough (lack of starch), and in gliadins and glutenins. The samples were studied in the hydrated state, in the form of powder, film or in solution. Analysis of the studies presented in this review indicates that an adequate amount of water is a critical factor affecting gluten structure.     

Interactions and antioxidant stability of sesamol in dry-emulsions

Dry emulsions prepared from saccharose (SAC), Labrafil^? M 1944 CS, sesamol (SEOH), and hydroxypropylmethylcellulose (HPMC) or sodium caseinate (SC) by grinding or dissolution, and different desiccation techniques (spray (SD)- or freeze (FD)-drying, or heating at 60 °C) were investigated to determine possible interactions between mixture components. The goal of this study was to determine the best formulation which will regenerate perfectly, after water dilution of dry emulsions, the initial liquid emulsion with the same characteristics that before drying. The morphological state of SAC and dry emulsions were determined by scanning electron microscopy analysis (SEM) analysis. Glass transition temperature, and melting (endothermic), decomposition (endothermic), oxidation (exothermic) peak temperatures and enthalpies were measured by differential scanning calorimetry (DSC). The antioxidant activity of emulsions was evaluated through their ability to reduce 1,1-diphenyl-2-picrylhydrazil (DPPH) free radical. SEM analysis showed that SD-prepared, SC-containing dry emulsions formed better spherical particles with smooth surface at about 5 μm diameter as compared to emulsion containing HPMC. These former emulsions also showed more thermal stability by DSC. The combined results of the three analytical techniques emphasized the importance of the dry emulsion process regarding the efficiency and the thermal stability of antioxidant substances. A specific physical and/or chemical combination (such as hydrogen bond) sufficiently stable, at about 150 °C, could be suggested when the technique used for dry emulsion preparation was SD. After water dilution, this dry emulsion obtained from quaternary mixture: SAC, Labrafil^?, SEOH and SC, will regenerate the initial liquid emulsion with the same characteristics that before drying.     

Partially fluorinated sulfonated poly(arylene sulfone)s blended with polybenzimidazole

A partially fluorinated and sulfonated poly(arylene sulfone) (SPSO) was successfully synthesized via nucleophilic polycondensation of 2,2‐bis(4‐fluorophenyl)hexafluoro‐propane with 4,4′‐thiobisbenzenethiol (TBBT). In a second step, the prepared poly(arylene sulfide) was oxidized to SPSO. The polymer was blended with the polybenzimidazole PBIOO^® to obtain a mechanically stable membrane. This film was compared with other polymer blends, which were synthesized in our group in the last years. We were especially interested in the influence of different bridging groups such as ether, ketone, and sulfone groups. The affect on properties such as water uptake (WU), thermal stability, proton conductivity, and oxidative stability were analyzed in this work. Additionally, the blend membranes were characterized by gel permeation chromatography. The novel SPSO blend shows a high molecular weight, and its blend membrane with PBIOO has an excellent onset of ? SO₃H group splitting‐off temperature (T_onset) of 334 °C. The proton conductivity amounts to 0.11 S cm^?1, and the water uptake reaches 30%. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

On-line FT-Raman spectroscopic monitoring of starch gelatinisation and enzyme catalysed starch hydrolysis

The hydrolysis of starch by α-amylase and amyloglucosidase and the kinetics of these technically important reactions were investigated by FT-Raman spectroscopy. During the technical starch hydrolysis process, three reactions proceed one after the other but partly in parallel: the gelatinisation, the hydrolysis of starch to dextrin (liquefaction) by α-amylase, and the hydrolysis of dextrin to glucose (saccharification) by glucoamylase. These three reactions were studied separately. Potato starch or dextrin in concentrations of 50 g/l were suspended or dissolved in water, the reaction chamber was placed in a heated water bath, and defined, varied amounts of enzymes in solution were added. The reactions were monitored on-line in a bypass loop. The greatest spectral changes were observed due to the swelling and gelatinisation of starch. The liquefaction of starch to dextrin was started with the addition of α-amylase at a temperature of 80°C and the spectral changes were monitored. In a similar way, a solution/suspension of dextrin was used to investigate the reaction of glucoamylase at 50°C. Both enzymatic reactions were performed at four different enzyme activities. All reactions showed distinctive spectral changes, which can, in principle, be evaluated for the determination of the degree of starch hydrolysis. As a Nd:YAG laser at 1064 nm was used, fluorescence excitation was not observed despite the use of crude, technical-grade enzymes. The findings demonstrate the potential use of Raman spectroscopy in monitoring and control of technical enzyme reactions.     

Characterization of hydroxypropylmethylcellulose (HPMC) using comprehensive two-dimensional liquid chromatography

Various hydroxyl-propylmethylcellulose (HPMC) polymers were characterized according to size and compositional distributions (percentage of methoxyl and hydroxyl-propoxyl substitution) by means of comprehensive two-dimensional liquid chromatography (LC×LC) using reversed-phase (RP) liquid chromatography in the first dimension and aqueous size-exclusion chromatography (aq-SEC) in the second dimension. RP separation was carried out in gradient-elution mode applying 0.05% TFA in water and 1-propanol, while 0.05% TFA in water was used as mobile phase in aqueous SEC. A two-position ten-port switching valve equipped with two storage loops was used to realize LC×LC. Detection of HPMC was accomplished by charged-aerosol detection (CAD). Data processing to visualize chromatograms was carried out using Matlab software. The significant influence of the LC×LC temperature on (the retention of) HPMC was studied using a column oven which allowed accurate temperature control. Due to the phenomenon of thermal gelation, which is a result of methyl and hydroxypropyl substitution of anhydroglucose units from the cellulose backbone, we were able to obtain additional, specific information on compositional characteristics of various HPMC samples. As the retention behaviour of gelated and non-gelated polymer proved to be different, the fraction of the polymer that is gelated in the chromatographic column could be monitored at different temperatures. Moreover, the temperature at which half of the polymer is gelated could be correlated with the cloud-point temperature. As a result, differences in inherent cloud points of modified cellulose can be used as a further distinguishing property in "temperature-responsive" LC×LC.