Dynamic Rheological and Thermal Properties of Acetylated Sweet Potato Starch

Dynamic rheological and thermal properties of acetylated sweet potato starch (SPS) pastes (5%, w/w) were evaluated as a function of the degree of substitution (DS). The transition temperatures (T_o, T_p and T_c) and enthalpy of gelatinization (ΔH) of acetylated SPS, which were determined using differential scanning calorimetry, were lower than those of native starch, and significantly decreased with an increase in DS. Magnitudes of storage modulus (G′), loss modulus (G′′) and complex viscosity (η*) of acetylated SPS pastes were determined using a small‐deformation oscillatory rheometer. Dynamic moduli (G′, G′′ and η*) values of acetylated SPS pastes except for 0.123 DS were higher than those of native starch, and they also decreased with an increase in DS. The tan δ (ratio of G′′/G′) values (0.37–0.39) of acetylated SPS samples were lower than that (0.44) of native starch and no significant differences were found among acetylated SPS samples, indicating that the elastic properties of SPS pastes were affected by acetylation but did not depend on DS. The G′ values of acetylated SPS during aging at 4°C for 10 h were much lower than those of native starch, showing that the addition of acetyl groups produced a pronounced effect on the retrogradation properties of SPS.     

Effect of low and high acetylation degree in the morphological, physicochemical and structural characteristics of barley starch

Barley starch was acetylated at two levels (low degree: LD (0.9), and high degree: HD (2.7)) substitution and the morphological, physicochemical and structural of the resultant acetylated barley starch were determined. The acetylated barley starches presented the signal at 1226 cm⁻¹ that corresponds to the C-O stretching of acetyl groups. The morphological study showed fusion of starch granules in the acetylated starch with HD. This effect was evident in the pasting test, because the viscoamylograph profile of HD starch showed the absence in peak viscosity, viscosity breakdown and viscosity setback. The peak gelatinization was similar for native and LD and decrease in the HD acetylated starch. The gelatinization enthalpy value showed difference among the samples, indicating that the loss of the ordered double helices more than the crystallinity loss was higher in the HD acetylated barley starch. In the retrogradation test, acetylation affected both retrogradation and enthalpy value, because acetylated barley starch with HD substitution at three storage days had 3.2 j/g and with LD 4.8 j/g. The molecular weight and z-average radius of gyration values decreased due to the acetylation process, indicating depolymerization of starch components as it was evidenced by the increase in short chains level in the acetylated samples.     

Gelatinization and Thermal Properties of Modified Cassava Starches

The thermal properties of seven commercial modified cassava starches, including oxidized, acetylated, cross‐linked, and combined acetylated and cross‐linked starches were studied by differential scanning calorimetry (DSC) in the glassy and rubbery states. Increase in gel hardness in the rubbery state during storage was also monitored, as well as gelatinization behavior. The modified starches were prepared from granular starch and had a degree of substitution in the range 0–0.053. The glass transition temperatures (T_g) of the modified starches were 3–6°C significantly lower than that of the non‐modified starch. The physical aging peak temperatures were also significantly reduced by 2–3°C, compared to the non‐modified starch, while aging enthalpies increased. Starch modifications did not decrease amylopectin retrogradation significantly. During storage, the oxidized starch gel became significantly harder than the non‐modified starch gel, while the hardness of the acetylated and/or cross‐linked starch gels was significantly reduced, which confirmed that acetylation or cross‐linking can decrease hardness, even when the extent of modification is limited. Different modifications controlled different properties of the starch system, with cross‐linking and acetylation influencing the gelatinization behavior and the changes in starch gel texture during storage, respectively.     

The Acetylation of Starch by Reactive Extrusion

Potato starch has been acetylated in a counter rotating twin screw extruder using vinylacetate and sodium hydroxide. The desired starch acetylation reaction is accompanied by an undesired parallel base catalysed hydrolysis reaction of vinylacetate and a consecutive hydrolysis reaction of the acetylated starch. Also deacetylation may occur. During the extrusion process sodium hydroxide, vinylacetate, granular potato starch and water were supplied to the extruder. Conversions up to 100% could be achieved. The degree of substitution could be varied from 0.05 to 0.2. Selectivities from vinylacetate towards starch of up to 80% could be achieved. From reaction kinetics and experiments it could be concluded that the deacetylation reaction could be neglected. The degree of gelatinisation appeared to be a major key parameter. Increasing the gelatinisation in an early stage of the extrusion process, at high starch concentrations and temperatures, increases the selectivity and degree of substitution. The gelatinisation degree can be increased by applying high shear and temperatures to the starch granule and by using screws with modified geometries.     

乙酰化酸解复合变性淀粉的制备及性能研究

本文以玉米淀粉为原料,以盐酸为酸解剂,醋酸酐为乙酰化试剂,氢氧化钠为酰化催化剂对酸解乙酰基复合变性淀粉合成工艺进行了研究。考察了反应时间、反应温度、pH值、酸含量对酸解淀粉流度、乙酰化淀粉取代度及产品性能的影响。实验结果表明,升高酸解温度、增加酸解时间和酸含量将加速淀粉的降解。采用流度法测定酸解淀粉的粘度,采用酸碱滴定法测定了乙酰化酸解淀粉的取代度。     

Study on the morphology,crystalline structure,and thermal properties of Fritillaria ussuriensis Maxim. starch acetates with different degrees of substitution

Fritillaria ussuriensis Maxim. starch acetates with different degrees of substitution (DSs) were prepared by reacting native starch with glacial acetic acid/acetic anhydride using sulfuric acid as catalyst. XRD of acetylated starch revealed that there was loss of crystallinity with increasing DS. The carbonyl group signal at 1750 cm⁻¹ appeared in the FTIR spectra. The intensity of this peak increased whereas the intensity of the hydroxyl groups at 3000–3600 cm⁻¹ decreased. The thermal behavior of the samples was investigated and the results showed that the acetylation decreased the gelatinization temperatures and ΔH_gel, and thermal stability of high DS acetylated starch (DS = 2.82) was much better than that of the original starch and partially substitute starch acetate (DS = 1.52). The SEM suggested that most of the starch granules were disintegrated into many visible fragments along with the increasing of DS. The starch acetate with different DS prepared in this paper has many potential uses in food and pharmaceutical applications for its lower gelatinization temperature and thermal stability properties.     

Facile preparation of sago starch esters using full factorial design of experiment

A facile solvent‐free method to acetylate sago starch (Metroxylon sagu) is reported. Microwave (100 W) was used as the heating source and the heating time was varied from 2 to 10 min with the temperature of acetylation maintained at 100°C under continuous stirring. Using a 2⁴ full factorial design of experiment, it was found that the degree of substitution (DS) of acetylated sago starch was strongly affected by the ratio of starch to acylating reagents, the ratio of acetic anhydride to acetic acid as the acylating reagents, the concentration of iodine as catalyst and reaction time. The physicochemical characteristics of the acetylated sago starch were assessed based on the FTIR spectra, the XRD spectra, the water absorption index (WAI), and the water solubility index (WSI). SEM was used to study the surface morphology of the acetylated sago starch at different DS.     

Contribution to the characterization of acetylated protein fractions of vicia faba in view of their functional properties

Whilst the emulsifying properties of the protein fraction of vicia faba are almost independent on the acetylation degree, the shear modulus of the gels produced by heat denaturation increases at first with increasing acetylation degree, decreases with further increase of the acetylation, and comes finally to zero for very high acetylation degrees. By changes of pH and by influence of added NaCl, CaCl₂, AlCl₃, and starch, the shear modulus of gels of acetylated protein fractions of vicia faba can be increased, by addition of sunflower oil it can be decreased. On the base of studies on the fraction profile and on the changes of the content of sulfhydryl and disulfide groups of the protein fractions of vicia faba and the corresponding gels in dependence on the acetylation degree, an interpretation of the results is given.     

Functional and dynamic rheological properties of acetylated starches from two cultivars of cassava

The starches derived from two different cultivars of cassava were modified with acetic anhydride. The increase in swelling power and solubility of the cassava starch (CS) pastes treated with different acetic anhydride concentration could be attributed to easier hydration, resulting from reduction of interaction between starch chains due to the substitution. The transition temperatures (T_o, T_p and T_c) and enthalpy of gelatinisation (ΔH) of acetylated CS, were determined. The values were lower than those of native starches. Rheological properties of CS pastes (5% w/w) as a function of the degree of substitution were evaluated in dynamic shear force measurements. Magnitude of storage modulus (G′), loss modulus (G′′) and complex viscosity (Eta*) of acetylated CS pastes were determined also. Dynamic moduli (G′, G′′ and Eta*) values of acetylated sweet cultivar pastes were generally higher than those of native starch whereas the acetylated samples of the bitter cultivar were lower than those of native starch. The magnitudes of G′ were greater than those of G′′ and Eta* at all frequencies (ω). The fact that all the tan δ (ratio G′′/G′) values (0.7–0.48 and 0.25–0.44) were less than one is an indication that the samples are more elastic than viscous. The acetylated starches could find promising industrial uses in food products like Lemon curd and Mayonnaise and other non‐food applications.     

高取代度酸解乙酰化淀粉及其纳米颗粒的制备

为了提高乙酰化淀粉在生物医学和靶向给药系统方面的应用,本文以普通玉米淀粉为原料,依次进行醇介质中的酸解和乙酰化处理,制备得到了高取代度的酸解乙酰化淀粉纳米颗粒,并且通过傅里叶变换红外光谱、X射线衍射、接触角测量、糊化曲线、扫描电子显微镜等表征手段探究了酸解条件对淀粉颗粒理化性质的影响。随后,用反溶剂法制成纳米颗粒,并确定了其粒径范围。结果表明:当酸解所用的乙醇体积浓度为70%,盐酸浓度为12.0 mol/L,温度为65 ℃时,酸解乙酰化淀粉的取代度由0.84提高至1.33,疏水性显著提高（P<0.05）,样品颗粒粒径减小;通过反溶剂法制备淀粉颗粒,能够得到粒径在200 nm左右的淀粉纳米颗粒。     

乙酰化羟丙基淀粉改性次序及程度研究

为确定复合改性对淀粉性质的影响,从而为复合改性淀粉在食品中的应用提供参考。以玉米淀粉为原料,在羟丙基淀粉及乙酰化淀粉2种单一改性淀粉研究的基础上,采用分光光度法确定单一改性淀粉取代度,并以复合取代度为指标,探讨乙酰化羟丙基复合改性淀粉的改性次序及改性程度对复合改性淀粉制备的影响。结果表明:水解作用与空间位阻是影响复合改性效果的重要因素;乙酰化羟丙基复合改性淀粉合理的改性次序应为先羟丙基化后乙酰化,且在一定范围内,乙酰化反应不受羟丙基化程度的影响。     

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.     

Aerobic Biodegradation of Extruded Polymer Blends with Native Starch as Major Component

The aerobic biodegradation of extruded blends containing native starch and an acetylated compound (starch or cellulose) was studied with the Bacillus amyloliquefaciens strain and also with the Biolen mixture known for its amylolytic activity. In the presented experiments, the rate of biodegradation is related to the percentage of acetylated compound in the blend. In fact, if the blend hydrolysis is facilitated by the amorphous state of the substrate, the inhibitory action of the acetyl group content is the major factor responsible of the weak hydrolysis. For instance, the conversion of the carbon material into CO₂ decreases strongly from 39% (native starch alone) to 7% (equimolar blend of starch and acetylated compound). All the other parameters used to estimate the hydrolysis extent (as the production of reducing sugars or acetic acid release) lead to the same conclusion.     

A Study of Native and Chemically Modified Potato Starch. Part I: Analysis and Enzymic Availability in vitro

The availability of native and chemically modified potato starch to α-amylase was studied in vitro (distarch phosphate, acetylated distarch phosphate and hydroxypropyl distarch phosphate). Enzyme availability was also related to results obtained during analysis of starch and dietary fibre, The degree of substitution (DS) was determined by ¹HNMR spectroscopy and the substitution sites were evaluated by gasliquid chromatography and mass spectrometry. Substitution with acetyl- and hydroxypropyl groups reduced the availability of drum-dried starch derivatives to α-amylase. In contrast, the susceptibility of raw starch increased after introduction of hydroxypropyl groups. Cross-linking with phosphate only had but minor effects on enzyme availability. The recovery of starch during analysis depended on (a) degree of hydrolysis to glucose (b) whether or not the substitution groups were removed. The lowest yields were observed when analyzing substituted derivatives after boiling and enzymic hydrolysis (60-70%). Enzymically unavailable starch was not recovered as dietary fibre when using an enzymic gravimetric assay.     

Effect of Acetylation on Some Properties of Corn and Potato Starches

Corn starch and starches separated from different potato cultivars were acetylated to evaluate the effect of plant source on the physicochemical, morphological, thermal, rheological, textural and retrogradation properties of the starches. Corn starch showed a lower degree of acetylation than potato starches under similar experimental conditions. The degree of acetylation for different potato starches also differed significantly. Morphological examination revealed that the granules of acetylated Kufri Chandermukhi and Kufri Sindhuri starches tended to appear as fused and less smooth than native starch granules. Acetylation of corn and potato starches decreased the transition temperatures and enthalpy of gelatinization and increased swelling power and light transmittance. However, the change in these was greater in the potato starches with higher percentage of small sized granules. Acetylated starches showed higher peak G', G'' and lower tan δ than their counterpart native starches during heating. Among the starches from different cultivars, the change in the rheological parameters after acetylation differed to a significant extent. The retrogradation was observed to be negligible in the acetylated cooked starch pastes. Results implied that the change in functional properties of starches with acetylation depends on source and granule morphology of native starch.     

Influence of acetylation on physicochemical, functional and thermal properties of potato and cassava starches

Starches were isolated from cassava (Manihot esculenta) and potato (Solanum tuberosum) tubers. They were further modified by acetylation. The physicochemical, functional and thermal properties of native and modified starches, prepared using acetic anhydride at different times (10 and 20 min) were compared. Potato starch (Sipiera/20) showed higher acetyl percentage and degree of substitution values than cassava (2425/20) starch when acetylated for 20 min. Proximate analysis revealed that the acetylated starches retained more moisture than the native ones. Above 75 °C, acetylation improved the water binding capacity of the native cassava starch; the same trend was observed for potato starch from 60 to 90 °C after acetylation. The X-ray powder diffraction patterns derived from acetylated potato starches were similar to its native form, which was expected as B-type pattern; the same trend was observed for modified cassava starch. However the modified starches showed increased crystalline index.     

Process‐product studies on starch acetylation reactions in pressurised carbon dioxide

An in‐depth study on the effect of process conditions (pressure, temperature and type of catalyst) on the acetylation of starch with acetic anhydride in pressurised carbon dioxide is described. A total of 22 experiments were performed and the experimental data were analysed using non‐linear multivariable regression. The highest degree of substitution (DS) value (0.46) was obtained using K₂CO₃ as the catalyst at 90°C, 15 MPa pressure, and a catalyst to starch ratio of 0.5 mol/mol anhydroglucose units (AGUs). Important product properties of the acetylated starch prepared in CO₂ like viscosity in water and relevant thermal properties were determined and compared with typical products prepared in an aqueous system.     

Bestimmung der Substitutionsmuster von chemisch modifizierten Stärken

Determination of the Substitution Pattern of Chemical Modified Starches. Methods for the investigation of oxidized starches, starch ethers and starch esters with respect to their degree and position of substitution are described. Oxidized starches were directly hydrolyzed and the hydrolysis products analized as trimethylsilylderivatives. The classical methylation analysis was applied for starch ethers; alternatively the permethylated starch was submitted to reductive depolymerization. Methylation of starch esters proceeded with methyltriflate under retention of acyl groups and hydrolytic or reductive degradation. All degradation products were acetylated and investigated by combined gaschromatography-masspectrometry.     

Characterization of Acetylated Waxy Maize Starches Prepared under Catalysis by Different Alkali and Alkaline‐Earth Hydroxides

The effects of the catalyst used in acetylation, including sodium hydroxide (NaOH), potassium hydroxide (KOH), and calcium hydroxide (Ca(OH)₂), on the chemical and physicochemical properties of acetylated waxy maize starch were investigated. The Ca(OH)₂‐catalyzed acetylated starch exhibited a slightly higher pasting temperature and a lower β‐amylolysis limit compared with acetylated starch prepared under NaOH or KOH catalysis, but no difference was observed for their thermal properties. The carbohydrate profiles of isoamylase‐debranched acetylated starches and their β‐limit dextrins were characterized by high‐performance size‐exclusion chromatography. The Ca(OH)₂‐catalyzed acetylated starch showed a elution profile that was different from those of the other two acetylated starches with a greater proportion of saccharides eluted at a longer retention time. However, the differences in pasting temperature, β‐amylolysis limit, and carbohydrate profile among the acetylated starches diminished when ethylenediaminetetraacetic acid (EDTA) was added. The results suggest that calcium might induce intermolecular crosslinking through chelation with oxygen of the anhydroglucose units and this type of crosslinking was promoted in acetylation catalyzed by Ca(OH)₂.