Starch hydroxyalkylation: Physicochemical properties and enzymatic digestibility of native and hydroxypropylated finger millet (Eleusine coracana) starch

Starch was isolated from finger millet (Eleusine coracana) and it was etherified with propylene oxide to produce hydroxypropylated derivative. The specific specie used in this study is African finger millet known as jeero. The yield of starch obtained from finger millet on dry weight basis was 52.4%. Progressive increases in molar substitution (MS) were observed as the volume of propylene oxide added to the reaction medium increased. The X-ray pattern of native finger millet starch conforms to the ‘A’ diffraction pattern characteristics of cereal starches. Prominent peaks were observed at around 2θ=15°, 17°, 18° and 23° and weaker peaks at around 2θ=20° and 26°. No pronounced differences were observed between the diffractograms of native starch and the hydroxypropyl derivatives. Hydroxypropylation improved the free swelling capacities of the native starch at all temperatures studied (30–90 °C). Turbidity of unmodified finger millet starch paste increased progressively as the days of storage increased. Turbidity reduced remarkably after hydroxypropylation and reduction in turbidity was observed as the MS of the modified starches increased. Hydroxypropylation reduced pasting temperature, increased peak viscosity but reduced setback value. In addition, hydroxypropylation reduced percentage syneresis of the unmodified starch. Retrogradation properties monitored with differential scanning calorimetry reveals that starch retrogradation reduced reasonably after hydroxypropylation. Carbon 13 NMR spectroscopy reveals that hydroxypropylation took place predominantly on carbon 6 on the anhydroglucose unit (AGU).     

Effect of Hydroxypropylation on the Properties of White Yam (Dioscorea rotundata) Starch

Starch isolated from white yam (Dioscorea rotundata) was subjected to hydroxypropylation under different conditions. Corresponding increases were observed between the molar substitution (MS) and the volume of propylene oxide added to the reaction mixture. After hydroxypropylation, a slight reduction in the intensity of the peak at 2θ = 19.6° was observed and the doublet peak at 23.8°, which was present in native starch, was no longer seen. Hydroxypropylation enhanced the free swelling capacity (FSC) and solubility. Setback and retrogradation of native starch declined after hydroxypropylation. Turbidity of native starch paste and syneresis were higher with storage time. The results also indicate that enzymatic digestibility improved as the MS increased, while the reverse was observed for starch paste turbidity, syneresis, setback and retrogradation. This study presents relevant information that could strategically position D. rotundata starch and its hydroxypropylated derivatives for industrial applications.     

Physicochemical characterization of chemically modified corn starches related to rheological behavior,retrogradation and film forming capacity

An integral approach of chemical modification effects on physicochemical and functional properties of corn starch was performed using different and complementary techniques. Acetylated, acetylated crosslinked, hydroxypropylated crosslinked, and acid modified corn starches were analyzed. Substitution and dual modification reduced significantly amylose concentration. Chemical modification decreased granules crystallinity degree. A significant increase in swelling power was observed in substituted and dual modified starches at 90 °C, besides these treatments decreased gelatinization temperature and enthalpy. Acid modified starch pastes showed a Newtonian behavior while substituted and dual modified ones exhibited a viscoelastic response. Dynamic rheological properties of modified starch pastes were not affected by post gelatinization time while native starch pastes developed a more rigid structure during storage. Retrogradation of substituted starch pastes after 12 days at 4 °C was reduced, since syneresis degree and hardness increase were significantly lower than those of native pastes. It was demonstrated that only substituted and native starches exhibited film forming capacity.     

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

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

Substituent distribution within cross-linked and hydroxypropylated sweet potato starch and potato starch

Revealing the substituents distribution within starch can help to understand the changes of starch properties after modification. The distribution of substituents over cross-linked and hydroxypropylated sweet potato starch was investigated and compared with modified potato starch. The starches were cross-linked with sodium trimetaphosphate and/or hydroxypropylated with propylene oxide. The native and modified starches were gelatinized and hydrolysed by pullulanase, β-amylase, α-amylase and a combination of pullulanase, α-amylase and amyloglucosidase. The hydrolysates were analysed by HPSEC, HPAEC and MALDI-TOF mass spectrometry. Cross-linking had only a slight effect on the enzymatic hydrolysis, where hydroxypropylation evidently limited the enzymatic hydrolysis. The results obtained suggest that the hydroxypropyl substituents are not distributed regularly over the starch chains. Although the average substitution was around 2 hydroxypropyl groups per 10 glucose units, in the enzyme digests of hydroxypropylated starches, oligomer fragments of 10–15 glucose units, carrying 5–8 hydroxypropyl groups, were identified. It is hypothesised that higher levels of substituents are present in the amorphous regions and periphery of clusters of starch granules. This is the first time that the location of hydroxypropyl groups within sweet potato starch has been examined in this detail. Despite significant differences in granule architecture between starches from potato and sweet potato, similar patterns of hydroxypropylation have been found.     

Preparation of hydroxypropyl corn and amaranth starch hydrolyzate and its evaluation as wall material in microencapsulation

Hydroxypropylation of starches lends it useful physicochemical and functional properties that are industrially important. The literature on hydroxypropylation using organic solvents for obtaining higher molar substitution (MS) is scantily available. The present work reports on hydroxypropylation of corn and a waxy amaranth starch to different MS with propylene oxide in an alkaline-organic medium (isopropanol). The synthesis was followed in terms of MS. The parameters optimized were starch:isopropanol ratio (w/w), reaction temperature, reaction time and the quantity of alkali required in the process. A maximal MS of 0.180 and 0.162 were obtained for hydroxypropyl corn starch (HPSC) and hydroxypropyl amaranth starch (HPSA), respectively. Enzymatic hydrolysis of the HPSC and HPSA of the above MS was carried out on a 30% (w/v) solution at a pH of 6.5 and 95 °C for varying time periods using 0.1% (w/w based on starch) bacterial α-amylase, termamyl. The hydrolysis was terminated by adjusting the pH to 3.5 using 0.1 N HCl. The hydrolyzates were characterized in terms of dextrose equivalent and viscosity. The hydrolyzate obtained after 3 h of hydrolysis was spray dried and compared to gum arabic with respect to encapsulation of model flavourings, orange oil and lemon oil.     

Swelling Characteristics of Native and Chemically Modified Wheat Starches as a Function of Heating Temperature and Time

The effects of hydroxypropylation (molar substitution, MS 0.05, 0.12, and 0.18) and cross‐linking (0.03%, 0.1%, and 0.2%) on swelling properties of wheat starch granules at several temperatures and heating times were investigated by laser diffraction particle size analysis. Starch samples were dispersed in water at temperatures ranging from 30 to 90°C, for 1 to 360 min. All starch granules exhibited distinct bimodal size distributions: small B‐granules with mean diameter of 2.3 μm and large A‐granules with mean diameter of 20.4 μm. As temperature increased, the B‐granules swelled more than A‐granules. Swelling of A‐granules sharply increased at 60°C. Swelling was more pronounced with increasing molar substitution of hydroxypropyl groups, while increased swelling was not observed in cross‐linked starches. The dependence of swelling capacity on heating time was different at 60 and 80°C as well as amongst modified starches. As heating time was prolonged, mean granule sizes for native, control, and hydroxypropylated starches at 80°C decreased after reaching maximum size due to loss of granule integrity, while those at 60°C showed no significant change.     

The Reactivity of Porcine Pancreatic alpha-Amylase Towards Native,Defatted and Heat-moisture Treated Potato Starches Before and After Hydroxypropylation

Potato starch was defatted (hot 75% n-propanol) and heat-moisture treated (100°C, 30% moisture) for various time intervals. The results showed that the above treatments increased the susceptibility of potato starch granules (heat-moisture treated > defatted) towards hydrolysis by porcine pancreatic α-amylase. These differences can be accounted for by the structural changes that occur within the amorphous and crystalline regions of the starch granule during defatting and heat-moisture treatment. Native, defatted (7 h) and heat-moisture treated (100°C, 30% moisture, 16 h) potato starches were hydroxypropylated (to different levels of molar substitution [MS]) with propylene oxide (2 → 20 %). The results showed that the alkaline reagents (NaOH and Na₂SO₄) used during hydroxypropylation increased the susceptibility of the above starches (native > defatted > heat-moisture treated) towards hydrolysis by α-amylase. Addition of propylene oxide to alkali treated starches, further enhanced their susceptibility, towards α-amylase. However, granule susceptibility towards α-amylase did not increase exponentially with increase in MS. The extent of hydrolysis began to decrease at MS levels of 0.29 (native), 0.28 (heat-moisture treated) and 0,26 (defatted).     

Pasting properties of hydroxypropylated starches before or after proteinase treatment

To examine the effect of starch protein on hydroxypropylation, corn (normal and waxy) and potato starches were hydroxypropylated with propylene oxide at two levels (8.3 and 12.3% based on dry basis of starch weight) before or after proteinase (thermolysin) treatment, and then pasting properties of the starches were measured. For normal corn starch, protein appeared to be involved in hydroxypropylation, especially at the higher concentration of reagent (12.3%); the starch hydroxypropylated after proteinase treatment (Enz‐HP) showed less reaction efficiency than that only hydroxypropylated (HP) or proteinase treated starch after hydroxypropylation (HP‐Enz). This suggests a possible reaction between some of the reagent and the starch proteins that exist in the channel and surface of the starch granules. However, not much difference was found with the waxy corn starch, as it contains much lower amounts of amylose and protein than normal corn starch. The potato starch, which has no channels, showed complicated protein effects. For potato starch, a different access of the enzyme and chemical reagents to the granule matrix could be possible.     

In vitro Digestibility of Hydroxypropylated and Cross-linked Waxy and Non-waxy Rice Starches

In vitro digestibility of hydroxypropylated and cross-linked waxy and non-waxy rice starches was investigated to find the proper resistant starch (RS) assaying method for chemically modified starches. RS and total dietary fiber (TDF) content of hydroxypropylated and cross-linked waxy and non-waxy rice starches were measured using the approved AOAC RS assay procedure (AOAC method 2002.02) and the AOAC TDF assay procedure (AOAC method 985.29). Hydroxypropylation did not alter the RS content of waxy and non-waxy rice starches (less than 1% of RS). Cross-linking also did not change the RS content of waxy and non-waxy rice starches (less than 1% of RS). It is interesting to note that non-RS content decreased with increasing hydroxypropylation (97-80%) and cross-linking (99-95%) in both waxy and non-waxy rice starches. This indicates that some fraction of RS in hydroxypropylated and cross-linked waxy and non-waxy rice starches cannot be measured using approved AOAC RS and TDF assay procedures. Therefore, the RS and TDF assay procedures performed in this study are not appropriate to determine the RS content of chemically modified starch. Further investigation is needed to develop a method to determine the RS content of chemically modified starch.     

Influence of hydroxypropylation on retrogradation properties of native,defatted and heat-moisture treated potato starches

Recent studies have shown that defatting and heat-moisture treatment cause structural changes within the amorphous and crystalline regions of potato starch. Furthermore, the alkaline reagents (NaOH and Na₂SO₄) used during hydroxypropylation has been shown to cause structural changes within the amorphous and crystalline regions of native, defatted and heat-moisture treated starches. In this study, we have compared (using different techniques) the retrogradation properties of potato starch before and after physical (defatting and heat-moisture treatment), and chemical (alkaline treatment and hydroxypropylation) modification. Turbidity measurements showed that changes in turbidity during storage (4°C for 24 h and then at 40°C for 29 days) of native, defatted and heat-moisture treated gelatinized starch pastes were influenced by the interplay of two factors: (1) interaction between leached starch components (amylose–amylose, amylose–amylopectin, amylose–amylopectin), and (2) interaction between granule remnants and leached amylose and amylopectin. In alkali treated gelatinized native, defatted and heat-moisture treated starch pastes, turbidity changes on storage was influenced by aggregation of granule remnants. Hydroxypropylation decreased the rate and extent of increase in turbidity during storage of native, defatted and heat-moisture treated starches. The change in turbidity during storage of hydroxypropylated starch pastes was influenced by the interplay between: (1) steric effects imposed by hydroxypropyl groups on chain aggregation, (2) aggregation between small granule remnants, and (3) settling of large granule remnants beneath the path of the spectrophotometer beam. Stored gelatinized pastes of native, defatted and heat-moisture treated starches gave a `B' type X-ray pattern. A similar pattern was also observed after alkaline treatment, and hydroxypropylation. However, the X-ray intensity of the strong reflection at 5.2 Å decreased after alkaline treatment and hydroxypropylation. The retrogradation endotherm (monitored by differential scanning calorimetry) occurred after 2 days storage in native, defatted and heat-moisture treated starches. A similar trend was also observed after alkaline treatment. However, the retrogradation endotherm appeared only after 7 days in hydroxypropylated starches. The enthalpy of retrogradation in all starches decreased on alkaline treatment and hydroxypropylation.     

Effect of acetylation,oxidation and annealing on physicochemical properties of bean starch

Black and Pinto bean starches were physically and chemically modified to investigate the effect of modification on digestibility and physicochemical properties of bean starch. The impact of acetylation, oxidation (ozonation) and annealing on the chemical composition, syneresis, swelling volume, pasting, thermal properties and digestibility of starches was evaluated. The physicochemical and estimated glycemic index (eGI) of the Black and Pinto bean starches treated with ozone were not significantly (P > 0.05) different than that of their respective control starches. Annealed starches had improved thermal and pasting properties compared to native starches. Acetylated starches presented reduced syneresis, good pasting properties and lower eGI. Also, all modified starches had increased levels of resistant starch (RS). Therefore, the digestibility and physicochemical properties of bean starch were affected by the type of modification but there were no significant (P > 0.05) differences between the Black and Pinto bean starches.     

Chemical and Enzymatic Modifications of the Pasting Properties of Legume Starches

Refined legume starches were evaluated for their Brabender Visco/Amylograph properties in their native form and after chemical and enzymatic pretreatment during incubation for 20 h at room temperature. Although exhibiting the characteristic restricted paste viscosities of legume starches, native lentil starch showed much higher viscosity parameters than navy bean starch while field pea starch had very low, stable viscosities. Pretreatments with mineral acids, alkali or enzymes failed to significantly alter the amylographs of the 8% slurries (w/v). Removal of surface lipids on the refined starch granules with propanol/water (3:1 v/v) or chloroform/methanol (2:1 v/v) increased paste viscosities substantially, as did the complexation of the starches with palmitic acid or glyceryl monopalmitate. None of the treatments resulted in complete dissolution of the starch granules and the modified starches showed no improvement in gel syneresis during storage.     

Suitability of pigeon pea and rice starches and their blends for noodle making

The physicochemical and pasting properties of pigeon pea and rice starches were studied to assess their suitability for noodle making. Amylose content, solubility and freeze thaw stability of pigeon pea starch were significantly higher than those of rice starch (p < 0.05). The pasting properties of peak viscosity, final viscosity, breakdown and set back showed higher values for pigeon pea starch, whereas hot paste viscosity and pasting temperature were higher for rice starch. Rice starch noodles revealed less cooking time (4 min) and less percent solids loss, whereas pigeon pea starch noodles had higher cooking time (12 min), higher percentage of water absorbed during cooking, more hardness and cohesiveness. Rice starch noodles scored higher for their transparency and slipperiness over pigeon pea starch noodles. Blending of pigeon pea starch with rice starch had significant effects on the cooking and sensory quality of noodles. Among starch blends, 70:30 blend of the pigeon pea and rice starches respectively resulted in good quality of noodles especially in terms of their higher transparency, slipperiness, overall acceptability and cohesiveness values. Blending of pigeon pea starch with 30% rice starch could produce noodles with superior quality as compared to native pigeon pea and rice starch noodles.     

Physicochemical properties and amylopectin chain profiles of cowpea,chickpea and yellow pea starches

Starches from cowpea and chickpea seeds were isolated and their properties were compared with those of commercial yellow pea starch. Amylose contents were 25.8%, 27.2%, and 31.2%, and the volume mean diameter of granules, determined in the dry state, were 15.5, 17.9, and 33.8 μm for cowpea, chickpea and yellow pea starches, respectively. All three legume starches showed a C-type X-ray diffraction pattern and two-stage swelling pattern. Amylopectin populations were isolated and the unit chain profiles were analyzed by HPLC after debranching with pullulanase. The degree of polymerization (DP) of short chain populations was about 6–50 and the populations of long chain had a DP of 50–80. Cowpea showed a lower weight ratio of short:long chains than chickpea and yellow pea starches. The larger portion of long side chains in cowpea amylopectin can be correlated with a higher gelatinization temperature, greater pasting peak and a slight difference in crystalline structure found for cowpea starch. Chickpea and yellow pea starches exhibited similarity in unit chain profile of amylopectin as well as in gelatinization temperature and pasting profile, while they differed in amylose content, particle size and syneresis. It is assumed that the chain length distribution of amylopectin has a large influence on starch properties.     

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 properties of Pinhão (Araucaria angustifolia, Bert, O. Ktze) starch phosphates

Physicochemical properties of pinhão (seeds of Paraná pine) starch phosphates were evaluated and compared to corn starch phosphates. The phosphorylation process used yielded starch phosphates with three different degrees of substitution (DS): low (0.015), medium (0.07) and high (?0.12). Medium and high DS starch phosphates had higher cold water binding capacity, swelling power, and paste clarity, but lower paste syneresis (at 5 °C and after freeze-thaw cycles) than native starches (P<0.05). Low, medium, and high DS corn starches had higher solubility than native starches (3.8-, 8-, and 6-fold higher; P<0.05), but the solubility of pinhão starch increased only in medium DS starch phosphates (3-fold higher; P<0.05). Low DS starch phosphates had viscosity curves similar to native starches. In contrast, medium and high DS starch pastes had peak viscosity at room temperature, reached the minimum viscosity when heated to 95 °C, and had low setback.     

Enzymatic hydrolysis of granular native and mildly heat-treated tapioca and sweet potato starches at sub-gelatinization temperature

The effect of mild heat treatment (below gelatinization temperature) towards the susceptibility of granular starch to enzymatic hydrolysis was investigated. Tapioca and sweet potato starches were subjected to enzymatic hydrolysis with a mixture of fungal α-amylase and glucoamylase at 35 °C for 24 h. Starches were hydrolyzed in native (granular) state and after heat treatment below gelatinization temperature (60 °C for 30 min). The dextrose equivalent (DE) value of heat-treated starch increased significantly compared to native starch, i.e., 36–50% and 27–34% for tapioca and sweet potato starch, respectively. Scanning electron microscopy examination showed that enzymatic erosion occurred mainly at the surface of starch granules. Hydrolyzed heat-treated starch exhibited rougher surface and porous granules compared to native starch. X-ray analysis suggested that enzymatic erosion preferentially occurred in amorphous areas of the granules. The amylose content, swelling power and solubility showed insignificant increase for both starches. Evidently, heating treatment below gelatinization temperature was effective in enhancing the degree of hydrolysis of granular starch.     

Effect of calcium and hydroxypropylation on crystallinity and digestibility of rice starches

The digestibility of native and hydroxypropyl rice starches in the presence of calcium was investigated. Calcium interacted with native and hydroxypropyl rice starches and altered their relative crystallinity. Hydroxypropylation was measured in terms of molar substitution (MS) which in turn enhanced calcium binding. Depending upon the amount of calcium added (50–250 μg calcium per g dry starch) and levels of MS (ranging from 0·02 to 0·12), 25·4– 34·1 μg calcium was bound per g of hydroxypropyl starch. Native starch bound 25·4 μg calcium per g dry starch, which was much less than the hydroxy-propylated starches. Crystallinity decreased with the increase of MS and calcium concentration. Digestibility of ungelatinised hydroxypropyl starches increased with MS (2·5–4·1 mg reducing sugar released per g dry starch) and the trend is reversed in the gelatinised form. Calcium-induced amylolysis of the starches by porcine pancreatic α-amylase but somehow inhibited amyloglucosidase attack. © 1998 SCI.     

Ultrasound Effects on the Structure and Chemical Reactivity of Cornstarch Granules

The changes of structure and chemical reactivity of ultrasound‐treated cornstarch (UTCS) granules are presented and discussed. It was found by polarized light and scanning electron microscopy (SEM) that the crystalline structure of UTCS granules did not change, but the amorphous area was slightly destroyed. Pores or channels were detected in the UTCS granules. X‐ray diffraction revealed that UTCS had the A‐type crystalline pattern of native cornstarch, which were not markedly changed. The gelatinization temperature and enthalpy of gelatinization (ΔH) of UTCS first increased and then slightly dropped with increasing degree of hydrolysis (DH). An increase in the DH of UTCS from 0 to 3.1 % resulted in an insignificant change in the degree of substitution (DS) and reaction efficiency (RE). Further increases in the degree of hydrolysis up to 15.7 % resulted in an obvious increase in the DS and RE, but increase in the DH to even higher values drastically decreased DS and RE. Compared with hydroxypropylated cornstarch, the pasting temperature of hydroxypropylated UTCS increased, but UTCS exhibited a lower maximum viscosity. The breakdown of hydroxypropylated starch paste was reduced after ultrasonic treatment before hydroxypropylation. The setback value increased after ultrasonic pretreatment when the degree of hydrolysis was < 7.8 % but decreased at DH > 7.8 %.