Comparative Studies on Some Physico-chemical, Thermal, Morphological, and Pasting Properties of Acid-thinned Jicama and Maize Starches

Comparative studies on acid hydrolysis of jicama and maize starch were carried out using concentrations of hydrochloric acid of 1.5%, 3.0%, and 4.5% (w/v), for 3 and 6 h, at 40°C. Native maize and jicama starches showed important morphological, thermal, and structural differences from those of tubers and cereals which potentially offer diverse industrial applications. Jicama starch showed low amylose content (12%) and small size of starch granules. Due to these characteristics, jicama starch was more susceptible to degradation during hydrolysis process than maize starch. Under the experimental conditions employed, the acid degradation was not particularly severe, as shown by scanning electronic microscopy analysis which showed small degraded zones and similar X-ray patterns in both starches. However, jicama starch was more susceptible to acid hydrolysis than maize starch, as revealed by the considerable increase in water solubility index, damaged starch, and crystallinity values. Also, the higher susceptibility of jicama starch than maize starch to the hydrolysis conditions was reflected in the sugar content release during hydrolysis. The relative crystallinity of hydrolyzed maize starches decreased during hydrolysis, while those of hydrolyzed jicama starches increased attributable to the lower amylose content of jicama starch in relation to maize starch. Maize and jicama hydrolyzed starches showed low viscosity values with relation to their native starch counterparts. However, native jicama starch showed lower viscosity values than maize starch, suggesting a lower internal stability of the starch granules during hydrolysis. Both native and hydrolyzed maize starches showed higher enthalpy, T _o, T _p, and T _c values than jicama starch and the broadening of the endotherms decreased during the hydrolysis of both starches.     

Comparative studies on morphological and crystalline properties of B-type and C-type starches by acid hydrolysis

Comparative studies on acid hydrolysis of B-type Fritillaria starch and C-type Rhizoma Dioscorea and Radix Puerariae starches were carried out using a scanning electron microscope (SEM) and X-ray diffraction (XRD). Fritillaria, Rhizoma Dioscorea and Radix Puerariae starches were hydrolyzed with 2.2 mol/L at 35 °C for 2, 4, 8, 16 and 32 days, respectively. The SEM and XRD results revealed that B-type starch and C-type starch displayed different hydrolysis mechanisms. The acid corrosion started from the exterior surface of B-type starch granules followed by the interior core of starch granules. However, the hydrogen ion primarily attacked the interior of the C-type starch granules and then the exterior of starch granules. B-type starch granule started to crack at the hydrolysis period of 4 days while C-type starch granule was not cracked until the hydrolysis progressed up to 16 days. The crystalline type of B-type starch was not changed with increasing hydrolysis time. However, the crystalline type was gradually changed from C-type to A-type for the Rhizoma Dioscorea and Radix Puerariae starches with increase in the hydrolysis time. This result showed that the B-type polymorphs present in the C-type starch granule was preferentially hydrolyzed during the first stage of hydrolysis.     

Physicochemical,thermal, and rheological properties of acid-hydrolyzed sago (Metroxylon sagu) starch

The effects of acid hydrolysis on physicochemical and rheological properties of sago starch were investigated. Sago starch was hydrolyzed in hydrochloric acid at 50 °C for 6, 12, 18, and 24 h. The molecular weight distribution, physicochemical, thermal, and rheological properties of acid-hydrolyzed sago starch (AHS) were determined. After 24 h of hydrolysis, molecular weight of amylopectin and amylose were decreased to 3.57 × 10⁵ and 6.5 × 10⁴ g/mol, respectively. Differential scanning calorimetry studies showed that the gelatinization temperature and enthalpy of AHS increased with increasing degree of hydrolysis. Hydrolyzed sago starch containing low molecular weight fractions exhibited cold water solubility up to 100%. Setting temperature of AHS decreased with increasing hydrolysis time but amylose content and gel strength increased in the first 12 h of acid hydrolysis but decreased with extended hydrolysis time. Hydrolyzed sago starch in concentrations lower than 8 g starch per 100 g water was cold water soluble and could be used to modify properties of starch for specific applications such as yogurt and concentrated milk processing.     

Mild hydrolysis of resistant starch from maize

To investigate structural changes of resistant starch (RS) caused by mild-acid treatment, native maize starch, retrograded (RS3), and cross-linked (RS4) resistant starches, prepared from maize starch, were hydrolyzed with 0.1 M HCl at 35 °C for 30 days. The hydrolysis rate of RS3 was shown to be the highest, at 44.1% after 30 days of the hydrolysis. The hydrolysis rapidly progressed upto 10 days but gradually changed after that. Native starch and RS4 showed less than 5% of hydrolysis during the period of hydrolysis. As for the RS level of the residue after the hydrolysis, RS4 did not show any significant change, but RS3 exhibited an increase of up to 25.9% after 30 days, which led to 88% increase in comparison with 13.8% at the initial stage. As a result of examining the molecular weight (MW) of RS3 by the SEC-MALLS-RI system, the non-hydrolyzed RS3 exhibited three peaks, having MW 53.4 × 10⁶, 7.4 × 10⁶, and 0.8 × 10⁶, respectively, but the MW of the molecules decreased to 4.9 × 10⁶ and 0.6 × 10⁶ after 7 days of hydrolysis. It was difficult to verify the MW of RS4 because this was not dispersed in 1 M NaOH. The crystallinity of native starches, RS3 and RS4, by X-ray diffractometry of the residue hydrolyzed with 0.1 M HCl was equal to that of the non-hydrolyzed starch. The peak intensity at 2θ = 17° of RS3 increased sharply after hydrolysis.     

酸解时间对大米淀粉结构性质的影响

以4种不同直链淀粉含量的大米淀粉(0%的优糯3号、10.90%的稻花灿、21.03%的聚两优、28.46%的华优香占)为原料,酸解处理不同时间,以酸解大米淀粉的酸解率、颗粒形貌、结晶性质、溶解度的变化为指标衡量不同酸解时间对大米淀粉结构及性质的影响。结果表明,不同直链淀粉含量的大米淀粉具有不同的耐酸性,酸解时间对不同直链淀粉含量大米淀粉的结构和性质有着不同的影响。大米淀粉酸解率与直链淀粉含量成反比,优糯3号为50%而华优香占仅为30%;所有淀粉颗粒在酸解后均产生一定程度的破碎,偏光十字变形直至消失,酸解相同时间,直链淀粉含量高的大米淀粉破碎率低;酸解未改变淀粉的晶型,仍为A晶型;随着酸解时间的延长相对结晶度增加;淀粉的溶解度随着酸解时间的增加而增大。     

Effects of high energy milling on some functional properties of jicama starch (Pachyrrhizus erosus L. Urban) and cassava starch (Manihot esculenta Crantz)

In this study, the effect of high energy milling using a Spex ball mixer mill on some functional properties of cassava starch (Manihot utilissima) and jicama starch (Pachyrrisus erosus) were investigated. The properties of individual granules were strongly influenced by the high moisture of ball milling (friction and heat) and physicochemical properties of their amorphous and crystalline zones. High energy milling resulted in a partial fragmentation of the starch granules, increasing the water absorption index (WAI) and the water solubility index (WSI). Increasing moisture content the viscosity was decreased, attributable to the fragmentation of starch granules produced by the milling and favored by the increase of moisture content.The crystallinity of cassava and jicama starches milled with high moisture contents and longer milling times was decreased. Thermal properties of both ball-milled starches were modified. The enthalpies were lower than native starch indicating that ball milling destroys the crystallinity and double helical order arrangements. Also, the resolution of the peaks was slightly decreased. Ball-milled jicama and cassava starches showed some functional characteristics of gelatinization that possibility their use in food systems as stabilizing, additives, moisture retainers and thickeners.     

Tailoring a New Sizing Agent via Structural Modification of Pregelled Starch Molecules Part 1: Carboxymethylation and Grafting

Pregelled starch (PS) was subjected to acid hydrolysis using phosphoric acid to prepare pregelled starches having different molecular sizes. The degraded pregelled starches were carboxymethylated at different reaction times. The carboxymethyl derivatives were grafted with either methacrylamide (MAam) or methacrylonitrile (MAN) as vinyl monomers using ceric ammonium nitrate (CAN) as initiator. Suitability of the new graft derivatives of pregelled starch as sizing agent of cotton yarns was studied. It is shown by the data that the extent of carboxymethylation, expressed as carboxyl content, increases by increasing the extent of hydrolysis and reaction time. Furthermore, the graft yield, expressed as mmol MAam or MAN monomer/100 g graft copolymer (grafted carboxymethylated pregelled starch or grafted carboxymethylated hydrolyzed pregelled starch) increases with increasing extent of carboxymethylation and degree of hydrolysis and follows the order: MAam > MAN. In addition cotton yarns sized with grafted carboxymethylated hydrolyzed pregelled starch – irrespective of the grafting monomer used – have better mechanical properties (tensile strength, elongation at break, and abrasion resistance) than hydrolyzed pregelled starches, carboxymethylated pregelled starch and carboxymethylated hydrolyzed pregelled starches.     

Physicochemical properties of cassava,potato and jicama starches oxidised with organic acids

The oxidising effects of organic (acetic, citric and lactic) acids on the physicochemical properties of starches from cassava, potato and jicama were investigated. Cassava starch oxidised with lactic and citric acids had the highest carbonyl contents (5.43 and 5.84 g kg^?1 respectively), while oxidised potato starch had the highest carboxyl contents. Oxidised jicama starch showed the lowest carbonyl and carboxyl contents. Oxidation increased the maximum viscosity of cassava starch (from 426.61 to 670.11 relative viscosity units (RVU)) and jicama starch (from 160.17 to 561.50 RVU) but decreased that of potato starch (from 669.44 to 206.92 RVU). When carbonyl and carboxyl groups were incorporated into jicama starch granules, the resistance of these granules to stirring at constant temperature (holding) increased, as did their final and retrogradation viscosities. However, the behaviour of oxidised cassava and potato starches, as indicated by a Rapid Visco Analyser, was different. The highest values of endotherm enlargement were found for native and oxidised jicama starch, while the lowest values were found for native and oxidised cassava starch. Native and oxidised potato starch had the highest enthalpy values (14.30–18.30 J g^?1), while jicama starch had the lowest (9.50–11.9 J g^?1). The high intrinsic viscosity of native potato starch was attributed to B‐type starch with a longer‐than‐average amylopectin chain length and a lower degree of crystallinity. Oxidised granules showed little erosion in the form of grooves; on the contrary, oxidation left the grains with a very smooth surface. Copyright © 2007 Society of Chemical Industry     

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.     

Characterization of nanoparticles prepared by acid hydrolysis of various starches

Various starches of different AM contents and origins such as wx maize, normal maize, high AM maize, potato, and mungbean starches were hydrolyzed using a H₂SO₄ solution (3.16 M) at 40°C for 7 days, and the starch particles were isolated from the hydrolysates by centrifugation. The hydrolysis rates varied from 61.4 to 90.9% depending on the starch type. Unexpectedly, A‐type starches were more resistant to the acid hydrolysis than B‐type starches. XRD results revealed that the starch particles with B‐crystalline type exhibited a decrease in peak intensity. In addition, in a DSC analysis, the crystals remaining in the B‐type starch particles were readily disrupted in the water dispersion so that no melting endotherm appeared. Electron microscopy confirmed that the starch particles had round or oval shapes with diameters ranging from 40 to 70 nm, which possibly represented the starch blocklets in granules. The acid degraded mainly AM and long AP chains, resulting in increasing the proportion of short chains.     

Formation of starch spherulites: Role of amylose content and thermal events

Commercial maize starches and potato starches of two cultivars differing in physicochemical composition (granule size distribution; amylose to amylopectin ratio) and crystallinity were heated to 180 °C and then cooled by fast quench using a differential scanning calorimeter (DSC), in order to produce spherulitic starch morphologies. Among the raw maize starches, waxy maize starch had highest relative crystallinity (49%) whereas a lowest crystallinity of 33–39% was calculated for high-amylose maize starches. Potato starches showed a relative crystallinity of 50%. The temperatures and enthalpies of gelatinisation and melting varied among all the starches. High-amylose maize starches showed higher transition temperatures of gelatinisation (T_gel), whereas waxy maize starch had lowest T_gel and enthalpy of gelatinisation (ΔH_gel). Similarly, a considerable variation in parameters related with crystalline melting (T_m1, T_m2 and ΔH_m1, ΔH_m2) was observed for different starches. The superheated gels of different starches treated using DSC were subjected to polarised microscopy, to confirm the formation of spherulites. Both the high-amylose starch gels showed the presence of spherulites exhibiting birefringence and a weak crystalline pattern. No birefringence was observed for waxy maize starch gel, while potato starch gels had some birefringence. The particle size distribution of high-amylose maize starch gels analysed through Zetasizer showed the sizes of spherulitic particles fall in the range of 300 nm–900 nm. The scanning electron micrographs of the dried high-amylose maize starch gels showed the presence of round spherulites consisting of several aggregated spherulitic particles. Amylose content and melting of crystallites during heating play an important role during recrystallisation of amylose (spherulite morphologies).     

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.     

Structural modification of waxy,regular, and high‐amylose maize and hulless barley starches on partial acid hydrolysis and their impact on physicochemical properties and chemical modification

Waxy (WX), regular (RA), and high‐amylose (HA) maize and hulless barley (HB) starches were subjected to partial acid hydrolysis with 1.0 and 2.2 N HCl for 30–240 min. In both starches, the extent of hydrolysis with 1.0 N HCl followed the order: HA>WX>RA, whereas with 2.2 N HCl, the order was: HA>WX>RA (maize) and WX>HA>RA (HB), respectively. The relative crystallinity increased (HA>WX>RA) and the X‐ray pattern remained unchanged, whereas the swelling factor decreased (WX>RA>HA in maize and WX>HA>RA in HB) at both acid concentrations. Starches hydrolyzed with 1.0 N HCl exhibited increased gelatinization temperatures (WX>RA>HA in maize, WX>HA ∼ RA in HB), a narrower gelatinization temperature range (WX>RA>HA in maize, WX>RA ∼ HA in HB) and a decreased gelatinization enthalpy (WX>HA>RA in maize and HB). Acid hydrolysis increased the accessibility of the phosphorylating reagent into the amorphous regions. The extent of phosphorylation was more pronounced (maize>HB) in starches hydrolyzed with 1.0 N HCl for 60–90 min. The bound phosphorus content (BPC) followed the order: HA>WX>RA in maize and HB starches hydrolyzed with 1.0 N HCl for 240 min. In both starches, the extent of cationization was not influenced either by acid concentration or hydrolysis time. In general, acid hydrolysis significantly affected the reactivity of starch towards phosphorylation, where the optimum hydrolysis condition differed with starch source. The results would benefit the starch industry, since the amount of the phosphorylating reagent required for increasing thermal stability and/or freeze‐thaw stability could be decreased substantially, if starches are subjected to partial acid hydrolysis prior to derivatization.     

Characterisations of kabuli and desi chickpea starches cultivated in China

The characterisation of starches from kabuli and desi type chickpea seeds was investigated by monitoring amylose content, swelling power, solubility, synaeresis, water-binding capacity and turbidity properties. Total amylose and apparent amylsoe content were 31.80% and 29.93% for kabuli and 35.24% and 31.11% for desi, respectively. The shape of starch granules varied from round to oval or elliptic. The transition temperatures (T_o, T_p and T_c) were (62.237, 67.000 and 72.007 °C) and (59.396, 68.833 and 77.833 °C) for kabuli and desi starches, respectively. The ΔH value of kabuli type was higher than that of desi type. The crystal type of chickpea starches was a typical C_A-type pattern. Breakdown and setback viscosity of kabuli starch were lower than those of desi starch, indicating high heat and shear stability. Kabuli starch showed a higher value of M_w (5.382 × 10⁷ g/mol) than desi starch (3.536 × 10⁷ g/mol). Both kabuli and desi starches belonged to low glycaemic starches from measuring starch fractions and hydrolysis index.     

不同链淀粉含量玉米微晶淀粉理化性质研究

分别以蜡质玉米淀粉、玉米淀粉及高直链玉米淀粉为原料,在酸醇介质中制备不同水解率微晶淀粉,测定不同微晶淀粉水解性能并研究其颗粒形貌、结晶结构、溶解度及消化性。结果表明:淀粉颗粒内部结构致密性依次减弱,支链淀粉含量高的淀粉较易被试剂进攻;经酸醇处理后,三种微晶淀粉均保留原来晶型,颗粒形态没明显变化,没破碎和膨胀出现,但颗粒表面变粗糙;随直链淀粉含量增加,相似条件(水解率和温度)淀粉溶解度逐渐降低;in-vitro消化体系中三种淀粉及其微晶淀粉消化速度依次降低。     

Production and physicochemical properties of resistant starch from hydrolysed wrinkled pea starch

The content and physicochemical properties of resistant starches (RS) from wrinkled pea starch obtained by different molecular mass reduction processes were evaluated. Native and gelatinised starches were submitted to acid hydrolysis (2 m HCl for 2.5 h) or enzymic hydrolysis (pullulanase, 40 U g^?1 for 10 h), followed by hydrothermal treatment (autoclaving at 121 °C for 30 min), refrigeration (4 °C for 24 h) and lyophilisation. Native starch showed RS and total dietary fibre contents of 39.8% and 14.3%, respectively, while processed ones showed values from 38.5% to 54.6% and from 22.9% to 37.1%, respectively. From these, the highest contents were among acid‐modified starches. Processed starches showed endotherms between 144 and 166 °C, owing to the amylose retrogradation. Native and processed starches showed low viscosity, which is inversely proportional to the RS concentration in samples. The heat treatment promoted an increase in the water absorption index. The pea starch is a good source for obtaining resistant starch by acid hydrolysis.     

The effect of starch isolation method on physical and functional properties of Portuguese nuts starches. I. Chestnuts (Castanea sativa Mill. var. Martainha and Longal) fruits

The functionality of starch from chestnut (Castanea sativa Mill.) fruits isolated by alkaline and enzymatic methods were assessed. The studied properties included: solubility, swelling power, pasting properties, synaeresis, turbidity, and thermal and rheological behaviours. In addition amylose and resistant starch content were also evaluated. Results showed that the starch isolation method induced changes in most of those properties. Extracted starches (with high contents of amylose and resistant starch) showed low and similar swelling solubility values for all of the samples. Gelatinisation temperatures were also similar (61.5-63.0 °C), but the enzymatic method induced lower consistencies at 95 °C and after holding at this temperature. High values of setback were found, which were clearly affected by the isolation method. This parameter presented lower values for starches isolated by alkaline method (160 BU and 235 BU, respectively for Martainha and Longal). Starches did not present a peak consistency during pasting. Turbidity and synaeresis values were low at room temperature. Synaeresis increased when pastes were stored at low temperatures. This effect was more evident for the material isolated by enzymatic method. All of the isolation starches presented low enthalpy values (3.0-3.5 J/g), but the activation energy was higher for Martainha starches and for starches isolated by A3S method. Pastes showed viscoelastic behaviour, with a predominance of elastic property, forming strong gels after cooling. Longal variety seems to be less resistant to the effect of isolation method. In general starches isolated by the alkali method present the best functional properties as a food ingredient.     

Structural characteristics and in vitro digestibility of Mango kernel starches (Mangifera indica L.)

Structural characteristics and digestibility of starches isolated from the kernels of two mango cultivars (Chausa and Kuppi) were studied and compared with those of a commercial normal corn starch. Mango kernel starches showed an A-type X-ray diffraction pattern, with relative crystallinities of 35.4% and 38.3%, respectively for Kuppi and Chausa cultivars. The structural characterisation obtained, using high performance size exclusion column chromatography connected to multi-angle laser light scattering and refractive index detectors (HPSEC-MALLS-RI), revealed that the mango kernel starches had lower molecular weight (M_w) and radius of gyration (R_g) of amylopectin and amylose compared to those of corn starch. The M_w of amylopectin for Chausa and Kuppi starches were 179 × 10⁶ and 140 × 10⁶ g/mol, respectively. The amounts of readily digestible starch (RDS) and slowly digestible starch (SDS) were lower for mango kernel starch than those of corn starch. Resistant starch (RS) contents in the mango kernel starches (75.6% and 80.0%, respectively) were substantially higher than those of corn starch (27.3%). The glycemic index (GI) values for mango kernel starches were 48.8 and 50.9 (for Chausa and Kuppi, respectively), whereas that of corn starch was 74.8, indicating that the mango kernel starch granules were highly resistant to digestion with significant contents of RS.     

Properties of protease-treated maize starches

Commercially produced maize starches were treated with protease (Promod 25P) and their composition and properties were compared with untreated controls. It was found that, although protease treatment reduced the starch protein contents by 41%, 21% and 37% for the waxy, normal and amylomaize starches, respectively, it also caused some pits on the granule surfaces, which were evident by scanning electron microscopy (SEM), but no obvious decrease in granule dimensions (Coulter Counter Multisizer). The protein extraction was associated with decreases in starch lipid content by 42%, 40% and 45% (waxy, normal and amylomaize starches, respectively) and a decrease in total amylose content (30.7–26.0%) for the normal maize starch. The gelatinisation parameters of the starches by differential scanning calorimetry (DSC) in water, 0.001 M HCl or NaOH were less obviously affected by protease treatment in common with the swelling factors at 80 °C. The amount of α-glucan leached by the swollen (80 °C) granules was, however, increased by the protease treatment by factors of 3.8, 1.4, and 1.1, for the waxy, normal and amylomaize starches, respectively. Although proteases provide a useful tool for the purification of native starches, commercial protease preparations need to be controlled in terms of amylase content to prevent modifications to starch structure and properties during industrial processing.     

Nonthermal starch hydrolysis using ultra high pressure: I. Effects of acids and starch concentrations

Corn starches with 2 mol/l hydrochloric acid (HCl), 2 mol/l sulfuric acid (H₂SO₄) and 2 mol/l oxalic acid (C₂H₂O₄) were pressurized at 600 MPa for 30 min. Corn starch with C₂H₂O₄ formed a gel after ultra-high-pressure (UHP) treatment. Corn starch with HCl showed partial disintegration but starch with H₂SO₄ maintained its shape. Corn starch with HCl showed higher (0.42-0.47) degree of hydrolysis compared to starch with C₂H₂O₄ (about 0.14) and H₂SO₄ (0.13-0.14) regardless of increasing starch concentration up to 20 g/100 g sample. Main component of starch hydrolysate was maltose for HCl and oligosaccharides for H₂SO₄ and C₂H₂O₄. Crystallinity of starch with HCl decreased with decreasing starch concentration as observed by both differential scanning calorimetry (DSC) and X-ray diffraction. Therefore, UHP can be used for nonthermal starch hydrolysis and HCl would be a good catalyst for UHP starch hydrolysis compared to H₂SO₄ and C₂H₂O₄. This work provides a potential of nonthermal UHP processing for new starch hydrolysis method.