Characterization of starches isolated from Mexican pulse crops: Structural, physicochemical, and rheological properties.

This work aimed to characterize and compare the physicochemical properties of four pulse starches: bean, chickpea, lentil, and pea. Chemical proximate analysis, elemental composition, morphological grain characterization, crystalline structure, thermal analysis, FTIR analysis, and pasting properties were conducted. The proximate analysis shows that these starches have low fat, mineral, and protein content but high amylose values ranging from 29 to 36 % determined by colorimetry. Despite the high amylose content, the starches did not exhibit the typical behavior of an amylose-rich starch, with high peak viscosity and low breakdown and setback. It was found that this behavior was likely due to the large granule size of the ellipsoidal, spherical, and kidney-shaped granules and the high content of some minerals such as Na, Mg, K, Fe, Mn, P, and Si. The study also found that all pulse starches simultaneously contain monoclinic and hexagonal crystals, making them C-type starches. The findings were verified through the Rietveld analyses of X-ray diffraction patterns and differential scanning calorimetry, in which bimodal endothermic peaks evidenced both types of crystals being gelatinized.

Cassava starch esterification with formic acid for fabrication of electrospun fibers.

Formic acid is utilized to induce esterification and chemical gelatinization in starch, particularly in the fabrication of electrospun fibers for nanomaterial production. This study investigated the impact of different concentrations (15, 20, 25, and 30 %) of cassava starch and formic acid as a solvent on the characteristics of the resultant polymeric solutions and electrospun fibers. Morphology, size distribution, thermogravimetric properties, diffraction patterns, and relative crystallinity were evaluated for the electrospun fibers. The amylose content of starch varied from 16.5 to 23.7 %, decreasing with esterification, achieving a degree of substitution of approximately 0.93. The solution-rheology exhibited elastic behavior, with viscosity increasing as starch concentration increased, hindering the fabrication of fibers at 25 and 30 % starch. Successful electrospun fibers were formed using 15 % and 20 % starch, displaying homogeneous morphologies with mean diameters of 165 nm and 301 nm, respectively. Esterification influenced thermogravimetric properties, leading to fibers with reduced degradation temperatures and mass loss compared to native starches. The electrospun fibers presented an amorphous structure, indicating a drastic reduction in relative crystallinity from 35.2 % in native starch to 8.5 % for esterified starches. This study highlights the intricate relationship between starch concentration, esterification, and solution viscosity, affecting the electrospinnability and properties of starch-polymeric solutions.

Impact of cyclic and continuous dry heat modification on the structural, thermal, technological, and in vitro digestibility properties of potato starch (Solanum tuberosum L.): A comparative study.

Dry heat treatment (DHT) has been demonstrated as a viable method for starch modification, offering benefits due to its environmentally friendly process and low operational costs. This research modified potato starch using different DHT conditions (continuous-CDHT and cyclic-RDHT), with durations ranging from 3 to 15 h and 1 to 5 cycles, at 120 °C. The study investigated and compared the structural, thermal, pasting, and morphological properties of the treated samples to those of untreated potato starch, including in vitro digestibility post-modification. DHT altered the amylose content of the biopolymer. X-ray diffraction patterns transitioned from type B to type C, and a decrease in relative crystallinity (RC%) was observed. Morphological changes were more pronounced in starches modified by RDHT. Paste viscosities of both CDHT and RDHT-treated starches decreased significantly, by 61.7 % and 58.1 % respectively, compared to native starch. The gelatinization enthalpy of RDHT-treated starches reduced notably, from 17.60 to 16.10 J g-1. Additionally, starch digestibility was impacted, with cyclic treatments yielding a significant increase in resistant starch content, notably an 18.26 % rise. These findings underscore the efficacy of dry heat in enhancing the functional properties of potato starch.

Structural analysis of potato starch transformation during high-energy ball-milling: Oxygen and humidity content effects.

High Energy Ball-Milling (HEBM) modifies starchs' granule morphology, physicochemical properties, and chemical structure. However, understanding how the HEBM changes the starch chemical structure is necessary to control these modifications. Therefore, this study aimed to investigate the changes in potato starch's long- and short-range molecular order during HEBM at different environmental conditions such as oxygen (Air) and humidity content. Due to the correlation between the starch modification and the energy supplied (Esupp) by the HEBM, Burgio's equation was used to calculate this energy. The starch transformation was followed by X-ray diffraction, Fourier Transform-Infrared Spectroscopy, and Raman spectroscopy. A Principal Component Analysis (PCA) was conducted to reduce the HEBM variables. PAC analysis demonstrated that the different oxygen-humidity conditions do not affect the HEBM of potato starch. Based on the starch chemical structure transformation correlated with Esupp during HEBM, four stages were observed: orientation, modification, mechanolysis, and over-destruction. It was identified for the first time that at low milling energy (<1.5 kJ/g, orientation stage), the glycosidic rings change their orientation, and starch-water interaction increases while the starch's organization reduces. Ergo, the potato starch could be more susceptible to chemical modifications during the first two stages.

Natural fermentation of potato (Solanum tuberosum L.) starch: Effect of cultivar, amylose content, and drying method on expansion, chemical and morphological properties.

Natural fermentation with sun-drying is a modification that promotes the expansion capacity of starch, and its effects on potato starch have not been reported so far. The aim of this study was to evaluate the effects of the amylose content of potato (Solanum tuberosum L.) starches and natural fermentation followed by oven or sun drying on its properties. Cassava starch was also used a control. Native and fermented starches were evaluated based on their chemical composition, amylose, carboxyl and carbonyl content as well as their thermal, pasty, and morphological properties. The fermentation water was evaluated by pH and titratable acidity to control the process. Puffed balls were prepared to evaluate expandability, mass loss, porosity and texture. The fermentation intensity was greater for potato and cassava starch with low-amylose content than for potato starch with higher amylose content. In addition, the acidity of the fermentation water increased faster with cassava starch than with potato starches. The fermented potato starches with the highest amylose content had low acidity and low expansion capacity compared to the fermented potato and cassava starches with low-amylose content. Fermentation and sun-drying of low-amylose potato and cassava starches increased the expansion and reduced the hardness of the puffed balls.

Morphological, textural analysis and freeze-thaw stability of starches from legume grow in Cameroon.

Starches from some legume grown in Cameroon were evaluated for their granule structure and size, turbidity, firmness and gel strength, thermal and freeze-thaw properties. Amylose contents were in the range of 26.21%-44.85%. Morphological analysis of the starch granules showed bimodal distribution, multiple sizes and shapes from small spherical to the bigger kidney shape. Significant differences were observed among starch in light transmittance, firmness and gel strength. The thermal parameters of starches were evaluated using differential scanning calorimeter and significant differences were observed. The peak gelatinisation temperature was positively correlated to starch granule size but the amylose content showed no evidence of their impact on legume starch properties studied. The data reported can be useful to facilitate the selection of variety of legume and conditions closer to the desired application.

Effect of high-energy mechanical milling on the physicochemical and rheological properties of chayotextle (Sechium edule Sw.) starch.

This work evaluates the effect of high-energy mechanical milling time (7 levels, 20-80 min) on amylose content, crystallinity pattern, temperature and gelatinization enthalpy, morphology, and rheological properties of chayotextle (Sechium edule Sw.) starch. After 30 min of milling, granular structure was affected, and amylose values were the highest while crystallinity and gelatinization enthalpy decreased significantly. These changes allowed to obtain gels with viscoelastic properties where the elastic character (Ç´) prevailed upon the viscous modulus (Ǵ́). Native starch showed Tan δ values of 0.6, increased significantly (0.9) after 30 min of milling due to the surge in linear chains (amylose) and loss of granular structure. Native and modified starches showed high dependence on cutting or shear speed, presenting a non-Newtonian behavior (reofluidizers). These results indicate that mechanical grinding is an alternative to obtain modified starches with applications in the food industry.

Effect of adding high concentrations of retrograded starch with different amylose content on the physicochemical properties and sensory attributes of Greek-style yogurt.

It is well known that using retrograded starches confers many technological advantages, as well as health benefits when consumed in adequate doses; however, these properties are closely related to the type of starch and/or the treatment applied, therefore, it is of interest to add retrograded starch to popular products such as Greek yogurt. The aim of this work was to investigate the effect of adding two types of retrograded corn starch with different amylose content to a non-strained type of Greek-style yogurt. Retrograded starch from starch containing 27 % (RNS) or 70 % (RHS) amylose was added to yogurt at 0, 10, 12.5, or 15 g/100 g before storage at 4 °C for 14 d. The resistant starch (RS) content, pH, syneresis, flow behavior index, and consistency index, were measured every week. A sensory test was carried out in yogurt added with 12.5 g/100 g of retrograded starches to evaluate acceptance. Adding retrograded starch significantly reduced syneresis while increased the consistency, firmness, and resistant starch content of the yogurt. No significant differences in general acceptance were observed in samples added with RNS when compared to the control. Although a significant difference was observed after adding RHS, the acceptance of the product is still convenient. Adding a high concentration of retrograded starch could help to ensure doses enough for a prebiotic effect of RS with concentrations of 1.74 ± 0.37 to 2.32 ± 0.09 g/100 g and from 3.5 ± 0.08 to 4.21 ± 0.08 g/100 g when RNS or RHS is added respectively, while maintaining the quality characteristics of Greek-style yogurt during storage without compromising the acceptability.

Impact of Cassava Starch Varieties on the Physiochemical Change during Enzymatic Hydrolysis.

The enzymatic modification of starch extends its industrial use to flavor delivery and probiotic encapsulants, among other uses. However, it is not known how starch from different cassava varieties responds to enzymatic hydrolysis. Starches from two Ecuadorian cassava varieties (INIAP 650, an edible starch, and INIAP 651, an industrial starch) were partially modified at three enzymatic hydrolysis degrees (0%, 30%, and 50%), and their physicochemical properties were assessed. The structural analysis revealed that both varieties showed progressive structural damage as hydrolysis increases, probably due to exo-hydrolysis. However, deeper pores were observed in INIAP 651 with the SEM analysis. The crystallinity percentage obtained by XRD analyses remained constant in INIAP 651 and decreased (by 26%) in INIAP 650 (p < 0.05). In addition, the amylose−lipid complex index in INIAP 650 remained constant, while INIAP 651 increased (p < 0.05) at 30% hydrolysis (by 93%). In both varieties, hydrolysis increased (p < 0.05) the water holding capacity (WHC) (by 10−14%) and the water binding capacity (WBC) (by 16%), but 50% hydrolysis of INIAP 650 was needed to significantly affect these properties. No differences were observed in the varieties' thermal properties. Regarding the rheological properties, the variety did not influence the changes in the storage module (G') and the loss modulus (G″) with the hydrolysis (p > 0.05). However, the phase angle decreased significantly (p < 0.05) with the hydrolysis, being higher in the INIAP 650 variety than in the INIAP 651 variety. In general, the results indicate that the variety affects the response of the starch granule to enzymatic hydrolysis (noticeable in the principal component analysis, PCA) and opens up the possibility to modulate starch properties.

Effect of Microwave Irradiation on Acid Hydrolysis of Faba Bean Starch: Physicochemical Changes of the Starch Granules.

Starch is the most abundant carbohydrate in legumes (22-45 g/100 g), with distinctive properties such as high amylose and resistant starch content, longer branch chains of amylopectin, and a C-type pattern arrangement in the granules. The present study concentrated on the investigation of hydrolyzed faba bean starch using acid, assisted by microwave energy, to obtain a possible food-grade coating material. For evaluation, the physicochemical, morphological, pasting, and structural properties were analyzed. Hydrolyzed starches developed by microwave energy in an acid medium had low viscosity, high solubility indexes, diverse amylose contents, resistant starch, and desirable thermal and structural properties to be used as a coating material. The severe conditions (moisture, 40%; pure hydrochloric acid, 4 mL/100 mL; time, 60 s; and power level, 6) of microwave-treated starches resulted in low viscosity values, high amylose content and high solubility, as well as high absorption indexes, and reducing sugars. These hydrolyzed starches have the potential to produce matrices with thermo-protectants to formulate prebiotic/probiotic (symbiotic) combinations and amylose-based inclusion complexes for functional compound delivery. This emergent technology, a dry hydrolysis route, uses much less energy consumption in a shorter reaction time and without effluents to the environment compared to conventional hydrolysis.

Supramolecular structure and technofunctional properties of starch modified by high hydrostatic pressure (HHP): A review.

This review focuses on describing and discussing recent findings regarding the effects of high hydrostatic pressure (HHP) on the supramolecular structure and technofunctional properties of starch, as well as on analyzing the hypothesis to explain these changes. The non-thermal modification of starch through HHP involves complex supramolecular structural changes that depend on the botanical source, amylose content, and treatment intensity. Overall, the granular morphology, lamellar and crystalline structures, and double helices undergo different degrees of modification/disorganization during HHP, but these changes are distinguished from thermal modification by an improvement at the same gelatinization degree. The HHP-induced supramolecular modifications determine the properties of starch, including water solubility, swelling power, pasting, water and oil holding capacity, thermal properties, and in vitro digestibility.

Influence of physicochemical changes of the avocado starch throughout its pasting profile: Combined extraction.

This work focused on studying the effect of lamellae presence on the pasting profile of isolated avocado starch (C-type) obtained by a combined mechanical and ultrasonic process. Inductively Couple Plasma indicates that this starch is rich in P, K, Na, and Ca. This starch exhibits the most crystalline structure reported so far. The correlation between the morphological and structural properties throughout its pasting profile explains its apparent viscosity behavior. Granules exhibit a non-conventional irregular morphology with sizes ranging from 35 to 40 µm in their long side. DSC reveals endothermal transitions at 68 °C and 119 °C associated with the nanocrystals solvation and amylose-lipid complex, respectively. After gelatinization, the presence of lamellae originated from the partial fragmentation of the crystals. The pasting end exhibited a combined behavior between custard and hydrogel. This correlation could be considered a new methodology to understand the pasting behaviors in any starch.

Stability of fumonisin B1 and its bioaccessibility in extruded corn-based products.

Fumonisins are a group of mycotoxins commonly associated with corn-based products and require innovative alternatives to control exposure to its toxicity. The objective of this research was to determine the effect of amylose and resistant starch on fumonisin B1 (FB1) levels in extruded corn-based products as well as the toxin bioaccessibility upon digestion. Cornmeal contaminated with FB1 (1.5 µg/g) was extruded alone or combined with high-amylose corn starch (20%, w/w). FB1 was quantified both in the unextruded and extruded products by HPLC (high-performance liquid chromatography) fluorescence detector with pre-column derivatization. Samples were then subjected to an in vitro digestion model to evaluate the stability of the interaction between FB1 and the corn matrix extruded. The addition of high-amylose corn starch further reduced the detection of FB1 (74.9%), when compared with the effect of the extrusion alone (66.0%), confirming the binding of FB1 with the macromolecules or resistant starch. The bound fumonisin was stable upon simulated gastric digestion, and the duodenal bioaccessibility of free FB1 was lower than 35% when high-amylose corn starch ingredient was used in the product. Principal component analysis (PCA) showed that high-amylose corn starch and resistant starch content influenced the reduction of FB1 and its duodenal bioaccessibility. This study for the first time shows that addition of high-amylose corn starch during extrusion is an innovative strategy to reduce FB1 release under digestive conditions, therefore useful in mitigating the exposure to this mycotoxin.

Characterization of starches obtained from several native potato varieties grown in Cusco (Peru).

Ten native potato varieties grown in Cusco (at 3,672 m above sea level) were used for starches extraction (at a pilot scale), and their physicochemical, functional, morphological, and structural characteristics were assessed. The content of protein, apparent amylose and phosphorus ranged from 0.1% to 0.44%, 23.42% to 35.5%, and 0.07 to 0.10%, respectively. Starch granules revealed smooth surface, with ellipsoidal and spherical shapes, particle size analysis exhibited bimodal or multimodal distribution, while the averaged crystallinity was 27.7% assessed by XRD. Gelatinization temperatures of the starches ranged from 57.4 to 60.1 °C, 60.8 to 64.3 °C, and 68.4 to 71.1°C for To, Tp, and Tc, respectively; and the gelatinization enthalpies ranged from 15.4 to 17.1 J/g. Respect to pasting properties, the peak viscosity and setback viscosity ranged from 12,970 to 16,970 mPa⋅s and from 968 to 2498 mPa⋅s, respectively. Thermogravimetric analysis (TGA) revealed no significant relationship between apparent amylose content and thermal stability. Therefore, the results reveal subtle differences in the functional characteristics of the starches from the native varieties of potato studied, which can be recommended for food industry applications. PRACTICAL APPLICATION: This study contributes to show several varieties of native potatoes from Cusco and their valorization as nonconventional starch source. Describing the physicochemical, functional, and structural characteristics of these starches could be useful for food industry applications.

Ariá (Goeppertia allouia) Brazilian Amazon tuber as a non-conventional starch source for foods.

Ariá (Goeppertia allouia) is a tuber from the arrowroot's family widely found in the Brazilian Amazon. The tuber has a flavor similar to corn, besides high retrogradation when cooked, differing from other commercial starches. To enhance its added value, the Ariá starch was extracted to evaluate its potential as a food ingredient. The Ariá starch was compared to the commercially available corn and potato starches regarding their physicochemical, thermal, structural, and rheological properties based on the Duncan's test (p-value <0.05). The Ariá starch presented high amylose content (~38% w/w). Furthermore, the X-ray diffraction pattern confirmed its Type-C crystalline structure. The rheological properties showed that the starch gels presented high hardness and retrogradation as other studied starches. Ariá has great potential as a source of starch with low digestibility, increasing the satiety of food products.

Study of enantioseparation of ß-blockers using amylose tris(3-chloro-5-methylphenylcarbamate) as chiral stationary phase under polar-organic, reversed-phase and hydrophilic interaction liquid chromatography conditions.

In this study, we describe the experimental variables influencing enantioseparation of twelve ß-blockers when analyzed under polar-organic, reversed-phase and hydrophilic interaction liquid chromatography conditions on a column with immobilized amylose tris(3-chloro-5-methylphenylcarbamate) as chiral stationary phase. Regarding polar-organic mode, two component mobile phases consisting of methanol, ethanol or acetonitrile with the addition of basic additives such as diethylamine, triethylamine, mono-ethanolamine, ethylendiamine or trifluoroacetic acid/diethylamine mixture were evaluated. Studies of retention at different temperatures were also performed. In reversed-phase mode, mixtures consisting of methanol or acetonitrile with either aqueous boric acid-borate buffer or sodium hydrogen carbonate-carbonate buffer solutions were compared aiming to study the influence of organic modifier as well as buffer type and pH on resolution. In addition, a systematic evaluation of the retention factors of ß-blockers enantiomers in hydro-organic eluents containing acetonitrile in presence of diethylamine as additive was carried out by increasing progressively the water content, in order to check for retention dependencies indicative of the interplay of both hydrophilic interaction liquid chromatography and reversed-phase modes.

Amylose-lipid complex formation from extruded maize starch mixed with fatty acids.

Functional modifications of starch, such as paste properties, retrogradation, water absorption indexes, solubility, and swelling capacity, are induced by the amylose-lipid complex. This research comprehends the study of functional properties of extruded maize starch mixed with fatty acids (stearic acid, oleic acid, and maize oil) and the formation of amylose-lipid complexes. Maize starch with lipids (5 or 10 %), moisture (35 %) was extruded (single screw). Starch granule was modified by extrusion, to a lesser extent at 10 % of lipids, especially stearic acid, which covers starch granule surface. Viscosity decreased meaningfully with stearic acid addition. DSC showed both starch gelatinization enthalpy and amylose-lipid complex enthalpy for stearic or oleic acid, but it was just the first enthalpy for maize oil. X-ray diffraction showed orthorhombic crystals with or without the presence of lipids. Our results indicated that stearic acid yielded the highest amount of amylose-lipid complexes.

Chiral separation of several pesticides on an immobilized amylose tris(3-chloro-5-methylphenylcarbamate) column under polar-organic conditions. Influence of mobile phase and temperature on enantioselectivity.

In this work, the use of different solvents and temperatures was explored, aiming to evaluate their influence on the enantioseparation of pesticides by HPLC in polar-organic conditions, employing a column containing immobilized amylose tris(3-chloro-5-methylphenyl-carbamate). The chiral separation of seventeen different pesticides widely used as herbicides, fungicides, insecticides and precursors were studied. The mobile phases included methanol, ethanol, iso-propanol, n-propanol and acetonitrile; either pure or containing additives such as diethylamine, trifluoroacetic acid, formic acid, acetic acid or mixtures thereof. We studied the influence of these eluents on chiral separation of those pesticides in terms of retention factor, enantioselectivity, enantioresolution and peak symmetry. Regarding temperature influence, evaluated within the range 5 - 40 °C, nearly all the compounds decreased their retention and selectivity factors with the increase in temperature, although the effect was dependent on the mobile phase solvent. Moreover, estimation of thermodynamic parameters was performed based on linear van´t Hoff plots.

Extraction and characterization of starches from pigmented rice.

The aim of this work was to extract and characterize starch from three varieties of pigmented rice (named white, red and black), preserving the bioactive compounds. The extraction yield was 44.0%, 47.0% and 35.7%, respectively. The scanning electron microscopy showed that the granules of the three varieties presented polygonal and angular format and absence of impurities. The chemical analyzes, showed more than 83.0% of carbohydrates in the three compositions. There was retention of the phenolic compounds from the raw material in the starches. With regard to pasting properties of the starches, differences were observed in initial temperature, which was of 80.6 °C, 79.1 °C and 88.8 °C for the starches of white, red and black rice, respectively. Black rice starch also showed slightly higher crystallinity and thermal stability than white and red rice starches. Gels of red rice starch have higher syneresis in five freeze-thaw cycles, when compared to the others.

Influence of germination time on the morphological, morphometric, structural, and physicochemical characteristics of Esmeralda and Perla barley starch.

The aim of this study was to analyzing the impact of germination time on the morphology, crystallinity, gelatinization and viscosity properties on the starch of Esmeralda and Perla barley variety. The two barley were germinated for 1 to 8 days, at 26 °C and 65% relative humidity. Micrographs showed the presence of pinholes and eroded surfaces. Starch in Esmeralda was hydrolyzed completely at 8 days of germination. Birefringence was reduced from day 4, losing molecular structuring of the crystalline area. Morphometric data: fractal dimension, area, perimeter, circularity, and roundness decreased significantly along germination time in both varieties. The entropy increased significantly, from 0.79 to 10.09 in Esmeralda and from 0.46 to 7.57 in Perla. Relative crystallinity decreased significantly in the Perla from 24.7% to 23.6%. Viscosity peaks were also significantly reduced, pasting temperature was constant in Esmeralda but in Perla was significantly reduced from 95.43 to 95.19 °C with germination, the gelatinization temperature increased significantly in the Esmeralda while in Perla it remained constant. Enthalpy decreased significantly to 75.8% and 37% in Esmeralda and Perla respectively. The study of germination impact on structural and physicochemical properties is important to identify the use of hydrolyzed starches in the food industry or others.