Functional properties of starch cultivars of two Andean grains grown in Bolivia: Amaranth (Amaranthus caudatus) and canihua (Chenopodium pallidicaule).

The functional properties of Andean grain starches of two species, amaranth (Amaranthus caudatus) and canihua (Chenopodium pallidicaule), three cultivars each, were studied. The study focused on chemical composition, pasting properties, thermal properties, water solubility index (WSI), swelling power (SP), and granule morphology. All amaranth starches were waxy starches, with amylose content less than 5 %, which had some differences in chemical composition (p < 0.05). The pasting properties differed between the species, canihua showed more resistance, than amaranth, to heat and shear stress (higher cool paste (CPV) and lower breakdown (BD), ranged between 1250 and 1600 cP and -30 - 10 cP respectively. The amaranth starches presented only similar CPV with 800-1000 cP, while canihua cultivars presented similar PT and BD, and both species presented similar PV, around 1000 cP. Thermal properties (To, Tp, Tc, ΔH, and ΔT) differed among cultivars and species. These differences could be related to the homogeneity molecular structure and content of amylose in canihua cultivars and possibly to genotype factor. Polygonal shapes were the predominant shape of starch granules, ranged 1.0-1.4 µm and 0.8-0.9 µm, for amaranth and canihua starches respectively. Amaranth starches swelled quickly to disintegrate partially at the end, contrary to canihua starches. The thermal and pasting properties were correlated between them. SB, CPV, HPV, CS, were correlated to the content of amylose in canihua starches. One amaranth cultivar was significantly different from the others. Thus, according the functional properties differenced both species and some cultivars in each species. Additionally, the amaranth starch has the potential to be used in the food industry where heat and stress are applied such as extrusion, while canihua starches can be used in desserts or in cosmetic uses, based on their functional properties.

The waxy mutation in sorghum and other cereal grains reshapes the gut microbiome by reducing levels of multiple beneficial species.

Waxy starches from cereal grains contain >90% amylopectin due to naturally occurring mutations that block amylose biosynthesis. Waxy starches have unique organoleptic characteristics (e.g. sticky rice) as well as desirable physicochemical properties for food processing. Using isogenic pairs of wild type sorghum lines and their waxy derivatives, we studied the effects of waxy starches in the whole grain context on the human gut microbiome. In vitro fermentations with human stool microbiomes show that beneficial taxonomic and metabolic signatures driven by grain from wild type parental lines are lost in fermentations of grain from the waxy derivatives and the beneficial signatures can be restored by addition of resistant starch. These undesirable effects are conserved in fermentations of waxy maize, wheat, rice and millet. We also demonstrate that humanized gnotobiotic mice fed low fiber diets supplemented with 20% grain from isogenic pairs of waxy vs. wild type parental sorghum have significant differences in microbiome composition and show increased weight gain. We conclude that the benefits of waxy starches on food functionality can have unintended tradeoff effects on the gut microbiome and host physiology that could be particularly relevant in human populations consuming large amounts of waxy grains.

Improved Hydrolysis of Granular Starches by a Psychrophilic α-Amylase Starch Binding Domain-Fusion.

Degradation of starch granules by a psychrophilic α-amylase, AHA, from the Antarctic bacterium Pseudoalteromonas haloplanktis TAB23 was facilitated by C-terminal fusion to a starch-binding domain (SBD) from either Aspergillus niger glucoamylase (SBDGA) or Arabidopsis thaliana glucan, water dikinase 3 (SBDGWD3) via a decapeptide linker. Depending on the waxy, normal or high-amylose starch type and the botanical source, the AHA-SBD fusion enzymes showed up to 3 times higher activity than AHA wild-type. The SBD-fusion thus increased the density of enzyme attack-sites and binding-sites on the starch granules by up to 5- and 7-fold, respectively, as measured using an interfacial catalysis approach that combined conventional Michaelis-Menten kinetics, with the substrate in excess, and inverse kinetics, having enzyme in excess, with enzyme-starch granule adsorption isotherms. Higher substrate affinity of the SBDGA compared to SBDGWD3 was accompanied by the superior activity of AHA-SBDGA in agreement with the Sabatier principle of adsorption limited heterogenous catalysis.

Interactions of soy protein isolate with common and waxy corn starches and their effects on acid-induced cold gelation properties of complexes.

Soy protein isolate (SPI) was mixed with different concentrations of common starch (CS) and waxy starch (WS) from corn. The interactions of SPI with CS or WS and their effects on the acid-induced cold gelation properties of complexes were investigated. Compared with WS, SPI could bind to CS more strongly and formed a tighter SPI-CS non-covalent complex, which resulted in the increased ß-sheet and a more ordered secondary structure. The gel strength, water holding capacity (WHC), viscoelasticity, hydrophobic interactions and thermal stability of SPI-CS complex gels were enhanced as increasing CS concentration, and the complex with 2% of CS had the best gelation properties. Although adding WS reduced the gel strength, rheological properties and hydrophobic interactions of SPI-WS complex gels, it improved the WHC and thermal stability of the complex gels. Therefore, CS had a broader effect on improving acid-induced cold gelation properties of SPI than WS.

Synthesis and Characterization of Novel Patchouli Essential Oil Loaded Starch-Based Hydrogel.

Starch hydrogels are highly available, biocompatible and biodegradable materials that have promising applications in medical and pharmaceutical industries. However, their applications are very limited due to their poor mechanical properties and fragility. Here, we investigated, for the first time, conventional corn and waxy corn starch-based hydrogels for loading patchouli essential oil. The essential oil extracted by supercritical carbon dioxide with a yield reached 8.37 ± 1.2 wt.% (wet sample) at 80 °C temperature and 10 MPa pressure. Patchouli essential oil exhibited a 23 to 28 mm zone of inhibition against gram-positive and gram-negative bacteria. Waxy starch hydrogels had better properties in term of viscosity, water evaporation stability and the delivery of essential oil than conventional starch hydrogels. The viscosity and spreadability of a 6% waxy starch sample were 15,016 ± 59 cP and 4.02 ± 0.34 g·cm/s, respectively, compared with those of conventional starch hydrogel (13,008 ± 29 cP and 4.59 ± 0.88 g·cm/s). Waxy starch-based hydrogels also provided slower in vitro biodegradation behavior and sustained release of essential oil compared with conventional starch hydrogels. All the samples were biocompatible and non-cytotoxic to fibroblast cells; the addition of patchouli essential oil enhances the proliferation of the cells. The enhanced viscosity, good antibacterial and improved biocompatibility results of prepared hydrogels confirm their suitability for wound healing applications.

Revealing substitution priority and pattern of octenylsuccinic groups along the starch chain under a continuous mode.

Octenylsuccinic (OS) groups distribution was considered random under traditional batch mode (BM) process due to excessive available octenyl succinic anhydride (OSA) at early stage, making the functionality optimization of OSA starch under restricted substitution degree (DS) difficult. To reveal the priority rule of substituent position at starch molecular level, a continuous mode (CM, dropwise OSA addition) was applied for OSA starch preparation. Initial OSA substitution was predominately at the branching points of amylopectin backbone, then successive at the branching points of shorter and longer chains with increasing DS. As DS increased over 1.49%, substitution started occurring along the chains and moved towards the non-reducing ends until DS reached 6.65%. At similar DS, more branching point substitutions occurred at CM starch, showing superior emulsifying property over BM starch. OSA substitution priority rule does exist under controlled OSA supply, which would facilitate OSA starch design with specific substitution pattern and favored functionality.

Evaluation of alginate-biopolymers (protein, hydrocolloid, starch) composite microgels prepared by the spray aerosol technique as a carrier for green tea polyphenols.

Effects of low methoxyl pectin, milk protein concentrate (MPC), and waxy starch on the encapsulation of green tea-polyphenols in alginate gels produced using spray aerosol technique were evaluated. MPC and waxy starch treated first by cold-renneted induced gelation method and gelatinization method, respectively. DSC thermal analysis and FTIR spectroscopy were used to prove the presence of polyphenols in gel matrixes. The encapsulation efficiency (%EE) and the polyphenols release were investigated using Folin-Ciocalteu assay. The results showed that the addition of biopolymers into alginate gels increased the encapsulation efficiency (%EE) but reduced the release percentage of polyphenol in water and simulated gastric fluid (SGF). Among the three biopolymers, cold-renneted MPC gave the best protection for polyphenols encapsulated in alginate microgels. It increased %EE from 63% to 68% in fresh gels, reduced the release percentage in water from 72% to 62% and reduced the release percentage in SGF from 76% to 67%.

Water Behavior of Aerogels Obtained from Chemically Modified Potato Starches during Hydration.

Aerogels are highly porous materials that are prepared by removing water held within a hydrogel in a manner that maintains the three-dimensional structure of the gel. Recently, there has been much interest in the preparation of aerogels from biopolymers, including starch. The applicability of native starches in the food industry is partially limited; therefore, the functional properties of starch are often improved by means of physical and/or chemical modification. The aim of the work was the analysis of molecular dynamics and the transport of water in aerogels obtained from native and chemically modified potato starches of the normal and waxy variety. Chemical modification with OSA (E 1450) as well as cross-linking with adipic anhydrite and acetylation (E 1422) had no significant impact on the hydration of potato starch aerogels as well as equilibrium water activity. The introduction of chemical moieties into starch macromolecules led to the improved binding of water by the biopolymer matrix; this was especially evident in the case of waxy starch derivatives. A increase in the amylopectin-to-amylose ratio of starch used for production of aerogels resulted in a decrease of equilibrium water activity along with spin-lattice relaxation time.

Formation and structural evolution of starch nanocrystals from waxy maize starch and waxy potato starch.

The formation and structural evolution of starch nanocrystals from waxy maize starch (WMS) and waxy potato starch (WPS) by acid hydrolysis were studied. The relative crystallinity, the short-range molecular order, and the double-helix content of WMS and WPS increased significantly during the initial stage of acid hydrolysis, indicating that acid preferentially eroded the amorphous regions of starch granules. With time, there was increased destruction of lamellar structures, causing the granules to completely disintegrate to form nanocrystals. WMS and WPS displayed different hydrolysis mechanisms. WPS was more susceptible to acid hydrolysis than WMS, and WMS exhibited an endo-corrosion pattern and WPS showed an exo-corrosion pattern. WMS nanocrystals had a parallelepiped shape, and WPS nanocrystals were round. This difference in shape is likely due to the different packing configuration of double helices in native starches.

Investigating the potential of slow-retrograding starches to reduce staling in soft savory bread and sweet cake model systems.

The potential anti-staling property of starches with slow-retrograding amylopectin was studied in soft wheat bread and cake model systems. Normal rice, waxy rice, and wheat starches were processed by drum drying or extrusion, and native starch was used as a comparator. Extrusion processing causing amylopectin fragmentation can reduce intermolecular retrogradation of rice starch. Starches were incorporated into model breads and cakes as partial replacements for flour on a dry weight basis (3 and 6% for cakes, 5 and 15% for breads). Starches pregelatinized by extrusion had moderate molecular fragmentation, as indicated by RVA and HPSEC-MALLS-RI. Starches previously shown to have lower intermolecular retrograding amylopectin (normal rice, waxy rice) resulted in minor to moderate reductions in hardness and other textural properties as indicated by texture profile analysis (TPA) in breads and cakes upon storage for up to 12 wk. A higher degree of starch fragmentation is suggested to produce lower staling. Incorporation of normal and waxy rice starches resulted in softer breads and cakes than wheat starch, which could be attributed to the shorter external and internal amylopectin chains of rice starch. Higher inclusion (15%) of slow-retrograding waxy rice in the bread model system showed the most potential for anti-staling property.

Thermal and pasting properties and digestibility of blends of potato and rice starches differing in amylose content.

In this study, waxy or normal potato starches (WPS or NPS) were blended with waxy, low-amylose or high-amylose rice starch (WRS, LARS or HARS) in different ratios (100:0, 80:20, 60:40, 40:60, 20:80 and 0:100). Pasting profiles of blends were additively between those of the component starches separately except for some mixtures of WRS and potato starches. Twin or even three gelatinization peaks were observed for potato-WRS or potato-HARS blend, while only one peak was observed in potato-LARS blend. Addition of WRS enhanced the nutritional profile of blends containing WPS by decreasing the rapidly digestible starch level. Microscopy revealed that addition of WRS was beneficial for the development of dense and compact structure of gels of blends compared with their counterparts, which may be because few amylose chains leached to inhibit the interaction between swollen potato and rice starch granules. Besides, peak, trough, breakdown and final viscosity as well as gelatinization enthalpy showed significantly negative correlations with amylose leaching. Non-additive behaviours were observed for properties, but more independent behaviour was observed between potato starch and LARS or HARS. Results suggested that properties of blends of potato and rice starches differing in amylose content varied through different extents of amylose leaching.

Functionality of Native Starches in Food Systems: Cluster Analysis Grouping of Rheological Properties in Different Product Matrices.

Industrial application of starch as a texture-forming agent is primarily limited to preparations obtained from waxy corn and potatoes. The main reason behind this is its functionality, which depends mostly on rheological properties. However, in food product matrices, these properties change. Despite the vast amount of information on the rheological properties of various starches, the rational choice of thickener appears to be an extremely difficult task. The aim of the work is to systemize the information on the rheological properties of most popular starches in matrices of various food products, applying principal component and cluster analyses. The investigated material is potato and corn starch of the normal and waxy varieties. Binary mixtures containing salts or sweetening agents, as well as four different food products (ketchup, mayonnaise, pudding, and jelly), are investigated. It was found that compared to normal varieties, waxy starches reveal many similar rheological properties in all investigated models and food systems. Furthermore, in most applications, one waxy starch variety may be substituted by another, with no significant impact on the rheological properties and texture of the food product. Moreover, waxy starch preparations are less altered by the presence of cosolutes, i.e., salts and sugar alcohols. Starch model systems were proven to be useful only for rapid thickener screening tests and cannot be recommended as a final reference for the quality design of food products.

Breeding buckwheat for nutritional quality.

Common buckwheat (Fagopyrum esculentum Moench, CB) and Tartary buckwheat (Fagopyrum tataricum (L.) Gaertn., TB) are used in human nutrition. The idea to screen in the haploid phase for genes affecting low amylose concentration opens the possibility for the effective search of low amylose (waxy) genotypes in CB populations. Self-pollinated homozygous plants of TB might allow us to use a part of endosperm for screening of amylose content. Phenolic substances have a significant inhibitory effect on the digestion of CB and TB proteins, thus metabolites may have impact on protein digestibility. Digestion-resistant peptides are largely responsible for the bile acid elimination. Breeding to diminish polyphenols and anti-nutritional substances might have negative effects on the resistance of plants against pests, diseases and UV-radiation. Bread and pasta are popular CB and TB dishes. During dough making most of CB or TB rutin is degraded to quercetin by rutin-degrading enzymes. The new trace-rutinosidase TB variety makes possible making TB bread with considerable amount of rutin, preserving the initial rutin from flour. Breeding CB and TB for larger embryos would make it possible to increase protein, rutin, and essential minerals concentration in CB and TB grain.

The effect of graded inclusions of waxy starch hull-less barley and a multi-component exogenous carbohydrase on the growth performance, nutrient digestibility and intestinal morphometry of broiler chickens.

1. A 21-d experiment was conducted to investigate the effect of graded inclusions of waxy starch hull-less (WSHL) barley and a multi-component exogenous carbohydrase on the growth performance, nutrient digestibility and intestinal morphometry of broiler chickens. Five levels of WSHL barley inclusion (0, 65, 130, 195 and 260 g/kg) in a wheat-based diet, and two levels of enzyme supplementation (0 and 150 g/tonne of feed) were evaluated in a 5 × 2 factorial arrangement of 10 dietary treatments. All diets were equivalent in metabolisable energy and digestible amino acid content. A total of 400, one-d-old male broilers (five cages/treatment; eight birds/cage) were used in the experiment. 2. Regardless of enzyme supplementation, feed intake declined (P < 0.001) with increasing inclusion of WSHL barley. Increasing levels of WSHL barley (P < 0.001) and supplemental enzyme (P < 0.01) increased gain to feed ratio. 3. Birds fed diets with 0 g/kg WSHL barley showed the lowest (P < 0.001 to 0.01) digestibility for all nutrients except starch. Only starch digestibility was improved (P < 0.05) by enzyme supplementation. The nitrogen-corrected apparent metabolisable energy improved with increasing inclusion of WSHL barley (P < 0.001) and supplemental enzyme (P < 0.001). Increasing inclusion of WSHL barley increased the relative weight of gizzard (P < 0.001) and reduced jejunal digesta viscosity (P < 0.01). Supplemental enzyme (P < 0.001) reduced digesta viscosity. 4. All levels of WSHL barley inclusion improved digestibility of dry matter, nitrogen and fat, whilst energy utilisation improved at inclusions of 130 g/kg WSHL and above, probably due to lowered digesta viscosity and better development of the gizzard. Gain to feed ratio, starch digestibility, energy utilisation and jejunal digesta viscosity can benefit from carbohydrase supplementation in wheat-based diets, regardless of barley inclusion level.

Identification and validation of mutation points associated with waxy phenotype in cassava.

BACKGROUND: The granule-bound starch synthase I (GBSSI) enzyme is responsible for the synthesis of amylose, and therefore, its absence results in individuals with a waxy starch phenotype in various amylaceous crops. The validation of mutation points previously associated with the waxy starch phenotype in cassava, as well as the identification of alternative mutant alleles in the GBSSI gene, can allow the development of molecular-assisted selection to introgress the waxy starch mutation into cassava breeding populations. RESULTS: A waxy cassava allele has been identified previously, associated with several SNPs. A particular SNP (intron 11) was used to develop SNAP markers for screening heterozygote types in cassava germplasm. Although the molecular segregation corresponds to the expected segregation at 3:1 ratio (dominant gene for the presence of amylose), the homozygotes containing the SNP associated with the waxy mutation did not show waxy phenotypes. To identify more markers, we sequenced the GBSS gene from 89 genotypes, including some that were segregated from a cross with a line carrying the known waxy allele. As a result, 17 mutations in the GBSSI gene were identified, in which only the deletion in exon 6 (MeWxEx6-del-C) was correlated with the waxy phenotype. The evaluation of mutation points by discriminant analysis of principal component analysis (DAPC) also did not completely discriminate the waxy individuals. Therefore, we developed Kompetitive Allele Specific PCR (KASP) markers that allowed discrimination between WX and wx alleles. The results demonstrated the non-existence of heterozygous individuals of the MeWxEx6-del-C deletion in the analyzed germplasm. Therefore, the deletion MeWxEx6-del-C should not be used for assisted selection in genetic backgrounds different from the original source of waxy starch. Also, the alternative SNPs identified in this study were not associated with the waxy phenotype when compared to a panel of accessions with high genetic diversity. CONCLUSION: Although the GBSSI gene can exhibit several mutations in cassava, only the deletion in exon 6 (MeWxEx6-del-C) was correlated with the waxy phenotype in the original AM206-5 source.

Stored Gelatinized Waxy Potato Starch Forms a Strong Retrograded Gel at Low pH with the Formation of Intermolecular Double Helices.

Waxy potato amylopectin has longer internal and external linear chains than rice or corn amylopectin that are capable of retrograding to a higher degree, but its molecular recrystallization is impeded by unprotonated phosphate groups. Here, we studied whether retrogradation and gel properties of waxy potato starch can be enhanced by lowering pH. The gel strength of waxy potato starch was strongly inversely correlated with pH, going from 10 to 4, and its magnitude was higher at pH values in which the ζ potential of the system was low. Waxy potato starch formed a strong aggregate gel driven by the formation of intermolecular double helices (G' drop25-95 °C ≈ 1358 Pa, melting ΔH = 9.5 J/g) when conditions that reduce electrostatic repulsion (pH 4, ζ = -1.7) are used, a phenomenon that was not observed in low-phosphorylated waxy cereal starches (i.e., waxy rice and corn).

Structure, properties and potential applications of phytoglycogen and waxy starch subjected to carboxymethylation.

The structure and properties of phytoglycogen (PG) and waxy starch (WS) from different mutants subjected to carboxymethylation (CM) were investigated. FT-IR analysis confirmed the carboxymethylation of PG and WS. The degree of substitution (DS) increased with increasing of the ratio of monochloroacetic acid to anhydroglucose unit, while DS of CM-PG was higher than that of CM-WS using equivalent modification conditions. The weight-average molecular weight (Mw) and radius of gyration (Rz) of CM-WS increased with the DS, whereas the Mw increased and Rz was nearly constant for CM-PG. The zeta-potential of CM-WS reduced and the viscosity increased significantly as DS increased, while the viscosity of CM-PG was remarkably lower than that of CM-WS with equivalent of DS. The increase of DS in CM-starches resulted in a substantial reduction of RDS accompanied by the increase of SDS and RS. The results revealed the promising application of CM-PG as a potential carrier system for bioactive ingredients.

Synthesis and succinylation of starch nanoparticles by means of a single step using sonochemical energy.

In the present research work, esterified nanoparticles with 2-octen-1-ylsuccinic anhydride were synthesized from waxy corn starch, to our knowledge for the first time, in a single step of ultrasonic treatment. First, the ultrasound time to produce non-esterified nanoparticles was studied. The results showed that non-esterified nanoparticles had sizes ranging from 63 to 48 nm, as well as polydispersity indexes (PDI) ranging from 0.458 to 0.224 and ζ-potential values ranging from -16 to -24 mV in ultrasonication times ranging from 20 to 100 min. Succinylated nanoparticles were obtained at 80 min with two degrees of substitution i.e., 0.003 and 0.01, hydrodynamic sizes of 57 and 83 nm, PDI of 0.479 and 0.91, and ζ-potential values of -6.27 and -14.03 mV, respectively. The succinylation of nanoparticles was confirmed by FTIR spectroscopy, and it was possible to elucidate the conversion of amylopectin molecules into amylose blocks. The nanoparticles showed stability during storage in aqueous suspension at 4 °C. By means of the ultrasonic technology, destructuring of the waxy corn starch and, at the same time, the succinylation of the nanoparticles in a total time of 120 min was effectively achieved.

Settling volume and morphology changes in cross-linked and unmodified starches from wheat, waxy wheat, and waxy maize in relation to their pasting properties.

Normal wheat, waxy wheat and waxy maize starches were cross-linked with 0.01, 0.03 and 0.06% (sb) phosphorus oxychloride. The objective of this study was to correlate the morphology changes and settling volume to the pasting properties of those cross-linked and unmodified starches. Pasting and microscopic data for waxy maize starch and its cross-linked products was similar to waxy wheat starch, except changes occurred at ∼5 °C higher in temperature. At 6% solids, waxy wheat starch cross-linked with 0.01% POCl3 had a greater settling volume and a higher pasting viscosity than the cross-linked waxy maize starch, but at 7 and 8% solids, waxy maize starch cross-linked with 0.03% and 0.06% POCl3 had a higher pasting viscosity. At 6% starch solids, particle volume fraction appeared to be the dominant factor controlling consistency, but at higher starch solids contents, the deformability (rigidity) of swollen granules became important in controlling viscosity.

Thermal, Structural, and Rheological Characterization of Waxy Starch as a Cryogel for Its Application in Food Processing.

Starch is the major component of cereal, pulses, and root crops. Starch consists of two kinds of glucose polymers, amylose and amylopectin. Waxy starch-with 99⁻100% amylopectin-has distinctive properties, which define its functionality in many food applications. In this research, a novel material was prepared through the cryogelification of waxy starch (WS) using four cycles of freezing and thawing in indirect contact with liquid nitrogen at -150 °C. Polyvinyl alcohol (PVA) was used as a reference. The cryogels were characterized using several validation methodologies: modulated differential scanning calorimetry (MDSC), scanning electron microscopy (SEM), rheology, and Fourier transform infrared (FTIR) spectroscopy with diffuse reflectance (DR). Based on the number of freeze⁻thaw cycles, significant changes were found (P < 0.05) showing important structural modifications as well as reorganization of the polymeric matrix. Two cryogelification cycles of the WS were enough to obtain the best structural and functional characteristics, similar to those of PVA, which has already been tested as a cryogel. From these results, it is concluded that WS has potential as a cryogel for application in food processing.