RESUMEN
This study aims to understand the molecular and supramolecular transformations of wheat endosperm biopolymers during bread-making, and their implications to fabricate self-standing films from stale white bread. A reduction in the Mw of amylopectin (51.8 × 106 vs 425.1 × 106 g/mol) and water extractable arabinoxylans WEAX (1.79 × 105 vs 7.63 × 105 g/mol), and a decrease in amylose length (245 vs 748 glucose units) was observed after bread-baking. The chain length distribution of amylopectin and the arabinose-to-xylose (A/X) ratio of WEAX remained unaffected during bread-making, suggesting that heat- or/and shear-induced chain scission is the mechanism responsible for molecular fragmentation. Bread-making also resulted in more insoluble cell wall residue, featured by water unextractable arabinoxylan of lower A/X and Mw, along with the formation of a gluten network. Flexible and transparent films with good light-blocking performance (<30 % transmittance) and DPPH-radical scavenging capacity (~8.5 %) were successfully developed from bread and flour. Bread films exhibited lower hygroscopicity, tensile strength (2.7 vs 8.5 MPa) and elastic modulus (67 vs 501 MPa) than flour films, while having a 6-fold higher elongation at break (10.0 vs 61.2 %). This study provides insights into the changes in wheat biopolymers during bread-making and sets a precedent for using stale bread as composite polymeric materials.
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Amilopectina , Pan , Harina , Triticum , Xilanos , Triticum/química , Pan/análisis , Harina/análisis , Biopolímeros/química , Xilanos/química , Amilopectina/química , Resistencia a la Tracción , Arabinosa/química , Xilosa/química , Glútenes/químicaRESUMEN
Brown macroalgae represent a sustainable and abundant source of lipids with acknowledged functional and health benefits. Nonetheless, macroalgae lipidome has been poorly unraveled due to lipids complex structural and chemical diversity. In this study, a comprehensive lipidomic analysis was performed in four macroalgae: Saccharina latissima, Fucus vesiculosus, Fucus serratus and the invasive Sargassum muticum, using HILIC-C30RP-HRMS. Neutral lipids (tri-, di-glycerides) comprised 72-82% of total lipids (TL) with a highly unsaturation profile (27-49% depending on species). The polar lipidome comprised glycolipids, phospholipids, betaine lipids and sphingolipids with varied content among macroalgae. S. latissima displayed the greatest level of glycolipids (23% of TL), by contrast with the dominance of long-chain polyunsaturated betaine lipids (10-18% of TL) in the other species, particularly in S. muticum. Phospholipids and sphingolipids were detected in low abundance (<1.7% of TL). This study elevated the potential of brown macroalgae as an emerging reservoir of bioactive lipids with nutritional relevance.
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Lipidómica , Lípidos , Phaeophyceae , Algas Marinas , Algas Marinas/química , Algas Marinas/metabolismo , Lípidos/química , Lípidos/análisis , Phaeophyceae/química , Phaeophyceae/metabolismo , Glucolípidos/química , Glucolípidos/metabolismo , Glucolípidos/análisisRESUMEN
Polyphenol partitioning during mechanical (cold-pressing) and physiological (digestion) extraction at the individual polyphenol and subclass level was investigated. UHPLC-ESI-QTOF-MS/MS analysis yielded a comprehensive identification of 45 polyphenols whose semi-quantification revealed a hierarchical clustering strongly determined by polyphenol structure and their location within the apple tissue. For instance, pomace retained most flavonols and flavanols (degree of polymerization DP 5-7), which were highly hydrophobic, hydroxylated, or large (>434 Da), and more abundant in peel. In vitro digestion UHPLC-ESI-QTOF-MS/MS analysis of whole apple (and its corresponding matrix-free extract) clustered polyphenols into five main groups according to their interaction with plant cell walls (PCWs) during each digestion phase. This grouping was not reproduced in pomace, which exhibited a greater matrix effect than whole apple during oral and gastric digestion. Nevertheless, the interaction between most polyphenol groups, including dihydrochalcones, flavanols (DP 1-4) and hydroxycinnamic acid derivatives, and pomace PCWs was lost during intestinal digestion.
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Malus , Polifenoles , Polifenoles/análisis , Espectrometría de Masas en Tándem , Antioxidantes/análisis , Extractos Vegetales/química , Análisis por ConglomeradosRESUMEN
Acetylated starch shows enhanced thermal stability and moisture resistance, but its compatibilization with other more hydrophilic polysaccharides remains poor or unknown. In this study, the feasibility of thermomechanically compounding organocatalytically acetylated pea starch (APS), produced at two different degrees of substitution with alkanoyl groups (DSacyl, 0.39 and 1.00), with native pea starch (NPS), high (HMP) and low methoxyl (LMP) citrus pectin, and sugar beet pectin (SBP, a naturally acetylated pectin) for developing hot-pressed bioplastics was studied. Generally, APS decreased hydrogen bonding (ATR-FTIR) and crystallinity (XRD) of NPS films at different levels, depending on its DSacyl. The poor compatibility between APS and NPS or HMP was confirmed by ATR-FTIR imaging. Contrariwise, APS with DSacyl 1 was effectively thermomechanically mixed with the acetylated SBP matrix, maintaining homogeneous distribution within it (ATR-FTIR imaging). APS (any DSacyl) significantly increased the visible/UV light opacity of NPS-based films and decreased their water vapor transmission rate (WVTR, by ca. 11 %) and surface water wettability (by ca. 3 times). In comparison to NPS-APS films, pectin-APS showed higher visible/UV light absorption, tensile strength (ca.2.9-4.4 vs ca.2.4 MPa), and Young's modulus (ca.96-116 vs ca.60-70 MPa), with SBP-APS presenting significantly lower water wettability than the rest of the films.
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Pisum sativum , Almidón , Resistencia a la Tracción , PectinasRESUMEN
Algae are a rich but unexplored source of fibers with the potential to contribute to the next generation of prebiotics. The sulfated brown algae polysaccharide, fucoidan, is mainly composed of the deoxy-hexose L-fucose, which can be metabolized to 1,2-propanediol (1,2-PD) or lactate by gut microbes as precursors of propionate and butyrate. It was the aim of this study to investigate the impact of fucoidan on the fermentation capacity of the fecal microbiota and to compare to fucose. In batch fermentations of fecal microbiota collected from 17 donor samples, fucose promoted the production of propionate while no consistent effect was observed for commercial fucoidan and Fucus vesiculosus extract prepared in this study containing laminarin and fucoidan. H2S production was detected under all tested conditions, and levels were significantly lower in the presence of fucose in a dose-dependent manner. The addition of high fucose levels led to higher relative abundance of microbial 1,2-PD and lactate cross-feeders. Our results highlight that fucose and not fucoidan addition impacted fermentation capacity and increased the proportions of propionate and butyrate, which allows for precise modulation of intestinal microbiota activity.
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Fucosa , Propionatos , Polisacáridos/farmacología , Ácidos Grasos Volátiles , Butiratos , LactatosRESUMEN
Pectin structure-miscibility-functionality relationships in starch films remain unknown. In this study, five citrus pectins (CPs) with 17 to 63 % of degree of methyl esterification (DM) and sugar beet pectin (SBP, rich in acetyl moieties and rhamnogalacturonan-I domains) were investigated for composition and structure and, further, blended with pea starch (3:1 starch-pectin weight ratio) to fabricate self-standing films. The incorporation of pectin resulted in a two- to three-fold increase in tensile strength and Young's modulus (up to 52.2 and 1837 MPa, respectively, using CP with low DM) without compromising elongation at break. Starch-SBP films presented the lowest strength among pectin films. Lower film moisture and water vapor permeability were attained with CP of high DM, or with SBP, whereas surface wettability was explained by counteracting factors affecting film compositional heterogeneity. Films made with high methoxyl CP, or with SBP, showed lower overall H-bonding (FTIR) and starch crystallinity (XRD). A DM above 57 % negatively affected the mixing and interfacial adhesion of pectin with starch, as shown by Attenuated Total Reflection-FTIR imaging. Pectins with the lowest purity, presumably with the greatest content in xyloglucan, as suggested by HPAEC, presented ~20 % higher elongation at break than the other films.
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The chemical safety of representative polysaccharide films made with pea starch, organocatalytic acetylated pea starch and pectin was investigated at different migration conditions (20 °C/10 days, 70 °C/2 h) using two official simulants signifying hydrophilic (simulant A, 10% ethanol) or lipophilic (simulant D1, 50% ethanol) foods. Migrating semi-volatile and non-volatile compounds were identified and semi-quantified by ultra-high performance liquid chromatography-trap ion mobility time-of-flight mass spectrometry (UHPLC-TIMS-TOF-MS/MS), whereas their toxicity was evaluated by in silico models based on qualitative structure activity (QSAR). Physicochemical analysis revealed polymer wash-off into the simulants. Migration testing at 70 °C for 2 h using simulant D1 resulted in detectable concentrations of glycerol (≤72.1 mg/kg), monoacetylated maltose (≤6.5 mg/kg), and dibutyl phthalate (DBP) (≤0.5 mg/kg, compliant with the existing legislative migration limits) in samples containing acetylated starch. Migrating 3-ß-galactopyranosyl glucose (≤8.9 mg/kg) and 2,5-diketo-d-gluconic acid (≤4.9 mg/kg) were detected at 20 °C/10 days. In-silico toxicity emphasized no significant toxicity and categorized organocatalytic acetylated pea starch of no safety concern.
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Alimentos , Espectrometría de Masas en Tándem , Polímeros/análisis , Almidón , Etanol/análisis , Embalaje de Alimentos , Contaminación de Alimentos/análisisRESUMEN
This study aims to enhance the understanding of the structure of maize phytoglycogen nanoparticles, and the effect of shear scission on their architecture, radius, stiffness, and deformability. Compared to amylopectin, phytoglycogen had a lower A:B chain ratio, a lower number of chains per B chain, and a much higher number of Afingerprint chains. Phytoglycogen (Mw = 28.0 × 106 g/mol) was subjected to high-shear extrusion with varying Specific Mechanical Energies (SMEs) using different screw speeds, showing a maximum stable molecular weight Mw of â¼9.31 × 106 g/mol and a particle radius R reduction of 36 %, with a corresponding 20 % increase in the average mass density. Atomic force microscopy force spectroscopy revealed that nanoparticles extruded at the lowest SME (122 Wh/kg) exhibited a 20 % increase in Young's modulus. Higher SME values (up to 488 Wh/kg) resulted in an overall decrease in stiffness without further significant reductions in radius.
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Amilopectina , Nanopartículas , Amilopectina/química , Módulo de Elasticidad , Microscopía de Fuerza Atómica/métodos , Peso Molecular , Nanopartículas/químicaRESUMEN
Organocatalytic acetylation of pea starch was systematically optimized using tartaric acid as catalyst. The effect of the degree of substitution with alkanoyl (DSacyl) and tartaryl groups (DStar) on thermal and moisture resistivity, and film-forming properties was investigated. Pea starch with DSacyl from 0.03 to 2.8 was successfully developed at more efficient reaction rates than acetylated maize starch. Nevertheless, longer reaction time resulted in granule surface roughness, loss of birefringence, hydrolytic degradation, and a DStar up to 0.5. Solid-state 13C NMR and SEC-MALS-RI suggested that tartaryl groups formed crosslinked di-starch tartrate. Acetylation increased the hydrophobicity, degradation temperature (by ~17 %), and glass transition temperature (by up to ~38 %) of pea starch. The use of organocatalytically-acetylated pea starch with DSacyl ≤ 0.39 generated starch-based biofilms with higher tensile and water barrier properties. Nevertheless, at higher DS, the incompatibility between highly acetylated and native pea starches resulted in a heterogenous/microporous structure that worsened film properties.
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Pisum sativum , Almidón , Acetilación , Almidón/análogos & derivados , Almidón/química , AguaRESUMEN
Drum-drying results in pregelatinized starch with relatively low starch fragmentation and a great ability to absorb water and swell at room temperature. However, the effect of the degree of cold particle swelling and the thickening potential of drum-dried starch on its suitability as oil replacer in low-fat oil-in-water emulsions has received little attention. In this work, the potential of three pregelatinized drum-dried starches with almost identical molecular structure (as measured by size exclusion chromatography) and Water Binding Capacity (WBC), but different swelling behavior, was investigated to replace up to 60% oil in a mayonnaise-like emulsion system. The microstructure, stability, and rheology of the oil-in-water emulsions were noticeably affected by the substitution of oil with a pregelatinized drum-dried starch paste. Specifically, reduced-fat emulsions presented smaller droplet-size, a higher consistency index and increased emulsion stability, especially against freeze-thaw cycles, compared to the control full-fat mayonnaise. Importantly, the differences in cold swelling behavior (rather than simply assessing WBC) greatly influenced the consistency index and stability of low-fat emulsions, and results showed that drum-dried starch particles with high swelling potential perform better as oil replacers.
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This work investigates the partial solubilization of cell wall polysaccharides in okra flours and the changes in the profile of free and bound phenolics through twin-screw extrusion. The comparison between extruded wheat flour-native okra flour (EWF-OF) and extruded wheat flour-extruded okra flour (EWF-EOF) composite blends revealed that extrusion led to an increase of soluble dietary fiber from 7.76 to 10.02 g/100 g. Extrusion of okra also resulted in a significant increase of free and bound phenolic acids, the latter consisting mostly of ferulic acid, as well as the thermal degradation of free epigallocatechin, and the binding of a small portion of quercetin-3-O-glucoside likely to a carbohydrate fraction. Bread crumbs from EWF-EOF (at 15% replacement level) exhibited a significantly lower hardness and higher elasticity, cohesiveness and resilience (from 28.28 N, 0.94, 0.49 and 0.17 to 7.54 N, 0.99, 0.70 and 0.35, respectively), which closely resembled the textural attributes of wheat bread.
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Abelmoschus , Harina , Pan , Dureza , TriticumRESUMEN
The quantification of α-Galacto-oligosaccharides (GOS) in beans has been increasingly approached through different methodologies. However, reported GOS contents revealed up to 8-times disparity, which cannot be only attributed to the bean cultivar and underlines the need of using validated analytical methodologies. This study aimed to optimize and validate the extraction of the most abundant GOS found in beans, namely raffinose, stachyose and verbascose, and comparatively assess their determination by High-Performance Anion Exchange Chromatography/Pulsed Amperometric Detector (HPAEC/PAD) and Gas Chromatography/Mass Spectrometry (GC/MS). Hot sonication followed by shaking with 70% ethanol resulted in excellent GOS extraction efficiencies (92.54-107.94%). GC/MS determination was more reliable than HPAEC/PAD, with limits of quantification of 4.48-224.31â¯mg/kg and intra/inter-day repeatabilities <10%. The analysis of six bean varieties proved the feasibility of the GC/MS methodology, displaying total GOS contents from 1453.07⯱â¯169.31 to 2814.34⯱â¯95.28â¯mg/100â¯g. Stachyose was significantly (pâ¯<â¯0.05) the main GOS in all samples.
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Cromatografía por Intercambio Iónico/métodos , Análisis de los Alimentos/métodos , Cromatografía de Gases y Espectrometría de Masas/métodos , Oligosacáridos/análisis , Oligosacáridos/química , Phaseolus/químicaRESUMEN
The objective was to determine structural and physicochemical properties of beef emulsion modeling systems prepared with native breadfruit flour and four different extruded breadfruit flours. Extrusion conditions for the flours were summarized as two different specific mechanical energies (74 or 145 kJ/kg) and four unique melt temperatures (83 °C, 100 °C, 105 °C, or 126 °C). Meat emulsions formulated at 3% replacement of beef with native or extruded breadfruit flours were compared with control (no additional flour) formulations. Replacement of beef with breadfruit flour (either native or extruded) did not significantly change cooking loss or instrumental redness values of cooked meat emulsions. Interestingly, replacement of beef with the fully gelatinized extruded breadfruit flours altered viscosity during heating as indicated by lower values for storage modulus (44.75% to 62.53% decrease compared with control) and lower values for loss modulus (25.90% to 52.54% decrease compared with control). This resulted in meat emulsions with a significant reduction in textural hardness (28.78% to 37.62% decrease compared with control).
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Artocarpus , Productos de la Carne/análisis , Animales , Bovinos , Color , Culinaria , Emulsiones/análisis , Manipulación de Alimentos/métodos , Temperatura , ViscosidadRESUMEN
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.
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Pan , Oryza , Amilopectina , Harina , AlmidónRESUMEN
Folin-Ciocalteu and the more recent Fast Blue BB (FBBB) reactions are used for the quantification of total phenolics in food matrices. Despite its known interferences, Folin-Ciocalteu is still widely employed, considering Solid Phase Extraction (SPE) as clean-up step only in a few cases. Meanwhile, FBBB has shown no interferences for the determination of total phenolics in fruits and cereals, although its utilization in other popular matrices containing potential interferences, such as legumes, remains unexplored. In this study, the total phenolic content of 24 flours from legumes, cereals, fruits, nuts and plant seeds was evaluated by Folin-Ciocalteu and FBBB, with and without SPE. Folin-Ciocalteu showed interferences for 75% of the flours (attributed to reducing sugars and enediols), whereas FBBB only for legumes and nuts (attributed to the presence of tyrosine), both methods in those matrices requiring SPE. Although both SPE-FBBB and SPE-Folin-Ciocalteu presented excellent reproducibility, SPE-FBBB displayed 1.5 times higher sensitivity.
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Compuestos de Diazonio/química , Fabaceae/química , Fenoles/análisis , Extractos Vegetales/análisis , Nueces/química , Extractos Vegetales/química , Semillas/químicaRESUMEN
The objective was to modify functional properties of breadfruit flours using twin-screw extrusion and test the physicochemical properties of the extruded flours. Extruded breadfruit flours were produced with twin-screw extrusion using different last barrel temperature (80 °C or 120 °C) and feed moisture content (17% or 30%). These conditions resulted in four extruded flours with different mechanical (specific mechanical energy, SME) and thermal (melt temperature) energies. At temperatures below the gelatinization of the native starch (<70 °C), swelling power was increased in all extruded treatments. Solubility was dramatically increased in high-SME extruded flours at all tested temperatures. Water holding capacity was dramatically increased in the low-SME extruded flours. A two-fold higher cold peak viscosity was obtained for low SME-high temperature extruded flour compared with the other extruded flours. Low SME-low temperature extruded flour still exhibited a hot peak viscosity, which occurred earlier than in native flour. Setback was decreased in all extruded flours, especially in high-SME treatments. The incorporation of extruded flours into soy protein gels did not affect cooking loss, while hardness and springiness decreased with the addition of extruded flours. Overall, extrusion of breadfruit flour altered functional flour properties, including water holding capacity and pasting properties, and modified the texture of soy protein gels.
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A structure-digestion model is proposed to explain the formation of α-amylase-slowly digestible structures during amylopectin retrogradation. Maize and potato (normal and waxy) and banana starch (normal and purified amylopectin through alcohol precipitation), were analyzed for amylose ratio and size (HPSEC) and amylopectin unit- and internal-chain length distribution (HPAEC). Banana amylopectin (BA), like waxy potato (WP), exhibited a larger number of B3-chains, fewer BS- and Bfp-chains and lower S:L and BS:BL ratios than maize, categorizing BA structurally as type-4. WP exhibited a significantly greater tendency to form double helices (DSC and 13C-NMR) than BA, which was attributed to its higher internal chain length (ICL) and fewer DP6-12-chains. However, retrograded BA was remarkably more resistant to digestion than WP. Lower number of phosphorylated B-chains, more S- and Bfp-chains and shorter ICL, were suggested to result in α-amylase-slowly digestible structures through further lateral packing of double helices (suggested by thermo-rheology) in type-4 amylopectins.
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The pasting profile of starchy tissues is conventionally measured by recording the apparent viscosity (η) in heating/cooling cycles. However, conventional rheometers show critical limitations when the starch is embedded in compact protein-rich cotyledon matrices, as occurs in pulses. In this work, the pasting profile of 13 red kidney beans (Phaseolus vulgaris) from the same cultivar but different growing locations was investigated using a heating/cooling cycle at higher temperature (130 °C) and pressurized conditions, using both water and brine as cooking solvents. It was hypothesized that the continuous measure of η at these conditions of flours from the dry seed would correlate with the texture, as determined by the mini-Kramer cell, of the beans after the entire process of soaking and canning. Furthermore, mechanistic answers were obtained by investigating their composition (starch, protein, and ash content) and physical properties (water holding capacity, seed ratio and weight). Interestingly, as opposed to the pasting profile at 95 °C, pasting indicators at 130 °C, including trough and final viscosity, strongly correlated with starch and protein content, seed coat ratio and, remarkably, with the firmness of the beans after canning when brine was incorporated. These results clearly show that small beans with a high protein content would bring about a more compact matrix that restricts starch from swelling and results in canned beans with a hard texture, which can be predicted by a lower pasting profile of the whole bean flour.
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While it is known that salivary amylase changes perceived thickness in starch-based foods, the dynamics of oral breakdown of starch has not been related to that of sensory perception. This work examines the associations between in-mouth oral breakdown of starch by α-amylase and thickness of a semisolid product measured instrumentally and using a sensory panel. Pureed carrots made with added waxy maize (w/w) (0% (control), 0.4% (S0.4) and 0.8% (S0.8)), were tested for dilution and hydrolysis effects with the addition of water and saliva and measuring viscosity (shear of 10 s-1), viscoelasticity (10-0.01 Hz at 0.1% strain) and maltose release. Sensory testing was conducted using progressive profiling. Control and S0.8 pureed carrots showed similar viscosities at 10 s-1 while S0.4 was lower. Addition of saliva had the highest impact on viscosity drop for S0.8. Viscoelastic properties of pureed carrots decreased with starch addition which decreased further with water/saliva incorporation. Starch breakdown measured in terms of maltose release did not change with starch concentration and oral processing times. Unlike instrumental viscosity results, perceived thickness of purees increased with starch concentration. During oral processing, thickness decreased at a constant rate across all samples highlighting the dilution effect of saliva. A relation was observed only between oral viscosity and starch hydrolysis and not rheological measurements. This indicates that changes in starch hydrolysis during oral processing can be used as an indicator of rate of drop in perceived viscosity in starch-based semi-solid foods such as pureed carrots.
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Almidón , alfa-Amilasas , Hidrólisis , Boca , PercepciónRESUMEN
This work investigates the effect of drying okra pods by different techniques [freeze-drying (FD), sun-drying (SD), oven-drying (OD) and microwave-drying (MD)] on the molecular structure, physicochemical and antioxidant properties of the subsequently extracted OP. Remarkably, although the degree of methyl esterification (â¼41.1 %) remained similar among samples, the content of galacturonic acid (62.67-68.77 %), average number molecular weight (MnI: 758.8-808.5â¯kDa, MnII: 20.9-24.2â¯kDa), and to a greater extent the apparent viscosity of an aqueous solution of pectin molecules, water holding capacity (0.21-10.71â¯g/g) and emulsifying activity (42.3-72.7 %) and stability (38.6-53.5 %), decreased with the drying temperature in the order of FD-OPâ¯>â¯SD-OPâ¯>â¯OD-OPâ¯>â¯MD-OP. On the other hand, only FD-OP presented a higher proportion of galactan and/or arabinan side chains [(Araâ¯+â¯Gal) / Rhaâ¯=â¯12.37%] compared to the rest of the samples, with values ranging from 7.79 to 9.17%. FD-OP and SD-OP resulted in lower DPPH and ABTS radical scavenging activities.