Variety, growing conditions and processing method act on different structural and biochemical traits to modify viscosity in tomato puree.

The texture of tomato products can be modified by choice of variety, their growing conditions and/or processing method, but no clear explanation exists of the mechanisms that transform fruit tissue, how they act on texture, or whether genetics and processing impact the same physical parameters. We therefore conducted a study that processed 4 varieties produced under low/high nitrogen supply, into puree using both hot and cold break processes. No specific rheological signature allows discrimination between cultivar-induced or process-induced textural changes, but that they can be distinguished by sensory analysis. Growth conditions impacted but was not sensory distinguished. Both caused significant variations in 7 of 11 physico-chemical parameters, but the order of importance of these traits controlling texture varied, depending on whether the cause was genetic or process-related. Analysis of alcohol insoluble solids revealed a specific signature in pectin composition and conformation that could be linked to particle aggregation in the presence of lycopene-rich particles.

Probing gallic acid-starch interactions through Rapid ViscoAnalyzer in vitro digestion.

Phenolic compounds are known inhibitors of starch digestion through binding with α-amylase. However, a growing body of research shows that phenolic-starch interactions at the molecular level may interfere with this inhibition potential. In this study, we evaluated the effect of Gallic Acid (GA) as a model phenolic compound on starch digestion kinetics carried out in vitro in a Rapid ViscoAnalyzer (RVA). The results showed that when GA was added before cooking of starch in order to promote starch-GA complexation, the rate of digestion of starch was similar to that of starch alone, and faster than when GA was added after cooking of starch. The results demonstrated that when GA was introduced after cooking of starch, GA inhibited α-amylase strongly and that inhibition increased with starch paste viscosity only for potato and wheat starches. No correlation was found between starch molecular characteristics and the inhibiting capacity of GA at different starch concentrations. However, the apparent influence of starch chain length distribution suggested that physical effects (such as the absorption of GA at the surface of the starch paste) may play a role in the capacity of GA to inhibit α-amylase.

Contrasting effects of polysaccharide components on the cooking properties of roots, tubers and bananas.

BACKGROUND: Consumer preferences for boiled or fried pieces of roots, tubers and bananas (RTBs) are mainly related to their texture. Different raw and cooked RTBs were physiochemically characterized to determine the effect of biochemical components on their cooking properties. RESULTS: Firmness in boiled sweetpotato increases with sugar and amylose contents but no significant correlation was observed between other physicochemical characteristics and cooking behaviour. Hardness of boiled yam can be predicted by dry matter (DM) and galacturonic acid (GalA) levels. For cassava, no significant correlation was found between textural properties of boiled roots and DM, but amylose and Ca2+ content were correlated with firmness, negatively and positively, respectively. Water absorption of cassava root pieces boiled in calcium chloride solutions was much lower, providing indirect evidence that pectins are involved in determining cooking quality. A highly positive correlation between textural attributes and DM was observed for fried plantain, but no significant correlation was found with GalA, although frying slightly reduced GalA. CONCLUSION: The effect of main components on texture after cooking differs for the various RTBs. The effect of global DM and major components (i.e. starch, amylose) is prominent for yam, plantain and sweetpotato. Pectins also play an important role on the texture of boiled yam and play a prominent role for cassava through interaction with Ca2+ . © 2023 Bill and Melinda Gates Foundation. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Varietal and environmental influences on organoleptic and cooking quality of water yam (Dioscorea alata) landraces.

BACKGROUND: Yam is a major staple food that provides both energy (starch) and bioactive compounds. However, there is a lack of knowledge on its cooking quality. We have determined the cooking quality of five varieties of water yam (among those most appreciated by consumers), when they were steamed or boiled. The yams were grown in two contrasting locations with regard to pedoclimatic conditions. RESULTS: Ratio of length to mean circumference of the tuber, difficulty to peel, cooking time, color attributes, hardness of steamed pulp, and dry matter (DM) and starch contents significantly varied among varieties. Cooking time and hardness of the cooked pulp, either steamed or boiled, were higher for tubers grown at the drier location, with vertisols, than at the rainy one, with a ferralitic soil. The raw pulp was richer in starch at the rainy location. We found no correlation between either textural properties or DM and the cooking time. A slight (r = 0.44) but significant correlation was recorded between the DM of the raw pulp and the hardness of the steamed product. CONCLUSION: We propose a comprehensive multicriteria approach for determination of yam cooking quality, textural properties, color attributes and chemical composition, along with varietal and environmental influences. This approach takes into consideration the complexity of food quality, allows a better understanding of its determinants and provides a basis for useful guidelines for breeders. © 2023 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Native and fermented waxy cassava starch as a novel gluten-free and clean label ingredient for baking and expanded product development.

Amylose-free and wild-type cassava starches were fermented for up to 30 days and oven- or sun-dried. The specific volume (ν) after baking was measured in native and fermented starches. The average ν (across treatments) for waxy starch was 3.5 times higher than that in wild-type starches (17.6 vs. 4.8 cm3 g-1). The best wild-type starch (obtained after fermentation and sun-drying) had considerably poorer breadmaking potential than native waxy cassava (8.4 vs. 16.4 cm3 g-1, respectively). The best results were generally obtained through the synergistic combination of fermentation (for about 10-14 days) and sun-drying. Fermentation reduced viscosities and the weight average molar mass led to denser macromolecules and increased branching degree, which are linked to a high loaf volume. The absence of amylose, however, was shown to be a main determinant as well. Native waxy starch (neutral in taste, gluten-free, and considerably less expensive than the current alternatives to cassava) could become a new ingredient for the formulation of clean label-baked or fried expanded products.

Experimental and theoretical investigation on interactions between xylose-containing hemicelluloses and procyanidins.

During processing of plant-based foods, cell wall polysaccharides and polyphenols, such as procyanidins, interact extensively, thereby affecting their physicochemical properties along with their potential health effects. Although hemicelluloses are second only to pectins in affinity for procyanidins in cell walls, a detailed study of their interactions lacks. We investigated the interactions between representative xylose-containing water-soluble hemicelluloses and procyanidins. Turbidity, ITC and DLS were used to determine the relative affinities, and theoretical calculations further ascertained the interactions mechanisms. Xyloglucan and xylan exhibited respectively the strongest and weakest interactions with procyanidins. The different arabinoxylans interacted with procyanidins in a similar strength, intermediate between xyloglucans and xylans. Therefore, the strength of the interaction depended on the structure itself rather than on some incidental properties, e.g., viscosity and molar mass. The arabinose side-chain of arabinoxylan did not inhibit interactions. The computational investigation corroborated the experimental results in that the region of interaction between xyloglucan and procyanidins was significantly wider than that of other hemicelluloses.

Analysis of consumer-oriented quality characteristics of raw and boiled plantains in Cameroon: implication for breeding.

This study aimed at understanding users' demand for raw and boiled plantains in rural and urban areas in West and Littoral regions of Cameroon. Surveys conducted in eight rural localities consisted of key informant interviews, gender-disaggregated focus group discussions, market and individual interviews. Processing and cooking diagnoses were done with restaurant cooks in urban areas, to know the details of plantain processing and boiling and to understand the quality characteristics of raw plantain that give a most-liked boiled plantain. Local favourite landraces, most cultivated landraces in Cameroon (Batard and Big ebanga) and a new CARBAP/CIRAD hybrid (CARBAP K74) were used. The preference for plantain cultivars was both gender and region-dependent. High-quality plantain should be mature, with big fingers and having a dark green peel colour. The fruit length and girth, pulp pH, dry matter content and firmness were found to be relevant postharvest quality characteristics for plantain breeding improvement.

Multiscale Structure of Starches Grafted with Hydrophobic Groups: A New Analytical Strategy.

Starch, an abundant and low-cost plant-based glucopolymer, has great potential to replace carbon-based polymers in various materials. In order to optimize its functional properties for bioplastics applications chemical groups need to be introduced on the free hydroxyl groups in a controlled manner, so an understanding of the resulting structure-properties relationships is therefore essential. The purpose of this work was to study the multiscale structure of highly-acetylated (degree of substitution, 0.4 < DS ≤ 3) and etherified starches by using an original combination of experimental strategies and methodologies. The molecular structure and substituents repartition were investigated by developing new sample preparation strategies for specific analysis including Asymmetrical Flow Field Flow Fractionation associated with Multiangle Laser Light Scattering, Nuclear Magnetic Resonance (NMR), Raman and Time of Flight Secondary Ion Mass spectroscopies. Molar mass decrease and specific ways of chain breakage due to modification were pointed out and are correlated to the amylose content. The amorphous structuration was revealed by solid-state NMR. This original broad analytical approach allowed for the first time a large characterization of highly-acetylated starches insoluble in aqueous solvents. This strategy, then applied to characterize etherified starches, opens the way to correlate the structure to the properties of such insoluble starch-based materials.

Influence of ionic plasticizers on the processing and viscosity of starch melts.

Maize starch was plasticized by glycerol, choline chloride ([Chol][Cl]) and ionic liquids (Choline acetate ([Chol][Ace]), 1-Ethyl-3-methylimidazolium Chloride ([EMIM][Cl]) and 1-Ethyl-3-methylimidazolium acetate ([EMIM][Ace]). Melt rheology at 120 °C was assessed with a twin-screw micro-compounder used for processing small quantities (8-10 g), and with a capillary rheometer with pre-shearing (Rheoplast). Qualitative agreement was found between shear viscosities obtained by both rheometry devices, showing the interest of the micro-compounder for screening of plasticizers' influence. The lower shear viscosity values were obtained in presence of [EMIM][Ace] whereas [Chol][Cl] led to the largest ones. Rather than processing induced macromolecular degradation, the glass transition temperature depressing effect of the plasticizers was found to better explain viscosity differences. This underlines the strong influence of the nature of the plasticizers on starch melt rheology. Finally, results from extensional viscosity shows the specific influence of [EMIM][Ace], suggesting that this plasticizer could be particularly relevant for thermoplastic starch processing.

Macromolecular characteristics and fine structure of amylomaltase-treated cassava starch.

This work investigates the macromolecular structure of native and amylomaltase (AM) treated cassava starch at various reaction times. AM-treated starches showed lower amylose content compared to their parental starch. Long chain proportions (DP 25-80) increased with reaction time up to 4 h and then slightly decreased at 24 h. Macromolecular and fine structure of AM-treated starches for 5 min (AM5min) and 4 h (AM4 h) were characterized more deeply by using HPSEC-MALLS and H1 NMR combined with ß-amylolysis and MALDI-TOF-MS. Molar mass and dispersity of both AM-treated starches were lowered. Nevertheless, AM5min had longer external chains whereas AM4 h exhibited a larger and denser macromolecular core. A cyclo-structure with DP 8 was found in both AM-treated starches; however, AM4 h contained cyclo-structures with various sizes (DP 8-32). Finally, by controlling reaction time and substrate constituents, which are important factors affecting the AM action modes, AM-treated starch with various structural features can be obtained.

Multi-scale characterization of thermoplastic starch structure using Second Harmonic Generation imaging and NMR.

Starch granules can be extruded to obtain a thermoplastic material. Thermoplastic starch (TPS) usually requires a significant break down of the starch granular organization to form a continuous polysaccharide matrix. In this work, we extrude potato starch with and without a plasticizer and store samples at high humidity to generate recrystallization. A multi-scale investigation of the microstructure is performed by combining different techniques: WAXS and solid-state NMR to describe macromolecule organization and Second Harmonic Generation (SHG) imaging to provide spatial information. Finally, the ability of the material to swell and remain sound in water is assessed. Glycerol-plasticized samples swell the least despite many granules with native-like structure embedded in the starch matrix. Glycerol limits the fragmentation and melting of the granules and crystallites during extrusion but also reduces the proportion of starch molecules in constrained conformations, enabling the formation of a polymer network that can sustain the penetration of water.

Thermal, conformational and rheological properties of κ-carrageenan-sodium stearoyl lactylate gels and solutions.

Polysaccharide-surfactant blends are widely used in foods. However, their possible mutual interactions have not been extensively studied. The purpose of this work was to examine how the anionic surfactant sodium stearoyl lactylate (SSL) affects different properties of κ-carrageenan solutions and gels. Rheometry, differential scanning calorimetry, asymmetrical flow field-flow fractionation coupled with multiangle laser light scattering, among others, were used to determine the flow and viscoelastic behavior, thermal transitions, and conformation changes, respectively. Interference caused by SSL is postulated as the primary factor to explain the variations in the conformation of κ-carrageenan in gels and solutions. However, electrostatic repulsions between κ-carrageenan and SSL can also be involved. These latter interactions are more important for high SSL concentrations (13 mmol dm-3) without addition of KCl, because of the higher net negative charge density of the system. SSL significantly modifies the properties of κ-carrageenan in aqueous media.

How does temperature govern mechanisms of starch changes during extrusion?

Potato and pea starches were processed on a twin-screw extruder under various moisture and thermomechanical conditions, chosen to keep material temperature Te close to starch melting temperature, Tm, whilst avoiding die expansion. Extruded rods were analysed by asymmetrical flow field flow fractionation coupled with light scattering, X-ray diffraction, DSC, and light microscopy with image analysis. Molar mass of extruded materials decreased more for potato than for pea starch, when specific mechanical energy SME increased, likely because of larger amylopectin sensitivity to shear. No crystallinity was detected when ΔT = (Tm-Te) ≤ 0. Residual gelatinization enthalpy ΔHg decreased with ΔT. As illustrated by larger ΔT values for ΔHg = 0, decreasing moisture favored melting, likely by increasing solid friction. The fraction of granular remnants of potato starch was inversely correlated to SME. These results could be explained by considering starch melting during extrusion as a suspension of solid particles embedded in a continuous amorphous matrix.

Macromolecular structure and film properties of enzymatically-engineered high molar mass dextrans.

New α(1→2) or α(1→3) branched dextrans with high molar masses and controlled architecture were synthesized using a dextransucrase and branching sucrases. Their molecular structure, solubility, conformation, film-forming ability, as well as their thermal and mechanical properties were determined. These new dextrans present structures with low densities from 9,500 to 14,000gm-3 in H2O/DMSO medium, their molar mass, size and dispersity increase with increasing branching degree (weight-average molar mass up to 109gmol-1 and radius of gyration around 500nm). Dextrans exhibit a glass transition between 40.5 and 63.2°C for water content varying from 12.2 to 14.1%. The effect of branching is mainly observed on the ability of dextran to crystallize. They have a good film-forming ability with a storage modulus which varies from 2 to 4GPa within a relative humidity range of 10-50%.

A dextran with unique rheological properties produced by the dextransucrase from Oenococcus kitaharae DSM 17330.

A gene encoding a novel dextransucrase was identified in the genome of Oenococcus kitaharae DSM17330 and cloned into E. coli. With a kcat of 691s-1 and a half-life time of 111h at 30°C, the resulting recombinant enzyme -named DSR-OK- stands as one of the most efficient and stable dextransucrase characterized to date. From sucrose, this enzyme catalyzes the synthesis of a quasi linear dextran with a molar mass higher than 1×109g·mol-1 that presents uncommon rheological properties such as a higher viscosity than that of the most industrially used dextran from L. mesenteroides NRRL-B-512F, a yield stress that was never described before for any type of dextran, as well as a gel-like structure. All these properties open the way to a vast array of new applications in health, food/feed, bulk or fine chemicals fields.

Choline chloride vs choline ionic liquids for starch thermoplasticization.

Native starch containing 12% water was melt processed in presence of 23% of various plasticizers at 120°C, either by simple compression molding or by extrusion using a laboratory scale microcompounder. Glycerol, a typical starch plasticizer, was used as a reference and compared to three choline salts: raw choline chloride (which is a solid in dry state with a melting point above 300°C), and two ionic liquids synthesized from this precursor (choline acetate and choline lactate, liquids below 100°C). These ionic plasticizers were shown to allow a more efficient melting of native starch in both processes. The investigation of macromolecular structure changes during processing shows that this efficiency can be ascribed to a starch chain scission mechanism, resulting in lower specific mechanical energy input need for starch thermoplasticization compared to glycerol plasticized starch. Compared to the synthesized ionic liquids, raw commercial choline chloride leads to a good compromise between limited chain scission, and final water uptake and thermomechanical properties.

Effect of xyloglucan molar mass on its assembly onto the cellulose surface and its enzymatic susceptibility.

Xyloglucan from tamarind seed has been submitted to an ultrasound treatment that reduces its molecular size to investigate the impact of molar mass on the interaction with cellulose. A low molar mass xyloglucan fraction (XGu, 1.04×105gmol-1) was purified and its adsorption on the cellulose nanocrystal (CNC) surface has been investigated comparatively to the native fraction that presents high molar mass (XGn, 10.28×105gmol-1). XGn arranged as loops and tails on CNCs whereas XGu formed trains onto the cellulose surface. Despite the extended conformation, XGu is able to cross-link cellulose nanocrystals in the layer-by-layer CNC-XG-CNC assemblies. Hydrolysis of model films by a xyloglucan-specific endoglucanase confirmed the greater accessibility of XGn loops and tails compared to the XGu trains. More importantly, in situ ellipsometry revealed that the presence of loops and tails facilitated swelling of CNC layers linked by XGn whereas the CNC-XGu-CNC structure did not experience swelling.

Structure of branching enzyme- and amylomaltase modified starch produced from well-defined amylose to amylopectin substrates.

Thermostable branching enzyme (BE, EC 2.4.1.18) from Rhodothermus obamensis in combination with amylomaltase (AM, EC 2.4.1.25) from Thermus thermophilus was used to modify starch structure exploring potentials to extensively increase the number of branch points in starch. Amylose is an important constituent in starch and the effect of amylose on enzyme catalysis was investigated using amylose-only barley starch (AO) and waxy maize starch (WX) in well-defined ratios. All products were analysed for amylopectin chain length distribution, α-1,6 glucosidic linkages content, molar mass distribution and digestibility by using rat intestinal α-glucosidases. For each enzyme treatment series, increased AO content resulted in a higher rate of α-1,6 glucosidic linkage formation but as an effect of the very low initial branching of the AO, the final content of α-1,6 glucosidic linkages was slightly lower as compared to the high amylopectin substrates. However, an increase specifically in short chains was produced at high AO levels. The molar mass distribution for the enzyme treated samples was lower as compared with substrate WX and AO, indicating the presence of hydrolytic activity as well as cyclisation of the substrate. For all samples, increased amylose substrate showed decreased α- and ß-amylolysis. Surprisingly, hydrolysis with rat intestinal α-glucosidases was higher with increasing α-1,6 glucosidic linkage content and decreasing M¯w indicating that steric hindrance towards the α-glucosidases was directed by the molar mass rather that the branching density of the glucan per se. Our data demonstrate that a higher amylose content in the substrate starch efficiently produces α-1,6 glucosidic linkages and that the present of amylose generates a higher M¯w and more resistant product than amylopectin. The combination of BE→AM→BE provided somewhat more resistant α-glucan products as compared to BE alone.

Plant-crafted starches for bioplastics production.

Transgenically-produced amylose-only (AO) starch was used to manufacture bioplastic prototypes. Extruded starch samples were tested for crystal residues, elasticity, glass transition temperature, mechanical properties, molecular mass and microstructure. The AO starch granule crystallinity was both of the B- and Vh-type, while the isogenic control starch was mainly A-type. The first of three endothermic transitions was attributed to gelatinization at about 60°C. The second and third peaks were identified as melting of the starch and amylose-lipid complexes, respectively. After extrusion, the AO samples displayed Vh- and B-type crystalline structures, the B-type polymorph being the dominant one. The AO prototypes demonstrated a 6-fold higher mechanical stress at break and 2.5-fold higher strain at break compared to control starch. Dynamic mechanical analysis showed a significant increase in the storage modulus (E') for AO samples compared to the control. The data support the use of pure starch-based bioplastics devoid of non-polysaccharide fillers.