Pectin–sucrose–Ca2+ interactions: effects on rheological properties

The effects of varying concentrations of pectin (4.5–6.5%, w/w), sucrose (40–60%, w/w) and calcium (20–60 mg/g pectin) on the viscoelastic properties of pectin dispersions at pH 3.0 were investigated. Pectin samples used were extracted from pomelo fruit peels (Citrus grandis) grown in Malaysia. The dynamic rheological parameters (G′, G″, δ and η*) of pectin–sucrose–calcium dispersion were determined at 1.5% strain from 90–20°C at a cooling rate of 3°C min⁻¹. Plots of G′ and G″ against frequency (rad s⁻¹) showed G″>G′ throughout the frequency range with no occurrence of crossover for most of the pectin dispersions. In addition both storage (G′) and loss (G″) moduli of the dispersions increase on cooling. Increasing pectin, sucrose and calcium concentrations increased G′ and G″ with pectin having the greatest effect. Interactions amongst the three factors were also studied. At lower pectin concentrations, addition of Ca²⁺ increased G′ at all temperatures. This effect was also observed at higher pectin concentrations at 20°C but not at 90°C. The opposite effect was observed with the addition of sucrose, i.e. addition of sucrose at a higher pectin concentration increased G′ whereas at a lower pectin concentration no effect was observed. Interaction between calcium and sucrose gave rise to an increase in G′ when Ca²⁺ was added at high sucrose concentrations, but a decrease in G′ was evident at low sucrose concentrations. Dispersions of pectin alone or in combination with sucrose exhibited a more liquid-like behaviour with G″>G′. However, in the presence of Ca²⁺, mechanical spectra of G′>G″ were obtained.     

Sweetness and texture perception in mixed pectin gels with 30% sugar and a designed rheology

Pure low-methoxyl (LM) pectin and mixtures of LM and high-methoxyl (HM) pectin in different ratios were used to produce gels with control over the rheological parameter storage modulus (G′). The gels either had similar pectin concentrations and different G′ values, or different pectin concentrations and similar G′ values. All gels were prepared with 30 g/100 g sugar, in the presence of 0.1 g/100 g CaCl₂, at pH 3.5; these are conditions that favour gel formation of both LM and HM pectin.The gels were compared for their sensory characteristics; specifically sweetness, sourness, thickness, and glueyness. Sweetness was found to increase with increasing storage modulus (G′) in pectin gels of similar pectin concentration, but different G′ values. Gels with higher proportions of LM pectin were perceived as sweeter than those with low LM pectin ratios. These gels also had increasing loss modulus (G″), and increasing differences between G′ and G″, which indicates that diffusion has a bearing on the perception of sweetness in pectin gels. Thickness and glueyness were mostly determined by total pectin concentration. Thickness also increased with increasing LM pectin concentration while glueyness increased with increasing HM pectin concentration.     

Butternut and beetroot pectins: Characterization and functional properties

The physicochemical characteristics and functional properties of butternut (Cucumis moschata Duch. ex Poiret) and beetroot (Beta vulgaris L. var. conditiva) pectins obtained by enzymatic extraction from by-products of vegetable processing have been evaluated. The molecular mass distribution was determined using Gel Permeation Chromatography using light scattering, refractive index and UV detectors and the samples were found to be highly heterogeneous and polydisperse. M_w values of 136,000 and 1,309,000 g/mol were determined for butternut and beetroot pectins respectively. Butternut pectin had a high degree of methyl esterification. In the presence of high concentrations of sugar and at low pH, this pectin did not form gels but instead produced viscous solutions. Solutions showed pseudoplastic flow behaviour with a shear thinning index of 0.68 as determined from the Power law model. Beetroot pectin had a low degree of methyl esterification and formed gels with addition of Ca²⁺ at concentrations of 10 mg/g pectin or higher. The maximum value of the storage modulus was obtained at a Ca²⁺/GalA ratio of 0.25. The thermal stability of gels suggested that hydrogen bond interactions prevailed in the absence of Ca²⁺, whereas electrostatic junction zones increasingly developed between pectin chains as the calcium concentration increased. Aqueous solutions of butternut and beetroot pectins significantly reduced surface tension and both samples were able to form stable oil-in-water emulsions. It was found that protein and/or polyphenol – rich fractions present in the pectins adsorbed at the oil–water interface and were responsible for the emulsification properties.     

The impact of concentration,temperature and pH on dynamic rheology of psyllium gels

Structural aspects of the psyllium gum prepared from the seed husk of the plant of Plantago ovata Forsk was characterized by dynamic rheology and microscopy. Dynamic rheological properties of psyllium gel in the linear viscoelastic region, as a function of concentration (2, 2.5 and 3% w/w), temperature (5–95 °C) and pH (2.5–10) were investigated. Mechanical spectra of the psyllium gels were obtained by frequency sweep measurement classified into that of weak gels because G′ was larger than G″ throughout the tested frequency range and the separation of the two moduli (tan δ) was greater than 0.1. The phase angle increased with temperature and a peak associated with gel melting appeared at about 40 °C. All gels at different pH presented a typical weak gel spectrum. Scanning electron microscopy showed porous structures with different pore-size distribution for psyllium gels under different conditions in terms of concentration, pH and temperature.     

Small and large deformation viscoelastic behaviour of selected fibre blends with gelling properties

Dietary fibres can be used as valuable functional ingredients in baked goods, as thickeners and gelling agents as a result of their ability to modify the structural properties of the matrix in which they are embedded. Viscoelastic behaviour of 12 selected gel–fibre blends (carboxymethylcellulose, hydroxypropylmethylcellulose, locust bean gum, high ester pectin, fructo-oligosaccharide and gluco-oligosaccharide) prepared at 10% concentration (w/v) was investigated at 25 °C and 95 °C by applying both fundamental and empirical rheological techniques to explore their usefulness/suitability as structural ingredients in diluted and weakened baking systems such as gluten free matrices. Mechanical and thermo-mechanical properties were recorded by using a controlled stress rheometer, measuring the storage modulus (G′), the loss modulus (G″) and the complex viscosity (η*). Textural characteristics were assessed by using a TAXTplus Texture Analyser with different attachments. Penetration and back extrusion tests were used for solid and liquid-like samples, respectively. The overall results indicated that (i) carboxymethylcellulose and pectin formed the strongest and the weakest gels, respectively, and that (ii) temperature had a significant effect on gel strength improvement especially for locust bean gum. A 30% substitution of hydrated fibres (cellulose derivates, galactomanans and high ester pectin) by prebiotics (fructo-oligosaccharides and gluco-oligosaccharides) led to a significant decrease of gel structure rigidity when compared to an identical system without prebiotic addition. Only locust bean gum exhibited an opposite behaviour inducing an increase in values of both dynamic moduli (G′ and G″) and static hardness. Significant relationships between dynamic (rheometry) and static (texture analysis) methods were found. Strengthening and structuring ability of some fibre blend gels endorsed them to be used as promising functional ingredients to make gluten-free bread by using low cost thickeners' agents.     

Ultrasonic processing influences rheological and optical properties of high-methoxyl pectin dispersions

The effect of high-intensity ultrasound on the rheological and optical properties of high-methoxyl pectin dispersions was studied. Pectin solutions (1.15 wt% pectin, 41.4 wt% sucrose) were treated with high-intensity ultrasound at intensity levels ranging from 0 to 40 W cm⁻² for various times (0–60 min). Samples were adjusted to pH 1.5 to initiate gelation and their dynamic rheological properties (G′, G″) were recorded as a function of time using a rotational rheometer. Ultrasonically pretreated pectin dispersions formed weaker gels with increasing sonication power and time. After 4 h, log G′ of the pectin dispersion that was pretreated at the highest intensity level (40 W cm⁻² and 30 min) was approximately five times lower than log G′ of the untreated dispersion. The change in phase angle [arctan (G′/G″)] with time indicated that the rate of gelation decreased as ultrasonic intensity and application time increased. The turbidity of ultrasonically pretreated pectin dispersions decreased by 50% yielding more transparent gels. Results were attributed to an overall reduction in the average molecular weight of pectin due to cavitational effects. A power law model was fitted to the flow curves of ultrasonically pretreated pectin dispersions to determine both flow behavior index n and consistency coefficient K. With increased sonication power and application time, n increased from 0.6 to 0.97 indicating that the flow behavior changed from viscoelastic to Newtonian.     

The effect of pH on gel structures produced using protein–polysaccharide phase separation and network inversion

Forming heat-induced gels through combined effects of micro-phase separation of whey protein isolate (WPI; 5%, w/v, 100 mm NaCl) by pH change (5.5, 6.0, and 6.5), and addition of κ-carrageenan (0–0.3%, w/w), were evaluated. The microstructure of WPI gels was homogeneous at pH 6.0 and 6.5 and micro-phase separated at pH 5.5. Addition of 0.075% κ-carrageenan to WPI solutions caused the microstructure of the gel to switch from homogeneous (pH 6.0 and 6.5) to micro-phase separated; and higher concentrations led to inversion of the continuous network from protein to κ-carrageenan. Protein solutions containing 0.075% (w/w) κ-carrageenan produced gels with increased storage modulus (G′) at pH 6.5 and decreased G′ at pH 5.5. All gels containing 0.3% (w/w) κ-carrageenan had κ-carrageenan-continuous networks. It was shown that microstructural and rheological changes were different in WPI and κ-carrageenan mixed gels when micro-phase separation was caused by pH rather than ionic strength.     

Stabilization of oil-in-water emulsions by enzyme catalyzed oxidative gelation of sugar beet pectin

Enzyme catalyzed oxidative cross-linking of feruloyl groups can promote gelation of sugar beet pectin (SBP). It is uncertain how the enzyme kinetics of this cross-linking reaction are affected in emulsion systems and whether the gelation affects emulsion stability. In this study, SBP (2.5% w/v) was mixed into an oil-in-water emulsion system (4.4% w/w oil, 0.22% w/w whey protein, pH 4.5). Two separate, identically composed, emulsion systems were prepared by different methods of preparation. The emulsions prepared separately and subsequently mixed with SBP (referred as Mix A) produced significantly larger average particle sizes than the emulsions in which the SBP was homogenized into the emulsion system during emulsion preparation (referred as Mix B). Mix B type emulsions were stable. Enzyme catalyzed oxidative gelation of SBP helped stabilize the emulsions in Mix A. The kinetics of the enzyme catalyzed oxidative gelation of SBP was evaluated by small angle oscillatory measurements for horseradish peroxidase (HRP) (EC 1.11.1.7) and laccase (EC 1.10.3.2) catalysis, respectively. HRP catalyzed gelation rates, determined from the slopes of the increase of elastic modulus (G′) with time, were higher (P < 0.05) than the corresponding laccase catalyzed rates, but the final G′ values were higher for laccase catalyzed gels, regardless of the presence of emulsions or type of emulsion preparation (Mix A or Mix B). For both enzymes, rates of gelation in Mix A were higher (P < 0.05) than in Mix B, and higher stress was needed to break the gels in Mix A than in Mix B at similar enzyme dosage levels. These differences may be related to a lower availability of the feruloyl groups for cross-linking when the SBP was homogenized into the emulsion system during preparation.     

Comparison of pressure treatment and heat treatment of skim milk with added starch on subsequent acid gelation of milk

Skim milk with added starch (waxy rice starch or potato starch at levels of 0-1.5 g/100 g) was either pressure-treated (500 MPa, 20 °C, 30 min) or heat-treated (80 °C, 30 min) and subsequently acidified (using glucono-δ-lactone) to form acid milk gels. In the second part of the study, the pH of the skim milk samples was adjusted from the natural condition (pH 6.64) to pH 6.5, 6.6 or 6.9 before the pressure or heat treatment and re-adjusted back to pH 6.64 after the respective treatment. The rheological properties of the samples during acidification and of the final acid gels were studied. The storage modulus, G′, of the final acid milk gels increased as more waxy rice starch was added to milk before pressure or heat treatment. However, acid milk gels made from pressure-treated milk with added potato starch did not show significant changes in the G′ of the final acid gels whereas those made from the heat-treated counterparts showed a marked increase in the final G′ as the potato starch level increased. Waxy rice starch was gelatinised in milk by both pressure treatment and heat treatment whereas potato starch was gelatinised by heat treatment only. Increasing the pH of milk before pressure or heat treatment increased the final G′ of the acid milk gel produced on subsequent acidification of the milk and the final G′ was increased further by the addition of waxy rice starch before the pressure or heat treatment.     

Pectin from low quality ‘Golden Delicious’ apples: Composition and gelling capability

Pectin was acid-extracted from low quality ‘Golden Delicious’ apple fruit, yielding 16% (w pectin/w apple fruit). Composition and some of its physicochemical and functional properties were assessed. The pectin fraction presented a galacturonic acid content of 65% (w/w), an esterification degree of 57%, an intrinsic viscosity, [η], of 307 ml/g and a molecular weight (Mw) of 112 kDa. Pectin gels were obtained in 60% (w/v) fructose and pH 2.7. Pectin gels at 2.0% and 3.0% (w/v) presented hardness values of 10.2 and 20.4 g after 12 h at 4 °C. The gel hardness was greatly affected by aging (20% and 25% decrease in 48 h for gels at 2% and 3%, respectively). The results attained suggest the use of this gum as a potential texturing agent for the food industry.     

Effect of heat treatment,pH, sugar concentration,and metal ion addition on green color retention in homogenized puree of Thompson seedless grape

Homogenized puree of Thompson seedless (Vitis vinifera ‘Thompson Seedless’) grape was treated under different conditions, including heating time (5–30 min), temperature (20–80 °C) and pH (2–10). Treatments with separate additions of glucose, fructose, and sucrose at concentrations of 100–600 g/L and salts of MgCl₂, ZnCl₂, GuSO₄, and KCl at concentration of 1 g/L were also tested at 20 °C up to 30 min. Relative chlorophyll pigment retention (CR) was measured at 664 nm. The chlorophyll pigments were the most stable at 20 °C and the nature pH of grape puree (pH 3.4). Increasing temperature and changing pH reduced CR. After 30 min treatment at 80 °C, CR decreased to lower than 20% and 50% at pH 2 and 5, separately. Increasing fructose and sucrose concentrations reduced CR at pH 3, but increased it at most levels at pH 4. Increasing glucose concentration protected chlorophyll pigment from reduction in some cases at pH 3 and 4. CR increased with addition of metal ions increased at pH 4, but decreased at pH 3. Conditions of 23.3 °C, pH 4.5, and 120 g/kg fructose and 210 g/kg glucose produced the highest CR value.     

Rheological behaviour of uncross-linked and cross-linked gelatinised waxy maize starch with pectin gels

Rheological characterisation of uncross-linked (UPS) and cross-linked (CPS) waxy maize starch with pectin was conducted to determine the influence of pectin on the properties of the starch. The viscoelastic behaviour of 5% (w/v) gel systems containing UPS and CPS polysaccharides at 25 °C was evaluated by small angle deformation oscillation rheometry. Viscoelasticity measurements of the cross-linked polysaccharides indicated that the elastic component increased after cross-linking. Among all gels studied, the properties of the CPS mixtures (ratios 2:3 and 3:2) showed quite high storage (G′) and loss (G″) moduli (compared with gels of other ratios), indicating that gels of these two particular ratios had the greatest degree of elasticity and were very well structured. The results suggest that cross-linking between starch and pectin molecules can give rise to novel rheological properties.     

Rheological and high gelling properties of mango (Mangifera indica) and ambarella (Spondias cytherea) peel pectins

Ambarella and mango peels are good sources of pectins (15–20%), with high degree of methylation (60–78%) and high molar masses. Ambarella and mango ( Améliorée and Mango varieties) peel pectins were extracted using HCl or oxalic acid/ammonium oxalate (OAAO). Purified pectins were analysed for their flow behaviour and phase diagrams were established at pH 3 as sucrose vs. pectin concentration. The gelation kinetics and mechanical spectra of these pectin gels were studied and compared to those of commercial citrus (lime) pectins. At a concentration of 1% (w/v), all pectic solutions had a shear thinning behaviour but at 0.6% (w/v), only OAAO-extracted pectins exhibited such behaviour. Phase diagrams showed that at pH 3, gelation of OAAO mango extracted pectins was possible at low polymer concentration (0.2%; w/w) for a sucrose concentration of 60% (w/w). OAAO-extracted pectins exhibited a higher gelling ability than HCl-extracted ones. Sucrose (45–50%) and pectin (0.2–0.6%) concentration had a deep impact on the gel strength. Our results enable to conclude that the OAAO extraction from mango and ambarella peels allowed the recovery of pectins that exhibit high gelling properties.     

Nanostructural modification of a model homogalacturonan with a novel pectin methylesterase: Effects of pH on nanostructure,enzyme mode of action and substrate functionality

A Carica papaya pectin methylesterase (CpL-PME) present in a commercial papain preparation was used to modify the amount and distribution of anionic charge in a population of a model pectic homogalacturonan (HG) at pH 4.5 and pH 7.5. Introduced negatively charged demethylesterified blocks (DMB) were excised as oligomers with limited endo-polygalacturonase (EPG) digestion, and then separated and quantified by high performance anion exchange chromatography. Exhaustive EPG digestion was also performed and the concentrations of mono-, di- and tri-galacturonic acid (GalA) produced were estimated. The CpL-PME mode of action was modeled while the HG population's nanostructure and the resulting functionality of the modified pectin were characterized. The results indicated that average DMB size and number of these “average” blocks per molecule increased as the overall degree of methylesterification (DM) decreased by CpL-PME treatment (P < 0.05). Average DMB size differed depending on the reaction pH at each DM. Absolute degree of blockiness (DB_abs) increased as DM decreased and demonstrated a linear relationship with the DM at both reaction pH values. Significant positive correlations between DB_abs and average DMB size were observed for both pH series (P < 0.05). The enzyme mode of action, modeled in silico, demonstrates a processive multiple attack mechanism. Functionally, the storage modulus of ionotropic gels formed from the processed substrates increased as DM decreased, and as DB_abs and average DMB size increased with highly significant correlations (P < 0.001). These results indicate it is feasible to engineer pectin nanostructure and functionality with CpL-PME.     

Rheology and microstructure of myofibrillar protein-plant lipid composite gels: Effect of emulsion droplet size and membrane type

Composite gels were prepared from 2% myofibrillar protein (MP) with 10% imbedded pre-emulsified plant oils (olive and peanut) of various particle sizes at 0.6 M NaCl, pH 6.2. Dynamic rheological testing upon temperature sweeping (20-70 °C at 2 °C/min) showed substantial increases in G′ (elastic modulus) of MP sols/gels with the addition of emulsions, and the G′ increases were inversely related to the emulsion droplet size. Furthermore, gels containing emulsified olive oil had a greater (P < 0.05) hardness than those containing emulsified peanut oil. Regardless of oil types, MP-coated oil droplets exhibited stronger reinforcement of MP gels than Tween 80-stablized oil droplets; the latter composite gels had considerable syneresis. Light microscopy with paraffin sectioning revealed a stable gel structure when filled with protein-coated oil droplets, compared to gels with Tween 80-treated emulsions that showed coalesced oil droplets. These results suggest that rheological characteristics, hardness, texture, and water-holding capacity of MP gels were influenced by type of oils, the nature of the interfacial membrane, and the size of emulsion droplets.     

Rheological properties of whey protein isolate stabilized emulsions with pectin and guar gum

Dynamic oscillatory and steady-shear rheological tests were carried out to evaluate the rheological properties of whey protein isolate (WPI) stabilized emulsions with and without hydrocolloids (pectin and guar gum) at pH 7.0. Viscosity and also consistency index of emulsions increased with hydrocolloid concentration. At γ = 20 s⁻¹, the value of viscosity of the emulsion with 0.5% (w/v) pectin was about fivefold higher than that of the emulsion without pectin. Flow curves were analyzed using power law model through a fitting procedure. Flow behaviour index of all emulsions except for containing 0.5% (w/v) guar gum was approximately in the range of 0.9–1.0, which corresponds to near-Newtonian behaviour. The shear thinning behaviour of emulsions containing 0.5% (w/w) guar gum was confirmed by flow behaviour index, n, of 0.396. Both storage (G′) and loss modulus (G″) increased with an increase in frequency. Emulsions behaved like a liquid with G″ > G′ at lower frequencies; and like an elastic solid with G′ > G″ at higher frequencies. Effect of guar gum was more pronounced on dynamic properties. Phase angle values decreased from 89 to <10° with increasing frequency and indicated the viscoelasticity of WPI-stabilized emulsions with and without pectin/guar gum.     

Pectin recovery from apple pomace: physico-chemical and functional variation based on methyl-esterification

This study explored the valorisation of apple pomace by extracting pectin with both high and low degrees of esterification (DM). Two types of pectin were extracted with a DM of 43.29% being low methoxyl (LM) pectic polysaccharide and high methoxyl (HM) pectin with a DM of 65.88%. HM pectin was characterised by a WHC and OHC of 1.3 g g⁻¹ and 0.4 g g⁻¹, respectively, compared to 0.32 g g⁻¹ and 0.14 g g⁻¹, respectively, for LM pectic polysaccharide. HM pectin possessed greater purity indicated by 69.18% GalA, whereas LM pectic polysaccharide possessed 41.26% GalA. HM pectin revealed better functionality in terms of high emulsifying activity which was concentration-dependent, and emulsion stability than LM pectic polysaccharide. The solubility of HM pectin was 90.8%, which is preferable for various industrial applications. LM pectic polysaccharide was characterised by a higher % radical-scavenging activity in a concentration-dependent manner. XRD analysis revealed LM pectic polysaccharide to possess higher crystallinity (53%) and SEM analysis revealed its surface to be rough and coarse.     

Effect of Lepidium perfoliatum seed gum addition on whey protein concentrate stabilized emulsions stored at cold and ambient temperature

In this study the effect of Lepidium perfoliatum seed gum on the properties of whey protein concentrate (WPC) stabilized corn oil-in-water emulsions at pH 7 was investigated. Various concentrations (0–0.6% w/v) of L. perfoliatum seed gum were used together with 2% (w/v) WPC to emulsify corn oil in water at a ratio of 1:5. Quality attributed such as particle size distribution, creaming profile and coalescence rate during storage at 4 and 25 °C; surface and interfacial tension; zeta potential and viscosity of the emulsions were determined. The results indicated that the addition of L. perfoliatum seed gum had no significant effect on zeta potential but the surface and interfacial tension increased with the rise of gum concentration. It was also found that the addition of L. perfoliatum seed gum to WPC emulsions at a critical concentration of 0.2% (w/v) caused flocculation of oil droplets, which resulted in marked increase in particle size and the creaming rate. However at higher gum concentrations beyond this value, the particle size remained constant, apparently because of the high viscosity of the aqueous phase. At all concentrations tested, emulsions stored at 4 °C were more stable except for those containing 0.2% L. perfoliatum seed gum.     

Functionality and yield of pectin extracted from Palmyra palm (Borassus aethiopum Mart) fruit

Large numbers of fruits from Palmyra palm (Borassus aethiopum Mart), a common, native tree of tropical regions, are underutilized and left to spoil. This work was conducted to assess pectin content of Palmyra palm fruit, and to develop a reliable protocol for pectin extraction. Yield and galacturonic acid content of Palmyra palm fruit soluble solids were investigated at various pH (natural pH of 5.2–5.5, 2.5, 7), time (30–120 min) and temperature (70 °C, 80 °C, 90 °C). Yield and galacturonic acid content of extracted soluble solids were strongly dependent (p < 0.0001) on temperature, time and pH of extraction and ranged from 47 to 149 g kg⁻¹ and 682 to 880 g kg⁻¹ dry weight, respectively. High galacturonic acid (808–852 g kg⁻¹) were obtained at 70 °C and 90 °C under natural pH; at 70 °C pH 7 and pH 2.5 at all temperatures studied. Analysis of pectin extracted at natural pH (30 min, 90 °C) revealed highly esterified pectin with good gelling and emulsifying properties. Production of galacturonic acid of more than 650 g kg⁻¹ dry weight indicates that Palmyra palm fruit could serve as an excellent raw material for industrial pectin production.