J.A. Lopes da Silva

Studies on a purification method for locust bean gum by precipitation with isopropanol

Abstract A commercial sample of locust bean gum was dissolved in hot water, centrifuged, and the supernatant and the sediment were recovered. Part of the supernatant was freeze-dried and the rest was poured into isopropanol to yield a precipitate of purified gum. This precipitate was recovered and a part of it was subjected to a second purification with isopropanol; an almost pure galactomannan sample was obtained. Another sample of the crude gum was fractionated on the basis of its solubility in water at different temperatures. Five fractions were obtained with mannose to galactose ratios (M/G) increasing with the temperature of fractionation. The purified samples exhibited higher M/G ratios and number average molecular weights (M n ) than the crude gum, whereas the opposite was observed with the freeze-dried sample. The polydispersity index decreased quite significantly in purified samples, meaning that they were more homogeneous than the original sample. Intrinsic viscosities were lower for the purified samplesv The flow behaviour of aqueous solutions of the gums was studied in the concentration range 0.6–1.2 g/dl: the solutions of the crude gum had higher viscosities than those of the purified and the freeze-dried gums at similar concentrations, throughout the shear rate range.

Calcium-mediated gelation of an olive pomace pectic extract

Pectic raw material was extracted from the alcohol insoluble residue of olive pomace. After purification, the olive pectic extract (OPE) contained 48% of galacturonic acid (GalA) and 31% of arabinose, in a total sugar content of 72%, and a degree of methylesterification (DM) of 43%. Phase diagrams were established to define the physical state of the OPE/calcium systems, at pH 3 and 7, as a function of GalA and calcium concentration. The rheological properties of the OPE/calcium systems were investigated by small-amplitude oscillatory tests. Kinetics of gel ageing and the viscoelastic properties of the cured gels were evaluated as a function of GalA and calcium concentration at pH 3 and 7. Compared with the observed behaviour of a citrus pectin, taken as representative of a commercial low-methoxyl pectin, the OPE showed higher critical GalA and calcium concentrations for gelation to occur, a larger region corresponding to homogeneous gel, and gels characterised by lower viscoelastic moduli, at similar GalA and calcium concentrations.

Temperature dependence of the formation and melting of pectin-Ca2+ networks: a rheological study

Abstract Small deformation dynamic rheometry was used to characterise the calcium-induced gelation of low-methoxyl pectins, at two different pH values. The gelation kinetics was interpreted with basis on the change of the storage modulus with time, taken as a measure of changes in cross-linking density within the pectin–calcium network. The temperature influence on the rate of gel formation and ageing was evaluated, as well as the temperature sensitivity of the cured gels. The formation and the softening/melting of pectin–calcium networks were also studied under non-isothermal conditions. The structural diversity of the two pectin samples had a great influence on the gelation kinetics and thermal behaviour of these pectin–calcium networks, due to differences in the steric arrangement or environment and/or availability of the chelating groups. An association mechanism is suggested to predominate under conditions of low availability of dissociated carboxylic groups, due to a low pH, higher degree of methylation, or steric constraints introduced by acetylation or neutral side chains, different from the classical ‘egg-box’ model, and where non-ionic hydrogen bonding and hydrophobic interactions may co-exist and cooperate with coordinative binding of calcium-ions.

KINETICS AND THERMAL BEHAVIOUR OF THE STRUCTURE FORMATION PROCESS IN HMP/SUCROSE GELATION

The concentration and temperature dependence of the gelation kinetics of high-methoxyl pectin (HMP; 60% sucrose, pH 3) was investigated using measurements of small-amplitude oscillatory shear. The rate of gelation close to the gel point can be described as a second-order rate process using the kinetic model of Ross-Murphy (Carbohydr. Polym. 1991, 14, 281) and a critical exponent close to that predicted by the percolation approach. The modulus after a long ageing time showed a power concentration dependence with an exponent around 3.1, higher than the classical square of concentration dependence, which was probably either due to the nonequilibrium state of the HMP gels even after long ageing times, or due to the proximity of the concentration range studied to the critical gelling concentration. The gelation rate of HMP/sucrose systems is strongly dependent on the temperature. An Arrhenius relationship was applied to describe this dependence. Two different processes are proposed to explain the discontinuity observed, each one having rates with different temperature dependence. The applicable kinetics at longer times are quite different, with a lower dependence on polymer concentration and ageing temperature. A non-isothermal kinetic model was used to describe the gelation process of the HMP/sucrose system during cooling.

Influence of temperature on the dynamic and steady-shear rheology of pectin dispersions

Abstract The influence of temperature on the dynamic and steady-shear rheology of ionic polysaccharides, high-methoxyl and low-methoxyl pectins, has been studied and compared with the behaviour of locust bean gum, a virtually neutral biopolymer. Using the time-temperature superposition principle, the rheological parameters were reduced to an arbitrary reference temperature. Activation energies were calculated and their dependence on temperature and shear rate analysed. Concerning the viscosity dependence on temperature, two approaches have been considered: one associated with the theory of absolute reaction rates leading to an Arrhenius type equation, and the other associated with the free volume theory, expressed by the Williams-Landel-Ferry equation. The difficulties encountered in the superposition of the dynamic properties of the pectin dispersions, the high activation energies, yield values and elastic plateau at low oscillatory frequency, are consistent with a macromolecular organization of these polymers dominated by important aggregation phenomena, which could be attributed to important intermolecular interactions like hydrogen bonding and hydrophobic interactions, especially in conditions of low degree of ionization of the carboxylic groups.

Rheological study into the ageing process of high methoxyl pectin/sucrose aqueous gels

Abstract The ageing process of high methoxyl pectin (HMP)/sucrose gels was followed at different ageing temperatures by small amplitude oscillatory experiments. Dynamic mechanical measurements allowed the characterisation of the point at which the system undergoes the sol/gel transition. The HMP/sucrose system is extremely sensitive to temperature variation during ageing, especially in the lower temperature range. The viscoelastic behaviour through the gel point changes with the ageing temperature, probably due to variations in mobility of the pectin chains, and consequently, in the lifetime of junction zones. Weaker pectin networks are formed under thermal conditions unfavourable to the development of hydrophobic interactions. Gel time and elastic modulus have a complex dependence on temperature, which could be attributed to the different thermal behaviour of the intermolecular interactions that stabilise the nonpermanent cross links of these physical networks.

Rheology of galactomannan–whey protein mixed systems

Abstract The rheological behaviour of whey protein/galactomannan mixtures in aqueous solutions was studied under gelling conditions of the protein component, at neutral pH and at a pH close to the protein isoelectric point. The presence of the neutral polysaccharide had significant effects on the formation and viscoelastic behaviour of the cured gels. This effect was dependent on the structural organisation of the protein network. At pH 7 the galactomannan had a general positive effect on WPI gel formation. It is suggested that under these conditions, the protein network forms a continuous phase that accommodate the polysaccharide chains, acting as a filler of the protein network. The minimum protein concentration for gelation to occur, the gelation temperature and time all decrease in the presence of the galactomannan. Under pH conditions near the whey protein isoelectric point, different effects were observed as a result of the galactomannan addition. At low WPI concentration, the galactomannan had a detrimental influence on the protein network formation, but a negligible effect or even a positive influence on the gelation process at higher concentrations.

Viscoelastic behaviour of mixtures of locust bean gum and pectin dispersions

Abstract Viscoelastic properties of single-component systems — locust bean gum (LBG), high-methoxyl (HMP) and low-methoxyl (LMP) pectins- and of HMP/LBG and LMP/LBG blends, were studied using dynamic oscillatory and steady-shear methods. The mechanical spectra of HMP/LBG blends showed characteristics intermediate between the individual components. A possible weak antagonistic interaction was found between LMP and LBG, especially in the mixture with similar amount of each single-component solution. Correlation between dynamic and steady-shear viscosities was compared with the empirical rule of Cox and Merz. Departures from the Cox-Merz rule were observed for the HMP dispersions, whereas for the LMP and the LBG dispersions the Cox-Merz rule prediction was satisfactory. The different behaviour of LMP relative to the HMP dispersions can be attributed to the lesser extent of intermolecular association and higher hydrodynamic volume, due to the higher charge density.

Evidence for the Aging of Wax Deposits in Crude Oils by Ostwald Ripening

Abstract The ageing of wax deposits is known to occur in paraffinic waxes forming in pipelines and storage tanks. It is characterized by a hardening of the deposit and an increase in paraffin content. A mechanism for the ageing of deposits, based on diffusion caused by temperature-concentration gradients within the wax, has been previously proposed. This work presents evidence indicating Ostwald Ripening to be another ageing mechanism of wax deposits. Rheology of paraffinic crudes, kept isothermally at temperatures in the neighborhood of the pour point, shows a kinetic of hardening of the oil samples. The X-ray diffraction and Cross Polar Microscopy indicate this phenomenon to be caused by an increase of the crystallites size with time. The DSC measurements support the idea that recrystallization takes place in the wax sample. The evidence gathered shows another ageing mechanism based on the recryztallization of the paraffins, such as Ostwald Ripening, to be responsible for the ageing of wax deposits besides the diffusion mechanism previously proposed

Effect of galactomannans on the viscoelastic behaviour of pectin/calcium networks

Abstract An investigation was carried out on the effect of the addition of galactomannans to pectin/calcium networks with different structural and rheological characteristics. For those pectin/calcium gels characterized by an elastic equilibrium modulus, the addition of the galactomannan increased both the storage and loss moduli, especially at short time scales. This increase was greater than that which could be expected by simple additivity of the viscoelastic properties of each isolated system. The pectin/calcium network remained the continuous gel matrix controlling the viscoelastic behaviour of these systems at low frequency. For pectin/calcium systems close to the sol-gel transition or at low pH, the mixed systems evolved towards the behaviour of viscoelastic liquids in the presence of increasing concentration of the non-gelling polymer. These overall results suggest that there is no specific interaction and that the changes in the rheological properties of the pectin gels are due to galactomannan microphase separation limited by the entrapment of these macromolecules in the pectin-calcium network.