Arjen Bot

Acid-induced gelation of heat-treated milk studied by diffusing wave spectroscopy

Fresh skim milk is a stable colloidal system containing casein micelles and whey proteins. By decreasing the pH, the casein micelles become unstable and a gel is formed. During heat treatment at temperatures higher than 70 degrees C, the major whey proteins, e.g. alpha-lactalbumin and beta-lactoglobulin denature and start to interact with each other and with casein micelles. This changes the colloidal properties of the casein micelles. In this article, the pH-induced gel formation of heat-treated milk and the role of whey proteins was studied. Heat treatment in the range 70-90 degrees C induced a shift in gelation pH of skim milk to more alkaline pH values. This shift was directly related to whey protein denaturation. By using WPF milk it was shown that beta-lactoglobulin is principally responsible for the shift in gelation pH. alpha-lactalbumin caused neither alone nor in combination with beta-lg, an effect on the gelation pH. Heat treatment of milk for 10 min at 90 degrees C resulted in complete denaturation of the beta-lg present in skim milk but it is estimated that the casein micelles are coated only up to 40% by whey proteins when compared with pure whey protein aggregates.

Large deformation rheology of gelatin gels

Abstract We studied the linear and the non-linear elastic behaviour, the breaking stress and breaking strain of gelatin gels as a function of a number of experimental conditions: gelatin concentration, gelatin bloom value, ageing time, ageing temperature, pH, NaCl and CaCl2 concentration, whey protein concentration, the amount of pre-shearing, strain rate or compression speed, using both shear deformation and compression. We analyzed the stress-strain curves using the BST-equation (Blatz et al., Trans. Soc. Rheol. 18, (1974) 145) and extracted a parameter that characterizes the linear elastic behaviour at small deformations (the moduli E or G) and one that characterizes the non-linear elastic behaviour at large deformations (the elasticity parameter n). The phenomenological BST equation describes rheological experiments adequately both in shear deformation and in compression. We found that the modulus correlates with the breaking stress. For the non-linear elastic properties of gelatin, we found that the elasticity parameter n correlates with the breaking strain Qualitatively, the non-linear elastic properties can be explained by assuming that the gelatin chains are partially in a crystalline triple helix state (the cross-links) and partially in a random coil state (the network bonds): the more extensive the rigid cross-link regions, the shorter and more stretched the network bonds become as a result of an externally applied deformation. The network bonds behave as anharmonic springs under extreme extension. Manipulation of the breaking strain was attempted in two ways: (i) by changing the (non-linear) elasticity parameter of the gel: this is possible by using a gel that has been further aged; (ii) by adding defects to the gel structure: this is possible by either pre-shearing the gel or by adding whey protein particles. The pre-shearing gives rise to a temporary effect, the addition of whey protein particles to a permanent effect.

Molecular theory of strain hardening of a polymer gel: Application to gelatin

The elasticity of gelatin gels at large deformation has been measured for various experimental conditions. The general pattern is that stress increases with strain in a nonlinear way up to the point where the gel fails. To interpret this nonlinear stress increase, we studied a number of molecular models by Monte Carlo simulation and by mean‐field methods. The effect of finite polymer length is studied via the FENE model (finite extensible nonlinear polymer connections) and via the exact statistics of Kramers’ model (chains of freely rotating stiff rods) for a small number of elements per chain. To investigate the effect of fractal connections, the end‐point distribution that comes forward from scaling theory has been generalized to arbitrary fractal dimension. Finally we studied a heterogeneous network model: connections formed by rods and coils. We also discuss the consequence of microphase separation. Combining experiment and theory we conclude the following: (i) The elastically active network connectio...

Differential Scanning Calorimetric Study on the Effects of Frozen Storage on Gluten and Dough

ABSTRACT Water transport from the gluten to the starch paste during frozen storage of a dough was studied by analysis of the differential scanning calorimetry (DSC) peak shape for gluten and dough. The results indicate that in gluten stored at -15°C, the water content in the gluten phase decreased by ≈1% over the first three weeks. An apparent steady state was attained over this period and the amount of ice did not increase further. Such changes were not observed for samples stored at -25°C. Qualitatively similar observations were made for dough stored at either -15 or -25°C. The greater sensitivity of dough to frozen storage is tentatively attributed to a slightly lower glass transition temperature in dough.

Organogel-Emulsions with Mixtures of β-Sitosterol and γ-Oryzanol: Influence of Water Activity and Type of Oil Phase on Gelling Capability

In this study, water-in-oil emulsions were prepared from water containing different salt concentrations dispersed in an oil phase containing a mixture of β-sitosterol and γ-oryzanol. In pure oil, the β-sitosterol and γ-oryzanol molecules self-assemble into tubular microstructures to produce a firm organogel. However, in the emulsion, the water molecules bind to the β-sitosterol molecules, forming monohydrate crystals that hinder the formation of the tubules and resulting in a weaker emulsion-gel. Addition of salt to the water phase decreases the water activity, thereby suppressing the formation of sitosterol monohydrate crystals even after prolonged storage times (∼1 year). When the emulsions were prepared with less polar oils, the tubular microstructure was promoted, which significantly increased the firmness of the emulsion-gel. The main conclusion of this study is that the formation of oryzanol and sitosterol tubular microstructure in the emulsion can be promoted by reducing the water activity and/or by using oils of low polarity.

Multicomponent Hollow Tubules Formed Using Phytosterol and γ-Oryzanol-Based Compounds: An Understanding of Their Molecular Embrace

The formation kinetics of self-assembling tubules composed of phytosterol:gamma-oryzanol mixtures were investigated at the Canadian Light Source on the mid-IR beamline using synchrotron radiation and Fourier transform infrared spectroscopy (FT-IR). The Avrami model was fitted to the changing hydrogen bonding density occurring at 3450 cm(-1). The nucleation process was found to be highly dependent on the molecular structure of the phytosterol. The nucleation event for cholesterol:gamma-oryzanol was determined to be sporadic whereas 5alpha-cholestan-3beta-ol:gamma-oryzanol and beta-sitosterol:gamma-oryzanol underwent instantaneous nucleation. One-dimensional growth occurred for each phytosterol:gamma-oryzanol mixture and involved the evolution of highly specific intermolecular hydrogen bonds. More detailed studies on the cholesterol:gamma-oryzanol system indicated that the nucleation activation energy, determined from multiple rate constants, obtained using the Avrami model, was at a minimum when the two compounds were at a 1:1 weight ratio. This resulted in drastic differences to the microscopic structures and affected the macroscopic properties such as turbidity. The formation of the phytosterol:gamma-oryzanol complex was due to intermolecular hydrogen bonding, which was in agreement with the infrared spectroscopic evidence.

Molecular theory of the yield behavior of a polymer gel: Application to gelatin

A microscopic model for the endpoint separation dependent scission rate of a polymer connection in a network is developed. The predicted dissociation rate is proportional to the exponential of the bond force, which is in line with experiments. This atomistic description is thereupon incorporated in a mesoscopic theory to describe strain hardening and failure of physical gels. The resulting theory has been analyzed by a new numerical algorithm, which is some 100 to 1000 times faster than the algorithm described in the literature. We applied this theory to gelatin. To arrive at the correct nonlinear rheologic behavior of the gel, the non‐Gaussian nature of the polymer endpoint distribution has to be taken into account. There are four important physical quantities that describe the nonlinear rheology of gelatin. For relatively small shear strain (0<γ<1), stress increases nonlinearly with strain when a gel is deformed (strain hardening). The strain at which the gel ruptures (the yield strain γy) increases qui...

Manipulation of glycemic response with isomaltulose in a milk-based drink does not affect cognitive performance in healthy adults

Previous research suggests that glucoregulation and nutrient interventions, which alter circulating glucose, impact cognitive function. To examine the effect of modulating glycemic response using isomaltulose on cognitive function 24 healthy male adult participants consumed energy and macronutrient-matched milk-based drinks containing 50 g isomaltulose, 50 g sucrose or a water control in a counterbalanced within-subject design. Interstitial glucose was measured continuously in 12 subjects and all provided 9 capillary measures on each test day. A 30-min cognitive test battery was administered before and twice (+35 and +115 min) after drink ingestion. Immediate, delayed, recognition, verbal and working memory, and psychomotor performance were assessed. Glycemic profiles induced by the drinks differed significantly during the first but not the second post-drink test battery. Neither administration of the sucrose nor isomaltulose drinks produced consistent effects on verbal or working memory, or psychomotor performance. This study used isomaltulose as an investigative tool to lower glycemic response. Importantly, it demonstrates a lack of effect of modulating glucose on cognitive performance based on reliable, continuously measured glycemia. It refutes the hypothesis that glycemia is associated with cognitive performance and questions the suggestion that isomaltulose has an effect on cognitive performance.

Effect of water on self-assembled tubules in β-sitosterol + γ-oryzanol-based organogels

Mixtures of β-sitosterol and γ-oryzanol form a network in triglyceride oil that may serve as an alternative to the network of small crystallites of triglycerides occurring in regular oil structuring. The present x-ray diffraction study investigates the relation between the crystal forms of the individual compounds and the mixture in oil, water and emulsion. β-Sitosterol and γ-oryzanol form normal crystals in oil, in water, or in emulsions. The crystals are sensitive to the presence of water. The mixture of β-sitosterol + γ-oryzanol forms crystals in water and emulsions that can be traced back to the crystals of the pure compounds. Only in oil, a completely different structure emerges in the mixture of β-sitosterol + γ-oryzanol, which bears no relation to the structures that are formed by both individual compounds, and which can be identified as a self-assembled tubule (diameter 7.2±0.1 nm, wall thickness 0.8±0.2 nm).

The adsorption of Ba on Ag(111)

The growth behaviour of barium on silver(111) at room temperature is investigated by AES, XPS, MEIS, TDS, work function measurements and by monitoring the secondary-electron-emission crystal current. It is shown that, for low coverage, initially a 2D monolayer is formed. For higher coverages the overlayer formed resembles a structure formed by Poisson or Stranski-Krastanov growth with small islands. As evaporation continues the islands become very large or the sticking coefficient drops to zero. Annealing the Ag with more than one monolayer of Ba on top shows a large work function decrease of 0.6 eV to an unusually low value of 1.9 eV. The lowering of the work function can partly be explained by the formation of large clusters. Coadsorption experiments with H2 indicate that the H2 sticking coefficient on Ba/Ag(111) is constant and that the H2 adsorbs dissociatively into one binding state. From the experiments an inelastic mean free path of 11+or-1 AA for 351 eV electrons and 17+or-1 AA for 1113 eV and 1119 eV electrons is deduced.