Phase Behavior of Ternary Polymer Mixtures in a Common Solvent.

The Edmond-Ogston model for phase separation is extended to ternary polymer mixtures in a common solvent (de facto a quaternary mixture). The model assumes a truncated virial expansion of the Helmholtz free energy up to the second-order terms in the concentration of the polymers, and the second virial coefficients (B11, B22, B33, B12, B13, B23) are the six parameters of the model. New results from this model are presented in relation to earlier work on binary mixtures: a necessary condition for the virial coefficients for the occurrence of phase separation in two or three phases, an analysis of the different regions of (local) thermodynamic instability using the Descartes sign rule, an expression for the critical curves, a relation between the tangents in points along the critical curve, a relation between the concentration of components in the different phases according to the so-called Lambert-W function, and a consistency check for the composition of coexisting phases in ternary mixtures. The obtained results are evaluated in the maximally symmetric version of the model, where (B11, B22, B33) are equal and (B12, B13, B23) are equal, which leads to two remarkable observations: the concentration range over which two phases are formed is relatively narrow; not all phase separation occurs within a Gibbs triangle, but also, "out-of-Gibbs-triangle" binodals are observed. These results lead to a deeper insight into the phase behavior of ternary mixtures and show promise as a stepping stone toward modeling phase separation in mixtures with many components.

Exploring how changes to the steroidal core alter oleogelation capability in sterol: γ-oryzanol blends.

Oleogels based on sterols such as ß-sitosterol blended with the sterol ester γ-oryzanol are a very interesting class of systems, but there are aspects of their formation and structure that remain elusive. It has previously been shown that a methyl group on the C30 position of the sterol-ester plays an important role in gelation. This work explored the effect that having C30 methyl groups on both the sterol and the sterol-ester had on the gelation process and subsequent gel structure. Lanosterol and saponified γ-oryzanol (which was synthesized as part of this study) were identified as materials of interest, as both feature a methyl group on the C30 position of their steroidal cores. It was observed that both sterols formed gels when blended with γ-oryzanol, and also that lanosterol gelled sunflower oil without the addition of γ-oryzanol. All of these gels were significantly weaker than that formed by ß-sitosterol blended with γ-oryzanol. To explore why, molecular docking simulations along with AFM and SAXS were used to examine these gels on a broad range of length scales. The results suggest that saponified γ-oryzanol-γ-oryzanol gels have a very similar structure to that of ß-sitosterol-γ-oryzanol gels. Lanosterol-γ-oryzanol gels and pure lanosterol gel, however, form with a totally different structure facilitated by the head-to-tail stacking motif exhibited by lanosterol. These results give further evidence that relatively slight changes to the molecular structure of gelators can result in significant differences in subsequent gel properties.

Erratum: Addition to "Phase-Separating Binary Polymer Mixtures: The Degeneracy of the Virial Coefficients and Their Extraction from Phase Diagrams".

[This corrects the article DOI: 10.1021/acsomega.1c00450.].

Phase-Separating Binary Polymer Mixtures: The Degeneracy of the Virial Coefficients and Their Extraction from Phase Diagrams.

The Edmond-Ogston model for phase separation in binary polymer mixtures is based on a truncated virial expansion of the Helmholtz free energy up to the second-order terms in the concentration of the polymers. The second virial coefficients (B 11, B 12, B 22) are the three parameters of the model. Analytical solutions are presented for the critical point and the spinodal in terms of molar concentrations. The calculation of the binodal is simplified by splitting the problem into a part that can be solved analytically and a (two-dimensional) problem that generally needs to be solved numerically, except in some specific cases. The slope of the tie-lines is identified as a suitable parameter that can be varied between two well-defined limits (close to and far away from the critical point) to perform the numerical part of the calculation systematically. Surprisingly, the analysis reveals a degenerate behavior within the model in the sense that a critical point or tie-line corresponds to an infinite set of triplets of second virial coefficients (B 11, B 12, B 22). Since the Edmond-Ogston model is equivalent to the Flory-Huggins model up to the second order of the expansion in the concentrations, this degeneracy is also present in the Flory-Huggins model. However, as long as the virial coefficients predict the correct critical point, the shape of the binodal is relatively insensitive to the specific choice of the virial coefficients, except in a narrow range of values for the cross-virial coefficient B 12.

The Phase Behavior of γ-Oryzanol and ß-Sitosterol in Edible Oil.

The phase behavior of binary mixtures of γ-oryzanol and ß-sitosterol and ternary mixtures of γ-oryzanol and ß-sitosterol in sunflower oil was studied. Binary mixtures of γ-oryzanol and ß-sitosterol show double-eutectic behavior. Complex phase behavior with two intermediate mixed solid phases was derived from differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS) data, in which a compound that consists of γ-oryzanol and ß-sitosterol molecules at a specific ratio can be formed. SAXS shows that the organization of γ-oryzanol and ß-sitosterol in the mixed phases is different from the structure of tubules in ternary systems. Ternary mixtures including sunflower oil do not show a sudden structural transition from the compound to a tubule, but a gradual transition occurs as γ-oryzanol and ß-sitosterol are diluted in edible oil. The same behavior is observed when melting binary mixtures of γ-oryzanol and ß-sitosterol at higher temperatures. This indicates the feasibility of having an organogelling agent in dynamic exchange between solid and liquid phase, which is an essential feature of triglyceride networks.

Stability of aqueous food grade fibrillar systems against pH change.

We report that the stability of an aqueous food grade fibril system upon pH change is affected by the presence of peptides that are formed during the process of fibril formation. We discuss several other relationships between food relevant properties and nano-scale characteristics, and compare these relationships for aqueous fibril systems to those of oil based fibril systems. In such fibril systems, dynamics, self-organisation, and sensitivity to external conditions, play an important role. These aspects are common to complex systems in general and define the future challenge in relating functional properties of food to molecular scale properties of their ingredients.

Elucidation of density profile of self-assembled sitosterol + oryzanol tubules with small-angle neutron scattering.

Small-angle neutron scattering (SANS) experiments have been performed on self-assembled tubules of sitosterol and oryzanol in triglyceride oils to investigate details of their structure. Alternative organic phases (deuterated and non-deuterated decane, limonene, castor oil and eugenol) were used to both vary the contrast with respect to the tubules and investigate the influence of solvent chemistry. The tubules were found to be composed of an inner and an outer shell containing the androsterol group of sitosterol or oryzanol and the ferulic acid moieties in the oryzanol molecule, respectively. While the inner shell has previously been detected in SAXS experiments, the outer shell was not discernible due to similar scattering length density with respect to the surrounding solvent for X-rays. By performing contrast variation SANS experiments, both for the solvent and structurant, a far more detailed description of the self-assembled system is obtainable. A model is introduced to fit the SANS data; we find that the dimensions of the inner shell agree quantitatively with the analysis performed in earlier SAXS data (radius of 39.4 +/- 5.6 angstroms for core and inner shell together, wall thickness of 15.1 +/- 5.5 angstroms). However, the newly revealed outer shell was found to be thinner than the inner shell (wall thickness 8.0 +/- 6.5 angstroms). The changes in the scattering patterns may be explained in terms of the contrast between the structurant and the organic phase and does not require any subtle indirect effects caused by the presence of water, other than water promoting the formation of sitosterol monohydrate in emulsions with aqueous phases with high water activity.

Organogel-emulsions with mixtures of ß-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 ß-sitosterol and γ-oryzanol. In pure oil, the ß-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 ß-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.

The Influence of Concentration and Temperature on the Formation of γ-Oryzanol + ß-Sitosterol Tubules in Edible Oil Organogels.

The gelation process of mixtures of γ-oryzanol and sitosterol structurants in sunflower oil was studied using light scattering, rheology, and micro-scanning calorimetry (Micro-DSC). The relation between temperature and the critical aggregation concentration (CAC) of tubule formation of γ-oryzanol and sitosterol was determined using these techniques. The temperature dependence of the CAC was used to estimate the binding energy and enthalpic and entropic contribution to the tubular formation process. The binding energy calculated at the corresponding temperatures and CACs were relatively low, in order of 2 RT (4.5 kJ mol(-1)), which is in accord with the reversibility of the tubular formation process. The formation of the tubules was associated with negative (exothermic) enthalpy change (ΔH(0)) compared with positive entropy term (-T ΔS(0) >0), indicating that the aggregation into tubules is an enthalpy-driven process. The oryzanol-sitosterol ratio affected the aggregation process; solutions with ratio of (60 oryzanol-40 sitosterol) started aggregation at higher temperature compared with other ratios.

Effect of hydrolysed egg protein on brain tryptophan availability.

Serotonin synthesis critically depends on plasma levels of tryptophan (TRP). Earlier studies have shown that for mood and cognitive benefits to occur, the ratio between TRP and other large neutral amino acids (LNAA) has to be increased by approximately 40 %. The present study investigated the dose-dependent effects of a TRP-rich hydrolysed protein (egg-protein hydrolysate, EPH) on the plasma TRP:LNAA. Moreover, it was investigated whether EPH could increase TRP:LNAA in the presence of 2 g of milk protein (MP). In a randomised double-blind crossover design, plasma amino acids were measured every 30 min for 3·5 h after ingestion of a drink containing either three different doses of 4, 8 and 12 g EPH containing 270, 560 or 800 mg of TRP, respectively, the combination of 4 g EPH and 2 g MP (74 mg TRP), or 4 g MP (148 mg TRP) in twenty healthy subjects with a mean age of 52 years. All three EPH doses caused significant increases of TRP:LNAA above 40 % at 30, 60 and 90 min after consumption in a dose-dependent manner. Compared with the 4 g EPH, the increase in TRP:LNAA in the 4 g EPH with 2 g MP condition was significantly lower at 60 min (63 v. 44 %, P < 0·001) and did not differ significantly at 90 min (58 v. 53 %, P>0·05). The present study showed that a low dose of 4 g EPH with even the addition of 2 g MP was sufficient to increase the ratio of TRP:LNAA above 40 %. Thus, EPH offers a viable ingredient to increase TRP availability.

Multicomponent hollow tubules formed using phytosterol and gamma-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.

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.

Stability of whey-protein-stabilized oil-in-water emulsions during chilled storage and temperature cycling.

The stability of heat-treated and/or acidified, partly-crystalline-fat-based, whey-protein-stabilized oil-in-water (o/w) emulsions against partial coalescence was investigated during chilled storage (at 5 degrees C) and repeated temperature cycling (three times between 5 and 25 degrees C). Experiments focused on the evolution of firmness and droplet size (using pulsed field gradient NMR and scanning electron microscopy). Besides the effects of denaturation and/or acidification, the influence of the droplet size of the dispersed phase on emulsion stability was investigated also. It was found that heat treatment or acidification before emulsification led to unstable emulsions during temperature cycling, whereas heat treatment after acidification resulted in stable emulsions.