An-Najah Staff

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.

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 Å for core and inner shell together, wall thickness of 15.1 ± 5.5 Å). However, the newly revealed outer shell was found to be thinner than the inner shell (wall thickness 8.0 ± 6.5 Å). 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.

Mixtures of γ-oryzanol and β-sitosterol were used to structure different oils (decane, limonene, sunflower oil, castor oil, and eugenol). The γ-oryzanol and β-sitosterol mixtures self-assemble into double-walled hollow tubules (∼10 nm in diameter) in the oil phase, which aggregate to form a network resulting in firm organogels. The self-assembly of the sterol molecules into tubules was studied using light scattering and rheology. By using different oils, the influence of the polarity of the oil on the self-assembly was studied. The effects of temperature and structurant concentration on the tubuler formation process were determined and the thermodynamic theory of self-assembly was applied to calculate the change in Gibbs free energy (ΔG0), enthalpy (ΔH0), and entropy (ΔS0) resulting from the aggregation of the structurants was determined. The self-assembly was found to be enthalpy-driven as characterized by a negative ΔH0 and ΔS0. A decreasing polarity of the oil promotes the self-assembly leading to formation of tubules at higher temperatures and lower structurant concentrations.

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.