The role of solvent composition (polar minor components, PC) on β‐sitosterol/γ‐oryzanol oleogel formation, appearance, and properties is studied. Solvent composition is altered via thermal treatment and the elimination of natural PC from untreated sunflower and canola oil. A maximum in oleogel hardness is found. DSC reveals that sol‐gel transition is increasingly suppressed with the level of PC. This is attributed to two distinct mechanisms: enlarged interactions of PC with the structuring elements and a reduction in diffusion due to a higher solvent viscosity. Gel‐sol‐transition consists of two concurrent processes: decomposition of tube bundles (peak fronting) and the dissolution of tubes (peak). The peak area decreases with increasing solvent permittivity while simultaneously the area of the fronting increases. Gel‐sol‐transition temperatures are practically invariable for all samples indicating that the maximum in gel hardness cannot be related to changes in the solubility of the sterols. AFM microscopy reveals that the arrangement of the elements of scaffolding changes considerably with the level of PC. This work demonstrates the strong impact of PC on the self‐assembly of β‐sitosterol/γ‐oryzanol and oleogel properties. A detailed characterization of the oils is thus inevitable to perform trustworthy research. Practical Applications: It is widely known that a high intake of saturated fatty acids increases the risk of suffering from cardiovascular diseases. Unfortunately, their ability to provide unique texture to food products can hardly be met. Oleogelation has the potential to deliver the solid structure necessary for various fat‐based food products by transferring an oil rich in essential fatty acids into a solid‐like structure. Moreover, the nutritional value of these oils remains nearly unchanged. It is found that oil composition, precisely the fatty acid composition of the TAGs and minor oil components have a profound impact on oleogel properties. Fundamental understanding of network properties and formation of oleogels helps to maximize their capability for industrial application. The work presented reveals that detailed documentation of the quality of the oils, in particular the fatty acid composition and presence of polar minor components, is a necessary prerequisite to conduct reliable scientific work in the field oleogel research. Hardness and spatial arrangement of network building blocks of of β‐sitosterol/γ‐oryzanol oleogels is modified in the presence/absence of polar minor components.
In this contribution, a new model to predict the thermodynamic properties, namely enthalpy of fusion (ΔHf) and melting temperature (Tm), of pure triglycerides (TAGs) is presented. Different contributions to these properties could be expressed by means of repetitive structural attributes deduced from molecular structures. Carefully formulated configurational and geometrical simplifications enabled to attribute physical meaning to most of the parameters. Overall, the number of adjustable parameters is successfully minimized to less than half compared to the well‐known model proposed by Wesdorp in “Liquid‐multiple solid phase equilibria in fats: theory and experiments” (1990). Comparing both models revealed that the new model surpasses the reference model considering desirable prediction quality, thermodynamical consistency, and the number of adjustable parameters. Practical application: The successful description of the phase behavior of TAG mixtures is crucial to understand complex phenomena in fat‐based products. This objective is based on reliable predictions of pure component properties and non‐ideal mixing in liquid‐ and solid‐phases. The newly formulated model gives reliable descriptions of experimental data and predictions of unknown data of TAGs — both thermodynamically consistent. Those are of benefit as prerequisite for any meaningful effort to predict the solid‐liquid phase behavior of TAG mixtures as well as crystallization kinetics.
In 1990, a well-known model to predict pure component properties of triglycerides was presented by Wesdorp in "Liquid-multiple solid phase equilibria in fats: theory and experiments" and has been shown to perform well despite making thermodynamically inconsistent predictions for certain test cases. In this study, the underlying parameter set is improved to deliver more physically consistent predictions, i.e., increasing melting point and enthalpy of fusion with increasing stability of the polymorphs, without deterioration of the primary model quality to describe the available experimental data. Interestingly, when a curated dataset containing only thermodynamically consistent data is compared to a broader dataset, it appears that the model's efficacy is highly dependent on the quantity of data, specifically the number of unsaturated triglycerides data. Quality and thermodynamic consistency of model predictions and the condition of a reliable description of monoacid triglycerides as a subset is discussed, addressing a potential interdependence.
This contribution presents an extensive literature survey of the calorimetric properties, namely enthalpy and entropy of fusion, of alkyl‐based molecules. Building on the well‐known linear correlation of the named properties to the carbon number in n‐alkanes, saturated fatty acids (FA), and saturated monoacid triglycerides (TAGs), the calorimetric properties of TAGs are reviewed. No straightforward correlation using a single ordering parameter, i.e., carbon number, can be derived for TAGs. This is not surprising due to the complexity of this particular class of molecules differing in alkyl‐chain distribution over the glycerol backbone and chain saturation. A linear correlation of enthalpy and entropy of fusion is evident for molecule classes for which both properties correlate linearly with the carbon number, e.g., n‐alkanes. Despite the complexity of TAGs, it is possible to establish a linear correlation between enthalpy and entropy of fusion even though no underlying single ordering parameter can be identified. A linear fit reveals discrepancies between saturated and unsaturated molecules but independence of polymorphic forms and chain length differences in mixed‐acid TAGs. Moreover, the slopes of the linear fits for data on n‐alkanes, saturated FA, and saturated mono‐acid TAGs are found to be in the vicinity of the melting temperature of polyethylene.
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