Fernanda Peyronel

Structure and functionality of edible fats

Fat-structured food materials are an important component of our diet. The role that fat plays in material functionality, flavor perception, texture and health characteristics is due in large part to its physical properties. An understanding of these physical properties is relevant from scientific, technological and medical perspectives. The physical properties of fat materials, are, in turn, governed by a complex confluence of the various structural levels in a fat material beginning with triglyceride molecules. The formation of nanoscale structural elements by these molecules is the first step in the formation of a fat material as we know it. This review shows how these microstructural elements can be imaged and characterized. It is also shown that the formation of these nanocrystals is affected by the attendant crystallization parameters. Through simulation and a discussion of van der Waals forces, it is shown that these nanoscale elements assemble into colloidal aggregates with fractal character. The influence of microstructure on the mechanical properties of a fat material is explained using a variety of mechanical models. Lastly, this review examines methods by which the properties and characteristics of the various structural levels can be engineered. Shear has been shown to affect the polymorphism and phase transition kinetics of triglyceride crystals. As well, shear has been shown to modify the aggregation of nanocrystals, with consequences for the porosity and diffusivity of oil through the fat crystal network.

Edible oil structures at low and intermediate concentrations. II. Ultra-small angle X-ray scattering of in situ tristearin solids in triolein

Ultra-small angle X-ray scattering has been used for the first time to elucidate, in situ, the aggregation structure of a model edible oil system. The three-dimensional nano- to micro-structure of tristearin solid particles in triolein solvent was investigated using 5, 10, 15, and 20% solids. Three different sample preparation procedures were investigated: two slow cooling rates of 0.5°/min, case 1 (22 days of storage at room temperature) and case 2 (no storage), and one fast cooling of 30°/min, case 3 (no storage). The length scale investigated, by using the Bonse-Hart camera at beamline ID-15D at the Advanced Photon Source, Argonne National Laboratory, covered the range from 300 A to 10 μm. The unified fit and the Guinier-Porod models in the Irena software were used to fit the data. The former was used to fit 3 structural levels. Level 1 structures showed that the primary scatterers were essentially 2-dimensional objects for the three cases. The scatterers possessed lateral dimensions between 1000 and 4...

Edible oil structures at low and intermediate concentrations. I. Modeling, computer simulation, and predictions for X ray scattering

Triacylglycerols (TAGs) are biologically important molecules which form the recently discovered highly anisotropic crystalline nanoplatelets (CNPs) and, ultimately, the large-scale fat crystal networks in edible oils. Identifying the hierarchies of these networks and how they spontaneously self-assemble is important to understanding their functionality and oil binding capacity. We have modelled CNPs and studied how they aggregate under the assumption that all CNPs are present before aggregation begins and that their solubility in the liquid oil is very low. We represented CNPs as rigid planar arrays of spheres with diameter ≈50 nm and defined the interaction between spheres in terms of a Hamaker coefficient, A, and a binding energy, VB. We studied three cases: weak binding, |VB|/kBT ≪ 1, physically realistic binding, VB = Vd(R, Δ), so that |VB|/kBT ≈ 1, and Strong binding with |VB|/kBT ≫ 1. We divided the concentration of CNPs, ϕ, with 0≤ϕ= 10−2 (solid fat content) ≤1, into two regions: Low and intermedia...

Ultra small angle x-ray scattering in complex mixtures of triacylglycerols

Ultra-small angle x-ray scattering (USAXS) has been used to elucidate, in situ, the aggregation structure of unsheared model edible oils. Each system comprised one or two solid lipids and a combination of liquid lipids. The 3D nano- to micro-structures of each system were characterized. The length scale investigated, using the Bonse-Hart camera at beamline ID-15D at the Advanced Photon Source, ANL, ranged from 300 Å-10 µm. Using the Unified Fit model, level-1 analysis showed that the scatterers were 2D objects with either a smooth, a rough, or a diffuse surface. These 2D objects had an average radius of gyration Rg1 between 200-1500 Å. Level-2 analysis displayed a slope between -1 and -2. Use of the Guinier-Porod model gave s ≈ 1 thus showing that it was cylinders (TAGwoods) aggregating with fractal dimension 1 ≤ D2 ≤ 2. D2 = 1 is consistent with 1D structures formed from TAGwoods, while D2 = 2 implies that the TAGwoods had formed structures characteristic of diffusion or reaction limited cluster-cluster aggregation (DLCA/RLCA). These aggregates exhibited radii of gyration, Rg2, between 2500 and 6500 Å. Level-3 analyses showed diffuse surfaces, for most of the systems. These interpretations are in accord with theoretical models which studied crystalline nano-platelets (CNPs) coated with nano-scale layers arising from phase separation at the CNP surfaces. These layers could be due to either liquid-liquid phase separation with the CNPs coated, uniformly or non-uniformly, by a diffuse layer of TAGs, or solid-liquid phase separation with the CNPs coated by a rough layer of crystallites.A fundamental understanding of the self-organizing structures arising in these systems helps advance the characterization of fat crystal networks from nanometres to micrometres. This research can be used to design novel fat structures that use healthier fats via nano- and meso-scale structural engineering.

Characterization of the nanoscale structure of milk fat.

The nanoscale structure of milk fat (MF) crystal networks is extensively described for the first time through the characterization of milk fat-crystalline nanoplatelets (MF-CNPs). Removing oil by washing with cold isobutanol and breaking-down crystal aggregates by controlled homogenization allowed for the extraction and visualization of individual MF-CNPs that are mainly composed of high melting triacylglycerols (TAGs). By image analysis, the length and width of MF-CNPs were measured (600 nm × 200 nm-900 nm × 300 nm). Using small-angle X-ray scattering (SAXS), crystalline domain size, (i.e., thickness of MF-CNPs), was determined (27 nm (d001)). Through interpretation of ultra-small-angle X-ray scattering (USAXS) patterns of MF using Unified Fit and Guinier-Porod models, structural properties of MF-CNPs (smooth surfaces) and MF-CNP aggregations were characterized (RLCA aggregation of MF-CNPs to form larger structures that present diffused surfaces). Elucidation of MF-CNPs provides a new dimension of analysis for describing MF crystal networks and opens-up opportunities for modifying MF properties through nanoengineering.

Revisiting the crystallization behavior of stearyl alcohol : stearic acid (SO : SA) mixtures in edible oil

Mixtures of stearyl alcohol and stearic acid were some of the first identified oleogelators with potential for food applications. Previously, a synergistic enhancement in gel strength was identified at a stearyl alcohol:stearic acid (SO:SA) ratio of 7:3 and 8:2, which was attributed to their needle-like crystal morphology. In the present study, we have meticulously characterized this system with a variety of techniques at different gelator ratios. Accelerated oil loss tests showed the stability of the gels mirrors the mechanical strength with ∼1 wt% oil loss in the firm gels and >10 wt% in the weak formulations. X-ray diffraction and light microscopy suggest that the crystal networks which form the hardest gels (8:2, 7:3) and weakest gels (5:5, 4:6) are similar, and thus crystal morphology and crystal size cannot solely explain the observed enhancement in mechanical strength and stability. Scanning electron micrographs clarified that all oleogels crystalized in a platelet-like, rather than needle-like microstructure. Using the scaling theory of cellular solids, the enhancement in mechanical strength of the 8:2 SO:SA oleogel was shown to be mainly due to an increase in the scaling exponent of the hardness to the mass fraction of the crystalline material, and not the total amount of crystalline network solids, the size of the platelets or the interactions between them.

Aggregation in complex triacylglycerol oils: coarse-grained models, nanophase separation, and predicted x-ray intensities.

Triacylglycerols (TAGs) are biologically important molecules which form crystalline nanoplatelets (CNPs) and, ultimately, fat crystal networks in edible oils. Characterizing the self-assembled hierarchies of these networks is important to understanding their functionality and oil binding capacity. We have modelled CNPs in multicomponent oils and studied their aggregation. The oil comprises (a) a liquid component, and (b) components which phase separately on a nano-scale (nano-phase separation) to coat the surfaces of the CNPs impenetrably, either isotropically or anisotropically, with either liquid-like coatings or crystallites, forming a coating of thickness ?. We modelled three cases: (i) liquid?liquid nano-phase separation, (ii) solid?liquid nano-phase separation, with CNPs coated isotropically, and (iii) CNPs coated anisotropically. The models were applied to mixes of tristearin and triolein with fully hydrogenated canola oil, shea butter with high oleic sunflower oil, and cotton seed oil. We performed Monte Carlo simulations, computed structure functions and concluded: (1) three regimes arose: (a) thin coating regime, Δ < 0.0701 u (b) transition regime, 0.0701 u ≤ Δ ≤ 0.0916 u and (c) thick coating regime, Δ > 0.0916 u. (arbitrary units, u) (2) The thin coating regime exhibits 1D TAGwoods, which aggregate, via DLCA/RLCA, into fractal structures which are uniformly distributed in space. (3) In the thick coating regime, for an isotropic coating, TAGwoods are not formed and coated CNPs will not aggregate but will be uniformly distributed in space. For anisotropic coating, TAGwoods can be formed and might form 1D strings but will not form DLCA/RLCA clusters. (4) The regimes are, approximately: thin coating, 0 < Δ < 7.0 nm transition regime, 7.0 < Δ < 9.2 nm and thick coating, Δ > 9.2 nm (5) The minimum minority TAG concentration required to undergo nano-phase separation is, approximately, 0.29% (thin coatings) and 0.94% (thick coatings). Minority components can have substantial effects upon aggregation for concentrations less than 1%.

Condensation versus diffusion. A spatial- scale-independent theory of aggregate structures in edible oils: applications to model systems and commercial shortenings studied via rheology and USAXS

Understanding how solid fats structures come about in edible oils and quantifying their structures is of fundamental importance in developing edible oils with pre-selected characteristics. We considered the great range of fractal dimensions, from 1.91 to 2.90, reported from rheological measurements. We point out that, if the structures arise via DLA/RLA or DLCA/RLCA, as has been established using ultra small angle x-ray scattering (USAXS), we would expect fractal dimensions in the range ~1.7 to 2.1, and ~2.5 or ~3.0. We present new data for commercial fats and show that the fractal dimensions deduced lie outside these values. We have developed a model in which competition between two processes can lead to the range of fractal dimensions observed. The two processes are (i) the rate at which the solid fat particles are created as the temperature is decreased, and (ii) the rate at which these particles diffuse, thereby meeting and forming aggregates. We assumed that aggregation can take place essentially isotropically and we identified two characteristic times: a time characterizing the rate of creation of solid fats, , where is the rate of solid condensation (cm3 s−1), and the diffusion time of solid fats, , where is their diffusion coefficient and is the typical average distance that fats must move in order to aggregate. The intent of this model is to show that a simple process can lead to a wide range of fractal dimensions. We showed that in the limit of very fast solid creation, the fractal dimension is predicted to be that of DLCA, ~1.7, relaxing to that of RLCA, 2.0–2.1, and that in the limit of very slow solid creation, , the fractal dimension is predicted to be that obtained via DLA, ~2.5, relaxing to that of RLA, 3.0. We predict that, given a system which satisfies our model assumptions and which can either be cooled rapidly or cooled slowly to yield fractal dimensions and then . This is supported by both rheological [1] and USAXS measurements [2, 3] even though the latter models do not conform to the assumptions of those presented here.

Edible fat structures at high solid fat concentrations: Evidence for the existence of oil-filled nanospaces

We have characterized the surfaces of grain boundaries in edible oils with high solid fat content by combining ultra-small angle x-ray scattering (USAXS) with theoretical modelling and computer simulation. Our results will lead to understand the solid structures formed at the time of manufacturing fats like confectionery fats as well as pave the way for the engineering of innovative fat products. Edible fats are complex semi-solid materials where a solid structure entraps liquid oil. It was not until USAXS combined with modelling was used that the nano- to meso-structures for systems with less than 20% solids were understood. The interpretation of those results utilized models of crystalline nanoplatelets represented by rigid close-packed flat aggregates made of spheres and was allowed to aggregate using the Metropolis Monte Carlo technique. Here, we report on systems containing between 50% and 90% solids. We modelled the solid phase as being formed from seeds onto which solids condensed thereby giving ri...

Molecular Insights into the Eutectic Tripalmitin/Tristearin Binary System

A molecular interpretation of the eutectic behavior of a binary mixture of tristearin (SSS) and tripalmitin (PPP) triglycerides was formulated using computer simulations and experimental techniques (calorimetry and X-ray scattering). A eutectic composition was identified using both experimental and computer simulation techniques at a composition of 70% PPP and 30% SSS, in agreement with previous findings in the literature. The decrease in the melting temperature at the eutectic composition can be ascribed to an interplay between enthalpic and entropic effects. In particular, a lower global melting enthalpy at the eutectic composition was detected here, caused by a less efficient packing of the triglycerides in the crystal. On the other hand, a higher crystalline disorder is reflected in a lower change in the entropy of melting. The simultaneous decrease in global enthalpy and entropy has a contrasting effect on the melting temperature, with a slight melting point depression found in both experiment and simulations, resulting from a combination of enthalpic and entropic factors. Computer simulations showed, in fact, that the eutectic effect can be ascribed to the reduction of crystalline order when SSS molecules are incorporated into the PPP crystal structure. This decrease of the crystalline order is due to the protrusion of SSS end-chains (last three carbons of each alkyl chain) into the interlamellar space between adjacent lamella. These end-chains disturb the orderly stacking of the lamella, as evidenced by low-density regions in the interlamellar space. Thus, the greater disorder of the last atoms of the SSS alkyl chains is consequently due to the greater conformational freedom. At molecular level, in fact, the conformational freedom of terminal atoms of SSS surrounded by shorter PPP molecules is larger than the conformational freedom of longer SSS in the neighborhood of short PPP.