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Polymorphic crystallization of cocoa butter (CB) in a bulk system was examined for the influence of adding talc particles at different concentrations (0.1%-5%). While the system was cooled from the melt and subsequently heated, changes in the heat flow and crystal structure of CB were analyzed using differential scanning calorimetry (DSC) and synchrotron radiation X-ray diffraction (SR-XRD). Synchrotron radiation microbeam X-ray diffraction (SR-µ-XRD) was employed to determine lamellar-plane directions of CB crystals occurring with talc addition. At any cooling rates (0.1-15 °C/min) applied, talc promoted CB crystallization to elevate the onset crystallization temperature logarithmically with the increasing concentration of talc; this effect became more prominent at higher cooling rates. Talc also acted as a polymorphic stabilizer, so that CB crystallized in more stable forms even when cooled at the highest rate of 15 °C/min. Moreover, a highly ordered lamellar-plane direction was extensively observed for CB crystals occurring with 0.1% talc addition, which was disturbed by 0.5% talc addition probably due to the spatial dispersion of densely populated talc particles in their randomized orientation. These heterogeneous nucleation effects indicate the potential of talc particles to be used for quality and productivity control of CB-based products.

The binary phase behavior of triacylglycerol (TAG) mixtures constituted by PPP (tripalmitin) and either POP (1,3-dipalmitoyl-2-oleoyl-glycerol), OPO (1,3-dioleoyl-2-palmitoyl-glycerol), or MCPOP/OPO (molecular compound formed by POP/OPO at a 1:1 concentration ratio) was determined by differential scanning calorimetry (DSC), synchrotron (SR-) and laboratory-scale X-ray diffraction (XRD). Steric hindrance due to saturated-unsaturated acyl chain interactions and differences in the thermal stability of TAGs seemed to dictate the independent polymorphic crystallization and transformation observed under kinetic conditions, as well as the very asymmetric eutectic-type phase diagrams obtained from the study of thermodynamically stabilized PPP/POP, PPP/OPO, and PPP/MCPOP/OPO mixtures. Moreover, the solid integration determined for MCPOP/OPO in the βPPP crystalline phase (20-25%), halfway between that of OPO (

High-commercial-value products are often susceptible to food fraud. Among them, Iberian dry-cured ham is highly appreciated due to its particular and sensory, but also nutritional, properties. There are four different Iberian ham categories (namely bellota, recebo, cebo de campo and cebo), which directly depend on the rearing system of the pig during the last stage of the fattening phase. However, there is still a lack of a normalized and robust method capable of authenticating the different product categories and, therefore, preventing mislabeling. In the present work, we characterized the polymorphic behavior of raw (before curing) lipid extracts belonging to the four categories of Iberian pig. A total of 80 different samples were analyzed by DSC, and synchrotron radiation XRD experiments were carried out for selected ones. The results obtained showed that bellota and recebo categories exhibited essentially the same crystallization and polymorphic behavior and this was significantly different (p

The present study aims at observing the crystallization and polymorphic behavior of cocoa butter (CB) in fresh cacao beans with DSC and X-ray diffraction techniques. Underlying idea of this study was to relate the necessary conditions of germination of cacao beans to the crystallization of CB, which are present in oil-in-water emulsion droplets (lipid bodies) with diameters of 1-2 μm. Different cooling and heating conditions, with rates of 15, 2, 0.5, and 0.1 °C/min, were applied to fresh cacao beans and compared to bulk CB. The results showed that the crystallization temperatures (Tc) of CB in fresh cacao beans were lower than those of bulk CB at all the experimental conditions. In addition, polymorphic behavior of the occurrence of metastable and stable forms of CB was also different between the fresh cacao beans and the bulk state. The thermal behavior of fresh and dried cacao beans that have different geographical origins was also analyzed. This study indicates that the germination conditions of cacao beans are extended to low-temperature environmental areas by reducing the Tc value of CB in fresh beans than of the bulk oil. The results were consistent with the germination experiments of fresh cacao beans at different temperatures.

We examined the influence of dynamic thermal treatment (variation of cooling/heating rates) on the polymorphic crystallization and transformation pathways of 1-palmitoyl-2,3-dioleoyl glycerol (POO), 1-stearoyl-2,3-dioleoyl glycerol (SOO), and 1-palmitoyl-2-oleoyl-3-linoleoyl glycerol (POL), which are major saturated-unsaturated-unsaturated (SUU) triacylglycerols (TAGs) of vegetable oils and animal fats (e.g., palm oil, olive oil, and Iberian ham fat). Using mainly a combination of differential scanning calorimetry (DSC) and synchrotron radiation X-ray diffraction (SR-XRD), we analyzed the polymorphic behavior of TAGs when high (15 °C min− 1), intermediate (2 °C min− 1), and low (0.5 °C min− 1) cooling and heating rates were applied. Multiple polymorphic forms were detected in POO, SOO, and POL (sub-α, α, β'2, and β'1). Transient disordered phases, defined as kinetic liquid crystal (KLC) phases, were determined in POO and SOO for the first time. The results demonstrated that more stable forms were directly obtained from the melt by decreasing the cooling rates, whereas less stable forms predominated at high cooling rates, as confirmed in our previous work. Regarding heating rate variation, we confirmed that the nature of the polymorphic transformations observed (solid-state, transformation through KLC phase, or melt-mediation) depended largely on the heating rate. These results were discussed considering the activation energies involved in each process and compared with previous studies on TAGs with different saturated-unsaturated structures (1,3-dioleoyl-2-palmitoylglycerol, 1,3-dipalmitoyl-2-oleoyl-glycerol, trioleoyl glycerol, and 1,2-dioleoyl-3-linoleoyl glycerol).

Foods with high added value, such as Iberian dry-cured products, are susceptible to fraud. Many attempts have been made to differentiate the commercial/quality categories of Iberian dry-cured hams by analytical determinations. However, as discrimination by such means is not fully reliable, legislation to prevent fraudulent practice is based on administrative controls and certification. Here, new analytical approaches based on ultrahigh resolution mass spectrometry (UHRMS) and crystallographic techniques applied to the lipid fraction, in combination with chemometrics, are studied. The results of the triacylglycerol profile determined by UHRMS and the fingerprint provided by the thermograms obtained by differential scanning calorimetry offer the promise of analytic discrimination of Iberian dry-cured ham categories. In addition, these determinations, in combination with chemometrics, may prove extremely useful to authenticate many foods containing high to moderate amounts of lipids.

The complexes [Cu(PhOBz)2(dPy)]2 (PhOBz = 4-phenoxybenzoate; dPy = pyridine (1), 3-phenylpyridine (2), 4-benzylpyridine (3) and 4-phenylpyridine (4) and the complex [Cu(PhOBz)2(4-Phpy)2(H2O)] (5) were prepared and fully characterized. X-ray crystal structures of the five complexes have been determined. Complexes 1–4 consist of binuclear units where both Cu(II) are linked by four syn–syn carboxylate bridges, showing a paddle-wheel unit. The compound 5 is mononuclear and the metal center is coordinated to two PhOBz in monodentate form, two 4-Phpy ligands and one H2O molecule with slightly distorted square pyramidal geometry. Finally, the magnetic properties of compounds 3 and 5 have also been studied, confirming the different strength interactions between Cu(II) cations.

We systematically examined the phase behavior of binary mixtures of mixed-acid triacylglycerols (TAGs) containing palmitic and oleic acid moieties 1,3-dioleoyl-2-palmitoyl-glycerol (OPO), 1,2-dipalmitoyl-3-oleoyl-rac-glycerol (PPO), and 1,2-dioleoyl-3-palmitoyl-rac-glycerol (OOP), which are widely present in natural fats and are employed in the food, pharmaceutical, and cosmetic industries. Differential scanning calorimetry and X-ray diffraction methods were applied to observe the mixing behavior of PPO/OPO, OOP/OPO, and PPO/OOP under metastable and stable conditions. The results led to three conclusions: (1) Eutectic behavior was observed in PPO/OPO. (2) Molecular compound (MC) crystals were formed in the mixtures of OOP/OPO and PPO/OOP. (3) However, the MC crystals occurred only under metastable conditions and tended to separate into component TAGs to form eutectic mixture systems after 17 months of incubation. These results were contrary to those of previous studies on 1,3-dipalmitoyl-2-oleoyl glycerol (POP)/OPO and POP/PPO in which the MC crystals were thermodynamically stable. We determined that specific molecular interactions may cause this different phase behavior (stability of POP/OPO and POP/PPO MC crystals and metastability of OOP/OPO and PPO/OOP MC crystals). All results confirm the significant effects of molecular structures of glycerol groups, interactions of fatty acid chains, and polymorphism of the component TAGs on the mixing behavior of mixed-acid TAGs.

The extent of crystallization and transformation of lipids, and their network formation, play decisive roles in determining physical properties (e.g., hardness, texture, rheology, and spreadability) of lipid-based food products. In these products, the lipid materials are present in rather complicated physical states such as mixtures of solid and liquid lipids or emulsified with water phases. In addition, various external influences are applied during actual production in a factory. Therefore, exploration of lipid crystallization under multiple external influences is necessary to improve the functionality of lipid-based food products.

This study examined the influence of different thermal treatments on the crystallization and transformation of trioleoyl glycerol (OOO) and 1,2-dioleoyl-3-rac-linoleoyl glycerol (OOL). Two triacylglycerol (TAG) samples were cooled at 0.5-15 °C·min(-1) and heated at 2 and 15 °C·min(-1). The polymorphic characteristics of the two TAGs were analyzed in situ using differential scanning calorimetry, Raman spectroscopy, and synchrotron radiation X-ray diffraction. Multiple polymorphic forms were identified in OOO (α, β'2, β'1, β2, and β1) and OOL (α, β'2, and β'1). Larger quantities of more stable forms (e.g., β2 and β1 of OOO and β'1 of OOL) were obtained when the samples were slowly cooled and heated. In contrast, less stable polymorphs were obtained with increased cooling and heating rates. Polymorphic transformations occurred in either solid-state or melt-mediation and were influenced by heating rates. The results were analyzed by considering the activation energies for crystallization and transformation of stable and less stable polymorphic forms in comparison with previous studies on 1,3-dipalmitoyl-2-oleoyl-glycerol and 1, 3-dioleoyl-2-palmitoyl-glycerol.

We examined the influence of kinetics on the polymorphic behavior of 1,3-dioleoyl-2-palmitoyl glycerol (OPO), a triacylglycerol (TAG) present in natural oils such as olive oil and human breast milk. Pure OPO was heated at 15 °C min−1 in all cases. The polymorphic crystallization of OPO was studied at different cooling rates (15, 2, 1, and 0.5 °C min−1), and the dynamic polymorphic transformations were characterized on heating by simultaneously using Differential Scanning Calorimetry (DSC) and Synchrotron Radiation X-Ray Diffraction (SR-XRD) with small-angle X-ray diffraction (SAXD) and wide-angle X-ray diffraction (WAXD). Thermo-Optical Microscopy (TOM) was also used in order to observe the polymorphic transitions. Polymorphic forms of OPO were identified and characterized. As the cooling rate decreased, more stable forms crystallized, not following the Ostwald step rule, although in most cases concurrent crystallization occurred and the whole process was highly complex.

The kinetic properties of crystallization and structural transformation are important, particularly for the application of polymorphic crystal systems in pharmaceutical, biomedical, food technology, and other applications. Triacylglycerols (TAGs) are the main components of alimentary fats and oils. Fat structures and compositions determine their physical properties (e.g., rheology, morphology, and texture), where polymorphism exerts a strong influence. There are different polymorphic forms of TAGs: the most general ones (in increasing stability) are: α form, which crystallizes in the hexagonal system, β' form (orthorhombic system) and β form (triclinic system). In this study, several techniques, like Synchrotron Radiation X-Ray Diffraction, Thermal Analysis and Thermo-optical Microscopy, were used in order to characterize the polymorphism under the kinetic point of view of some TAGs present in edible oils and fats. Therefore, the role of some kinetic parameters (e.g. cooling and heating rates) is highlighted.