Production of Cocoa Butter Substitute via Enzymatic Interesterification of Fully Hydrogenated Palm Kernel Oil, Coconut Oil and Fully Hydrogenated Palm Stearin Blends.

This research synthesized structure lipids (SL) from blends of fully hydrogenated palm kernel oil (FHPKO), coconut oil (CNO) and fully hydrogenated palm stearin (FHPS) by enzymatic interesterification (EIE)using rProROL, an sn-1,3-specific lipase from Rhizopus oryzae, as a catalyst. Five physical blends of FHPKO:CNO:FHPS were prepared with the following wt. ratios: 40:10:50, 50:10:40, 60:10:30, 70:10:20 and 80:10:10. The EIE reactions were carried out at 60℃ for 6 h in a batch-type reactor using rProROL 10% wt. of the substrate. It was found that EIE significantly modified the triacylglycerol compositions of the fat blends resulting in changes in the crystallization and melting behavior. In particular, SL obtained from EIE of blend 70:10:20 exhibited high potential to be used as a cocoa butter substitute (CBS) because it showed similar solid fat content curve to the commercial CBS and crystallized into fine spherulites and desirable ß' polymorph.

Synthesis of cocoa butter alternatives from palm kernel stearin, coconut oil and fully hydrogenated palm stearin blends by chemical interesterification.

BACKGROUND: Chemical interesterification (CIE) is one of the important technological processes for the production of zero-trans fats. The aim of this study was to produce trans-free cocoa butter alternatives (CBAs) from palm kernel stearin (PKS), coconut oil (CNO) and fully-hydrogenated palm stearin (FHPS) blends via CIE using sodium methoxide as a catalyst. The physicochemical properties, crystallization and melting behavior, solid fat content (SFC), crystal morphology and polymorphism of the structured lipids (SLs) obtained and the corresponding physical blends (PBs) were characterized and compared with commercial CBAs. RESULTS: After CIE, randomization of fatty acid distribution within and among triacylglycerol (TAG) molecules of PKS, CNO and FHPS resulted in a modification in TAG compositions of the PKS/CNO/FHPS blends and improved the properties and crystallization behavior of the blends. SFC and slip melting points of all SLs decreased from those of their respective PBs. In particular, SLs obtained from CIE of blends with 60-70% wt. PKS (blend ratios 60:10:30 and 70:10:20) exhibited the melting characteristic, SFC curves, crystal morphology and polymorphic form most similar to the commercial CBAs. In addition, these blends melted almost completely at body temperature, an improvement from that of the commercial CBAs. CONCLUSION: SLs obtained from CIE of blends with 60-70% wt. PKS has high potential to be used commercially as trans-free CBAs for the confectionery industry. © 2021 Society of Chemical Industry.

The Effect of Polyglycerol Esters of Fatty Acids on the Crystallization of Palm Olein.

This research investigated the effect of polyglycerol ester of fatty acids (PGE) on the crystallization of palm olein (POL). Three PGEs were studied: two solid-state PGEs (PGE1105 and PGE1117) and one liquid-state PGE (PGE1155). The addition of 0.5-5% wt. PGEs influenced the crystallization kinetics of POL and this depended on the type and concentration of the emulsifiers. During cooling down with a cooling rate of 5℃/min, the samples containing PGE1105 and PGE1117 started to crystallize at higher temperatures when compared with POL but the crystallization began at lower temperatures for the samples containing PGE1155. All samples with added PGEs exhibited lower solid fat content than that of POL after 12 h of crystallization time. The number of crystals decreased with an increase in the crystal size with PGE addition but there was no effect on polymorphism. Overall, the results suggested that PGE1105 and PGE1117 enhanced the early stages of POL crystallization possibly via the template effects but suppressed the later stages, whereas PGE1155 delayed the whole process of POL crystallization. The application of POL is often limited by its tendency to get cloudy at low temperatures during long-term storage. Based on the results, 1-5% wt. PGE1155 could be used to delay or prevent the crystallization of POL at low temperatures.

Assessment of rheological methods to study crystallization of palm oil fractions.

This study provides an evaluation of the use of rheology to characterize soft, semi-hard, and hard fats in relation to determine the crystallization onset, crystallization behavior, as well as microstructure development using either a plate-plate or a starch pasting cell (SPC). The results from this study demonstrate that when applying rheology to study fat crystallization, the results must be interpreted with care. The application of a plate-plate geometry allowed for sensitive evaluation of the initial nucleation phase, which was not possible with an SPC. Both geometries could provide information on crystallization behavior in terms of one-step or two-step crystallization. However, in the late stage of the crystallization process, when the fat crystals form a strong network, the SPC could not describe differences in the rheology of the fat-crystal network, which was a possibility by the use of a plate-plate geometry. Thus, oscillatory rheology with a suitable geometry can be used to evaluate the entire crystallization process.

The Effect of Hard Lauric Fats on the Crystallization Behavior of Cocoa Butter Substitute.

This work investigated the crystallization and melting behavior of cocoa butter substitute (CBS) blended with two hard lauric fats: fully hydrogenated palm kernel oil (FHPKO) and krabok seed fat (KSF). The aim was to find a way to increase the heat resistance of CBS for the production of heat-resistant compound chocolate (HRCC). Adding FHPKO to CBS increased the crystallization rate with a decrease in crystallization induction time but did not increase the heat resistance. In contrast, all KSF-CBS blends exhibited higher heat resistance than CBS and crystallized into ß' form, a preferred polymorph for fats used in compound chocolate. Only the blends with 10-60% KSF melted completely at the body temperature, indicating that they would leave no waxy mouthfeel, but the blends with 30 and 40% KSF exhibited a significant decrease in the crystallization rate compared to the original CBS. Therefore, the KSF-CBS blends with 10, 20 and 60% KSF are recommended for future use as fats for HRCC production.

Oleogelation of emulsified oil delays in vitro intestinal lipid digestion.

Oleogelation is shown to delay the in vitro digestion of soybean oil (SBO) dispersed within an oil-in-water (O/W) emulsion. Rice bran wax (RBX) was used as an oleogelator at concentrations of 0, 0.25, 0.5, 1 and 4 wt% of the emulsions. All emulsions, which contained 1 wt% whey protein and 20 wt% oil and were prepared via hot homogenization, were kinetically stable against phase separation during the experimental timeframe (4 weeks), except at 4 wt% RBX where wax crystals 3-5 µm in length appeared within the dispersed oil phase, and which resulted in some emulsion instability. Rheological and thermal analysis of the emulsions and their corresponding SBO-RBX blends showed that the RBX led to formation of rigid oil droplets. Both in vitro gastric and intestinal digestion resulted in extensive oil droplet coalescence in all emulsions. Free fatty acid (FFA) release profiles showed that dispersed phase oleogelation delayed intestinal lipid digestion, with this effect enhanced up to 1 wt% RBX. A further increase to 4 wt% increased the rate of lipid digestion, which was ascribed to emulsion instability resulting from growth of intra-droplet RBX crystals.

Structure and rheology of oleogels made from rice bran wax and rice bran oil.

Structural and rheological properties of oleogels consisting of 0.5-25 wt% rice bran wax (RBX) in rice bran oil (RBO) were explored. RBX was an efficient, thermoreversible oleogelator capable of structuring RBO at concentrations as low as 0.5 wt% RBX. A qualitative temperature-composition phase diagram showed that oleogels containing higher concentrations of RBX were expectedly the most resistant to melting. In oleogels at higher RBX concentrations, polarized light microscopy revealed the presence of a network of interlinked, long aspect ratio wax crystal needles up to 50 µm long. Upon heating, RBX crystals did not undergo any structural transition, based on the constant short spacings at ~ 4.16 and ~ 3.73 Å, indicative of an orthorhombic subcell, and d001 long spacing at 74-76 Šthat persisted until RBX fusion. This long spacing was ascribed to the presence of wax esters consisting of long-chain saturated fatty acids (C24 and C22) esterified to C28 - C34 saturated fatty alcohols. During cooling from 90 to 20 °C, the increase in oleogel viscosity resulting from the RBX liquid-solid phase transition was corroborated by DSC-based crystallization onset and enthalpy data. Similarly, elastic moduli and hardness both rose with increasing RBX concentration. This study, which demonstrated that RBX can structure RBO with distinct concentration-dependent properties, serves as the foundation for the development of oleogel-based approaches to saturated and trans fats replacement in processed foods.

Lauric fat cocoa butter replacer from krabok (irvingia malayana) seed fat and coconut oil.

Lauric fat cocoa butter replacer (LCBR) was produced from a blend of krabok seed fat (KSF) and coconut oil (CO). Four fat blends with different ratios of KSF/CO (20/80, 40/60, 60/40 and 80/20 (%wt)), CO, KSF and a commercial LCBR (C-LCBR) were characterized using various techniques. It was found that blend 60/40 exhibited SFC curve and crystallization/melting behavior most similar to that of C-LCBR. The blend met the requirements to be considered as LCBR and has potential as an alternative to commercial LCBR that are being used nowadays and hence it was recommended as LCBR (called R-LCBR). The polymorphic behavior of both C-LCBR and R-LCBR was investigated and both fats displayed mainly short spacing pattern associated with ß' polymorph, a required polymorph for LCBR. The compatibility between R-LCBR and CB was investigated by mixing the R-LCBR with CB in different proportions and softening due to the eutectic effect was observed in the mixed fats. This limits the proportion of CB and the R-LCBR in compound coatings to no more than 5% of CB in the total fat phase.

Studies of fatty acid composition, physicochemical and thermal properties, and crystallization behavior of mango kernel fats from various Thai varieties.

Mango kernel fat (MKF) has received attention in recent years due to the resemblance between its characteristics and those of cocoa butter (CB). In this work, fatty acid (FA) composition, physicochemical and thermal properties and crystallization behavior of MKFs obtained from four varieties of Thai mangoes: Keaw-Morakot (KM), Keaw-Sawoey (KS), Nam-Dokmai (ND) and Aok-Rong (AR), were characterized. The fat content of the mango kernels was 6.40, 5.78, 5.73 and 7.74% (dry basis) for KM, KS, ND and AR, respectively. The analysis of FA composition revealed that all four cultivars had oleic and stearic acids as the main FA components with ND and AR exhibiting highest and lowest stearic acid content, respectively. ND had the highest slip melting point and solid fat content (SFC) followed by KS, KM and AR. All fat samples exhibited high SFC at 20℃ and below. They melted slowly as the temperature increased and became complete liquids as the temperature approached 35°C. During static isothermal crystallization at 20°C, ND displayed the highest Avrami rate constant k followed by KS, KM and AR, indicating that the crystallization was fastest for ND and slowest for AR. The Avrami exponent n of all samples ranged from 0.89 to 1.73. The x-ray diffraction analysis showed that all MKFs crystallized into a mixture of pseudo-ß', ß', sub-ß and ß structures with ß' being the predominant polymorph. Finally, the crystals of the kernel fats from all mango varieties exhibited spherulitic morphology.

Characterization of physicochemical and thermal properties and crystallization behavior of krabok (Irvingia Malayana ) and rambutan seed fats.

Fatty acid composition, physicochemical and thermal properties and crystallization behavior of fats extracted from the seeds of krabok (Irvingia Malayana) and rambutan (Nephelium lappaceum L.) trees grown in Thailand were studied and compared with cocoa butter (CB). The krabok seed fat, KSF, consisted of 46.9% lauric and 40.3% myristic acids. It exhibited the highest saponification value and slip melting point but the lowest iodine values. The three fats displayed different crystallization behavior at 25°C. KSF crystallized into a mixture of ß' and pseudo-ß' structures with a one-step crystallization curve and high solid fat content (SFC). The fat showed simple DSC crystallization and melting thermograms with one distinct peak. The rambutan seed fat, RSF, consisted of 42.5% arachidic and 33.1% oleic acids. Its crystallization behavior was more similar to CB than KSF, displaying a two-step crystallization curve with SFC lower than that of KSF. RSF solidified into a mixture of ß' and pseudo-ß' before transforming to ß after 24 h. The large spherulitic microstructures were observed in both KSF and RSF. According to these results, the Thai KSF and RSF exhibited physicochemical, thermal characteristics and crystallization behavior that could be suitable for specific applications in several areas of the food, cosmetic and pharmaceutical industries.