Effect of Palm Oil Enzymatic Interesterification on Physicochemical and Structural Properties of Mixed Fat Blends

The physicochemical properties of binary and ternary fat systems made of commercial samples of palm oil (PO) blended with anhydrous milk fat (AMF) and/or rapeseed oil (RO) were studied. Physical properties such as solid fat content by pulsed‐Nuclear Magnetic Resonance (p‐NMR), melting profile by differential scanning calorimetry (DSC), and polymorphism of the blends were investigated. Palm oil was then batch enzymatically interesterified for 27 h, using Lipozyme^® TL IM as biocatalyst, and further blended with AMF and/or RO in the same way. The objective of the present work was to evaluate the effect of batch enzymatic interesterification (B‐EIE) of palm oil on physical characteristics of the investigated fat blends. For that purpose, iso‐solid diagrams have been constructed from p‐NMR data. It was shown that B‐EIE of palm oil modifies its melting behaviour, but also its polymorphic stability and miscibility with other fats. Under dynamic conditions, after B‐EIE, the non‐ideal behaviour (eutectic) detected at low temperatures in the ternary PO/AMF/RO system disappears in the corresponding EIE‐PO/AMF/RO. After static crystallization followed by a tempering, the hardness of palm oil is increased after B‐EIE, as well as the hardnesses of the blends containing this fat compared to the native one. Polymorphism stability of the binary and ternary fat systems is also modified after B‐EIE compared to the corresponding native systems.     

Physical Properties of <Emphasis Type="Italic">trans</Emphasis>-Free Bakery Shortening Produced by Lipase-Catalyzed Interesterification

Lipase-catalyzed interesterified solid fat was produced with fully hydrogenated soybean oil (FHSBO), and rapeseed oil (RSO) and palm stearin (PS) in a weight ratio of 15:20:65, 15:40:45 and 15:50:35. The interesterified fats contained palmitic (27.8–44.6%), stearic (15.6–16.2%), oleic (27.5–36.5%) and linoleic acids (8.0–13.5%). After interesterification of the blends, the physical properties of the products changed and showed lower melting points and solid fat contents, different melting and crystallization behaviors as well as the formation of more stable crystals. The produced interesterified fats (FHSBO:RSO:PS 15:20:65, 15:40:45 and 15:50:35 blends) contained desirable crystal polymorphism (β′ form) as determined by X-ray diffraction spectroscopy, a long plastic range with solid fat content of 51–63% at 10 °C to 4–12% at 40 °C, and melting points of 39 (15:50:35), 42 (15:50:45) and 45 °C (15:20:65). However, a reduction in tocopherols (α and γ) content and a reduced oxidative stability were observed in the interesterified fats. The physical properties of the interesterifed fats were influenced by the amount of PS, resulting in more hardness and higher solid fat contents for 15:20:65 than 15:40:45 and 15:50:35 blends. The present study suggested that the produced interesterified fats containing trans-free fatty acids could be used as alternatives to hydrogenated types of bakery shortenings.     

Changes in triacylglycerol molecular species and thermal properties of blended and interesterified mixtures of coconut oil or palm oil with rice bran oil or sesame oil

Blended oils were prepared by mixing appropriate amounts of coconut oil (CNO) or palm oil (PO) with rice bran oil (RBO) or sesame oil (SESO) to get approximately equal proportions of saturated/monounsaturated/polyunsaturated fatty acids in the oil. These blended oils were subjected to interesterification reactions using lipase to randomize the fatty acid distribution on the glycerol molecule. The fatty acid compositions of the modified oils were evaluated by gas chromatography while changes in triacylglycerol molecular species were followed by HPLC. The triacylglycerol molecular species of the blended oils reflected those present in the parent oil. Interesterification of the blended oils resulted in the exchange of fatty acids within and between the triacylglycerol molecules, resulting in alterations in the existing triacylglycerol molecules. Emergence of new triacylglycerol molecular species following interesterification was also observed. The thermal profiles of the native, blended and interesterified oils were determined by differential scanning calorimetry. Thermal behaviour, melting and crystallization properties of the modified oils showed significant changes reflecting the changes in the triacylglycerol molecules present in the oil. Therefore, interesterification of oils introduces significant changes in the physical properties of oils, even though the overall fatty acid composition of blended and interesterified oils remains the same.     

Formation of Granular Crystals in Margarine with Excess Amount of Palm Oil

Crystallization behavior of palm oil and tripalmitin (PPP) in a model margarine system was investigated. The model margarine was held in a programmable oven, heated to 5 °C for 12 h and then 20 °C for a further 12 h. After 3 weeks, the model margarine was evaluated by polarization microscopy. Granular crystals were observed in the margarine containing an excess amount of palm oil and PPP. The concentration of higher-melting fatty acids was higher in the crystals relative to the surroundings. Likewise, the presence of lower-melting fatty acids was lower in the crystals. The polymorphic structure of the margarine with excess palm oil and PPP was determined to be all β′ by X-RD spectra. The result suggested that the agglomeration of higher-melting point triglycerides (TAGs), such as PPP in this study, led to the formation of granular crystals in the margarine without β polymorphic emergence.     

Melting and Solidification Properties of Palm Kernel Oil,Tallow, and Palm Olein Blends in the Preparation of Shortening

Ternary systems composed of palm kernel oil (PKO), tallow, and palm olein (POo) were studied in terms of their physical properties such as solid fat content (SFC), melting characteristics by DSC and polymorphism by X-ray diffraction. Ternary phase behavior was analyzed with isosolid diagrams. The results showed that as the POo content of the blends was increased the SFC value decreased, while the increase of tallow content increased the SFC value. Eutectic effects within the ternary system were confirmed from the deviation of the measured SFC from the calculated SFC for corresponding thermodynamically ideal blends. The deviation reached a maximum when the amounts of PKO and POo are both about 45%. X-ray diffraction results showed that addition of PKO into the blends promoted stabilization in the β′ crystalline form.     

Crystallization Kinetics of Cocoa Fat Systems: Experiments and Modeling

Isothermal crystallization kinetics of unseeded and seeded cocoa butter and milk chocolate is experimentally investigated under quiescent conditions at different temperatures in terms of the temporal increase in the solid fat content. The theoretical equations of Avrami based on one-, two- and three-dimensional crystal growth are tested with the experimental data. The equation for one-dimensional crystal growth represents well the kinetics of unseeded cocoa butter crystallization of form α and β′. This is also true for cocoa butter crystal seeded milk chocolate. The sterical hindrance due to high solids content in chocolate restricts crystallization to lineal growth. In contrast, the equation for two-dimensional crystal growth fits best the seeded cocoa butter crystallization kinetics. However, a transition from three- to one-dimensional growth kinetics seems to occur. Published data on crystallization of a single component involving spherulite crystals are represented well by Avrami’s three-dimensional theoretical equation. The theoretical equations enable the determination of the fundamental crystallization parameters such as the probability of nucleation and the number density of nuclei based on the measured crystal growth rate. This is not possible with Avrami’s approximate equation although it fits the experimental data well. The crystallization can be reasonably well defined for single component systems. However, there is no model which fits the multicomponent crystallization processes as observed in fat systems.     

Effects of Lipid Structure Changed by Interesterification on Melting Property and Lipemia

Interesterification or the randomization reaction changes fatty acid positional distribution and solid fat content of fats, which may consequently affect fat absorption and metabolism. It is well established that saturated fatty acids in the sn‐2 position of triacylglycerols (TAG) have better digestibility and lower postprandial chylomicron clearance compared to those in the sn‐1,3 positions in animal experiments. TAG structure is also shown to affect fasting lipid level and atherosclerosis in animals, but fat interesterification it has been shown to not affect fasting lipid level in human adults. However, its effect on postprandial responses is controversial. In this review, the complex results of studies of interesterification and lipemia were briefly discussed. More importantly, the confounding of two factors that are both changed by interesterification, TAG structure and solid fat content as the main limitation on understanding how interesterification affects lipemia is emphasized. Separation of the two factors is possible using paired fats as demonstrated. This paper also discusses some intriguing effects of fats having saturated fatty acids in the sn‐2 position and the need for future research.     

Fats from Chemically Interesterified High-Oleic Sunflower Oil and Fully Hydrogenated Palm Oil

Chemical interesterification of different lipid materials has considerable potential for the production of a wide variety of special fats with improved functional and nutritional properties. The present study aimed to evaluate the chemical interesterification of blends of high-oleic sunflower oil (HOSO) and fully hydrogenated palm oil (FHPO) in the ratios (% w/w) of 80:20, 70:30, 60:40 and 50:50. The blends were characterized in triacylglycerol composition, melting point, solid fat content and crystallization behavior, and some applications in food products were suggested. The interesterification altered the solid fat content, melting point and crystallization isotherm of the samples, after the levels of trisaturated triacylglycerols decreased and disaturated–monounsaturated and monosaturated–diunsaturated triacylglycerol contents increased, due to the randomization of fatty acids. The modification in the triacylglycerol composition promoted greater miscibility between the HOSO and FHPO fractions, creating new application possibilities for the food industry.     

An Interesterified Palm Olein Test Meal Decreases Early-Phase Postprandial Lipemia Compared to Palm Olein: a Randomized Controlled Trial

Palm oil that has been interesterified to produce a higher proportion of palmitic acid (16:0) in the sn‐2 position reduces postprandial lipemia in young, normolipidemic men and women, but effects in older subjects with higher fasting triacylglycerol (TAG) concentrations are unknown. We tested the hypothesis that high‐fat meals rich in interesterified palm olein (IPO) decrease lipemia and alter plasma lipoprotein fraction composition compared to native palm olein (NPO) in men aged 40–70 years with fasting TAG concentrations ≥1.2 mmol/L. Postprandial changes in plasma lipids following meals containing 75 g fat (NPO and IPO) were compared using a randomized, double‐blind crossover design (n = 11). Although there were no significant differences in plasma TAG concentrations between meals over the total 6‐h postprandial measurement period, IPO resulted in a decreased plasma TAG response during the first 4 h of the postprandial period (iAUC 1.65 mmol/L h, 95 % CI 1.01–2.29) compared to NPO (iAUC 2.33 mmol/L h, 95 % CI 1.58–3.07); meal effect P = 0.024. Chylomicron fraction TAG concentrations at 4–6 h were slightly reduced following IPO compared to NPO [NPO?IPO mean difference 0.29 mmol/L (95 % CI ?0.01–0.59), P = 0.055]. There were no differences in IDL fraction TAG, cholesterol or apolipoprotein B48 concentrations following IPO compared with NPO. In conclusion, consuming a meal containing palm olein with a higher proportion of 16:0 in the sn‐2 position decreases postprandial lipemia compared to native palm olein during the early phase of the postprandial period in men with higher than optimal fasting triacylglycerol concentrations.     

Synthesis,photoluminescence properties and energy transfer behavior of color-tunable fluorapatite phosphor Sr9Gd(PO4)5(SiO4)F2:Tb3+/Sm3+

Tb³⁺-Sm³⁺ co-doped Sr₉Gd(PO₄)₅(SiO₄)F₂ (SGPSF) phosphors were prepared through a solid-state reaction, and their luminescence properties as well as energy transfer mechanism have been investigated in detail. The SGPSF:Tb³⁺, Sm³⁺ phosphors system could be efficiently excited at wavelengths ranging from 200 to 500 nm, which is well matched with the spectra of near ultraviolet chips. The emission of SGPSF:Tb³⁺, Sm³⁺ phosphor covers the entire visible region with sharp peaks in the blue, green, and red regions. The emission color of SGPSF:Tb³⁺, Sm³⁺ could be adjusted from green (0.275, 0.378) to red (0.519, 0.295) by controlling the doping content of Sm³⁺/Tb³⁺.     

Crystal packing of a homologous series β′-stable triacylglycerols

From a homologous series of C _nC_n+2C_n (n = even) triacylglycerols which are β′-stable, Guinier X-ray powder diffraction photographs were used to determine cell parameters and space groups. The powder diffraction patterns are consistent with a pseudo-orthorhombic unit cell with space group lc2a. Only one axis is changing as a function of chain lengthening. The experimental results were used to propose a β′-crystal packing for triacylglycerols. In contrast to earlier proposed β′-crystal structures, the acyl chains of this structure are not tilted with respect to the methyl-end group plane. Furthermore, with only one molecule in the asymmetric unit, overall orthogonal chain packing is obtained when the intramolecular acyl zigzag planes are parallel.     

Characteristics of Mango Kernel Fats Extracted from 11 China-Specific Varieties and Their Typically Fractionated Fractions

11 China‐specific mango varieties, i.e., Tainong, Xiangya, Okrong, Keitt, Chiin Hwang, Guifei, Yuexi, Biantao, Guixiang, Zihua and Guire, were selected from South China, and the kernels were separated from pulps and then dried to extract mango kernel fats (MKF). 5.65–11.14 % of the fats could be obtained from dried kernels using hexane extraction, and their iodine values, slip melting points, triacylglycerols, sn‐2 fatty acids and micronutrients were analyzed. MKF were comprised predominantly of triacylglycerols reaching 85.09–92.72, and 78.28–84.37 % of oleic at the sn‐2 position. 29.99–55.44 % of SOS, 11.17–23.34 % of SOO and 13.10–19.79 % of POS occupied the main percentages of triacylglycerols, indicating MKF have diversified application after fractionation. Certain variety characterized as moderate values mentioned above, therefore, was selected and then fractionated by two‐stage processes to produce typical MKF fractions. The stearin (Fraction‐II) fractionated from the first solid fraction (Fraction‐I) with 68.09 % of SOS and 15.43 % of POS was more suitable as cocoa butter improver, while the olein (Fraction‐III) produced from the first liquid fraction was rich in SOO (45.59 %), POO (11.37 %) and OOO (11.14 %), which are considered as ideal cooking oil or frying fat ingredients. In addition, high amounts of micronutrients, including sterol, tocopherol and squalene, were also found in MKF ranged from 3837 to 7085, 81 to 916, and 164 to 941 mg/kg among different varieties, respectively. In particular, squalene levels were higher compared with most of other vegetable oils.     

Characterization and Oxidative Stability of Human Milk Fat Substitutes Enzymatically Produced from Palm Stearin

Production of human milk fat substitutes (HMFSs) from three types of palm stearin with palmitic acid (PA) of 91.3, 70.3 and 62.6 %, respectively, was scaled up to a kilogram scale. The physiochemical properties of these products including fatty acid profiles, triacylglycerol compositions, tocopherol contents, oxidative stability and melting and crystallization profiles were compared with those of HMFSs from lard, butterfat and tripalmitin and fats from infant formulas. Based on their chemical compositions, HMFSs from palm stearin with PA contents of 70.3 and 62.6 % produced by enzymatic acidolysis were found to have the highest degree of similarity to human milk fat, which indicated that these HMFSs were the most suitable for use in infant formulas. However, HMFSs from palm stearin with PA content of 91.3 % had the highest tocopherol contents. By investigation of the primary and secondary oxidation products during accelerated oxidation, the oxidative stability of HMFSs was found to be positively correlated to the contents of tocopherols, and the volatile oxidation compounds with the highest relative contents in HMFSs were aldehydes analyzed by solid-phase microextraction-GC–MS. All HMFSs had final melting points lower than body temperature.     

Physicochemical Properties of Interesterified Blends of Fully Hydrogenated Crambe abyssinica Oil and Soybean Oil

The chemical interesterification of blends of soybean (SO) and fully hydrogenated crambe oil (FHCO) in the ratios of 80:20, 75:25, 70:30, 65:35, and 60:40 (w/w), respectively, was investigated. FHCO is a source of behenic acid. The blends and the interesterified fats were analyzed for fatty acid and triacylglycerol composition, regiospecific distribution, slip melting point, solid profile, and consistency. The regiospecific analysis of the TAG indicated random insertion of saturated fatty acids at sn-2 of the glycerol of the interesterified blends with more significant alterations at sn-2 than at sn-1 and sn-3. The gradual addition of FHCO increased the solid fat content and the slip melting point. The chemical interesterification formed new TAG facilitating the miscibility between SO and FHCO. The 70:30 interesterified blend was suitable for general use, 60:40 for use as a base stock. At 35 °C, the 65:35 interesterified blend showed suitable plasticity for use in products with fat contents below 80 %. FHCO, rich in behenic acid, is not associated with increased total cholesterol and LDL cholesterol, and it can be used as a low trans fat. FHCO is not associated with increased total cholesterol and LDL cholesterol, and it can be used as a low trans fat alternative.     

Dielectric and impedance spectroscopy of Bi(Ca0.5Ti0.5)O3 ceramic

Bismuth calcium titanate (BiCa_0.5Ti_0.5O₃) ceramic, fabricated by a ceramic processing technique, has been characterized using a variety of experimental techniques. Analysis of basic crystal structure using X-ray diffraction data exhibits the orthorhombic system. Measurements and detailed analysis of some electrical parameters (i.e.,dielectric constant, loss tangent (energy loss), electrical impedance and modulus, conductivity, etc.) of Bi(Ca_0.5Ti_0.5)O₃ in a wide range of frequency (10³–10⁶ Hz) and temperature (30–500 °C) have provided some interesting and useful data and results on structure–properties relationship, conduction mechanism, etc.The role of interface, space charge polarization and Maxwell–Wagner dielectric relaxation in getting high dielectric constant of the material at low frequencies and high temperatures has been discussed. Study of temperature dependence of Nyquist plots clearly shows the contributions of grains in resistive and capacitive properties of the material. The frequency of the applied electric field and temperature strongly affect the dielectric (permittivity and dissipation of energy) and electrical (impedance, electrical modulus and conductivity) characteristics of the material.