Lipase-Catalyzed Synthesis of Cocoa Butter Equivalent from Palm Olein and Saturated Fatty Acid Distillate from Palm Oil Physical Refinery

Cocoa butter equivalent was prepared by enzymatic acidolysis reaction of substrate consisting of refined palm olein oil and palmitic?Cstearic fatty acid mixture. The reactions were performed in a batch reactor at a temperature of 60?°C in an orbital shaker operated at 160?RPM. Different mass ratios of substrates were explored and the compositions of the five major triacylglycerol (TAG) of the structured lipids were identified and quantified using cocoa butter-certified reference material IRMM-801. The reaction resulted in production of cococa butter equivent with TAG compostion (POP 26.6 %, POS 42.1, POO 7.5, SOS 18.0 %, and SOO 5.8 %) and melting temperature between 34.7 and 39.6?°C which is close to that of the cocoa butter. The result of this research demonstrated the potential use of saturated fatty acid distillate (palmitic and stearic fatty acids) obtained from palm oil physical refining process into a value-added product.     

Monitoring batch lipase catalyzed interesterification of palm oil and fractions by differential scanning calorimetry

The melting profiles of palm oil, palm olein, and soft palm mid fraction were investigated by differential scanning calorimetry (DSC) before, during and after enzymatic interesterification. The DSC melting profiles of the three palm fats changed drastically due to the random redistribution of the fatty acids on the glycerol occurring upon interesterification. A high melting peak (already present for native palm oil) was observed for the three interesterified products and attributed to the increase in trisaturated triacylglycerols; modifications of the shape of the medium-melting peak (observed in the three products) were attributed to modifications within the mono-unsaturated triacylglycerols. In view of the drastic changes observed, the applicability of DSC to monitor enzymatic interesterification reactions was considered. While the degree of interesterification was supposed to be completed after 8 h according to the HPLC data, significant modifications were still observed within the DSC melting profiles. Minor changes within the structure of the medium-melting peak were selected as indicator of the reaction progress, and it was shown that intensities of DSC melting endotherms can be used to monitor the enzymatic interesterification reaction of these palm products.     

Identification of volatile aroma compounds in processed cheese analogues based on different types of fat

The simple and rapid solid-phase micro-extraction method using gas chromatography was used for the identification and quantification of volatile aroma compounds in various types of processed cheese analogues produced from different types of fat (butter, butter oil, coconut oil, palm oil, and sunflower oil). In total, 31 organic compounds belonging to five chemical groups were identified, with the alcohols and fatty acids quantitatively predominant. The contents of the aroma compounds (the so-called aroma profiles) of the analogues and corresponding fats used as raw materials were compared. Significant differences (p < 0.05) were found between samples. The highest total content of aroma compounds was found in coconut oil analogue ((547.30 ± 9.82) mg kg^?1), the lowest in palm oil analogue ((372.01 ± 16.16) mg kg^?1). The concentrations of aroma compounds in fats were substantially lower (p < 0.05) than in analogues. Hence, the largest number of aroma analogues came from Edam cheese used for production as a protein source.     

Thermostability and polymorphism of theobroma oil and palm kernel oil as suppository bases

Thermal stability of pharmaceutical ingredients is an important aspect. In this study, we adopted differential scanning calorimetry (DSC) to investigate thermal stability of suppository bases, theobroma oil (cocoa butter) and a palm kernel oil (PKO) blend. The study shows theobroma oil possesses six polymorphic forms whilst the palm kernel oil blend has three. Upon rescanning, the PKO blend does not show changes in the enthalpy of fusion and the melting point with time, whilst the theobroma oil shows significant reduction, and only regained its thermal stable state after 10 days. This indicates that PKO blend possesses better thermal stability.     

An investigation of frequently consumed edible oils in Turkey in terms of omega fatty acids

The fatty acid profiles of frequently consumed oils and crops cultivated in Turkey were investigated in regard to omega fatty acids. Analyses were carried out on commercially sold oils, sunflower, olive, and fish oils, and oils extracted from fatty seeds of hazelnut, walnut, olive, sunflower, poppy, sesame, and pumpkin, and butter produced in Turkey. Hazelnut and olive oils were found to be rich in omega-9 (oleic acid 18:1), walnut, poppy seed, sesame, and pumpkin seed were rich in omega-6 (linoleic acid 18:2), and butter was rich in short chain fatty acids and omega-9. Fish oil, from mackerel, was the richest in omega-3 fatty acids and fatty acid diversity. There were some alterations between commercially sold oils and oils extracted from seeds in regard to fatty acid percentages and variety.     

Characterization,thermal properties and phase transitions of amazonian vegetable oils

Thermal profiles of buriti pulp oil (Mauritia flexuosa Mart.), tucumã pulp and kernel oils (Astrocarium vulgare Mart.), rubber seed oil (Hevea brasiliensis), passion fruit oil (Passiflora edulis) and ucuúba butter (Virola surinamensis) were analyzed by thermogravimetry (TG/DTG) and differential scanning calorimetry (DSC). Gas chromatography and calculated iodine values were performed to determine the fatty acid profile and to measure the degree of unsaturation in these oils, respectively. The TG curves showed three steps of mass loss, which can be attributed to the degradation of polyunsaturated, monounsaturated and saturated fatty acids. The DSC crystallization and melting curves are reported and depended on the fatty acid composition. Usually, oil samples with a high degree of saturation showed crystallization and melting profiles at higher temperatures than the oils with a high degree of unsaturation. The data obtained by physicochemical analysis of oil samples were analyzed by principal component analysis and hierarchical cluster analysis to increase understanding of the data set, examining the presence or absence of natural groupings between samples.     

Rheological properties of doughs with buckwheat and quinoa additives

Rheological properties of doughs prepared from wheat flour with buckwheat and quinoa flour addition (2.5 mass %, 5.0 mass %, 7.5 mass %, and 10 mass %) were investigated using a farinograph and compared with those of standard dough (without addition of pseudocereals). The following characteristics were determined: water absorption capacity, water consumption, dough growth time, level of dough softening, dough stability, mechanical resistance, and dough elasticity. Dough stability showed a linear decrease with the increasing content of pseudocereals. Doughs containing quinoa flour were more stable than those with buckwheat flour addition. Dough growth time was reduced with increasing amounts of buckwheat flour but it was not affected in the case of quinoa flour addition. From the comparison of the studied characteristics it can be concluded that an addition of lower amounts of quinoa (up to 5.0 mass %) to wheat flour will not significantly impair rheological properties of the dough but provides for enhanced nutritional value of the prepared bakery products.     

Compositional Shift in Fatty Acid Profiles of Lipids Obtained from Oleaginous Yeasts upon the Addition of Essential Oil from <Emphasis Type="Italic">Citrus sinensis</Emphasis> L.

Tailoring lipids from oleaginous yeasts to contain specific types of fatty acid is of considerable interest to food, fuel, and pharmaceutical industries. In this study, the essential oil obtained from Citrus sinesus L. has been used to alter the fatty acid composition of two common oleaginous yeasts, Rhodosporidium toruloides and Cryptococcus curvatus. With increasing levels of essential oil in the medium, the metabolic flux of the fatty acid biosynthesis pathway shifted towards saturated fatty acid production. Essential oil reduced the activities of elongase and ?9 desaturase. This made the lipid obtained from both these yeasts rich in saturated fatty acids. At certain specific concentrations of the essential oil in the medium, the lipid obtained from R. toruloides and C. curvatus cultures was similar to mahuwa butter and palm oil, respectively. Limonene is the major constituents of orange essential oil. Its effect on one of the oleaginous yeasts, R. toruloides, was also studied separately. Effects similar to orange essential oil were obtained with limonene. Thus, we can conclude that limonene in orange essential oil brings about compositional change of microbial lipid produced in this organism.     

Development and Physicochemical Properties of Low Saturation Alternative Fat for Whipping Cream

We developed an alternative whipping cream fat using shea butter but with low saturation. Enriched stearic-oleic-stearic (SOS) solid fat was obtained from shea butter via solvent fractionation. Acyl migration reactant, which mainly contains asymmetric SSO triacylglycerol (TAG), was prepared through enzymatic acyl migration to obtain the creaming quality derived from the β’-crystal form. Through enzymatic acyl migration, we obtained a 3.4-fold higher content of saturated-saturated-unsaturated (SSU) TAG than saturated-unsaturated-saturated (SUS) TAG. The acyl migration reactant was refined to obtain refined acyl migration reactant (RAMR). An alternative fat product was prepared by blending RAMR and hydrogenated palm kernel oil (HPKO) at a ratio of 4:6 (w/w). The melting points, solid fat index (SFI), and melting curves of the alternative products were similar to those of commercial whipping cream fat. The alternative fat had a content of total unsaturated fatty acids 20% higher than that of HPKO. The atherogenic index (AI) of alternative fat was 3.61, much lower than those of whipping cream fat (14.59) and HPKO (1220.3), because of its low atherogenic fatty acid content and high total unsaturated fatty acids. The polymorphic crystal form determined by X-ray diffraction spectroscopy showed that the β’-crystal form was predominant. Therefore, the alternative fat is comparable with whipping cream that requires creaming quality, and has a reduced saturated fat content.     

Rapid,non-destructive determination of butter adulteration by means of photopyroelectric (PPE) calorimetry

The study focuses on the application of the photopyroelectric (PPE) technique combined with gas chromatography to detect adulteration of cow milk-obtained butter. The thermal diffusivity and effusivity have been directly measured using back and front PPE detection, respectively, and the results have been correlated with the composition of adulterated butter samples. The back detection configuration has been used in the case of butter adulterated with palm oil, and a possible correlation of the thermal diffusivity with total amount of monounsaturated fatty acids composition has been proposed. For butter adulterated with soy milk, we used the front PPE configuration in order to measure the samples’ thermal effusivity. A strong dependence of the value of thermal effusivity as a function of soy milk content was found.     

Comparative quantitative fatty acid analysis of triacylglycerols using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and gas chromatography.

Quantitative analyses of fatty acids from five triacylglycerol products, coconut oil, palm kernel oil, palm oil, lard and cocoa butter, were carried out using two analytical methods: matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) and gas chromatography (GC), in an effort to validate the application of MALDI-TOFMS in quantitative fatty acid analysis. For the GC analysis, transmethylated products were used, whereas, for the MALDI-TOF analysis, saponified products were used. Under MALDI-TOF conditions, the acids were detected as sodiated sodium carboxylates [RCOONa + Na](+) consistent with the mode of ionization that was previously reported. Thus, the MALDI-TOF mass spectrum of saponified coconut oil showed the presence of sodiated sodium salts of caprylic acid (7.5 +/- 0.67, m/z 189), capric acid (6.9 +/- 0.83, m/z 217), lauric acid (47.8 +/- 0.67, m/z 245), myristic acid (20.4 +/- 0.51, m/z 273), palmitic acid (9.8 +/- 0.47, m/z 301), linoleic acid (0.9 +/- 0.07, m/z 325), oleic acid (4.8 +/- 0.42, m/z 327) and stearic acid (2.0 +/- 0.13, m/z 329). Saponified palm kernel oil had a fatty acid profile that included caprylic acid (3.5 +/- 0.59), capric acid (4.7 +/- 0.82), lauric acid (58.6 +/- 2.3), myristic acid (20.9 +/- 1.5), palmitic acid (7.2 +/- 1.1), oleic acid (3.8 +/- 0.62) and stearic acid (1.2 +/- 0.15). Saponified palm oil gave myristic acid (0.83 +/- 0.18), palmitic acid (55.8 +/- 1.7), linoleic acid (4.2 +/- 0.51), oleic acid (34.5 +/- 1.5), stearic acid (3.8 +/- 0.26) and arachidic acid (0.80 +/- 0.22). Saponified lard showed the presence of myristic acid (1.5 +/- 0.24), palmitic acid (28.9 +/- 1.3), linoleic acid (13.7 +/- 0.67), oleic acid (38.7 +/- 1.4), stearic acid (12.8 +/- 0.64) and arachidic acid (2.4 +/- 0.35). Finally, for saponified cocoa butter, the fatty acid distribution was: palmitic acid (32.3 +/- 1.0), linoleic acid (2.6 +/- 0.35), oleic acid (34.9 +/- 1.7) and stearic acid (30.3 +/- 1.6). Quantitative gas chromatographic analysis of the corresponding methyl esters from these triacylglycerol products yielded data that were mostly in agreement with the MALDI-TOFMS data. The MALDI-TOF experiment, however, proved to be superior to the GC experiment, particularly with regard to baseline resolution of unsaturated acids. Furthermore, the ability of MALDI-TOFMS to detect low concentrations of fatty acids rendered it more sensitive than the GC methodology.     

复热食用植物油结构变化的红外吸收光谱分析

利用衰减全反射(ATR)傅立叶红外光谱(FTIRS)法对市售优质品牌的8种植物油(转基因豆油、非转基因豆油、葵花籽油、花生油、玉米油、红花籽油、调和油、橄榄油)未加热及反复高温加热后的红外二阶导数光谱进行比较,发现复热食用油在反复高温加热下会使不饱和脂肪酸亚油酸、亚麻酸的含量降低,饱和脂肪酸棕榈酸和硬脂酸的含量增加;顺式脂肪酸的含量下降,反式脂肪酸的含量明显增加。确定以二阶导数光谱中3 009、988、966 cm-13处特征吸收峰的峰高判定是否为反复加热用油。此方法样品用量少、分析速度快,可从整体上了解油品的质量及成分,并可作为市场复热食用油的快速筛查方法,也可为地沟油检测方法的建立提供理论依据。     

Chemical characterization of unconventional palm oils from Hyophorbe indica and two other endemic Arecaceae species from Reunion Island

Abstract

Chemical characteristics of novel seed oils, yet not investigated, from three endemic Arecaceae (palm) species from Reunion Island are described. Fatty acid profiles are performed using two-dimensional gas chromatography-mass spectrometry. Carotenoid contents are determined by high performance liquid chromatography-mass spectrometry. The results of the investigations emphasize the particular composition of the unconventional red seed oil from Hyophorbe indica. Characteristic features of this oil reveal a high degree of unsaturation (50% of polyunsaturated fatty acids, with a high content (17%) of omega-3), which is possibly a unique fatty acid composition in the Arecaceae family. The two other palm oils from Dictyosperma album and Latania lontaroides contain high level of saturated fatty acids very similar to that of the edible palm oil. H. indica oil is also very rich in valuable carotenoids; in particular, lutein, β-carotene and lycopene are detected in a high content (respectively 45, 23 and 35?mg.kg^?1 in oil).     

Comparison of the oxidative stability of soybean and sunflower oils enriched with herbal plant extracts

The present study was conducted to determine and compare the oxidative stability of soybean and sunflower oils using differential scanning calorimetry (DSC). These edible oils were enriched with marjoram (Origanum majorana L.), thyme (Thymus vulgaris L.), and oregano (Origanum vulgare L.) extracts at three different concentrations and synthetic antioxidant (BHA). The fatty acid composition of studied oils was determined by gas chromatography mass spectrometry to evaluate the content of unsaturated fatty acids that are sensitive to oxidation process. Oil samples were heated in the DSC at different heating rates (4.0, 7.5, 10.0, 12.5, and 15.0 °C min^?1) and oxidation kinetic parameters (activation energy, pre-exponential factor, and oxidation rate constant) were calculated. The results showed that the oxidative stability of sunflower oil samples enriched with oregano extracts and soybean oil supplemented with thyme extracts was improved compared to samples without the addition of herbal plant extracts and the synthetic antioxidant.     

Liquid chromatographic detection of Dowtherm A contamination in oleochemicals and edible oils.

A rapid and direct liquid chromatographic (LC) technique is described for the determination of a eutectic mixture of diphenyl oxide and biphenyl such as Dowtherm A thermal heating fluid (THF) in oleochemicals and palm olein. Analysis is performed with an RP-18 column with fluorescence detection (excitation at 247 nm and emission at 310 nm). The isocratic mobile phase (1.0 mL/min) consists of methanol and water (90 + 10, v/v). A linear calibration model (correlation coefficient = 0.9999) was developed directly from used Dowtherm A THF with the biphenyl peak (4.70 min) as a marker. Average recoveries from spiked glycerin, fatty alcohol mixture, methyl ester mixture, fatty acids, and palm olein were 90.9-108.7%, with a detection limit of 0.1 microgram/mL. The technique requires no prior sample cleanup nor extraction steps and is good for quality assurance purposes.     

Fatty Acid Composition of Tobacco Seed Oil and Synthesis of Alkyd Resin

The fatty acid composition of tobacco seed oil revealed that the oil is rich in unsaturated fatty acids, having linoleic acid （71.63%）, oleic acid （13.46%） and palmitic acid （8.72%） as the most abundant unsaturated and saturated fatty acids respectively. So the tobacco oil was characterized as semi-drying type on the basis of fatty acid composition. The synthesis of alkyd resin was carried out by alcoholysis or monoglyceride process using an alkali refined tobacco seed oil, pentaerythritol, cis-1,2,3,6-tetrahydrophthalic anhydride along with lithium hydroxide as catalyst. The alkyd resin so prepared was found to be bright and of low color with high gloss. The drying and hardness properties and adhesion of the tobacco seed oil derived alkyd resin were also found a bit superior to those of other alkyd resins of the same oil length. In addition, the water and acid resistance of the said alkyd was also found comparable to the other alkyds.     

葵子油脂肪酸2-氨基-2-甲基-丙醇化学修饰气相色谱-质谱分析

以2-氨基-2-甲基-丙醇为脂肪酸的化学修饰试剂,气相色谱一电子轰击质谱（GC-EI MS）分析葵子油脂肪酸。2-氨基-2-甲基-丙醇将脂肪酸羧基修改为含氮杂环,使在EI源中避免了链烯基中碳碳双键的移动。解析了葵子油脂肪酸2-氨基-2-甲基-丙醇化学修饰产物的EI质谱图,讨沦了烯酸中碳碳双键的定位规则,确定了葵子油脂肪酸中碳碳双键的位置。鉴定出葵子油6种脂肪酸,不饱和脂肪酸相对含量为89．41％,其中人体必需脂肪酸9,12-十八碳二烯酸含量占65．30％。本方法为不饱和脂肪酸中双键的定位提供了新的技术手段。     

超高效合相色谱-质谱法快速分析食用植物油中常见脂肪酸

建立了超高效合相色谱-质谱(UPC²-MS)快速分析6种食用植物油(玉米油、葵花籽油、大豆油、茶油、菜籽油、花生油)中棕榈酸、硬脂酸、油酸、亚油酸、亚麻酸等5种常见脂肪酸的方法,并比较了这6种食用油中上述5种脂肪酸的含量差异。采用皂化反应对植物油进行前处理,以ACQUITY UPC² BEH 2-EP色谱柱(100 mm×2.1 mm, 1.7 μm)为分析柱,以超临界CO₂-甲醇/乙腈(1:1, v/v)为流动相进行梯度洗脱,流速为0.8 mL/min。在电喷雾负离子模式下进行检测,外标法定量。结果表明:5种脂肪酸标准物质在0.5~100 mg/L范围内呈现良好的线性关系,相关系数为0.9985~0.9998,定量限(S/N≥10)为0.15~0.50 mg/L;在3个添加水平下,样品的加标回收率为89.61%~108.50%;方法重复性的相对标准偏差(RSD)为0.69%~3.01%。该方法简单、快速、分离效果好,无需对脂肪酸样品进行衍生化,已成功地用于玉米油、葵花籽油、橄榄油、茶油、大豆油和花生油等6种食用油中常见脂肪酸含量的测定。     

Lipase-Catalyzed Acidolysis of Palm Mid Fraction Oil with Palmitic and Stearic Fatty Acid Mixture for Production of Cocoa Butter Equivalent

Cocoa butter equivalent (CBE) was prepared by enzymatic acidolysis reaction of substrate consisting of refined palm mid fraction oil and palmitic–stearic fatty acid mixture. The reactions were performed in a batch reactor at a temperature of 60 °C in an orbital shaker operated at 160 RPM. Different mass ratios of substrates were explored, and the composition of the five major triacylglycerols (TAGs) of the structured lipids was identified and quantified using cocoa butter certified reference material IRMM-801. The reaction resulted in production of cocoa butter equivalent with the TAGs' composition (1,3-dipalmitoyl-2-oleoyl-glycerol 30.7 %, 1-palmitoyl-2-oleoyl-3-stearoyl-rac-glycerol 40.1%, 1-palmitoy-2,3- dioleoyl glycerol 9.0 %, 1,3-distearoyl-2-oleoyl-glycerol 14.5 %, and 1-stearoyl-2,3-dioleoyl glycerol 5.7 %) and with onset melting temperature of 31.6 °C and peak temperature of 40.4 °C which are close to those of cocoa butter. The proposed kinetics model for the acidolysis reaction presented the experimental data very well. The results of this research showed that palm mid fraction oil TAGs could be restructured to produce value added product such as CBE.     

The Role of Lignocellulosic Composition and Residual Lipids in Empty Fruit Bunches on the Production of Humic Acids in Submerged Fermentations

The aim of this research was to study the production of humic acids (HA) by Trichoderma reesei from empty fruit bunches (EFBs) of palm oil processing, with a focus on the effects of lignocellulosic content and residual lipids. EFBs from two different soils and palm oil producers were previously characterized about their lignocellulosic composition. Submerged fermentations were inoculated with T. reesei spores and set up with or without residual lipids. The results showed that the soil and the processing for removal of the palm fresh fruits were crucial to EFB quality. Thus, EFBs were classified as type 1 (higher lignocellulosic and fatty acids composition similar to the palm oil and palm kernel oil) and type 2 (lower lignocellulosic content and fatty acids composition similar to palm oil). Despite the different profiles, the fungal growth was similar for both EFB types. HA production was associated with fungal growth, and it was higher without lipids for both EFBs. The highest HA productivity was obtained from type 1 EFB (approximately 90 mg L⁻¹ at 48 h). Therefore, the lignocellulosic composition and the nature of the residual lipids in EFBs play an important role in HA production by submerged fermentation.