The present study is focused on the effect of the TTABr/MX/H2O-nanoparticles on the rate of piperidinolysis of ionized phenyl salicylate where TTABr represents tetradecyltrimethylammonium bromide and MX = NaCl, NaBr and CnH2n+1CO2Na with n = 4, 5, 6 and 7. Pseudo-first-order rate constant for the piperidinolysis of ionized phenyl salicylate at 35°C and constant concentration [PSa(-)]T = 0.2 mM, [Pip]T = 0.1 M, [NaOH] = 30 mM, [TTABr]T and different [MX] follow an empirical relationship which gives two empirical constant, (X)kcat and K(X/S). The value of relative counterion (X) binding constant, RX(Br) were calculated from the relationship; RX(Br) = (X)kcat/(Br)kcat. The values of RX(Br) for X = C4H9CO2(-), C5H11CO2(-), C6H13CO2(-), and C7H15CO2(-) are increasing with increase in the number of alkyl chain of counterion X.
A novel adsorbent, palm fatty acid coated magnetic Fe3O4 nanoparticles (MNP-FA) was successfully synthesized with immobilization of the palm fatty acid onto the surface of MNPs. The successful synthesis of MNP-FA was further confirmed by X-Ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and Energy dispersive X-Ray spectroscopy (EDX) analyses and water contact angle (WCA) measurement. This newly synthesized MNP-FA was applied as magnetic solid phase extraction (MSPE) adsorbent for the enrichment of polycyclic aromatic hydrocarbons (PAHs), namely fluoranthene (FLT), pyrene (Pyr), chrysene (Cry) and benzo(a)pyrene (BaP) from environmental samples prior to High Performance Liquid Chromatography- Diode Array Detector (HPLC-DAD) analysis. The MSPE method was optimized by several parameters such as amount of sorbent, desorption solvent, volume of desorption solvent, extraction time, desorption time, pH and sample volume. Under the optimized conditions, MSPE method provided a low detection limit (LOD) for FLT, Pyr, Cry and BaP in the range of 0.01-0.05 ng mL(-1). The PAHs recoveries of the spiked leachate samples ranged from 98.5% to 113.8% with the RSDs (n = 5) ranging from 3.5% to 12.2%, while for the spiked sludge samples, the recoveries ranged from 81.1% to 119.3% with the RSDs (n = 5) ranging from 3.1% to 13.6%. The recyclability study revealed that MNP-FA has excellent reusability up to five times. Chromatrographic analysis demonstrated the suitability of MNP-FA as MSPE adsorbent for the efficient extraction of PAHs from environmental samples.
The environmental impacts of palm oil mill effluent (POME) have been a concern due to the water pollution and greenhouse gases emissions. Thus, this study was conducted to recover the value-added products from POME source before being discharged. The samples, before (X) and after (Y) the pre-recovery system in the clarification tank were sampled and analysed and proximate analysis indicated that both samples are energy rich source of food due to high contents of fats and carbohydrates. GCMS analysis showed that the oil extracts contain predominantly palmitic, oleic, linoleic and stearic acids. Regiospecific analysis of oil extracts by quantitative 13C-NMR spectroscopy demonstrated that both oil extracts contain similar degree of saturation of fatty acids at sn-2 and sn-1,3 positions. The samples are rich in various phytonutrients, pro-vitamin A, vitamin E, squalene and phytosterols, thus contributing to exceptionally high total flavonoid contents and moderate antioxidant activities. Overall, samples X and Y are good alternative food sources, besides reducing the environmental impact of POME.
Behaviors of cationic and nonionic mixed micelles in the form of hexadecyltrimethylammonium bromide (HDABr) and hexadecyltrimethylammonium bromide-Polyethylene glycol hexadecyl ether (C16E20), in the presence of inert salts (NaBr and 3,5-dichlorosodium benzoate), by the use of reaction probe between Pp and ionized PhSH (Pp = piperidine and PhSH = phenyl salicylate), has been reported in this work. The values of RXBr (RXBr denotes ion exchange constants obtained in the presence of micelles of different structural features) or KXBr (KXBr denotes ion exchange constants obtained in the presence of micelles of the same structural features) for 3,5-Cl2C6H3CO2- were almost the same at three different [HDABr]T (0.006, 0.010 and 0.015 M). The average value of RXBr or KXBr determined, in the presence of pure HDABr micelles, using semi empirical kinetic (SEK) method appeared to be almost 2½-fold larger (RXBr or KXBr = 198) than that in the presence of mixed HDABr-C16E20 micelles (RXBr or KXBr = 78). Rheological measurements indicated the existence of wormlike/twisted micelles and vesicle at 0.015 M pure HDABr, various [3,5-Cl2C6H3CO2Na], and 25 and 35℃ whereas there were evidence of only spherical micelles in the presence of mixed HDABr-C16E20 ([HDABr]T = 0.015 M and [C16E20]T = 0.006 M) at both temperatures.
This paper examines the interactions of degumming and bleaching processes as well as their influences on the formation of 3-monochloropropane-1,2-diol esters (3-MCPDE) and glycidyl esters in refined, bleached and deodorized palm oil by using D-optimal design. Water degumming effectively reduced the 3-MCPDE content up to 50%. Acid activated bleaching earth had a greater effect on 3-MCPDE reduction compared to natural bleaching earth and acid activated bleaching earth with neutral pH, indicating that performance and adsorption capacities of bleaching earth are the predominant factors in the removal of esters, rather than its acidity profile. The combination of high dosage phosphoric acid during degumming with the use of acid activated bleaching earth eliminated almost all glycidyl esters during refining. Besides, the effects of crude palm oil quality was assessed and it was found that the quality of crude palm oil determines the level of formation of 3-MCPDE and glycidyl esters in palm oil during the high temperature deodorization step of physical refining process. Poor quality crude palm oil has strong impact towards 3-MCPDE and glycidyl esters formation due to the intrinsic components present within. The findings are useful to palm oil refining industry in choosing raw materials as an input during the refining process.
The impact of microwave roasting on the thermooxidative degradation of perah seed oil (PSO) was evaluated during heating at a frying temperature (170°C). The roasting resulted significantly lower increment of the values of oxidative indices such as free acidity, peroxide value, p-anisidine, total oxidation (TOTOX), specific extinctions and thiobarbituric acid in oils during heating. The colour L* (lightness) value dropped gradually as the heating time increased up to 12 h, whereas a*(redness) and b* (yellowness) tended to increase. The viscosity and total polar compound in roasted PSO was lower as compared to that in unroasted one at each heating times. The tocol retention was also high in roasted samples throughout the heating period. The relative contents of polyunsaturated fatty acids (PUFAs) were decreased to 94.42% and saturated fatty acids (SFAs) were increased to 110.20% in unroasted sample, after 12 h of heating. On the other hand, in 3 min roasted samples, the relative contents of PUFAs were decreased to 98.08% and of SFAs were increased to 103.41% after 12 h of heating. Outcome from analyses showed that microwave roasting reduced the oxidative deteriorations of PSO during heating.
Also recognized as carbohydrate liquid crystals, glycolipids are amphiphiles whose basic unit comprises of a sugar group attached to an alkyl chain. Glycolipids are amphitropic, which means these materials form liquid crystal self-assemblies when dry (thermotropic) as well as when dissolved in solvents (lyotropic/surfactants) such as water. Many glycolipids are also naturally derived since these can be found in cell membranes. Their membrane and surfactant functions are largely understood through their lyotropic properties. While glycolipids are expected to play major roles as eco-friendly surfactants in the global surfactant market, their usefulness as thermotropic liquid crystal material is, to date, unknown, due to relatively lack of research performed and data reported in the literature. Understandably since glycolipids are hygroscopic with many hydroxy groups, removing the last trace water is very challenging. In recent time, with careful lyophilization and more consistent characterization technique, some researchers have attempted serious studies into "dry" or anhydrous glycolipids. Motivated by possible developments of novel thermotropic applications, some results from these studies also provide surprising new understanding to support conventional wisdom of the lyotropic systems. Here we review the dry state of glycosides, a family of glycolipids whose sugar headgroup is linked to the lipid chain via a glycosidic oxygen linker. The structure property relationship of both linear and anhydrous Guerbet glycosides will be examined. In particular, how the variation of sugar stereochemistry (e.g. anomer vs. epimer), the chain length and chain branching affect the formation of thermotropic liquid crystals phases, which not only located under equilibrium but also far from equilibrium conditions (glassy phase) are scrutinized. The dry glycolipid assembly has been subjected to electric and magnetic fields and the results show interesting behaviors including a possible transient current generation.
The in situ polymorphic forms and thermal transitions of refined, bleached and deodorized palm oil (RBDPO), palm stearin (RBDPS) and palm kernel oil (RBDPKO) were investigated using coupled X-ray diffraction (XRD) and differential scanning calorimetry (DSC). Results indicated that the DSC onset crystallisation temperature of RBDPO was at 22.6°C, with a single reflection at 4.2Å started to appear from 23.4 to 17.1°C, and were followed by two prominent exothermic peaks at 20.1°C and 8.5°C respectively. Further cooling to -40°C leads to the further formation of a β'polymorph. Upon heating, a of β'→βtransformation was observed between 32.1 to 40.8°C, before the sample was completely melted at 43.0°C. The crystallization onset temperature of RBDPS was 44.1°C, with the appearance of the α polymorph at the same temperature as the appearance of the first sharp DSC exothermic peak. This quickly changed from α→β´ in the range 25 to 21.7°C, along with the formation of a small β peak at -40°C. Upon heating, a small XRD peak for the β polymorph was observed between 32.2 to 36.0°C, becoming a mixture of (β´+ β) between 44.0 to 52.5°C. Only the β polymorph survived further heating to 59.8°C. For RBDPKO, the crystallization onset temperature was 11.6°C, with the formation of a single sharp exothermic peak at 6.5°C corresponding to the β' polymorphic form until the temperature reached -40°C. No transformation of the polymorphic form was observed during the melting process of RBDPKO, before being completely melted at 33.2°C. This work has demonstrated the detailed dynamics of polymorphic transformations of PKO and PS, two commercially important hardstocks used widely by industry and will contribute to a greater understanding of their crystallization and melting dynamics.
In this research, the palm oil ester (POE)- based nanoemulsion formulation containing quercetin for pulmonary delivery was developed. The nanoemulsion formulation was prepared by high energy emulsification method and then further optimized using D-optimal mixture design. The concentration effects of the mixture of POE:ricinoleic acid (RC), ratio 1:1 (1.50-4.50 wt.%), lecithin (1.50-2.50 wt.%), Tween 80 (0.50-1.00 wt.%), glycerol (1.50-3.00 wt.%), and water (88.0-94.9 wt.%) towards the droplet size were investigated. The results showed that the optimum formulation with 1.50 wt.% POE:RC, 1.50 wt.% lecithin, 1.50 wt.% Tween 80, 1.50 wt.% glycerol and 93.90 % water was obtained. The droplet size, polydispersity index (PDI) and zeta potential of the optimized formulation were 110.3 nm, 0.290 and －37.7 mV, respectively. The formulation also exhibited good stability against storage at 4℃ for 90 days. In vitro aerosols delivery evaluation showed that the aerosols output, aerosols rate and median mass aerodynamic diameter of the optimized nanoemulsion were 99.31%, 0.19 g/min and 4.25 µm, respectively. The characterization of physical properties and efficiency for aerosols delivery results suggest that POE- based nanoemulsion containing quercetin has the potential to be used for pulmonary delivery specifically for lung cancer treatment.
High-Performance Liquid Chromatography (HPLC) methods via evaporative light scattering (ELS) and refractive index (RI) detectors are used by the local palm oil industry to monitor the TAG profiles of palm oil and its fractions. The quantitation method used is based on area normalization of the TAG components and expressed as percentage area. Although not frequently used, peak-area ratios based on TAG profiles are a possible qualitative method for characterizing the TAG of palm oil and its fractions. This paper aims to compare these two detectors in terms of peak-area ratio, percentage peak area composition, and TAG elution profiles. The triacylglycerol (TAG) composition for palm oil and its fractions were analysed under similar HPLC conditions i.e. mobile phase and column. However, different sample concentrations were used for the detectors while remaining within the linearity limits of the detectors. These concentrations also gave a good baseline resolved separation for all the TAGs components. The results of the ELSD method's percentage area composition for the TAGs of palm oil and its fractions differed from those of RID. This indicates an unequal response of TAGs for palm oil and its fractions using the ELSD, also affecting the peak area ratios. They were found not to be equivalent to those obtained using the HPLC-RID. The ELSD method showed a better baseline separation for the TAGs components, with a more stable baseline as compared with the corresponding HPLC-RID. In conclusion, the percentage area compositions and peak-area ratios for palm oil and its fractions as derived from HPLC-ELSD and RID were not equivalent due to different responses of TAG components to the ELSD detector. The HPLC-RID has a better accuracy for percentage area composition and peak-area ratio because the TAG components response equally to the detector.
Saturated fats are commonly claimed to raise human blood cholesterols and contribute to cardiovascular disease. Previous literature data were highlighted that although palm oil is 50% saturated, it does not behave like a saturated fat. Human trials were conducted to compare the effects on serum cholesterol levels given by palm olein and monounsaturated oils. It was postulated that saturation/unsaturation of the fatty acids situated at sn-2 positions of triglycerides in the fat molecules determine the induced blood lipid levels but not the overall saturation of oils. The results showed that the lipid parameters (LDL and HDL) effects induced by these oils are similar with no significant differences. This study provides concrete evidence that the unsaturation levels of these oils at sn-2 position of TG are similar (90-100%) which are claimed to be responsible for the lipid parameters. In conclusion, the public negative perception on believing that the overall saturation of oils is detrimental to health should be corrected because in fact the unsaturation at sn-2 positions of the saturated vegetable fat such as palm olein and cocoa butter make them behave like mono-unsaturated oils, unlike saturated animal fats that possess a high content of saturated fatty acids at sn-2 position.
The study was aimed at evaluating the effects of vegetable oils on emulsion stability. Palm olein (POo), olive oil (OO), safflower oil (SAF), grape seed oil (GSO), soybean oil (SBO) and sunflower oil (SFO) with different degree of saturation levels were chosen as major ingredient of oil phases. All the emulsions were stored at 4℃, 27℃ and 40℃ for 35 days and subjected to all the stability tests, including temperature variation, centrifuge test, cycle test, pH and slip melting point. The results indicated that POo exhibited the highest stability, followed by SAF, OO, GSO, SFO and SBO. In addition, the results implied that the degree of saturation levels of vegetable oils does give significant effect on emulsion stability based on the centrifuge testing for an approximate 30% usage level of oil. The POo-based emulsion exhibited good emulsion stability throughout the experimental period indicated that POo could be a good carrier oil for various applications in cosmetic industry.
Lipase-catalyzed production of palm esters was performed via alcoholysis of palm oil and oleyl alcohol in solvent and solvent-free systems using a 2 L stirred tank reactor (STR). Two immobilized lipases were tested and Lipozyme RM IM exhibited superior performance in both reaction systems. Reusability studies of the enzymes in a solvent-free system also demonstrated the high stability of Lipozyme RM IM as shown by its ability to yield more than 70% palm esters with up to 19 cycles of reusing the same enzymes. Modification of the enzyme washing process improved the stability of Lipozyme TL IM in a solvent system as demonstrated by maintaining 65% yield after 5 times of repeated enzyme use. The scale up process for both lipases was conducted in the presence of solvents by using the impeller tip speed approach. Lipozyme RM IM-catalyzed reaction in a 15 L STR produced 85.7% yield and there was a significant drop to 60.7% in the 300 L STR, whereas Lipozyme TL IM had a lower yield (65%) when the reaction volume was increased to 15 L. The low yields could be due to the accumulation of enzymes at the bottom of the vessel. Purification of palm esters via solvent-solvent extraction revealed that more than 90% of oleyl alcohol was extracted after the third extraction cycle at 150 rpm impeller speed with reduced palm esters: ethanol ratio (v/v) from 1:4 to 1:3.
Refined palm-pressed mesocarp fibre oil (PPFO), which can be obtained from one of the by-products of palm oil milling, palm-pressed mesocarp fibre, is categorized as palm sludge oil. So far, it has been given less attention and underutilized until some recent scientific reports revealing its high content of phytonutrients, carotenoids and vitamin E, which have been proven scientifically to possess anti-oxidant activity. The study evaluated the stability of PPFO as a carrier for plant-based emulsion. PPFO was extracted and examined for its positional distribution of fatty acids, saturation levels and iodine value (IV) using NMR spectroscopy. The PPFO-based emulsion was then prepared and subjected to stability tests, including temperature variation, centrifuge test, cycle test, pH and slip melting point for 28 days. Phase separation was observed from PPFO-based emulsion stored at 40℃ from day-21 onwards while no creaming found in all the palm olein-based emulsions stored at the three storage temperatures. Nevertheless, results indicated that the PPFO-based emulsion passed all the tests above showing insignificant phase separation (p > 0.05) compared with those of palm olein commonly used in emulsion preparation. The findings suggested that PPFO enriched with valuable phytonutrients could be used as an alternative carrier oil in emulsion formulation, which is an important component in personal care products.
The present study revealed the optimization of nanoemulsion containing palm oil derivatives and Parthenium hysterophorus L. crude extract (PHCE) as pre-emergence herbicide formulation against Diodia ocimifolia. The nanoemulsion formulation was prepared by high energy emulsification method, and it was optimized by mixture experimental design (MED). From the optimization process, analysis of variance (ANOVA) showed a fit quadratic polynomial model with an optimal formulation composition containing 30.91% of palm kernel oil ester (PKOE), 28.48% of mixed surfactants (Tensiofix and Tween 80, 8:2), 28.32% of water and 12.29% of PHCE. The reading of both experimental and predicted particle size in the verification experiment were acceptable with a residual standard error (RSE) was less than 2%. Under the optimal condition, the smallest particle size obtained was 140.10 nm, and the particle was shown by morphology analysis to be spherical and demonstrated good stability (no phase separation) under centrifugation and different storage conditions (25 ± 5°C and 45°C). Nanoemulsion stored for 60 days exhibits monodisperse emulsion with a slight increase of particle size. The increase in particle size over time might have contributed by Ostwald ripening phenomenon which is shown by a linear graph from Ostwald ripening rate analysis. In the in vitro germination test, P. hysterophorus nanoemulsion (PHNE) was shown to cause total inhibition of D. ocimifolia seed at lower concentration (5 g L-1) as compared to PHCE (10 g L-1). The finding of the research could potentially serve as a platform for the development of palm oil based formulation containing plant crude extract for green weed management.
An optimal ratio of omega-6 to omega-3 (ω-6/ω-3) polyunsaturated fatty acids (PUFA) in the diet prevents the pathogenesis of many inflammatory diseases. This study aimed to synthesize and characterize ternary oil blends with optimal ω-6/ω-3 ratios using olive (OL), sunflower (SU), and cress (CR) oils. The oxidative stability, thermal profile, fatty acid (FA) and tocopherol compositions, and the physicochemical properties of the blends were used to determine their quality. Oil mixtures were prepared with 2, 3, 4, and 5 ω-6/ω-3 ratios. FA composition and tocopherol content were the most important factors affecting the oxidation and thermal stabilities of the oils. All oil mixtures showed good quality indices. Thus, synthetized oil blends with high oxidative stability, high antioxidant content, optimal ω-6/ω-3 ratios, and recommended FA compositions can influence human health. The composition of healthy oil blends with optimal ω-6/ω-3 ratios was expressed mathematically and depicted graphically in a ternary diagram.
Red palm olein is known to be high in carotenes and vitamin E (tocols) and possess various nutritional benefits. This study evaluates the effect of prolonged heating using three common cooking techniques i.e. deep-fat fryer, microwave oven and conventional oven, on the profiles of carotenes and tocols as well as the physico-chemical changes occurring in red palm olein when compared to conventional palm olein. Physico-chemical changes in all oils were gauged based on their peroxide, p-anisidine and total oxidation values, acidity, and fatty acid composition. Both red palm olein and palm olein were thermally stable based on their lower rate of hydrolytic and oxidative degradations as well as higher tocols retention, which allow the oils to undergo heating up to 3 hours using deep-fat fryer and conventional oven. Nevertheless, red palm olein seemed not suitable for prolonged heating processes considering lower retention of carotenes. Microwave heating also influenced the stability of phytonutrients.
Allium ampeloprasum L., commonly known as wild leek, is an edible vegetable that has been cultivated for centuries. However, no detailed studies have been undertaken to valorize A. ampeloprasum seed oil. This study aims to evaluate the physicochemical properties, chemical composition, and antioxidant activity of A. ampeloprasum seed oil. The seed oil content was found to be 18.20%. Gas chromatographymass spectrometry (GC-MS) showed that linoleic acid (71.65%) was the dominant acid, followed by oleic acid (14.11%) and palmitic acid (7.11%). A. ampeloprasum seed oil exhibited an oxidative stability of 5.22 h. Moreover, γ- and δ-tocotrienols were the major tocols present (79.56 and 52.08 mg/100 g oil, respectively). The total flavonoid content (16.64 µg CE /g oil) and total phenolic content (62.96 µg GAE /g oil) of the seed oil were also determined. The antioxidant capacity of the oil, as evaluated using the ABTS assay (136.30 µM TEAC/g oil), was found to be significant. These findings indicate that A. ampeloprasum seeds can be regarded as a new source of edible oil having health benefits and nutritional properties.
The study was designed to evaluate the nutritive value, thermal stability and consumer acceptance of cupcakes baked with red palm olein compared to palm olein. Thermal stability was evaluated for acidity, peroxide, p-anisidine and total oxidation value (cumulative between peroxide and p-anisidine values), as well as fatty acid composition. The concentrations of phytonutrients including tocopherols and tocotrienols, alpha- and beta-carotene after baking were also determined. Acceptance of the cupcakes was assessed using a structured hedonic scale of five points by 29 panelists. As compared to initial test oil (red palm olein), acidity (red palm olein, 0.07±0.01% vs cupcakes containing red palm olein, 0.09±0.01%; P=0.0232), peroxide value (red palm olein, 0.33±0.05 meq O2 kg-1 vs cupcakes containing red palm olein 0.73±0.06 meq O2 kg-1; P=0.0011) and total oxidation value (red palm olein, 2.24±0.13 unit vs cupcakes containing red palm olein, 3.09±0.17 unit; P=0.0012) were found to be higher in cupcakes containing red palm olein, which is within the acceptable rancidity range (peroxide value < 7.5 meq O2 kg-1) for snack food category. No changes were found on oxidative parameters (acidity, peroxide, p-anisidine values and total oxidation value) in cupcakes containing palm olein. Cupcakes made with red palm olein retained nearly 100% of alpha- and beta-carotenes upon baking. Tocopherol homologues were stable in both comparisons, with 95% retention as compared to tocotrienol homologues (~85%). Cupcakes made from red palm olein received higher score (mean=3.29) in sensory evaluation as compared to cupcakes containing palm olein (mean=3.07). The study, therefore, encourages the inclusion of red palm olein in the formulation of bakery products.
Approximately 900 tonne of crude palm oil (CPO) underwent washing using 5 to 10% hot water (90 to 95°C) at a palm oil mill. The aim of the CPO washing was to eliminate and/or reduce total chlorine content present in the conventional CPO, as it is known as the main precursor for the formation of 3-monochloropropane-1, 2-diol esters (3-MCPDE). By a simple hot water washing, more than 85% of the total chlorine was removed. However, washing did not have significant (p > 0.05) effect on other oil quality parameters such as the deterioration of bleachability index (DOBI), free fatty acid (FFA) content and diacylglycerol (DAG) content of the oil. The latter has been established as the main precursor for glycidyl esters (GE) formation. The treated CPO was then transported using tankers and further refined at a commercial refinery. Refining of washed CPO resulted in significantly (p < 0.05) lower formation of 3-MCPDE, but GE content remained slightly high. Post-treatment of refined oil significantly reduced the GE content (p < 0.05) to an acceptable level whilst almost maintaining the low 3-MCPDE level. The study has proven that water washing of CPO prior to refining and subsequent post-refining is so far the most effective way to produce good quality refined oil with considerably low 3-MCPDE and GE contents. Dry fractionation of refined palm oil showed these contaminants partitioned more into the liquid olein fraction compared to the stearin fraction.