In this study, chemical properties, amino acid contents, fatty acid compositions of sesame seeds dependin on growing locations of sesame plants were evaluated. Protein contents of sesame seeds changed between 20.80% (Afghanistan) and 26.01% (India). Oil contents of seeds were changed between 44.69% (Mozambique) and 55.37% (Niger-Kany). Crude fiber contents of sesame seeds ranged from 17.30% (Ethiopia-Volega) to 28.78% (Mozambique). The highest protein, crude oil and crude fiber were found in India, Niger-Kany and Mozambique sesame seed samples, respectively. In addition, while glutamic acid contends of seeds change between 3.28% (Uganda and Niger-Benje) and 4.57% (India), arginine contents of seeds ranged from 2.36% (Uganda) to 3.10% (India). The total amino acid contents of sesame seeds ranged from 18.12% (Uganda) to 23.51% (India). Palmitic acid contents of sesame oils ranged from 7.93% (Uganda) to 9.55% (Burkina Faso). While oleic acid contents of sesame seed oils are found between 35.88% (Mozambique) and 44.54% (Afghanistan), linoleic acid contents of oils ranged from 37.41% (Afghanistan) to 47.44% (Mozambique). The high amount of protein, oil contents, amino acids and unsaturated fatty acids can be positively considered from the nutritional point of view.
The health benefits of conjugated linoleic acid (CLA), a functional lipid with anti-cancer, anti-obesity, and hypotensive activity, have garnered increasing attention. The current study was conducted to determine the oxidative stability of CLA in the form of triacylglycerol (CLA-TAG) and phosphatidylcholine (CLA-PC) at the sn-2 position. Oxidation was performed at 30°C or 40°C in the dark. Hydroperoxides, as the primary oxidation products, were analyzed using diphenyl-1-pyrenylphosphine. Thiobarbituric acid reactive substances (TBARS) and volatile compounds were monitored as secondary oxidation products. The results suggest that CLA-PC was more stable against oxidation than CLA-TAG from the perspective of suppression of the generation of hydroperoxides and TBARS. However, CLA-PC produced more volatile compounds than CLA-TAG. We suggest that choline was released during the oxidation of CLA-PC, and acted as an antioxidant. The ensuing reaction between choline and hydroperoxide induced the generation of volatile compounds such as pentanal, hexanal, and heptanal.
In this work, the evolution of virgin olive oil from 4 olive varieties when stored at 5°C, 10°C and 20°C for a period of up to 3 years was studied. Free acidity increased progressively for the 4 varieties, staying below the limit for extra virgin olive oil, even at the highest temperature. The peroxide value also increased, reaching its maximum after about 28 months of storage, when some samples stored at 20°C exceeded the limit for extra virgin olive oil. The maximum values for K270 and K232 were reached at the end of the storage period, also exceeding the limit for extra virgin olive oil in the case of some varieties stored at 20°C. Oxidative stability decreased by 38%-50% depending on the storage temperature and the variety. Most of the color indexes increased in value because of the degradation of the oil pigments.
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.
The development of human milk fat substitutes (HMFSs), rich in palmitic acid (16:0) at the sn-2 position of triacylglycerol (TAG) and rich in unsaturated fatty acids (FAs) (oleic acid, 18:1 and linoleic acid, 18:2) at the sn-1(3) positions, has gained popularity. In this study, HMFSs containing polyunsaturated fatty acids (PUFAs) predominantly at the sn-2 position were prepared, and their oxidation stabilities were compared. First, a non-PUFA-containing HMFS (NP-HMFS) was produced by enzymatic reactions using Novozyme® 435 and Lipozyme® RM-IM as the enzymes and lard as the raw material. Second, HMFSs, containing 10 % PUFA at the sn-2 or sn-1(3) position, were individually prepared by enzymatic reactions using lard and fish oil as raw materials. Here, sn-2-PUFA-monoacylglycerol (MAG) was extracted from the reaction solution using a mixture of hexane and ethanol/water (70:30, v/v) to produce high-purity sn-2-PUFA-MAG with 78.1 % yield. For the PUFA-containing HMFS substrates, comparable oxidation stability was confirmed by an auto-oxidation test. Finally, HMFSs containing 10 % or 2 % sn-1,3-18:1-sn-2-PUFA-TAG species were prepared by enzymatic reactions and subsequent physical blending. The oxidative stability of sn-1,3-18:1-sn-2-PUFA-HMFS was two-fold higher than that of 1/2/3-PUFA-HMFS in which each PUFA was located without stereospecific limitations in TAG. The removal of PUFA-TAG molecular species with higher concentrations of unsaturated units had a significant effect. In addition, the oxidation stability increased with the addition of tocopherol as an antioxidant. Thus, the combined use of two strategies, that is, the removal of PUFA-TAG molecular species with high concentrations of unsaturated units and the addition of antioxidants, would provide a PUFA-containing HMFS substrate with high oxidative stability.
Aim of this study was to evaluate the effect of star fruit (Averrhoa carambola L.) by-products (peel and residue) on stability of sesame (Sesamum indicum) oil against oxidation. Antioxidant properties of extract of peel and residue at different time durations of extraction were determined and found that peel contains higher antioxidant potential than residue. Thus, extract of peel obtained after 24 h extraction was used to study its effectiveness on oxidative stability of sesame oil during accelerated oven storage and frying using the butylated hydroxytoluene (BHT) (200 ppm) as the reference antioxidant (positive control) and oil without added antioxidant as the negative control. The oxidative stability of the oil was determined by evaluating peroxide value, p-anisidine value, thiobarbituric acid reactive substances (TBARS) value, total oxidation (TOTOX) value, conjugated diene (CD) and conjugated triene (CT) values, and iodine value. Peel extract at different concentrations (200-1000 ppm) was tested. The oil added with peel extract exhibited higher stability against oxidation than the controls during oven storage test. Extract at 1000 ppm significantly increased the stability of sesame oil during frying as compared with controls. Thus, star fruit peel extract could be an alternative to synthetic antioxidants to suppress oxidation of edible oils.
Phthalates (PAEs) and polycyclic aromatic hydrocarbons (PAHs) are ubiquitous contaminants in environment and foodstuffs. The objective of this study was to investigate the contamination possibility of phthalates and PAHs in packaged and canned fishes. For this purpose, tuna, salmon, sardine and mackerel canned and packaged with different liquid ingredients (water, olive oil, sunflower oil, mixture of sunflower and canola oil) attained from local markets in Turkey in 2019, were analyzed for presence of diethylhexyl phthalate (DEHP), dibutyl phthalate (DBP), butyl benzyl phthalate (BBP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) and benzo(a)anthracene (BaA), benzo[a]pyrene (BaP), benzo(b)fluoranthene (BbF), chrysene (Chr). The instrumental analyses were performed by gas chromatography-mass spectrometry (GC-MS) and high-performance liquid chromatography fluorescence detection (HPLC-FLD). In all analyzed samples, the levels of DBP, BBP, DINP and DIDP were less than their LOQ, so these phthalates were not quantified. The highest DEPH content was found 650 µg/kg in sample 2 (tuna in olive oil, packaged in plastic package). The highest sum of PAH 4 concentration was 9.97 µg/kg in sample 4 (salmon canned in sunflower oil). Some samples (19 samples) were free for all analyzed PAEs and PAHs. All levels of these persistent organic pollutants were lower than regulation limits of Turkey and EU.
Chicken skin -a poultry meat industries waste- has been used in this work as a source for the production of pure free fatty acids. Chicken skin fat was extracted using dry rendering method. Physical and chemical parameters of that fat were determined. Also, its fatty acids composition has been identified by GC-MS after its esterification as oleic, palmitic, linoleic, stearic, myristic, lauric, linolenic, behenic, arachidonic, arachidic, palmitoleic, and paullinic acids, and others as traces. The extracted fat was then hydrolyzed into mixture of free fatty acids and glycerol, the free fatty acid mixture was separated, then it was cooled in order to separate saturated and unsaturated fatty acids from each other. Oleic, Palmitic, Linoleic and Stearic Acids were extracted individually in pure form using supercritical CO2 extractor. Moreover, oleic, linoleic, palmitoleic, linolenic, and paullinic acids were extracted individually in pure form using cooling centrifuge sigma 3-18KS. All of the separated individual fatty acids were confirmed according to their melting point, GC-MS after esterification, elemental analysis and mass spectrometry (ms) of the corresponding methyl ester in order to detect the corresponding molecular ion peak. Therefore, these new two methods could afford the very expensive pure fatty acids with a low cast.
We studied the physicochemical properties of 1:1 stoichiometric complexes of acylglutamic acids (CnGlu) with tertiary alkylamines (CnDMA) in water at their low and high concentrations. Static surface tensiometry suggested that the critical micelle concentration (cmc) decreased with increasing hydrophobic chain length of the complexes. In addition, CnGlu-CnDMA yielded lower cmc than the C12Glu single system. In the region of high concentrations, several phase states including isotropic liquid (L1) phase, hexagonal liquid crystal (H1) phase, bicontinuous cubic liquid crystal (V1) phase, and lamellar liquid crystal (Lα) phase were observed. Assemblies with lesser positive curvature tend to be formed with increasing complex concentration, increasing temperature, and increasing hydrophobic chain length. Additionally, the complex formation resulted in the molecular assemblies with lesser positive curvature.
In this study, an N-heterocyclic carbene (NHC)-based metal coordinate surfactant (MCS), NHC-Au-MCS, in which the NHC framework afforded the bonding of the Au(I) at the linkage of the hydrophilic and hydrophobic moieties, was synthesized. The structure of NHC-Au-MCS was confirmed by 1H and 13C NMR spectroscopic measurements together with elemental analysis. Matrix-assisted laser desorption/ionization (MALDI), laser desorption/ionization (LDI), and electrospray ionization mass spectrometry (ESI-MS) indicated the distinct reactivity of NHC-Au-MCS, such as the exchange of Br to Cl and the formation of a cationic Au complex, where the two NHC ligands were coordinated to an Au(I) center upon laser activation. The surface tension and dynamic light scattering (DLS) measurements revealed that the coordination of Au(I) to NHC reduced the critical micelle concentration (CMC) of NHC-Au-MCS (1.3×10–5 M), which resulted in the formation of micelles at concentrations higher than the CMC in water. We also confirmed that the surface-active Au(I) complex of NHC-Au-MCS catalyzed the hydration of 1-dodecyne to 2-dodecanone in water in the absence of an organic solvent. On the basis of the detailed mechanistic investigations regarding the reactivity of NHC-Au-MCS, we revealed that NHC-Au-MCS partially translated into Au nanoparticles (AuNPs), which facilitated alkyne hydration. These mechanistic studies were supported by UV-vis measurements, transmission electron microscopy (TEM), and LDI-MS.
Ion specific effect, which is also known as Hofmeister effect, has been reported in numerous systems including ionic surfactant aggregates. Acyl amino acid surfactants have attracted growing attentions in the field of novel surfactants research due to their environmentally benign characteristics. The objective of this study was to investigate the effect of different salts containing NH4+ and tetraalkylammonium (TAA+), where alkyl = methyl (TMA+), ethyl (TEA+), and propyl (TPA+), cations on the dilational rheological properties of interfacial film are stabilized by potassium N-cocoyl glycinate (KCGl). The interfacial behaviors were studied using oscillating drop shape analysis method. The interfacial tensions (IFTs) and dilational rheological parameters results illustrate that KCGl in the presence of salts has better interfacial activity and stronger intermolecular interaction, indicating that added cations contribute to denser molecular packing at oil-water interface. Ion specific effects were observed in the system. Among the cations, KCGl shows highest dilational modulus in the presence of NH4+. The overall interaction between cations and headgroups of KCGl decreases in the sequence NH4+ >TMA+ >TEA+ ≈TPA+, which follows Hofmeister series. The increasing hydrophobicity of TAA+ prevents the interaction between cations and KCGl’s headgroup, and therefore prevent amphiphiles from packing closely at interface. The results present a theoretical origin for useful application of KCGl in cosmetics, petroleum and daily chemical industries.
In this study, lipase from Thermomyces lanuginosus (TLL) was immobilized onto the parent and organic groups modified SBA-15, and the enzymatic properties of the obtained immobilized TLL samples were investigated. 1) Activity of SBA-15-TLL at 2862.78 ± 293.24 U/g was obtained. 2) Most of the organic groups modification favored a great improvement in activity, and higher activity over 12000 U/g was observed for N-phenylaminomethyl and phenyl group modification. 3) Most of the supported TLL showed better thermostability in air while poor in phosphate buffer, with over 80% vers less than 20% of their initial activity retained after 4 h incubation at 70℃. 4) The n-dodecyl, phenyl and N-phenylaminomethyl group functionalization decreased the sensitivity of immobilized TLL in extreme pH values. 5) The n-octyl and 2-(propoxymethyl)oxirane group modification confered the supported TLL good reusability, and over 60% of their initial activity was retained after five successive cycles of reuse.
D-ribose-oleic acid esters were produced with or without a biocatalyst, using in the same organic media, dimethyl sulfoxide (DMSO): tert-butanol (TBU) or 2-methyl-2-butanol (2M2B). The yield of the ester product was above 90% in both of the reactions. The biocatalyst used was lipase B of Candida antarctica. Molecular characterization was performed by using all the analytical methods available: IR, 1H-NMR and 13C-NMR, HSQC, and ESI-MS.
The present research evaluated the protective effect of basil essential oil nanoemulsion (BNO) and its parent basil essential oil (BO) towards steatohepatitis. Chemical composition of BO was assessed followed by formulation into different BNOs using the low energy spontaneous emulsification technique. An ideal formula of BNO was selected among the others based on its ultra-fine particle size (15.42 nm) and physical stability at 25-37°C, which was then tested in steatohepatitis rat model along with BO. Rats were divided into four groups, the first was fed on balanced diet (C), and the other groups were maintained on high fructose saturated fat diet deficient in choline to induce steatohepatitis, one of such groups served as control steatohepatitis (SC), the other groups received daily oral dose of BO and BNO, respectively. Microbiota (Firmicutes and Bacteroidetes) were counted in colon content and their ratio (F/B) was calculated. Liver fat, plasma lipid profile, plama interlukin-6, plasma lipopolysaccharides and plasma and colon content of lipocaline were assessed with histopathological examination of liver and colon. Results showed that the major volatile components of BO were linalool (60.9 %), eugenol (5.1 %) and eucalyptol (9.5%). SC group exhibited significant increase in liver lipids, plasma triglycerides, total cholesterol (TC), low density lipoprotein cholesterol and significant reduction in high density lipoprotein-cholesterol (HDL-C) compared to C group. Significant increase in plasma TC/HDL-C, interlukin-6, and lipocaline and F/B ratio and lipocaline in colon content were demonstrated in SC group without changes in plasma lipopolysaccharides compared to C. Histopathology of SC group showed liver fatty degeneration and fibroblasts activation while the colon demonstrated erosion and mucosal epithelium detachment. Treatment with either BNO or BO showed improvement compared to SC group. BNO was superior in reducing F/B ratio, liver lipids and histopathological changes. BO was more efficient in reducing TC, triglycerides and low density lipoprotein cholesterol. It is concluded that BO and BNO reduced the progression of nonalcoholic steatohepatitis in rat model. Gut microbiota in relation to steatohepatitis and related new therapies needs further investigations.
Glucosylceramide (GlcCer), a major sphingolipid in plants and fungi, is known to have food functions, such as preventing intestinal impairment and enhancing the moisture content of skin. This study investigated the influence of fermentation on the composition and function of lipophilic components containing GlcCer in plant-based foods; we compared the effects of ethanol extracts from sake rice (SR) and sake lees (SL) on colon impairment in mice. GlcCer and ceramide (Cer) levels in SL were much higher than those in SR, and GlcCer in SL contained 9-methyl-trans-4,trans-8-sphingadienine as a fungi-specific sphingoid base. 1,2-dimethylhydrazine (DMH) treatment markedly increased the formation of aberrant crypt foci (ACF) and the levels of TNF-α and lipid oxidation in mice colons. However, dietary SR or SL significantly suppressed these DMH-induced changes, and SR demonstrated stronger effects than SL. In addition, dietary SR or SL suppressed the expression of apoptotic and anti-apoptotic proteins induced by DMH treatment. This study suggests that SR or SL intake could reduce colon ACF formation via the suppression of inflammation and oxidation-induced cell cycle disturbances. When compared to SR, the weaked effects of SL rich in GlcCer may be the result of the changes in sphingolipid composition (sphingoid base and Cer) and differences in the concentration of other bioactive compounds produced or digested during fermentation.
This study reports the biological activity of essential oils from fertility tree and horseradish tree leaves, and the mechanisms by which these oils promote insecticidal activity using Drosophila melanogaster as a model organism. Adult D. melanogaster were exposed to these essential oils at a final concentration of 10 µL/g for 24 hours. The exposure of flies to the essential oil resulted in significant decrease in their survival and fecundity. In addition, the essential oils produced significant reduction in acetylcholinesterase activity and induced oxidative stress in the flies as evidenced by an increase in reactive oxygen species, thiol and thiobarbituric reactive substance levels, as well as catalase activity. The essential oils were also characterized by gas chromatography coupled with mass spectrometry. Constituents such as terpenoids, Bis (2-ethylhexyl) phthalate, benzeneacetaldehyde, phytol, octadecane, 9,12-octadecadienoic acid (Z,Z)- methyl ester, heneicosane, eicosane and others were characterized. Therefore, our results point out to the potential application of fertility tree and horseradish tree leaf essential oils as natural alternatives to synthetic insecticides in agricultural and pest control practices, especially against dipterans.
Piperitenone oxide, a major chemical constituent of the essential oil of spearmint, Mentha spicata, induces differentiation in human colon cancer RCM-1 cells. In this study, piperitenone oxide and trans-piperitenone dioxide were prepared as racemic forms by epoxidation of piperitenone. The relative configuration between two epoxides in piperitenone dioxide was determined to be trans by 1H NMR analysis and nuclear Overhauser effect spectroscopy (NOESY) in conjunction with density functional theory (DFT) calculations. Optical resolution of (±)-piperitenone oxide by high-performance liquid chromatography (HPLC) using a chiral stationary phase (CSP) afforded both enantiomers with over 98% enantiomeric excess (ee). Evaluation of the differentiation-inducing activity of the synthetic compounds revealed that the epoxide at C-1 and C-6 in piperitenone oxide is important for the activity, and (+)-piperitenone oxide has stronger activity than (–)-piperitenone oxide. The results obtained in this study provide new information on the application of piperitenone oxide and spearmint for differentiation-inducing therapy. Furthermore, natural piperitenone oxide was isolated from M. spicata. The enantiomeric excess of the isolated natural piperitenone oxide was 66% ee. Epoxidation of piperitenone with hydrogen peroxide proceeded in a phosphate buffer under weak basic conditions to give (±)-piperitenone oxide. These results suggest that the nonenzymatic epoxidation of piperitenone, which causes a decrease in the enantiomeric excess of natural piperitenone oxide, is accompanied by an enzymatic epoxidation in the biosynthesis of piperitenone oxide.
The drying process used for persimmon fruit (Diospyros kaki) can alter the composition of nutrients, and especially vitamins. We visually determined whether the amounts of vitamin A1, vitamin B6 and vitamin C vary after drying persimmon fruit, using matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) imaging. Drying altered the amount of moisture between the fruit interior and surface. Vitamin A1 is lipophilic and localized at the desiccated outer regions (pericarp) and not in the inner region (mesocarp and endocarp), and its concentration was increased 3.4 times in dried fruit compared with raw persimmon. Vitamin B1 and B6 are water-soluble and concentrated in the moist mesocarp. The vitamin C content of dried persimmon is decreased by drying in the sun. The drying process affected the localizations and amounts of all the vitamins. The observed opposite localization of vitamin A1 compared to B1 and B6 was due to vitamin A1 being lipophilic and B1 and B6 being water soluble. Multiplevitamin imaging using MALDI-MSI has great potential for enhancing commodity value and for visually investigating the effects of manufacturing processes.