Triglyceride Composition of Pinus sibirica Oil

The triglyceride composition of pine oil was investigated by reversed-phase HPLC. The fatty-acid composition of the oil was calculated (mol %): 18:3, 17.1 ± 2.0; 18:2, 49.0 ± 2.3; 18:1, 23.8 ± 2.1; 18:0, 2.5 ± 0.1; 16:0, 6.3 ± 2.2. The retention times of the triglycerides containing octadecatrienoic acid were consistent with the 18:3(5,9,12) structure.     

Rapid characterization of edible oils by direct matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis using triacylglycerols

Direct matrix-assisted laser desorption/ionization time-of-flight mass spectrometric (MALDI-TOFMS) analysis of solutions of edible fats/oils yielded spectra useful for their rapid differentiation and classification. Results also reflected the individual fatty acid components and their degree of unsaturation. After dissolution in hexane, MALDI-MS analysis revealed spectra showing characteristic triacylglycerols (TAGs), the main fat/oil components, as sodium adduct ions. The Euclidean distances calculated using the mass and intensity values for 20 TAGs were used to evaluate and compare spectra. With cluster analysis, animal fats grouped together differently than vegetable oils and the individual oils grouped together by type. The ion abundances for the individual TAGs and their presumed compositions were used to approximate the overall fatty acid composition of canola, soybean, corn, olive and peanut oil, as well as lard. Using this approach the calculated fatty acid compositions and degree of unsaturation generally fell within about 4% of literature values. When the degree of saturation was compared with values calculated from the package labeling the differences were about 7%.     

Composition and structure of the triacylglycerols ofHippophaë rhamnoides seeds

The composition and structure of the triacylglycerols (TAGs) of the seeds of ripe fruit of the sea buckthorn of the Dar Katuni, Maslichnaya, and Shcherbinka-1 varieties have been investigated with the aid of lipase hydrolysis. The amounts of fatty acid (FA) residues in the 2-positions of the TAGs, the concentrations of the FAs in the 1,3-positions, the position-type and position-species compositions of the TAGs, and also the values of the enrichment factors (EFs) and inclusion-selectivity factors (SFs) of the unsaturated FAs in the positions of the TAGs were determined. As in the seeds of the majority of other plants, in the sea buckthorn it is mainly the unsaturated FAs that are concentrated in the 2-positions of the TAGs (mol. %): linoleic (L, 47–49.6); linolenic (Le, 32.4–36.9), and oleic (0, 12.8–18.5). The EF and SF values for the O, L, and Le acids in the TAGs of the Dar Katuni variety were, respectively, 1.11, 1.21, and 0.97, and 1.00, 1.10, and 0.88. In contrast to the TAGs of the flesh of sea buckthorn fruit, palmitoleic acid is a minor component of the TAGs of the seeds (0.6–0.9 mol.%). Among the types of TAGs, trisaturated (72.4–76.2) and monosaturated-diunsaturated (22.1–25.3) predominate. According to calculation, the seeds may contain from 57 (Maslichnaya) to 98 (Shcherbinika-1) position-species of TAGs with concentrations >0.01 mol.%. The predominating species among them are LLLe (11.5–14.1), LLeLe (7.8–10.5), LeLLe (5.5–7.2), and LLL (6.0–6.9). The composition and structure of the TAGs of the seeds have also been reliably established with the aid of a mathematical method based on Litchfield's empirical formulas for determining the amounts of FAs in the 2-positions of TAGs.Institute of Plant Physiology, Academy of Sciences of the USSR, Moscow, and Gor'ki Agricultural Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 52–57, January–February, 1987.     

Determination of the triglyceride composition of pomegranate seed oil by reversed-phase HPLC and spectrophotometry

An increment approach and the control of the position of convergence points is proposed for the determination of the fatty acid composition of triacylglycerides (TAGs) from seed oil of pomegranate. reversed-phase HPLC under conditions ensuring the absence of artifacts is shown to distinguish TAGs formed by isomer-conjugated octadecatrienic acids.     

Characterization of <Emphasis Type="Italic">Opuntia ficus indica</Emphasis> seed oil from Tunisia

The lipid fraction of Opuntia ficus indica seeds was extracted and analyzed for its chemical and physical properties such as acid value, free fatty acid percentage (% FFA), iodine index, peroxide value, and saponification value as well as refractive index and density. The yield of seed oil was calculated as 11.75%. The acid and free fatty acid values indicated that the oil has a fairly low acidity. The triacylglycerols, fatty acids, sterols, and tocopherols were identified and their concentrations determined. The main TAGs were LLL (25.60%), OLL (21.53%), PLL (15.53%), and POL + SLL (12.73%). Linoleic acid (60.69%) was the dominant fatty acid, followed by oleic (21.42%) and palmitic (12.76%) acids, respectively. A high level of sterols making up 16.06 g/kg seed oil was present. The sterol marker, β-sitosterol, accounted for 71.60% of the total sterol content in the seed oil. Among the tocopherols present in the oil, γ-tocopherol (421.08 mg/kg) was the main constituent.     

Determination of the fatty acid composition of saponified vegetable oils using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

A method using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) for the determination of the fatty acid composition of vegetable oils is described and illustrated with the analysis of palm kernel oil, palm oil, olive oil, canola oil, soybean oil, vernonia oil, and castor oil. Solutions of the saponified oils, mixed with the matrix, meso-tetrakis(pentafluorophenyl)porphyrin, provided reproducible MALDI-TOF spectra in which the ions were dominated by sodiated sodium carboxylates [RCOONa + Na]+. Thus, palm kernel oil was found to contain capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, and stearic acid. Palm oil had a fatty acid profile including palmitic, linoleic, oleic, and stearic. The relative percentages of the fatty acids in olive oil were palmitoleic (1.2 +/- 0.5), palmitic (10.9 +/- 0.8), linoleic (0.6 +/- 0.1), linoleic (16.5 +/- 0.8), and oleic (70.5 +/- 1.2). For soybean oil, the relative percentages were: palmitoleic (0.4 +/- 0.4), palmitic (6.0 +/- 1.3), linolenic (14.5 +/- 1.8), linoleic (50.1 +/- 4.0), oleic (26.1 +/- 1.2), and stearic (2.2 +/- 0.7). This method was also applied to the analysis of two commercial soap formulations. The first soap gave a fatty acid profile that included: lauric (19.4% +/- 0.8), myristic (9.6% +/- 0.5), palmitoleic (1.9% +/- 0.3), palmitic (16.3% +/- 0.9), linoleic (5.6% +/- 0.4), oleic (37.1% +/- 0.8), and stearic (10.1% +/- 0.7) and that of the second soap was: lauric (9.3% +/- 0.3), myristic (3.8% +/- 0.5), palmitoleic (3.1% +/- 0.8), palmitic (19.4% +/- 0.8), linoleic (4.9% +/- 0.7), oleic (49.5% +/- 1.1), and stearic (10.0% +/- 0.9). The MALDI-TOFMS method described in this communication is simpler and less time-consuming than the established transesterification method that is coupled with analysis by gas chromatography/mass spectrometry (GC/MS). The new method could be used routinely to determine the qualitative fatty acid composition of vegetable oils, and, when fully validated by comparison with standard analytical methodologies, should provide a relatively fast quantitative measurement of fatty acid mixtures and/or soap formulations that contain saturated and unsaturated hydrocarbon moieties.     

Triacylglycerols of oiticica oil

The composition of the triacylglycerols (TAGs) of oiticica oil has been studied by enzymatic hydrolysis with pancreatic lipase. It has been established that the majority of TAGs of the 96 types present have a mixed character. The four main types make up 60% of the total TAGs and the remainder consist of minor components. A high content of TAGs with octadeca-9,11,13-trienoic acids (including licanic) in the extreme positions has been detected.DeceasedKalinin Polytechnic Institute. Moscow Branch of the All-Union Scientific-Research Institute of Fats. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 316–319, May–June, 1980.     

Essential oil composition of aerial parts from Algerian Anacyclus monanthos subsp. cyrtolepidioides (Pomel) Humphries

The chemical composition of the essential oil from the aerial parts of Anacyclus monanthos subsp. cyrtolepidioides (Pomel) Humphries (Asteraceae) growing in a semi-arid region of Algeria was investigated for the first time. The essential oil was obtained by hydrodistillation and fully characterized by gas chromatography-mass spectrometry (GC-MS). A total of 97 compounds were identified. The essential oil was found to be rich in trans-chrysanthenyl acetate (9.8 ± 2.0%), (E)-β-farnesene (7.4 ± 1.5%), germacrene D (6.9 ± 1.3%) and myristicin (4.8 ± 0.8%).     

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.     

Determination of fatty acid compositions and cholesterol levels of some freshwater fish living in Porsuk Dam,Turkey

We determined the oil content, fatty acid composition, and cholesterol content of common carp (Cyprinus carpio), crucian carp (Carassius carassius), chub (Leusiscus cephalus), and tench (Tinca tinca) by GLC. The saturated fatty acids (SFA), monounsaturated fatty acids (MUFA), and polyunsaturated fatty acids (PUFA) levels were found to be 36.49%, 31.92%, 31.59% in common carp; 32.92%, 32.21%, and 34.87% in crucian carp; 36.19%, 32.91%, and 30.90% in chub; and 32.86%, 30.77%, and 36.37% in tench, respectively. The cholesterol (mg/100 g oil) levels of common carp, crucian carp, chub, and tench were determined by GLC methods as 119 ± 2.64 mg, 170.37 ± 2.36 mg, 94.68 ± 3.13 mg, and 179.84 ± 6.75 mg, respectively. Thus, the cholesterol contents of the analyzed freshwater fish species were low but their PUFA contents and nutritional values were high. Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 15–17, January–February, 2009.     

Quantification of triacylglycerol regioisomers by ultra‐high‐performance liquid chromatography and ammonia negative ion atmospheric pressure chemical ionization tandem mass spectrometry

The regioisomer composition of triacylglycerols (TAGs) in various vegetable oils was determined with a new liquid chromatography/tandem mass spectrometry (LC/MS/MS method). A direct inlet ammonia negative ion chemical ionization (NICI) MS/MS method was improved by adapting it to LC negative ion (NI) atmospheric pressure chemical ionization (APCI) MS/MS system using ammonia as nebulizer gas. The method is based on the preferential formation of [M–H–RCOOH–100]^? ions during collision‐induced dissociation by loss of sn‐1/3 fatty acids from [M–H]^? ions. Calibration curves were created from nine reference TAGs: Ala/L/L, Gla/L/L, L/L/O, L/O/O, P/O/O, P/P/O, Po/Po/V, Po/Po/O, and C/O/O. The calibration curves were used to quantify the regioisomer compositions of selected TAGs in rapeseed oil, sunflower seed oil, palm oil, black currant seed oil, and sea buckthorn pulp oil. The method discriminates the different regioisomers and the results obtained by this method were in good agreement with previous results. This proves that this new method can be used for the determination of regiospecific distribution of fatty acids in TAGs. Copyright © 2009 John Wiley & Sons, Ltd.     

Analysis of Free Amino Acids and Protein Contents of Mature Human Milk from Turkish Mothers

Abstract

This study was designed to evaluate free amino acid (FAA) composition and total protein in mature human milk from Turkish mothers. Free amino acid concentrations in mature human milk were determined in all subjects using a high‐performance liquid chromatography (HPLC) with postcolumn derivatization system, with a fluorescence detector. Total protein content was determined by the classical biuret method. Total protein concentration was found to be 1.3±0.4 mg/dl. Glutamic asid plus glutamine is the most abundant amino acid (1275 µmol/L), followed by taurine (353 µmol/L) and alanine (261 µmol/L). Glutamic acid plus glutamine accounts for the most free amino acids in mature human milk and their sum represents 40% of total FAA. On the other hand, some amino acid derivatives such as citrulline, ethanolamine, ammonium, ornithine, ortophosphoserine, and phosphoethanolamine, not usually a part of protein, are determined and this fraction represented ～21% of the total FAA in mature human milk in the present study.     

Electrodetermination of Gallic Acid Using Multi-walled Carbon Nanotube Paste Electrodes and N-Octylpyridinium Hexafluorophosphate

In this work, the determination of gallic acid was performed using surface-renewable carbon paste electrodes fabricated with multi-walled carbon nanotubes (MWCNT) and a mixture of N-octylpyridinium hexafluorophosphate (OPyPF₆) ionic liquid with mineral oil (MO) as binder. This system shows remarkable amperometric sensor characteristics and promotes a better electronic transfer. An electroanalytical study of gallic acid shows a linear range from 4.98±0.25 to 74.1±2.2 μmol L⁻¹, with R²=0.9958 and an experiment a limit of detection of 2.70±0.08 μmol L⁻¹ (S/N=3), and a sensitivity of 0.029 μA μmol⁻¹ L.     

Enantiomeric separation of asymmetric triacylglycerol by recycle high-performance liquid chromatography with chiral column

In our previous studies, we employed recycle HPLC for the separation of triacylglycerol (TAG)-positional isomers (PIs). In this study, a recycle HPLC system equipped with a polysaccharide-based chiral column was applied to the enantiomeric separation of some asymmetric TAGs having straight-chain C16-C18 acyl residues. As a result, 1,2-dipalmitoyl-3-oleoyl-rac-glycerol (rac-PPO), 1,2-dioleoyl-3-palmitoyl-rac-glycerol (rac-OOP), and 1,2-dipalmitoyl-3-linoleoyl-rac-glycerol (rac-PPL) were resolved into their respective enantiomers. However, neither 1,2-dioleoyl-3-linoleoyl-rac-glycerol (rac-OOL), consisting of only unsaturated fatty acids, nor 1,2-dipalmitoyl-3-stearoyl-rac-glycerol (rac-PPS), consisting of only saturated fatty acids, was resolved. These results suggest that the asymmetric TAGs, used in this study, having both a palmitic acid moiety and an oleic acid (or a linoleic acid) moiety at the sn-1 or sn-3 positions are resolved by the chiral column. This new chiral separation method can be used in combination with atmospheric pressure chemical ionization mass spectrometry to determine the sn-OOP/sn-POO ratio in palm oil. This method is applicable for the chiral separation of asymmetric TAGs in palm oil.     

"Dilute-and-shoot" triple parallel mass spectrometry method for analysis of vitamin D and triacylglycerols in dietary supplements

A method is demonstrated for analysis of vitamin D fortified dietary supplements that eliminates virtually all chemical pretreatment prior to analysis, which is referred to as a “dilute-and-shoot” method. Three mass spectrometers, in parallel, plus a UV detector, an evaporative light-scattering detector (ELSD), and a corona charged aerosol detector (CAD) were used to allow a comparison of six detectors simultaneously. Ultraviolet data were analyzed using internal standard, external standard, and response factor approaches. The contents of gelcaps that contained 2,000 IU (50 μg) vitamin D₃ in rice bran oil, diluted to 100 mL, were analyzed without the need for lengthy saponification and extraction. Vitamin D₃ was analyzed using UV detection, extracted ion chromatograms, selected ion monitoring (SIM) atmospheric pressure chemical ionization mass spectrometry (APCI-MS), and two transitions of multiple reaction monitoring (MRM) APCI-MS. The internal standard, external standard, and response factor methods gave values of 0.5870 ± 0.0045, 0.5893 ± 0.0041, and 0.5889 ± 0.0045 μg/mL, respectively, by UV detection. The values obtained by MS were 0.6117 ± 0.0140, 0.6018 ± 0.0244, and 0.5848 ± 0.0146 μg/mL by SIM and two transitions of MRM, respectively. The triacylglycerols in the oils were analyzed using full-scan APCI-MS, electrospray ionization (ESI) MS, up to MS⁴, an ELSD, and a CAD. The method proved to be very sensitive for vitamin D₃, as well as triacylglycerols (TAGs), allowing identification of intact TAGs containing fatty acids up to 28 carbons in length. LC-ESI-MS of glycerin polymers is also demonstrated.     

Studies on reaction of reduced lipoic acid with Mukaiyama reagent and its application for pharmaceutical and food analysis

A new sensitive method for the determination of lipoic acid (LA) in selected food items based on its reaction with Mukaiyama reagent (2-chloro-1-methylpyridinium iodide, CMPI) was developed. It was stated that CMPI reacts with reduced form of lipoic acid (dihydrolipoic acid, DHLA) and the stable product is produced. The spectrum of the labeled form of DHLA exhibits new band at 312?nm. Based on its spectral characteristics new spectrophotometric and UV–high-performance liquid chromatography (HPLC) methods of LA determination were elaborated. Both methods allowed determination of the analyte in the concentration range of 5?×?10^?6–1?×?10^?4?mol?L^?1 with limit of detection 0.39?×?10^?6 and 0.77?×?10^?6?mol?L^?1 for spectrophotometric and HPLC method, respectively. The practical usability of newly developed methods was checked by determination of lipoic acid contents in its pharmaceutical preparate Revitanerw. The proposed method was precise and accurate. The relative error of determination did not exceed ±0.067%. As chromatographic method allowed the determination of analyte in the presence of complex matrix, it was applied for assay of free fraction of α-lipoic acid in selected food items. A procedure of LA isolation from biological matrix was developed. The extraction with dichloromethane allowed quantitative recovery at 102.94?±?4.20%. The green barley appeared to be the richest source of LA.     

Bioelectrochemical evaluation of the total phenols content in olive oil mill wastewaters using a tyrosinase–colloidal gold–graphite–Teflon biosensor

The use of a robust tyrosinase biosensor, fabricated from graphite–Teflon rigid electrode matrices modified with gold nanoparticles, for the estimation of the total phenols content in olive oil mill wastewaters (OMW), is proposed. The performance of this bioelectrode using both continuous stirring and flow-injection amperometry was studied. A potential value of ?0.10?V was selected for the sensitive and stable detection of various phenolic compounds present in OMW samples: catechol, 3,4-dihydroxycinnamic acid (caffeic acid), 3,4-dihydroxyphenylacetic acid (DOPAC), 4-hydroxyphenylacetic acid, 4-hydroxyphenylethanol (tyrosol), and 4-hydroxyphenylpropionic acid. Using catechol as the target phenol, linear calibration graphs were obtained in the 1.0?×?10^?8???8.0?×?10^?6?mol?L^?1 (batch) and 1.0?×?10^?7???1.0?×?10^?5?mol?L^?1 (FI) concentration ranges, with slope values of 750?mA?L?mol^?1 and 103?mA?L?mol^?1, respectively. Batch amperometry was chosen for the analysis of real samples because of its higher sensitivity. For example, the limit of detection for caffeic acid was 80?nM. The ‘pool’ of phenolic compounds was estimated in OMW obtained from different extraction systems and containing phenols at diverse levels of concentration. A comparison of these results with those obtained by applying the Folin–Ciocalteau spectrophotometric reference method was carried out.     

Formation of MSeO4(aq) complexes (M2+ = Mg2+, Co2+, Ni2+, Cu2+, Cd2+) studied as a function of temperature by affinity capillary electrophoresis

Complexation of divalent cations (Mg²⁺, Co²⁺, Ni²⁺, Cu²⁺, Cd²⁺) by selenate ligand was studied by ACE (UV indirect detection) in 0.1 mol/L NaNO₃ ionic strength solutions at various temperatures (15, 25, 35, 45 and 55°C). For each solution, a unique peak was observed as a result of a fast equilibrium between the free ion and the complex (labile systems). The migration time corresponding to this peak changed as a function of the solution composition, namely the free and complexed metal concentrations, according to the complexation reactions. The results confirmed the formation of a unique 1:1 complex for each cation. The thermodynamic parameters were fitted to the experimental data at 0.1 mol/L ionic strength: (25°C) = ?(6.5 ± 0.3), ?(7.5 ± 0.3), ?(7.7 ± 0.3), ?(7.7 ± 0.3), and –(8.1 ± 0.3) kJ/mol and = 2.5 ± 0.2, 4.7 ± 0.4, 4.5 ± 0.6, 8.4 ± 1.1, and 7.2 ± 0.6 kJ/mol for M²⁺ = Mg²⁺, Co²⁺, Ni²⁺, Cu²⁺, and Cd²⁺, respectively. Complexes with alkaline earth and transition metal cations could be distinguished by their relative stabilities. The effect of the ionic medium was treated using the specific ion interaction theory and the thermodynamic parameters at infinite dilution were compared to previously published data on metal–selenate, metal–sulfate, and metal–chromate complexes.     

A Solid Film Electrode of Intermetallic Ag2Hg3.02 for the Direct Determination of Folic Acid in Fresh and Processed Fruit Juices

AgSIE was used for the direct analysis of folic acid (FA), with a detection limit and lower level of quantitation of 6.8×10^?10 mol L^?1 and 2.3×10^?8 mol L^?1. The analysis in fresh and processed fruits was done without any sample pretreatment. In strawberry and acerola juices, FA concentration level values were below the method detection limit. FA was detectable in peach (77.7±0.4 µg L^?1 and 64.4±0.5 µg L^?1), Persian lime (45.4±0.7 µg L^?1), pineapple Hawaii (66.2±0.4 µg L^?1), pear pineapple (35.3±0.6 µg L^?1), cashew (54.4±0.5 µg L^?1), passion fruit (73.2±0.3 µg L^?1), and apple (84.4±0.5 µg L^?1).     

Comprehensive two-dimensional liquid chromatography×gas chromatography: evaluation of the applicability for the analysis of edible oils and fats

Edible fats and oils are complex mixtures containing a wide range of (classes of) compounds. The most important group of compounds are the triglycerides (triacylglycerides, TAGs). Because of the large number of possible fatty acid combinations, an enormous number of TAGs is possible. In the present feasibility study, the applicability of different modes of comprehensive two-dimensional LC×GC for detailed oil and fat analysis is evaluated. Comprehensive LC×GC was found to be an extremely powerful analytical method for the analysis of complex TAG samples. Using the new comprehensive set-ups, TAGs can be separated according to two independent parameters: carbon number vs. number of double bonds, or fatty acid composition vs. number of double bonds. The information content of comprehensive separations by far exceeds that of the current generation of analytical methods. The quantitative results of the separations show a good agreement with data obtained from standard analytical methods. The comprehensive methods studied can also be used for fingerprinting of oil samples, as well as for the analysis of target compounds or compound groups. Highly detailed separations of olive oil samples were obtained. Zooming in on one region of the chromatogram allowed reliable analysis of wax esters without interferences of sterol esters.