Unusual fatty acids in compositae: γ-Linolenic acid in Saussurea spp. seed oils

The plant family Compositae is known to produce a set of unusual fattly acids in their seed oil. Saussurea, a genus of the Compositae is less studied in respect to the fatty acid compsition of their seed oil. Only Saussurea candicans was reported to contain crepenynic acid (33%) as seed oil component. In continuation of our exploration of the portential of wild oil seeds, fatty acids in seed oils of seven Saussurea species (S. amara, S. salicifolia, S. lipschitzii, S. pseudoalpina, S. pricei, S. parviflora, and S. dorogostaiskii) growing in Mongolia a were investigated by means of capillary GLC on capiallary columns of different selectivity (Silar 5 CP and BPX 70). γ-Linolenic acid was found at levels up to 11% of the consitituent fatty acids of Saussurea spp. seed oils. This is the first time that γ-Linolenic acid has been found in members of the plant family Compositae. Moreover, the number, position and configuration of the double bonds in γ-linolenic acid and that of other fatty acids was additionally confirmed by silver ion thin layer chromatography and infrared spectroscopy. The occurence and distribution of γ-linolenic acid, which has found considerable interest for pharmaceutical and dietary use, may be of chemotaxonomical significance in the plant family Compositae.     

Compositions of the seed oil of the Borago officinalis from Iran

In order to investigate the composition of borage (Borago officinalis L.) seed oil, this research was performed under the field conditions at Shahriyar and Garmsar zones, Iran during the 2012 planting year. The oil yield of borage was 31.46% and 33.7% at Shahriyar and Garmsar zone, respectively, and nine and eight fatty acids were identified in the seed oil of borage at Shahriyar and Garmsar, respectively – palmitic, linoleic, stearic and γ-linolenic acids were dominant in the seed oil of borage from both zones. Unsaturated fatty acid content was more than the saturated fatty acids in both zones. The ratio of linoleic acid and α-linolenic acid in the borage cultivated at Shahriyar and Garmsar zones was 2.13 and 2.29. The fatty acid profile of Garmsar borage, oleic and oleic/linoleic acid ratio, increased. Locations with different ecological conditions resulted in changes in both seed oil content and fatty acid profile of borage.     

Unusual Δ5cis-fatty acids in seed oils of Cimicifuga species

A range of unusual fatty acids with cis-5-unsaturation had been reported in the seed oil of Caltha palustris. Seed oils of Cimicifuga spp. have now been found to contain the same unusual fatty acids as are present in Caltha, plus several other minor fatty acids to give a more complex and more unsaturated seed oil fatty acid pattern. The gas chromatographic fatty acid patterns found seem to be consistent and chemotaxonomically significant, because essentially the same pattern was found in several species of the genus Cimicifuga. These findings may shed a new light on the relation of Cimicifuga to Caltha, and to other genera in the plant family Ranunculaceae. The situation is illustrated by capillary GLC seed oil fatty acid methyl ester “fingerprints” obtained from Cimicifuga and Caltha, and is discussed in relation to other genera. The occurrence in nature of several of these unusual fatty acids, and their chemotax-onomic significance is discussed. The close relation of GLC fatty acid patterns of Caltha and Cimicifuga could indicate monophyly and/or their belonging to the same tribe or subtribe. These observations are not in accordance with the phylogenetic systematic schemes of the genera in this plant family as published by various authors.     

Analysis of the Dynamic Decomposition of Unsaturated Fatty Acids and Tocopherols in Commercial Oils During Deep Frying

The decomposition of unsaturated fatty acids and tocopherols in 10 commercial edible oils during deep frying was investigated. The dominant tocopherol in oils rich in polyunsaturated fatty acids (PUFAs) was γ-tocopherol, except for natural perilla oil (δ-tocopherol dominant), and the main tocopherol in oleic acid-rich oils was α-tocopherol. The PUFA-rich oils had higher tocopherol contents than the oleic acid-rich oils. Both the reduction rate of total unsaturated fatty acid (TUFA) and total tocopherol (TToc) were linear with frying time (t). The decomposition rate of TToc is faster than that of TUFA since the slope values obtained from fitting equations (Y?=?k t) k_TToc (1.520–14.483) were obviously larger than for k_TUFA (0.155–0.270). By establishing a dynamic decomposition index, unsaturated fatty acids and tocopherol in oils showed dynamic decomposition over multiple frying cycles. The obtained results showed that decomposition characteristics of oils are related to their fatty acid compositions.     

The Constituents of the Leaves of Chamaecyparis Formosensis Matsum

Forty one terpenoidal compounds were isolated from the essential oil of Chamaecyparis formosensis Matsum. The dominant component is α-pinene. Other major components include β-pinene, 3-carene, α-terpineol, γ-muurolene, and kaurene.     

Polymer-Attached Thiazolium Salts-Catalyzed Addition of Aldehydes to α, β-Unsaturated Carbonyl Compounds

A homogeneous catalyst, 3-benzyl-5-(2-hydroxyethyl)-4-methyl-1,3-thiazolium chloride, for addition of aldehydes to activated double bond, was attached to 20% cross-linked polystyrene-divinylbenzene copolymer. The attached catalysts could be easily removed from the reaction mixture. Polymer-attached thiazolium salts in the presence of triethylamine are active catalysts for addition of aromatic and aliphatic aldehydes to α,β-unsaturated ketones to yield γ-diketones.     

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).     

RP-LC for Determination of Plastochromanol, Tocotrienols and Tocopherols in Plant Oils

An isocratic high performance liquid chromatographic method, with the application of C₁₈ and C₃₀ reverse-phase column and fluorescence detection, is described for the analysis of plastochromanol, tocotrienols and tocopherols in plant seed oils. The solvent systems have been optimized to obtain high resolution for all tocochromanols and relatively short analysis time. The use of reverse-phase columns for plastochromanol analysis, previously not reported, enables very sensitive and selective detection of plastochromanol which under the described separation conditions did not interfere with tocochromanols or any other compounds. The sample extraction method is fast, simple and highly efficient. The obtained results show that plastochromanol was present in most of the investigated seed oils. Its level was the highest in flax (17–30 mg/100 g oil), rape (8.5–9), camelina (4.3), peanut (1.95), corn (1.69) and grape (1.31) seed oils. Its level in the other investigated oils was below 1 mg/100 g oil, and only in sesame and coconut oils it was not detected. Tocotrienols were found in most of the oils but their content was usually very low (<<1 mg/100 g oil) with the exception of grape, milk thistle and corn oils where it reached >1 mg/100 g oil. Tocopherol content and isomer composition was within the earlier reported literature values for the investigated oils.     

RP-LC for Determination of Plastochromanol,Tocotrienols and Tocopherols in Plant Oils

An isocratic high performance liquid chromatographic method, with the application of C₁₈ and C₃₀ reverse-phase column and fluorescence detection, is described for the analysis of plastochromanol, tocotrienols and tocopherols in plant seed oils. The solvent systems have been optimized to obtain high resolution for all tocochromanols and relatively short analysis time. The use of reverse-phase columns for plastochromanol analysis, previously not reported, enables very sensitive and selective detection of plastochromanol which under the described separation conditions did not interfere with tocochromanols or any other compounds. The sample extraction method is fast, simple and highly efficient. The obtained results show that plastochromanol was present in most of the investigated seed oils. Its level was the highest in flax (17–30 mg/100 g oil), rape (8.5–9), camelina (4.3), peanut (1.95), corn (1.69) and grape (1.31) seed oils. Its level in the other investigated oils was below 1 mg/100 g oil, and only in sesame and coconut oils it was not detected. Tocotrienols were found in most of the oils but their content was usually very low (<<1 mg/100 g oil) with the exception of grape, milk thistle and corn oils where it reached >1 mg/100 g oil. Tocopherol content and isomer composition was within the earlier reported literature values for the investigated oils.

     

A New Method for Olive Oil Screening Using Multivariate Analysis of Proton NMR Spectra

A new NMR-based method for the discrimination of olive oils of any grade from seed oils and mixtures thereof was developed with the aim of allowing the verification of olive oil authenticity. Ten seed oils and seven monovarietal and blended extra virgin olive oils were utilized to develop a principal component analysis (PCA) based analysis of ¹H NMR spectra to rapidly and accurately determine the authenticity of olive oils. Another twenty-eight olive oils were utilized to test the principal component analysis (PCA) based analysis. Detection of seed oil adulteration levels as low as 5% v/v has been shown using simple one-dimensional proton spectra obtained using a 400 MHz NMR spectrometer equipped with a room temperature inverse probe. The combination of simple sample preparation, rapid sample analysis, novel processing parameters, and easily interpreted results, makes this method an easily accessible tool for olive oil fraud detection by substitution or dilution compared to other methods already published.     

Physico-chemical properties of Tecoma stans Linn. seed oil: a new crop for vegetable oil

Tecoma stans Linn. is known to have various medicinal and therapeutic properties. However, to our knowledge, no information is available regarding their seed oils. In this study, the fatty acid (FA) compositions, physico-chemical properties and antioxidant capacities of T. stans seed oils (TSOs) were investigated. The oil content of the seeds was 15%. The FAs of the TSOs were analysed by GC–MS. α-Linolenic (45.47%), oleic (23.56%), linoleic (11.48%), palmitic (6.09%) and stearic (4.12%) acids were the major detected FAs. γ-Linolenic acid and stearidonic acid, unusually FAs, were also present (1.04% and 6.65%, respectively). The total tocol content in the TSOs was found to be 266.06 mg/100 g. The main component was γ-tocopherol (78.93%). The total phenolic content (168.69 mg GAE/100 g oil) and total flavonoid content (5.54 mg CE/g oil) were also determined in the TSOs.     

Silver-phase high-performance liquid chromatography–electrospray mass spectrometry of triacylglycerols

Silver-phase chromatography hyphenated with on-line electrospray mass spectrometry can be applied to characterize triacylglycerols present in vegetable oils with respect to their degree of unsaturation, the position of the most unsaturated fatty acid and the carbon number (CN). The CN information obtained with silver-phase HPLC–ESP–mass spectrometry is complementary to the unsaturation information obtained by silver-phase HPLC-flame ionization detection. Both information is essential to monitor or study modified vegetable oils on the presence of non-natural triacylglycerols. The quantitative results obtained with the method are in agreement with the results obtained in the silver-phase HPLC-flame ionization detection and with theoretical values calculated from the fatty acid distribution of the oil. Silver-phase HPLC–ESP-mass spectrometry gives direct information on fatty acid position and triacylglycerol CN, for each of the triacylglycerols in the sample. This in contrast with non-aqueous reversed-phase HPLC hyphenated with on-line atmospheric pressure chemical ionization-mass spectrometry, which requires a more extensive data processing. The results obtained with silver-phase HPLC–ESP-mass spectrometry can be presented in a three-dimensional overview (relative amount, CN, fatty acid position) serving as a fingerprint for the oil.     

Separation of γ-linolenic and other polyunsaturated fatty acids from Boraginaceae via supercritical CO2

Essential fatty acids were extracted from Echium amoenum (Boraginaceae) seed oil via supercritical carbon dioxide and the results were compared with conventional Soxhlet method as the base case of 100% recovery. The response surface methodology was used to optimize the effective extraction parameters. The chemical composition of recovered oil was analyzed by polar and non-polar gas chromatograph-flame ionization detector columns. The experimental results indicated that echium seed contained 25 wt% oil and the maximum extraction oil recovery of 92% was obtained via supercritical CO(2) at optimal operating conditions (43°C, 280 bar, 1.5 mL/min, 25 min static time and 130 min dynamic time). At similar operating conditions, applying 2.5 and 5 mol% ethanol as a modifier enhanced the recovery to 96 and 112%, respectively. The results showed that supercritical fluid extraction is a viable technique for separation of constituents such as γ-linolenic acid (7-8%), palmitic acid (6-7%), stearic acid (3-4%), oleic acid (12-13%), linoleic acid (19-20%), α-linolenic acid (40-41%) and stearidonic acid (8-9%) from Boraginaceae.     

Die Kristallstrukturen von Me3SiI · β-Picolin und Me3SiI · γ-Picolin Vergleich der Lewis-Basen Pyridin, β-Picolin und γ-Picolin

The Crystal Structure of Me₃SiI · β-Picoline and Me₃SiI · γ-Picoline A Comparison between the Lewis-Bases Pyridine, β-Picoline, and γ-Picoline The reaction of Iodinetrimethylsilane with β- und γ-Picoline (Pic) leads to solid 1 : 1 compounds Me₃SiI · β-Picoline 1 , Me₃SiI · γ-Picoline 2. The reaction was performed at room temperature. Yellow single crystals were obtained by sublimation. Single crystal X-ray investigations confirm that both compounds are ionic [Me₃SiPic]⁺I^?. The comparison of β-Picoline with γ-Picoline and Pyridine (Py) demonstrates that the presence of a methyl group and also its position has no significant influence on the Si? N bond length in compound 1, 2 and on the adduct Me₃SiI · Py.     

Characterization of plant oils on a monolithic silica column by high-performance liquid chromatography-atmospheric pressure chemical lonization-mass spectrometry

Summary Five plant oils (peanut, pumpkin seed, sesame seed, soybean, and wheat germ) have been analyzed by high-performance liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (HPLC-APCI-MS). Gradient elution was performed with acetone-acetonitrile mobile phases on a short monolithic silica column (SilicaROD, RP-18e, 50 mm×4.6 mm). Identification of plant oil triacylglycerols (TAG) was based on the pseudomolecular ion [M+H]⁺ and the diacylglycerol [M−RCO₂]⁺ fragments. Positional isomers of triacylglycerols were identified from the relative intensities of the [M-RCO₂]⁺ fragments. Principal-component analysis, used to find similarities and differences between the different oils, indicated that the different plant oils could be clearly differentiated according to their triacylglycerol composition. Presented at Balaton Symposium '01 on High-Performance Separation Methods, Siófok, Hungary, September 2–4, 2001     

Convenient esterification of poly(γ-glutamic acid) produced by microorganism with alkyl halides and their thermal properties

The esterification of poly(γ-glutamic acid) (γ-PGA) produced by Bacillus subtilis F2-01 with alkyl halides was carried out at 60°C in N-methyl-2-pyrrolidinone (NMP) in the presence of sodium bicarbonate to obtain the corresponding esterified γ-PGA. The thermal properties of these γ-PGA esters were examined by differential scanning calorimetry and thermogravimetry. γ-PGA esters were more stable than free acid type γ-PGA, which decomposed at 210°C. Melting temperature (T_m) of γ-PGA esters could be observed at 230-250°C. T_m of γ-PGA n-alkyl esters reached a maximum at an alkyl chain length of n = 3. © 1995 John Wiley & Sons, Inc.     

Fatty acid profile of <Emphasis Type="Italic">Trichosanthes kirilowii</Emphasis> Maxim. seed oil

Fatty acid profile data for refined cold-pressed Trichosanthes kirilowii Maxim. seed oil, in comparison to other commercially available oils — olive, rapeseed and camellia, are presented. Trichosanthes kirilowii Maxim. seed oil has high oleic and linoleic acid content and high polyunsaturated acid content. Squalene elutes as a distinct peak in the GC chromatograph. For a positive identification, MS detection was used. In the samples analyzed, squalene occurred in the range of 57.4–68.2 mg g⁻¹.     

Comparative analysis of essential oil composition from flower and leaf of Magnolia kwangsiensis Figlar & Noot.

The essential oils from Magnolia kwangsiensis Figlar & Noot. were obtained using hydrodistillation, and analysed by GC and GC–MS. A total of 31, 27 and 26 constituents were identified in the oils from male flower, female flower and leaf of M. kwangsiensis, and they comprised 99.2, 98.5 and 96.2% of the oils, respectively. Monoterpene hydrocarbons predominated in the oils and accounted for 48.3% of male flower oil, 54.0% of female flower oil and 44.6% of leaf oil. The compositions of flower oils were quite similar but with different content, and were different from those of leaf oil.     

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.