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The compositions of neutral lipids (NL) from fruit of L. barbarum, commercially available (I) and introduced (II), and wild L. ruthenicum (III) were studied. The contents of NL in fruit of I (6.1%), II (3.7%), and III (7.54%) and the fatty acid (FA) compositions were determined. The class composition of NL from I, II, and III was established. The FA compositions of all acyl-containing NL classes were determined. The position-forms (21 forms) and types (4 types) of the triacylglyceride (TAG) compositions of II were established using pancreatic hydrolysis. It was shown that the 2-position in TAG molecules was occupied mainly by unsaturated FA.

Lipids from seeds of Pulmonaria mollis (Boraginaceae) from two RF climate zones, i.e., Krasnodar Krai (I) and Republic of Bashkortostan (II), were characterized. The neutral lipid (NL) contents of I were greater than those of II (33.8 and 20.5%, respectively). The NL classes were characterized. A larger amount of polyunsaturated fatty acids (PUFAs) concentrated in NL and triacylglycerides (TAGs) from I and II [in NL (%, respectively): 65.6 and 65.0, including α-18:2, 28.8 and 31.9; γ-18:3, 18.5 and 14.5; α-18:3, 12.7 and 14.5; 18:4, 5.7 and 4.1; in TAG (%, respectively): 63.5 and 66.0, including α-18:2, 29.4 and 32.3; γ-18:3, 17.15 and 14.36; α-18:3, 12.5 and 14.6; 18:4, 4.5 and 4.7]. Fractions enriched in PUFAs γ-18:3 (47.1%) and 18:4 (21.2%) were obtained. The ω-6/ω-3 ratios in the lipid PUFAs were 2.7:1-2.2:1.

Amides were prepared from N-deacetyllappaconitine and unsaturated oleic, linoleic, α-linolenic, and γ-linolenic fatty acids.

The compositions of lipids, fatty acids (FAs), and triacylglycerides (TAG) from seeds of Pulmonaria obscura growing in the Republic of Bashkortostan were studied. The contents of neutral (NL) and polar lipids and the composition of FAs of all acyl-containing NL classes were identified and determined. The largest amounts of polyunsaturated FAs were concentrated in total NL (88.9%, including γ-18:3, 24.3; α-18:3, 10.4; and 18:4, 3.5%) and TAG (85.3%, including γ-18:3, 21.4; α-18:3, 10.7; and 18:4, 3.5%). The speciation (39 species > 0.5%) and type (three types) of TAG were established using pancreatic hydrolysis.

The compositions of neutral lipids (NL) and fatty acids (FA) from subterranean parts of the introduced plants Helleborus abchasicus and H. caucasicus (Ranunculaceae) were established and compared with those of the wild species. The FA from diacyl- and triacylglycerides and free FA from these introduced species had elevated contents of unsaturated acids because of 18:2. The lipid-soluble NL constituents included 10 identified sterols, the major ones of which were cholesterol, sitosterol, and lanosterol. NL from H. abchasicus (introduced and wild) and H. caucasicus (wild) exhibited pronounced anti-inflammatory activity at the level of Voltaren and moderate wound-healing activity.

Fifty Ribes species and R. nigrum-based cultivars from eight Ribes sections were surveyed for γ-linolenic acid (GLA, 18:3, n-6)- and stearidonic acid (SDA, 18:4, n-3)-rich oils. R. pallidiflorum, R. glabellum and R. pubescens seed oils contain noticeable GLA amounts: 13.3, 11.8, and 11.9% of total fatty acids (FA), respectively. However, the highest GLA contents were found in the seed oils of several blackcurrant cultivars, highlining Ribes 'Myuryucheene' with 20.2% GLA of total FA. Principal Component Analysis showed that similarities in FA profiles allow grouping species as botanical criteria for Ribes sections do. The main GLA-taxa detected in this study correspond to blackcurrant cultivars, all of them native to Siberia. Considering that such cultivars are notable fruit-producers, its cultivation in Siberia besides producing fruits in very difficult agronomic areas, could produce a valuable by-product, i.e. the seeds, which will add economic value to agricultural systems if devoted to GLA-rich oils extraction.

Neutral (NL) and polar (PL) lipids including glyco- (GL) and phospholipids (PhL) were isolated and their contents were determined from seeds and rhizomes with roots (RR) of Helleborus abchasicus and H. caucasicus in two development phases that were introduced into Pyatigorsk Botanical Garden. The amount of NL in subterranean organs increased from flowering to fruiting phases. The PL content in roots of H. abchasicus increased during fruiting and was independent of the vegetation stage in H. caucasicus. GL dominated in RR. The GL and PhL ratio in seeds was practically identical. The fatty-acid composition of all lipid groups in the two development phases of the introduced plants was determined. Subterranean organs and seeds of the two Helleborus species contained alkaloids, a part of which was extracted with the PL. The alkaloid content in RR during fruiting was 0.63% in H. abchasicus; 0.49%, in seed pulp; 0.26%, in H. caucasicus; and 0.05% in seed pulp of the starting raw material mass.

Lipids from seeds of the plants Cynoglossum officinale (1), Echium vulgare (2), and Lappula squarrosa (3) of the family Boraginaceae growing in the Republic of Bashkortostan were studied. Four polyunsaturated acids, linoleic (LA), γ-linolenic (GLA), α-linolenic (ALA), and stearidonic (SA), were identified among the fatty acids. The principal acids of the neutral lipids (NL) were 18:1 and 18:2 in 1, ALA in 2 and 3, and GLA in approximately equal amounts in all three samples. The highest amount of SA (16.8 %) was found in 3. Unsaponified components of NL samples were identified by GC/MS. Alkaloids were observed in the pulp and polar lipids.

In continuation of research on the lipid composition of seed oil from Oenothera biennis growing in Krasnodar Territory [1], we studied the effect of long-term (12 months) storage on the content of the principal fatty acids palmitic (16:0), stearic (18:0), oleic (18:1), linoleic (18:2), and -linolenic (18:3). An oil sample from Oenothera biennis seeds (~1 mL) was placed in a tube (~2 mL), closed with a stopper, and stored in a refrigerator at 8°C. A sample was taken each month. The fatty acid composition was determined (Table 1). The composition and content of fatty acids in the samples were practically constant and within the uncertainty limits of the experiment. The presence or absence of oxidized lipids was determined by hydrolyzing a sample of oil that was stored for one year, isolating the fatty acids, and preparing the methyl esters, which were analyzed for the presence of oxidized fatty acids by analytical TLC (ATLC) using solvents 1–3. The models were methyl esters of fatty acids from castor oil that contained monohydroxyand dihydroxy-fatty acids. However, spots corresponding to oxidized fatty acids were not observed in the studied sample. Oil of O. biennis is known to contain tocopherols [2, 3], which we identified previously in the neutral lipids [1]. GC/MS of the unsaponified fraction of O. biennis oil identified the natural antioxidants -, -, and -tocopherol from their mass spectra using the AMDIS software [4]. The antioxidant activity of the oil was analyzed using a model system based on radical-chain oxidation of methyloleate initiated by azodiisobutyronitrile (AIBN). The advantage of this model system is that the oxidation process in it is very similar to the lipid oxidation process in living systems. Studies of natural compounds using this system and analogous apparatus are rather rare. Figure 1 shows typical kinetic curves for oxygen absorption during initiated oxidation of methyloleate without an inhibitor and with O. biennis seed oil. It can be seen from the curves that the reaction occurred with an induction period. The rate of uninhibited oxidation of methyloleate and the oxidation rate of methyloleate inhibited by the oil components after complete consumption of the inhibitor were the same. Therefore, our experimental conditions did not reveal the contribution from oxidation of the oil itself. The reduced oxidation rate in the initial portion (induction period) indicated that an additional pathway for consumption of peroxide radicals had opened.

The composition of lipids and fatty acids from seeds of Oenothera biennis growing in the RF near Kazan’ was determined. The content of γ-linolenic acid in all groups of acyl-containing lipids in the oil to be 4.4%.

Polyunsaturated fatty acids (PUFA), gamma-linolenic (GLA), alpha-linolenic (ALA), and stearidonic (SA), exhibit high biological activity [1]. Various attempts have been made to prepare PUFA fractions enriched in one PUFA or another for use in drugs and dietary products. A method based on the different solubilities of sodium salts of FA in EtOH that was used for this enabled PUFA concentrates to be obtained from seed oil of Echium fastuosum, Borago officinalis, and Anchusa azurea (Boraginaceae) [2]. We obtained good results for the isolation of FA fractions enriched in ALA and GLA from linseed oil and seed oil of B. officinalis by using low-temperature crystallization at –80°C from CH3CN:Me2CO (7:3) [3]. The resulting fraction (mother liquor) from linseed oil, which contains 55% ALA, consisted of 88.5% ALA; from total FA of B. officinalis with 23.4% GLA, 88.3% of this FA. Crystallization of FA from hexane solution (10%) at –70°C enabled GLA and SA concentrates to be obtained from E. fastuosum seed oil. This method could be used on an industrial scale [4]. Fractions with high GLA and SA contents could be obtained by chromatographic methods such as HPLC, CC over silica gel and over silica gel impregnated with AgNO3, and centrifugal preparative chromatography (CPC). However, they are suitable only for laboratory studies [5]. Extraction by supercritical CO2 in order to isolate and enrich oils in GLA and SA did not give the desired result [6–8]. Fractionation of urea complexes of FA was used to isolate epoxytetraenoic acid from total FA of fish and microalgae [9]; a mixture of GLA with ALA, from FA of Ribes nigrum seed oil [10] and from FA of seed oil of A. azurea, E. fastuosum, and S. scophila [11]. As a rule, a urea:FA ratio of 4:1 (by mass) is used [9]. Production of FA fractions enriched with PUFA using urea complexes (clathrates) depends primarily on the initial set of PUFA and their content in the oil. The main difficulty in producing FA fractions with a high SA content is the presence in oils of SA and its precursor ALA. Until now, plants with oil that contains only SA have not been found [1]. Studies of seed lipids from several species of the family Boraginaceae indigenous to the Republic of Bashkortostan found that Lappula squarosa seed lipids contained >70% PUFA including >16% SA [12]. Separation of the FA from Lappula seed oil as the urea clathrates afforded fractions enriched with PUFA. For this, mild alkaline hydrolysis (10% KOH solution in MeOH, 70–80°C, 30 min) isolated from the oil the total FA. EtOH was used as the solvent to prepare the urea complexes because it was shown earlier that enrichment of PUFA in it occurred better by using FA from B. officinalis seed oil as an example [13]. FA were separated in two steps [13]. In the first step, a mixture of FA (0.8 g) was treated with a saturated solution of urea in EtOH (FA:urea ratio 1:3 by mass), stirred on a magnetic stirrer with heating (60°C) until totally dissolved, and left at room temperature for 3 h and then at 10°C for 24 h. The resulting clathrate crystals were separated on a Schott filter and washed with cold saturated urea solution in EtOH to produce mother liquor 1 and a precipitate of crystalline FA urea complexes, clathrates 1. The yield of FA fractions (mass% of starting FA) was 36.25 and 57.5, respectively (Table 1). Next, the FA compositions of the mother liquor and clathrates were analyzed. The mother liquor was evaporated to half the volume in a rotary evaporator, diluted with H2O, and extracted with Et2O in order to isolate the FA from it. The Et2O extracts were washed with H2O and dried over anhydrous Na2SO4. The solvent was evaporated. The resulting FA (0.29 g, mother liquor 1) were methylated by diazomethane and studied by GC (Table 1).

Data for changes on storage under natural conditions for 11 months of moisture, oil content, acid and hydroperoxide number, and protein content of ground seed of Viburnum opulus were reported. The amino-acid and fatty-acid compositions were determined.

The variation of the composition of neutral and polar lipids and lipophilic components during maturation of guelder rose (V. opulus L., fam. Caprifoliaceae) fruits was investigated. During fruit ripening, all lipid groups are accumulated, the highest accumulation rate being observed in the first period of maturation. In nonpolar lipids, this is due to a substantial increase in the content of triacylglycerides, whereas the contents of free fatty acids, methyl esters of fatty acids, monoacylglycerides, and especially esters of triterpenoid compounds decrease. During early maturation, all acyl-containing classes of lipids contain large amounts of saturated fatty acids (mainly, 16:0), whose content decreases during ripening, while the contents of unsaturated 18:1 and 18:2 acids increase.

Neutral, polar glyco-, and phospholipids of Aconitum septentrionale K. (northern aconite) are studied. The fatty-acid composition of acyl-containing lipid classes is determined. The oil is demonstrated to possess biological activity. It stimulates reparative regeneration of skin and is more effective than dog-rose oil.

Methyl and triterpenyl fatty-acid esters and triterpenic acids are isolated and identified from seeds ofViburnum opulus(Caprifoliaceae). The biological activity of pigments and proteins is determined

Hexane extract of licorice (Glycyrrhiza glabra L.) roots was obtained and investigated. Hydrocarbons, sterol ethers, triacylglycerides, free fatty acids, and free sterols were identified. The extract contains 70% neutral and 30% polar lipids. It is established that the lipid fraction of licorice roots is more effective than the analogous fraction of rosehip oil in stimulating the reparative regeneration of skin. In addition, this fraction also exhibits pronounced antiinflammatory and antiulcer effects, while being virtually nontoxic. Based on these results, the lipid fraction of licorice roots can be recommended as a parent substance for creating effective preparations in various medicinal forms.

Lipid components of the seeds ofViburnum opulus (Caprifoliaceae family) were investigated. The neutral lipids consist of eight classes, the glycolipids consist of three classes, and the phospholipids contain seven classes. The fatty-acid contents of all of the acyl-containing lipids were determined. The 18∶2 fatty acid is the main component of all the lipid fractions. The content of saturated acids is greater in the glycolipids and phospholipids. The lipophilic components, higher fatty alcohols and sterols, were identified.

The possibility of using the direct alkaline transesterification of seed lipids for the express analysis of fatty acid compositions has been shown on 11 samples of plant seeds.

A petroleum ether extract ofGlycyrrhiza glabra L. roots was investigated. The extract contains 70% neutral lipids and 30% polar lipids. Hydrocarbons, sterols esters, triacylglycerols, free fatty acids, free sterols, and diacylglycerols were identified. The fatty acid contents of all of the acyl-containing lipids were determined. Fourteen fatty acids were identified; the 18 ∶ 2 fatty acid prevails among the unsaturated acids, and the 16 ∶ 0 acid prevails among the saturated acids.

Methyl (9Z)-12-oxooctadec-9-enoate isomerizes stereoselectively in 86% yield into methyl (10E)-12-octadec-10-enoate in the presence of a complex H2O2-BF3-Et2O.

The procedure for synthesizing optically active methyl 12-oxo-9,10-epoxyoctadecanoate (enantio- meric purity ∼90%) was developed, starting from ricinolic acid methyl ester.

Methyl (9Z)-12-oxooctadec-9-enoate isomerizes stereoselectively in 86% yield into methyl (10E)-12-octadec-10-enoate in the presence of a complex H2O2-BF3-Et2O.

The procedure for synthesizing optically active methyl 12-oxo-9,10-epoxyoctadecanoate (enantio- meric purity ∼90%) was developed, starting from ricinolic acid methyl ester.

The composition of the neutral lipids of leaves of a cotton plant of the wilt-resistant variety 175-F, the set of components in the fatty acid composition of the lipid classes, and the partial structures of the triacylglycerides have been determined. The changes taking place in the composition and structure of these lipids on artificial infection of the plant by the fungal pathogenVerticillium dahliae have been elucidated.

Free fatty acids and diacylglycerols containing them have been isolated from the leaves of a cotton plant of a wilt-resistant variety. The composition and structures of the hydroxylipids have been determined by a combination of the methods of IRS, UVS, GLC, and the mass spectrometry of TMS derivatives, and changes in the composition of the hydroxy acids taking place on artificial infection of the plant with the fungusVerticillium dahliae Kleb. have been revealed.

The composition of the cuticular lipids of young leaves of cotton plants of the wilt-resistant variety 175-F has been determined and it has been established that on artificial infection of the plant with cotton wilt(Verticilliuim dahliae) the component composition of these lipids did not change but the level of the 18:0, 18:1, and 18:2 acids in esters of fatty acids with alkanol, sterols, and triterpenols fell.

The amount, qualitative and class compositions, and total fatty acid composition of the free, bound, and strongly bound lipids of kernels of the seeds of cotton plant of variety 175-F have been determined, and with the aid of enzymatic hydrolysis the strongly bound lipids have been isolated from the cottonseed kernels in the native form. It has been established that more than half the weight of the lipids comprises neutral varieties and the remainder are polar components. The lipids of the more stable lipid-protein complexes possess a higher degree of saturation.

A comparative analysis has been made of the amounts of lipids and their fatty-acid compositions in the seeds of the lines of agenetic collection of cotton plants of the speciesGossypium hirsutum and their hybrids and the variety Tashkent-1. The results obtained on the fatty-acid compositions of some hybrids make it possible to recommend the use of individual lines of cotton plants as donors for improving the food-value indices of cottonseed oil.

A new alkaloid, ternatine (C24H33NO5), was isolated from aerial parts of theDelphinium ternatum plant. According to the1H,13C NMR, IR, and mass spectra of the base and its triacetate, ternative was assumed to have the structure of 4β-methyl-7α-isobutyryloxy-11α,15β,19β-trihydroxyhetisane.

The influence of the degree of ripeness of the seeds of the cotton plant on their lipid composition has been studied. It has been established that as the seeds ripen their lipid composition becomes simpler, and in the developing cotton seeds the biosynthesis of triglycerides takes place with the participation of the mono-and diacylglycerides as intermediates.

A comparative study has been made of the lipid composition of healthy roots of the cotton plant of the Tashkent-1 variety (I) and of the corresponding plants infected withVerticillium dahliae Kleb. (II) grown under field conditions. The action of the factors of infection stress and seasonal and climatic conditions change the lipid metabolism. In lipids (I) and (II) seven classes of neutral lipids (NLs), three classes of glycolipids, and six classes of phospholipids (PLs) were identified and their fatty acid compositions were determined. It was established that in (II) there was a smaller amount of total lipids, NLs, and PLs, and an increased level of polyphenolic pigments, but the level of gossypol pigments with free aldehyde groups was unchanged. In the NLs of (II), as compared with (I), there were more triacylglycerols, sterols, triterpenols, and squalene. Complex changes were observed in the fatty acid composition of the acyl-containing lipids.

A stereospecific analysis has been made of the triacylglycerols of cottonseed oil, as a result of which it has been established that the saturated and 16:1 acids mainly occupy the sn-1 position, while 18:1 and 18:2 acids esterify the sn-2 and sn-3 positions of the triacylglycerides to equal extents.

Eight new components of the hydoxy acids have been found in the seed oil of the cotton plant of variety Tashkent 1: six monohydroxy acids, of which three are isomeric hydroxyoctadecenoic, two are hydroxyheptadecenoic, and one is a hydroxy-octadecanoic acid, and two polyhydroxy acids — trihydroxystearic and dihydroxy-octadecinoic acids. The main acids in the combined material were 12-hydroxyoctadec-9-enoic acid and a trihydroxydecanoic acid.

The total fatty acids of cotton seeds include 31 components. The 18:3 acid that is the main component of the early-ripe seeds is present mostly in the mono-, di-, and triacylglycerides. The distribution of the fatty acids in the triacylglycerides of the early-ripe seeds is not characterized by selectivity.

The qualitative and quantitative set of lipid components of the seeds of healthy cotton plants of the variety Tashkent-1 and plants infected with verticillium wilt have been studied. It has been established that the compositions of the lipids of the two samples differ considerably. The greatest differences are observed in the amounts of total lipids, gossypol, and low-molecular-weight volatile acids.

The surface lipids of the coat and the lipids of the kernel of the seeds of a wild form of the medium-fibered cotton plantGossypium mexicanum var.nervosum have been studied in comparison with cultured species. Using the methods of CC, TLC, and GLC, and UV and mass spectrometry, in the cuticular lipids ofG. mexicanum three classes of neutral lipids have been detected, and in the kernel lipids 10 classes of neutral lipids, 2 classes of glycolipids, and 7 classes of phospholipids. The structures of the epoxyacyl-, hydroxyacyl-, and diacylglycerols of the kernel have been established. The greatest differences between the seeds of the wild form of the cotton plant and the cultured species are the greater weight of the seed coat, the presence in it of a considerable amount of the 18:1 and of medium-molecular-weight fatty acids, and a higher level in the kernel of gossypol pigments, polar lipids, and acylglycerols containing the 18:2 acid.

A comparative study has been made of the lipid composition of defective and first-grade cotton seeds after their prolonged storage under industrial conditions. On the basis of the change in the lipids of the seeds subjected to thermal spoilage it is proposed to consider the process of spontaneous heating as a group of enzymatic processes taking place mainly in not fully ripe seeds when they are damaged by pathogenic microflora.

The lipid composition of the seeds ofSecurinega suffruticosa (Euphorbiaceae) has been studied, and eight classes of lipids have been identified with a predominance of triacylglycerols; the fatty acid compositions and structures of the triacylglycerols have been determined. Among the hydroxy acids of the hydroxyacylglycerols 13 components belonging to saturated, monoenic, and dienic acids of the C17, C18, and C20 series have been identified; 12-hydroxyheptadecanoic and 12-hydroxyeicosanoic acids are new.

A method for the partial separation of the combined octadecadienoic acids isolated from the hydrogenation of sunflowerseed oil has been developed. This method is considered as the first stage of the separation of the octadecdienoic acids into the individual isomers.

It has been established that the oil of the ripe seeds of the cotton plant of variety 108-F contains 9,10-epoxyoctadec-cis-12-enoic (I) and 12,13-epoxyoctadec-cis-9-enoic (II) acids. In addition, 9-hydroxyoctadecacis,trans-10,12-dienoic (III) and 13-hydroxyoctadeca-cis,trans-9,11-dienoic (IV) acids, found previously in other oils, have been detected.

IR spectroscopy has been used to determine the content of hydroxy groups in cottonseed oil in relation to the periods of ripening. It has been found that the largest amount of hydroxy groups is present in the oil of the early stages of ripeness.