The content and fatty acid (FA) composition of FA neutral acylglycerols (NAG), a mixture of 1,2,3-triacyl-sn-glycerols (TAG) and 3-acetyl-1,2-diacyl-sn-glycerols (acDAG), were determined in the seeds ...and arils of fruits of 14 Euonymus L. species. On the average, the seeds exceeded the arils in the absolute and relative dry matter content 2.9- and 1.9-fold, respectively, and separate plant species greatly differed in NAG composition. The proportions of TAG in the NAG of seeds and arils were 4–5 and ~98 %, respectively. The degree of FA unsaturation in aril NAG was higher than in the seed NAG, and in acDAG—higher, than in TAG. In the NAG, 14 major FA molecular species (excluding minor FA) were found, and linoleic, oleic, palmitic, and linolenic acids were predominant. NAG of separate taxonomic units of the genus Euonymus L. differed from each other in the concentration of major FA as well as other FA. So, by using statistical analysis, it was definitely established that the species from the subgenus Euonymus were characterized by an increased content of linoleic acid, while those from the subgenus Kalonymus, by the predominance of oleic acid. Meanwhile, the species of the section Euonymus were marked by an enhanced concentration of a number of hexa- and octadecenoic FA positional isomers.
Positional-species composition (PSC) of 1,2,3-triacyl-sn-glycerols (TAG) from the arils of mature fruits of 13 species of Euonymus L. genus was established. The residues of six major fatty acids ...(FA), palmitic, stearic, hexadecenoic (H), octadecenoic (O), linoleic (L), and linolenic, were present in the TAG. PSC of TAG was determined by their partial lipase hydrolysis. By using hierarchical cluster and principal component analyses, it was definitely demonstrated that separate taxonomic units forming this genus were significantly distinguished as regards PSC of TAG. In particular, the Euonymus subgenus greatly exceeded the Kalonymus subgenus in both total content of L in TAG and in the rate of its incorporation into their mid-position, while TAG of Kalonymus were marked by a prevalence of O-TAG and sn-2-O isomers. Thus, these subgenera were significantly distinct in the rate of incorporation of O and L residues in the sn-2 position of TAG molecules. Meanwhile, the TAG from the Euonymus section species were marked by an enhanced concentration of H and the incorporation of H in UUU TAG was much more active than in other TAG types. As for positional-type composition of TAG, saturated FA were always virtually absent in the sn-2 position of Euonymus aril TAG.
The dynamics of the fatty‐acid (FA) composition of neutral acylglycerols (NAGs) composed of 1,2,3‐triacyl‐sn‐glycerols (TAGs) and 3‐acetyl‐1,2‐diacyl‐sn‐glycerols (acDAGs) was determined in the fruit ...seeds and arils of three Euonymus L. species at three stages of their maturity. The NAG composition comprised 29 FAs, linoleic, oleic, palmitic, and α‐linolenic acids being predominant. Noticeable amounts of other FAs, such as lauric, myristic, hexadec‐9‐enoic, stearic, (Z)‐vaccenic, and arachidic acid, etc., could also be present. In the course of maturation, the qualitative composition of major FAs remained nearly unchanged, while the unsaturation index of FAs in seeds and in TAGs, as well as, but to a lesser extent, in arils and in acDAGs, respectively, always decreased. This decline was brought about by a sharp fall of the α‐linolenate level, a decrease of the linoleate content, and a corresponding rise in the oleate content. It is suggested that, in both seeds and arils, both classes of NAGs were formed at the expense of the same FA pool; the quantitative composition of this pool was characteristic of a given fruit part and strongly changed during maturation. The accumulation of TAGs in E. europaeus fruits was accompanied by a conversion of hexadec‐9‐enoic acid into (Z)‐vaccenic acid via the C2‐elongation reaction.
Small amounts of a mixture of fatty acid short‐chain‐alkyl esters (FASCAEs) were obtained from the fruits of twelve plant species of Celastraceae family, and in five of them the FASCAEs were present ...not only in the arils but also in the seeds. These mixtures contained 32 individual FASCAE species, which formed four separate fractions, viz. FA methyl, ethyl, isopropyl, and butyl esters (FAMEs, FAEEs, FAIPEs, and FABEs, resp.). The FASCAE acyl components included the residues of 16 individual C14–C24 saturated, mono‐, di‐, and trienoic FAs. Linoleic, oleic, and palmitic acids, and, in some cases, also α‐linolenic acid predominated in FAMEs and FAEEs, while myristic acid was predominant in FAIPEs. It can be suggested that, in the fruit arils of some plant species, FAMEs and FAEEs were formed at the expense of a same FA pool characteristic of a given species and were strongly different from FAIPEs and FABEs esters regarding the mechanism of their biosynthesis. However, as a whole, the qualitative and quantitative composition of various FASCAE fractions, as well as their FA composition, varied considerably depending on various factors. Therefore, separate FASCAE fractions seem to be synthesized from different FA pools other than those used for triacylglycerol formation.
Among 55 fatty acids found in four alpine plants, 9 fatty acid species were identified for the first time in higher plants and 2 species, 16:2ω5 (
1), and 17:2ω5 (
2), may be new to science.
Fatty ...acid composition and structure in total lipids from the green above-ground parts of four alpine plants,
Oxygraphis glacialis,
Primula macrophylla,
Rhodiola pamiroalaica, and
Swertia marginata, were established by GC and GC–MS. A total of 55 fatty acids was detected, and 48 of them were identified. Ubiquitous palmitate, linoleate, and linolenate predominated in the lipids accounting for about 72–90% of the total fatty acids. At the same time, the latter contained numerous species, which were unusual for higher plants and included saturated odd-numbered
n-acids (six C
15–C
25 species, 0.26–1.40%), saturated even-numbered very-long-chain
n-acids (six C
20–C
30 species, 1.00–2.49%),
iso-acids (nine C
15–C
26 species, 0.64–1.53%),
anteiso-acids (four C
15–C
20 species, 0.08–1.57%), certain uncommon mono- and dienoic acids, as well as 16:3ω3, 18:3ω6, and 18:4ω3 acids that are absent from the most higher plants. Nine fatty acids were found here for the first time in higher plants and two may be new to science. The evidence on the unusual fatty acids is discussed with respect to their distribution in living organisms, pathways of biosynthesis, and chemotaxonomic role.
Changes in the quantitative composition of triacylglycerols (TAGs) in maturing sea buckthorn (Hippophaë rhamnoides L.) seeds were determined by lipase hydrolysis. As a whole, the rate of synthesis of ...separate TAG classes increased in proportion to both their unsaturation and relative content (weight percent) in total TAGs. Up to the 80th day of maturation, the formation of triunsaturated TAGs was predominant. Subsequently, at the terminal stage of seed ripening, the absolute content (in nanomoles per seed) of a major group of these TAGs containing linolenic and linoleic acyls decreased by ∼7%, and the increase in the total TAG content was mainly due to the synthesis of TAG molecules including stearic and palmitic acyls in the rac-1,3 positions, as well as those containing oleate in the sn-2 position. At each maturation stage, the composition of the TAGs formed was controlled both by the composition of fatty acids available for TAG synthesis and by the rate of incorporation of a particular fatty acid into the sn-2 position of the TAGs. Keywords: Sea buckthorn; Hippophaë rhamnoides L.; seed maturation; fatty acids; triacylglycerols; lipase hydrolysis; sn-2 acylation of glycerol; positional-type composition; positional-species composition; kinetic constant of relative rate of biosynthesis
Coordination complexes of unsaturated
rac-1,2-diacylglycerols (DAGs) with silver ions were separated by adsorption and reversed-phase TLC (silver ion TLC and silver ion RP-TLC, respectively). During ...silver ion TLC, silver ion complexes are formed by an indeterminate number of coordination centers of various nature and only at the adsorbent surface; separation of the complexes proceeds according to an adsorption mechanism, and there is an inverse exponential relationship between DAG unsaturation and their mobility. With silver ion RP-TLC, the complexes are formed only with double bonds, only in solution, and at a 1:1 ratio; the complexes are fractionated by lipophilic partitioning between two liquid phases, and the relationship between the unsaturation of DAGs and their mobility is a direct linear one. Nevertheless, in spite of all these differences, the use of both methods demonstrated that DAG species characterized by a coiled acyl configuration always greatly exceeded in polarity those with the same unsaturation, but with the configuration close to an extended one; in the former group, this excess amounted to two- to three-fold and 30–40% for silver ion TLC and silver ion RP-TLC, respectively. In addition, for both versions of silver ion LC, these two groups of species differ from each other quantitatively, but not qualitatively, in the pattern of the relationship between the unsaturation and mobility of DAG complexes. Thus, under all conditions of silver ion LC studied here, the polarity of DAG complexes and, therefore, their mobility are conditional not only on the number of double bonds, but also on their configuration.
Acetylation of phosphatidylethanolamine (PE) yielding its
N-acetamide (AcPE) brings about changes in the charge and conformation of the polar head group. As a result, the POC bond of AcPE can be ...hydrolysed, with the formation of ethanolamine (EA)
N-acetamide (AcEA), under much more mild conditions than the respective bond in the original PE. Thus, introduction of an acyl substituent into the PE amino moiety exerts a profound effect on the course of hydrolysis of the PE POC bond separated from this moiety by two CH
2 segments.
