Hydrocarbon and multibranched ester waxes from the uropygial gland secretion of grebes (Podicipediformes).

The uropygial gland secretion of some grebes (Podicipediformes) had been shown to contain saturated and unsaturated aliphatic hydrocarbons and monoester waxes. While ester waxes are common constituents of preen gland secretions, nonisoprenoid hydrocarbons have not been detected hitherto. The wax constituents are very complex, belonging to several multibranched homologous series, including unusual acids with ethyl branches. The waxes were identified by gas-liquid chromatography-mass spectrometry and equivalent chain length comparisons. A method for the prediction of equivalent chain length values of unknown methyl esters is offered. The results are discussed from a chemotaxonomic viewpoint.     

Diesters of 3-hydroxy fatty acids produced by the uropygial glands of female mallards uniquely during the mating season

The uropygial gland secretions produced by female mallards (Anas platyrhynchos) throughout the year were analyzed by thin-layer chromatography and combined gas-liquid chromatography and mass spectrometry. Most of the year, the secretion was composed of wax esters. With the beginning of the mating season in the middle of March, a polar component appeared which became the dominant and sole component of the secretion through April and May and as the mating season ended in June, wax esters became the sole component of the secretion. The polar components were identified to be diesters of n-C8, n-C10, and n-C12 3-hydroxy acids with n-C16 and n-C18 alcohols and n-C6 to C16 even chain acids. Immediately after the diester-producing period the female uropygial glands produced very long chain wax esters composed of fatty acids longer than C12. By the end of August, shorter chain wax esters composed of C6 and C12 acids became the dominant components of the secretion and this composition, previously considered characteristic of mallards, remained constant until March. The observed disappearance of the short chain waxes during the postnuptial period is similar to that in males. The dramatic changes in the composition of the uropygial glands similar to those observed in the female mallards during the mating season have not yet been observed in any other species.     

Skin surface lipids of the mole Scalopus aquaticus

Skin surface lipids of the mole Scalopus aquaticus were found to consist principally of squalene (70%), wax esters (15%), and sterol esters (5%), together with small amounts of triglycerides, free fatty acids, free fatty alcohols, and free sterols. Analysis of the fatty acids occurring free and as wax esters and sterol esters showed these to consist of approximately equal amounts of saturated and monounsaturated compounds. The saturated fatty acids consisted predominantly of odd-carbon anteiso and even-carbon straight-chain compounds, with minor amounts of even-carbon iso-branched chains. The unsaturated fatty acids had double bond positions that would have been produced by delta 9-desaturation of C14, C16 and C18 straight chain saturated precursors. Both the free and the esterified fatty alcohols had chain structures corresponding with those of the fatty acids but of somewhat greater average chain length. Discovery of a major proportion of squalene in the sebum of this animal extends the number of non-human species that have this characteristic to four, all of which inhabit a damp environment, suggesting that squalene conveys some biological advantage under these conditions.     

Volatile constituents of larval osmeterial secretions in Papilio protenor demetrius

Remarkable differences were found between the chemical composition of the osmeterial secretions of 5th and the previous larval instars of a swallowtail, Papilio protenor demetrius Cr.The secretion of 5th instar larvae consisted principally of aliphatic acids and their esters: iso-butyric acid, 2-methylbutyric acid, methyl iso-butyrate, methyl 2-methylbutyrate, ethyl iso-butyrate and ethyl 2-methylbutyrate. The secretions of 4th and 3rd instar larvae, which were substantially the same in their chemical constitution, predominantly comprised mono- and sesquiterpenoids such as α-pinene, β-myrcene, limonene, β-phellandrene, (Z)-β-ocimene, (E)-β-ocimene, β-elemene, β-caryophyllene, germacrene-B and caryophylleneoxide. The relative content of sesquiterpenic components exceed 80%.Such chemical disparity appeared to be associated with the conspicous change of body colouration at the fourth larval ecdysis.     

The chemical composition of the uropygial gland secretion of rock dove Columba livia

The uropygial gland is a holocrine secretory gland of birds. The lipid and the waxy sebum that the gland secretes is coated on the beak and transferred to the plumage in preening. The composition of the gland secretions from birds of different species has been determined, but little is known about the lipids of the secretion of the gland of the rock dove Columba livia. The amount of secretion, the total lipid content and the fatty acids composition of the secretion of C. livia captured in the nonbreeding season was reported. The mean amount of the secretion within the gland was 30 mg; the mean lipid content of the secretion was 0.385 mg/mg of secretion, which was equivalent to approximately 38% of the secretion. The weight of the secretion relative to gland weight was 32%. If we assume that the amount of the gland secretion constitutes a valid parameter to determine the degree of the gland development, our results indicate that the physiological role of the gland does not depend upon gland mass (GW); the rock dove in particular has a small gland, but its secretion represented 32% of the gland's mass. The composition of the lipids extracted from the gland secretion consisted of C14 to C20 fatty acids, most of them were unsaturated. The secretion of the gland contained approximately 59% of unsaturated fatty acids with a prevalence of oleic acid (37%) and a low content of linoleic (6%) and arachidonic acids (7%). The saturated long chain fatty acids were mainly 14:0, 16:0 and 18:0 in a percentage of approximately 34%. No sexual differences were found in any of the evaluated parameters.     

EFFECT OF HYPERPHENYLALANINEMIA ON FATTY ACID COMPOSITION OF LIPIDS OF RAT BRAIN MYELIN

Abstract— We have studied the fatty acid compositions of cerebral myelin lipids in phenyl-alanine-treated and control rats. The proportion of long chain fatty acids and the ratio of unsaturated to saturated fatty acids of whole brain lipids was low in the penylalanine-treated animals. Both of these reductions were more pronounced in the myelin from phenylalanine-treated rats. The ratio of unsaturated to saturated fatty acids in ethanolamine phosphatides was markedly decreased in the hyperphenylalaninemic condition. The reduction in the proportion of long chain fatty acids was predominant in non-hydroxy fatty acids in cerebrosides and ethanolamine phosphatides. The lipid composition of the myelin expressed as mole percentages of individual phospholipid and sphingolipid components was not significantly different in the two groups of rats, nor did it change with age. Our results indicate a deficiency in the fatty acid elongation and desaturation system in the brains of phenylalanine-treated rats. We suggest that in hyperphenylalaninemic rats, a reduction in the amounts of unsaturated fatty acid and long chain fatty acid alters, respectively, the biochemical reactivity and the stability of the myelin.     

Oregano essential oil as an inhibitor of higher fatty acid oxidation

Inhibition of the oxidation of fatty acids methyl esters by oregano essential oil was studied using capillary gas chromatography. A mixture of fatty acids which contained saturated, mono-, di-, and polyunsaturated acids with 16–24 carbon atoms was extracted from mice brain. Changes in the composition of esters in hexane solutions both in the presence of oregano essential oil and without it were examined during their autooxidation in light for 1 year. It was found that the oxidation rate of unsaturated fatty acids increases with increasing degree of their unsaturation. Oregano essential oil inhibited the oxidation process. Antioxidant activity of the oil increased with increase of its concentration. It was shown that carvacrol and thymol are the main antioxidant components of oregano oil.     

Synthesis and properties of methyl 5-(1'R,2'S)-(2-octadecylcycloprop-1-yl)pentanoate and other omega-19 chiral cyclopropane fatty acids and esters related to mycobacterial mycolic acids

A 23-26-carbon chain length range of omega-19 (1'R,2'S) cyclopropane fatty acids, related to mycobacterial mycolic acids, has been prepared. The key cyclopropyl intermediate, (1'R,2'S)-(Z)-1-formyl-2-octadecylcyclopropane, underwent Wittig chemistry with various reagents to provide vinylic precursors, which were selectively reduced to the corresponding saturated omega-19 cyclopropane fatty acids or esters. The 24-carbon omega-19 cyclopropane ester was made by chain elongation of the 23-carbon ester. Saturated and unsaturated chiral cyclopropane acids and esters were assayed, using wall extracts of Mycobacterium smegmatis; the incorporation of 14C-acetate was used to measure inhibition or stimulation of mycolic acid synthesis. Minor inhibition (2-3%) was shown by the 23- and 24-carbon saturated esters; all the other compounds were stimulants. The most effective (38-55%) stimulators of mycolate synthesis were the unsaturated esters with 23- and 26-carbons and the saturated and unsaturated 25-carbon acids.     

Use of Dufour's gland secretion in nest defence and brood nutrition by hover wasps (Hymenoptera, Stenogastrinae)

Social wasps of the subfamily Stenogastrinae produce an abdominal secretion that is used in two distinct biological contexts. First, the secretion plays an important role in larval nutrition where it serves as a substrate in which food is placed by the adults for eventual consumption by the larvae. Second, in several species, females apply the same secretion to the substrate on which their nests are constructed, where it constitutes a sticky barrier that defends the immature brood from predation by ants. This paper describes for the first time ant guard construction behaviour of three species of stenogastrine wasps belonging to the genera Eustenogaster and Liostenogaster. The identification of compounds making up these secretions was also performed by gas chromatography-mass spectrometry. Ant guards and brood secretions were similar, with saturated and unsaturated long chain hydrocarbons and alcohols as major components. We further confirm that the glandular source of abdominal secretion is the Dufour's gland. This gland contains the same hydrocarbons, and in the same proportions as ant guards and brood secretion. We discuss the fundamental importance of Dufour's gland secretion in the social life of these wasps by comparing species with and without ant guards within the subfamily.     

DISCOVERING EXCEPTIONAL DIVERSIFICATIONS AT CONTINENTAL SCALES: THE CASE OF THE ENDEMIC FAMILIES OF NEOTROPICAL SUBOSCINE PASSERINES

The study of continental adaptive radiations has lagged behind research on their island counterparts in part because the mere identification of adaptive radiations is more challenging at continental scales. Here, I demonstrate a new method based on simulations for discovering clades that show exceptionally high phenotypic diversity. The method does not require a phylogeny but accounts for differences in age and species richness among clades and incorporates effects of the phylogenetic structure of data. In addition, I developed a new multivariate measure of phenotypic diversity, which has the advantage over other measures of disparity in that it takes covariation into account. I applied these methods to a clade of endemic Neotropical suboscine passerines, within which the family Furnariidae has been considered an adaptive radiation. I found that the families Thamnophilidae, Furnariidae, and Dendrocolaptidae have experienced a higher rate of cladogenesis than have other clades. Although Thamnophilidae is exceptionally diverse in body size, only Furnariidae and Dendrocolaptidae are exceptionally diverse in shape. The combination of high rates of cladogenesis and high morphometric diversity in traits related to feeding and locomotion suggest that the clade Furnariidae‐Dendrocolaptidae represent an authentic continental adaptive radiation.     

Lipid composition of the extracellular matrix of Botrytis cinerea germlings

Six simple lipid classes (mono-, di- and tri-acylglycerols, free fatty acids, free fatty alcohols and wax esters) were identified by TLC in the extracellular matrix of Botrytis cinerea germlings and the molecular components of each class were characterized using GC-MS. The relative amounts of fatty acids and fatty alcohols within each lipid class were determined by GC-FID. Over all the lipid classes, the most abundant saturated fatty acids were palmitic (ca. 30%) and stearic acid (ca. 22%). Palmitoleic and oleic acids made up ca. 21% and 24% (respectively) of the free fatty acids, while erucic (ca. 4.1%) and linoleic (ca. 3.6%) acids were the most abundant unsaturated fatty acids in the acylglycerides. The acylglycerides also contained almost 35% long chain fatty acids (C20:0 to C28:0). Six fatty acids were identified which had odd-numbered carbon chain lengths (C15:0, C17:0, C19:0, C21:0, C23:0 and C25:0). Of these, pentacosanoic acid made up almost 14% of the fatty acids in the acylglycerides. Three methyl-branched chain fatty acids, namely isopalmitic, isoheptadecanoic and anteisopalmitic, were identified in the ECM, all in small amounts. Of the fatty alcohols identified, only palmityl and stearyl alcohols were found in the free form (ca. 57% and 43%, respectively) but arachidyl alcohol (ca. 47%) and 1-octacosanol (ca. 30%) were the most abundant fatty alcohols found in the wax ester fraction.     

FATTY ACID ABNORMALITY IN ADRENOLEUKODYSTROPHY

—Recent clinical and morphological evidence established that adrenoleukodystrophy is a distinct X-linked genetic disorder. Fatty acid compositions of lipids in the brain, adrenal and serum from seven patients were examined. Cholesterol esters of both brain and adrenal contained substantial proportions of fatty acids longer than C₂₂ (11.8–41.9% of total in the brain and 13.4-34.8% of total in the adrenal), while cholesterol esters from normal and pathological control specimens contained very little. These very long chain fatty acids were generally saturated in brain cholesterol esters but significant amounts of unsaturated long chain fatty acids were also present in adrenal cholesterol esters. The long chain fatty acids showed bell-shaped distribution with C₂₅ or C₂₆ at the peak. Ganglio-sides from patients’white matter also showed increased proportions of very long-chain fatty acids, up to 50% of the total. Qualitatively similar but much milder fatty acid abnormalities were also found in galactosylceramide of the brain. On the other hand, fatty acids and fatty aldehydes of brain glycerophospholipids, adrenal free fatty acids, triglycerides and glycerophospholipids were not abnormal. Furthermore, serum cholesterol esters from two patients did not show the long-chain fatty acid abnormality found in brain and adrenal cholesterol esters. Sequential extractions with acetone and hexane established that the characteristic birefringent material in the brain and adrenal is indeed cholesterol esters with very long chain fatty acids. This type of fatty acid abnormality has not been described in other pathological conditions and may well represent the unique biochemical abnormality that is directly related to the fundamental genetic defect underlying adrenoleukodystrophy.     

Different role of saturated and unsaturated fatty acids in beta-cell apoptosis

It is believed that free fatty acids contribute to the pathogenesis of type 2 diabetes in humans. We have recently shown that lipoapoptosis of human beta-cells is specifically induced by saturated fatty acids while unsaturated had no effect. In the present study we tested the effect of co-incubation of different saturated and unsaturated free fatty acids on lipoapoptosis in beta-cells. RIN1046-38 cells and isolated human beta-cells were incubated with combinations of saturated fatty acids (palmitate, stearate) and mono- or polyunsaturated fatty acids (palmitoleate, oleate, and linoleate). Cells were incubated for 24-72 h with 1mM fatty acids. All unsaturated fatty acids tested completely prevented palmitate- or stearate-induced apoptosis of rat and human beta-cells as assessed by flow cytometric cell cycle analysis and TUNEL assay. This might suggest that apoptosis in vivo is predominantly determined by the content of unsaturated fatty acids in a mixed fatty acid pool.     

Ticks collected on birds in the state of São Paulo,Brazil

The present study reports a collection of Amblyomma spp. ticks in birds from several areas of the state of São Paulo, Brazil. A total of 568 tick specimens (404 larvae, 164 nymphs) were collected from 261 bird specimens. From these ticks, 204 (36%) specimens (94 larvae, 110 nymphs) were reared to the adult stage, being identified as Amblyomma longirostre (94 larvae, 90 nymphs), Amblyomma calcaratum (13 nymphs), Amblyomma nodosum (2 nymphs), and Amblyomma cajennense (5 nymphs). Additionally, 39 larvae reared to the nymphal stage and 8 nymphs that died before reaching the adult stage were identified as A. longirostre according to peculiar characters inherent to the nymphal stage of this species: scutum elongate, and hypostome pointed. The remaining 271 larvae and 46 nymphs were identified as Amblyomma sp. Ticks were collected from 51 species of birds distributed in 22 bird families and 6 orders. The order Passeriformes constituted the vast majority of the records, comprising 253 (97%) out of the 261 infested birds. Subadults of A. longirostre were identified from 35 species of Passeriformes, comprising 11 families (Cardinalidae, Dendrocolaptidae, Fringillidae, Furnariidae, Parulidae, Pipridae, Thamnophilidae, Thraupidae, Turdidae, Tyrannidae, and Vireonidae), and from 1 species of a non-passerine bird, a puffbird (Bucconidae). Subadults of A. calcaratum were identified from 5 species of Passeriformes, comprising 5 families (Cardinalinae, Conopophagidae, Pipridae, Thamnophilidae and Turdidae). Subadults of A. nodosum were identified from 2 species of Passeriformes, comprising two bird families (Thamnophilidae and Pipridae). Subadults of A. cajennense were identified from 2 species of non-passerine birds, belonging to 2 different orders (Ciconiiformes: Threskiornithidae, and Gruiformes: Cariamidae). Birds were usually infested by few ticks (mean infestation of 2.2 ticks per bird; range: 1–16). Currently, 82 bird species are known to be infested by immature stages of A. longirostre, with the vast majority [74 (90%)] being Passeriformes. Our results showed that Passeriformes seems to be primary hosts for subadult stages of A. longirostre, A. calcaratum, and A. nodosum. However, arboreal passerine birds seem to be the most important hosts for A. longirostre whereas ground-feeding passerine birds seem to be the most important for both A. calcaratum and A. nodosum. In contrast, the parasitism of birds by subadults of A. cajennense has been restricted to non-passerine birds.     

Cholesteryl esters as a depot for very long chain fatty acids in human meibum

Human meibomian gland secretions (also known as meibum) were analyzed for the presence of cholesteryl esters (Chl-E) using HPLC in combination with atmospheric pressure chemical ionization mass spectrometry. A special procedure based on detection of the in-source generated ion m/z 369 was developed to monitor all Chl-E simultaneously. The structures of the detected compounds were studied using in-source and postsource fragmentation of the precursor (M+H)(+) ions. In concordance with previous studies, Chl-E were found in all of the tested samples and comprised approximately 31% of the entire lipid pool (w/w, dry weight). There were at least 20 different saturated and unsaturated Chl-E species observed, whose fatty acid residues ranged from C18 to C34. Monounsaturated fatty acids were the most visible components of the Chl-E pool. The eleven most prominent compounds were: C20:0-, C22:1-, C22:0-, C24:1-, C24:0, C25:0-, C26:1-, C26:0-, C28:1-, C28:0-, and C30:1-Chl-E. Other Chl-containing compounds were detected but not identified at the time. Therefore, Chl-E are a depot for very long chain saturated and monounsaturated fatty acids in human meibum.     

Regulation of leptin secretion from white adipocytes by free fatty acids

Norepinephrine stimulates lipolysis and concurrently inhibits insulin-stimulated leptin secretion from white adipocytes. To assess whether there is a cause-effect relationship between these two metabolic events, the effects of fatty acids were investigated in isolated rat adipocytes incubated in buffer containing low (0.1%) and high (4%) albumin concentrations. Palmitic acid (1 mM) mimicked the inhibitory effects of norepinephrine (1 microM) on insulin (10 nM)-stimulated leptin secretion, but only at low albumin concentrations. Studies investigating the effects of the chain length of saturated fatty acids [from butyric (C4) to stearic (C18) acids] revealed that only fatty acids with a chain length superior or equal to eight carbons effectively inhibited insulin-stimulated leptin secretion. Long-chain mono- and polyunsaturated fatty acids constitutively present in adipocyte triglyceride stores (oleic, linoleic, gamma-linolenic, palmitoleic, eicosapentanoic, and docosahexanoic acids) also completely suppressed leptin secretion. Saturated and unsaturated fatty acids inhibited insulin-stimulated leptin secretion with the same potency and without any significant effect on basal secretion. On the other hand, inhibitors of mitochondrial fatty acid oxidation (palmoxirate, 2-bromopalmitate, 2-bromocaproate) attenuated the stimulatory effects of insulin on leptin release without reversing the effects of fatty acids or norepinephrine, suggesting that fatty acids do not need to be oxidized by the mitochondria to inhibit leptin release. These results demonstrate that long-chain fatty acids mimic the effects of norepinephrine on leptin secretion and suggest that they may play a regulatory role as messengers between stimulation of lipolysis by norepinephrine and inhibition of leptin secretion.     

Effects of various non-esterified fatty acids on the transfer of cholesteryl esters from HDL to LDL induced by the cholesteryl ester transfer protein

The effects of saturated, monounsaturated and polyunsaturated non-esterified fatty acids on the rate of transfer of radiolabeled cholesteryl esters from high density lipoproteins (HDL) to low density lipoproteins (LDL), induced by the cholesteryl ester transfer protein (CETP), have been studied. Human high-density lipoproteins-subfraction 3 (HDL3) containing radiolabeled cholesteryl esters were incubated with LDL at 37 degrees C with or without CETP and in the absence or in the presence of non-esterified fatty acids. Less than 6% of the total radioactivity was recovered in the LDL fraction after incubation of HDL3, and LDL for 3 h at 37 degrees C in the absence of CETP, regardless of whether or not non-esterified fatty acids were added. The addition of CETP to the incubation mixture induced a time-dependent redistribution of radiolabeled cholesteryl esters from HDL3 to LDL. Non-esterified fatty acids were found to alter the rate of transfer of cholesteryl esters induced by CETP. While short chain saturated non-esterified fatty acids (caprylic and capric acids) had no effect on the rate of transfer of cholesteryl esters, the medium and long chain ones (lauric, myristic, palmitic and stearic acids) significantly increased the CETP-mediated transfers from HDL3 to LDL. At low concentrations, unsaturated fatty acids also stimulated the CETP-mediated redistribution of radiolabeled cholesteryl esters from HDL3 to LDL. As the concentration of either oleic, linoleic or arachidonic acids increased to higher levels, a significant proportion of fatty acids remained unassociated with lipoprotein particles. Under these circumstances the transfer process was inhibited. These results show that non-esterified fatty acids can modulate the CETP-mediated transfer of cholesteryl esters from HDL to LDL and that this effect is dependent on both the length and the degree of unsaturation of their monomeric carbon chain.     

角蜡蚧和日本龟蜡蚧蜡泌物的超微结构及化学成分分析

采用扫描电镜和气相色谱/质谱联用技术研究了角蜡Ceroplastes ceriferus (Fabricius) 和日本龟蜡蚧C. japonicus Green蜡泌物的超微结构及化学成分。结果表明,这2种蜡蚧分泌蜡质和形成蜡壳的过程基本相似。在1、2龄期分泌的蜡质为“干蜡”,蜡壳为星芒状,虫体周缘的蜡芒均为2大节,与其2个龄期发育相对应,每一个大节又分为若干小节。同时,虫体背面中央蜡质堆积成帽状,也分为均匀的多层。由此说明泌蜡过程具有节律性。虫体周缘与蜡芒对应的突起区上分布着密集的刻点状腺孔,每一个腺孔分泌1根蜡丝,这在以往玻片标本中是观察不到的。雌性第3龄幼虫和成虫期,虫体分泌“湿蜡”,形成龟背状蜡壳,泌蜡腺孔主要为三格腺和四格腺。在肛突区发现了密集的泌蜡腺孔,排列为纵条纹状。从角蜡蚧蜡泌物甲酯化处理样品中检测到14个组分,从直接测试 (未经甲酯化处理) 样品中检测到14个组分;而从日本龟蜡蚧则分别检测到10个组分和25个组分。它们的主要成分是一系列高级的长链饱和与不饱和的烃、脂肪酸、脂肪醇、酯类、醛类以及杂环、多环或大环状化合物。对它们可能的生物生态学功能进行了讨论。     

The nature of fatty acid modifies the equilibrium position in the esterification catalyzed by lipase

The equilibrium position in lipase mediated esterification of various fatty acids and butanol was studied. The influence of the chain length and the presence of unsaturations in the fatty acids on the equilibrium position was measured and predicted. To predict equilibrium position the program TREP extended (TREPEX) based on the UNIFAC group contribution method was used. Using an equilibrium constant of 35, calculated on the basis of thermodynamic activities, the equilibrium position between butanol and saturated and/or unsaturated fatty acids with different chain lengths can be predicted. The ester mole fraction at equilibrium increases with the fatty acid chain length, and for fatty acids with the same carbon number, the highest values are found for unsaturated fatty acids. For reaction systems containing two saturated fatty acids, a slightly higher mole fraction is obtained for the fatty acid with the higher chain length, while for mixtures consisting of saturated and unsaturated fatty acids, the mole fractions of the unsaturated esters are lower than those of the saturated ones, regardless the chain length of the fatty acid. These experimental results are in good agreement with the calculations with TREPEX.