The Effects of Insect Extracts and Some Insect-Derived Compounds on the Settling Behavior of Liposcelis bostrychophila

Extracts of whole booklice (Liposcelis bostrychophila)—sequentially extracted in hexane and aqueous 80% methanol (80%MeOH)—repel conspecifics. A methanol-soluble fraction (MFr) of the 80% methanol extract was more repellent than either its corresponding water fraction (WFr) or the hexane extract. The repellent effect of the MFr was repeatable across extracts prepared on different occasions over a 1 month period. Gas chromatography, mass-spectrometry (GC-MS) analyses showed that saturated (C₁₆; C₁₈) monoenoic (C_16:1; C_18:1) and a dienoic fatty acid (C_18:2) and the corresponding methyl esters of all but C_16:1 and C₁₈ constituted approximately 95% and 30%, of the detected compounds in the methanol fractions and the hexane extract, respectively. Qualitative thin layer chromatography showed that cholesterol was present in methanol fractions and the hexane extract, and also enabled tentative identification of triacylglycerols and phospholipids in the methanol fractions. Extracts of wheatgerm, dried skimmed milk powder, active yeast, and wholemeal flour—L. bostrychophila dietary components—were analyzed by GC-MS, and C₁₆, C_18:1 and C_18:2 were detected, indicating that C₁₈ and the methyl esters were not directly extractable and/or that they were products of booklice metabolism. A fatty acid amide (stearamide) previously identified in cuticular extracts of L. bostrychophila was not detected, and therefore was not responsible for the observed biological activity. Pure fatty acids and fatty acid methyl esters repelled settling of L. bostrychophila at 10 mM, with the exception of palmitic and stearic acids, indicating, among other things, a difference between the efficacy of saturated and unsaturated fatty acids. The effect of concentrations <10 mM was less significant, although palmiteoleic acid appeared to be attractive to L. bostrychophila at 0.1 mM. Fatty acids and fatty acid methyl esters were at a much lower concentration than 10 mM in the repellent methanol fractions, indicating that an interaction between known and as yet unidentified compounds is likely. The significance of fatty acids in relation to the biology and behavior of L. bostrychophila and their potential for use in traps and monitoring are discussed.     

Characterization of skin-surface lipids from the monkey (Macaca fascicularis)

Skin-surface lipids from the monkeyMacaca fascicularis are composed of sterol esters (38%), cholesterol (4%) and two types of wax diesters, identified as Type II (IIa and IIb, 17% and 40%, respectively). Type IIa contained diesters of 1,2-alkanediols esterified with two molecules of long-chain (C₁₄−C₃₄) fatty acids having straight and branched chains. In the diesters IIa, fatty acids shorter than C₁₉ predominated in position 1, and fatty acids longer than C₂₀ predominated in position 2. Type IIb contained diesters of 1,2-alkanediols esterified with C₄ and C₅ branched-chain fatty acids (predominantly isovaleric acid) at position 1 and long-chain (C₁₄−C₂₇) acids, having straight and branched chains, at position 2. The shortchain acids were converted to 2-nitrophenylhydrazides and analyzed by high-performance liquid chromatography (HPLC). Ammonia chemical ionization (CI)-gas chromatography (GC)-mass spectrometry (MS) resolved the intact diesters IIb into 12 peaks corresponding to molecular weights ranging from 597 to 748, and showed that the molecular species, such as C₂₁−C₁₆−C₅ (diol, fatty acid in position 2, fatty acid in position 1), C₂₂−C₁₆−C₅ and C₂₃−C₁₆−C₅, were prevalent. The fatty acids from both diesters were mostly (>98%) saturated. The 1,2-alkanediols from both diesters consisted of C₁₆−C₂₆ saturated straight- and branched-chain components. The acyl groups of sterol esters contained 86% C₁₄−C₃₄ branched-chain acids. The unsaturated fatty acids (5.4%) belonged to a straight-chain monoenoic series having extremely long chains (C₁₈−C₃₄). The branched-chain structures in the fatty acids and diols were iso and anteiso. These results show the species-specific profile for the skin-surface lipid synthesis.     

Some monomethyl-branched fatty acids from ruminant fats: Open-tubular GLC separations and indications of substitution on even-numbered carbon

Isomeric methyl esters of fatty acids in three groups (C₁₅, C₁₇, C₁₉) have been isolated from ruminant fats. Basic structural analysis by physiochemical techniques indicated that these odd-numbered fatty acids were even chain with a single methyl branch on the chain. High resolution open-tubular gas liquid chromatographic studies indicate that, with the exception of iso acid impurities in these fractions, only even-numbered carbons of the fatty acid chains bear the methyl branch.     

Additive effects of acyl-binding site mutations on the fatty acid selectivity of Rhizopus delemar lipase

The fatty acid specificity and pH dependence of triacylglycerol hydrolysis by the Rhizopus delemar lipase acylbinding site mutant Val206Thr+Phe95Asp (Val, valine; Thr, threonine; Phe, phenylalanine; Asp, aspartic acid) were characterized. The activity of the double mutant prolipase was reduced by as much as 10-fold, compared to the wild-type prolipase. However, the fatty acid specificity profile of the enzyme was markedly sharpened and was dependent on the pH of the substrate emulsion. At neutral pH, strong preference (10-fold or greater) for hydrolysis of triacylglycerols of medium-chainlength fatty acids (C_8:0 to C_14:0) was displayed by the variant prolipase, with no hydrolysis of triacylglycerols of short-chain fatty acids (C_4:0 to C_6:0) and little activity manifested toward fatty acids with 16 or more carbons. At acidic pH values, the fatty acid selectivity profile of the double mutant prolipase expanded to include short-chain triacylglycerols (C_4:0, C_6:0). When assayed against a triacylglycerol mixture of tributyrin, tricaprylin and triolein, the Val206Thr+Phe95Asp prolipase displayed a high selectivity for caprylic acid and released this fatty acid at least 25-fold more efficiently than the others present in the substrate mixture. When presented a mixture of nine fatty acid methyl esters, the wild-type prolipase showed a broad substrate specificity profile, hydrolyzing the various methyl esters to a similar extent. Contrastingly, the double mutant prolipase displayed a narrowed substrate specificity profile, hydrolyzing caprylic methyl ester at nearly wild-type levels, while its activity against the other methyl esters examined was 2.5- to 5-fold lower then that observed for the wild-type enzyme.     

Fatty acids of bovine milk glycolipids and phospholipids and their specific distribution in the diacylglycerophospholipids

Milk lipids were fractionated by silicic acid column chromatography and preparative thinlayer chromatography (TLC). Ceramide monohexoside (CMH), ceramide dihexoside (CDH), phosphatidyl ethanolamine (PE), phosphatidyl choline (PC), phosphatidyl serine (PS), and sphingomyelin (Sph) were isolated, and the purity of each was checked by infrared spectroscopy and TLC. The diacylphospholipids were hydrolyzed with phospholipase A and the products separated by TLC. Fatty acid methyl esters were prepared from the various fractions and analyzed by gas chromatography. The glycolipids, CMH and CDH, and Sph contained large amounts of long-chain saturated fatty acids, especially C_22:0, C_23:0, and C_24:0, PE, PS, and PC contained C₁₀-C₂₂ normal and branched-chain saturated fatty acids, and C₁₅-C₂₀ unsaturated fatty acids (mainly monoenes). The distributions of saturated acids between the α′- and β-positions were respectively: PE, 46 and 11%; PS, 65 and 19%; and PC, 72 and 53%. PC was exceptional in that there was 10.8% myristic acid in the β-position and only 5.6% in the α′-position. PE and PS were similar in composition except that in PE oleic acid was evenly distributed, and in PS was largely in the β-position. In general, PC was much more saturated than PE or PS, and there was no overall pattern governing the specific distribution of the fatty acids in the three diacylphospholipids. Comparison with PC from other bovine tissues and from egg lecithin showed that fatty acids are located much less specifically in milk phospholipids than in PC from other sources. Presented at the AOCS Meeting, Houston, Texas, April, 1965.     

The structures of the branched fatty acids in the wax esters of vernix caseosa

By combined gas liquid chromatography-mass spectrometry a series of monomethyl branched fatty acids was found in the fatty acid moiety of the wax esters of vernix caseosa. The methyl branch occurred on the even C-atoms of chains ranging from C₁₁ to C₁₇ (some 43 compounds in all). Except for the iso acids and possibly some of the anteiso acids, these could be formed by replacement of malonyl CoA with a molecule of methyl malonyl CoA at the point of the branch. Smaller amounts of fatty acids also were found with two methyl branches occurring on the even C-atoms of chains ranging from C₉ to C₁₅.     

Fractional vacuum distillation of herring oil methyl esters

Methyl esters of a Canadian Atlantic herring oil containing 62% monoethylenic fatty acids were subjected to batch fractional distillation under vacuum on a pilot plant scale, to study the feasibility of fractionating fatty acid esters of marine oils of low iodine value into monounsaturated fractions with increased commercial value for industrial chemical uses. A total of 64 methyl ester fractions were collected and analyzed by gas liquid chromatography. Recoveries of the major saturated and monounsaturated acids were close to 100%, and some fractions contained over 90% of the desired 22:1 long chain monounsaturated acids. The short chain polyunsaturated acids were recovered in good yields, but the long chain highly unsaturated acids were recovered in yields of 60% or less due to oxidative and thermal decomposition in the particular apparatus employed. If small amounts of unsaturated acids are acceptable, fractional distillation of low iodine value marine oils could inexpensively supply fractions with high concentrations of methyl esters of longer chain (C₂₀ and C₂₂) monounsaturated and shorter chain (C₁₄) saturated acid or (C₁₆) saturated-monounsaturated acid mixture.     

Synthesis and Surface Active Properties of Sulfonated Acrylate Esters Based on Al‐Cedre Oil

Sulfonated acrylate esters have been synthesized by using renewable raw materials such as fatty alcohols of Al‐Ceder oil. Mixed fatty acids were isolated from Al‐Ceder oil by hydrolysis; both saturated and unsaturated fatty acids were isolated from the mixed fatty acids. The methyl esters of mixed fatty acid, saturated and unsaturated acids of Al‐Cedre oil were subjected to reduction with (LiAlH4) to give the corresponding fatty alcohols. The products of the reduction process were saponified and the hydroxyl values were estimated to further confirm the reduction occurrence. The acrylate esters were synthesized by esterification of acrylic acid with fatty alcohols of C_16:0, C_18:0, C_18:1, and C_18:2 mixed saturated, mixed unsaturated and mixed fatty acids of Al‐Cedre oil, respectively. This esterification was followed by addition of NaHSO₃ to form bisulfite adducts. The structures of the prepared surfactants were characterized by IR and ¹HNMR spectroscopy. A series of useful surface parameters, stability towards acids and base hydrolysis and calcium stability have been determined.     

Biochemical and physiological studies of certain ticks (Ixodoidea): Isolation and partial identification of a new fatty acid in eggs ofDermacentor andersoni Stiles (Ixodidae)

Gas liquid chromatographic analysis of the fatty acid methyl esters from eggs ofDermacentor andersoni Stiles (Ixodidae) revealed the presence of significant quantities (15% total fatty acids) of an unidentified component with a retention time between C_18∶3−C_22∶0 fatty acids. Smaller amounts of the unidentified component (ca. 5% total fatty acid) also were detected in host rabbit serum. Purified, the unidentified component's methyl ester collected from the tick eggs by preparative gas liquid chromatography was partially identified and characterized by chemical and spectroscopic analyses. The evidence suggests that the unidentified component is a methyl branched C₁₅ tricarboxylic acid containing two vicinal carboxylic acid groups. Biosynthesis of the unidentified component by the tick is under investigation.     

Cyclic fatty acid monomer formation in frying fats. I. Determination and structural study

The formation of monomeric cyclic fatty acids was studied in a model system in which partially hydrogenated soybean oil (PHSO) was heated intermittently for 80 hr of simulated deep fat frying. Oil samples (fresh and heated) and their methyl esters were fractionated according to their molecular size using gel permeation chromatography (GPC). Oils and GPC fractions were analyzed for cyclic monomers by the following steps: (i) preparation of fatty acid methyl esters (FAME); (ii) microhydrogenation of FAME; (iii) urea fractionation of hydrogenated FAME; (iv) analysis by capillary gas liquid chromatography (GLC), and (v) structural characterization of cyclic monomer peaks by mass spectrometry (GC-MS). Under simulated frying conditions the concentration of cyclic monomers increased from 736 ppm (0.07%) in fresh oil to 1803 ppm (0.18%) in heated oil. GC-MS with capillary columns allowed the identification of several C₁₈ α-disubstituted cyclohexane and cyclopentane isomers as hydrogenated methyl esters. Other noncyclic and contaminant compounds eluting within the expected GLC retention range of cyclic monomers also were identified in all the samples and GPC fractions.     

Fatty acids,fatty alcohols,wax esters,and methyl esters fromCrambe abyssinica andLunaria annua seed oils

Crambe abyssinica andLunaria annua, members of the Cruciferae family, have seed oil glycerides containing ca. 55–65% of C₂₂ and C₂₄ unsaturated fatty acids. Fatty acids were prepared by saponification; fatty alcohols, by sodium reduction of glycerides; liquid wax esters, byp-toluenesulfonic acid-catalyzed reaction of fatty acids with fatty alcohols; and methyl esters, by reaction of fatty acids with diazomethane. Solid hydrogenated glyceride oils and wax esters were compared with several commercial waxes. Chemical and physical constants were determined for the seed oils and their derivatives. Position of unsaturation in theCrambe fatty acids was determined by gas chromatographic analysis of the permanganate-periodate degradation products. The major dicarboxylic acid was brassylic (C₁₃), proving the docosenoic acid to be erucic. Presented in part at the AOCS meeting in New Orleans, La., 1962. A laboratory of the No. Utiliz. Res. & Dev. Div., ARS, U.S.D.A.     

Übergangsmetallkatalysierte Oxidationen ungesättigter Fettsäuren — Synthesen von Keto- und Dicarbonsäuren

Transition-metal Catalyzed Oxidation of Unsaturated Fatty Acids — Synthesis of Ketocarboxylic Acids and Dicarboxylic Acids Terminal unsaturated C₁₀–C₁₄-fatty acid methylesters (9-decenoic-, 10-un-decenoic-, 13-tetradecenoic methylesters) were converted to methylketocarboxylic methylesters (yields: 60–75%, isolated) by oxidation with O₂/H₂O at roomtemperature under catalysis of PdCl₂/CuCl₂. Using RhCl₃/FeCl₃ at 80°C yields of 40–60% were obtained. For the first time methyl oleate was converted directly to a mixture of 9-oxo- and 10-oxo-stearic acid methylester by palladium catalyzed oxidation. In DMF/H₂O the selectivity to these two ketoesters was 85% (15% isomers), in dioxane/H₂O the selectivity droped to 55% while the yield of the oxostearic acid esters climbed to 70%. The Mn-catalyzed oxidative cleavage of methylketocarboxylic acid esters with O₂ at 115°C led in each case to a mixture of two dicarboxylic acid esters in a molar ratio of 2 : 1. Starting with 9-oxodecanoic acid azelaic and suberic acid were obtained at a conversion rate of 90%. Analogous 10-oxoundecanoic acid led to C₁₀/C₉- and 13-oxotetradecanoic acid led to C₁₃/C₁₂-dicarboxylic acids. The oxidative cleavage of 9-/10-oxostearic acid methylester yielded mixtures of C₈–C₁₀-monocarboxylic acids and methylesters of C₈–C₁₀-dicarboxylic acids.     

Quantitation of fatty acids from flue-cured tobacco by combined preparative thin layer chromatography-gas chromatography

Flue-cured tobacco was subjected to alkaline hydrolysis, and, after acidification, the fatty acids and nonsaponifiables were extracted into hexane. Treatment of the hexane extract with diazomethane yielded fatty acid methyl esters. The methyl esters were separated from interfering hydrocarbons and sterols by preparative thin layer chromatography (PTLC). After addition of an internal standard, the esters were quantitated by gas chromatography on the column packing, Silar 10C. Quantitation of the C₁₄-C₃₂ fatty acid esters was possible by means of temperature programming.     

θ3 fatty acids in freshwater fish from south brazil

Lipid and fatty acid levels in the edible flesh of 17 freshwater fish from Brazil’s southern region were determined. Analyses of fatty acid methyl esters were performed by gas chromatography. Palmitic acid (C_16:0) was the predominant saturated fatty acid, accounting for 50–70% of total saturated acids. Oleic acid (C_18:1θ9) was the most abundant monounsaturated fatty acid. Linoleic acid (C_18:2θ6), linolenic acid (C_18:3θ3), and docosahexaenoic acid (C_22:6θ3) were the predominant polyunsaturated fatty acids (PUFA). The data revealed that species such as truta, barbado, and corvina were good sources of eicosapentaenoic acid (C_20:5θ3) and docosahexaenoic acid (C_22:6θ3), and that most freshwater fish examined were good sources of PUFA θ3.     

The fatty acids of menhaden oil

Summary The methyl esters of a specimen of menhaden oil have been fractionated in an efficient still. The C₁₂, C₁₄, C₁₆, and C₁₈ main fractions have been studied, mainly by low temperature crystallization procedures. The oil has been shown to contain traces of lauric and dodecenoic acids. The C₁₄ acids are made up of 2.2% tetradecenoic acid and 97.8% of myristic; based on the whole ester composition of Table I, these values amount to 0.1 and 6.8%, respectively. The C₁₆ acids are palmitic, 50.9%; hexadecenoic, 46.6%; and hexadecatrienoic (including a small amount of tetrenoic acid) 2.5%, or based on the whole esters, 15.5, 14.1 and 0.8%, respectively. A very rough calculation of the composition of the C₁₈ fraction gives the following reults, values based on the whole esters being included in parenthesis: stearic, 11.5 (3.1); octadecenoic, 58.6 (15.7); octadecadienoic, 13.4 (3.6); octadecatrienoic, 7.2 (1.9); and octadecatetrenoic, 9.3% (2.5%). In the course of this investigation the following acids and their methyl esters were isolated from the oil by crystallization procedures; myristic, tetradecenoic (80%), palmitic, hexadecenoic, stearic, and oleic. Evidence was presented that the octadecenoic acids of this oil were a mixture of oleic acid with isomeric acids of this series, a finding which is in agreement with a recent report from this laboratory (11), describing the multiple nature of the octadecenoic acids of a number of animal fats. Presented in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Graduate School.     

The composition of furan fatty acids in the crayfish

Capillary gas chromatography-mass spectrometry (GC-MS) analysis of the sterol ester fatty acid methyl esters of the crayfish hepatopancreas revealed the presence of at least 30 kinds of unusual furan fatty acids (F acids), which accounted for 28.49% of the total sterol ester fatty acids. On the other hand, only small amounts were found in triacylglycerols (0.5%) and phospholipids (0.7%). Among the F acids, 17 acids were the hitherto unknown ones, the major component being 12,15-epoxy-13,14-dimethyleicosa-12,14-dienoic acid (F₆) (41.83% of the total F acids). These novel acids possessed chain lengths of C₁₂ to C₂₂, with the largest concentration at C₂₀ (45.38%), C₁₈ (41.97%) and C₁₆ (10.35%). Odd-numbered F acids also were found, though in a very small amount (0.4%). In the living things other than the crayfish, the longest chain F acid (C₂₄) was detected in the sterol ester of the carp hepatopancreas. The bullfrog, an amphibian, and the turtle, a reptilian, were found to have F acids as well in their livers. Olefinic furan fatty acids, which were detected by GC-MS, were found to have resulted during the analytical process from cyclodehydration of the diketo-ene formed by autoxidation of the F acids.     

Direct determination of saturated fatty acids in fats,oils, and methyl esters

Summary A direct gravimetric method has been developed for the determination of saturated fatty acids in fats, oils, and methyl esters. The procedure involves methanolysis of the triglycerides to produce methyl esters, followed by oxidation of the unsaturated methyl esters by potassium permanganate. The undesired, acidic oxidation products are removed by alkaline washing and the saturated methyl esters thus isolated are weighed directly. The method is intended for the determination of saturated fatty acids having C₁₆ or longer carbon chains. Small quantities of C₁₄ saturated acids will be included in the determination if present with other higher saturated acids. The method is applicable to both natural and hydrogenated vegetable oils. It is not applicable to oils containing large amounts of C₁₄ and lower saturated acids. Concentrations of saturated acids ranging from 3 to 90% in known glyceride mixtures and from 0.3 to 95% in mixtures of methyl esters were determined with an average difference from the calculated value of 0.8%. Replicate determinations on samples in the 10 to 30% saturates range gave a standard deviation of 0.3 to 0.4%. Presented at the spring meeting, American Oil Chemists’ Society, New Orleans, La., April 28 to May 1, 1957     

Jojoba oil wax esters and derived fatty acids and alcohols: Gas chromatographic analyses

HCl-catalyzed ethanolysis followed by saponification readily surmounts the resistance of long chain wax esters to direct hydrolysis by alkali. Additionally, choosing ethyl instead of methyl esters allows baseline separations between long-chain alcohols and corresponding esters in gas liquid chromatographic (GLC) analysis of total alcohol and acid components before saponification. Liquid wax esters were analyzed on a temperature-programmed 3% OV-1 silicone column. Geographical and genetic effects on the variability of jojoba oil composition were investigated with five different seed samples. Major constituents in jojoba seed oil from shrubs in the Arizona deserts, as indicated by GLC analyses of oil, ethanolysis product, isolated fatty alcohols and methyl esters of isolated fatty acids, were C₄₀ wax ester 30%, C₄₂ wax ester 50% and C₄₄ wax ester 10%; octadecenoic acid 6%; eicosenoic acid 35%, docosenoic acid 7%, eicosenol 22%, docosenol 21% and tetracosenol 4%. Oil from smaller leaved prostrate plants growing along California’s oceanside showed a slight tendency toward higher molecular size than oils from the California desert and Arizona specimens. The wax esters are made up of a dispro-portionately large amount of docosenyl eicosenoate and are not a random combination of constituent acids and alcohols.Lunaria annua synthetic wax ester oil was used as a model for evaluating the analytical procedures. Presented at the AOCS Meeting, Chicago, September 1970 No. Utiliz, Res. Dev. Div., ARS, USDA.     

Stereospecific hydration of unsaturated fatty acids by bacteria

Three new 10-hydroxy fatty acids, all optically active, have been prepared by the anaerobic microbiological hydration of acis-9 double bond. Substrates that formed these new hydroxy fatty acids are linoleic, linolenic, and ricinoleic acids. The hydroxyl group has the D configuration and the methyl esters are levorotatory. Infrared, mass spectral, specific rotation and ultraviolet data on these compounds were determined. There was no migration of the unreated double bonds at C₁₂ and C₁₅ in linoleic or linolenic acids. The presence of a double bond in the 10-hydroxy fatty acids significantly increased the optical rotation of the methyl esters. The hydratase enzyme showed unusual specificity among Δ⁹ unsaturated acids. While it hydrates methylene interrupted and hydroxy unsaturated acids, it failed to hydrate either 9-decenoic, 12,13-epoxy- or 12-keto-cis-9-octadecenoic acids or sterculic acid. Presented at the AOCS Meeting, San Francisco, April 1969. No. Marketing and Nutrition Res. Div., ARS, USDA.     

Fatty Acid Composition in Ergosteryl Esters and Triglycerides from the Fungus Ganoderma lucidum

Free and esterified ergosterols are detected almost solely in fungi and are often employed as a biomarker of living fungi. In this work, the fatty acid composition and δ¹³C values of major fatty acids in triglycerides and ergosteryl esters from the fungus Ganoderma lucidum were analyzed by gas chromatography–mass spectrometer and gas chromatography–isotopic ratio mass spectrometer, respectively. The results showed that the fatty acid profiles varied in triglycerides and ergosteryl esters. The percentage of saturated fatty acids in ergosteryl esters was remarkably higher than that in triglycerides, where C_18:1^Δ9c was the predominant fatty acid and constituted 61.26 % of the total fatty acids. In contrast, C_16:0 was the predominant fatty acid and constituted 71.88 % of the total fatty acids in ergosteryl esters. The study suggests that, after fungal death, free ergosterols in the cell membrane of the dead fungus were esterified with preferentially saturated fatty acids, mainly C_16:0, from triglycerides and then stored in lipid particles for a longer period while free ergosterol markedly decreased. The δ¹³C values of C_16:0, C_18:0, C_18:1 and C_18:2 in ergosteryl esters exhibit a pronounced depletion in ¹³C compared with that in triglycerides within the range of ?1.3 to ?0.9 ‰, supporting the above inference. It is again suggested that free ergosterol in the cell membrane should be used as an indicator of living fungi, and ergosteryl esters in the lipid particles should not be included in the measurement of living fungal biomass.