Cuticular lipids of insects: V. Cuticular wax esters of secondary alcohols from the grasshoppersMelanoplus packardii andMelanoplus sanguinipes

Wax esters of secondary alcohols constitute 18–20% of the cuticular lipid extract ofMelanoplus packardii and 26–31% of the cuticular lipids ofMelanoplus sanguinipes. The total number of carbons in the wax esters range from 37–54 with 41 predominating in both species. The fatty acids ofM. packardii wax esters are 16∶0, 18∶0, 14∶0, 20∶0 and 12∶0 in decreasing quantity. The fatty acids ofM. sanguinipes wax esters are 18∶0, 20∶0, 16∶0 22∶0, 14∶0, 19∶0 and 17∶0 in decreasing quantity. The secondary alcohols from the wax esters ofM. packardii are C₂₅, C₂₃ and C₂₇ in decreasing quantity, and the secondary alcohols of theM. sanguinipes are C₂₃, C₂₅, C₂₁, C₂₇, C₂₄, C₂₂ and C₂₆ in decreasing quantity. Each secondary alcohol consists of two to four isomers with the hydroxyl group located near the center of the chain. Montana Agriculture Experiment Station, Journal Series No. 332.     

Leaf wax of oats

Leaf wax of oats (Kelsey variety) consists of hydrocarbons (5%), esters (10%), free alcohols (45%), free acids (2.5%), β-diketone (5.5%), hydroxy-β-diketones (2.5%), and unidentified (29%). Wax on leaf blades contains more free alcohols than wax on leaf sheaths, and wax on the flag leaf sheath contains more β-diketone than wax on the rest of the plant. Principal hydrocarbons are C₂₉, C₃₁, and C₃₃. The esters, mainly C₄₄–C₄₈ and C₅₂, are probably C₁₈–C₂₂ and C₂₆ esters of hexacosanol. Free alcohols are almost entirely hexacosanol. The β-diketone is hentriacontane-14, 16-dione. Hydroxy β-diketones are a mixture of 5-, 6- and 7-hydroxyhentriacontane-14, 16-diones in the proportions 58∶35∶7. The wax also contains a small amount (0.5%) of 1,16-hexacosanediol. IRCC No. 13472.     

Properties, composition, and analysis of grain sorghum wax

Grain sorghum wax has been judged to be a potential source of natural wax with properties similar to carnauba wax. Approximately 0.16–0.3% (w/w) wax can be extracted from grain sorghum depending on the efficiency of the organic solvents. Although the melting points of carnauba wax and sorghum wax are similar, i.e., 78–86 and 77–85°C, respectively, they differ in acid values, i.e., 2–10 and 10–16, respectively, and saponification numbers, i.e., 77–95 and 16–49, respectively. Improved knowledge of the properties, composition, and analysis of grain sorghum wax would assist in efforts for industrial application of this product. Major components of sorghum wax are hydrocarbons, wax esters, aldehydes, free fatty alcohols, and FFA. The hydrocarbons consist mainly of C₂₇ and C₂₉, and the aldehydes, alcohols, and acids are mainly C₂₈ and C₃₀. The wax esters are mostly esters of C₂₈ and C₃₀ alcohols and acids.     

Mass spectrometric analysis of the fatty acids and nonsaponifiable lipids ofEimeria tenella oocysts

The fatty acids and nonsaponifiable lipids ofEimeria tenella oocysts were analyzed by gas liquid chromatography and combined gas liquid chromatographymass spectrometry. The fatty acids detected were identified as C_14∶0, C_16∶0, C_16∶1, C_18∶0, C_18∶1, and C_18∶2. Though the wt of the fatty acid fraction decreased during sporulation from 91 μg per 10⁶ oocysts to 47 μg per 10⁶ oocysts, the relative amounts of these fatty acids did not change appreciably. The nonsaponifiable lipids ofE. tenella consisted of cholesterol and unbranched primary alcohols of 22, 24, 26, 28, 30, and 32 carbons. Mass fragmentography demonstrated that each species of alcohol consisted of saturated and monounsaturated derivatives. Trimethylsilyl ethers of fatty alcohols were found to offer several important advantages over free alcohols for mass spectrometric characterization. Before sporulation, most fatty alcohols were in the oocyst wall. During sporulation, the wt of the nonsaponifiable lipids increased from 16 μg per 10⁶ oocysts of 44 μg per 10⁶ oocysts due largely to synthesis of C₂₄ and C₂₆ alcohols. The newly synthesized fatty alcohols were not deposited in the oocyst wall.     

The effect of a fat free diet on esterified monoenoic fatty acid isomers in rat tissues

Rats were maintained 120–140 days on a normal diet (group 1) or one deficient in fatty acids (group 2). Isomer composition was determined of monoenoic fatty acids (16∶1, 18∶1) isolated from total lipids of heart, kidney, lung, brain and lumbar fat, and from separated neutral lipids and phospholipids of heart and kidney. Group 1: The number of major isomers of C_16∶1 and C_18∶1 was similar in all tissues but their proportions varied in different tissues and types of lipid. Group 2: The proportions of 16∶1(n−7) increased and of other 16∶1 isomers decreased in all tissues; 18∶1(n−9) was increased at the expense of (n−7) in heart, to a lesser extent in kidney, and was little changed in lung, lumbar fat, or brain. The decrease in proportion of 18∶1(n−7) was greatest in heart-muscle phospholipids. C_20∶3 comprised 95% (n−9) and 5% (n−7) in heart and kidney lipids. The changes in group 2 probably represent the body’s attempts to maintain lipids with the physical and chemical properties necessary to normal biological function. Nomenclature of fatty acids as in IUPAC-IUB Commission on Biochemical Nomenclature, “The nomenclature of lipids,” J. Biol. Chem. 242:4845–49 (1967).     

Gas-chromatographic analysis of the aliphatic fractions of brown coal wax

The individual composition of the fractions of wax isolated from brown coal from the Sergeevskoe deposit was studied using gas chromatography. It was found that the aliphatic constituents of wax are C₁₄–C₄₂ n-alkanes with high coefficients of oddness, C₁₄–C₃₀ saturated alcohols, C₁₄–C₃₆ higher fatty acids, and esters. The contribution of unsaturated compounds was found. The structure and formation conditions of coal are considered.     

Volatile compounds produced by irradiation of butterfat

Anhydrous butterfat was irradiated at 6 megarads in a special glass reaction flask, and the headspace and total condensate samples were examined by wide-range (−180C to 125C) gas chromatography combined with mass spectrometry. The nature and amounts of volatile compounds were not greatly influenced by whether the butterfat was irradiated under oxygen or under vacuum, nor (apart fromn-alkanoic acids) by storage for 1 and 9 weeks. Carbon dioxide was produced in greatest amount. Of the remaining compounds, aliphatic hydrocarbons predominated both in number and amount. Aliphatic oxygenated compounds including carbonyl compounds were isolated in relatively small amounts. The following compounds were identified positively: C_1–13 n-alkanes; C_4–9 2-methylalkanes; C_2–14 alk-l-enes; C_2–9 alk-l-ynes; C_2–5 n-alkanoic acids; C_1–5 n-alkan-l-ols and propan-2-ol; C_2–8 n-alkanals and 2-methylbut-2-enal; C_3–5,7 alkan-2-ones; C_1–4 n-alkyl formates, vinyl and isoamyl formate, methyl acetate and methyln-hexanoate; and carbon dioxide. Visiting Scientist from Division of Dairy Research, C.S.I.R.O., Highett, Victoria, Australia.     

The high content of monoene fatty acids in the lipids of some midwater fishes: Family myctophidae

The total lipids of eleven species of Myctophids caught at depths between 20 and 700 m in the northern Pacific Ocean were analyzed using silicic acid column chromatography (lipid classes) and capillary gas chromatography (fatty acid and fatty alcohol composition). The major components in the lipid classes were triacylglycerols or wax esters; triacylglycerols were the dominant acyl neutral lipids (68.1–96.1%) in eight species, and wax esters were found as the dominant lipid (85.5–87.9%) in three species. The major fatty acids and alcohols contained in the was esters of the three fishes were 18:1n–9, 20:1n–9, 20:1n–11, and 22:1n–11 for fatty acids, and 16:0, 18:1, 20:1, and 22:1 for fatty alcohols. Fatty acids in the triacylglycerols ranging from C₁₄ to C₂₂ were predominantly of even chain length. The major components were 16:0, 16:1n–7, 18:1n–9, 20:1n–11, 22:1n–11, 20:5n–3 (icosapentaenoic acid), and 22:6n–3 (docosahexaenoic acid). In both the triacylglycerols and the wax esters, the major fatty components were monoenoic acids and alcohols. It is suggested from the lipid chemistry of the Myctophids that they may prey on the same organisms as the certain pelagic fishes such as saury and herring, because the large quantities of monoenoic fatty acids are similar to those of saury, herring, and sprats whose lipids originate from their prey organisms such as zooplanktons which are rich in monoenoic wax esters.     

Distinctive medium chain wax esters,triglycerides, and diacyl glyceryl ethers in the head fats of the pacific beaked whale,Berardius bairdi

Lipids were extracted from the mandibular fat body (jaw), the fatty forehead (melon), and the dorsal blubber of a Pacific beaked whale (Berardius bairdi) and separated into lipid classes by preparative thin layer chromatography. The head fats were mixtures of wax esters and triglycerides with a very small amount of diacyl glyceryl ether. The blubber fat contained 97% was ester and 3% triglyceride. Gas liquid chromatography (GLC) of the intact lipid classes indicated an unusually low C₂₆–C₃₀ range for most of the jaw and melon wax esters compared to the more normal C₃₂–C₄₀ molecules found in the blubber. Distinctive lower molecular weight C₂₄–C₄₀ triglycerides occurred in the head fats vs. the usual C₄₄–C₅₈ range in the blubber. Most diacyl glyceryl ethers were in the C₃₅–C₄₆ range, below the molecular weight of hexadecyldipalmitoyl glyceryl ether (C₄₈). GLC of the derived fatty acid methyl esters showed that the lower molecular weight neutral lipids in the head fats were due to high levels of iso-10∶0, n−10∶0, iso-11∶0, iso-12∶0, n−12∶0, and iso-13∶0 acids. The wax ester fatty alcohols and the alkoxy chains of the glyceryl ethers were mostly the C₁₄–C₂₀ chain lengths commonly observed in marine organisms. The distinctive medium chain neutral lipids in the jaw and melon fats of this whale may be related to the postulated acoustical role of these tissues in echolocation.     

Sperm oil replacements from selectively hydrogenated soybean and linseed esters: Special lubricants

Soybean and linseed oils were selectively hydroenated with copper-on-silica gel catalyst. The linolenate content of the oils was reduced to diene and monoene with no appreciable increase in saturates. Hydrogenated soybean oils contained 68–76% monoene, 11–18% diene, 0% conjugated diene and triene, 1–6% conjugatable diene, 0–0.3% conjugatable triene, and 23–40% isolatedtrans double bonds. Hydrogenated linseed oils contained 44–54% monoene, 35–45% diene, 0% conjugated diene and triene, 0–7% conjugatable diene, 0–02% conjugatable triene, and 44–59% isoaltedtrans double bonds. Esters of fatty acids, derived from these selectively hydrogenated oils, were prepared with trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, ethylene glycol, C₁₈ saturated cyclic alcohols, primary C₁₂–C₁₈ saturated (nC₁₂, nC₁₄, nC₁₆, nC₁₈) alcohol, and primary C₁₆–C₁₈ saturated (nC₁₆, nC₁₈) alcohol blends. Measurements of viscosities and of smoke, flash, and fire points indicate that these esters are possible replacements for sperm oil. Certain of them, after sulfurization, also have potential as extreme pressure lubricant additives. Presented at the AOCS meeting in Philadelphia, September 1974.     

Occurrence of wax esters and 1-O-alkyl-2,3-diacylglycerols in goat epididymal sperm plasma membrane

Two unusual lipid classes were detected by thin-layer chromatography in the neutral lipids derived from goat cauda-epididymal sperm plasma membrane. The lipids were identified as wax esters and 1-O-alkyl-2,3-diacylglycerols based on chromatographic properties, identity of their hydrolysis products, and infrared/¹H nuclear magnetic resonance spectral evidence. The membrane containedca. 3 and 5 μg/mg protein of wax esters and alkyldiacylglycerols, respectively. The relative proportions of wax esters and alkyldiacylglycerols in the total neutral lipids were 1.5% and 2.4%, respectively. The lipids contained fatty acids with chain lengths of C₁₄ to C₂₂. The major fatty acids of the wax esters were 14∶0, 16∶0, 16∶1ω7, 18∶0 and 18∶1ω9. The fatty acids in alkyldiacylglycerol were 16∶0, 18∶0, 22∶5ω3 and 22∶6ω3. Alkyldiacylglycerol was particularly rich in docosahexaenoic acid 22∶6ω3) representing 30% of the total fatty acids. The alcohols of wax ester were all saturated with C₂₀–C₂₉ carbon chains. The deacylated products derived from alkyldiacylglycerols were identified as hexadecyl, octadecyl and octadec-9′-enyl glycerol ethers.     

Volatile compounds produced by copper-catalyzed oxidation of butterfat

Anhydrous butterfat treated with copper and stored under vacuum at 38C in the dark for 9 weeks yielded the C_5–8 n-alkanes, acetic acid and the C_4,5,7,9 alkan-2-ones. The same butterfat stored under oxygen for 1 week yielded the C_1,2,3,5-7 n-alkanes, the C_2,4–6,8 alk-l-enes, the C_7,8 alk-l-ynes, the C_2–6 n-alkanoic acids, ethanol, the C_2–7 n-alkanals, 3-methylbutanal and 4-methylpentanal, the C_1–4 n-alkyl formates, ethyl acetate and propionate,n-propyl acetate and propionate, and butanone. Both treatments yielded carbon dioxide. All samples including those not treated with copper yielded butane-2,3-dione. Visiting Scientist from Division of Dairy Research, C.S.I.R.O., Highett, Victoria, Australia.     

Lipase-catalyzed synthesis of hydroxy stearates and their properties

Hydroxy fatty acid (HFA) esters of long-chain alcohols, such as hydroxy stearates, have potential applications from lubricants to cosmetics. These esters were synthesized enzymatically to overcome the problems associated with chemical processes. An immobilized lipase, Rhizomucor miehei, was employed as catalyst in the esterification reaction between hydroxy-stearic acid as a source of HFA and monohydric fatty alcohols (C₈–C₁₈). The yields of esters were in the range of 82–90% by conducting the reactions at 65±2°C, 2–5 mm Hg pressure, and 10% lipase concentration. The products were analyzed by infrared spectroscopy, and some of their analytical characteristics were determined.     

Correlation of heats of combustion with empirical formulas for fatty alcohols

Gross heats of combustion (Hg) for the homologous series of saturated fatty alcohols C₁₀–C₂₂ were measured in a Parr adiabatic calorimeter according to ASTM D240 and D2015. The measured values for these alcohols ranged from 1582 to 3453 kg-cal/mole. We developed equations that related carbon number (CN) or chain length, electron number (EN) or number of valence electrons and molecular weight (MW) to calculated Hg by linear regression analysis (LINREG). These equations are: Hg=26.00+155.60 CN; Hg=26.00+25.94 EN; and Hg=−172.2+11.00 MW. R squared values for all three equations were 0.99. The results obtained with LINREG were compared to a literature method. Comparisons were made for both the fatty alcohols above and C₁–C₅, C₇, C₈ and C₁₆ alcohols of the literature method. For the former alcohols there was no difference in accuracy or precision between the two methods. For the latter alcohols LINREG was both more accurate and precise. Measured Hg vs. chain length for C₁–C₂₂ alcohols showed a perfect linear relationship. Thus, knowing chain length, Hg can be predicted accurately for alcohols in this range. Presented in part at the AOCS meeting in New Orleans, LA, in May 1987.     

Leaf wax ofPortulaca oleracea

Wax coating the leaves and stems ofPortulaca oleracea consists of hydrocarbons (21%), esters (53%), acids (2%), alcohols (4%), diol monoesters (2%), and unidentified material (15%). Lesser amounts of esterified and free β-amyrin and lupeol, stigmast-4-en-3-one and free diols also are present. The principal component of the hydrocarbons is C₃₃. The C₄₀-C₅₆ esters are C₂₂-C₂₈ alcohol esters of C₂₀-C₂₆ acids; free alcohols are C₂₂-C₃₀; free acids are C₁₆-C₃₆; diols of diol monoesters and free diols are C₂₀-C₂₆. Presented at the AOCS Meeting, Ottawa, September 1972. NRCC No. 14037.     

Effects of hydrocarbon structure on fatty acid,fatty alcohol,and β-hydroxy acid composition in the hydrocarbon-degrading bacterium <Emphasis Type="Italic">Marinobacter hydrocarbonoclasticus</Emphasis>

The lipids of the gram-negative bacterium Marinobacter hydrocarbonoclasticus grown in a synthetic seawater medium supplemented with various hydrocarbons as the sole carbon source were isolated, purified, and their structures determined. The hydrocarbons were normal, iso, anteiso, and mid-chain branched alkanes, phenylalkanes, cyclohexylalkanes, and a terminal olefin. According to the sequential procedure used for lipid extraction, three pools were isolated: unbound lipids extracted with organic solvents (corresponding to metabolic lipids and to the main part of membrane lipids), OH⁻ labile lipids [mainly ester-bound in the lipopolysaccharides (LPS)], and H⁺ labile lipids (mainly amide-bound in the LPS). Each pool contained FA, fatty alcohols, and β-hydroxy acids. The proportions of these lipids in the unbound lipid pools were 84–98%, 1.1–11.6%, and 0.1–3.6% (w/w), respectively. The chemical structures of the lipids were strongly correlated with those of the hydrocarbons fed; analytical data suggested a metabolism essentially through oxidation into primary alcohol, then into FA and degradation via the β-oxidation pathway. Subterminal oxidation of the hydrocarbon chains, α-oxidation of FA or double-bond oxidation in the case of the terminal olefin, were minor, although sometimes substantial, routes of hydrocarbon degradation. Cyclohexyldodecanedid not support growth, likely because of the toxicity of cyclohexylacetic acid formed in the oxidation of the alkyl side chain. In the OH⁻ and H⁺ labile lipid pools, β-hydroxy acids, the lipophilic moiety of LPS, generally dominated (28–72% and 64–98%, w/w, respectively). The most remarkable feature of these cultures on hydrocarbons was the incorporation in LPS of β-hydroxy acids with C_odd, ω-unsaturated, iso, or anteiso alkyl chains in addition to the specific β-hydroxy acid of M. hydrocarbonoclasticus, 3-OH-n-12∶0. These β-hydroxy acids were tolerated insofar as their geometry and steric hindrance were close to those of the 3-OH-n-12∶0 acid.     

Predicting cetane numbers of n-alcohols and methyl esters from their physical properties

Cetane numbers (C#) for the homologous series of straight-chain, saturated n-alcohols, C₅−C₁₂ and C₁₄, were determined according to ASTM D 613. Measured C# ranged from 18.2–80.8 and increased linearly with carbon number (CN). Regression analyses developed equations that related various physical properties or molecular characteristics of these alcohols to calculated C#. The degree of relationship between measured and calculated C# was expressed as R². The decreasing order of the precision with which these properties correlated with C# was: boiling point (bp)>melting point (mp)>CN>heat of combustion (HG)>refractive index (n²⁰ _D)>density (d). This ranking was based upon R² (0.99–0.96) and the Average % error (2.8–7.2%). C# were also determined for straight-chain homologs of saturated methyl esters with CN of 6, 10, 12, 14, 16 and 18. C# ranged from 18.0–75.6 and increased curvilinearly with CN. Equations were also developed that related physical properties of these esters to C#. The precision with which these properties correlated with C# was: bp>viscosity (V)>heat of vaporization (HV)>HG>CN>surface tension (ST)>mp>n²⁰ _D>d. R² ranged from 0.99 for bp to 0.98 for d. Equations for the alcohols were linear or quadratic, while equations for the esters were linear, quadratic or cubic based upon statistical considerations that included a Student’s t-test. With related physical properties and these equations, accurate predictions of C# can be made for saturated n-alcohols and methyl esters.     

Paraffinic hydrocarbon composition of earthworms (Lumbricus terrestris)

The paraffinic hydrocarbon fraction of the lipids extracted from earthworms (Lumbricus terrestris) contains ca. 88%n-alkanes and 12% branched alkanes and other hydrocarbons. Then-alkanes range from C₁₃ through C₃₃, and their most interesting feature is the even-over-odd carbon number predominance in the C₁₃−C₂₄ range. The nonnormal hydrocarbons consist primarily of monomethyl-substituted alkanes. Other hydrocarbons that have been identified include the C₁₆. C₁₈, C₁₉ and C₂₀ isoprenoids and the C₁₈, C₂₀ and C₂₂ n-alkylcyclohexanes.     

Preparation of alcohols from cyclic fatty acids

Saturated C_18- and C₂₀-cyclic alcohols have been prepared by catalytic hydrogenation of methyl esters from cyclized linseed monomeric acids, purified saturated C₁₈-cyclic acids, ethylene adduct of conjugated soybean fatty acids, and ethylene adduct of conjugated octadecadienoic acids. The cyclic alcohols have also been prepared from free acids of crude cyclic linseed, cyclic linseed monomeric, and ethylene adduct of 9,11,t,t,-octadecadienoic. Conversion of esters and acids was 88–99% by hydroxyl determination; by gas-liquid chromatographic analysis, almost quantitative Hydrogenations were carried out with 10%, by weight, copper chromite catalyst, an initial hydrogen pressure of 2,100 psi, and a temperature of 280C for 3–5 hr. Preliminary evaluations indicate that saturated C_18- and C₂₀-cyclic alcohols have a potential use in cosmetic formulations. Presented AOCS meeting in Minneapolis, Minn., 1963. No. Utiliz. Res. & Dev. Div., ARS, USDA.     

Conversion of polyunsaturates in vegetable oils tocis-monounsaturates by homogeneous hydrogenation catalyzed with chromium carbonyls

Chromium carbonyl complex catalysts were used to selectively hydrogenate polyunsaturates in vegetable oils into products retaining 90% to 95%cis configuration and their liquid properties. The product from soybean oil contained 42–69% monoene, 10–40% diene and 0–4% triene. The product from safflower oil contained 73–82% monoene and 8–17% diene. About 45–55% of the double bonds in monoenes from hydrogenated soybean oil remained in the C₉ position, and the rest was distributed between C₁₀, C₁₁, and C₁₂. Preliminary oxidative and flavor stability evaluations showed that these hydrogenated soybean oils compared favorably with a commercial sample of hydrogenated-winterized soybean oil. Liquid fatty acids prepared by saponification of hydrogenated soybean and safflower oils (IV 90–100) had analyses about the same as those of commercial oleic acid. Presented before the Division of Agricultural and Food Chemistry, 156th American Chemical Society National Meeting, Atlantic City, N.J., September 1968.