n-Hexyl Laurate and Fourteen Related Fatty Acid Esters: New Secretory Compounds from the Julid Millipede, Anaulaciulus sp.

A total of fifteen saturated fatty acid esters were newly identified from the secretions of an unidentified Anaulaciulus sp. (Julida: Julidae). The fatty acid components of the esters were composed of normal chain acids (from C₁₀ to C₁₄) and of branched chain acids (from iso-C₁₂ to iso-C₁₅ and anteiso-C₁₅). The alcohol moieties were all composed of normal chain alcohols varying from n-butanol to n-octanol. The most abundant component found in the total esters was n-hexyl laurate (64.7%). Novel compounds identified from the millipede secretion extracts include six branched iso- and anteiso-fatty esters, an odd-numbered C₁₁-fatty acid ester, a C₁₃-fatty acid ester, and a C₇-alcohol ester, all of which were previously undescribed natural products. In addition, a characteristic mixture of benzoquinones, such as 2-methyl-1,4-benzoquinone, 2-methoxy-3-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, 2-methoxy-6-methyl-1,4-benzoquinone, and 2,3-dimethoxy-5-methyl-1,4-benzoquinone were identified from the secretions, together with trace amounts of 1,4-benzoquinone.     

Inulin polysaccharide having pendant amino acids: Synthesis and characterization

Inulin polysaccharide was esterified with N-protected α-amino acids (N,N′-di-benzylocarbonyl-L -lysine and N-benzylocarbonyl-glycine) under a mild condition (room temperature) and within short reaction times (6 h). The esterification reactions were conducted in the presence of dicyclohexylcarbodiimide and 4-(dimethylamino)pyridine as a catalyst. The optimal reaction time (6 h) was determined by monitoring the concentration of free carboxylic acid of the N-protected amino acids during the reaction. The degree of substitution per fructose unit was 0.95 for inulin-lysine and 1.01 for inulin-glycine. The resulting biopolymer was deprotected by catalytic transfer hydrogenation method using 1,4-cyclohexadiene as an effective hydrogen donor. The structures, molecular weight, and thermal properties of the amino acid esters of inulin were determined by Fourier transform infrared spectroscopy, ¹H and ¹³C NMR, UV, viscosity, and dicyclohexylcarbodiimide. This new modified inulin polysaccharide would have the potential as a biomaterial for biomedical applications. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 953–963, 1998     

Methyl Esters (Biodiesel) from and Fatty Acid Profile of Gliricidia sepium Seed Oil

Increasing the supply of biodiesel by defining and developing additional feedstocks is important to overcome the still limited amounts available of this alternative fuel. In this connection, the methyl esters of the seed oil of Gliricidia sepium were synthesized and the significant fuel‐related properties were determined. The fatty acid profile was also determined with saturated fatty acids comprising slightly more than 35 %, 16.5 % palmitic, 14.5 % stearic, as well as lesser amounts of even longer‐chain fatty acids. Linoleic acid is the most prominent acid at about 49 %. Corresponding to the high content of saturated fatty acid methyl esters, cold flow is the most problematic property as shown by a high cloud point of slightly >20 °C. Otherwise, the properties of G. sepium methyl esters are acceptable for biodiesel use when comparing them to specifications in biodiesel standards but the problematic cold flow properties would need to be observed. The ¹H‐ and ¹³C‐NMR spectra of G. sepium methyl esters are reported.     

Polymers containing sulfur in the side chain

We synthesized new thiodicarboxylic acids, p-tolylmethylthiomethylsuccinic acid and 1-naphthylmethylthiomethylsuccinic acid, and thiodiols, 2-(p-tolylmethylthiomethyl)-1,4-butanediol and 2-(1-naphthylmethylthiomethyl)-1,4-butanediol, by the addition of dimethyl itaconate with p-tolylmethanethiol or 1-naphthylmethanethiol, followed by hydrolysis or reduction, respectively, of the resultant dimethyl esters. These difunctional monomers were used for the synthesis of new linear polyesters and polyurethanes containing sulfur in the side chain. The polyesters were synthesized by melt polycondensation of the obtained acids with 2,2′-oxydiethanol. We found reduced viscosity, molecular weight (by GPC), and softening temperature for the reaction products. Low molecular weights, low softening temperature, and very good solubility in organic solvents are their characteristics. The polyurethanes were prepared by polyaddition diols with hexamethylene diisocyanate and tolylene diisocyanate in benzene. They were characterized by reduced viscosity and some tensile properties. The polyurethane derived from 2-(p-tolylmethylthiomethyl)-1,4-butanediol and hexamethylene diisocyanate (η_red. 1.17 dL/g) behaves like a high elasticity thermoplastic elastomer. Thermal stability of all polymers was determined by thermogravimetric analysis. The structure of the monomers and polymers were confirmed by elemental analysis and FTIR and ¹H-NMR spectroscopy. © 1996 John Wiley & Sons, Inc.     

Organoselenium-mediated cyclization of hydroxyolefinic fatty acids and m-CPBA oxidation of selenium-containing 1,4-epoxy acids

Chlorophenylselenenylation methodology is shown to cause cyclization of naturally occurring β- and γ-hydroxyolefinic acids. The phenylseleno-substituted 1,4-epoxides (tetrahydrofurans) thus obtained are oxidized by m-chloroperbenzoic acid (m-CPBA). Reaction of phenylselenenyl chloride with methyl 12-hydroxyoctadec-cis-9-enoate (methyl ricinoleate) gave methyl 9,12-epoxy-10-phenylselenenyloctadecanoate in useful yields. A similar reaction of phenylselenenyl chloride with methyl 9-hydroxyoctadec-cis-12-enoate afforded a quantitative yield of methyl 9,12-epoxy-13-phenylselenenyloctadecanoate. Oxidation of selenium-containing 1,4-epoxy esters by m-chloroperbenzoic acid (1 equivalent) yielded the respective olefinic 1,4-epoxy esters, while 5 equivalent m-CPBA afforded the corresponding oxirane esters of epoxytetrahydrofurans in high yields. The structure of the individual reaction products have been established from analytical and spectral data and corroborated by a study of their mass spectra.     

Fatty acids of Thespesia populnea: Mass spectrometry of picolinyl esters of cyclopropene fatty acids

Thespesia populnea belongs to the plant family of Malvaceae which contain cyclopropane and cyclopropene fatty acids. However, previous literature reports vary regarding the content of these compounds in Thespesia populnea seed oil. In this work, the content of malvalic acid (8,9‐methylene‐9‐heptadecenoic acid) in the fatty acid profile of Thespesia populnea seed oil was approximately 7% by GC. Two cyclopropane fatty acids were identified, including dihydrosterculic acid. The methyl and picolinyl esters of Thespesia populnea seed oil were also prepared. The mass spectrum of picolinyl malvalate was more closely investigated, especially an ion at m/e 279, which does not fit the typical series of ions observed in picolinyl esters. It is shown that this ion is caused by cleavage at the picolinyl moiety and contains the fatty acid chain without the picolinyl moiety. This type of cleavage has previously not been observed prominently in picolinyl esters and may therefore be diagnostic for picolinyl esters of cyclopropene fatty acids. The NMR spectra of Thespesia populnea methyl esters are also discussed. Practical applications: The work reports the fatty acid composition of Thespesia seed oil whose derivatives have not yet been extensively utilized for industrial purposes, for example, biodiesel. Knowing this composition is essential for understanding potential uses and, for example, in case of biodiesel the fuel properties. Besides this issue, some data (mass spectrometry and NMR) crucial for obtaining the composition information are analyzed in detail. The biodiesel properties of methyl esters of Thespesia populnea will be reported separately.     

Direct esterification of fatty acids with phenylalkanols by using dicyclohexylcarbodiimide

A mild one‐pot esterification method of fatty acids with alcohols at room temperature is described. The reaction of undec‐10‐enoic acid (I) with 1‐phenylethanol in the presence of N,N'‐di‐cyclohexylcarbodiimide and 4‐(N,N‐dimethylamino)pyridine gave 1'‐phenylethyl undec‐10‐enoate in quantitative yield. Similar reactions were also carried out with (Z)‐octadec‐9‐enoic acid, (Z)‐12‐hydroxyoctadec‐9‐enoic and (Z)‐9‐hydroxyoctadec‐12‐enoic acids. In addition, compound (I) was allowed to react with diphenyl methanol to form its corresponding ester. The structure elucidation of the prepared esters is based on the elemental analysis and spectral data (IR, ¹H‐ and ¹³C‐NMR, MS).     

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.     

Hydrogenation of synthetic cis‐1,4‐polyisoprene and natural rubber catalyzed by [Ir(COD)py(PCy3)]PF6

In the presence of chlorinated solvents, the catalytic complex [Ir(COD)py(PCy₃)]PF₆ (where COD is 1,5‐cyclooctadiene and py is pyridine) was an active catalyst for the hydrogenation of synthetic cis‐1,4‐polyisoprene and natural rubber. Detailed kinetic and mechanistic studies for homogeneous hydrogenation were carried out through the monitoring of the amount of hydrogen consumed during the reaction. The final degree of olefin conversion, measured with a computer‐controlled gas‐uptake apparatus, was confirmed by Fourier transform infrared spectroscopy and ¹H‐NMR spectroscopy. Synthetic cis‐1,4‐polyisoprene was used as a model polymer for natural rubber without impurities to study the influence of the catalyst loading, polymer concentration, hydrogen pressure, and reaction temperature with a statistical design framework. The kinetic results for the hydrogenation of both synthetic cis‐1,4‐polyisoprene and natural rubber indicated that the hydrogenation rate exhibited a first‐order dependence on the catalyst concentration and hydrogen pressure. Because of impurities inside the natural rubber, the hydrogenation of natural rubber showed an inverse behavior dependence on the rubber concentration, whereas the hydrogenation rate of synthetic rubber, that is, cis‐1,4‐polyisoprene, remained constant when the rubber concentration increased. The hydrogenation rate was also dependent on the reaction temperature. The apparent activation energies for the hydrogenation of synthetic cis‐1,4‐polyisoprene and natural rubber were evaluated to be 79.8 and 75.6 kJ/mol, respectively. The mechanistic aspects of these catalytic processes were discussed on the basis of observed kinetic results. The addition of some acids showed an effect on the hydrogenation rate of both rubbers. The thermal properties of hydrogenated rubber samples were determined and indicated that hydrogenation increased the thermal stability of the hydrogenated rubber but did not affect the inherent glass‐transition temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4219–4233, 2006     

The metabolism of neutral lipids in the spur dogfish,Squalus acanthias

Cell free studies have shown that liver and intestine are the major sites of synthesis of triacyl glycerols inSqualus acanthias. The liver and to a lesser extent the intestine and stomach are major sites of wax ester synthesis. Muscle does not synthesize either triacyl glycerols or wax esters significantly. In vivo studies have shown that intravenously injected (³H) fatty alcohol is massively oxidized to (³H) fatty acid, the bulk of which appears in muscle. Liver appears to export both free fatty acids and triacyl glycerols to serum and thence to muscle. Free fatty acids, triacyl glycerols, wax esters and cholesteryl esters are all turned over within 48 hr inSqualus serum. The turnover of triacyl glycerols greatly exceeds the turnover of alkyl diacyl glycerols.     

Biodegradable polymers based on renewable resources. V. Synthesis and biodegradation behavior of poly(ester amide)s composed of 1,4:3,6‐dianhydro‐D‐glucitol, α‐amino acid,and aliphatic dicarboxylic acid units

A series of poly(ester amide)s were synthesized by solution polycondensations of various combinations of p‐toluenesulfonic acid salts of O,O′‐bis(α‐aminoacyl)‐1,4:3,6‐dianhydro‐D ‐glucitol and bis(p‐nitrophenyl) esters of aliphatic dicarboxylic acids with the methylene chain lengths of 4–10. The p‐toluenesulfonic acid salts were obtained by the reactions of 1,4:3,6‐dianhydro‐D ‐glucitol with alanine, glycine, and glycylglycine, respectively, in the presence of p‐toluenesulfonic acid. The polycondensations were carried out in N‐methylpyrrolidone at 40°C in the presence of triethylamine, giving poly(ester amide)s having number‐average molecular weights up to 3.8 × 10⁴. Their structures were confirmed by FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopy. Most of these poly(ester amide)s are amorphous, except those containing sebacic acid and glycine or glycylglycine units, which are semicrystalline. All these poly(ester amide)s are soluble in a variety of polar solvents such as dimethyl sulfoxide, N,N‐dimethylformamide, 2,2,2‐trifluoroethanol, m‐cresol, pyridine, and trifluoroacetic acid. Soil burial degradation tests, BOD measurements in an activated sludge, and enzymatic degradation tests using Porcine pancreas lipase and papain indicated that these poly(ester amide)s are biodegradable, and that their biodegradability markedly depends on the molecular structure. The poly(ester amide)s were, in general, degraded more slowly than the corresponding polyesters having the same aliphatic dicarboxylic acid units, both in composted soil and in an activated sludge. In the enzymatic degradation, some poly(ester amide)s containing dicarboxylic acid components with shorter methylene chain lengths were degraded more readily than the corresponding polyesters with Porcine pancreas lipase, whereas most of the poly(ester amide)s were degraded more rapidly than the corresponding polyesters with papain. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2721–2734, 2001     

Analysis of hydroxylated fatty acids from plant oils

A novel process has been described recently for the preparation of hydroxylated fatty acids (HOFA) and HOFA methyl esters from plant oils. HOFA methyl esters prepared from conventional and alternative plant oils were characterized by various chromatographic methods (thin-layer chromatography, high-performance liquid chromatography, and gas chromatography) and gas chromatography-mass spectrometry as well as¹H and¹³C nuclear magnetic resonance spectroscopy. HOFA methyl esters obtained fromEuphorbia lathyris seed oil, low-erucic acid rapeseed oil, and sunflower oil contain as major constituents methylthreo-9,10-dihydroxy octadecanoate (derived from oleic acid) and methyl dihydroxy tetrahydrofuran octadecanoates, e.g., methyl 9,12-dihydroxy-10,13-epoxy octadecanoates and methyl 10,13-dihydroxy-9,12-epoxy octadecanoates (derived from linoleic acid). Other constituents detected in the products include methyl esters of saturated fatty acids (not epoxidized/derivatized) and traces of methyl esters of epoxy fatty acids (not hydrolyzed). The products that contain high levels of monomeric HOFA may find wide application in a variety of technical products.     

Chemoenzymatic epoxidation of unsaturated fatty acid esters and plant oils

In the presence of an immobilized lipase fromCandida antacrtica (Novozym 435^R) fatty acids are converted to peroxy acids by the reaction with hydrogen peroxide. In a similar reaction, fatty acid esters are perhydrolyzed to peroxy acids. Unsaturated fatty acid esters subsequently epoxidize themselves, and in this way epoxidized plant oils can be prepared with good yields (rapeseed oil 91%, sunflower oil 88%, linseed oil 80%). The hydrolysis of the plant oil to mono- and diglycerides can be suppressed by the addition of a small amount of free fatty acids. Rapeseed oil methyl ester can also be epoxidized; the conversion of C=C-bonds is 95%, and the composition of the epoxy fatty acid methyl esters corresponds to the composition of the unsaturated methyl esters in the substrate. Based partly on a lecture at the 86th AOCS Annual Meeting & Expo, San Antonio, Texas, May 7–11, 1995.     

Extraction of aconitic acid from mixtures of organic acids and cane molasses solutions using supported liquid membranes

This paper details experimental trials of aconitic acid transport from defined mixtures of organic acids (trans‐aconitic, oxalic, malic and citric) and from cane molasses solutions using a supported liquid membrane (SLM) apparatus. The SLM was impregnated with tributyl phosphate extractant combined with Shellsol 2046 diluent. The transport rates of the organic acids, bulk impurities and glucose were measured. The conditions varied were: extractant to diluent ratio (1:3–3:1), organic acid concentration (2.5–40 mg cm^?3 organic acid), pH of departure phase (1–5.5) and temperature (22–80 °C). Results for the organic acid mixtures showed that aconitic acid and oxalic acid were transported at much greater rates than malic and citric acids. Aconitic acid was transported to a significant degree with recovery of 400 g kg^?1 over a 24 h period. Operation at temperatures higher than 22 °C caused instability of the membrane and bulk leakage across the membrane. With molasses, the purity of the aconitic acid recovered ranged between 400 and 600 g kg^?1 (dry basis) with aconitic acid transport rates of 0.17–0.25 g m^?2 min^?1. The extraction of other acids (oxalic, malic and citric) and impurities was significantly less, hence a process to produce high purity aconitic acid based on this method is technically feasible. © 2002 Society of Chemical Industry     

Synthesis and characterization of some long-chain diesters with branched or bulky moieties

Several novel fatty diesters with bulky moieties were synthesized by esterification of mono- or bifunctional fatty acids or with mono- or bifunctional alcohols using p-toluenesulfonic acid as catalyst. They were characterized by ¹H and ¹³C nuclear magnetic resonance as well as positive chemical ionization (PCl) mass spectrometry. The PCl mass spectra of the resulting diol diesters and diacid diesters are discussed and compared. The compounds were investigated as potential additives for improving the cold flow properties of vegetable oil esters used as biodiesel. Retired.     

Synthesis of water-soluble cellulose esters applying carboxylic acid imidazolides

Water-soluble, non-ionic cellulose esters with a degree of substitution in the range from 0.11 to 3.0 were synthesized homogeneously using ionic liquids (1-butyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, and 1-allyl-3-methylimidazolium chloride) as reaction medium. Highly substituted 3,6,9-trioxadecanoic acid esters and 3,6-dioxaheptanoic acid esters of cellulose were obtained via the activation of the carboxylic acids with N,N’-carbonyldiimidazole. The products were characterized by the means of FTIR-, ¹H- and ¹³C NMR spectroscopy.     

Unconventional Synthesis of Pullulan Abietates

Pullulan abietic acid esters (pullulan abietates) of different degree of substitution (DS) were synthesized homogeneously in N,N-dimethylacetamide using differently in situactivated abietic acid derivatives. In situ activation was achieved with p-toluenesulfonyl chloride, N,N‘-carbonyldiimidazole and iminium chloride formed from oxalyl chloride/N,N-dimethylformamide. The DS values of the biopolymer esters determined by acid-base titration after saponification indicated that in situ activation with p-toluenesulfonyl chloride is most efficient while in case of the in situ activation with N,N‘-carbonyldiimidazole almost no polymer degradation occured. The pullulan abietates were characterized by elemental analysis, GPC, FTIR-, ¹H- and ¹³C NMR spectroscopy.     

cis-5-Monoenoic fatty acids in some chenopodiaceae seed oils

Methyl esters from seed oils of four Chenopodiaceae species are unusual in that they contain methylcis-5-hexadecenoate (4.6–12%) and methyl 5-octadecenoate (1.1–1.2%). There are indications of small amounts of 18∶2^5,9 and 18∶3^{5, 9, 12} along with unsaturated acids commonly found in seed oils-oleic (14–21%), linoleic (53–57%) and linolenic (3.5–7.8%). Fatty acid composition of the oils was determined by gas chromatography, and positions of the double bonds were established by application of gas chromatography-mass spectrometry to the methoxylated methyl esters. N. Market. Nutr. Res. Div., ARS, USDA.     

Synthesis of 9,9,9-trideutero-1,4-dihydroxynonane mercapturic acid (<Emphasis Type="Italic">d</Emphasis><Subscript>3</Subscript>-DHN-MA), a useful internal standard for DHN-MA urinalysis

Racemic 1,4-dihydroxynonane mercapturic acid (DHN-MA) and 9,9,9-trideutero-1,4-dihydroxynonane mercapturic acid (d ₃-DHN-MA) are synthesized on a 400-mg scale (over-all yield ∼40%) by a two-step sequence involving Michael addition of N-acetyl-l-cysteine to methyl-4-hydroxynon-2(E)-enoate or methyl 9,9,9-trideutero-4-hydroxynon-2(E)-enoate, followed by reduction of the intermediate adducts with lithium borohydride. The requisite starting methyl esters are obtained, respectively, from heptanal or 7,7,7-trideuteroheptanal and methyl 4-chlorophenyl-sulfinylacetate via a sulfoxide piperidine and carbonyl reaction described in the literature. The 7,7,7-trideuteroheptanal is easily prepared by classical methods in four steps from 6-bromo-1-hexanol. ¹³C NMR data indicate that DHN-MA as well as d ₃-DHN-MA are obtained as mixtures of four diastereomers. Preliminary results show that d ₃-DHN-MA could be used as an internal standard for mass spectrometric quantification of DHN-MA in human urine.     

Gas chromatographic behavior of fatty acid derivatives for mass spectrometry on low‐polarity capillary columns

The gas chromatographic properties of four derivatives of fatty acids (FA), namely fatty acid methyl esters, picolinyl esters, N‐acyl pyrrolidides and 4,4‐dimethyloxazoline derivatives, which contain various structural features (double bonds, branching, hydroxyl group) in their acyl chains have been compared on a low‐polarity capillary column with a mass spectrometer as detector. Temperature programming rates yielding the highest resolution were optimized for each derivative by means of computer‐assisted column temperature optimization software. Indeed, the Drylab software represents a valuable assistance for estimating the optimum analysis conditions. Time and efforts required for such method development can greatly be reduced. Different parameters (derivatization procedure, total run time, resolution and response factor) are discussed. N‐Acyl pyrrolidides and picolinyl esters appear quite powerful for structure elucidation of polyunsaturated FA by GC‐MS, and both these types of FA derivatives can be very well separated on a low‐polarity phase.