160

ABSTRACTS FROM AOCS JOURNALS

The following obstroctJ were taken {rom paptfrs which appearedin the Januory iUUf of JAOCS.

ModiricatiOD of Jojoba Oil lor Lubeieent FormulationsV.K. Bhatia. Atk. Chaudhry, G.A. Sivasankaran. R.P.s. Bisht andMeenu KashyapIndian Institute of Petroleum, Dehradun-248 005, India

Jojoba oil has good lubricity and it can be utilized as a componentin lubricating oil formulations. The physicochemical properties ofthe oil when compared with those of mineral oil base stocks showedthat the pour point. acid value and oxidative stability were thelimiting factors in its use as a base stock. Studies were carried outto improve these properties. The results indicated that these prop-erties can be modified by physical and chemieal methods and alsoby additive treatment. It has also been possible to increase theviscosity of jojoba oil by partial sulfurization, resulting in widen-ing the scope of it.! utilization in developing lubricant formulati~

EUicient Synthtllis of Fatty l\tonoglyceride Sulfattll frnm FattyAcids and Fatty Acid Methyl EstersFahim U. AhmedColgaLeoPalmolive Company. Corporate Technology Center. 909River Road. Piscataway. NJ 08864

An efficient high yield synthesis of fatty monoglyeeride sulfate!!from fatty acids or fatty acid methyl esters. glycerine andchlorosulfurlc acid in chloroform using stoichiometric amounts ofreagents WSJ! developed. Sodium coco monoglyeeride sulfate wasprepared in 79% yield with 93% purity from coco fatty acids.Similarly, sodium palm kernel monoglyceridesulfate in 57% yieldand sodium palm monoglyceride sulfate in 71% yield were obtainedfrom palm kernel fatty acid methyl esters and palm fatty acids.respectively. This new synthetic method produced better qualityproducts with higher active ingredients and improved yieldswithout having to use such cost prohibitive. high purity. fatty acidmonoglycerides, and it reduced the undesirable aqueous sodiumsulfate by-product by 60% over a eurrent commereial process. Theproduct's composition and purity were confirmed by clltionic titra-tion, infrared und C·13 NMR spectroscopy.

Adsorption of Soy Oil Free FaUy Acids by Rice Hull AshAndrew Proctor and Sevugan PelnniappenDepartment of Food Science and Technology. The Ohio StateUniversity. Columbus. OH 43210·1096

Studies demonstrated t.hllt free fatty acids can be adsorbed froma soybean oilJhexane miscella by inorganic rice hull ash. A 1% dosewas effective in diminishing free fatLy acid coneentraelcns but acidactivation reduced the adsorption. Binding of free fatty acidsfollowed a Freundlich isotherm with smaller doses of ash adsorb-ing more efficiently. Addition of isopropanol to the miscella pro-moted the adsorption. while water deactivation of the ash had noeffect. pceaibly because water occupied sites not accessible to freefatty acids. Impaired adsorption behavior of ash heated above700°C could have been due to disruption of the crystal form. Theadsorption behavior of rice hull ash may be more fully underslOOdwith a better knowledge of adsorbent structure.

AppliCl".ion of a Rapid Tra.n_Lerification Method for Identifica·tion of Individual FaUy Acid" by Ga" Chrom ..tography on Threel>ifferent Nut Oil,P.C. fourie and O.S. BassonDepartment of Food Science, University of Stellenbosch, Stellen-bosch. 7600. Republic of South Africa

The lack of uniformity of analytical techniques employed for

quantification of fatty acids led to the successful implementationof a rapid transesterification method using tettamethylammoniumhydroxide to determine and compare the total fatty acid contentof almond. pecan and macadamia oils. Palmitic. oleic and linoleicacids comprised the largest part of the total fatty acid content inalmond and pecan oils. Although oleic acid was also tbe main een-stituent of macadamia oil. its concentration wea eubstaatially lowerthan in the other oils.

Hydrogenatten of Carboxyli<: Acids by Rhenium·OamiumBimetallic CatalystKoji YO&hino, Yasushi Kajiwara, Naotake Takaishi, YO&hialtilnemoto and Jiro TsujiOKIlO Institute for Fundamental Research Laboratories. Kao Corp ..2606, Akabane, lchikei-mechi. Tochigi 321·34, Japan and OTokyoInstitute of Technology, Megro. Tokyo 152. Japan

Hydrogenation of carboxylic acids to alcohols at low temperatureand under low pressure was achieved by using a new catalystsystem, a rhenium-osmium bimetallic catalyst. The most activecatalyst WIL!I prepared by the reduction of the corresponding metaloxides with hydrogen in the presence of succinic acid. Decancicacid was hydrogenated to decenol in high conversions at25"'100 atm and 100 "'120°C. Decene was formed as a by-produceby cverreducucn of the alcohol. The selectivity of alcohol was im-proved by the addition of thiophene as a modifier of the catalyst.

Solvent Extraction of the Oils of Rubber, Melon. Pumpkin andOilbean SeedsJ.C. Atlah and J.A. lbemesiDepartment of Pure and Industrial Chemistry, University ofNigeria. Nsukka Anambra State. Nigeria

Solvents of differing dielectric constant were used to extract oilsfrom the seeds of: rubber (H9uea brasiliensis [Kunth] Muc11.Arg.),melon tColocynthis vulgaris Schrlld), fluted pumpkin (Telfairio DC-

cidentolia Hook f.1and oilbean (Pentaclethro mocrophylln Benthl,The aim was to exa.mine the effect of solvent polarity on oil yieldand oil properties.

The one were extracted under Soxhlet conditions with the follow·ing aolventai petroleum benzene (60-8O°CI, cyclohexane, isopropylether, ethyl acetate. tetrahydrofuran. propan.2-o1 and acetone. Theoils were characterized by acid number. iodine value and color in-tensity determinations.

The oil yields of each seed in different solvents ranged as follows:08.0-64.4% {pumpkin), 56.1-59.1% [melon]. 40.6-48.8% (rubber)and 35.4-43.3% (oilbelln). The equilibrium extracting capacity ofeach solvent was found to depend on two factors. namely, thenature of the oil and the polarity of the solvent, Both factors werefound to determine the acid number. iodine value and color inten-sity of each oil.

The Remo .....1 of Melals from Edible Oil by a Membrane Extrac-tion ProcedureJ.T.F. Keurentjtll. Th.G.J. Bosklopper, L.J. van Dorp aDdK. van't Riet

Wageningen Agricultural University, Dept, of Food Science. Foodand Bioengineering Group, De Dreijen 12. 6703 BC Wageningen.The Netherlands

Edible oill may contain tr8Celllof metals.. In oil refining proceduresthl!!'H!metab have to be removed to guarantee oxidatively ltableproductlJ. In this study we present a hollow fiber membrane ex·traction system for the removal of metals from an oil. Several es-traction liquids were tested, of which an ammonia solution givesthe best distribution coefficient tm = 11.7). From mass transfercalculaticns it follows that the resistance to mass transfer in theextreetice ph8lJfl in t.he fiber wall can be neglected compared to

INFORM. Vol. 1, no. 2 (February 1990)

161

ABSTRACTS FROM AOCS JOURNALS

nickel and are.ne-Cr1COI3 mixtures. Effects of temperature. pres-sure, catalyst concentration and catalyst preparation procedureon the hydrogenation rate. selectivity. catalyst life and quality ofthe oil were eJ:amined and compared with that of commercial nickelcatalysLS. A brief discussion about continuous hydrogenations ofeenote oil with commercial fixed bed eatelyate is also included.

the resistances in the oil phase inside the fibers and the extrac-tion phase oUWlidethe fibers. A cost evaluation shows that sucha membrane extraction can be profitable in conventional refiningif more than 1.5% bleaching earth has to be added in surplus toremove metals.

Continuous Ultrasonic Degumming of Crude Soybean Oil

K.J. Moulton, Sr. aDd T.L. Mounts

U.S. Department. of Agriculture, Agricultural Research Service,Northern Regional Research Center, 1815 N. University Street,Peoria. IL 61604

The Rhodium-C.talyzed Deutualion of Unsaturated Triglycerides

R.O. Adlof

U.S. Department of Agriculture. Agricultural Research Service.Northern Regional Research Center. 1815 N. University Street.Peoria. I L 61604

Ultrasonic energy has been applied to continuous degumming forthe efficient removal of phospholipids from crude soybean oil. Thecrude oil and water (2.0'10 by weight) were pumped through anultrasonic processing cell. oil and hydrated gums were separatedby centrifugation. and the recovered oil was veeuum bleacbed 11M!degummed and bleached oil had a residual phosphorus content ofless than iO ppm and was subsequently deacidified-deodorized inall-glass laboratory deodorization equipment. Odor and flavorevaluation indicated that the salad oil produced by the process ofultrasonic degumming/deodorization-deacidifiction was equivalentin quality and stability to a conventionally processed salad oil

Tripalmitoiein. triolein. trilinolein and trilinoienin were deuteretedwith deuterium gas and Wilkin80n's catalyst (f~h3P13RhCIU)j.Recrystallization of the products from acetone yielded highly puredeuterium-labelled trigiycerides (TGI. The deuterated TG were con'verted to methyl esten: and analyzed by gas chromatography/massspectroscopy to determine the deuterium distribution. Methylpa1mitate-9.1~ (from tripalmitoleinl and methyl st.earate-9.1O-d2(from triolein) yielded isotopic diatributiona of 93~91'.10d2• methylstearate-9.10.l2.13~ (from trilinoieinl of 74% d4 and methylstearate-9.IO.12.13.15.16-dt; Ifrom trilinoieninl of only 58% ~'Because the deuterium·labelled TG were to be used in humanmetabolism studies. atomic absorption spectroscopy was used todetermine if any residual rhodium was present. No rhodium wasdetected at 70 ppb (the minimum detection limit).

Test Procedure for Evaluation of CatalYI;u! for Nitrile Reduction

F.E. Friedli and R.M. Gilbert

Shere. Chemical Company. Dublin. Ohio

A procedure was developed that examines the effectiveness ofnickel catalysts for the hydrogenation of fatty nitriles to amines.Rates of reaction. selectivity. and olefinic reduction were theparameters studied. The procedure can be used for new catalystscreening and is ideally suited for quality assurance testing of pro-duction catalysts. It involves the reduction of nitriles to amlnesat410°FI210°CI and 500 psig using a.2% Ni loading level. A mix-ture of primary and secondary amines is obtained which ischaracteristic of the catalyst's selectivity. Both sponge and sup-ported nickel catalysts were tested using tallow nitriles as thefeedstock.

Properties or the Aqueous Vesicle Dispersion Formed with Poly{oJr.·yelhylenelhydrogenated Castor Oil

Minako TanakP. Hidenori Fukuda and Teruo Horiuchi

Applied Research Laboratories II. Lion Corporation No. 13·12.'l-chome, Hirai. Edcgewe-ka. Tokyo. 132. Japan

Associated properties of the aqueous disperaien of poly(ox·yethylenelhydrogenated castor oil ether(HCO-IOI were studied bymeans of polarized microscopy. Ireeze-Iractured electronmicroscopy. particle size analysis. ESR spin labelling and IH·NMR spectra. A stable mulullamellar vesicle with an averagediameter of ca. 0.4 II is formed from the HCO·10 concentrationbelow 20 wt% whose phase shows a concentric lamella.

The hydrophilic layer of the vesicle is more rigid than thehydrophobic core. The fluidity around the spin label12NS inccr-porated in the HCO-IO vesicle significantly decreased withtemperature: however. both spin labels 5NS and 16NS did notchange significantly.

The mecbenlem of fluidit.y change with temperature was dis>cussed in t.erms of the dehydration of ethylene oxide and thebreakdown of hydrogen bonding in the HCC).lO vesicle.

Recent Advances in Canola Oil Hydrogenations

S.8. KlSseojlu and E.W. LUllasFood Protein Research and Development Center. Texas Engineer-ing Experiment Station. Texas A&M University. College Station,TX 77843

Rapeseed oil has been the source of edible oils in many parts ofthe world. In the last decade. Canadian plant breeders havedeveloped new rapeseed cultivars which yield oil low in erucic acidand meal low in glucosinolale!l. These cultivars were named"cancle" by the Canadian rapeseed industry. Literature on thehydrogenation eharacteristlcs of canola oil is limited; however. inrecent yean. aeveral aspects of ceoota oil hydrogenations with corn-mercial nickel catalysts have been reported including the forme-tion of tran...isomers. trisaturated glycerides and physical proper-ties. In addition. as the methods for determination of sulfur com-pounds in canola oil developed. the effect of some isothiocyanat.eson the hydrogenation rate was further investigated to determinethe relative cata.lyst poisoning ability of several of these sulfur com-pounds. However. during the last few years. most of the effortswere directed towards development of novel. selective and activecatalysts for canola oil hyd~natioIDl. These studies cover a widerange of homogeneous and heterogeneous catalysts including sulfurpoisoned nickel. gold euppceeed on siUca. arene-CriCOJ3•RuCI2(COJtlPPh3~ palladium on carbon. palladium hlac.k and

The following abi/trru!ti/ were taken from pClp«rs which appearedin the January issue of Lipids.

A Study of the Slructurell and Reactiona of Some MethylSublitituted UnNturated CIS Eeter Intermediate8 in tbe Syn·thesis of a Racemic Mixture of IG-MetbyloctadeeaDoic Acid

Marcel S.f. Lie Ken Jie and David W.Y. Leung

Department of Chemistry. University of Hong Kong. PokfulamRoad. Hong Kong

Methyl IG-undeeenoate was hydrated to methyl tG-hydroxyun·decanoate using mercury (II) acetate in aqueous tetrahydrofuran(THFJ. Chromie ac.id oxidation of methyl tG-bydroltyundecano-ate gave methyl ID-oxoundecanoat.e. which was hydrolyzed to

INFORM, Vol. 1. no. 2 (February 1990)

162

ABSTRACTS FROM AOCS JOURNALS

IO-oxoundecanoic acid. Reaction of n-octyl magnesium bromidecomplex in THF with IG-oxoundecanoic acid furnished lo-hydroxy·ID-methyloctadecanoic acid after hydrolysis. The latter compoundwas esterified, and dehydration of methyilo-hydroxy.lQ-methy\·octadecanoate with p-tolueneaulfonic acid in benseee gave II mix-ture of unsaturated branched fatty ester intermediates: /Ju methyl1Q·methyl·g·octadeeenoate, 1Il-methyl-I Q-octadeeenoate and1O-octyJ-' u-uedecenoete. Treatment of the mixture of unsaturatedbranched fatty ester intermediates with mercury (II) acetate inmethanol gave exclusively methyl IO·methoxy-IO-methylocta·decanoate. Epoxidation of the lIame mixture of unsaturated fattyesters with m-chloroperberaolc acid provided II mixture of epoxyderivatives: methyl 9,1Q·epoxY-l Q-methyloctadecanoate.10, ll-epoxy-' G-methyl«tadecanoate and 2-octyl-oxiraneoDon~ate. Catalytic hydrogenation of the mixture of unsaturated fattyestera gave a racemic mixture of methyllo-methyloctadecanoate.which Willi hydrolyzed to lo-methylOCladecanoic acid. The struc-tures of the mixture of unsaturated branched fatty ester in-termediates and their derivativea were characterized by chemicaland spectroscopic analyses.

Recovery of Fisb Oil· Derived ratty Acids in Lymph of ThoracicDuel·Cannulated Wistar RatsMarla Reicks. James Hoadley. Subramaniam Satchithananda.mand Kim M. Morehouse

Food and Drug Administration. 200 CSt... S.W .• Washington. DC20204

The absorption of equivalent doses of eicosepentaenoie anddocosahe.laenoic acids was compared in rats when administeredas the ethyl eater concentrate. ethyl ester concentrate plus olivenil. tree fatty acid or trtecylglycerolimennaden oil). Lymph wascollected from a thoracic duct cannula for 24 hr after dosing viaan indwelling duodenal catheter. After 24 hr, the absorption ofeicosapentaenoic acid was greater for the free fatty acid andmenhaden oil than for the ethyl ester form. but dccceehexeencicacid absorption was comparable for alI forms. Other rats hadgreater plasma levels of eicosapentaenoic and docosahexaenoicacids 5 hr after oral gavage dosing with menhaden oil than didrats dosed with the ethyl ester form.

Intestinal Absorption of Unconjugated Dihydro",y Bile Acids: Non·Mediation by the Carrier Sy.tem Involved in Long Chain FattyAcid AbsorptionWolfg.ng Stremmela and Alan r. Hofmannb

aDivision of Gastroenterology. Department of Internal Medicine.University Clinics of Dusseldorf. Moceenstrasee 5. 4000 Dusseldorf,Federal Republic of Germany. and bDiviaion of Gastroenterology.Department. of Medicine. School of Medicine. University of Califor·nia at San Diego. La Jolla. CA 92093

Experiment8 were performed using isolated mucosaJ cells from therat jejunum or using the perfused jejunum in the anesthetized ratto test whether lipophilic unconjugeted dihydroxy bile acids areabsorbed from the proximal small intestine via the same carriermechanism involved in the uptake of long chain fatty acids. Withisolated jejunal mucosal cells, the cellular uptake rate of deoxycholicacid or chenodeoxycholic acid increased linearly with time. showedno evidence of 88turation, and was not decreased by the presenceof a monospecific antibody to the membrane fatty acid bindingprotein. In contrast. oleate uptake was eaeureble, was inhibitedby the eeme antibody. but was not affected by the presence ofchenodeoxycholic acid or deoxycholic acid. Bile acid uptake byisolated enterocyt.es occurred at one-eighth the rate of fatty aciduptake if expressed in relation to total solute concentration; if ex-pressed in relation to monomeric eeoceeweuon. initial bile acid up-take was four orders of magnitude slower than fatty acid uptake.

In the isolated perfused jejunal segment. chenodeoxycholic acidand deoxycholic acid uptake was not influenced by the presenceof the antibody to membrane fatty acid binding protein. whereasabsorption of oleate was inhibited by more than 70%. These e.l·periment8 indicate that absorption of unconjugated lipophilicdihydroxy bile acids in the rodent jejunum does not involve thecarrier mediated uptake mechanism involved in the absorption oflong chain fatty acids-the mechanism is likely to be passivenonionic diffusion.

The Uptake of (R,R.RIo·Tocopherol by Human Endothelial Cellain Culture

Alvin C. Chan and Khai Tran

Department of Biochemistry. Faculty of Health Sciences, Univer-sity of Ottawa, 451 Smyth Rd.. Ottawa, Ontario. Canada KIH 8M5

Endothelial cells from human umbilical cord vein in culture incor-porate physiological and pharmacological amounts of (R.R.RIo-tocopherol in a time-dependent and dose-dependent manner. In-corporated tocopherol was found to associate predominantly wiLhmembrane fractions of the cell. When expressed on the basis oforganelle protein. the highest amount of tocopherol was found inplasma membrane. and decreasing amounts in mitochondria, en-doplasmic reticulum and cytosol. With the relatively wide rangeof tocopherol concentrations used in these studies (23.2-92.8 ~1).there Wl8 no apparent toxicity on the cells as judged by unalteredcell numbers and cell viability. When the cells were enriched withtocopherol and cell tocopherolleve1s were monitored in tocopherol·free medium. there was a rapid phase of tocopherol disappearance.which was followed by a slower phase, The half.time for the disap-pearance of incorporated tocopherol was found to be approximately65 ± 8.6 hr (mean ± SD. n = 8\. The results of this study clearlyshow that human endothelial cells in culture are a feasible modelfor the study of vitamin E uptake. The cell culture model couldpotentially be used 1.0 study other fat-soluble vitamins and essen-tial nutrients.

Identification of Vitamin &Dependent Water Soluble FluorescentCompounds in Mouse Tislluet!

John D. Manwllring and A. Saari Csallany

Department of Food Science and Nutrition, University of Min-nesota, 1334 Eckles Avenue. St.. Paul, MN 5(il08

The present paper describes the identification of two vitamin E-dependent. water soluble fluorescent compounds in mouse tissues.Ultraviolet and fluorescent spectroscopy. derivatization withl·dimethylamino-naphtaJen&5·9ulfonyl chloride (dansyl chloride)and cochromatography using high performance liquid chromatog-raphy (HPLC) were utilized for the identification of the unknowncompounds. The water soluble fluorescent compounds in mousetissues were identifM!das tyrosine and tryptophan.. Tbecompoundswere previously found to increase significantly in vitamin E defi-ciency in various tissues.

Erred8 of Dietary Fish on on Biliary Phospholipids andPrOtltaglandin Synthesis in the Cbclesterel-Ied Prairie Dog

Michael 1.. Booker. Thayer E. Scott and Waytle W. La Morte

Surgical Research Sect:ion.. Department of Surgery. Boston Univer-sity Med.ieal School. 80 ElllIt Concord St., Boston. MA 02118

Cholesterol gallstone formation in the prairie dog is accompaniedby an increase in the percentage of biliary phospholipids contain·ing arachidonic acid. and an increase in gallbladder prostaglandin(POI synthesis. but the pathogenetic significance of these changesis unclear. Dietary supplementation with eicosapentaenoic acid

INFORM. Vol 1. no. 2 (February 1990)

163

ABSTRACTS FROM AOCS JOURNALS

(EPA), an omega-S fatty acid which is commonly found in fish oil.decreases prostaglandin synthesis in some tissues by replacingarachidonic acid, and by competitively inhibiting prostaglandinsynthesis. We studied the effect of dietary fish oil on gallbladderPG synthesis, and the relative abundance of various molecularspecies of phosphatidylcholines and phosphatidylethanolaminesin bile and gallbladder epithelium in the cholesterol-fed prairie dog.Prairie dogs were maintained for 4 weeks on one of four diets; i)control, ii) cholesterol-supplemented (0.34%). iii) menhaden oil(50 gfkg chow}, or IV)cholesterol plus menhaden oil. Supplemen·tation with menhaden oil resulted in 8 replacement of arachidonicand linoleic acids with EPA and docosahexaenoic acids in thephospholipids of bile and gallbladder mucosa. In ehclestercl-fedanimals. supplementation with menhaden oil prevented increasedgallbladder PG synthesis. Menhaden oil also reduced the incidenceof cholesterol monohydrate crystals among cholesterol-fed animals(9/20 with cholesterol plus menhaden oil va 21/22 with cholesterolalone]. but the improvement could not clearly be attributed todecreased PG synthesis since supplementation with menhaden oilalso increased the total phospholipid concentration in bile. anddecreased the degree of cholesterol saturation. These resultsdemonstrate that dietary supplementation with omega-3 fattyacklssignificantly influences biliary phospholipids, and decreases theincidence of cholesterol monohydrate crystal formation in thisanimal model.

Auto:o:idation of Polyunsaturated TriacylglYCfl"ols, J. Trilinoleoyl·glycerolW.E. Neff, E.N. Frankel and K, Miyashita

Northern Regional Research Center, Agricultural Research Ser-vice, U.S. Department. of Agriculture. Peoria, IL 61604

The bydroperoxidea and secondary produete formed from triolinoleoylglycerol autoxidized at 40aC were isolated and character-ized to clarify their contribution to oxidative deterioration ofvegetable oils. The prcdueca were purified by high performanceliquid chromatography (HPLCI and identified, as intact triecyl-glycerols, by ultraviolet, infrared, lH NMR and 13C NMRanalyses, and after derivatization by lipolysis, gas chromatography,and gas chromatography-mesa spectrometry. The main, primaryproducts included monc-. bis- and tris-s-bydrcpercxy-srens-lOicis-12-; 9-hydroperoxy·troIl1l·12; 13-hydroperoxy-cis-9,trons·ll; and13·hydroperoxy·trolls-9,tronll-ll·linolenoyl glycerols. The etruc-tures of the minor secondary prcdueta analyzed after derivatiza-tion were consistent with known oxidative degradation productsof linoleate hydroperoxides. HPLC analyses showed that the bis-and trfs-hydropeeoxldea were formed from the meno-hydroperox-ides during autoxidation at peroxide values above 18 and28 meqlkg. Studies on the further oxidation of the mono-hydro-peroxides support a mechanism for the consecutive formation ofbis· and tais-hydrepercxides from the monohydroperoxides. HPLCanalyses showed that no preferential oxidation occurred betweenthe US}-and 2·triglyceride positions. Hydroperoxides of linoleatetriacylglycerols may be important precursors of volatile compoundscontributing to off-flavors of vegetable oils.

Autoxidation of Polyunsaturated Triacylglycerols. II. Trilinolen-oylglycerol

E.N. Frankel. W.E. Ndf and K. Miyasbita

Northern Regional Research Center, Agricultural Research Ser-vice, U.S. Department of Agriculture, 1815 N. University St.,Peoria. lL 61604

The hydroperoxides and secondary products formed from tri-llnclenoylglycerol autoxidized at 40°C were isolated and char-acterized to clarify the mechanism of Qridative deterioration ofpolyunsaturated ve~table oils. The products were purified by high

performance liquid chromatography (HPLCI and identified eitheras intact triacylglycerols spectrophotometrlcally, or after lipolysis(pancreatic Jipasel and capillary gas chromatography and gO!!chromatography·mass spectrometry. The products included 9-. 12-,13-, and te-mcnc-. bis·, tris-hydropernxy. 9· and I6-hydroperoxyepidioxy, 9- and 16·hydroperoxy bicycloendoperoxy and 9,12-,13,16·, and 9,16·dihydroperoxy linolencylglycerols. The mono-hydropeeoxidea and hydroperoxy epidioxides were the only mainpreduets initially formed at peroxide values (PV) below 30. Bis-and tris-bydroperoxides were formed consecutively as minor pro-ducts from the mono-hydroperoxides at PV's between 31 and 47.Hydroperoxy bicycloendoperoxidea and mono-dihydroperoxideswere also formed as minor secondary products at PV's above 75.H PLC analyses show a small preference for the formstion of 16-hydroperoxides on the I(S)'position over the z-posttion of trilino-leneylglyeerol. However, there was no selectivity for the forma-tion of the 9-, 12- and 13·hydroperoxides and for the hydroperoxyepidioxides between the !i31· and the 2'positions in trilinolen-oylglycerol. Mono-hydroperoxides and hydroperoxy epidicxidea oflinolenate triacyiglycerols may be important precursors of volatilecompounds contributing to oxidative deterioration of vegetable oils.

Autoxidation of Polyunsaturated Triacylglycerols. Ill. SynlhelicTriacylglycerols Containing Llnoleete and Linclenate

K. l\1iyashita, E.N. Frankel. W.E. Neff and R.A. Awl

Northern Regional Research Center. Agricultural Research Ser-vice, U.S. Department of Agriculture, 1815 North University St ..Peoria. lL 61604

Four triacylglycerols containing linoleat.e (L) and linolenat.e (Lnlin specific positions were synthesized to determine the effect offatty acid position on their relative rates and products of autox-idation. Analyses by reversed-phase high performance liquidchromatography (HPLC) showed that autoxidation of L- and Ln-containing triacylglycerols form monohydroperoxides andhydropemxy epidioxidea as tbe main products. The peroxyl radicalsof intemall2- and 13-mono-hydroperoxides of Ln triacylglycerolcomponents cycJized rapidly and their relative triacylglycerol pcai-tion had no influence on their rates of cyclization. A good linearrelation was obtained between total H PLC peak areas (detectedat 235 nm) of the main oxidation products and peroxide values.Reversed phase H PLC analyses thus provide a useful method toestimate oxidation of polyunsaturated triaeylglycerols. The ratiosof Ln to L mcno-hydropercxides were twice the ratios of Ln to Lin the triacylglycerol substrates. Ln triacylglycerol components,therefore. oxidized twice as much as the L components. At. 40°C,LnLnL oxidized slightly faster than LnLLn with respective induc-tion periods of 45 and 47 hr. LLnL oxidized faster than LLLn withrespective induction periods of 56 and 60 hr. Dilinolenoyl-Iinoleoylglycerols are, therefore. slightly less stable to oxidationwhen Ln is in the 1,2· than the l.3-triacylglycerol position. Dilincle-cyl-Iinolenoylglycerols are less stable when L is in the 1.3· thanthe 1,2·triacylglycetol position.

Incorporation of Linolenic Acid and Its Conversion to y-LinolenicAcid in FungiYasushi Kamisaka(l, Toshihiro YokochiO, Toro NakaharaO andOaemu Suzukib

0Biological Chemistry Division and bOrganic Chemistry Division,Nationa! Chemical Laboratory for industry, Higashi I-I. Tsukuba.lbarakl. 305, Japan

The incorporation of 1J-I4C]linoleic acid (LAI into lipids of Mor-tierello romonnion(l var. (lngu/ispol'll was studied to determinewhich lipid classes participated in the .66-desaturation of Il.14C).LA. [1_14CILA was rupid1y taken up into fungal celli! and eltter;-fied into various lipids. Comparison of Lhe profile of [1·14C]LA

INFORM, Vol. 1. no. 2 (February 1990)

164

ABSTRACTS FROM Aoes JOURNALS

incorporation between fungal cells at the exponential ~wth phaseand the stationary growth phase showed that [I_I CJLA incor-poration into most lipids-except for triacylglycerol (TGI andphosphatidylcholine (PC}-were greatly reduced lit the stationarygrowth phase, Desaturation of Il·14CjLA into y-linolenic acid(GLA) readily occurred at the exponential growth phase. but wasgreatly decreased at the stationary growth phase. Moreover, pulse-chase experiments revealed that the rediolabel inccrpereted intophosphatidylserine (PS) and PC rapidly turned over. while that inTG and diacy\gJyceroIIDG) accumulated after the 4 hr chase. tiladdition to the change of the radiolabel in individual lipids. thecontent of radiolabeled GLA converted from Il·HC]LA variedwith individual lipids. In phospholipids such as PC,pbosphatldylethenolamine iPEI and PS. radiolabeled GLA rapid-ly increased after 1 hr and then decreased after 4 hr. On the otherhand. a gradual increase in radiolabeled GLA until 4 hr was ob-served in TG. These results suggest that LA. which has beenesterified into phospholipids such as PC. PE and PS. is readilydeearueeted to GLA. which is then transferred to TG. These dif-ferences in the fate of GLA derived from LA between phospholipidsand neutral lipids may be reflected in the GLA content In the in-dividual lipids.

The Diat.ribution and Phylogenetic Significance of Oesmethyl·sterols in Chenopodillm and Atriplex: Coexistence of t/· and4"·SterolaSihua x,«. Glenn w. Pattersono• William R. Lusbyh. Kathy M.Schmida and Thomas A. Salta

aOepartment of Botany. University of Maryland. College Park.MO 20742. and blnseet and Nematode Hormone Laboratory.USDA. Beltsville. MD 20705

Twenty-one species in the Cbenopedieceee were analyzed for sterolcomposition. In ten of eleven species of Chenopodium. the majordesmethylsterols were 41·sterols accompanied by lower peeper-tions of lls·sterols. In C fremontii this pattern was reversed. Thesterol profiles of five species of Atriplex were characterized by thecoexistence of 41• and 4~·sterols in ratios of 0.3:1 to 0.4:1. MaleAtriplex plants contained higher proportions of 46·sterols thanfemale AI,ri~lex plants. One Cerotoides and two Solicornia speciescontained 40·sterols as their predominant sterols.

Binding of Galaclosylsphingosine jPsychosinel by Albumin

Hidekl IgisuO, Masato Matsuokall lind Neorekn Hamasakib

11 Institute of Industrial and Ecological Sciences. University of Oc-cupational and Environmental Health. Kitakyushu 807. Japan: andbDeparunent of Clinical Chemistry and Laboratory Medicine.Faculty of Medicine. Fukuoka University. Fukuoka 814.()1. Japan

On applying \3Hlgalactooylsphingosine (psychcsinel and albuminto a gel filtration column. either as a pre-incubated mixture or asseparate solutions. the lipid and albumin co-eluted. When albuminand [3H)gslactosylsphingosine were incubated with Sephadex0·50. the concentration of galactosylsphingosine outside the gelincreased as the concentration of albumin increased. These cbser-vations indicate that albumin binds galactcsylsphingosine. By us-ing an equilibrium gel procedure. it was estimated that one moleculeof albumin has 7.4 binding sites for galactooylsphingosine, and thatthe dissociation constant is 3.9 X 10-6 M. These values appearcompatible with the potency of albumin to suppress gedectcsyl-sphingosine-induced hemolysis.

Identification of the New 23·Melhyl·5.9-pentacosadienoic Acid inthe Sponge Cribrocholillo vOl/cllllU1I

Nestor M. Carballeria and Elba O. Reyes

Department of Chemistry. University of Puerto Rico. Rio Piedras.Puerto Rico 00931

The phospholipid fatty acids from the sponge Cribroehalinauascutum were studied. revealing the presence of t.he new 23·met.hyl·5.9-pentacosadienoic acid (26:2) which completes the rso-anleiso 26:2 (4S.9) series. Ot.her phospholipid fatty acids isolatedinclude 2&methyl·S.9-heptacosadienoic 128:2) and 25-methyl·S.9·beptacosedienoic 128:2). as well as the branched acids 8-methyl·hexadecanoic and Lt-methyloctadecanotc. The fatty acids describedin this work were found in pboaphatidylethanolarnine. phospha-cldylserlne. and phosphatidylinositol. The sterol composition of C.vasculum consisted of petrosterot. an interesting cyclopropane con-taining sterol. and the more common sitosterol. The phospholipidfatty acid composition of the demosponge Ircinia strobiliI/O is alsoreported upon.

AOCS Mission StatementTo be a forum for t.he exchange of ideas, informationand experience among those wit.h a professional inter-est. in the science and technology of fats. oils and

Declaration by the Governing BoardThe American Oil Chemists' Society is organized forcharitable, educational and scientific purposes. It. doesnot. have as its purpose the promotion of any product,manufacturers. laboratory or business. Members ofthe Society. and employees of the Society, do not andmay not speak for or on behalf of the Society withoutthe expressed permission of t.he Governing Board.

related substances in ways that promote personalexcellence and provide for a high st.andard of qualit.y.

This prohibition includes the use of t.he American OilChemists' societ.y logo or letterhead when making astatement of a technical or economic nature. Mem-bers of the Societ.y, or employees of the Society. speakonly for themselves when giving opinion or makingstatements concerning technical matters and economicmatters.

INFORM. Vol. 1. no. 2 (February 1990)