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Ether Lipids Based on thl' Glycer)'1 Ether Skfleton: Present State,Future POlential. Kouichi UrataCl and Naol.ke Takaishib• OTochigiResearch Laboratory. Kao Corporation, 2606, Abbane, Ichika.imachi.Haga-gun. Tochigi, 321-34, Japan and b-rokyo Research Laboratory, KaoCarporation. Sumida-ku. Tokyo 131, Japan.

Lipids from natural SOIIn:e5 consist mainly of saponifiable substances.such as glycerides, along wnh some unsaponifiablc lipids. some of whichare ether lipids. Typical ether lipids are moncalkyl ethers of glycerin. alsocalled alkyl/alken)'l glyceryl ethers. Alkyl/alkenyl glyceryl ethers neveabo been reponed in marine organisms and in human feces. Severalchemical syntheses of such ether lipids have been reported. Typical exam-ples are alkyl glycery! ether fonnalion by the addition reaction of alkylglyridyl ether and the IelomeriUlion reactioo of butadiene with glycerinand a U'aIIsition metal catalyJl Characteristic chemical S1I'UCtU~ such asterpene alkyl glyteryl ethers. archaebacterial macrocydic ether lipids, andglyceryl ethers of condensed. cyclic planar molecules. have been obtainedas well. Over the pW few decades, industry has shawn much interest inthe chemistry and application of highly branched fatty acids. For example,isostearyl glyceryl ether (GE-IS) with methyl branching in the middlechain was already known. but it is now prepared at an industrial scale byproprietaty aJkyl glycidyl ether methods. The characteristic behavior ofGE-IS towan! weter, such as formation of water-in-oil emulsions contain-ing large amounl$ of water and of liquid crystals. has made it applicablefor use in hair and skin-care ccsmencs. Based on these studies and consid-erations, glyceryl ether lipids, which are rarely investigated. may becomeone of the most important and useful lipids in the industry.[JAOCS 71. gl9-83O (1996)]

Appllc:alions of Phase- 1'rall!iftr Calalytlc Reactions to Falty Acids andTheir Derlvatlvl'5: Present Stale and Future Potential. Kouichi UrDtaaand Naotake Takaishib, aTochigi Research Laboratory. Kao Corporation,Tochigi 321-34, Japan and Prokyo Research Laboratory. Kao Corporation.Tokyo 131. Japan.

Phase-transfer catalysts (PTe). which accelerate reactions betweenliquid(organic)-liquid(water) and liquid-solid nerercgeoeccs states. havebeen investigated and developed. Several processes with PTC have suc-ceeded in industrial processes involving fatly acids and their derivatives.For example. preparation of fatty alkyl glycidyl ethers, from which fatlyallryl glyceryl ethers and their derivatives can be obtained. has been car-ried out with PTC. However, some problems remain to be solved. Forexample, preparation of the fntly alkyl glycidyl ether by a PTC reactionWilli considered, hut typical problems to be solved included: (i) how toreuse or recover the catalysts; (ii) how to control the heterogeneous reac-tion without obstacles to produce useful chemical materials; (iii) how tosatisfy the environmental requirements for the catalysts; and (iv) are theremore effective catalysl$? We address these problems based on our ownexperiences with phase-uanster catalytic Williamson ether syntheses offolly alkyl glycidyl ethers. Moreover, we describe recent developments inphase-transfer catalytic reactions related to oleochernistry. such as transi-tion mctaJ<atal~ reactions orlong<hain olefins in liquid(organic)-liq-uid(water) or liquid-solid heterogeneous states. Based on these results, wehave considered the potential of PTC as a synthetic tool in oleochemistry.(JAOeS 71. 831-839(1996»)

Synthelib and Characterization of Clean,ble SurfactanlS Derived tromPoIy(etbylene glycol) Monomethyl Ether; Chengyun Yue'"l.J. Milton Har-risi'. Per-Erik Hellbergb, and Karin Bergstromb, lI(:hemistry DepartmentThe University of Alabama in Huntsville. Huntsville, Alabama 35899 andbAkzo Nobel Surface Chemistry AB, S-444 85 Stenungsund. Sweden.

A series of noncyclic acetal-linked cleavable surfactanl.5 were simplyprepared by condensation of aldehydes with poly(ethylene glycol)monomethyl ethers. All of the products wen: characteritcd by IH nuclearmagroetic resonance. Their hydrophile-lipophile balance, surface tension.cloud point. critical micelle concentration. and foam height were deter-

mined. Hydrolysis kinetic studies. followed by gas Chromatography.showed that they had higher hydrolytic reactivity in acidic solution thancyclic acetal-linked cleavable surfactants.[JAOeS 73. &41-&45 (1996»)

Synlhcsel ot Long·Chaln QuatemllJ)' Ammonium Salts from Fatly Al-cohols by Mlcrowan IrradJalkm. Yu-Un JiangQ• Yu-Qiao Hua. JunPangb, and Yun-Cheng Yuantl, QSchQol of Chemical Engineering, DahanUoiversity of Technology, Dalian 116012. China and bDalian Institute ofChemical Physics, Dalian. OJinL

The phase-transfer cataJySl$, long<hain quaternary ammonium sall$.were rapidly symhesized from fauy alcohols by the reactions with hydro-gen lu\1ides in the presence of trialkyl amlne$ under microwave ilT1ldiation.The cataJySts could be widely applied in a variety of quick and new organicreactions. whether by conventional heating or under microwave imldiation.The reaction efficiencies under microwave irradiation were higher thanthose obtained with con\'Cnlion.al heating.[JAOCS 71, &41-850(1996»)

The Biocon"ersion of Ethanol to B\n<;urflloCtantsand Dye by a No ..d C0-production Tfdmiqut.. M. OsmanO, Y_lshigamia• J. Somcyab. and HaraldB. Jensenc. aNDtional Institute of Materials and Chemical Research. Or-ganic Chemicals Division, Applied Interfacial Chemistry. Tsukuba.Jbaraki305. Japan. bNational Institute of Life Science and Human Technology.Depanrnent of Applied Microbiology, Tsukuba, lbarili 305. Japan. and'Department of Biochemistry and Molecular Biology. University ofBergen. Bergen. Norway.

Rhamnolipids. multifunctional glycolipid biosurfectams. and pyocya-eine. a phen.u1lC dye, were coproduced by PuiUJomoNu BOPIOO fromethanol IS the sole carbon source. Bacterial growth was dependent on theethanol concentration in the medium. Pyocyanine was produced only dUT-ing the exponential phase, while rhamnolipids production continued dur-ing the stationary phase. indicating two diffen:nt ways of production foreach of the products. Maximum coproduction capacity Willi observed at aconcernretion of 3" ethanol; yield of rhamnolipids Willi 3 gil. and ofpyocyanine 0.2 gil. The producl$ were characterized to confirm theirchemical Structures.[JAOeS 71, 851-856(1996)]

An Improved Failing-.-lIm Reactor for Viscou'l Liquids. F.I. Talens. J.M.GutitlTCz, and C. Mons, Department of Chemical Engineering, Universityof Barcelona. 08028 Barcelona. Spain.

This paper presents the design of a sulfonation reactor that is intendedfor enhanced performance when the viscosity of the liquid phase increases.thus reducing gas-liquid transfer rates. The proposed design allows ade-quate transfer rates to be maintained by progressively increasing the shearstress exerted by the gas over the liquid film. The effectiveness ofihe de-sign has been tested in runs in which dcdecylbenzene and louryl alcohol1.80E arc sulfonated/sulfated.IJAOeS 71, g51-861 (1996)]

Quantilathe-Structure-Effect Relationship for Some Technical Nonlon-k Surfactants. Asa Lindgren, Michael Sjtinrtim, and Svante Wold, UmdUniversity, 901 g1 Urne", Sweden.

The detergency effect has been examined for a series of technical non-ionic surfactams with the use of statistical experimental designs andrevealed a plateau in each of the response surfaces obtained. The surtac-tant concentrations and washing temperatures. needed to reach the edge ofeach detergency effect plateau. were also determined. These conditions,which define the edge of the plateau, could be well modeled from thephysicochemical propenies of the surfactanl$ with the usc of partial leastsquares of latent struCtures. It was also possible to point out the impor-tance of the different physicochemical properties. If an experimentaldesign has been utilized, the detergency effect of a nonionic surfactant canbe modeled from multiple linear regression as a function of surfactantconcentration. washinl time, and washing temperature. We have shownhow these regression coefficienl.5 can be modeled from the phyaicochemi-cal properties of the surfactanlS. Partial least squares of latent structureswere used to estimate these models as .....ell. We also demonstrated howthese models can be used to ~ict the regression coefficients of a surfac-tant not included in the model estimations. The resultant regression coc:ffi·cients can then be used to predict the detergency effects of this surfactant

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al diffm:nt variable settings. The detergency effects thus obtained an: ingood agreement with measured data ecqulred under corresponding condi-tions.[JAOCS 71. 863-875 (1996»)

Solubilizing Effects Caused by the NonloDlc Surfactant Octyl Gluco-side In Phosphalldylchoiinc Llposomts. Alfonso de III Maza and JoseLuis Parra, Departamento de TensioactiVQ5,Centro de In\'cstigaci6n y De-sarrollo (C.I.D.l, Consejo Superior de Investigaciones Cientfflcas(C.SJ.c.). 08034 Barcelona. Spain.

Thc me<:hanisms governing the interaction of the nonionic sunacUlIltoctyl glucoside (OG) on phosphatidylcholine (PC) liposomes we", inves-tigated. Pcnneability alterations were detected as II change in 5(6)·car-bollynuo=in (Cf) released from the interior of vesicles. and bilayersolubilization was dererrmned 15 IIdecrease in the static light scattered byjfposome suspensions, A direct relationship was established in the initialinteraction Steps (10-50'1> CF release) between the growth of vesicles, theleakage of entrapped CF. and the effective molar ratio of surfactant tophospholipid in bilayers (Re). This dependence was also detected duringthe solubilization range of Re values between 1.3 and 3.0. where thedecrease in the surfactant-PC aggregate size and in the light scattering ofthe system depended on the Re parameter and. hence on the compositionof these aggregates. The free OG ccncentrauons at subsolubilizing andsolubilizing levels showed lower and similar. respectively. values than itscritical micelle concentration (CMC). 1bcsc findings indicated that thealterations in bilayer permeability were due to the action of surfactantmonomers. whereas bilayer solubilization was determined by the forma-tion of mixed micelles. This finding supports the generally acceptedassumption that the concentration of free surfactant must reao:h the CMCfor solubilization \0 occur.(JAOeS 73. 8TI--883 (1996)]

SurflK't: ACl.hily and PremktUar Aggrq;ation of Some NO\'d Diqualtr-nary (;tomlni Surfactants. Milton J. Rosen and Letian Liu. SurfactantResearch Institute. Brooklyn College. CUNY. Brooklyn. New York11210.

A series of novel cationic gemini surfacrants. C"HZ" + IN+(CH3)ZCHZCHOHCHOHCH2N+(CH3)2 C"Hb! + I •2Br-. haveteen synthe$ized. and their surface properties WCf'C investigated in waltr.0.1 N NaC!. and 0.1 N NaBr at 25°c' From surface tension-log molarconcentration plots. the pC2(}Ocritical micelle concentration (CMC). andYcMC wlues have teen determined. and the arealmolecule at the aquCQtJssolution/air interface was calculated. When the number of carbon atoms inthe alkyl (hydrophobic) chains is above a certain number. which dependsupon the molecular environment. the surface activity of the compounds isless than expected. This appears to be due to formation of small. solubleaggregates below the CMC, Equilibrium constants calculated for thisaggregation indicate that a series of o1igomers are formed.(JAoes 73. 88S-B90(1996)]

Surface-Tension Properties or Some Polydispersed Alkyl-SubstitutedPolyoxyelhylated PhenylsulfonamJdes. J.W. Hampson and D.O. Cornell.USDA. ARS. ERRC. Wyndmoor. Pennsyh'allia 19038.

Twenty-nine laboratory-prepared polydlsperse nonionic surracrams,derived from polyoxyethylated N-alkylphenylsulfonamides [R+SOzN(R')(EO)"H). have been chanicterized. EO is ethyoxylation; R is hydrogen. /1-

butyl or I-butyl; R' is hexyl. octyl. or decyl; and (EO)" is varied from(EO)4 to (EO)20' Surface tension in equeoes solution was studied. Thecritical micelle concentration. surface excess. minimum area permolecule. effectiveness of surface-temion reduction. and free eOCf!:y ofmicelle formation were calculated from the surface-tension measure-ments. The critical micelle concentrations for the derivatives in which R'• hexyl .....ere considerably higher than the corresponding derivativeswhere R' is cetyl or decyl. The grealcst surface-tension redoction wasfound in the R' = ,,-octyl derivatives where R is I-butyl with (E019 or rr-butyl with (EO)II'[JAOCS 73. 891--895 (1996»)

Molar Volun.e and U1lr11SOnicSiudies or Europlom Soaps In Mixed Or-ganic Solvents. K.N. Mehrotrau. M. Chauhana. and R.K. SlIuklab. aDe_partmeru of Chemistry. Institute of Basic Sciences and bDcpartrmmt ofChemistry. R.B.S. College. Agm - 282 002. India.

The uhrasonic velocity and density measurements of europium soapsin a mixture of benzene and methanol (3;2. vol/vol) were used to evaluate\'arious acoustic parameters and molar volume and 10 detennioe the criti-cal micelle ccecemrecon. The results showed that the uhrasenic velocity.specific acoustic impedance. molar sound velocity. and molar compress-ibilily increase. and intermolecular free length. adiabatic compressibility.and relative association ~ase with increasing concenlration and chain-length of the soap. The results .....ere interpreted in terms of soap-solventinteraction.[JAOCS 73. 897-902(1996)]

Effect or Homolog Distribution on the To):icily or Alcohol Etho:lYlales.M.T. Oarcfatl. I. Ribosaa. J. S'ncbez Leala. and W. Hrccwchb• uDeparta·mente de 'renstcecuvcs CID/CSIC. Barcelona. Spain and bInstitute ofHeavy Organic Synthesis "Blecbownia," Kedzierayn-Kozle. Poland.

Previous work established a high correlation between the potentialenvironmental toxicity of oxyethylenated non ionic surfactants and theaverage degree of ethoxylanoe. For this reason, it was considered of inter-est to determine whether a nUTrOW-or broad-range homolog distributionof pclydisperse commercial alcohol ethoxylates .....ould influence toxicity.Ethoxylated fany alcohols. bolh linear and branched. were synthesizedwith sodium hydroxide or an unconventional calcium-based catalyst. Tox-icity tests were run on Daph"ia magllll and luminescent marine bacteria.Toxicity of ethoxylared alcohols as a function of type of ethcxylatehomolog distribution (narrow or broad) and average degree of polyalidi-tion is analogous for both lest species. However. narrow-range ethoxylatesshow lower loxicity values than conventional Clhoxylates. Differences intoxicity values between broad- and narrow-range elhoxylales depend onthe degree of ethoxylation.(JAOeS 73. 903--906 (1996)]

Surfact'_Aclin Properties or No,·el Cationic Surfactants with TwoAlkyl Chains and Two Ammonlo Groups. Tae-Seong Kim. ToshlyukiKida. YoItji Nakatsuji. TO!ihikazu Hirao. and lseo Ikeda, Depanment ofApplied Cbcmistry. Faculty of Engineerinl. Osaka University. Osaka S65.Japan.

A series of bis-quatemary ammonium salts was easily prepared by thereaction of I Iong-chain tm-alkylantine with epichIorohydrin. and thcir sur-face-a:ti\.'C pupenies were measumi The prcparal amphipathic IXI01jXIUnds

had good watc:r solubility and showed characteristic surfatt-active properties.particularly. u\remcly c.xcelIC1Itfoaming ability and foam stability for somespecirlC compounds. such as the compound with a doda:yl and a teU'lIdecylgroup as the lipophilic chains. Their critical micelle concentration. whichdecreased with increased alkyl chalnlength. is two orders of magnitude lowercompared with the conventiooaJ "JOtJO-(jl.llltemllfy ammonium salts. In com-parisoo with sudace-active propcnies of bis-quatmwy ammonium salts, pre-pared from various organic dichlorides. there me little differences based 011 thekind of connecting group in the surfoce-:lCIiveproperties u~pt for foaming,(JAOCS 73. 907-911 (1996)]

Call1iytic Effect or Dipotassium Glycyrrhizinate on the Hydrolysis orNonkmk £.slfr Sw1'actants. Misao Koidefl. Masahilw Takahashib. SeizeTamagakib. and Waichiro Tagakih. aPharmaceutical Laboratories of LionCorporation. Kanagawa 256. Japan and bDepartment of BioappliedChemistry. Faculty of Engiotering. O$aka Cily University. Osaka 558.Japan.

The fwnily of dipotassium glycyn1tidnate (GK2) catalyzes the hydrol·ysis of nonicnic ester surfactants (NES). such as hydrogenated castor oilwith 60 oxyethylenc units altached (HCO-6O) and reooostearate with 2Soxyethylenc units attached (SA·2S). C\'Cn in the pH range of 3-6.....hereNES arc generally stable in the absence of GKl. Long-chain fauy acidsabo accelerate the hydrolysis reaction. Analyses. based on circulardichroism spectrOScopy. and empirical force field caIculations suggest thata GK2 and an NES molecule form an energetically stable complex I'iahydrophobic interactions in which the ester carbonyl is in close contactwith either one of the three different carboxyl groups in OK2. ao:ting as ...ao:id catalyst.[JAOCS 73. 913-920 (1996)]

Environmentally Acceptable Drag-Reducing SurfaClants ror Dl5trlctHeating and Cooling. J. Harwigsson" and M. Hellstenb. aOepanment orPhysical Chemistry I, S-221 00 Lund. Sweden and bAkzo Nobel Surface

INFORM. Vol. 7, no. 8 (Augusll996)

Chemistry AB, S-444 85 Sreeungsuod. S.....eden.The aim of this work was to find drag-reducing surfactants for both

district heating and cooling that are environmentally IIIOf"e acceptable thanthe organic salts of quaternary ammonium compounds that so far navedominated this application. vonex inhibition of test solutions in gill."beakers has been used to screen a large number of surfllClant mixtures.various electrolytes, and temperatures. For the most interesting products.the pressure drop in a test loop was measured at various now rates andtemperatures. N-cetyl sarcosinate and N-stearyl betaine, the latter togetherwith Na-dodecylbenuoe sulfonate, give good drag reduction (DR) prop.erties at 6S-100 and 45-85"C, respectively, The !oIUroSinate is sensitive topH changes. whereas the betaine-sulfonate complex is more robust.Etboxylmes of oleic acid monoethanolamlde show good DR properties atO-2SQC. At an increased salt concentration, a mixture of this surfactantwith an ethoxyllted oleyl alcohol worked ...·eU. AI a still higher salt con-centration. e.l .. sea water. a combination of N-cetyl bctainc and alkylben-zene sulfonate dM.JwedDR.[JAOCS 73. 921-928 (1996)1

Biodegradability and Aquatic TOll)dty orGI)'coside Surlactants and aNonionic Alcobol EthOJ()'late_ Terben Madsen. Gille Petersen. ConnieSeiere. and Jens Torslov. VKI Water Quality Institute, DK-2970 Hor-sholm. Denmark.

The environmental properties of three glycoside surfactanlS and onealcohol ethoxylate were examined by standardized laboratory methods.All of the surfactants biodegraded extensively in aerobic screening teStSand may be assumed to approach 100'l> removal in aerobic wastewatertreatment plants. except in cases of high loadings or otherwise exceptionalconditions. Anaerobic biodegradability tests showed that an ethyl glyco-side I1M)fIOeSter(EGE) and a linear alkyl polyglycoside (APG) wen: bothmineralized (>70'1» under methanogenic conditions. in contrast. abninchcd AP(; resisted anaerobic degradation .... -hile the alcobol ethoxy-late was partially mineralized by anaerobic bai:teria. The EGE surfactant.....as most rapidly mineralized in aerobic and anaerobic biodegradabilitytests. None of the surfactants inhibited respiration in activated sludge atthe highest concentration !Cited (200 mgfL). Tests with aquatic organismsshowed increasing toxicity in the following order. brnnched APG c EGE< linear APG < alcohol ethoxytere. Negligible aquatic toxicity wasobserved for the branched APG. while the atconot ethoxylate was highlytoxic to examined organisms. This evaluation demonstrates that consider-able variation in biodc:gradllbility and toxicity responses can be seen with-in structurally related glucose-based sunacrenu.1JAOeS 71, 929-933 (1996)[

EfTcelli of Braochlng upon Some Surfaclllnt Properties orSulrated Alco-hols. Anthony J. O'Lenick. Jr. and Jeffrey K. Parkinson, Siltech Inc .. Nor-cross. Georgia 30093.

A study was undertaken to determine the surfactant properties of vari-ous sulfated alcohols. Most notably. the Krafft point and the ability toemulsify decane .....ere studied. A series of sulfated Guerbet alcohol andGuerbet alcohol alkoxylete sulfates with 16 carbon atoms and an analo-gous series based upon eetyl alcohol, a linear C16. were studied ashydrop/lobes.[JAOCS 71. 935-937 (1996)[

Pelargomc Acid in Enhanced 011 Recovery. H. Noureddini and M.L.Rempe. Department of Chemical Engineering. University of Nebraska.Lincoln. Nebnlska 68,88-0126.

Oxidation of monoonsaturated fally acids. such as erucic and oleicacids. results in the formation of dibaslc fauy acids. such as brnssylic andazelaic acids. Dibasic acids find many industrial applications. Pelargonicacid is the co-product of the process. Expanded use of dibasic acids wouldrequire an expansion in the existing and possibly new uses for pelergonicacid and il5 derivatives. In this study. the potenual for using pelargonicacid in enhanced oil recovery is investigated. Experimental results are pre-sented for the enhanced oil recovery by waterflooding with the aid of asurfactant. In Silu fonnation of surfactant at the oil-water interface vs. theformation of surfacUlnt in the floodwater prior to injection is examined.[JAOCS 7J. 939-941 (1996)1

The Chemislry and Antloddanl Properties or Tocopherols andTocotrlenols- Afaf Kamal-Eldin and Lars-Ake Appelqvisr, Division ofFood Chemistry. Department of Food Science, Swedish University ofAgricultural Sciences. 750 07 Uppsala. Sweden.

This article is a review of the fundamental chemistry of the toco-pherols and «cceteecrs relevant to their enucodam action. Despite thegeneral agreement that a-tocopherol is the most efficient antioxidant andvitamin E homologue jn l·j,"O. there was always a considerable discrepan-cy in its MabsoluteMand "relativeM antioxidant effectiveness in I·irro. espe-cially when compared to 1-tocophcrol. Many chemical. physical, bio-chemical. physicochemical. and other factor.; seem responsible for theobserved discrepancy between the relative antioxidant potencies of thetocopneroi.s in 1';1'0 and jn vitro. This paper aims at highlighting some pos-sible reasotI$ for the observed diff~nces between the tocopherols tc-. ~,1-. and 5-) in relation to their inrerecncns with the important chemicalspecies inyolved in lipid peroxidancn, specifically trace metal ions. singletOllygen. nitrogen 0~ide5. and aminxldant synergists. Although literaturereports related to the chemistry of the tocotrienols are quite meager. theyalso ....ere included in the discussion in virtue of their structural and func-tional resemblance to the tocopherols.1Upids 3J. 671-701 (1996)1

H)'droperoDdes of EI')·thl'OC)"tePhospholipid Molecular Species Formedby LipoJ(}"genase Correlate ...ith a.Tocopherol Levels, Patrice llIcrond'l.Martine CouturierD. Jean Frant;ois Demelierb. and Frfd~riqueLemonnierv QINSERM U347. HOpital de Bidtre. 94276 Le KremlinBicetre and &Laboratoire de Biochimie. HOpital R. Deere. 75019 Paris .France.

lbe hydropero~ides corresponding to the main molecular species ofphosphatidylcholine (PC) and phosphatidylethanolamine (PE) were deter-mined after lipoxygenase treatment of erythrocyte membranes fromhealthy children. This work .....as a preliminary study prior to applying thisanalytical procedure to erythrocyte membranes from children with dis-eases associated with vitamin E deficiency. Tbe total molecular speciescorresponding to 20:4 and 22:6 associated with 16:0 and 18:0 were signif-icantly higher in PE (26.94:t 4.70 nmoUmg protein) than in PC (20.14:t6.70 nmoUmg protein): these concentrntions represented 63% of the totalmolecular species in PE and 22% in PC. However. the concentrations ofbydrcperoxides produced from these polyunsaturated fany acid molecularspecies .....ere in the same order of magnitude in PC (3.98 :t 1.56 nmoUrngprotein) and in PE (3.61 :t 1.63 nmoUmg protein). In contrast. the molecu-lar species concentrations containing two double bonds. such as 16:0118:2and 18:0118:2 and their corresponding hydroperoxides. were clearly moreelevated in PC than in PE. There was a positive relationship between theconcentrations of a-tocopherol and each hydroperoxlde of PC and PE,and this association was particularly strong in PE (P $ 0.0001). Theseresults suggest that a-tocopherol exerts a stabilizing effect towardhydrcpercxides. limiting their further degradation into peroxyl radicals.The protective effect of a-tocopherol could be more effective in PEbecause more polyuesmurated fauy acids were present.[Upids 31. 703-708 (1996)]

Plasma CODCC'ntra\iortsoCDihydro-Vitamin KI following Dietary Intake0( a Hydrogenated VItamin KI_Rkh Vegetable Oil. SW1IhL. Booth. Ken-neth W. Davidson, Alice H. Lichtenstein. and James A. Sadowski. JeanMayer USDA Human Nutrition Research Center on Aging 11.1Tufts Uni-versity. Boston. Massachusetts 02] 11.

Dihydro-vitamin K I is I dietary form of vitamin K I (phylloquinooe)produced during the hydrogenation of vegetable oils. To determine ifdihydro-vitamin K! is present in plasma following dietary intake of ahydrogenated fat. eight healthy adults consumed each of tw o diets con-taining JO'I, of calorie! from fat, of which 20% was either soybean oil ora partially hydrogenated soybean oil-based stick rlUII!arine. Of the fal5and oils llJ1aly;:ed. dihydro-vitamin K] was only found in the hydrogenat-ed products. The soybean oil diel contained ]80 ± 12 ~g (mean ± SO) of

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vitamin Ki'day and oondctectable levels of dihydro-vitamin K I ..... hereasthe slick margarine diet contained 199:t 7 Jig of vitamin K l/dJJ.y and 23:t2 Jig of dihydro-vaamln K ,!day. Arter consuming each. diel for five weeks.plasma dih.ydro-vilamin K, coecemrancns were higher (P = 0.002) in alleitlh.1 subjeclS when consuming the stid; margarine diet (0.56 j: 0.33nmoVL) compared 10 the soybean oil diet (0.12 1: 0.11 nmollL). TbereWI!i no significant change in plasma vitamin K I ccnceeeauoes when thetWOdiets were compared. In conclusion, dihydro-vitamin K I is detectablein plasma following dielllr)' intake of a hydrogenated vitamin K [-rich. veg-etable oil.IUpidJ J/. 709--713 (1996)]

Dlh)'dro-V1tamln KI: Primary t-ood Sources lind Estimated Dietary In.tllk~ In the American DieL Sarah 1... BoothQ, Jean A.T. Penninglonb, andJames A. Sadowskill, ClJean Mayer USDA Human Nutrition Research. Cen-ter on Aging at TUfts University, Boston, Messachuseus 0211 I and Ooivi-sion of Nutrition Research Coordination, National Institute of Health.Bethesda. Maryland 20892.

Dlhydro-vuamto K I was recently identified as a dietary form of vita-min K produced during the hydrogenation of vitamin Kj-rich vegetableoils. Dihydro-vitamin K I is absorbed. with measurable levels in humanplasma following dietary intake. To determine the primary food 5O\lTCeSofdihydro-vitamin KI in the American diet. 261 foods from the U.S. Foodand Drug Administration's (FDA) Total Diet Study (TDS) were analyzedby high-performance liquid chromatography. Of these foods. 36 containeddihydro-vitamin K I' Fast-food items that were otherwise poor sources ofvitamin KI.!iUCh as french fries and fried chicken. contained appreciableamounts o( dihydro-vilamin K I (36 and 18 ~gliOO g. respecth'ely). Thesenutrient values were then applied to the FDA TDS consumption modc:l 10determine average dietary intake of dihydro-vitamin K I in 14 age-gendergroups. With the excepuon of infants, all age-gender groups had estimat-ed mean daily dihydro-viuunin KI intakes of 12-24 pg. compared tomean daily vitamin K I intakes of 24-86 "g. lbc vitamin K I and dihydro-vitamin KI intakes were summed. and the dietary contribution of dihydro-vitamin K I was expressed as a percentage of tOlal vitamin K intake. Chil-dren reported the highest intakes of dihydro-vitamin Kl (JO% of totalvitamin K intake). followed by a progressive decrease in percentagecontribution with age. lbcre art: currently no data on the relative bioavail-ability of dihydro-Yitamin K I btu. given us abundance in the Americandiet. this hydrogenated form ofvitamin K werrems furthc:r investigation.(Lipids 3/.715-720 (1996)1

1'~nntJon of Chojesterol Cholelithiasis by Dietary Unsaturated Fats inHonuone- Treated Female Hamsters. Nariman Ayyad, Bertram I. Cohen.Akira Ohshima, and Erwin H. MosbllCh. Departments of Surgery. Beth Is-TIIelMedical Center. New York. New York and Albert Einstein College ofMedicine, Bronx, New York.

We examined the effect of diet on gallstone incidence and the compo-sition of biliary pbosphatidylcbolines in methyltestosterone-lrCated femalehamsters. These hamsters were fed a nutritionally adequate purifiedlithogenic diet containing 2% com oil. 4% benerfar. O.J% cholesterol. and0.05% methyltestosterone. resulting in II cholesterol gallstone incidence of86%. This incidence was lowered when mono- and polyunsaturated fats orfatty eckrs were added to the diet: 2.5,*, oleic lICid resulted in total preven-tion of cholesterol cholelithiasis. 2.5,*, linoleic lICK!.and 4% safflower oil(7g% linoleic acid content) reduced gallstone incidence 10 26 and 8%.respecnvely, An additional 4% bunerfat (29% oleic acid content) pro-duced gallstones in 50% of the animals. At the end of the 6-wk feedingperiod, the bile of all hamst~rs was supersaturated with eholcsterol. lbcmajor biliary pho5phatidykholine species in all groups were (slI-I-sIl-2):16:().lg:2. 16:0-18:1. 18:0-18:2, 16:0-20;4. and 18:2-18:2. The saffloweroil- and linoleic acid-fed hamstCB exhibited an enrichment of 16:0-18:2(16-18%): added butterfat or oleic acid increased the proportion of 16:0-18: I (9 and 25%. respectively). We conclude that the phospbatidykholinemolecular species in female hamster bile can be altered by dietaryfatslfany acids and that mono- and polyunsaturated fany acids playa rolein suppressing the induced cholelithiasis.(UpidJ J/, 721-721 (1996)]

1'llIteict and Aorta Arachidonic and Eicosapentllenolc Acid Levels andIn "iINl Eicosanoid Production In RIIUI fed Hlgh.fat Diets. Andrew J.Sonigorskia. Andrew J. Sinclairh. and Tomohito Hamazakiv. aSchool of

Human Nutrition and Public Health. Deakin Uninrsity. Geejong. Victoria.Australia J217. bDepanmenl of Food Science. Royal Melbourne Instituteof Technology, Melbourne, Victoria. Australia 3000. and C"fhc First De-partment of Internal Medicine. Toyama Medical and Pharmaceutical Uni-\mty. 2630 Sugitani Toyama-shl. 9JO..OI Japan.

ThcTe is signiflCllllt interest in the interrelationship bet ....een Iong<hainn·3 and n-6 fany ecsds due to their ability to modulate eicosanoid preduc-tion. In general, the intake of arachidonic acid (AA) results in enhancedeicosanoid production. whereas n-) polyunsatunlted fatly acids (PUFA)decrease the production of eicosanoids from AA. The purpose of thisstudy was 10 invcstigate whocthcr the effects of dietary AA on eiCOSllnoidproduction in the rat were correlated with the AA and EPA levels inplatelets and aorta Ieicosancid-preducing tissues). Four groups of maleSpregue-Dewley rats were fed a high-fat diet enriched with etcosepen-taenoic lICid (EPA) and docosahcxaenoic ecld (DHA) (apprcxtmately 100mglday of EPA + DHA) for 24 d. During the last 10 d. the four groupswere OI1Il1ysupplemented with 0, 30. 60. and 90 mglday of ethyl arachi-donate. A further group of rats was fed a control diet (without long-chainn·3 PUFA) for 24 d. In vitro aorta prostacyclin (PGI2) production. serumthrombcxane A2 (T~A2) production and plasma, and platelet and aortaphospholipid (PL) fany acids were measured. Enriching the diet with n-JPUFA resulted in significant reductions in tissue AA levels and anincrease in the n-) PUFA. particularly EPA. On this diet, the AA to EPAratio was 1:1 in platelet PL. and it was 2:1 in the anna PL. There were sig-nificant decreases in the in vitro PGI2 and TlIA2 production comparedwith the control animals. The inclusion of AA in the diet resulted inmarked increases in AA levels in the platelet and aona PL with ccrre-sponding decreases in EPA. lbc IO\\-'cstdose of AA (30 mglnt) reversedthe effects of 100 mgfday of no) PUFA on AA levels in platelet and aorticPL and on in vitro aorta PGI2 and Strum TlIA2 production. Tbe dietaryAA caused a differential (twofold) increase in TlIA2 relative to PGI2 forall three levels of AA supplemenution. There were greater changes in thele\'el5 of AA and/or EPA in plltelet PL compared with the anna PL.which might have IICCOWItcd for !he differential effects of these PUFA onthrombo~ane produCiion compared with PGI2 production in this study.[Upids 3J, 729-735 (1996)]

INFORM. Val. 7. no. 8 (Augusll996)

The Ratio ofn..fi to n.3 Polyunsaturated Fatty Acids in tbe Rat Diel AI·ters Serum lipid Levels and Lymphocyte Functions. N.M. Jeffery. P.Sanderson, E.l. Sherringtcn, E.A. Newebctrne. and P.e. Calder. Depart-ment of Biochemistry, University of Oxford. Oxford OX I JQU, UnitedKingdom.

Previous studies have reported that fceding rats diets rich in fish oils.which contain high proportions of the n-) polyunsaturated fatty acids(PUFA) etcosapentaencc and dccosehexaenoic ecjds, results in loweringof blood lipid levels and suppression of lymphocyte functions tested ex»tvo and in vivo. The effects of other n-3 PUFA. such as a-linolenic acid.which is found in high proportions in linseed oil. are Dot as well docu-mented. Therefore. in the presera study. weanling male rats were fed (Ofsix weeks on one of five high-fat (20% by weight) diets made by millingtogether sunflower and linseed oils: the resulting blends had n-61n-3PUFA ratios of 112.5:1 (pure sunflower oil), 14.8:1.6.5:1.0.8:1, and0.3): 1 (pure linseed oil); the levels of all other components in the dietwere identical. Tbe final body weight and total dissectable fat were lowcstin tlItS fed the pure linseed oil diet. Serum cboiestcrol, triacylglyccrol andnonesterified fany acid concentrations dccn:ascd as the n-61n-) PUFAratio of the diet decreased. TIle fatty acid composition of the serum and ofspleen lymphocytes was innuenced by the diet fed--there was a progres-sive decrease in the proportions of linoleic and arachidonic acids and aprogressive increase in !be proportion of a-linolenic acid as the n-6ln·JPUFA ratio of the diet decreased, Eicosapentacnoic and docusahenenoicacids were detccled in the serum but not in spll':C'nlymphocytes. Inclusionof u-llnclenic acid in the diet resulted in significant suppression of spleenlymphocyte proliferation in response to the T-<:ell mitogen concanavalin Aand in spleen lymphocyte natural killer cell activity, both measured a.';1'0. 1be localized graft 'Is. ~t response .• measure of cell-mediatedimmunity ill ,·i.,.,. progressively decreased as the n-6.'n-3 PUFA ratio ofthe diet decreased. Thus, this slUdy shows that dietary a-linolenic acidresults in lowered blood lipid levels end suppressed lymphocyte functionsu l'il'O and in vivo. With respect to these effects. u-llnolenlc ectd is aspotent as dietary fish oil.(Lipids 31. 737-745 (1996)]

DilTerentiaJ AlterAtions of Ethanolamine and ChoI.ine Pbo!ipbogl)'cerideMetabolism by OoIIbrAte and Retlnok Acid in HUIlUlIl FibroblllSl.'l AreNot Mediated by Phorbol Ester-Sensitive Protein Klnase C. Suzan G.Mandla. David M. Byers. Neale D. Ridgway, and Harold W. Cook, At-lantic Research Centre. Departments of Pediatrics and Biochemistry, Dal-housie University. Halifax, Nova Scotia B3H 4H7, Canada.

Peroxisomal prolifcmon and retinoids neve been reported to interactto regulate lipid metabolism, particularly ~-oxidation of fatty acids.Based on postulated interactions of these agents at the levels of receptorsand response elements. we examined whether interactions exist betweenthe peroxisomal proliferator. clofibrate (CLf). and retinoic acid (RA) inmodulation of pho:!;pbolipid turnover in culrured human skin fibroblasts,Treatment of cultured cells with either 25 v.M CLF Ot I J1M RA alonedecreased jl4c)ethanolamine incorporation into ethanolamine phospho-glycerides (EPG) by 2Q-3()'l,. and simultaneous exposure to both agentsresulted in additive inhibition. By contrast, [3H)choline incorporationinto phospholipid WII!i stimulated S-3()'l, by incubation with either agent;when CLF and RA were administered together. the stimulatory effects.....ere additive. Different types of pulse-chase studies examining effectson uptake. biosynthesis. and degradation of labelled phospholipids indi-cated stimulation of EPG degradation and inhibition of phosphatidyt-choline degntdation by CLF; no effect on caUibolism of either phospho-lipid WII!i observed with RA, Combinations of modifiers of protein kinaseactivity [4!i-12-0-tetradecanoylphorbol-13-acetate (~-TPA). 1-(5-iso-quinolinesulfonyl}-2-rm:thylpipcnll.ine dihydrochloride, N{2'·guanidi-noethyl}-5-isoquinolinesulfonamide hydrochloride. bis-indolylmaleimide.staurosporine[ indicated that !i-TPA-responsive protein kineses were notlnvelved. Accordingly. CLF and RA regulate biosynthesis and degroda-tion of ethanolamine and choline phosphoglycerides in cultured skinfibroblasts by different mechan151115that do not involve classical proteinkinase C (PKC) isoforms. even though turnover of phospholipids generat-ing lipid activators of PKC occurs.[Upids 3/,747-755 (1996)J

The High Content or Monoent "'aUy Adds in the Lipids or Some Mid-water fishes: Family l\tydophidac. Hiroaki Saito and Masakazu Murata.Laboratory of Lipid Chemistry, National Research Institute of FisheriesScience, Ministry of Agriculture. Forestry and Fisheries, Yokohama-shi236. Japan.

The total lipids of eleven species of Myctophids caught at depths be-tween 20 and 700 m in the northern Pacific Ocean were analyzed usingsilicic acid column Chromatography (lipid classes) and capillary gas chro-mato]!.raphy (funy acid and fatly alcohol composition). The major compo-nents in the lipid classes were trlacylglycerols or wex esters; triacylglyc-ercts were the dominant acyl neutrallipids {6g. 1-96. 1%) in eight species.and wax esters were found as the dominant lipid (85.5-87.9%) in threespecies. The major fatly acids and etcohcls contained in the wax esters ofthe three fishes were 18: In-9. 20: I n-9, 20; In-II, and 22: I n_11 for Iauyacids, and 16:0, 18: I, 20: I. and 22: I for fatty alcohols. Fatty acids in therriacylglycerols ranging from CI4 to C22 were predominantly of evenchain length. The major components were 16:0, 16: I n-7. 18; In-9. 20: In-

II, 22: In-II, 20:5n-3 (icosapentaenoic acid), and 22:6n-3 (docosahex-acnoic acid). In both the triacylglycerols and the wax esters. the major fanycomponents were monoenoic ectds and alcohols. It is suggested from thelipid chemistry of the Myctophids that they may prey on the same organ-isms as the certain pelagic fishes such as saury and herring. because thelarge quantities of monoenoic fatty acids are similar to those of saury, her-ring. and sprats whose lipids originate from their prey OTllanisms such aszooplanktons which are rich in monoenoic wax C5tCTS.[Upids 3/.757-763 (1996»)

Quanlitathe 31p Nuclear Magnetk RI'!SO!IllIlCe Analysis of the Phospho-lipids or Erythrocyte MembrAnes Using Detergent. M. Hossein Nouri-SorthabiD. Lesley C. Wrighrh, David R. Sullivan", and Philip W. KuchelD,DDepartmem of Biochemistry. University of Sydney. Sydney. N.S.W. 2006.bDepartment of infectious Diseases, wesunead Hospital, N.5.W. 2145,and 'Depanment of Clinical Biochemistry. Royal Prince Alfred Hospital.Camtr;roown. 2050. N.S,W .• Australia.

P Nuclear magnetic resonance (NMR) spectra of human erythro-cyte Iysates dissolved in sodium cholate were acquired. "The narrow res-onances of phospholipids were mostly well reserved. allowing identifi-cation and accurate quantitative analysis of phospholipid classes of theerythrocyte membranes. The ether-linked phosphatidylethanolaminecomponents of tbe erythrocyte membranes were identified. based on theremoval of plasmalogens by acldolysis and of diacyl phospholipidspecies by degradation using phospholipase A I' It was also shown thatthe introduction of double bonds on the acyl chains of phosphat idyl-choline shifted the 31 P NMR resonances to lower frequencies. Quanti-tative analyses of phospholipids from the spectra were based on theirapparent molar concentrations. "The recoveries of phospholipids fromerythrocytes were significantly higher than those using conventionalextraction procedures.[Upids 3/. 765-770 (1996)[

n-3 PoIJunsaturAted "'aUy Acid-Induced Changes in the MolecularSpecies ComposiUon of OiradJlglJcerol In Murine PeritonealMlICropbagcs Remaln Stable During Incubation u 1'11'0. Paola A. Marlg-nani and Rolf J. Sebaldt. Department of Medicine. FlICulty of Health Sci-ences, McMaster University. Hamilton. Ontario L8N 4A6. Canada.

Three- to four-week-old C57BU6 mice were maintained for fourweeks on diets in which the 10% lipid component was the ethyl esters ofeither com oil or n-3 polyunsaturated fatty acids (n-3 PUFA). Incubationof macrophages ex vivo for 14 h. a normal incubation time used formacrophage studies, in the absence of fetal calf serum, did not diminishthe extent of incorporation of 20:5n-3 (eicosapemaenoic acid) and 22:6n-3(docosahexaenoic acid) moieties into membrane phospholipids and intodiradylglycerol (DG) relative to that after a very abbreviated incubationtime. We conclude that studies uamining the effects of dietary n-j PUFAon DG formation and related physiological effects in macropheges can beperformed after a normal u v;,'o incubation of at least 14 h with.out expe-riencing a significant loss of incorporated n-3 PUFA.[Lipids 3/. 771-776 (I996)[

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