533

Rect'Dt Ad,'lInc:t:S in Mstssment of MarilM' Upid Oxidation by UsingFleerescence, Santiago P. AuOOu'1l·. Il15lillllO de Invesligacioncs Marinas(CSIC). 36208-Vigo. Spain.

Lipid changes during (ood pnxessing are imponant because of theirimpao;l on the final product quality. Lipid damage detection is limitedbecause o(the ability of lipid oxidation products (i.e., hydropcnuidcs andcarbonyl compounds) to produce imerxtion compounds by reac'ling withnucleophilic: food constituents. rtceresceece quantification al a singleexcitation/emission maximum of these inlmICtion compounds bas beenemployed in a qualiulI.ivc way as • complementary tool for food qualityasscssmcnL TIle present wort reviews recent research where simultaneOUSdetection II different e;IIcilaliorVcmission maxima was employed to assesslipid oxidation and quality changes during fish processing. A fluore!iCC.~cshirt rewards a higher wavelength maxima was detected as a result of Hptddamage: the shin was calculated as thoe ra1io (oF) between 1Wi>of the max-ima tested (393f463 om and 32714 [S nm) and was investigated along dif-ferent fish processes (freezing Dnd froun storage. refrigerated storage.cooking. and canning) and in complemenlnry model sysrerns where theinfluence of different fpctOl'S (time and temperature of processing. amineand aldehyde composition and content. fOrmllldehyde presence. and pHvalue of the medium) was checked. Determination of the of value provid-ed better results fOf quality change assessment in fish products than mostof the lipid quality indices. in addition to being rapid and sensitive.

Paper no. 18840 in JAOCS 74. 400-419 (April 1999).

lnnuence 0( Used ~-I')'lng 011 QUllllty and Nlltural Tocopherol Contenton Oxidative Stability or Fried Potatoes. G. M4nluc:z Ruizt'. M. MartfnPolvi]](/!. N. 10rgeh. M.V. Ruil Mtndez~. and M:C. Do~rganesa .••alnstituto de la Grasa. CSIC. 41012-Sevllla. SpDIn. and Deptc. deEngenharta e Tecnologie de Attmemos, UNESP. 5.1. Rio Prete, SiloPaulo. Brazil.

Sunflower oil (SO) and high-oleic sunflower oil (HOSO) .....ere usedto prepare fried potatoes by either diiIContinuous 01' continuous labora-tory frying. Fried potatoes thot hod been fried in oils of differing quali-ty were stored at 60°C for up to 30 d and evaluated for polar com-pounds. polymers. peroxide value. oil stability index. and u-tocopherclcontent. Results obtained through the various methods applied wereconsistent and indicated that the length of the induction period couldnot be explained only on the basis of the degree of ensaturetion or polarcompound levels in fried potatoes before storage. a-Tocopherol contentalso hod a significant influence as potatoes fried in HOSO, with 16%polar compounds and only 10 mg/k~ a-tocopherol at the starting pointof storage. were oxkllzed more rapidly than potatoes fried in SO with acomparatively higher degradation level. 19% polar compounds. and 100mg/kg e-rcccpherol.

Paper no. Jg114 in JADeS 76. 421-425 (April 1999).

Contribution or Chemical Components of Cornicabra Virgin OlinOils to Oxtdauve Stability. A Study orThree Suceesstve Crop Seasons.M.D. Salvador". F. Arunda. and G. Fregnpane. Universidad de Castilla -La Manclln. Facultod de Ciencias Qufmicas. Deportnmemo de Qu(micaAnalftica y Tecnologja de Alimentos, 13011 Ciudad Real. Spain.

Oxidation is the primary cause of virgin olive oil quality deterioration.This paper presents a correlation between oxidative stability. as deter-mined by the Rancimat method, and some choemical oomponems involvedin the oxidation process of a set of 14 Ccmjcebra virgin olive oilsobtained from three successive crop seasons (94195 to 96197). ResultsshcM'ed a dear influence of total polyphenols on virgin clive oil stability.with linear regression ooefflCjcnts which were similar foe the mree sea-sons studied. and a much lower contribution of a-toCOpherol and unsatu-rated fatty acids. mainly linoleic acid. A signifir:ant effect dependent onthe crop season was also ()bserved.

Paper no. J8920 in JAOCS 76. 427-432 (April 1999).

Structural Changc:s or Sinaplc Add and Sinapine Bisulfate DuringAutocla"ing with Respect 10 the [)e"elopnlent or Colored SUbstances.R. Caia. S.D. Amtfieldu .•. and J.L Charltonb. Departments ofaFoodScience and bChemisuy. University of Manitoba, Winnipeg. Manitoba.Canada RJT 2N2.

Structural changes in sinapic acid during autoclaving were studiedusing spectral analysis. thin-layer chromatography. high-performance liq-uid chromatogrllphy. nuclear ITUIgneticresonance (NMR). and mass spec-1rOSCOp)'. Coloe properties of sinapic acid and its dcrivati,'es ...'ere Sludiedby determining the ttansmitUlnCe spec:trUm, calculaling the Commissionleternatkmaje de I'Edairage 1931 trislimulus values and convening toHunter Lab values, It was found thai tbe colorless sinapic acid aqueoussolution (100 J.lglmL) turned yellow after 15 min in an autoda,~ at 1210Cand 0.1 MPa. Filtering thoeyellow aqueous solution through a 0,45-~ fiI·ter removed a brown solid consisting of at least ~ undetermined col-ored suhoitances and left a yellow liquid. A newly developed yellow sub-stance, syringaldehyde. was identified in ~ liquid phase by comparingthe NMR and mass spectra of the unknown with those of authenticsyringaldehyde. Thomasidioic acid was also fQUnd in the liquid phase.Under the SlIme autoclaying conditions, sinapine bisulfate showed no evi-cenee of any structural or color changes.

Paper no. 18901 in JAOCS 76, 433-441 (April 1999).

Assessment or Llpase- And Chemically Catlilyted Lipid ModificationStrategies for the Production or Structured Lipids. Wendy M. Willisand Alejandro G. MlII1Ingoni·. Department of Food Science, University ofGuelph. Guelph, Ontario. N1G 2WI. ClInnda.

llIe purpose of the present study was to devise a two-step re1K:tion toproduce partial glycerides, which would subsequently be used as sub-strates in both lipase-catalyzed and chemically catalyzed esterificationreactions with caprylic acid. The yields and kinetics of these t...'o-stepreactions were compared to established lipase-caUliyzed acidolysis andtransesterification as well IS to chemical lransesterification reactions.Acyl migration did IlOl occur during the hydrolysis oe short-path distilla-tion steps in thoepreparation of free fally aciu-free panilll glyceridc!i fOfesterification reactions. No significant differences in final yields (59.9%to 82,8'1> 110'/110' of t0101 triacylglycerols) of new structured lipids weredeteeted among lipase-cataly~ed (24 h) and choemically catalyzed (5 h)reactions; however. tile yield of new structured triacylglycerols (TAG)after 2 h was lower for Ilddolysis than for the other lipase-catalyzed reac-tions (P S 0.05). Since no differences in final yields were detected amongthe reactions. chemical esterification using hydrolyud oil could representthe best synthetic option, since it offers the advantage of positional distri-bution control associated with Iipase-cetelyzed reactions as well lIS rapidreaction times associated with chernically CUIPI)'1.ed reactions. Attentpts toevaluate the positional distribution of caprylic acid using allyl magnesiumbromide (Grignard reagent] were hampered by production of unknownspecies. which prevented aceunne determination of the concentration ofsome key fuuy acids.

Paper no. 19020 in JAOeS 76, 443-450 (April 1999).

Enzymatic S)'nthesls of ."lIl1y Alcohol Estcl'!I by Alcoholysis, B.K. De.D.K. Bhanacharyya'", and C. Bandhu, Department of ChemicalTechnology. Oil Technology Division. University of Calcutta. catccue100 009. W.B. Indio.

Lipase-cetelyzed conversions of some minor oils and fats like mowl1lh(Mlrdiruca /atifolia), mango (Mansifl!M indica) kernel. and sal (Slw,..arobusta) fats into low. medium. and high molecular weight alcohol estershave been investigated. In solvent-free medium. alcoholysis of the above-mentioned Iats with 10% (110'/110') Mrlcor miC'hl!i lipase produced alcoholesters in good yield. Tbe percentage molar OOI1YeT5ionsof C4' C8' CIO'CI2' C14' C16' C18' and C18:1 alcohols into corresponding alc~holesters ranged from 86.8 10 99.2. while the percentage molar ecnversrceson the basis of oil were in the range of 108.010 123.5.

Paper no. J8770 in JAOCS 76. 451-453 (April 1999).

Production of a "ery Low Saturate 011 Based on the Spedftcity of~otrichum ctmdidum Llpase. R.M.M. Diu· and MJ. Lee. UnileverResearch. Vlaard.ingen. The Netherlands.

Lipase B (GC8) produced by the fungus Gl!o,richum candidu,"CMtCC 335426 is known foe rts hiah specificily tOWllrdscU·A9 unsanmu-

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ABSTRACTS FROM AOCS JOURNALS

ed fany acids. The wild-type lipase (not genetically modified) as ....ell asthe lipase: cbtained by heterologous expression of the corresponding gcl"lC:in Pit;hia pa$/Qris (genetically modified) were studied in a process aiming10 produce an oil containing very little sarurared fany acids (5AFA). Theapproach described in this paper is based on the selective hydrolysis ofsunflower oil (12 .....SAFA) using the G. candidJlm type B (GeB) ttpases.Depending on the lipase input. up \0 60% w/w degree of hydrolysis WIISobralned within 6-8 h. Because of the high specificity of the GeB lipases(specificity rector -30). the level of unsaturates in the free fatty acid true-lion was >99% w/w. In cenrrasr with literature data. no loss of specificitywas observed, even III Ihe highest degree of hydrolysis obtained. Thoughboth OCB Ilpases are stable at 30·C, the rate of hydrolysis decreased con-slderably during the process. Product inhibition as well as tlrne-dependcmdeactivation (half-life ... 2 h) were shown to be involved. After sepllTll\ionof the oil phase, the unsaturated free fatty acids were recovered from themixture by evaporation and reconvened 10 triglycerides by enzymaticesterification with gly~rol. Because the GCB npeses have a "cry low effi-ciency rot csterification. this reaction was carried OOt with immobilizedRhiWlllucor michei lipase. Under continuous removal of !he water gener-ated during the process. >95% tnglycendes were obtained in less than 24h. Standard deodorization resulted in an odorless. colorless, and tastelessoil with less than I'll SAFA.

Paper no. J9014 in JAOCS 76. 455-461 (April 1999).

Effecl of Genetle Modification on the Distribution of MinorConstituents In Canola 011. S.L. Abldi". G.R. List. and K.A. Rennick.Food Quality and Safety Research, NCAUR. ARS, USDA. Peoria. Illinois61604.

Oil derived from different lines of genetically modified canolu vari·eties was unulyzed for phospholipids. toccpherors. and phytcsterors byvarious chrometogruphic techniques. As observed previously in genetical-Iy modified soybean oils, there was a decrease in the content and compo-sition of phosphatidic acid in three of the modified cencla oils derivedfrom the 12 varieties investigated. Normal-phase high-performance liquidchrurnatographic (HPLC) analyses showed small variations in the phos-pholipid content of major classes. despite few differences in their compo-sition. Reversed-phase HPLC data indicated that the molecular speciesdistribution of phcsphandylerhanclamine was significantly altered bygenetic modificDtion when compared to phosphalidylcholine. Impact ofoilseed modification on the tocopherol coruem was variable, with greater\'lIriation in !he concentration of (1- and y-tooophcrois than &tocopheroLPhytosterol composition WlI5 markedly affected by genetic modification,Brassicasterol. cempenerol. and ~-sitOSlerol levels were consistently low-ered in one genotype. whereas increased brassicasteroi content wasobserved in the other variety. In general. genetic modification of canotaseeds led to change5 in the distribution of phospholipids. tocopherols. andphyrostcrols.

Paper no. J8994 in JAOeS 76. 463-467 (April 1999).

The Seed "'lilly Acid Composition and the Distribution of L\,5·0IcfinlcAcids in the TrhlC)"lglycerols of Some Taxares (Ctlp/uliOfaxus IlndPodocarc"s). Robert L. Wolff"l·., Predersque Pedrono", Anne M.Merpcau . and Fronk. D. Gunstcnev. aISTAB. Laborntoire de LlpochlmleAllmetualre, blnstiUlI du Pin. Laboratoire des Substances V~g4!tales.Universit4! BordeBu~ 1. Talence. France. and "Sccnish Crop Researchtnsuune. Dundee. Scotland.

The fally acid compositions of the seeds from four C"phalOlllXlISspecies or varieties (plum yews; Cephelorexaceee) and rwe Podocarl/U$species (podocarps; Podocarpaceae) have been established. TItese compo-sitions were compared with those prcvioosly published rot some Taxaceaespecies (Tax"s and Tor/'e',}'a). Cephaiotaxaceae. Podccerpaceee. andT\axaceae belong to the Taxares suborder. A5-Olefinic acids are present inthe seed lipids from all species analyzed. In CtlphalofD.lU$. PodocarpU$,and Torrt)'D.the prominent A5-olefinic acid that occurs is the trienclc acid5.11.14-20:3 (sciadonic) acid. comprising from 6,7 to 26.4% of total fanyacids. In these species. the~. I I structure is Iargety favored over the 6S.9structure: lhc 5.9-18:2 (lUoleic) and 5.9.12-18:3 (pinolcnic) acids arc atthe limit of detection. in contrnst 10 Taxus and most Pinaceae species.where these two !lo5-0lefinic acids generally predominate. 14-Merhylhexadecnnolc acid. an habitual though minor component ofPmeceae and Ginkgo biloba seed lipids, could not be detected inCep/la/mGxlIs species studied here and was tentatively identified in truce

amounts only in one PodocarpU$ species. In addition to sciedcntc acid.e,.p/uJ/oraxU$ and Podocorpus seeds are cltarocteriud by unusually highamounts of 11.14-20:2 acid. in the range of 3.1-12.0%. This contrastswith most of the 170 species of conifers analyzed so far (from the familiesPtnaceae. Cupressaceae, Taxodiaceae. 'nxeceee. and Sciadopiryaceae.which belong 10 the Pinares suborder). where this acid is generally :S2%.A close resemblance between Tarre)'a grandts and three of theCt!l/haloraxus species analyzed might be indicative of some ph~letic rela-ticnshlp between the families Cephutorexeceee and Tnxnceae. I C nuclearmagnetic resonance spectroscopy of the seed oils from e, drupaceoe andp. andil1U$ has shown that !loS·olefinic acids are appnrent1y excluded fromthe internal position of triacylglycerols. which is a characteristic commonto all Coniferales species analyzed so far. and consequently of great antiq-uity.

Paper no. 1895 I in JADeS 76, 469-473 (April 1999).

Composition or Muscle Tissue Lipid! or SIh"er Carp and BigheadCarp. Gordana Vujk.ovit",.[)enl- KlU"loYitb. Ivan Vujk.ovi~'·, Istv,"V6r6sbaranyiC, and Branislava Jovanovitd. aTechnicli College.Uuniversity of Novi Sad, Faculty of Technology, CJnstitute for Field Cropsand Vegetubles. and 4aculty of Agriculture. Nevi Sad. YugOSlavia.

Lipids have a complex role in the nutritional value of roce. Somepolyunsaturated fatty acids. characterized as essential. arc extremelyimportant for human health. This is primarily related to a-linolenicacid (IS:3n-3), eicosapenteencic acid (20:5n-3) lind dccosahexeenoicacid (22:6n-3). Content of polyunsaturated n-3 fatty acids is usuallymuch higher in lipids of marine fish than in freshwater fish. Previousinvestigations have shown that muscle tissue of silver carp and bigheadcarp from fish farms may be a rich source of essential fatty acids.Because of thut, the objective of this work. was to examine cements andcomposition of fatty acids and totallipids in the muscle tissue of silverand bighend carp. with the aim to find out whether there are significantdifferences in this respect between the two species and to what extentthe harvest season can influence the composition of lipids in thesefreshwater fish. This study showed that mere is no significant differ-ence either in the content of polyunsaturated n-3 and n-6 rany acids. orin the n·61n-3 fatty acid ratio in these two fish species. The lipids ofboth the silver and bighead carp from the spring harvest have signifi·cantly higher contents of the n-3 acids and a significantly lower n-61n-3ratio than fish from the autumn harvest.

Paper no. 18878 in JADeS 76. 475-480 (April 1999).

A Simple M~thod for Regiospednc Analysis or Trtecylglycerels byGas Chromatograpby, Paul Angers and Joseph Arul-, Department ofFood Science and Nutrition and Dairy Research Center (STELA),Universit\! Laval. Qot!bec GIK 7P4. Canada.

A simple method for regiospeciflc analysis of trigtycerides was devel-oped. It consists of partial deacyleuon of triglycerides by ethylmagnesiumbromide follnwed by derivatizarion of monoglycerides with a-butyrylchloride. and direct analysis of dibutyrute derivatives of mcnoglyceriuesby gQSchromatography. The chromatographic conditions were carried nutwith mcnoglycerides of C 12 to C20 fuuy acids end resulted in separationof dibutyrate derivatives between those bearing the medium. or long-chainIetty acid in the sn-l{3) and sl1-2 posincos of glycerol. Beef tallow andgmpeseed and cotton seed oils were analyzed using this new method, andtheir regiospecific distributions were compared with literature data. Themethod does not require separation of products by thin-layer cbrcrnercg-mphy or special analytical equipment other than a standard gas Chromato-graph. and il can thus be used for routine regiospecific analysis of triglyc-erides.

Paper No. J8945 in JADeS 76. 481-484 (April 1999).

Determinatlen or Free Fatty Adds in Crude Palm 011 and R~nned-BI~acbed-DeOOorized Palm Gleln Using Fourier Transfonn InfraredSpectroscopy. Y.B. Che Mana.-. M.H. MohQ, and F.R. van de Voortb,QDepartment of Food Technology. Focully of Food Science andBiOtechnology. Universiti Pulrll Malaysia. 43400 UPM Serdang, Selangor.M~laysia. and boepartment of Food Science and Agrieultul1l! Chemistry.Macdonald Campus of McGill University. SI. Anne de Bellevue. QuebecH9X 3V9. Canada.

A rapid direct Fourier transform infrared (FTIR) spectroscopic methodusing a 100" BaF2 transmission cell was developed for tile determination

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535

of free fatty acid (FFA) in crude palm oil (CPO) and refined-bleached-deodorized (RBO) palm olein. ccvenng an analytical range of 3.0-6.5%and 0.07-0.6% FFA. respectively. The samples were prepared byhydrolyzing oil Willi enzyme in an lncubater. The optimal calibrationmodels were constructed based on partial least squares (PLS) analysisusing the fTIR carboxyl region (C=O) from 172210 1690 em-I. Theresulting PLS calibrations were linear over the range rested. The standarderrors of calibration ~SEC) obtained were 0.08% FFA for CPO with corte-lotion coefficient (R-) of 0.992 and 0.01% FFA for RBD palm olein withR2 of 0.994. The standard errors of performance (SEP) were 0_04% FFAfor CPO with H2 of 0.998 and 0,006% FFA for RHO palm olein with R2of 0.998, respectively. tn terms of reproducibility (T) and accuracy (al.both FTlR and chemical methods showed comparable results. Because ofits simplcr and more rapid anulysis. which is less than 2 min per sample.as wcll as the minimum usc of solvents and labor. FTIR has an advantageover the wet chemical method.

Paper 00. J8749 in JADeS 76. 48:>-490 (April 1999).

Rapid Determlnallon of cis and trans Content, Iodine Value, andSaponification Number of Edible Oils by Fourier Transfonn Near-Infrared Spt.'Clroscopy. H. U. F.R. van de VOOrt·. J. Sedman. and A.A.Ismail I. McGill lR Group. Deparunel\l of Food Science and AgriculturalChemistry. Macdonald Campus of McGill University. Ste. Anne deBellevue. Quebec. H9X 3V9 Canada.

Fourier transform near-infrared (FT-NIR) spectroscopy was evaluatedas a means of simultaneously determining the cis and trans content. iodinevalue (IV). and saponification number of neat fats and oils. Reference val-ues for these parameters were obtained from oils using a previously devel-oped mid-FTIR Edible Oil Analysis Package. Two partial least squarescalibrations were developed for a 5-mm heated flow cell. the first a pro-cess calibration based on hydrogenated soybean samples and the second IImore generalized calibration based on an oil sample matrix containingmany oil types and designed to remove any correlations among the param-eters measured. Each calibmricn performed well with its own validationsamples; however. only the ncnccrreleted calibration was able to analyzeoil samples accurately from a variety of sources. It was found that NIRanalysis maintained the internal constsrency between ciwrans and IV. andthe accuracy and reproducibility of the predictions were on the order of±L5 and ±I.O units. respectively. for all parameters evaluated. fT-NIR isshown 10 be a very workable means of determining cMransf1V valuesand saponification number for edible fats and oils. and it provides a rapidalternative to the commonly used chemical and physical methods present-Iy employed in the industry.

Paper no. J8909 in JADeS 76. 491-497 (April 1999).

Modulated Temperature Differential Scanning Calorimetry forExamination of Tristearin Polymorphism: I. Effect or OperationalParameters. Satish K. Singho .• , Ali Fathe Jalalib and Maggie Ald~nb.QDcpartment of Pharmaceutical Technology. Phurmacia and Upjohn AB.5-751 82 Uppsala. Sweden. bDePltrtmcnt of Pharmaceutical Chemistry.Physical and tnorguntc Chemistry. Biomedical Center. Uppsaf aUniversity. S-75 I 23 Uppsala, Sweden.

The transformations of tristearin were ellamined by modulated tem-perature differential scanning calorimetry (MTDSC) in order co study theeffect of operational parameters on the nature of infonnation obtainedfrom this technique. Tristearin has been used as 3 model polymorphic sys-tem showing metastable phases and complicated transformalion routesoccurring lit reilltively slow rates. T11e paramo:ten examined were underly-ing heating/cooling rates and tnc amplitude of modulation. TIle first con-clusion is that MTDSC enables o\'Crlapping a-melting and ~alliza-tion events to be separated. thus increasing the ioformation obtained com-pared to normal [llermal analysis. Other general conclusions IIJ'C tllatobservation of reversible processes is strongly influenced by the underly-ing heating rate; low to moderate lIeating rateS are recommended.Amplitude of modulotion has II complicated effect on the phenomenonbeing studied; wilen studying systems that e~bibit metast.able or polymor-phic transitions. ;t is recommended that a range of amplitudes be tested toenable confirmatinn of whether an observed "recrystallization" effect is anew phase or the SlIme phase as the one melting. Cooling with modulationdisturbs the crystulli7..ation process. possibly leading to smaller or imper-fect crystals; lIowever. the phases obtained are not different compared tonormal DSC. The usefulness or MTDSC in analyzing these types nr COl\}-

pllcated systems is primarily qualil.a[i\·e ar the mcmem. Some recommen-dations bave been mede as to the combinations of parameters for studyingsuch systems.

Paper no. J8832 in JADeS 76. 499--505 (April 1999).

Modulated Temperature Differential Scanning Calorimetry forExumlnatfun of Tristearin Polymorphism: 2. isothermalCrystll.lllZlIlion of Metastable Farms. Sansh K. Singh/I, •. Ali FatheJnlulib. and Maggie Aldc!nb• "Department of Pharmaceutical Technology,l'hannucia and Upjohn AB. S-75 I 82 Uppsala. Sweden. and bDepartmemof Pharmaceutical Chemistry. Physical and Inorganic Chemistry.Biomedical Center. Uppsala University. S-751 23 Uppsala. Sweden.

The transformations of tristearin were examined by modulated rem-perature diffcrential scanning calorimetry (MIDSC) in order to examinethe utility of this technique. Tristearin has been used as a model polymor-phlc system. showing metastable phases and complicated transformationroutes cccuring at relntively slow rates. TIle W-forms genefllted by tber-mal rreetmem under modulation do nOI differ significantly from thosegenerated by the oorresponding treatment without modulation. While thetOtal heat now uermcgrams an: similar. the decoevoluted reversing com-ponent shows that annealing. especially al 63°C. lias a significant effecton the crystal size and perfection of the solid phases formed. MIDSC alsoenables the melting of W to be separated from the simultaneous crystal-lization of the Ii form as evidenced in the cp component. Quamitntiveinterpretations about such systems cannot be ilrawn from MTDSC at thispoint in time.

Paper no. J9192 in JAOeS 76. 507-510 (April 1999).

Rubber-Toughening Epoxy Thermosets with Epoxldlzed Crambe 011.R. Raghavuchar. R.J. Letasi. P.V. Kola. Z. Chen. and J.L. Massingill·.Coatings Research Institute. Eastern Michigan University. Ypsilanti.Michigan 48197.

Epoxidized crumbe oil and rapeseed oil were synthesized by reactionof the oils with sr-chloropercxybenzcic acid. Formulating the neat epexi-dlzed oils with epo~y-amine systems gave two-phase rhermosers withepeaidized crambe oil. but not with epoxidized rapeseed oil. Glass transi-tion temperature. mechanical properties. and fracture toughness of theepcxidlzed crambe oil thcnnoset specimen were measured. Fractureroughness ~aluC$ of the epoxy lhc:nIIO:';Ctswere increased approximately100% by both 5 and 10% epcxidized crambe oil. Glass transition temper-ature and mechanical properties were affected only modestly.

Paper no. J8663 in JADes 76. 511-516 (April 1999).

Optimizing Production of Ethyl Esters or Grease Using 95% Ethanolby Response Surface Methodology, W.H. wu. T.A. Foglia·. W.N.Marmer. and J.G. Phillips. USDA. ARS. ERRC. Wyndmoor. Pennsylvania19038.

Previous research suggested that ethyl esters derived from recycledrestaurant grease might be 8 potential source of blociesel. Accordingly.response surface methodology (RSM) was employed to optimize reactionparamcrers-c-temperature. time. level of lipase. mole nnlo of reactants-c-lnthe PS-30 lipase-catalyzed transesterification reaction of grease to ethylesters using 95% ethanol. The regression equatlcn obtained by n modifiedcentral composite design of RSM predicted optimal reaction conditions of38.4OC. 2.47 h. 13.7 wt% lipase (PS-30). and a mole ratio of grease toethanol of [:6.6. Under these conditions the predicted optimal percentageethyl ester yield was 85.4%. Subsequent experiments using the. predictedpIIf1lIlltter combinations iooica[ed a trend where CJ<pcrimenud percentageyields of ethyl ester were consistently lower than predicted vetues. In aneffort to improve the expenmentar yield of esters. a $CC(lndportion of PS~30 lipase was added without success: however. the addition of 5% SP435one hour after the start of the initial reaction increased the yield of eStersto >96%. Neither lipase PS-3O nor lipase SP435 alone. however. gave theRSM-predicled yield of ethyl esters.

Paper 00. J8965 in JADeS 76. 517-521 (1999).

In-line lind Orr-line Trapping of Lipids Extracted from Chlck~n Liverby SupertrltlCQ! Carbon Dioxide. Shufen LiI. Robert J. Maxwell •. andAlan R. Lightfield. ERRC. ARS, USDA. Wyndmoor. Pennsylvania19038.

This supercritlcal fluid extraction ~tudy determined the retentive prop-crties of neutral alumina sorbent as an in-linc tfllP for lipid~ in the dynutn-

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ABSTRACTS FROM AOCS JOURNALS

tc SIBle over a pressure range of 49()....6SObar and temperatures of 40 and8O"C. Lipids were c;c.Irn<:led from a chicken liver matrix using supcn:riti·cal carbon dioxide over a 4O-min period 8\ a now rule of 3 Urnin (expand-ed gllS). then were quantified by high-performance liquid chromatographyusing un evepceatlve light-scanering delector. Approximately 30 and 18%.respeccively_ of the total extracted lipids were U'lIpped on the in-line alumi-l1li sorbeRI bed at ~C as !he opemling pRSSUfe increased from 490 \0680 bar. while the remaining lipids were trapped off-line alter C02decom~ion. The major lipid classes u-apped in-line were fall), acidsand cholesterol. whoereas only minor amoonlS of the leMi polar lipid class-es soch. as sterol esers and triacylglycerols wen: retained. AI 8O"C and680 bar. less than L!i'l> of the exeeced lotal lipids was trapped in-line.indicating the lack of adsorptive selectivity for lipids by alumina undeTthese conditions.

Paper no. J8lI11 in JAOeS 76. 523---528 (April 1999),

H)'drol)'lib or Palm Oil Catalyzed by !\bcroporous Cation·ExchlingedResln. C.J. Yow and K.Y. Licw·. School of Chemical Sciences. UniversitiSetns Mnlhysill. Penllng. Malaysia.

Hydrolysis of palm oil was studied using four typc;s of commercialH+ -exchanged resin with acidity in the region of 5 xlO-3 eq g-I but withdifferent pore volumes. specific surface areas. and pore diameters. Thereaction was carried OOt in a stirred balCh reactor in the liquid phase withcontinuous steam injection (or up to 14 h. The rate of hydrolysis did not

depe:nd on toW pore volume and specific surtece area but did depend onpore diameter. On exchanging H+ with La3+. c02+. and Na+. the me ofreaclion decreased markedly and was dependent on the degree ofex.cluulge. demonstrating tMt hydrolysis was caulyzed by H+ sites. TIleactivation encrgr (or the hydrolysis of the triglyttrides was estimated 10be 240 k.I moI- . A procedure 10 estimate the rates of the differem stagesof hydrolysis and hence the indil'idual rate constants of the fOl'\\'lIJ'dandreverse: reactions is Oescribed. The procedure yielded reasonable parame-ters for the reaction at 155"C up to 6 h of reaction time. when about Umol'll of triglycerides was hydrolyud.

Paper 00. J8946 in JItOCS 76. 529-533 (April 1999).

Ooc06llhuaenoic Acid Ingestion Inhibits Natural Killer Cell Activitland Production of Innllmmatory Mediaton in Young Healthy Men ,O.S. Ke11e>,"··, P.C. Taylor'!. G.J. Nelsen". Perla C. Schmidttl• AldoFerrellib Kent L. Ericksonc. Rina Yud. Ran;it K. Chandrae. and B.E.Madel, I'USOA, ARS. Western Human Nutrition Re$Carch Center.Presidio of San Francisco. California 94129. beellsville Human NutritionCenter. Beltsville. Maryland, CUniverslty of California. Davis. California.dUniversily of utsen. South Korea. I!'Memorial University ofNewfoundland. Canada. and/Western Regional Research Center. Albany.California.

The purpose of this study was to examine the effects of feedingdocosehexeeeoic acid (OHA) as triacylglycerol on the fotty acid compost-non, eicosanoid production. and select activities of human periphernlblood moncnccteer cells (PBMNC). A l2{)..d study with II healthy menWIIS conducted at the Membolic Research Unit of Western HumanNutrition Reach Center. Four subjects (control group) were fed the stabi·lillition diet throughout the study; the remaining seven subjects were fedthe baul diet (or the fin;t 30 d. followed by 6 g OHNd for the next 90 d.OHA rephlced an equivalent arnoum of linoleic acid; the two diel5 Wc:TC

comparable in their tOlal fat and all OIber nutrients. Both diets were 1i4Jp'

plemented with 20 mg 0 a·tocopherol acetate per day. PBMNC fatty acidcomposition and eicosanoid production were examined on day 30 and113; immune cell functions were tested on day 22. 30. 78. 85, 106. and113. OHA fceding increased il$ coocenU"1llion (rom 2.3 to 7.4 111\'11in the

PBMNC total lipids. and decreased aruchidonic ocid concentration from19.810 10.7 wt%. It also lowered prostaglandin E2 (PGE2) andleukceriene B4 (LT84) production. in response to lipopolysaccharide. by60-75'11. Natuntl killer cell activity and in "ir", secretion of interleukin-Iiiand tumor necrosis foclor a were significantly reduced by OHA fced·ing. These parameters remained unchanged in the subjects fed the controldiel. B-ce11 functiOll$ as reponed here and T-cell functions thllt ":e repoet-ed prel'ioosly were not altered by OHA Ieeding. Our results show thlllinhibitory effects of OHA on immune cell functions veried with the celltype. and that the inhibitory effcc:ts are not mediated through increasedproduction of PGE2 and LTB4.

Paper no. L8089 in Lipids 34. 317-324 (April 1999).

Lipoprotein (a) Metabolism t:Sllmated by Ntm5teady·Stale Kinetics.Klaus G. PDrhoferll· •• Thomas Demantb. Michael M. Rim.·r'!. H. ChristianGei"tI. Markus Oonner'l. and Peter Sch"''Ilndt'l. Departments of alntemalMedicine II and bClinical Chemistry. Klinikum Grosshadern. Ludwig-Muimilians UniveT!iity. Munich. Germany.

Lipoprotein (a) ILp(a») is a low·density lipoprotein (LOL) paniclewith an additional apolipoprotein named llpo(a). The concennanon ofLp(a) in plasma is determined 10 a large extent by the size of the apo(a)isoform. Because elevated Lp(a) concentrntions in plasma arc associatedwith risk fOf premature corornuy heart disease it is imponant to determinewhether variations in production or catabolism mediate differences inLp(a) concentration. We determined metabolic parameters of Lp(a) in 17parlerns with helCrol.ygous familial hypercholeslCrolemia or 5e\'c:TC mixedhyperlipidemia by fitting a rllOIIOCltponential function to IlK: rebound ofLp(a} plasma concentration following LOL-apllcresis. In 8 of those 17paticol'l this was done twice followln8 IWO different ~ Althoughthis approach allows one to estimate metabolic parwneters without the useof a tracer, it requires several major assumptions such as that apberesisitself docs not change produclion Of catabolism of Lp(a) and tMI Lp(a)metabolism can be described by a single ecmpartmenr. One epheresisdecreased Lp(a) concentrBtion !ry 59.1 2; 8.3'11. The fl1lCuonal catabolicnne ~FCR) was 0.16 2; 0.12 d-I and production rate 6.27 :!: 5.26 mg-kg'"Cd- . However. ceservec (concentration before first epberesis) and pre-dieted stClldy·state concentrations differed consldembly (more than 20'it0)in 9 of 17 patients. indicating that not all nssumplions were fulfilled in allpatients. Production rare btn not FCR WaS correlated with Lp(a) plasmacoocemrenon (r2 = 0.43. P = 0.0(4) and molecular weight of apo(a) (r2 =0.48. f':: 0.011). which confirms mdlotracer experiments showing thatvariations in Lp{a) plasma concentrations are due to differences in pro-duction not catabolism. When purametenl were estimated twice in a sub-group of eight patients. satisfactory reproducibility was observed in sixpatients. Although purometers determined on two occasions correlatedwell. only FCR was concordant (tnrrectass correlation coefficient). Thus.despite the limlraticns arising from the assumptions implicit to thismethod. metebollc parameters of Lp(1I) can be estimated from the reboundof plasma concentration following epberesls.

Paper no. L7904 in Upid'l J4. 325-335 (April 1999).

t"lIl1y Acid PronJe of BUcall Cheek Cell Phospholipids as an Index forDIetary Intake or Docosahexaenok Acid in Preterru Infants, Dennis R.Hoffman(J·b .•• Eileen E. Birch(J,c. David G. Birch<l·c. and RicardoUauyU·d. <lRetina Foundation of the Southwest. Dallas. Texas 75231;Departments of bPediMrics and cOphthalmology. Unil'ersity of TexasSouthwestern Medical Center lit Dallas. Texas: and dClinical NutritionUnit, Institute of Nutrition and Food Technology (lNTA). University ofChile. Santiago. Chile.

Check cells (buccal epithelia) were utilized as a noninvasive inde~ offuuy acid status in a study of the effects of n·3 long chain polyunsaturatedfauy add supplementation on visual function in prtterm infants. The fanyllCid profile of cheek cell phospholipids was directly correlated with thedietary dccosehexencic acid (DHA) intake of infants receiving: (i) primar-ily human milk; (ii) n·3 falty ecid-deflciem. com ell-based. commercialformula (CO): (iii) a·linolenic ocld-enriched. soy ell-based. cornrrrrcialformula: or (iv) experimentlll formula enriched with 50)' and marine oilsproviding II OHA level equiYalem 10 that in human milk. In II subset ofinfanl5 with complelC c~k cell fatty acid profiles and visual functionassessments, fRlCnn infants at both 36 wk (n • 63) and 57 wk (n = 45)polIlCOOCCption.ala~ bad signifICantly (P < 0.0005) reduced c~k cellphospholipid OHA levels in the n·3-deficient. CO-fed group ccmpeed to

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the OlhcT diet groups. 'The OHA COIllent in cheek cell phOsphOlipids washighly correlated (P < 0.0005) with thai of both lUI blood cell lipids andpl8!ima phcripbolipids al the)6.. and S7·wlr:; time points. 1be DHA conlenlin check cell lipids of infanl$ at 36 wt ....'a!J signifICantly correlated whhckcttominognphic respoo!it'S (r= -0.29: P < 0.03) and visuallCuity (r.-0.31; P e 0.02) as measured by visual-evoktd potentials (YEP). OJeekcell OHA was highly correlated (r = -0.57; P < O.IXXlS) with YEP acuityIII the 57-wI; time point. These results suggest thai the rany acid profile ofdied: cehs is a valid index of essential flUly acid Wltus. can be monilOfUlfrequently. and is associated with functional paBmelCl:5 in infants.

Paper DO. L8077 in Upids34, 337-342 (April 1999).

quem 10 differentiation. In summary, cells with the R 179E-mulants ofGi2a exhibila1 stimulated lipid turnover and accumulation in both undif-ferentiated and dlfferemiared cells.

Paper 110.L8014 in Lipids 34, 355-362 (April 1999)_

(solation and IdentirlCation of. Mouse Brain Protein Recognized byAnlisc'ra 10 Hrart Fau)' Add-Binding Protrio. Lixia PIP, Roland S.Annanb SIe\"ef! A. CaJrD. Andfey FI'OIov". W. Gibson Wood". FriedrichSpenel and Friedheim Schroedert!··. "Departmeru of Physiology andPharmarologX. T~as A&M University. TVMC. College Station. Texas77843-4466. Docpanment of Physical and Structural Chemistry. SmithKline: Beecham Pharmaceuticals. King of Prussia. Pennsylvania 19406-0939. cGeriatric Research, Education and Clinical Center. U.S. VeteransAdministration Medical Center and Departmem of Pharmacology.University of Minnesota School of Medicine. Minneapolis. Minnesota55417. and dDepartment of Biochemistry. University of Munster. O·48149 MUnster. Germany.

Although a novel brain-specific fatly acid-binding protein (B·FABPjwas recenny cloned, the identity of 9 second fatty acid·binding proteindetected with antibodies to the heart (H·FABP) has not been clearlyresolved. TIle present investigation. using matrix-assisted laser desorptionmass spectrometry. showed that this protein was a form of H·FABP whoseN·terminal amino acid was neither methionine nor WII5 it acerylated.Furthermore. isoelectric focusing revealed two major isoforms. D majorband pi 7.4 and a minor band pI 6.4. in a distribution panem opposite tothat observed for H·FABP in the heart. Tryptic peptide mass maps of thein-gel digested SOS polyacrylamide gel electrophoresis protein bandsshowed that the two isoforms differed only in a single peptide OOITCSpond·ing to residues 97-106 of the heart H·FABP sequence. This peptide hadan 1M + HI+ ion ofeitller 1205.62 (pi 7.4) or 1206.53 (pI 6.4). consistentwi1h a single amino acid substitution. Asp98 or Asn98. Whereas it is wellestablished that both H·FABP and B·FABP interoct with polyunsaturatedfatty acids, we showed that they also significantly alter plasma membranecholesterol dynamics in a manner opposite to that of another brain lipid-binding protein. sterol carrier protein·2. In summary. the data demonstrat·ed [or the first time that the H-FABP from brain. while nearly identical toH·FABP from heart, differed significantly in isoform distribution and inamino terminal structure from hean H·FABP. This suggests thaI the brainand heart H-FABP may not necessarily function identically in thesetissues.

Paper no. L7998 in lipids 34, 363-373 (April 1999).

Acyl·CoA Synthetase Activity In Lh'er MlCl"O$(lmes from Calcium-Denclent Rats, CarlO:'; A. Marra- and Marl. J.T. de Alaniz. Instituto Noc.de lnvesrigaciones Bioqufmicas (INIBIOLP). Consejo National deInvestigaciones Cientificas y Ttcnicas (CONICET). y C",tedra deBtcqutmlce. Facultad de Ciencias Mfdicas de la UNLP (UniversidadNacional de La Plata). La Plata, Argentina.

A study on the bnetic properties of the nonspecific ecyl-coeuzyme A(CoA) synthetase activity in liver microsomal vesicles from both normaland ca1cium-deficient WisillT rats was carried OUl After a 65-d treatment,the calcium-deficient diet reflected a 75% increase in the synthetase ectlv-ity with respect 10 control animals. The apparent Vm was significantlyenhanced. while the Km remained unchanged. We also provided experi-mental evidence about various fatty acids of different carbon length andunsaturation which depressed the biosynthesis of palmitoyl-Cca follow-ing different behaviors in control or calcium-deprived liver rmcrcscmes.In addition. we studied in detail the inhibition reflected by stearic. II·linolenic. or arachidonic acids. in the biosynthesis of palmitoyl·CoA inmicrosomal suspensions either from OOI1trolor hypocalcemic rats. In con-trol mjcrcscmes. stearic acid produced a pure competitive effect. while theother fany acids followed a mixed-type inhibition. 11Ie competitive effectof stearic acid was not observed in calcium-deprived microsomcs. AI thesame time. a mixed-type inhibition produced by either e-Hnclentc orarachidonic acid was diminished in deprived mtcrcsomes due to anincrease in the noncompetitive component (llKi). These changes observedin apparent lrinc:tic constants (Km. vm, Ki. and IlKi). as determined byLineweaver-Burks and Dixon plots. were attributed to the important ener-ations in the physicochemical properties of the endoplasmic reticulummembranes induced by the calclum-deflcieru diet. The solubilization ofthe enzyme: activity from both types of microsomes demonstrated thai thekinetic behavior of the enzyme depends on the microenvironment in themembrane. and that the calcium iOll plays a crucial role in determining thealterations observed.

Paper no. L8054 in Lipids 14. 343-354 (April 1999).

Metabolic Profile of Linoleic Acid in Siored Apple;: .·ormatlon of13(R)·Hydrolly·9(Z).II(E)·ochldecadlenoic Acid. Till Beuerje andWilfried Schwab •. Lehrstuhl fIIr Lebensrnitretcherme. UniversitDtWUrLburg. 0·97074 WGl7.burg. Germany.

During our ongoing project on the biosynthesis of R--{+)-octane·l.3·diolthe metabolism of linoleic acid was invesligated in stored apples afterinjection of (I.14C] .. [9.IO,[2.13.3Hj .• I3CIS- and unlabeled sub$tratcs.After differtnt incubation periods the products were analyzed by gas chro-matog-raphy-mIl55 spectroscopy (MS). high-p!"rfonnance liquid chro-matoglllphy-MS/MS. and HPLC·radiodeteclion. Water-soluble com-pounds and co-, were me major products whereas I3{R}-hydroxy· and13·ket0--9(Z).1 i(E}-octadecadienoic acid. 9(S}-hydroxy- and 9-1I:eto-]()(t.·).12(Z}-octadccadienoic acid, and the stereoisomcn of the 9.10.13-and 9.12.13-trihydroxyoctadccenoic acids were identified as the majormetabolites found in me diClhyl ether CXIr*:IS.. Hydropero~ides WCl"Cnot

detected. The ratio of 9J13-hydro~y- and 911J..-1r:et~ienoic acidwas 1:4 and 1;]0, respectively. Chiral phase HPLC of me melbyl esterderi\"ltivcs showed enantiomcrie CXCC5§CS of 75 'I> (R) and 65 'I> (S) for13·hydroxy-9(Z ).11 (E)-octadecadienoic acid and 9-hydrollY'IO(E).12{Z}-octadecadienoic acid. respectively. Enzymatically activehomogenates from apples were able to ccnven unlabeled linoicic acid intothe ~labo1itC!i. Radiotracer experiments showed that the transformationprodUCtS of linoleic acid were convened into {R}--«tane-l.3-diol. 13{R}-Hydroxy·9(Z).II{E}--«uu1ccadienoic acid is probably fonned in storedapples from 13·hydroperoxy·9(Z).1 [(E}-octadecadienoic acid. lt is possi-ble that the S·enantiomer of the hydroperoxide is primarily degraded byenzymatic side reactions. resulting in an enrichment of the R--cnantiomerand thu~ leading to the formation of 13(R)·hydroxy-9(Z).II(E)-ocmdcca·dienoic acid.

Puper no. L8069 in Upid .. 34. 375-380 (April 1999).

The Inhibitory Guanine Nucleotlde·Binding Protein GIZIl Inducesand I'otentiates Adipocyte DifTerentialion. Kjerstin E. Hovik·. Pengfelwut. and Jan O. Gcrdeladze. Institute of Medical Biochemistry.University of Oslo. Oslo. Norway.

TIle present srudy funhcr elucidates me involvement or the II-subunitof the GTP·binding protein Gi2 in the diffCl"Cntilllion of murine 3T3·LIcells. Contml and \'ector-transfected cells attained a fully differentiatedadipocytc phenotype showing ample lipid droplets. Cells expressing wildtype (WT)-Gi21l or the constitutively active R I 79E-Gi21l. however.became enlarged. less confluent. and produced large amounts of lipidJ.Differentiation consistently incrused the triglyceride (TAG) content incontrol cells. In both WT.Gi21l and R 179E-Gi2Ct clones. a markedincrease in TAG could be detected even prior toinsulinldexamethasonellsohulyl mcthyb.anthine exposure. The activity ofpalmitcyl-Coa synthetase (PCS) and glycerophosphate acyltnlnsrerase(GPAT) also increased upon differentiation. WT-Gi21l and R 179E·Gi2ilO\'CTCllpression also enhanced PCS and GPAT activities even before differ·entiation medium was added. The total amount of phospholipids (PL)generally increased upon dlfferentiencn: however. pre- and postdifferenti.anon values were insignificantly different in cells expressing WT·Gi21land R 179E.Gi2Il. Differentiation altered tile PL profile with a relativeshift from phcspharidyjcholtne and phcsphmldylethenolamine to phos-phatidyllnositot (PI) in differentiated ceus. Finally. differentiation yieldeda general increase in the activity of basal Pt-phosphclipase-C activity.Again. cells expressing WT·Gi2(l and R 179E.Gi21l demonslttlted elcvotedenzyme activity and enhanced second messenger accumulation subse-

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ABSTRACTS FROM AOCS JOURNALS

Melabolbm of Tnllu Fally Adds by HeplilOCytes.Manuel Guuruin<l,Wit KJeinb. Teresa GOmel del PulgarD, and Mllth J.H. Gcelenb,-,<lOi:paTlment of Biochemistry and Molecular Biology I School ofBiology. Complutense University. 28040-Madrid, Spain, and ~boralOf)'of Veterinary Biochemistry, Utrecht University, 3508 TD Utrecht. TheNetherlands.

The present work was undertaken 10 study the metabolism of fanyacids with ,rani double bonds by rat hepalOCYIe!l. In liver mitochondria.elaidoyl-CoA was I pccrer substnue for camitine palmitoyhlllnsferase I(CPT·I) !han oleoyl-CoA. Likewise. incubation of hepatocytes with oleicacid produced a more pronounced .uimulation of CPT-I than incubalionwith frons fauy acid5. This was not due 10 a differential effect of cis andImn.r rauy acids on &CCIyl-CoA carbo~ylase (ACC) Ktivily and malonyl.CoA levels. Elaidic .cid was metabolized by bep.aIOC)'IeS at a higher rate(han oleic lICid. Surprisingly. COIIlpued to oleic acid. elaidic lIICid was •bener substrate rOf miuxhondrial and. especially. peroxisomal oxidation.bul a poorer wb5lJl1i~ for cellular and very low dellSity lipoprotein triacyl-glycerol synthes.il. Results thus show that frons fatty acids are preferen-tially oxidized by hepatic perolliisome$. and that the ACC!malonyl-CoN'CPT-1 system for coordinale conuol of fauy acid rneubolism is notresponsible for the distinct hepatic utiliution of ds and frons fany acids.

Paper no. L80S3 in Upids 34. 381-386 (ApriJI999).

S}'nthesis or a Novd Llpopeptide with a-Mdanoc:yte-StimuillingHormone Peptide Ligand and Its Errect on Liposome Stabillly.YOIihikatsu Ogawat'. Hidehiko Kawaharr'.b. Nobu/tiro Yagia,b. MasatoKodlkaa ••• Taltnori TomohiroD. Tomoko Okadaa. Tauo Konakaharab•and Hiroaki Okuno"'. aBiomolecules Department. National Institute ofBioscience and Human.Technology. Ibaraki 30S-8S66, Japan. and"Faculty of Industrial Science and TechnoloaY. Science University ofTokyo. Chiba 278-0022. Japan.

Introduction of li~ into larget cells is important for drug deliv.cry systems. For this purpose. the surface of the liposome is equippedwith ligand peptldes, which may bind 10 specific receptors on the cellmembrane. An artifICial novellipopc:ptide (MSH-C4A2) containing the u-melanocyte·stimulating honnone (n-MSH) sequence and tWO long alkylchoins was deligned and synthesized. Ind the liposome. composed of eggphosphatidylcholine (EPC) and MSH-C4A2. was prepared. The stabilityof the liposome WQSestimated by measuring calcein leakage from theliposome inner phase. 'The stability of the liposome decreased upon addi-tion of MSH-A4C2. which seemed to be puributable to the amphiphilicproperty of the peptide moiety (a·MSH) of MSH-A2C4. The stabilitywas. however. recovered fairly welt upon addition of cbolesterel (Ch) Orphosphatldylglycerol (PC). It was concluded therefore that the ternarysystem. MSH·C4A2IChlEPC or MSH-C4A2/PGfEPC. is suitable forpreparing the functionalliposome.

Paper no. L8028 in Lipids 34,387-394 (April 1999).

Anomalous Enanlloseleclivlly In the Sharpless AsymmetricDlhydroJ(ylalion Reaction or 24-Nor-5~-cholesl-13.ene.3o:,7a.12(l_trlol: Synthesis of Subslrate.~ ror Studies or Cholesterol Slde·ChalnOxidation, Norman H. Eneln.b, Blshambar Dayalb,., Kashav Roob. andGerold SlIlenb, . QRoben Wood Johnson Medical School. New Brun,wick.New Jersey and bMedical Service. VA New Jersey Health Care System.Easl Orange. New Jersey 070lg and Departments of Medicine. Universityof Medicine ond Dentistry of New Jersey-New Jersey Medical School.Newark. New Jersey 07103.

Recently we described n block in bile acid synthesis in cerebmtendi-ncus xanthomatosis (CTX), P lipid storage disease related to on inbornerror of bile acid metabolism. In this disease a defecr in hepatic microso-mal (24S) hydroxylation blocks the transformation of S~-(:holestane.3«,7a, 12a.2S-tetrol into (24S) S~-cholestone-3a.7«.12a.24,2S-pentoland chelle acid. Mitochondrial cholesterol 27-hydrolliylation has also beenreponed to be abnormal in crx subjects. but the relative importance ofthe enzymatic defect in this alternative microsomal pathway (namely. Ihe24S hydroxylation of 5~-cholestDne-3«.7a.12a.2S_tetrol reteuve 10 theabnormality in mitochondrial 27-h)'drolliylase) hos 11(11 been established incrx. To delineate the sequence of side-chain hydrolli)'latioos and the en-zymatic block in bile acid synthesis. we synthesized the (23R and 23S)24-nor-5~-cholestane-3a,7a, 12a.23.2S-pento15 utilizing a modifiedSharpless asymmetric dihydroxylation reaction on 24-nor-S!kholest.23.ene-3a.7a.12a-triol. a C26 analog of the naturally oceurring C27 bile

aloohol. Sj}-cholest.24. ene-3a.7a.12a-triol. Stereospecific conversion ofthe unsaturated 24-nOl" triol to the corresponding chiral compounds (23Rand 23S). 24-nor-Sj}-cholestane-3a.7a.12a.D.25_pentols. was quantita-tive. However. converstoe of the unsaturated 24-nor triol to the chira! nor-pentols had absolute stereochemistry opposite to the products predicted bythe Sharpless sterie model. The absolute configuntions and enancomericexcess of the C26 ooe-pentots lind the C27 pentots (synthesized from Sf'-ebcresr-ze-ene-sc.ze.tze-uror for comparison) were confirmed bynuclear magnetic resonance and lanthanide-induced circular dichroismCotton eff«:1 measurements. 'rtese results may contribute to a betterunderstanding of the role of the 24S-hydrollylation vs. 27-h)'droll)'latioostep in cbctlc acid biO$ynthesis.

Paper no. I..8043 In Upids 34. 395-40S (April 1999).

Improl'ed ~pa"'tlon or Conjugated Fally Acid Methyl zsrers bySihu lon-Illgh-Perrormance Liquid Chromatography. NajibullahSehllQ, Rainer Rickenb, Magdi M. Mossobaa. John K.G. Krame,c.Manin P. Yura .....eee«. John A.G. Roacba• Ricbard O. Adlotd. Kim M.Morehousei'. JIlD FrilSCiJel'. Klaus D. Eulier', Hans Steintmrtb. and YuohK.,a.·. aU.S. Food and Drug Administration. Center for Food Safety andApplied Nutrition, Washirlj:lon. DC 20204. hJnstitule of Food Chemistry.Univers.ity of Hamburs. Hamburs. Gcnnany. cSoulhern Crop Protection,Food Reseatl:h Center. Agriculture and Aari-Food Canada. Guelph.Onwio. NIG 2WI. CaNda. and dUSDA-ARS_NCAUR. Peoria.. Illinois61604.

Operating from one to six silver ion-high-performance liquid chro-matography (Ag·-HPLC) columns in Jail'S progressively improved theresolution of the methyl C:SICrS of conjupted linoleic acid (Q.A) isomericmiatUfe5 from natun.! and comllll'l"Cial products. In nllurai products. the 8frons. 10 (is-oc:udecadieooic (18:2) acid WIL'iresolved from the moreabundant 7 frons. 9 cis-18:2. and the 10 f/'fU'IJ.12 cis-18:2 was separaledfrom the major 9 cis, II Il"Dns-18:2 peale. In addition. both II frons. i3cis·18:2 lind II cis. 13 fnuu-18:2 isomers were found in natural productsand were separated: the presence of the laller. II cu. 13 frons-18:2. wasestablished in commercial Q.A preparations. Three Ag+-HPLC columnsin aer1l'S appeared to be: the Wt compromise to obWn satisfactory resolu-lion of most CLA isomers round in natural products. A single Ag+ -HPLCcolumn in series with one of several normal-phase columns did notimprove the resolution of CLA isomers as compared to that of the formeralone. 'The 2Q:2 conjugated fony acid isomers II cis. 13 trons-20:2 and 12traM. 14 cis-20:2. whieh were synthesi~ed by alkali isomerization fromII (is, 14 cis-20:2. eluted in the same region of the Ag.-HPLC chro-matogram just before the corresponding geometric CLA isomers.1berefore. CLA isomers will require isolation based on chain length priorto Ag· -HPLC sepanllion. The pcsluom of conjugated double bonds in20:2 and 18:2 isomers were established by gas chromatography-electronioniZlltion moss spectrometry 11$ their 4.4-dimethylOlla2oline derivatives.The double-bond geometry was determined by gaschromatography-dlrect deposition- Fourier transform infrared spec-troscopy and by the Ag+-HPLC relauve elution order.

Paper no. L8079 in Upjds J4. 407--413 (April 1999).

Slmullanwu~ Determlnatlun or llllll- and SRR-o:.-Tocopherols andTheir Quinones in Rat Plasma and TiSSUe! by UsIng Chinl High-Performance Liquid Chromatography. Chikako Kiyosel'.·. KazuyoKltnekoO, Riho MuramalsuQ• Tadahiko Uedab. nnd Osamu IgarashiQ.alnslitule of Environmental Science for Human Life. OchancmtauUni~ersity, Thkyo. 112-8610. Japan. and b-rokyo Metropolitan ResearchInstitute for Environmental Protection, Tokyo. 136-0075. Jnpan.

We established II method to simultllneously determine RRR- and SRR-a-tocopherol (a-'fix) and their quinenes in biological samples by chiral-phase hfgh-perfurmence liquid chromatography (HPLC). a-Toe had ashoner retention time Ihnn n-tocopberylqulncnes (<<-TQ). and 2-(1mbt>-a-'fix was completely separated into two peaks: the first peak was RRR-a-Toc and the second SRR-isomer by chlral HPLC connected Chlralcel 00-H column and Sumichintl OA41oo column. In contrast. of the IWOpeaksof a·TQ. the fir.;t was the SRR-isomer. We also inv0:5ligated differences inthe distribution of RRR· and SRR-o.-TQ in rat tissues after oral admini5tra_tion of 2-ambo-a-Toc by the above HPLC method. RaIS deficient in vita-min E were divided into IWOgroups. control and experimental. and usseeswere collected at 3. 6. and 24 h aAer oml 2-nmbo-o.-Toc administration.'The concentrations of RRR_ and SRR-a-Toc and their Quinones in plll$ma

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539

the detergenc)' process in cnergy-efficienr washing machines. Detergencyand redeposition of radioiabeled oily soils can be: determined in a full-sizeherizental-axls washing mochine through 5Cintillation counting of washand rinse water samples. Measurements can be made after each wash pro-cess step end combin.ed to determine IOllll cycle detergency. This is a dis-tinct advantage over conventional reflectarlCe detergency methods whereonly total dcteq:ency at the end of the entire washing and rinsing processcan be conveniently measured. Also, in contrast If) indirect reflectancemethods. measurements of absolute sell removal an: obtained with thenKliotraccr method. In this study. soil redeposhion was determined bymeasuring residual radioaclivity on filbfic swatches and Ibm performing amaterial balance on the oily soil.

Paper 00. SI 102 in JSD 2. 167-173 (April 1999).

and each tissue were determined. The concentration of SRR-a-TQ in plas-ma and adrenal glands wllS not significantly different from RRR-a-TQ.However. the concentration of SRR-a-TQ in liver up to 6 h Arter oraladministration WlIS higher than that of RRR-a-TQ, and SRR- and RRR-tt·TQ levels .....ere similar at 24 h after oral administration. Therefore. wemay assume that !be formation of a-TQ in ~i\'(!was 001 dlfferent betweenRRR· and SRR-isomer and thai it WlIS not affected by the presence of u-Toe sreeoisoeers.

Paper 110. L7991 in lipids 14.415-422 (April 1999).

The Occurrence and Possible Significance of Diacylglfuryl EtherLipids in Abalone. Matthew M. Nelsorfl.·. f'f;ter D. NichOJSb. and DavidL... LeightonD-c• °Depanment of Biology. San Diego Stile Uni\·eJ"SilY.SanDiego. California 92182. bCSIRO Marine Reseatt:h. and Antarctic Co-operative Research Centre. Hobart. Tasmania. 7001. Australia. and"Marine Biocuhure. L..c:ucadia.Califomia 92024.

Gonadal and fOOl tissues of the grun abalone. HQliQ/is fo/~ns. raisedon artificial diets. were anaIyu:d for lipids using thin-layer chromatognl-phylflame-ionization detection and gas chromatography--mas5 5pectrome--try (OC-MS). Oiacylglyceryl ether (DAGE) was 0.7% of toW lipids inthe gonad. The major alkyl constituenl5 of the glyceryl ether dio15 in thegonad (as 'I> of toW dinls) were 16:0 (38'1» and Ig:1 (36'1». While levelsof DAGE in !be abalone fOOl were below fJame-ioniution detection lim-il5, glyceryl ether dio1s from them .....ere detected using !be more sensitiveGC-MS procedure. The major dinl components in the fOOl were 18:0(39'1» and 18:1 (32'1». To our knowledge. this is the fin;t report of DAGEin abalone tissues. Although ee precise role of OAGE in abalone remainsto be delermined.. a possible structural role may exist.

Paper no. L8034 in lipids 34. 423-427 (April 1999).

Synt.rglsm In lbe \,'etllng Propertil.'S or TeJ1llilry Surfactaot Mixtures.Hermann G. HauthalO, Peter Jilrgesb. Lothar MOblec. and UdoOhlerichd, •• QWILEY-VCH Verlag GmbH. Weinbeim. Germany,DttoechSi AG. Frankfurt a.M., Germany. COr. W. Kolb AG. Hedingen,Switzerland. and dKrllss GmbH_ Hamburg. Gmnany.

It bas been shown that lernary SUlfactant synergism can be predictedon the basis of nonidealily parameteB of binary subsystems derived fromadvancing contact angles. Siudies with appropriate .surfactant mixtures ofglucamides. ether sulfates. secondary alkane sulfona\C;. and alkylamido-propyl bewnes were performed on ~ubsua\e!i of different p:tlarity.

Paper no. SI043 in lSD 2, 175-180 (April 1999).

Interactions Between Anionically Modified H)'dro~fetbfl Celluloseand Cationic SurfactanlS. H. Lauer'··, A. StanO. H_ Hoffmann". and R.OOngesb, QUniversitlt Bayreuth. Physikallsche Chemic I, 0-95440BAyreUth. Germany. and Deliriant GmbH, lndusmepark Kalle-Albert. 0-65203 Wiesbaden. Germany.

Macroscopic properties of aqueous solutions of several modifiedhydrollycthyl cellulose (HEC) samples and their jmerecnons with cationicsurfactant! are studied by solubility. light scattering. electric birefrin-gence. rheology. and surface tension measurements. Modified HEC sam-ples carry anionic groups (an-HEC DO) and anionic and hydrophobicgroups in random distribution (HM·an-HEC 01-04). The molar substhu-lion of anionic (on) groups is about 0.07 in all samples while that of thehydrophobic (HM) groups ranges from 0 in an-HEC DO to 0.012 in HM-an-HEC 04. In II I wt% solution this corresponds 102.7 mM anionic ando to 0.46 111Mhydrophobic groups. In the dilute concemration range thepolymers behave like typical potyeieceotyres whereas in the semi-diluterange they resemble uncharged polymers. On addition of oppositelycharged ~urfIlClant~ the phase behavior of all polyelectrolytes is similar.With increasing surfactant concentrations the transparent solutionsbecome turbid and the phases separate. Finally. resclubillzation takcsplace with excess surfactant concentrations. With the HM-an-HEC com-pounds viscoelastic solutions ore formed with cationic surfactants. Theintermolecular interaction between hydrophobic pans of the polymers andthe surfactants and lmeracuons of oppositely charged ionic groups of thetwo componenl5 lead 10 formation of a temporary network with gel-likeproperties. With an·HEC the interaction can only take place »io charges.Viscosity enhancement with increasing surfactant concentnllion is there-fore lower with an-HEC than with HM-an-HEC compounds.

Paperno. SII20 inlSD 2, 181-191 (April 1999).

Journal of Surfactantsand Detergents

Phase Behavior or II Fragrance Compound S)'stem: WaterlPhcneth)'1AlcohoVLaurttb 41Glycerol. Stig E. FribergO·*. Abeer AI-Bawatfl. JoelD. Sandburg'", Jennifer L. Barbcrll. Qi Yina. and Patricia A, Aikcnsb.QOepartment of Chemistry. Clarkson University. Potsdam. New York13699-5810. and bICI Surfuctunts. Wilmington. Delaware 1985Q...5391.

The phase diagram of the system weterrpbe nethyl alcohol(PEAYLaureth 4 (L4)1g1ycerol was determined using visual observation,optical microscopy, small-angle X-ray diffractomelry. and the vapor pres-sure of phcnethyl alcohol measured by gas chromatographic analysis ofheadspace vapor at equilibrium. The phose diagram was shown to bedominated by three narrow isotropic liquid solubility regions along thewatcr/glycerol. glyceroVPEA. and PEA!L4 axes. Vapor pressure measure-IIICnts and tie-line determinations showed the final stale of formulationsafter evaporation of water 10 be emulsions of glyceroVPEA-in-LAIPEA orL4IPEA-in-glyceroIlPEA. PEA was predominantly dissolved in theL4IPEA phase because the chemical potential of PEA in glycerol washigh. even at modest cona:nlr.uions.

Paper 110. S 1070 in lSD 2. 159-165 (April 1999).Study on the Substrate Spedtk:lty or tt-Am)'lases That Contribute 10Soli Remo"al In OetergenLJ, Atsushi Tanaka and Eiichi Hos.hino·.Household Products Research Laboratories. Kao Corporation. 1334MilUllo. Wakayama. Wllkayama 64()...8580. Japan.

Tbe actions of tt-amylllSC!li in the degradation of amylose and amy-lopectin were investigated. and the contribution of the enzymatic hydroly·sis of high·viscosity gelatinized starch 10 !be remo\-al of food stains thatconllin starCh was chtuacterized. a-Amylases from Bodllus Qm)"lolique-faciens. 8. lichelliformis, Asperrillus Of)<JJe. and porcine pancreas wen:used to teSt the removal of curry stains. which an: hard 10 remove underIow·temperature washing conditions and include large amounts of starch.In a delClient. the enzyme from B. am)"loiiqut!fociens WlIS the most effec-tive in removing stains and hydrolyzed amylopectin IIIOIe efficiemly thanamylose as a result of the more efficient formation of an enzyme-sub-sirate complex in the former case. It is suggested that the cleaning poweror a.-amylases is due 10 !beir hydrolytic action. with enckKIegradalion of

Radiotracer Detergency Tullog in a Horizontal·Axls Wa.shlngMathlne. Deborab K. Passwater and Kirk H. Raney·. Shell ChemicalCompany. Houston. Texas n25I·1380.

Proposed regulations by the U.S. Department of Energy have spurreddevelopment of eeergy-efficient washing machines that utilize less Wlterand operate with lowcr energy requfremems than eooventlonal machines.As a result. major changes in wlSbing machine design are required.Among expected changes an: increased use or a horizontal-axis WISh tub.an increase in fabric-Io-wash liquor ratio. greater §urfllClallt concentTationin ee wash water, and reduced average washing temperat\llU. As a result.surfectants used in future detergent rormulations will be required to deaneffcctively in this new regime while producing minimal roam. Delergencytest methods utilinng radiOU"aCertechniques have be..-n developed to S1udy

INFORM. VOl. \0, no. 5 (May 1999)

ABSTRACTSFROM Aocs JOURNALS

amylopectin. whkh res.uhs in an effICient miuclion in Ihc degree of poly-meOution. The JiquefllClion of amy\optctin then eccejerees !he n:mo>'lllof food stains.

Paper no. SI074 in JSD 2. 193-199 (April 1999).

The ElTeet of 1'o1ixedSurfaclanl.'l on Enhandng Oil Recovery, M. EJ-BaUloone)', 111.AbdeJ·Moghny*. and M. Rarnai, Egyptian PetroleumResearch Institute (EPRI). Nasr City. Cairo. Egypt.

Micelles composed of mixed surfactams with different structures(mixed micelles) are of great theoretical IU1dindustrial ime=l This workpertains \0 mWlimiting interfacial tension (lF11 reductioo "10 surfactantpairs, In this respect. four types orrany acid amides based on lauric. myris-tic, palmitic, and stearic acids were blerKled with dodecyJ benzene sulfonicacid at a molar ratio of 4: I and designaled as AI_ A2_ A]. and A4_ respec-tively. The IFF WII51TICiLSUn:d for each blend al different oonccnll1llionsusing Badri CTUde oil. The most potent formula (t\V was evaluated forusing in enllanced oil ~very (EOR). The 1FT was le.w.d in Ibr: presenceof different electrolyte concmtr.uions with diffamt crude oils at diffemlltemperatures, Finally several runs .....ere de\'oced 10 smdy ~ displacementof Bm crude oil by ~ surfactant .solution using diffamt slug sizes of10, 20, and 4()'l, of pore volume (PV), The stUdy reveled that Badri crudeoil gave Ultra-low 1FT at lowest 5urfaclant COlIC:entration and O,5'l> ofNaC!, The ruovery factor at a slug size of2O'l> PV was 83% of original oilin place compared with 5K in case of conventional water flood.

Paper no, JSOI079 in JSD 2, 201-205 (April [999),

Cleaning I'frforrnancl" and Foaming Properties ofLlluroylllmidopropylbl"lllinelNonionk'l Mixed Systems. TakarnitsuTumurao,-. Tadashi liharah. Shigeo Nishidab, and Seiich Ohtab,a~1aterial Science Research Center and hBetler Living ResearchLaboratory, Lion Corponnioo, Tokyo, 132, Japan.

Lauroylamidoprcpylbetaine (LPB) has good cleaning and foamingperfonnanr:e with excellent low skin irritation. We ha\'e investigated therelationship between cleaning performance and foaming properties ofaqueous solutions comaining binary and ternary LPBloonionic surfactantsystems, Foaming preperties .....ere C\'D!uated by observing dynamic sur-face tension and aqueous con: thickness of a vertical foam film measuredby Fourier transform infrared spectroscopy. The LPBllau-royldiethanolami!.le (LOE) system has a positive synergistic effect oncleaning performance and foam stability, estimated from the greaseremovaltcst and dishwashing test for a light-duty detergent. However, thissystem shows very poor initial foam performance in both the sponge testand Rcss-Mlles foam test. This disad\'llI1tage of the LPBILOE system wasimproved using CI2En (pojycxyeihylene dodecy! ethers). Addition ofCI2En promoted dynamic surface tension lowering. indicating animprovement in the initial foaming performance. while maintaining clean-ing performunce nnd Ioam durability. Thus. the LPBILOEIC]2En ternary

!i)'51em has an excellent cleaning and foam petfonn.ance. as II lig,ht-dutyliquid detergent.

Paper 00, S]094 in JSD 2. 207-211 (April 1999).Mind Micelles or SGme Anionic·Anlonic, Cationlc-Cationie. andlooic-Nonionic Surfactants in Aqueous Media. Sambhav \fora, AluGeorge. Hemangi Desai, and Pratap Bahadur-, Depanment of ChemiSU)',South GujDnlt University. Surm-39S007,lndia.

Critical micelle concentrations (CMC) were obtained from tensiomct-ric studies on several binary surfactant mixtures (anionic-anionic. cation-ic-cationic. anionic-non ionic. and cationic·nonionic) in water at differentmole li'actions ((}..I). The composition of mixed micelles and the interac-tion parameter ~, evaluated from the CMC data for different systemsusing Rubingh's theory, are discussed. MlIl'ked interaction is observed forionic-nonionic systems. whereas it is weak in the case of similarlycharged surfactants. The influence of counterion valence in the fonnationof mixed micelles was investigated. and resuns suggest that in similarlycharged surfactant mixtures, the degree of countcrion binding does have amajor role in deciding the extent of interactions. Salt addition reveals aweakening of intenC1K!ns in ionic-nooionic s)'5tCms, and this is attributedto head group charge netJlT8liwion and dehydration of ~ ethylene oxideunits of the nonionic surfactants. Ooud point and viscosity data on thesesystems support the observation.

Paper no. S [1]0 in JSD 1, 213-221 (April 1999),

Rinsf-Added Fabric Soflener Technology al the Clese or the""""fntieth CfntuT)'. Matthew I. Levinsone, Stepan Company, Ncnhfleld.Illinois 60093.

This paper reviews rinse-added liquid fabric softener products Includ-ing current and emerging technologies related to composition. raw mDteri-als. and manufacturing processes, An introdu.ctory overview of the histori-cal drivers, market trends, advantages and disadVllntllges, and consumerhabits and practices that affect these products is also included,

Paper 00. S [129 in JSD 2. 223-235 (April 1999).

Biosurfllclllnt Production by Microorganisms on Uncono'fntionlllCarben Sources, Randhir S. Makkar and SwaTanj;t S. Cameotra'",Institute of Microbial Technology, Chandigam, India.

In recent years netural biosurfoctants have attmcted attention becauseof their low toxicity, biodegradability, and ecctcgical acceptability,HOVo'C\'er.for reasons of functionality and production cost. they are nOlcompetitive with chemical surfactams. Use of leexpensive substrates cendrastically decrease the production cost of biesurfactants. This reviewdescribes the use of unconventional carbon soun:es for bicsurfecrem pro-duction, These sources include urban as well as agroindustrial wastes,With suitable engineering and microbiological modifications, these wastescan be used as substrates for large-scale production of biosurfactarus.

Paper no. S [084 in JSD 1.237-241 (April 1999),

INFORM. \obi. ] O. no. 5 (May 1999)