bs,roo,s

_

EDITOR: S. KORITALA 9 ABSTRACTORS: J.C. Harris, M.G. Kokatnur, F.A. Kummerow, G. List, B. Matijasevic, K.D. Mukherjee, D.B.S. Min, R.A. Reiners, and P.Y. Vigneron t h e b r o a d peak is observed a n d this d i s a p p e a r s a t a b o u t 50 mol %.

9 Fats and Oils I~ESOLUTION OF DESMOSTEROL~ CHOLESTEROL~ AND OTHER STEROL ]NTERM]~DIATES BY REVERSE-PHASE HIGH~PRESSURE LIQUID C]SROM.~TOGRAPHY. E. H a n s b u r y a n d T.J. Scallcn, J. Lipid Res. I9, 742-6 (1978). A h i g h l y efficient technique h a s been developed for the resolution of several sterols t h a t are i n t e r m e d i a t e s in t h e b i o s y n t h e s i s of cholesterol a n d t h a t differ only by one carbon-carbon double bond or by one m e t h y l group. The technique described utilizes reverse-phase h i g h - p r e s s u r e liquid chrom a t o g r a p h y on a /~Bondapak-C~s column with acetonitrile as eluting solvent. METHOD FOR THE EXTRACTION AND CLEANUP OF ANIMAL FEED FOR THE DETERMINATION OF LIPOSOLUBLE VITAMINS D, A~ AND E BY tIIGH-PRESSURE LIQUID CHROMATOGRAPHY. H. Cohen and M. L a p o i n t e , J. elgric, ir Chem. 25, 1210 3 (1978). A highp r e s s u r e ]iquid c h r o m a t o g r a p h y ( L C ) p r o c e d u r e a n d clea~mp h a s been developed f o r the d e t e r m i n a t i o n of v i t a m i n s A, D, a n d E in feeds. The m e t h o d is q u a n t i t a t i v e for all three v i t a m i n s . ]Recovery studies on different feeds showed a n avera g e recovery of v i t a m i n A ( a c e t a t e ) , 96.4% ~ 2.4; v i t a m i n E acetate, 92.6% -4- 2.92; v i t a m i n DR, 91.25% ~ 5.9. M i n i m u m detectable a n m u n t s are: v i t a m i n A, 250 I U / k g ; v i t a m i n DR, 10,000 I U / k g ; v i t a m i n E, 5 I U / k g . The LC procedure was c o m p a r e d with a n A O A C eolorimetric procedure for the vitam i n s A a n d E. OXIDATION OF CHOLESTEROL BY DIOXYGEN SPECIES. L.L. Smith, et al., J. Am. Chem. See. 100, 6206-11 (1978). Reaction between cholesterol in a q u e o u s sodimn s t e a r a t e dispersions a n d H~-Oz yielded m a n y p r o d u c t s o f which 1g were isolated a m t identified. P r o d u c t s included 5,6a-epoxy-5a-cholestan-3fl-ol a n d 5,6fl-epoxy-5flcholestan-3fl-ol in 1:8 ratio r e p r e s e n t i n g direct reaction between cholesterol a n d H.~O~ a n d 5a-cholestane-3fl, 5,6fl-triol f o r m e d by h y d r a t i o n of the 5,6-epoxides; epimeric cholesterol 7-hydroperoxides, epimeric eholest-5-ene-3fl,7-diols, a n d 3fl-hydroxyeholest-5-en-7-one r e p r e s e n t i n g free-radical oxi d a t i o n of cholesterol by molecular oxygen derived by H20._, d i s p r o p o r t i o n a t i o n ; 5a-eholest-6-cne-3fl,5-diol, cholest-4,6-dien-3one, a u d 7a-stearatoxycholest-5-en-3fl-ol possibly derived f r o m singlet molecular oxygen released in ttsO~ d i s p r o p o r t i o n a t i o n ; a n d 5a-cholestane-3fl,6fl-diol. These results complete our studies of reactions between cholesterol a n d dioxygen species, reveali n g f o r the first time the several p a t h w a y s of oxidation of a biologica]Iy imlaortant s n b s t r a t e by dloxygen species. CONFORMATIONAL STRUCTURE OF GLYCEROL TRIVALERATE AND ITS RELATION TO PHOSPHOLIPIDS : STUDIES BY NMR AND POTENTIAL ENERGY CALCULATIONS. G. Govil, 1R.V. H o s u r a n d A. Saran, Chem. Phys. Lipids 21, 77-96 (1978). The s t r u c t u r e of a model lipid (glycerol trivalerate, G T V ) h a s been i n v e s t i g a t e d by ~H a n d ~aC N M R , a n d e n e r g y calculations b a s e d on classical p o t e n t i a l f u n c t i o n s ( C P F ) . The s t r u c t u r e of glycerol-ester pivot in G T V is characterized by a d y n a m i c equilibrium between two d o m i n a n t conformations. The c o n f o r m a t i o n a l pielure of the h y d r o c a r b o n chains a n d glycerol noiety in G T V is very sinfilar to t h a t in phospholipids. These r e s u l t s indicate caution in u s i n g the reported Crystal s t r u c t u r e of 1,2-dilauroy]D,L-phosphatidylethamolsmi~m as the only mode] for the org a n i z a t i o n o f lipid molecules in biologlcal m e m b r a n e s . ~"~IGH-SENSITIVITY

SCANNING

CALORIMETRIC

STUDY

OF

STEREOSPECIFIC 1H-NMR ANALYSIS OF TRIMETHYLSILYL DERIVATIVES OF GLYCERIDES WITH A CHIRAL SHIFT REAGENT. J. B u s a n d C.M. Lok, Chem. Phys. Lipids 21, 253-60 (1978). A proton m a g n e t i c r e s o n a n c e procedure with t r i ( 3 - h e p t a f l u o r o b u t y r y l - d e a m p h o r a t o ) p r a s c o d y m i u m ( I I I ) as a ehiral s h i f t r e a g e n t h a s been developed to determine the e n a n t i o m e r i c p u r i t y of monoglycerides, 1,2-diglycerides a n d triglycerides with one mone-uns a t u r a t e d f a t t y acid at position sn-1 or sn-3 a n d two s a t u r a t e d f a t t y acids at the two other glycerol positions. The addition of a chiral s h i f t r e a g e n t induces a u s e f u l e n a n t i o m e r i c s p l i t t i n g which allows the a c c u r a t e d e t e r m i n a t i o n of t h e ratio of both enantiomers. The t r i m e t h y l s i l y l ethers of 1,2-diglycerides are better suited for this p u r p o s e t h a n the aeetyl compounds. F o r monoglyeeridcs, the earlier published m e t h o d with the diacetates gives a better line s e p a r a t i o n in t h e ~H-NMR spectra. STUDIES ON THE PROPERTIES OF THE SINGLET OXYGEN-LIKE FACTOR PRODUCED DURING LIPID PEROXIDATION. E . K . Lai, K.L. F o n g a n d P.B. McCay, Biochim. Biophys. Acta 528, 497-506 (1978). The singlet oxygen reaction p r o d u c t of various t r a p p i n g a g e n t s is observed d u r i n g enzymic a n d n o n e n z y m i c pcroxidation of microsomes as well as d u r i n g the p e r o x i d a t i o n of p u r e lipids e x t r a c t e d f r o m microsomes. W e now wish to report t h a t purified f a t t y acid h y d r o p e r o x i d e alone, as well as pcroxidized m i c r o s o m a l lipid a n d cumene h y d r o p e r o x i d e also fornl the singlet oxygen reaction p r o d u c t with 2,5-diphenylf u r a n . The reaction p r o d u c t (cis-l,2-dibenzoylethylene) w a s observed to be f o r m e d in an anaerobic system, with or w i t h o u t E D T A . The d a t a indicate t h a t a reaction of hydroxyl radicals with 2,5-diphenylfuran c a n n o t a c c o u n t f o r t h e f o r m a t i o n o f dibenzoylethylene in these systems. TOTAL SYNTHESIS OF DL-19-HYDROXYPROSTAGLANDIN E1 AND DL-13-CIS-15-EPI-19-HYDROXYPROSTAGLANDIN Ez. C. L u t h y et al., J. elm. Chem. Soc. 100, 6211-7 (1978). A t o t a l s y n t h e s i s o f dl-19-hydroxyprostaglandin E~ (34) a n d dl-13-cis-15-epi-19h y d r o x y p r o s t a g l a n d i n E , (35) via the c o n j u g a t e a d d i t i o n of the dioctenyl c u p r a t e r e a g e n t 21 derived f r o m d/-1-iodo-3hydroxy-7-tert-butyldimethylsilyloxyoct-l-cis-cne (14) to dl-2( 6 - e a r b o m e t h o x y h e x y l ) - 4 - t e t r a h y d r o p y r a n y l o x y c y c l o p e n t-2-en-1one (23), followed by the stereospecific s u l f e n a t e - s u l f o x i d e t r a n s f o r m a t i o n on the r e s u l t a n t 13-cis-prostag]andin analogue, is reported. The p r e p a r a t i o n of the requisite cis-ior 14, prepared by two s y n t h e t i c sequences s t a r t i n g f r o m either am e t h y l c y c l o p e n t a n o n e or acrylonitrile, is described as well as the s e p a r a t i o n of t h e C-19 a a n d fl isomers.

MIXTURES

OF CHOLESTEROL WITH DIMYRISTOYL- AND DIpALMITOYLPHOSPHATIDYLCHOLINES. S. Mabrey, P.L. Marco, a n d J.M. S t u r t e v a n t , Biochemistry 17, 2464-8 (1978). A h i g h l y sensitive a n d stable s c a n n i n g microcalorimeter is employed in a r e i n v e s t i g a t i o n of the effect of cholesterol on m u l t i l a m e l l a r s u s p e n s i o n s of dimyristoylphosphatidylcholine (DMPC) and dipahnitoy]phosphatidylcholine ( D P P C ) . Below 20 reel % cholesterol the D P P C m i x t u r e s give h e a t - c a p a c i t y curves each of which can be resolved into a n a r r o w a n d a broad peak, s u g g e s t i n g the coexistence of two imnfiscib]e solid p h a s e s ; above 20 mot % only I. AM. OIL CHEMISTS' SOC., February 1979 (VOL. 56)

EFFECTS 01~ AIR~ OZONE, AND NITROGEN DIOXIDE EXPOSURE ON

T~E OXIDATION OF CORN AND SOYBEAN LIPIDS. R.~. B r o o k s a n d A.S. Csallany, J. Agric. Food Chem. 26, 1203-9 (1978). T h i s s t u d y w a s conducted to determine t h e oxidative effects induced b y exposure of corn a n d s o y b e a n seeds to air, n i t r o g e n dioxide (NO2) a n d ozone (03). W h o l e halves, a n d g r o u n d samples of s o y b e a n seeds a n d whole corn kernels were exposed to air, 15 p p m NO2, or 1.5 p p m 08 c o n t i n u o u s l y f o r 100 h at room t e m p e r a t u r e . Ground s o y b e a n s a m p l e s exposed to air, 15 p p m NO:, or 1.5 p p m Os i n c u r r e d t h e g r e a t e s t P U F A a n d tocophero] d e s t r u c t i o n a n d lipofuscin-like p i g m e n t formation.

T w o NEW VITAMIN ]) ISOMERS. FORMATION OF ( 3 S , 1 0 R ) - ( Z , Z ) 9,10-SECOCHOLESTA-5,7,14 TRIEN-3-OL AND ITS 10S*EPIMER FROM CIS-ISOTACHYSTEROL3 VIA FACILE (1,7) SIGMATROPIC REARRANGEMENTS. B.L. Onisko, H . K . Schnoes, a n d t t . F . Deluca, J. Org. Chem. 43, 3441-4 (1978). W a r m i n g a solution o f (3S)- (Z)-9,10-secocholesta-5 (10), 6,8 (14)-trien-3-ol (cis-isotachystero]~) in decane p r o d u c e d two n e w isomers of v i t a m i n D: (3S,10S)-(Z,Z)-9,10-secocholesta-5,7,14-trien-3-ol ( 5 a ) a n d (38,10R)-(Z,Z)-9,10-secoeholesta-5,7,14-trien-3-ol (bb). The reaction h a s been shown to be reversible, a n d to oecur v i a a n

147A

ABSTRACTS: FATS AND OILS intramolecular (1,7) hydrogen transfer.

O P T I M I Z A T I O N OP T H E YIELD IN S O Y B E A N

OPTI]~UM C O N P I O U K A T I O N OY LARGE-SCALE T E C H N I C A L PLAIqTS FOR S T R A I G H T DISTILLATION A N D F R A C T I O N A T I O N OP N A T U R A L FATTY/ ACIDS. H. Stage, Sullen, Ole, Fette, Wachse 104(16), 445-53 (1978). The review deals with the question as to how suitable connection and design of component elements can contribute to a reduction in operating costs in the light of ever rising energy prices and how, at the same time, the quality can be improved by careful t r e a t m e n t of the thermally and oxidatively very sensitive higher f a t t y acids, especially those with double bonds. DETECTION OF WAXES WITH UV RADIATION. W. Schmidt. Coating 1978, 11(1), 32 (1978). Fluorescence given by the different waxes is shown in a table. (World Surface Coatings Abs No. 435) REACTIONS OF FATTY ACIDS %VITH AMINES. II. SEQUENTIAL THERMAL REACTIONS OF STEARIC (OCTADECANOIC) ACID WITH SOME 1,2- AND 1,3-AMINOALCOHOLS A N D DIS-AMINES. R.N. Butler, C.B. O'Rcgan and P. Moynihan, J. Chem. Soc, Perkin Trans. 1(4), 373-7 (1978). Thermal reactions of stearic acid with 2-aminoethanol and 3-aminopropanol in a heavy hydrocarbon oil as solvent involved (1) salt formation, (2) stearoylation of the amino nitrogen, and (3) a stearoyl t r a n s f e r between two molecules of the stcaramidoalcohol to give the amidoester. Each successive step took place at a higher temperature. The reaction of the stearamidoalcohols with thionyl chloride involved rearrangements, and did not yield stable cyclised products. Thermal reactions of stearie acid with propane-l,3-diamine and with bis(2-hydroxycthyl)amine gave diantides and amidoesters. (World Surface Coatings Abs. No. 436) STRUCTURE AND SYNTHESIS OF POLYUNSATURATEDPATTY ACIDS. E. Ucciaai, Eev. Ft. Corps Gras. 25, 397-404 (1978). N a t u r a l polyunsaturated f a t t y acids have various structures. Almost all the possibilities which can occur between several double and triple bonds are represented. These structures are studied with respect to isomery and stcreochemistry as well as in respect to conformation. Consequences at the level of chemical and catalytic reactivity are seen by some representative structures. Thanks to analytical progress since a few years limits of the reasonable structural pureness have diminished and synthesis methods had to fit to this new situation. The improvement of organic synthesis permits actually univocal and selectif couplings C-C, the creation of highly stereoselectif bonds C = C and all the necessary synthons. Several examples are given and discussed in order to show this simultaneous evolution in analysis and synthesis of polyunsaturated f a t t y acids. STRUCTURE-CHEMICAL REACTIVITY RELATIONS SATURn-TED FATTY ACIDS. J . Graille,

OF

R.

RECENT ADVANCES IN DIRECT EXTRACTION PROCESSES OF OILS FROM OIL RICH SEEDS. M. Bernardini, Eev. Ft. Corps Gras, 25, 361-4 (1978). The oil cxtraction from seeds having a high content of oil ( 4 0 - 6 0 % ) is carried out according to two systems. The first system is using continuous presses (expellers) and a traditional solvent extraction device for residual oil from the press-cakes. The second system is using one direet solvent extraction device with two extractors in series. Comparative data of both processes show a significant advantage for direct extraction. Results concerning the treatments of different oilseeds are given. A D S O R P T I O N 0P STEARIC ACID ON p U R E A N D ~IIXED OXIDES. I~..L.

Madan and N.K. Bundle, J. Indian Chem. Sou. 54, 1113-6 (1977). The adsorption of stcaric acid from solutions in cyclohexane on tin oxide (in the form of gel and precipitate), antimony oxide and tln-antimony mixed oxides having various ratios of tin to antimony, has been investigated. I t is observed t h a t the mode of adsorption depends upon the surface acidity of the oxide. I n the case of tin oxide gel, tin oxide ppt. and the mixed oxides with S b : S n as 1:5 and 1:10, stearic acid is adsorbed with its hydrocarbon chain parallel to the surface. With antimony oxide and mixed oxides with higher percentage of antimony, the perpendicular orientation is adopted.

9 D r y i n g Oils and Paints T H E P E N U G R E E K OIL:COMPOSITION, PROPERTIES, POSSIBLE U S E S IN PAINTS A N D V A R N I S H E S INDUSTRY. J.C. B a c c o u et a~., /~ev. Fr. Corps Gras, 25, 353-9 (1978). The oil of Trigonella

foenum graecum L. (Fenugrcek) contains interesting proportions of ]inoleie and ]inolenie acids which are relatively steady, whatever geographic origin and growing conditions of this plant m a y be. This lcd to siccativity and standolization experiments. An oleoglycerophtalic resin has been obtained after classical refining t r e a t m e n t s (desodorisation, decoloration, wintering). I t was technologically suitable to be used in paints industry instead of drying oils and derivations. This oil is an interesting by-product in extraction from Fenugreek steroYdic sapogenins. I t s recovery contributes to valorization of this leguminous.

POLYUN-

Eev. Fr. Corps Gra~, 25,

405-12 (t978). The reactionat sites of polyunsaturated f a t t y acids are reviewed with regard to their interaction with a n t a g o n i s t s of different electronic n a t u r e : free radicals, anions. Some examples of substitution reactions by halogen atoms are given and structural consequences are seen. Catalytic oxidation and autoxidation of polyunsaturated acids are studied similarly. The ionic antagonists can cause conjugation reactions and, in consequence, typical eyclisation in the case of polyunsaturated. The particular structure of natural polyunsaturated is well suited to concerted participation reactions (anchimeric reactions). Some examples of simultaneous participation of two double bonds in intramolecular heterocyelisation processes are discussed. In conclusion, the eventual importance of actual knowledge on polyunsaturated specific reactivity is shown. STRUCTURE-CATALYTIC REACTIVITY OF POLYUNSATURATED PATTY ACIDS. G. Ceechi, Roy. Fr. Corps Gras, 25, 413-21 (1978). The structure of polyunsaturated f a t t y acids determines a certain, comp/ex and sometimes misunderstood catalytic reactivity. Some examples of reactions are discussed. Using as examples, isomerisation and hydrogenation, several elements of general cataiytie theory are reviewed. Emphasis is placed on activated complexes which result from olefin-metal interaetions. The organome?allie intermediaries are discussed, particularly in homogeneous catalysis; their contribution to selectivity is studied with several examples. The structural consequences of polyunsaturated activation by metals or their complexes are reviewed. In conclusion, f u n d a m e n t a l d a t a on catalysis are used to explain the catalytic t r a n s f o r m a t i o n of an oil.

148A

C R U S H I N G PLANTS.

Leysen, /~ev. Fr. Corps Gras, 25, 349-52 (1978). The different factors which occur in expenses for soybeans crushing installations arc very important. A control of material balance is necessary: quantity of unloaded beans, m a n u f a c t u r e d meals, produced oil and lecithin, and, a laboratory control of manufactured products which have to meet commercial specifications. Used energy and preventive maintenance of installations are two important points which are successively reviewed.

L I N S E E B OIL/METAL ACETYLACETONATESYSTEMS. IV. THERMOGRAVIMETRY. N. Indicator e~ aL, J. Coatings Teeh. 50, No 638, 54-61 (1978). Thermogravimetrie d a t a are presented for linseed oil containing small quantities of 15 metal acetylacetonates in the temperature range of 20-100 C. in air. Inhibition period, rate of increase in weight, m a x i m u m weight achieved and subsequent weight decrease are reported. Temperature parameters are presented. Results are discussed in terms of oil d ~ i n g mechanisms which have appeared in the literature. (World Surface Coatings Abs. No. 435).

DRIER COMPOSITION AND YELLOWING OF LINSEED 0IL FILMS. It. Rakoff, W..F. Kwolek and L.E. Gust. J. Coatings Teoh. 50, No 637, 51-5 (1978). The effect of drier composition on yellowing was studied spectrophotometrically with linseed oil as the vehicle and Morest paper as the substrate. The yellowncss indices produced by the naphthcnates and octoates of Co, Mn and Pb, either alone or in combinations of two or three driers, were analysed statistically. The results show t h a t time of exposure, thickness of the film, and cation type h a d significant effects on yellowing, while the role of concentration and type of anion were less apparent. Films t h a t contain two driers yellow in a way t h a t indicates t h a t the e f f e c t s of single driers are additive. (World Surface Coatings Abs. No. 435) STUDIES ON NON-TRADITIONAL OILS. I I . ACID CATALYSED ALCOHOLYSIS OF TOBACCO SEED OIL, A.S. Kulkarni, D. P r a d h a n and H.A. Bhakare,. J. Col. Sou. 16(3), 29-~2 (1977). Alcoholysis of tobacco seed oil using methanol and ethanol with J. AM. OIL CHEMISTS' SOC., February 1979 (VOL. 56)

ABSTRACTS: DRYING OILS AND PAINTS various acid catalysts such as hydrochloric, sulphuric and perchloric acids has been carried out. I t has been shown that for methanolysis sulphuric acid gives best yields of esters, while f~r ethanolysis hydrochloric acid gives best yields. (World Surface Coatings Abs. No. 436)

seopic concentration in the ]ipoprotein. These results support a mechanism in which rate-limiting dissociation of the dlglyceride analogue from one HDL particle into the aqueous phase precedes rapid diffusion and subsequent uptake by another such particle.

RECENT APPLICATIONS OF GEL PERMEATION CHROMATOGRAPHY IN

LIQUID CRYSTALS AND CHOLESTEROL NUCLEATION DURING EQUILIBRATION IN SUPERSATU}~ATED BILE ANALOGS. ]~.T. ~=[olzbach and C. Corbusier Bioehim. Biophys. Acta 528, 436-44 (1978). In recent work, apparent liquid crystal agglomeration to form typical solid cholesterol mlcroerystals was frequently observed photomicrographically in bile samples from prairie dogs fed a cholesterol-enriched diet, prior to solid crystal formation. We therefore have conducted a systematic study of time-course lipid compositional changes in the mesophase and micellar phase constituents of bile analog solutions while undergoing cholesterol nucleation during equilibration. In keeping with theoretical considerations, structural evidence for increased hydration is demonstrable near the point of complete equilibration when the mesophase is dissolving.

PAINT INDUSTRY. I. R.A. Ellis. Pig. l~esin Teeh. 7(4), 4(6 p p ) , (1978). The use of GPC for the analysis of oils, f a t t y acids and their derivatives, polyamide-modified alkyds, oligomeric po]yethers, esters and polyeslers, polyisocyanates and phenolformaldehyde resins is reviewed. (World Surface Coatings Abs. No. 435) E. Plunsch. Uses of hydrogenated castor oil are outlined. (World Surface Coatings Abs. No. 436) HYDROGENATED

CASTOR OIL (CASTOR OIL WAX).

Coating 11(2), 69 (1978).

EFFICIENT UTILISATION OF ROSIN ACIDS DURING TALL OIL DISTILLATION. A.A. Mariev and B.S. Filippov. Izv. VUZ, Lesnoi Zh. 20(1), 105-11 (1977). An investigation of product distribution from the distillation of tall oil indicated that about half of the rosin acids which are lost in distillation tars are degradation products. Rosin acid yields can be increased by using columns with Z-shaped titanium packing instead o f ceramic saddle packing. (World Surface Coatings Abs. l~o. 436) SOLVENT S~LECTION"FOR SEPARATING NEUTRAL SUBSTANCES FRO~I TALL 0IL PRODUCTS. I.P. Zhukova, A N . Trofimov and V.B. Kogan. Zh. Pr~kL Khim. 30(6), 1420-2 (1977). The selectivities of 32 different solvents toward the pairs f a t t y acids/ neutral components, fatty acid and rosin acid soaps/neutral components, neutral components/beta-sitosterol and soapflaetasitosterol were determined and tabulated. The most highly selective solvents for pairs of acid/neutral component type were hydrocarbons, ketones and esters; the least selective were alcohols. (World Surface Coatings Abs. No. 436)

9

Biochemistry and Nutrition

EFFECTS OF OEMF1BROZIL (CI-719), Gv.MC~IOL (01-720), CLO~IBRATE AND U.41792 ON CHOLESTRKOLDISTRIBUTION IN RAT PLASMA FRACTIONS OBTAINED BY POLYAlqlON PRECIPITATION. R.E. Maxwell, J.W. Nawrocki and P.D. Uhlendorf Artery 4, 303-13 (1978). Rats fed a diet containing cholesterol and cholie acid develop a marked depression of plasma HDL as measured by potyacrylamide gel electrophoresis or by the amount of cholesterol in the supernatant from precipitation with heparin + Mn *§ (SN-C). Evidence is summarized indicating that these two measurements, while qualitatively related, are not necessarily equivalent, the latter representing cholesterol associated with lipoproteins deficient in B and arginine~ricb apoproteins. Since there is evidence that the B and arginine-rich apoproteins are responsible for the initial atherogenic event of attachment of lipoproteins to cells, the ability of a compound to elevate SN-C may be of t h e r a p e u t i c potential( E - - A - I I ) COMPLEX OF HUMAN PLASMA LIPOPROTEINS. I. CHARACTERIZATION OF THI~ MIXED DISULFIDE AND ITS IDENTIFICATION IN HIGH DENSITY LIPOPROTEIN SUBFRACTION. K.H. Weisgraber and R.W. Mahley J. B i o i Chem. 253, 6281-8 (1978). A M~ -- 46,000 apoprotein designated as the a p o ( E - - A - I I ) complex has been isolated from the d < 1.006 fraction of human type I I I hyperlipoprotcinemic plasma and from the d = 1.063 to 1.125 fraction of normal human plasma. The a p o ( E - - A - I I ) complex was stable to treatment with 4 M guanidine, 8 M urea, and 2% sodium dodecyl sulfate but was dissociated into two subunits following reduction with fl-mercaptoethanol or dithiothreitol. The possible interconversion between the a p o ( E - - A - I I ) complex and the E and A-II apoproteins in vivo and its importance in lipoprotein metabolism remains to be determined. APOPROTEIN

KINETICS OF RAC-1-OLEYL-2-(4-(3-PYRENYL)BUTANOYL)GLYCEROL TRAI',rSFER RETWEEN HIGH DENSITY LIPOPROTEINS. S.C. Charlton, K , Hong and L.C. Smith, Biochemistry 17, 3304--9 (1978), The mechanism of transfer of diglyeeride between high density lipoproteina (HDL) was investigated with a pyrene-coutaining analogue whose fluorescent properties depend on the microI. AM, OIL CHEMISTS' SOC., February 1979 (VOL. 56)

MOLECULAR ORDER IN CIS AND TRANS UNSATURATED PHOSPHO-

LIPID BILAYERS. J. Seelig and N. \Vacspe-Sarcevic, Biochemistry 17, 3310-5 (1978). The influence of eis and trans double bonds on the hydrocarbon-chain organization of fluid lipid bilayers is investigated by means of deuterium nuclear magnetic resonance. Oleic acid and elaidic aeld have been deutersted se]ectlveiy at six and three different carbon atoms, respectively. The C = C bond vector is found to be aligned almost perpendicular to the bilayer surface; i.e., the angle between the bilayer normal and the C---C bond vector i~ only 7-8 ~ A similar orientation is likely for the trans double bond. PLASMA LEVELS O1~ APOLIPOPROTEIN All AND APOLIPOPROTEIN B IN HUI~IAN ATHEROSCLEROSIS. P . Avogaro et el., Artery 4, 385-94 (1978). In two series of patients affected by post infarction cardiopathy or complaining o f angina the plasma levels of spo-B and apo-A~ were recorded. Apo-B levels are higher and apo-A~ levels are lower in atherosclerotics than in controls; these findings have been recorded also in patients showing normal lipid plasma ]eve~s. LIPID-PROTEI~ ASSOCIATIONS IN CFIRo~IATOPHORES FROM T~IE PHOTOSYNTI:IETIC BACTERIUM RHODOPSEUDO~ONAS SPHAEROIDES. G.]~. Birrell, W.R. Sistrom, and O t I . Grifflth, Biochemistry 17, 3768-73 (1978). Lipid-protein interactions were examined in chromatophores isolated from the photosynthetic bacterium Rhodopseudomonas sphaeroides using lipid spin-labels. The chromatophores contain fluid bilayer and a significant amount of lipid immobilized by membrane proteins. For a typical preparation of cells grown under 600 ft-e illumination. 59% of the spin-labeled f a t t y acids were bound. Essentially the entire length of the 18-carbon fatty acid chain was immobilized, judging from results obtained with the spin-label at the 7, I2, and 16 positions. The changes in immobilized lipid with light level and polar head group suggest that the anntenna bacteriochlorophy]l-binding proteins preferentially associate with negatively charged llpids. CHAIN SHORTENING OF ERUCIC ACID BY SUBCELLULAR PAR~ICLZS ISOLATED FRO~" LIVER AND HEART OF RAT. P. Clouet and J . Bezard F E B S Lett. 93, 165-8 (1978). In several animal species, the presence in the diet of rape-seed oil rich in erucic acid (c~s-13-docosenoie) causes various pathological disorders, especially in the heart. Many workers have dealt with the morphological aspects of the affected organs; others with the metabolic modifications brought about by the diet. As erucie acid has often been considered responsible for such disorders, many studies have been made on the metabolism of this f a t t y acid. The purpose of this work was to determine in which cellular organelles, mltochondria or microsomes, these chainshortening reactions in liver and heart occur. LONG-TERM TREATMENT WITH METFORMIH IN A LARGE COHORT OF HYPERLIPIDEMIC PATIENTS. CT. Descovich et al., Artery 4, 348-59 (1978). Metformin (N,N-dimethyl biguanide) was given to a large cohort of hyperlipidemie patients (daily dose of 2,550 g) in an effort to control hyperlipidemia and to analyse possible cardiovascular changes. 254 patients completed a 6 month follow up; of these (134 males and 120 females), 92 were diagnosed as type IIA, 87 I I B and 81 type IV. This study shows the applicability of a hypolipidemie drug regimen in a relatively large patient sample from a

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ABSTRACTS: BIOCHEMISTRY AND N U T R I T I O N m e d i u m sized town. The p r e l i m i n a r y results also s u g g e s t t h a t this r e g i m e n m a y f a v o u r a b l y affect v a s c u l a r f u n c t i o n t e s t s in treated patients. DISTRIBUTION OF RADIOACTIVITY IN MYELIN LIPIDS FOLLOWING SUBCUTANEOUS I N J E C T I O N OF (:4C) STEARATE. N. GozlanDevillierre, N. B a u m a n n a n d J. Bourre, Biochi?n. Biophys. Acta 528, 490-6 (1978). Blood f a t t y acids are an i m p o r t a n t p a r a m e t e r for the s y n t h e s i s of b r a i n m y e l i n as e x o g e n o u s stearic acid is n e e d e d : a f t e r s u b c u t a n e o u s injection to 18day-old mice this labelled stearic acid is t r a n s p o r t e d into b r a i n myelin a n d i n c o r p o r a t e d into its lipids. H o w e v e r t h e acid is p a r t l y metabolized in t h e b r a i n b y elongation ( t h u s p r o v i d i n g very long chain f a t t y acids, m a i n l y lignocerie acid) or b y d e g r a d a t i o n to a c e t a t e u n i t s (utilized for s y n t h e s i s of m e d i u m chain f a t t y acids as p a l m i t i c acid, a n d cholesterol). These m e t a b o l i t e s are f u r t h e r incorporated into myelin lipids. BIOSYNTHESIS IN ESCHERICHIA COLI OF aN-GLYCEROL S-PHOSPHATE, A PRECURSOR OF PHOSPHOLIPID. J.]~. E d g a r a n d ]~.M. Bell, J. Biol. Chem. 253, 6348-53 (1978). T h e b i o s y n t h e s i s of sn-glycerol 3 - p h o s p h a t e ( g l y c e r o l - P ) , a p r e c u r s o r for t h e s y n t h e s i s o f phospholiplds, in Escheriehla coli is accomplished in a single step by reduction of the glycolytic i n t e r m e d i a t e , d l h y d r o x y a c e t o n e - p h o s p h a t e . The enzyme which catalyzes t h i s reaction, t h e b i o s y n t h e t i c glycerol-P d e h y d r o g e n a s e (EC 1.1.1.8), is s t r o n g l y i n h i b i t e d in vitro b y glycerol-P. T h e s e d a t a establish t h a t t h e p h y s i c a l p r o p e r t i e s of t h e wild t y p e a n d f e e d b a c k - r e s l s t a n t glycerol-P d e h y d r o g e n a s e s are similar a n d t h a t t h e m e c h a n i s m of glycerol-P inhibition does n o t involve association or dissociation. EFFECT OF MEMBRANE PHOSPHOLIPID COMPOSITIONAL CHANGES ON ADENYLATE CYCLASE IN L M CELLS. V.H. E n ~ e l h a r d , M. Olaser. a n d D R . Storm, Biochemistry 17, 3191-200 (1978). A d e n y l a t e cyclase activities were e x a m i n e d in m o u s e L M cell m e m b r a n e s which h a d been s u p p l e m e n t e d with p o l a r h e a d g r o u p s a n d / o r f a t t y acids. Basal, fluoride-, a n d PGE1s t i m u l a t e d activities v a r i e d s y s t e m a t i c a l l y w i t h c h a n g e s in phospholipid composition, a n d P G E r s t i m u l a t e d activities correlated with t h e a v e r a g e degree of u n s a t u r a t l o n of t h e phospholipid f a t t y acids or with t h e p r i m a r y a m i n o g r o u p c h a r a c t e r o f t h e phospholipld p o l a r h e a d g r o u p s . I n addition, t h e Km f o r A T P of b a s a l a d e n y l a t e cyclase w a s s y s t e m a t i c a l l y c h a n g e d b y b o t h p o l a r h e a d g r o u p a n d f a t t y acid supplem e n t a t i o n . I t is proposed t h a t a d e n y l a t e cyclase can exist in several different c o n f o r m a t i o n s in t h e m e m b r a n e d e p e n d i n g upon t h e p h o s p h o l i p i d composition. OF SPECIFIC F A T T Y A C Y L E N R I C H M E N T S ON MEMBRANE PHYSICAL PROPERTIES DETECTED WITH A SPIN LABEL PROBE. MiE. K i n g a n d A.A. Spcctor, J. Biol. Chem. 253, 6493-501 (1978). T h e f a t t y acyl composition of t h e E h r l i c h ascites cell p l a s m a m e m b r a n e was modified b y exposure of i n t a c t cells to m e d i a c o n t a i n i n g v a r i o u s f a t t y acids d u r i n g short term, s t a t i o n a r y culture. Differences in t h e f a t t y acyl composition of t h e isolated p l a s m a m e m b r a n e f r a c t i o n were m o s t a p p a r e n t in t h e choline phosphoglyceridcs, where e n r i c h m e n t s of 10 to 2 0 % occurred a f t e r 3 h of culture. Some modifications also were n o t e d in the e t h a n o l a m i n c phosphoglycerides, b u t t h e other m e m b r a n e p h o s p h o l l p i d f r a c t i o n s were only slightly affected. These r e s u l t s indicate t h a t p l a s m a m e m b r a n e lipid mobility, as m e a s u r e d w i t h a spin label probe, is sensitive to relatively s m a l l c h a n g e s in m e m b r a n e f a t t y acyl composition. Moreover, these c h a n g e s occur in cells t h a t are n o t g r o w i n g or dividing a n d a p p e a r to be p r o d u c e d as a result of the r a p i d t u r n o v e r of certain phospholipid pools in the m e m b r a n e . EFFECT

STEREOSPECIFIC SIDE CHAIN HYDROXYLATIONS IN THE BIOSYNTHESIS OF CHENODEOXYCHOLIC ACID. S. S h e f e r et ed., J. Biol. Chem. 253, 6386-92 (1978). T h i s p a p e r describes stereospecific side chain h y d r o x y l a t i o n s in the b i o s y n t h e s i s of chenodeoxycholic acid by liver nfitochondria a n d microsomes. T h e hyd r o x y l a t i o n of 5fl-cholestane-3a,Ta-diol w a s s t u d i e d in subcellular f r a c t i o n s of rat, g u i n e a pig, a n d r a b b i t livers. I n c u b a t i o n of 5fl-cholestane-3a,7a-diol resulted in hydroxylations at C-12, C-24, C-25, a n d C-26. On the b a s i s of t h e s e r e s u l t s it is n o t possible to d r a w firm conclusions concerning t h e relative i m p o r t a n c e of the m i c r o s o m a l 25-hydroxylase or t h e m i t o c h o n d r i a l 26-hydroxylase in chenodeoxyeholic acid synthesis. QUANTITATIVE ASPECTS OP FREE AND ESTERIFIED STEROLS IN SACCHAROMYCES CEREVISIAE UNDER VARIOUS CONDITIONS. S.

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T a k e t a n i , J. N a g a i a n d H. K a t s u k i , Biochim. Biophys. Acta 528, 416-23 (1978). F o r e x t r a c t i o n of free a n d esterified sterols f r o m y e a s t cells, a m e t h o d was devised in which b o t h f o r m s of stero]s were e x t r a c t e d with light p e t r o l e u m a f t e r t h e t r e a t m e n t of the cells with acetone, a n d t h e n w i t h dimethylsulfoxide. The c o n t e n t of sterol esters in the cells u n d e r aerobic conditions m a r k e d l y increased with time, a m o u n t i n g to 9 5 % of the total sterols u n d e r some conditions. I n t h e cells u n d e r aerobic conditions, t h e free sterols were f o u n d to consist m a i n l y of ergosterol, w h e r e a s the esterified sterols contained considerable a m o u n t s of zymosterol, ]anosterol, a n d other int e r m e d i a t e sterols besides ergosterol. REGULATION OF CHOLESTEROL ESTER SYNTHESIS IN CULTURED GLIAL AND NEURONAL CELLS. RELATION TO CONTROL OF CHOLESTEROL SYNTHESIS. J . J . Vo]pe, S.W. H e n n e s s y a n d T. W o n g , Biochim. Biophys. Acta 528, 424-35 (1978). R e g u l a t i o n of cholesterol ester s y n t h e s i s w a s s t u d i e d in cultured C-6 glial a n d n e u r o b l a s t o m a cells. P a r t i c u l a r e m p h a s i s w a s placed on the relation of t h i s r e g u l a t i o n to control of cholesterol synthesis. The effectors s t u d i e d were low d e n s i t y lipoprotein ( L D L ) a n d desmosterol. D i s t i n c t differences in r e g u l a t i o n were observed between the glial a n d neuronal cells. Suitable e x p e r i m e n t s i n d i c a t e d t h a t a l t e r a t i o n s in pool sizes of interm e d i a t e s did n o t c o n t r i b u t e to the genesis of t h e observed responses a n d s u g g e s t e d t h a t L D L a n d desmosterol produced their effects b y s t i m u l a t i n g esterification of p r i m a r i l y e n d o g e n o u s cholesterol. ( 1 4 C ) P A L M I T A T E U P T A K E IN ISOLATED RAT LIVER MITOCHONDRIA :

EFFECTS OF FASTING, DIABETES MELLITUS AND INHIBITORS OF CARNITINE ACYLTRANSFERASE. J.M. A m a t r u d a , et al., J. Lipid Res. 19, 688-94 (1978). The r a p i d association of Na-(16-:dC) p a l m i t a t e with isolated r a t liver m i t o c h o n d r i a w a s m e a s u r e d by a n oil s e p a r a t i o n method. T h i s association w a s time a n d t e m p e r a t u r e - d e p e n d e n t a n d as absolutely d e p e n d e n t on the presence of e x o g e n o u s A T P a n d C o A S H a n d p a r t i a l l y dep e n d e n t on exogenous carnitlne. C a r n i t i n e dependence was e n h a n c e d at lower c o n c e n t r a t i o n s o f (14C)palmitate. These studies d e m o n s t r a t e a m e t h o d of e v a l u a t i n g f a t t y acid association with m i t o c h o n d r i a which, because of its dependence on carnitine a n d c a r n i t i n e a c y l t r a n s f e r a s e I activity, m o s t likely r e p r e s e n t s true u p t a k e into m i t o c h r o n d r i a . F u r t h e r m o r e , these studies indicate t h a t the c a r n i t i n e - d e p e n d e n t u p t a k e of f a t t y acids into m i t o c h o n d r i a is e n h a n c e d in the two ketotic s t a t e s e v a l u a t e d a n d t h a t the c a r n i t i n e a c y l t r a n s f c r a s c s y s t e m m a y be a r e g u l a t o r y site in ketone b o d y production. CYCLIC A M P METABOLISM IN ADIPOSE TISSUE OF EXERCISETRAINED RATS. E . W . Askew, et al., J. Lipid Res. 19, 729-36 (1978). Cyclic A M P m e t a b o l i s m in e p i d i d y m a l adipose tissue of exercise-trained r a t s was e x a m i n e d to d e t e r m i n e if t r a i n i n g induced c h a n g e s in cyclic A M P p r o d u c t i o n or inactivation. B e g i n n i n g a t 7 weeks of age, male r a t s were physically t r a i n e d by 12 weeks of t r e a d m i l l r u n n i n g . P a i r - f e d control r a t s reinained s e d e n t a r y in their cages f o r t h e d u r a t i o n of the exp e r i m e n t . The r e s u l t s of this s t u d y indicate t h a t cyclic A M P production in response to n o r e p i n e p h r i n e s t i m u l a t i o n is n o t i n c r e a s e d by t r a i n i n g a n d m a y even be reduced, i m p l y i n g t h a t adipose tissue cyclic A M P levels m a y be u n d e r a g r e a t e r degree of control in t r a i n e d rats. M o d u l a t i o n of adipose tissue cyclic A M P levels m a y f u n c t i o n to r e g u l a t e more closely the d u r a t i o n of lipo]ysis in exercise-trained rats. EFFECTS OF ASCORBIC ACID DEFICIENCY ON ADRENAL ~ITOCHONDRIAL HYDROXYLATIONS IN GUINEA PIGS. I. Bjorkhcln, A. Kallnor, a n d K. K a r l m a r , J. Lipid Res. 19, 695-704 (1978). The effect of ascorbic acid deficiency on a d r e n a l h y d r o x y l a t i o n of cholesterol a n d deoxycorticosterone in g u i n e a p i g s was studied by u s i n g m i t o c h o n d r i a a n d isolated cytochrome P-450 f r a c t i o n s . The effects o b t a i n e d were c o m p a r e d with the effects of longt e r m t r e a t m e n t with A C T H . A d v a n c e d scurvy as well as treatm e n t with A C T H resulted in a n increase in the w e i g h t of t h e adrenals, the t o t a l a m o u n t of cytochrome P-450, t h e cholesterol side-chain cleavage activity, the cortisol level in p l a s m a , a n d t h e excretion of u n c o n j u g a t e d cortisol in urine. I t is concluded t h a t the level of a s c o r b a t e in t h e a d r e n a l s m i g h t be of some i m p o r t a n c e for the c a p a c i t y to convert cholesterol into pregnenolone. METABOLISM OF CHOLESTEROL-ENRICHED CHYLOMICRONS. CATABOLISM OF TRIGLYCERIDE BY LIPOPROTEIN LIPASE OF PERFUSED HEART AND ADIPOSE TISSUES. C.J. F i e l d i n g , J . P . Renston, a n d P.E. Fielding, J. Lipid Res. 19, 705-11 (1978). The chemical J. AM. OIL CHEMISTS' SOC., February 1979 (VOL. 56)

ABSTRACTS: BIOCHEMISTRY AND N U T R I T I O N a n d biochemical properties of cholesterol-enriched a n d cholesterol-poor chy]omicrons f r o m r a t l y m p h have been compared. The enriched particles, p r e p a r e d f r o m cholesterol-containing lipid dispersions, p a s s e d into t h e d u o d e n u m , h a d f o u r to ten t i m e s the cholesteryl ester c o n t e n t of the control chylomicrons b u t h a d t h e same c o n t e n t of t o t a l "core" (eholesteryl ester + triglyceride) lipid. B o t h chylonficron species h a d t h e s a m e p r o t e i n composition, t h e same pbospholipid composition, a n d the same composition of triglyceride f a t t y acids. I t is concluded t h a t cholesteryl ester c o n t e n t of chylomicrons u n d e r t h e conditions n e i t h e r affects their p r o t e i n composition nor h a s a m a j o r effect on their r a t e of reaction with liproprotein lipase. CYCLIC AMP-SENSITIVE ACTIVATION OP HEPATIC STEROL SYNTHESIS AND 3-HYDROXY-3-METHYL-GLUTARYL COENZYME A REDUCTASE. C.D. Goodwin a n d S. Margolis, J. Lipid Res. 19, 747-56 (1978). W e previously showed t h a t p r e i n c u b a t i o n of a 10,000 g s u p e r n a t a n t ISle) f r o m r a t liver f o r 20 mid a t 37~ d r a m a t i c a l l y increased the s u b s e q u e n t i n c o r p o r a t i o n of (~4C)acetate into sterols. No a c t i v a t i o n w a s seen w i t h (~4C) m e v a l o n a t e as s u b s t r a t e . I n the p r e s e n t studies we have exa m i n e d t h e effect of p r e i n c u b a t i o n on H M G CoA reductase. These r e s u l t s s u g g e s t t h a t h o r m o n e - i n d u c e d c h a n g e s in t h e cellular level of cyclic A M P m a y r e g u l a t e t h e activity o f H M G CoA r e d u c t a s e a n d t h e r a t e of h e p a t i c cholesterol synthesis. COMPOSITION OF PROTEINS OF MESENTERIO LYMPH CHYLOMICRGNS IN THE RAT AND ALTERATIONS PRODUCED UPON EXPOSURE OF CHYLOMICRONS TO BLOOD SERUM PROTEINS. K. [ulaizuIn], M. F a i n a r u , a n d R.J. Havel, J Lipid Res. 19, 712-22 (1978). P r o t e i n composition was deternlined in m e s e n t e r i c l y m p h chylom i c r o n s f r o m f a t - f e d rats. A m o n g the p r o t e i n s of intermediate molecular weight, a p o p r o t e i n s A - I a n d t h e a r g i n i n e - r i c h a p o p r o t e i n a c c o u n t e d f o r 3 1 % a n d 4 % of t h e total p r o t e i n mass, respectively. A p o p r o t e i n B a n d a p o p r o t e i n A - I V each a c c o u n t e d f o r a b o u t 1 0 % a n d p r o t e i n s of low molecular weight (C a p o p r o t e i n s a n d apoprotein A - I I ) accounted f o r most of the remainder. A p o p r o t e i n A - I also a c c o u n t e d f o r more t h a n 3 0 % of the p r o t e i n m a s s o f m e s e n t e r i c l y m p h ]ipop r o t e i n s of d e n s i t y less t h a n 1.006 g / m l ( s m a l l chylomicrons) o b t a i n e d f r o m r a t s f e d glucose. CHANGES IN BILIARY LIPID AND BILIARY BILE ACID COMPOSITION IN PATIENTS AFTER ADMINISTRATION OF URSODEOXYCHOLIC ACID. I. Makino a n d S. N a k a g a w a , J. Lipid Res. 19, 723-8 (1978). T w e n t y - t h r e e p a t i e n t s with g a l l s t o n e s were t r e a t e d w i t h two dosage levels of ursodeoxycholic acid, 600 r a g / d a y a n d 150 r a g / d a y . Two to three m o n t h s a f t e r t h e t r e a t m e n t , the m o l a r p e r c e n t a g e of cholesterol in bile significantly decreased (front 7.4 to 4.5 n m l e % in t h e 600 m g g r o u p a n d f r o m 7.6 to 4.0 m o l e % in the 150 m g g r o u p ) , so t h a t bile became u n s a t u r a t e d in m o s t p a t i e n t s in both t r e a t m e n t groups. However, t h e r e was no significa~t difference between the two groups. EFFECTS OF ACETATE~ ACETALDEHYDE, AND ETHANOL ON LIPOLYSIS IN ISOLATED RAT ADIPOCYTES. ~.Oo N i l s s o n a n d P. Belf r a g e , J. Lipid l~es. 19, 737-41 (1978). T h e effects of differe n t c o n c e n t r a t i o n s of acetate, acetaldehyde, a n d ethona], alone or in combination, on the lipolysis rate, m e a s u r e d as glycerol release, were s t u d i e d in isolated adipocytes f r o m f e d or f a s t e d rats, in t h e b a s a l s t a t e a n d at v a r i o u s levels of n o r e p i n e p h r i n e stinmlation. E t h a n o l , acetaldehyde, a n d a c e t a t e in combination i n h i b i t e d glycerol release to a n e x t e n t similar to t h a t of a c e t a t e alone. LIPIDS OF THE STREPTOMYCETES. ~TRUCTURAL INVESTIGATION AND BIOLOGICAL INTERRELATION. S.G.Batrakov a n d L.D. Bergelson, Chem, Phys. Lipids 21, 1-29 (1978). D u r i n g a s y s t e m a t i c i n v e s t i g a t i o n of lipids of Strepto~nycetes a series of c o m p o u n d s of biochemical a n d microbiological i n t e r e s t have been isolated a n d characterized. These include several m e n a q u i n o n e s , glycosyl diglycerides ( g l u c u r o n o s y l a n d isoaldobinosyl diglycerides), two o r n i t h i n o lipids a n d a diol phospholipid. Seine of these lipids were n o t k n o w n previously as c o n s t i t u e n t s of s t r e p t o m y c e t e cells a l t h o u g h they have been e n c o u n t e r e d elsewhere; others have proved to be novel ]ipids. T h e r e s u l t s of s t r u c t u r a l s t u d i e s of these lipids are reviewed a n d some of their possible biological f u n c t i o n s a r e discussed. PHOTOGENERATED REAGENTS FOR MEMBRANE LABELING. 2. PHENYLCARBENE AND ADAMANTYLIDENE FORMED WITHIN THE LIPID BILAYER. H. B a y l e y a n d J.R. Knowles, Biochemistry 17, 2420-3 (1978). P h e n y l c a r b e n e a n d a d a m a n t y l i d e n e have been genJ. AM. OIL CHEMISTS' SOC., February 1979 (VOL~ 56)

c r a t e d photochemically f r o m t h e c o r r e s p o n d i n g diazirincs within lipid bilayers. R e a s o n a b l e yields of labeled f a t t y acid side chains have been observed. The p r o d u c t s have been charaeterized by g a s c h r o m a t o g r a p h y - m a s s s p e c t r o m e t r y a n d derive both f r m n the i n s e r t i o n of t h e carbene into c a r b o n - h y d r o g e n bonds of s a t u r a t e d f a t t y acids a n d f r o m t h e a d d i t i o n of the carbene to the" c a r b o n - c a r b o n double b o n d s of u n s a t u r a t e d f a t t y acids. Carbenes g e n e r a t e d f r o m diazirines are evidently superior r e a g e n t s f o r t h e p h o t o l a b e l i n g of lipids a n d should be u s e f u l f o r i d e n t i f y i n g t h e i n t r i n s i c h y d r o p h o b i c sections of m e m b r a n e proteins. PHOTOGENERATED REAGENTS FOR MEMBRANE LABELING. 1. PHENYLNITRENE FORMED WITHIN THE LIPID BILAYER. H. B a y l e y a n d J.R. Knowles, Biochemistry 17, 2414-9 (1978). P h e n y ] n i t r e n e g e n e r a t e d photochemically f r o m p h e n y l azide t h a t is b o u n d to artificial p h o s p h o l i p i d vesicles labels the f a t t y acid c h a i n s of t h e lipids in low yield. The labeling yield varies f r o m a p p r o x i m a t e l y 3.3% w i t h s o y b e a n lecithin (which is h i g h l y u n s a t u r a t e d ) to a p p r o x i m a t e l y 0.25% w i t h d i m y r i s t o y l l e c i t h i n (which is completely s a t u r a t e d ) . L a b e l i n g is largely elimi n a t e d by reduced g l u t a t h i o n e in the a q u e o u s phase. P h e n y l azide itself is f u r t h e r c o m p r o m i s e d as a lipophilic r e a g e n t b y its r a t h e r low p a r t i t i o n coefficient into lipid bilayers, as meas u r e d b y equilibrium dialysis. THE MODULATION OF LIPID BILAYER FLUIDITY BY INTRINSIC POLYPEFTIDES AND PROTEINS. B.A. Cornell et al., F E B S Letters 90 (1), 29-35 (1978). T h e i m p o r t a n c e of lipid-bilayer fluidity f o r b i o m e m b r a n e s t r u c t u r e a n d f u n c t i o n is now well appreciated. The presence of molecules such as cholesterol w i t h i n the lipid b i l a y e r s t r u c t u r e is known to m o d u l a t e the b i l a y e r fluidity. E a r l y r e s u l t s u s i n g m o n o l a y e r s y s t e m s a n d described as ' c o n d e n s a t i o n effects' were explained a n d r a t i o n a l i s e d in t e r m s of this lipid-modulation effect. A whole r a n g e of physical techniques have s u p p o r t e d this i n t e r p r e t a t i o n i n c l u d i n g t h e use of N M R spectroscopic methods. BENZENE-LECITHIN INTERACTION IN LECITHIN-BENZENE SOLUTIONS, PART I I : OPTICAL STUDIES AND QUANTUM MECHANICAL CALCULATIONS. H. F r i s c h l e d e r et al., Chem. Phys. Lipids 21, 131-7 (1978). U V a b s o r p t i o n a n d CD s p e c t r a of dipalmitoylsn-glycerine p h o s p h a t i d y l c h o l i n e ( D P P C ) - benzene a n d D P P C cyclohexane s y s t e m s a t different t e m p e r a t u r e s (in t h e micellar a n d gel s t a t e ) as well as q u a n t u m chemical calculations of a b e u z e n e - t r i m e t h y l a m m o n i u m supermolecule d e m o n s t r a t e t h a t in t h e gel s t a t e of the D P P C - b e n z e n e s y s t e m a m o l a r f r a c t i o n of benezene molecules f o r m s a weak c h a r g e t r a n s f e r complex with t h e - - N § (CH3)3 moeity of D P P C . I n t h e gel s t a t e t h e r e exists a second f r a c t i o n of benzene molecules, the reo r i e n t a t i o n f r e e d o m of which is restricted by a liquid crystallike structure. MEASUREMENT OF REPULSIVE FORCES BETWEEN CHARGED PHOSPHOLIPID BILAYERS. A.C. Cowley et al., Biochemistry 17, 3163-8 (1978). B y u s i n g an osmotic s t r e s s t e c h n i q u e ( L e Neveu, D.M., et al. (1977) Biophys. J. 18, 209), we h a v e m e a s u r e d the n e t repulsive force between e g g lecithin bilayers c o n t a i n i n g various a m o u n t s of t h e c h a r g e d lipids p h o s p h a t i d y l g l y c e r o l a n d phosphatidy]inositol. W e conclude t h a t the h y d r a t i o n force d e m a n d s more a t t e n t i o n t h a n it h a s e n j o y e d h i t h e r t o in att e m p t s to u n d e r s t a n d bilayer m e m b r a n e i n t e r a c t i o n a n d fusion. LATERAL DIFFUSION IN PHOSPHOLIPID BILAYER MEMBRANES AND MULTILAMELLAR LIQUIDCRYSTALS. P . F . F a h e y a n d W . W . W e b b , Biochemistry 17, 3046-53 (1978). The lateral-diffusion coefficients ( D ) of a fluorescent lipid analogue, 3,3'-dioctadecyli n d o t r i c a r b o c y a n i n c ( d i I ) , have been m e a s u r e d in black lipid m e n l b r a n e s ( B L M s ) , in large (20-50-~m d i a m e t e r ) solventfree b i l a y e r an(l m u l t i l a y e r i n e m b r a n e vesicles, a n d in multilamellar liquid c r y s t a l s of dipa]mitoylphosphatidylcho]ine, dim y r i s t o y l p h o s p h a t i d y l c h o l i n e , a n d e g g lecithin. T h e y show t h a t D c h a n g e s by several orders of m a g n i t u d e at t h e liquid-crystal t r a n s f o r m a t i o n s of the solvent-free bilayers a n d multilayers. A simple m e t h o d of f o r m i n g small n u m b e r s of l a r g e solventfree vesicles is described. PHASE BEHAVIOR OF SYNTHETIC PHOSPHATIDYLGLYCEROLS AND BINARY MIXTURES WITH PHOSPHATIDYLCHOLINES IN THE PRESENCE AND ABSENCE OF CALCIUM IONS. E.J. F i n d l a y a n d P.G. B a r t o n , Biochemistry 1 7 ( 1 2 ) , 2400-5 (1978). U s i n g differential t h e r m a l analysis, s c a n n i n g c a l o r i m e t r y a n d light s c a t t e r i n g , t r a n s i t i o n t e m p e r a t u r e s a n d e n t h a l p y d a t a for the gel to liquid crystalline p h a s e t r a n s i t i o n s of five s y n t h e t i c phosphatidylglycerol s o d i u m salts ( P G - N a +) were m e a s u r e d . The

151A

ABSTRACTS: BIOCHEMISTRY AND NUTRITION

values obtained were almost identical with literature values for the corresponding phosphatidylcholines ( P C ) . However, transition t e m p e r a t u r e s for the fully p r o t o n a t e d f o r m s of the s a t u r a t e d phosphatidylglycerols ( P G - H § were approximately 20~ higher. I n sum, these results provide evidence for a high degree of miscibility of the phosphoglycerol and phosphocholine head groups, either in the presence or absence of Ca 2§ such t h a t the characteristic phase behavior of each mixture is determined primarily by differences in the hydrocarbon chain structure. DIETARY I~AT AND CHOLESTEROL METABOLISM IN ADULT RATS UNDERGOING RAPID TISSUE REPLETION. S.E. Carlson, C.N, Shiver and L. Arnrich, J. :Vutr. 108, 1170-9 (1978). An experimental model in which adult r a t s underwent rapid rates of tissue repletion a f t e r dietary restriction served to explore the influence of dietary f a t on cholesterol metabolism. Adult r a t s severely restricted in protein and energy were refed either 8 or 24 h o u r s per day for 10 days. Refeeding diets contained approximately 0% or 20% f a t by weight as safflower oil or beef tallow and 4% or 17% protein on an energy basis. Concentration or source of dietary f a t did not significantly influence either serum or hepatic cholesterol concentrations. The data s u g g e s t that, in the absence of exogenous cholesterol, high levels of p o l y u n s a t u r a t e d f a t m a y influence cholesterol metabolism primarily by increasing synthesis and excretion of bile acids. 9

Rdvertilerl" Index Alfa-Laval/De Laval-

112A & 113A

Analytical B i o C h e m i s t r y Labs. - 104A Armstrong Engineering Assoc. - 138A Artisan Industries, Inc. - 107A C.M. B e r n a r d i n i S.p.A. - 1 0 5 A Dravo Corporation - Cover 3 Eastman International - Cover 4 E l l i o t t A u t o m a t i o n Co. - 1 1 8 A & 1 3 1 A EMI C o r p o r a t i o n - Cover 2 Fratelh Gianazza S.p.A. - 122A & 123A F r e n c h Oil Mill M a c h i n e r y Co. -

103A

Grindsted Products - 127A H . L . S . , Ltd. - 1 2 5 A

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Industrial Filter & P u m p - 121A Masiero Industrial -

109A

N e u m u n z , Inc. - 1 1 1 A Shell C h e m i c a l C o m p a n y - 1 4 4 A & 1 4 3 A S i m o n - R o s e d o w n 8 , Ltd. - 9 9 A T M R , Inc. - 1 1 0 A Wurster & Sanger -

129A

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Business Name Title Company Address City State

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PETER K A L U S T I A N ASSOCIATES, INC. Management Consultation and Engineering Processing of Food Fats, Oils, Shortenings, Margarines, SpecialW Fats, Fatty Acids and Chemical Derivatives 239 Reserve Street, Boonton, New Jersey 07005 Telephone 201-334-3008 and 3043

Telephone .... SURPLUS . . . USED . . . AND REBUILT PROCESS EQUIPMENT... FOR THE EDIBLE OIL INDUSTRY.

Home Address City State

Zip

Telephone

Mail to: Joan Nelson, Circulation Manager, American 0il Chemists' Society, 508 South Sixth Street, Champaign, IL 61820

152A

PURCHASE AND SALE OF EQUIPMENT. CONSULTATION. "ZEKE"ZEHNDER

DuMond Company. ine. Watterson Louisville,

City Office KY

40218

Bldg. -

Suite

702

502/451-3901

J. AM. OIL CHEMISTS' SOC., February 1979 (VOL. 56)