R. A. REINERS, Editor. ABSTRACTORS: J. G. Endres, Kazuo Fukuzumi, J. Iavicoli, K. Kitsuta, F. A. Kummerow, Gladys Macy, E. G. Perkins, T. H. Smouse, J. A. Thompson and R. W. Walker

ABSTRACTS 9 Fats

and Oils

H. Kumlzuda, Tatsuo Nakahara, H. Uejo and A. Yanlauehi (Dept. of Chem., Faculty of Sci., K y u s y u Univ., Fukuoka, J a p a n ) . Bioehim. Biophys. Acta 137, 549-56 (1967). The ion-exchange properties of lipid films were studied by direct measurement of the adsorption of radioactive Ca -~+. I t was shown that films of phosphatidyl ethanolamine, soybean lecithin, egg lecithin, cephalin and proteolipid could take up Ca ~-" from the underlying solution. Chelating agents such as A T P and EDTA caused the desorption of bound Ca +2 from the lipid film. Isotopic exchange between the Ca ~+ in the lipid film and in the underlying solution took place easily. Decrease in p H reduced the adsorption of Ca :+ to the lipid fihn. The effects of Na § and K + on the adsorption equilibrium of Ca -~ were found to be ahnost the same. The rate of exchange between Ca ~+ bound to the lipid film and K + in the underlying solution was found to be much greater than t h a t between the bound Ca "-'§ and Na ~ in the solution. CATION-EXCHANGE PROPERTIES OF LIPIDS F I L ~ S .

GLYCOLIPIDS OF I~.IYCOBACTERIA AND RELATED NICROORGANISMS.

E. Lederer ( I n s t i t u t de Chimie des Substances Naturelles, CNIRS, Gif-sur-Yvette, and I n s t i t u t de Biocllimie, Faculte des Sciences de Paris-Orsay (Essonne), France). Chem. Phys. Lipids 1, 294 314 (1967). The following groups of glyeolipids are reviewed: 1) The toxic cord factors (6,6"-diesters of trehalose), 2) W a x D, a macromolecular peptidoglyeolipid having a d j u v a n t activity, 3) The mycosides A, B and C, which are deoxyhexose containing "type-specific" glycolipids of mycobacterial origin, 4) The phosphatidyl myo-inositol mannosides, 5) Carotenol-glycosides. Wherever possible, chemical structure, biosynthesis and biological activities are considered. INFRARED

SPECTRA

AND

POLYMORPHIS~I

OF

GIYCEROL

ETHER

DERIVATIVES. E. O. Oswald, C. Piantadosi, C. E. Anderson and F. Snyder (Dept. of Biochem. and Med. Chem., Univ. N. Carolina, Chapel Hil, N.C.). Chem. Phys. Lipids 1, 270-81 (1967). The i n f r a r e d spectra and the polyniorphic forms of the a- and fl-glycerol ethers, glycerol ether nlonoesters, and glycerol ether diesters were investigated. I t was concluded from these studies t h a t the a-ethers exist in at ]east two different crystalline forms, whereas the fl-ethers exist in only one form. The stable A form of both isoniers of the ethers probably has hexagonal packing of the side chains; however, the B form of the a-ethers may have triclinic packed chains. It was found t h a t the a-nlonoester fl-ethers and the fl-monoester a-ethers also exist in at least two crystalline forms. The lower melting form B of the fl-monoester a-ether does not correspond in crystalline structure to the lower melting form ]3 of the amonoester fl-ether. The results indicate t h a t there are at least three or possible four crystalline forms of dipahnitoyl-abatyl alcohol. F A T T Y ACIDS. PART

13,

THE

SYNTHESIS

OF ALL THE

CIS N-

0CTADECENOIC ACIDS. F. D. Gunstone and I. A. Ismail (ChenL Dept., St. Salvator's College, The Univ. of St. Andrews, Scotland). Chem. Phys. Lipids 1, 209-224 (1967). All the cis n-octadecenoic acids ('A= to A~;) have been synthesized along with several dodecenoic (A; to AI~), dodecynoic (A; to A~), and octadecynoie (A" to A~) acids required as intermediates. PART 14.

T H E CONVERSION Ol~ THE CIS OCTADECENOIC

ACIDS TO

THEIR TRANS ISOMERS. 1bid., 264-9. The methyl cis octadccenoates have been converted to their trans isomers by heating with seleniunl and also by irradiation by ultra violet light in the presence of diphenyl sulphide. I n the former method, but not in the latter, stereomutation is accompanied by extensive double bond migration. A p a r t f r o m the A'-' ismner all the equilibrium mixtures contain 74-80% of trans ester. The melting points of all the cis ancl t-raT~s octadeeenoic acids and some oetadeeynoic acids are presented and discussed. A STUDY ON LIQUID-GEL PARTITION OP STEROIDS AND STEROID DERIVATIVES ON LIPOPIXIILIC SEPHADEX GELS. P . E n e r o t h and

E. Nystrom (Dept. of ChenI., Karolinska Instltutet, Stockholm, Sweden). Biochim. Biophys. Acta 144, 149-161 (1967). A number of sterols and steroids have been ehromatographed on columns of methylated Sephadex G-15, G-25 and G-50 and of Sephadex LH-20 in single solvents. The results indicate t h a t a liquid-gel partition leading either to a straight or a reversed phase chromatography deternlines the separations. The size and shape of the steroid solute is also of importance.

496A

Depending on the nature of the solvent and the gel, ketonic steroids can be specifically excluded from o1' retarded on the column. THE

OCCURRENCE

OF

PRISTANE

AND

PHYTANE

IN

~AN

AND

ANI~IALS. J. Avigan, G. W. A. Milne and R. J. Highet (Lab. of Metabolism, National Heart Inst., National Inst. of Health, I)ethesda, Md., U S A ) . Biochim. Biophys. A c t s 144, 127-131 (1967). The concentration of the branched-chain hydrocarbons, pristane and phytane, was determined in a number of human and aninlal tissues by quantitative thin-layer and gas chromatography. In h u m a n serum and liver, pristane was found at concentrations of 2-9 tLg/g, and of 52 t~g/g in a single sample of h u m a n skin. The amounts of phytane were significantly lower and represented 1-35% of those in pristane in the various tissue samples analyzed. Rat liver and a number of bovine tissue samples contained similar concentrations of pristane and phytane to t h a t found in h u m a n organs. Pristane was found in livers from a number of shark species at a concentration of 2-5 ~ g / g and, in contrast to the m a m u m l i a n tissues, phytane was present at similar concentrations to those of pristane. The possible sources of these and other hydrocarbons found in animals are briefly discussed. ~[ONOGALACTOSYL DIGLYCERIDE :

A

NEW

NEUROLIPID.

J-.

~,'~.

Steim (Dept. of Chem., Brow21 Univ., Providence, R. L, U S A ) . Biochim. Biophys. A c t s 144, 118-26 (1967). Monogalactosyl diglyceride was isolated from bovine spinal cord and shown to be identical with the same lipid from spinach, except for f a t t y acid analysis. In particular, unequivocal evidence is presented for the presence of the glycosidic bond and the D configuration of the glyceryl moiety. In bovine spinal cord monogalactosyl diglyeeride, palmitic and oleic acids are dominant, together comprising 75% of the total f a t t y acids present. The lipid is present in the brains of all animals exaniined (cow, cat, pig, rat, h u m a n ) , but is absent from n m m n m r y gland, spleen, intestine and liver. A small amount was tentatively identified in kidney. In the brain the lipid is restricted to white matter, and is suggested to be a emnponent of myelin. ORNITHINE-CONTAINING LIPID IN ]:~HODOSPIRILLUM RUBRU~[. J-. A .

Depinto (Pioneering Lab. for Microbiol. ChenL, N. Reg. IRes. Imb., Peoria, Ill., U S A ) . Biochim. Biophys. A c t s 144, 113-117 (1967). An ornithine-containing lipid t h a t lacks phosphorus has been observed in Rhodospirillum rubrum. Ornithine-~*C is incorporated into lipid during growth. Formation of ornithine lipid does not seenl to be related to the synthesis of bacteriochlorophyll. Arginine repressed the formation of the ornithine lipid, but at the same concentration it repressed ornithine transcarbamylase twice as much. SEPARATION

OlV ACIDIC

PHOSPtIOLIPIDS

BY

ONE-DIMENSIONAL

THIN-LAYER CHRO:MATOGRAPHY. V. P. Skipski, M. Barclay, E. S. Reiehman and J. J. Good (Div. of Exptl. Chemotherapy, SloanKettering Inst. for Cancer ires., Rye, N. Y.). Biochim. Biophys. Aeta 137, 80-9 (1967). Three one-dimensional thin-layer chromatographic systems for separation of acidic phospholipids such as cardiolipin phosphatidic acid and phosphatidylglyeerol, are described. I. Silica gel with CaSO, binder, a two step developing system is used. The first solvent is acetone-light petrolemn (1:3, by vol), the second solvent is a mixture of chloroform nlethanol-acetie acid-water (80:13:8:0.3, by vol). The separated eonlpounds from the top of the chromatogram are : monoglvceride, cardiolipin, phosphatidic acid, eeranfidemonohexosides (cerebrosides), phosphatidylglycerol and phosphatidylethanolamine. II. Silica gel thin-layer plates are prepared with 0.1 M Na2COa. The first solvent is pyridine-light petroleum (3:1, by vol.); the second solvent is ehioroform-methanoI-pyridine-2 M NH~Ott (35:12:65:1, by vol.). The following compounds are separated by the two-step developing system (from the top of c h r o m a t o g r a m ) : eeramidemonohexosides, sulfatides and ceramidedihexosides (overlapping), phosphatidie acid, phosphatidylglycerol and eardiolipin. I I I : one step-development modification of System II. This system is suitable only for quantitative determination of phospholipids if the presence of glyeolipids is not deemed detrimental. AS'~" ~IhIETRIO

TRIGLYCERIDES

PROM

IMPATIENS

EDGEWORTtt II

SEED OIL. M. O, Bagby and C. IS. Smith (Northern Reg. IRes. Lab., Peoria, Ill.). Biochim. Biophys. Acta 137, 475-7 (1967). Impatiens edgeworthii Hook F. seed oil, which contains acetate, parinarate and the more common f a t t y acyl groups, was hy-

a. A~ o,L c.~.~isTs, soo, ooTo~ ~967 (voL ~ )

ABSTRACTS: d r o g e n a t e d to give m a i n l y a-acetodistearin. The h y d r o g e n a t e d oil p r o d u c e d a plane n e g a t i v e optical r o t a t o r y dispersion curve. C o m p a r i s o n of the dispersion curve with those of a-acetodiacyl trlglycerldes s y n t h e s i z e d by stereoselective m e t h o d s indicates t h a t the triglycerides of Impatiens edgeworthii seed oil have the (S) -configuration. T H E CONTAMINATING EFFECTS OF NON-ESTEI~IEIED F A T T Y ACIDS. S. A .

CEPHALINS

IN

ESTIMATING

I b r a h i m (Dept. of Biochem., F a c u l t y of Medicine, Univ. of K h a r t o u m , K h a r t o u m , S u d a n ) . Biochim.. Biophys. Acta 137, 413 419 (1967). A s t u d y h a s been m a d e of the c o n t a m i n a t i n g effects of phospholipids in the t i t r i m e t r i c p r o c e d u r e of Dole. P h o s p h a t i d e s were f o u n d to be e x t r a c t e d to v a r y i n g degrees in the h e p t a n e p h a s e of the m e t h o d of Dole. None of the l y s o p h o s p h a t i d e s was extracted. Unlike lecithin, p h o s p h a t l d y l e t h a n o l a m i n e a n d p h o s p h a t i d y l s e r i n e were f o u n d to be t i t r a t a b l e u n d e r the conditions used in the above method. Exclusion of cephalins by a d s o r p t i o n on silicic acid r e n m v e d the i n t e r f e r e n c e a n d allowed for accurate free f a t t y acid estimation. The significance of these findings is discussed in relation to the extensive use of the Dole procedure w i t h o u t modification. COLOR REACTIONS B E T W E E N F A T T Y 0 I L S AND SULFURIC ACID Y~'ITH AND W I T H O U T AM]~iONIUM IKOLYBDATE. S. A n s a r A h m e d , D.

l~amacher, B. A. R. S o m a y a j u l u a n d S. D. T h i r u m a l a I~ao (Oil Techn. Res. Inst., A n a n t a p u r , I n d i a ) . Oil Oilseeds J. (Bombay) 7 0 ( 9 ) , 8-10 (1967). The reaction of R a j n i s h K u m a r h a s been e x p a n d e d to include 25 f a t s a n d oils. I n addition to c a r r y i n g out the p r o c e d u r e described by R a j n i s h K u m a r , both conc e n t r a t e d s u l f u r i c acid a n d molybdic acid have been used separately. The f a t s a n d oils can be divided into two classes, those t h a t do n o t give a n y coloration or t u r b i d i t y a n d those t h a t give characteristic color changes, turbidities, or precipitates. Castor a n d m a r o t i oils are exceptions as their solutions show white opalescence even before a d d i t i o n of test reagent. C o n c e n t r a t e d s u l f u r i c acid alone shows the same reaction as c o n c e n t r a t e d s u l f u r i c acid with a m m o n i u m m o l y b d a t e in all cases except w i t h p a h n oil. W i t h s u l f u r i c alone, g r e e n color persists, a n d with a m m o n i u m lnolybdate, the g r e e n color c h a n g e s to blue. T H E VACCARINO PROCESS FOR OIL EXTRACTION FROM COTTONSEED

AND RICE BRAN. Oil Oilseeds J. (Bombay) 7 0 ( 9 ) , 4 - 6 (1967). This p a p e r s u m m a r i z e s t h e Vaccarino process as applied to cottonseed oil. The economic i m p o r t a n c e to I n d i a of b e i n g able to produce a degossypolized meal f o r h u m a n c o n s u m p t i o n is related. The V a c c a r i n o process could well be an economically a t t r a c t i v e m e t h o d to deoil rite bran. A t h i r d a p p l i c a t i o n (still u n d e r s t u d y ) is the use of the V a c c a r i n o process to deoi] fish meal. N o t only would an oil of excellent quality be obtained, b u t if the deodorization p r o b l e m could be overcome, a meal fit for h u m a n c o n s u m p t i o n could be obtained. P H O S P H A T I D E S OF S U NFLOWER SEED OIL AND T H E P O S S I B I L I T I E S OF PRODUCTION OF OILS W I T H H I G H P H O S F H A T I D E S CONTENT. A. D.

Popov a n d I. D. Mizev ( I n s t . of O r g a n i c Chem. Acad. of Sci., Sofia, B u l g a r i a ) . Rev. Franc. Corps Gras 1 4 ( 6 ) , 391-396 (1967). A s t u d y was m a d e of the effect of p h o s p h a t i d e s u p o n the flavor a n d oxidative s t a b i l i t y of sunflower seed oil a f t e r deodorization. I t was f o u n d t h a t the n o n h y d r a t a b l e phosp h a t i d e s do n o t adversely affect the deodorized oil either in flavor or stability. This leads to the possibility t h a t sunflower seed oil with a h i g h e r p h o s p h a t i d e c o n t e n t c a n be produced. A GENERAL METHOD FOR T H E TRANSFORMATION OF FATS INTO M E T H Y L ESTERS REGARDLESS OF THEIP~ FREE ACIDITY. ~ i . L o u r y

( I n s t . of F a t s a n d Oil, P a r i s , F r . ) . Rev. Franc. Corps Gras 1 4 ( 6 ) , 383-389 (1967). A r a p i d a n d complete t r a n s f o r m a t i o n of f a t s into m e t h y l esters is o f t e n useful, a n d is required for m o s t GLC analyses. Alkaline alcoholysis is u s e f u l for triglycerides devoid of free f a t t y acids. W h i l e on the other h a n d , acid alcoholysis which works well with free f a t t y acids, works slowly with triglycerides. The saponification-esterification m e t h o d , which is very difficult to p e r f o r m , also h a s the disa d v a n t a g e t h a t the short c h a i n f a t t y acids are lost d u r i n g the several w a s h i n g s . I n the p r e s e n t work, a m e t h o d is described which combines in succession the alcoholysis a n d esterification processes a n d t r a n s f o r m s all f a t s into m e t h y l esters, r e g a r d l e s s of their free acidity. A n o t h e r a d v a n t a g e is the p r e s e r v a t i o n of the short c h a i n f a t t y acids. The m e t h o d is r a p i d ; non-toxic m a t e r i a l s are used. I t is a d a p t a b l e to micro methods. The m e t h o d involves m e t h a n o l y s i s of the f a t or oil with sodium m e t h o x i d e in m e t h a n o l followed by esterification of a n y free or l i b e r a t e d f a t t y acids with m e t h a n o l u s i n g a n h y d r o u s hydrochloric acid as catalyst. The m e t h y l esters are t h e n ext r a c t e d f r o m the reaction m i x t u r e with p e t r o l e u m ether. The

498A

FATS

AND OILS

solvent is r e m o v e d u n d e r v a c u u m , a n d the r e s u l t i n g m e t h y l esters are stored u n d e r nitrogen. HYDROLYSIS OF FATS. C. D. Miserlis a n d J. R. ( T h e B a d g e r Co., Inc., C a m b r i d g e , M a s s . ) . t~ev. Franc. Corps Gras 1 4 ( 6 ) , 377-382 (1967). B e t w e e n 1964 a n d 1965 The B a d g e r Co. h a s s t a r t e d three u n i t s for the continuous h y d r o l y s i s of f a t s both in the U n i t e d States a n d in Great Britain. T h e i r a n n u a l j o i n t c a p a c i t y f o r the p r o d u c t i o n of f a t t y acids is over 90,000 tons. The technical description on one of the splitters a n d of a c o n t i n u o u s f a t t y acid distillation u n i t are described. Also described is an associated u n i t f o r tile recovery, purification a n d distillation of glycerin. This unit will produce more t h a n 11,000 tons p e r y e a r of n a t u r a l , superfine, p h a r m a c e u t i c a l a n d edible glycerin. CONTINUOUS

Ghublikian

O I L S FROM F I S H E S CAUGHT I N T H E INLAND SEA OF J A P A N . Y . C O M P O S I T I O N S OF HORSE-MACKEREL, SEA-EEL, SILLAGO SIHAMA~ SCI N A SCHLEGELLII~ BASS~ SURF-FISH~ GILTHEAD AND RED-PORGY

OILS. S h i g e r u H a m a d a a n d Shei-ichi Ueno. Yukaga~'~t 15, 419-23 (1947). Iodine n u m b e r s of these fish oils were in the r a n g e of 120-160. There was n o t m u c h difference in the composition of body, i n t e r n a l o r g a n a n d liver oils. The f a t t y acid were composed of C~o-C~ s a t u r a t e d a n d C~,~C22 h i g h l y uns a t u r a t e d acids. Tadaki Kazuhito Aoshima (Nagoya Inst. Technology). Yztkagaku 15, 423-5 (1967). C o n c u r r e n t use of h y d r o x y c a r boxylic acid with a n t i o x l d a n t gives g r e a t e r a n t i o x i d a n t effect t h a n the use of the a n t i o x i d a n t alone. E F F E C T OF HYDROXYCARBOXYLIC ACID AND FA T OXIDATION.

Bito

and

SELECTIVE REDUCTION OF SPERM

BLUBBER OIL U SI N G CADMIU]K-

ALUMINA AS CATALYST. Shigeo K i t a m u r a , S u s u m u T s u b o t a , Giichi A k a z o m e a n d K o i c h i M u r a l ( N e w J a p a n . Chem. Co., K y o t o ) . Yukagak~l 15, 355-60 (1967). Catalytic r e d u c t i o n of s p e r m b l u b b e r oil with c a d m i u m - a l u m i n a u n d e r h i g h p r e s s u r e of h y d r o g e n h a s been carried out f o r p r o d u c t i o n of u n s a t u r a t e d alcohol. The best result was obtained by u s i n g p a r t i a l p r e s s u r e of w a t e r 20-30 k g . / c m 2 at 300C a n d 30% c a d m i u m content in the catalyst. I N F L U E N C E OF HYDROLYSIS ON PARTLkL GLYCERIDE COMPOSITION

IN RICE BRAN OILS. H i r o s h i I n o u e a n d T a t s u o N o g u c h l (Ind. R e s e a r c h I n s t . H o k k a i d o ) . Ytl~:agak~L 15, 361-3 (1967). C h a n g e of mono-, di- a n d triglyceride c o u t e n t a n d of acid n u m b e r of f a t d u r i n g s t o r a g e of rice b r a n is given. DETERIORATION OF FRYING OILS I N CONTINUOUS WATER-SPRAYING AND H E A T I N G SYSTE]~I. I. CONTINUOUS WATER-SPRAYING AND H E A T I N G S Y S T E M AS A MODEL OF COMMERCLkL DEEP FAT FRYING.

Etsuji u ( F o o d Ind. Expl. Sta., H i r o s h i m a P r e f . ) . Yukagc~'u 16, 351-4 ( ] 9 6 7 ) . I n the c o n t i n u o u s w a t e r - s p r a y i n g a n d heati n g s y s t e m , s o y b e a n oil was tested a n d its chemical a n d physical c h a n g e s were determined. The effect of specific s u r f a c e area exposed in air f o r the d e t e r i o r a t i o n was e x a m i n e d by m e a n s of m e t a l float. The ratio of increase of viscosity of the d e t e r i o r a t e d oil was p r o p o r t i o n a l to the w i d t h of specific surface area, where the increase of acid value was g r e a t e r when f a t s u r f a c e was p r o t e c t e d by m e a n s of m e t a l float. T h u s , this continuous w a t e r - s p r a y i n g a n d h e a t i n g s y s t e m is considered suitable as a model of commercial deep f a t f r y i n g with simplicity a n d good reproducibility. I I . C H E M I C A L AND P]:IYSICAL CHANGES OF SOYBEAN OIL TREATED IN T H E CONTINUOUS WATER-SPRAYING AND H E A T I N G SYSTE]~[ COMPARED "WITH T H A T OF CONTINUOUS H E A T I N G W I T H O U T WATER.

Ibid. 410-12.

H e a t i n g of s o y b e a n oil with s p r a y i n g of w a t e r is a c c o m p a n i e d with a n increase in acid value, m o n o g l y e e r i d e content a n d h y d r o x y l value of the oil as well as the development of color. These c h a n g e s were n m c h less in the absence of water a l t h o u g h the e x t e n t of t h e r m a l oxidation of the oll was twice as m u c h more t h a n the f o r m e r case. I N C R E A S E IN INVASION BY STORAGE FU N G I AND I N FAT ACIDITY VALUES OF COMMERCIAL LOTS 0E SOYBEANS STORED AT .~,IOISTURE

CONTENTS OF 13.0--14.0%. C. 5[. C h r i s t e n s e n (Dept. of P l a n t P a t h o l o g y , Univ. of M i n n e s o t a , St. P a u l , M i n n . ) . Phytopathol. 57, 622-624 (1967). None of e i g h t s a m p l e s of soybeans, each r e p r e s e n t a t i v e of a different carload lot, increased a p p r e c i a b l y in invasion by s t o r a g e f u n g i or in f a t acidity value when stored at m o i s t u r e c o n t e n t s of 13.0 a n d 14.0% a n d 5C for 150-170 days. S a m p l e s stored at 13.0% m o i s t u r e c o n t e n t a n d 5C increased slightly in f a t acidity value a n d in invasion by f u n g i in 480-500 days. Those stored at the original m o i s t u r e cont e n t s and at 25C increased a p p r e c i a b l y in invasion by s t o r a g e f u n g i and in f a t acidity value, t h e increases b e i n g g r e a t e r at the h i g h e r m o i s t u r e c o n t e n t a n d at the l o n g e r s t o r a g e period. J

A~[. OIL CHEMISTS' SO('., OCTOBER 1 9 6 7 (V o L. 4 4 )

A B S T R A C T S : F A T S AND 0 I L S A ~,IICROBIAL SULFOLIPID. II. STRUCTURAL ST~'DIES. G. L. Mayers and T. H. Haines (Dept. of Chem., The City College of The City Univ. of New York, New York, N. Y.). Bioct~cmistry 6, 1665-70 (1967). A new sulfolipid, 1,14-doeosyl disulfate, was isolated from the phytoflagellate, Ochromonas danica, by solvent extraction, chromatography, ion-exchange gel filtration, and crystallization. Acid hydrolysis of the sulfatide produced a diol. The structures of the sulfatide and the dioi were determined by analysis, infrared spectroscopy, proton magnetic resonance spectrometry and mass spectrometry. The mass spectra of the analogous diols, eicosane-l,4-diol and octadeeane-l,12-diol, were studied. Eicosane 1,4-diol was synthesized via 1-hydroxy-4-eicosanone. REEINI~CG OF TAIL OIL. S.-C. Chang, H.-M. H u a n g and Y.-P. Ch'ou. Hua-Hsueh Shih-Chieh (Chem. World, China). 1965, No. 8, 360-2. Whilst tall oil is used extm~sively in the United States, its use in China has been restricted on account of technical problems in the refining. A f t e r one reduced-pressure distillation, the principal distillate still contains about 16-17% unsaponifiable m a t t e r and an A.V. ~ 160. In order to improve its usefulness, the N a O H and lime methods are used to eliminate the unsaponifiable matter and the ZnCh deceleration treatment is used to prepare high-acid light-colour tall oil. Esterification is f u r t h e r used to separate resin acids from tall oil to obtain tail oil f a t t y esters; then alkaline liquor is used to draw free resinie acid away. The authors conducted experiments to eliminate unsaponifiable material, on the deceleration treatment, and finally on the preparation of high A.V. light-colour tall oil. Experiments on the separation of resin acids by partial esterification of tail oil are also discussed. (Rev. Current Lit. P a i n t Allied Ind. No. 300.) STUDIES IN FAT S P L I T T I N G : I I

SPLITTING OF NON-EDIBLE OILS.

S. D. Vaidya, V. V. R. S u b r a h m a n y a n and J. G. Kane. lndian J. Tcch. 4, 301-4 (1966). Splitting of 7 non-edible oils, viz., (1) Karanja (Pongamia glabra), (2) Kavathi (HydTtoearpus wightiana), (3) K h a k a n (Salvadora oleoides), (4) K~tsttm (Schleichera trijuga), (5) Mahua (Madlnlca indica), (6) Neem (Azadirachta indica) and (7) Pisa (Actinodaph~te hoolceri), by the Twitchell method using commercial alkyl benzene sulphonic acid as the catalyst has been investigated. Splitting to the extent of 86-92% is obtained i,1 single-stage operation and over 95% in 2- and 3-stage operations. When the catalyst is taken initially in the f a t phase rather than in the aqueous phase, faster rates of f a t splitting are achieved. P r e t r e a t m e n t with dilute H.~SO, reduces the initial induction period in the case of some fats, such as Mah~ta, while for others, such as Neem oil, strong H_~SO, treatment is necessary to achieve satisfactory splitting. The effect of subjecting Xeem oil to different p r e t r e a t m e n t s on the rate of splitting and on the quality of f a t t y acids produced has been studied. The quality of f a t t y acids obtained is improved by subjecting the oil to hexane/methanol pretreatment. The ]yes produced in pressure splitting of Neem oil are acidic. (Rev. Current Lit. P a i n t Allied Ind. No. 300.) SILICONES. C V I I - - ~ V I O L E C U L A a SIZE DISTRIBUTION OF HIGtIVISCOSITY DII~IETHYL POLYSILOXANES. H . Reuther and G. 1%ichel.

Plaste zt. Kautschulc 13, No. 6, 341-3 (1966). The dimethyl polysiloxanes have been fractionated on a glass bead column using ethyl acetate and methanol as eluting liquids and the fractions examined viseometrically. (Rev. Current Lit. P a i n t Allied Ind. No. 300.) POLYCYCLIC AROMATIC HYDROCARBONS IN VEGETABLE OILS. A n o l l .

(U.S. Food D r u g Adnlin.). Brit. Ind. Biol. R. A. h~f. Bull. 5, No. 9, 611 (1966). No traces of polycyclie aromatic hydrocarbons were detected in safflower oil, although some were isolated from corn (maize), cottonseed, soyabean, g r o u n d n u t and olive oils. The majority of the corn oil samples contained some benzo [a]pyrene (1,2-benzopyrene, the carcinogenic isomer), but the highest level (0.0015 p.p.m.) was detected in a soybean oil sample, although only two of the nine soyabean oil samples gave a positive result. Refining solvents have not been implicated and it is thought t h a t the contamination may arise fronl the crude oils. (Rev. Current Lit. P a i n t Allied Ind. No. 300.)

THE POPE TESTING LABORATORIES Analytical Chemists

9 Fatty Acid

Derivatives

SYNTHETIC STUDIES ON SPHINGOLIPIDS. X I I . SPHINGOSINEPHOSPHORYLCHOLINE. D . Shapiro,

SYNTHESIS

O~'

E. S. Raehaman, Y. Rabinsohn and A. Diver-Haber (Daniel Sieff Research Inst., The Wizemann Inst. of Ski., Rehovoth, Israel). Chem. Phys. Lipids 1, 183-191 (1967). A synthesis of sphingosinephosphorycholine is reported, which involves a mild alkaline hydrolysis of its N-trifluoroaeetyl derivative. Sphingosinephosphoryleholine has been converted into N-stearoylsphingomyelin in good yield by treatment with p-nitrophenyl stearate. CHLOROHYDRIN STEARATE. COMPARISON OF THE TWO SYNTHESIZING METHODS AND THE INFRARED SPECTRA OF TIlE RELATED

CO~POUNDS. Gaku Izunli and Masayoshi K i t a (Gov. Ind. Res. Inst., N a g o y a ) . Yukagaku 16, 363-5 (1967). One step method of using benzyhnethylammonium chloride as the catalyst for reaction of epichlorohydrin with sodium stearate was superior to the two step method of using epichlorohydrin and sodimu stearate followed by the reaction by hydrogen chloride.

9 Biochemistry CA RBOH'~_'DRATE-LIPID

EFFECTS

and N u t r i t i o n ON

CHOLESTEROL

I~IETABOLISM.

Roslyn B. Alfin-Slater (School of Public Health, Univ. of Calif., Los Angeles). J. Dairy Sci. 50, 781-6 (1967). The marked differences in results with the different f a t s used indicate t h a t the effect of dietary lipids on serum and tissue cholesterol and cholesterol biosynthesis in liver is much greater than the carbohydrate effect. One of the conclusions to result from this study is that it is impossible to define the effects of a particular nutrient from one set of experimental conditions and without due consideration of the other constituents of the diet. N u t r i e n t : n u t r i e n t interrelationships are becoming more and more i m p o r t a n t in nutrition and disease conditions. FORCES BETVTEEN LECITHIN BII~IOLECULAI~ LEAFLETS ARE DUE TO A DISORDERED SURFACE LAYER. Y . A . P a r s e g i a n (Dept. o f

Chem., Mass. Inst. Technoh, Cambridge, Mass. 02139). Science 159, 939-42 (1967). The long-range repulsion observed between bileaflets of lecithin cannot be explained either with the usual view that the polar groups are arrayed eoplanar with the bileaflet surface or by the assumption t h a t charges protrude straight into the aqueous enviromnent. Statistical-thermodynamic analysis of experimental data suggests rather that structure of the leaflet surface is better described as a diffuse charge layer. Forces between leaflets are caused largely by entropy changes in the surface with leaflet separation. LIPID

COXfPOSITION

OF

MITOCHONDRIA

FRO_X[ BOVINE

HEART~

LIVER, AND KIDNEY. S. Fleischer, G. Rouser, Becca Fleiseher, Anna Casu, and G. Kritchevsky (Dept. of Molecular Biology, Vanderbilt Univ., Nashville, Tenn. 37203). J. Lipid Res. 8, 170-80 (1967). Highly purified preparations of mitochondria from bovine heart, liver, and kidney were isolated and characterized by electron microscopy, oxidative phosphorylation ability, eytoehrome c reductase activity, and cytochrome content. Components of lipid extracts of the preparations were determined by thin-layer chromatography, and spectrophotometric procedures. The major phospholipids were identified by their chronlatographic behavior, IR spectrometry and paper chromatography of their hydrolysis products. D . O. Shah and J. H. Schulman (Stanley-Thmnpson Lab., School of Eng., Colmnhia Univ., N. Y. 10027). J. Lipid Res. 8, 227-33 (1967). Surface potentials of mixed monolayers of dicetyl phosphate and eicosanyl trimethylanlmonium bromide (1:1) were the same on subso]ution of 0.02 M NaC1 or 0.01 M CaCI~, which indicated that ionic phosphate does not interact with Ca ++ in the presence of a neighboring trimethylammonium group. Surface potential-pH plots of dicetyl phosphate, and of dipahnitoyl, egg, and dioleoyl lecithins showed that as the p H of the subsolution is decreased the phosphate groups in the monolayer are neutralized in the order: dieetyl phosphate dipahnitoyl lecithin ~ egg lecithin ~ dioleoyl lecithin. The binding of cations (Na ~, Ca ++) to the phosphate group of lecithin also showed the same order. The binding of Ca ++ to egg phosphatidic acid mono]ayers, as measured by the increase in surface potential, is considerably greater than that to egg lecithin. T H E IONIC STRUCTURE OF LECITHIN MONOLAYERS.

T H E PLAST~IA FREE FATTY ACID REBOUND INDUCED BY NICOTINIC

2618y2 Main

500A

P.O. Box 903

Dallas, Tex.

_XCID. J. N. Pereira (Pharmacol. Res. Dept., Med. IRes. Lab., Chas. Pfizer & Co., Inc., Groton, Cann. 06340). J. Lipid Res. J. AM. OIL CHEMISTS' Soe.~ OCTOBER 1967 (VoI~. 44)

A B S T R A C T S : B I O C H E M I S T R Y AND N U T R I T I O N fl, 239-44 (1967). The time course of the nicotinic acidinduced changes in levels of plasma free f a t t y acids ( F F A ) was examined. The plasma F F A response of fasted dogs to graded doses of nicotinic acid was shown to be biphasic: an initial depression of the level of plasma F F A was followed by a rebound elevation to supernormal levels. F F A rebound was not seen after the administration of the nicotinic acid homologue, pyridylacetic acid, or a variety of nicotinic acid metabolites. A similar pattern of F F A response was observed in fasted, normal rats. Adrenaleetomy did not abolish the secondary elevation of F F A but did cause a somewhat delaye:l response. Hypophysectomy modified the time course of the r e s p o n s e - - t h e initial F F A decrease was p r o l o n g e d - - a n d the intensity of the F F A rebound was diminished. No rebound was observed in hypophysectomized, adrenaleetomized rats. In normal rats, nicotinic acid caused a significant rise in the level of plasma cortieosterone. REMOVAL OF T H E SPHINGOLIPID I M P U R I T Y FR05I PREPARATION OF YEAST P H O S P H A T I D Y L INOSITOL. W . E . Trevelyan (Distiller

Company (Yeast) Ltd., Great Burgh, Epsom, Surrey, E n g l a n d ) . J. Lipid Res. 8, 281-2 (1967). A cmnplex sphingolipld containing inositol and mannose, present in lipid extracted from toluene-autolyzed baker's yeast, was eluted from silicic acid colunms immediately after phosphatidyl inositol, and was the main nitrogenous impurity in crude preparations of this phospholipid. Nitrogen-free phosphatidyl inositol was obtained by rechromatography on almnina. Modifications to the chromatographic procedure also gave diphosphatidyl glycerol containing the theoretical 4.29% Y. METABOLISM

OF

DOUBLE-LABELED

CHYLOMICRON

CHOLESTERYL

ESTERS 1N THE RAT. S. H. Quarfordt and D. S. Goodman (Dept. of g e d . , Columbia Univ. College of Physicians and Surgeons, New York 10032). J. Lipid Res. 8, 264-73 (1967). Chylomicrons labeled in vitro with doubly-labeled cholesteryl esters were injected intravenously into fasted rats, and the tissue distribution and chemical form of each isotope were observed for 24 hr. The use of doubly-labeled cholestery] esters provided information about metabolism of both the sterol and the f a t t y acid moieties. Similar results were obtained with doubly-labeled cholesteryl palmitate, oleate and linoleate. I n each instance, nlost (80-90%) of the ehylonficron cholesteryl ester was removed from the plasma by the liver; small amounts were also taken up by all other tissues examined. There was no hydrolysis during uptake. In the liver the newly absorbed cholesteryl esters underwent slow hydrolysis (60% after 1 hr and 85-90% after 3.5 h r . ) ; the rate of reesterification of the liberated cholesterol was still slower. A f t e r 24 hr only 20-28% of the labeled cholesterol present in the animal was found in the liver. THIN-LAYER CIIROMATOGRAPHY OF STEROLS A L U M I N A IMPREGNATED %VITIt SILVER NITRATE.

cirrhosis of the liver (induced by 46-51 intramuscular injections of a mixtm'e of carbon tetrachloride and olive oil at 4-day intervals) have been compared with those of control animals injected with olive oil only. In cirrhotic animals, the concentration of lymph lipide was not greatly altered, but lymph flow, mid consequently the hourly transport of lipide by lymph were greatly increased; the increase in transport of cholesteryl esters, free cholesterol, and phospholipids by way of the thoracic and hepatic duct lyuiph was particularly striking. The concentration of these lipid fractions in serum from the cirrhotic rabbits was also increased. The differences normally observed between lipid f a t t y acid compositions of serum and lymph disappeared in cirrhotic animals; this is interpreted as due to increased hepatic permeability to lipoproteins. ]~ATES OF TISSUE UPTAKE OF PALMITIC ACID-IfidC CO~MPLEXED ~VlTH A[,BU~IIN BY TWO DIFFERENT PROCEDURES. ft. I. K e s s l e r ,

M. Demeny and H. Sobotka (Depts. Med. Chem., Mt. Sinai Hosp., New York City, N.Y. 10029). J. Lipid Res. 8, 185-90 (]967). The effect was investigated of two different methods of preparing an albunfin-pahnitic acid complex on the tissue uptake of the pahnitie acid, both in vivo and in vitro. Complex A was prepared by exposing monomolecular layers of palmitic acid-l-~C deposited on a solid surface to albmnin dissolved in buffer. Complex B was prepared by the interaction of albumin with a micellar solution of pahnitate-154C. The radioactivities and chemical compositions of the two complexes were ahnost identical. R a t epididymal f a t pads took up, during a 1 hr incubation, about 2.5 times as much palmitic acid from complex A as from complex B; the extent of esterification of the incorporated label was equal for the two complexes. The fractional turnover rate of palmitic acid of complex A, administered intravenously to dogs, was about twice that of pahnitie acid from emnplex B. The label of the two complexes reeireulated in the esterified f a t t y acid fraction of plasma to an equal extent. ACETATE4-~C INCORPORATION ACIDS OF P H O S P H O L I E I D S OF

INTO POLYUNSATURATED F A T T Y DEVELOPING CHICK BRAIN. K.

Miyamoto, L. M. Stephanides and J. Bernsohn (Northwestern

ON NEUTRAL I~. Kalnlnereck,

Wen-hui Lee, A. Paliokas and G. J. Schroepfer, Jr. (Dept. of ChenL and Chem. Eng., Univ. of Ill., Urbana, Illinois 61803). J. Lipid Res. 8, 282-4 (1967). Thin-layer chromatography for the rapid separation of several sterols on neutral alumina impregnated with silver nitrate is described. The method is particularly effective for sterols that differ in the number and location of olefinic bonds. SPHINGO~IYELINASE IN S P L E E N S FROM S U B J E C T S

NORI~IAL HUMAN SPLEENS AND IN W I T H N I E M A N N - P I c I ( DISEASE. t ). B .

Schneider and E. P. Kennedy (Dept. of Biol. Chem., H a r v a r d Med. School, Boston, Mass. 02115). J. Lipid Res. 8, 202-9 (1967). The purification and some of the properties are described of an enzyme from human spleen t h a t catalyzes the hydrolysis of sphingomyelin with the formation of ceramide and phosphoryl choline. The enzyme, which is located in the subcellular particulate fraction t h a t sedinIents between 700 and 8500g, is readily made soluble and has been partially purified. I t s p H optimum is between 4.5 and 5.0. I t is unaffected by divalent cations, chelating agents, and sulfhydryl reagents, but is inhibited by phosphate. The enzyme attacks sphingomyelin and dihydrosphingomyelin, b u t is inactive toward sphingosine, phosphoryl ehollne, O acetylsphingomyelln, and lecithin. In some of its properties, the enzyme frmn human spleen is different f r m n the previously studied sphingomyelinase frmn rat tissues. SERUM AND L Y M P I I LIPIDS IN R A B B I T S ~}VITI~I C A R B O N TETRACHLORIDE-INDUCED C I R R H O S I S OF T H E LIVER. M . Kotani, I<.

Seiki, A. Yamashita, A. Takashima, T. N a k a g a w a and Isoo Horii (Univ. Kyoto Ned. School, Kyoto, J a p a n ) . J. Lipid Re.*. 8, 181-4 (1967). L y m p h flow and the composition of lymph lipids from the hepatic and thoracic ducts of rabbits with

J. A,~. o ~ c ~ , H s ~ s ' soo., Oo~oB~, 1967 (vo~. ~m

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Kalamazoo Spice Extraction C o m p a n y P. O. Box 511, Kalamazoo, Michigan 49005

J

501A

ABSTRACTS:

BIOCHEMISTRY

Univ. Med. School, Chicago, 111. 60611). J. Lipid Res. 8, 191-5 (1967). The i n c o r p o r a t i o n of aeetate-l-~'C into the p o l y u n s a t u r a t e d f a t t y acids of g l y c e r o p h o s p h a t i d e s of chick e m b r y o n i c b r a i n h a s been studied. A f t e r the i n j e c t i o n of aeetate-l-~C into the yolk sac, differences were f o u n d in the degree of l a b e l i n g of the m a j j o r f a t t y acids of the w3 and w6 series. A r a e h i d o n i c aeid (20:4~o6) showed a high degree of r a d i o a c t i v i t y while doeosahexaenoic acid (22:6~o3) was poorly labeled, at a period of b r a i n development when both f a t t y acids were b e i n g actively deposited. Evidence is p r e s e n t e d to indicate t h a t the low activity in docosahexaeuoie acid is not explicable on the basis of either a low or h i g h rate of t u r n o v e r of this polyenoic acid. Similar results were obtained w h e t h e r the r a p i d early or slower late s t a g e of b r a i n development was examined. I t is s u g g e s t e d t h a t the elongation of ,,3 and co6 series acids m a y be u n d e r the control of different r e g u l a t o r y mechanisms. FAT AND CHOLESTEROL AND SERU~I CHOLESTEROL IN THE GERBIL. D. M. H e g s t e d a n d A n n a Gallagher (Dept. Nutr., H a r v a r d School Public H e a l t h , Boston, Mass. 02115). J. Lipid 2ges. 8, 210-14 (1967). Groups of gerbils were fed purified diets c o n t a i n i n g either 10 or 20% of safflower, olive or coconut oi1. E a c h diet was f e d w i t h o u t cholesterol and with 0.1 or 0.2% of a d d e d cholesterol. The a n i m a l s were bled a f t e r 2, 4 a n d 8 wks for the d e t e r m i n a t i o n of the level of s e r u m cholesterol. The m a j o r f a c t o r s affecting the level of s e r u m cholesterol were the k i n d of d i e t a r y oil, the a m o u n t of d i e t a r y cholesterol, a n d the l e n g t h of time the diet was fed. The level of safflower oil h a d a statistically significant effect b u t the level of olive or coconut oil h a d no significant effect. V a r i o u s other statistically significant i n t e r a c t i o n s were observed which m a k e simple i n t e r p r e t a t i o n s of the d a t a difficult. The levels of serum cholesterol achieved in the gerbils f e d the d i f f e r e n t oils with no or very tow levels of dietary cholesterol were similar to those seen in m e n f e d the s'mte oils. A l t h o u g h the gerbil is a p p a r e n t l y r e s i s t a n t to the development of atherosclerosis, it m a y be a u s e f u l model for s t u d y i n g the effect of d i e t a r y f a t s upon cholesterol nmtabolism. DIETARY

EFFECT oP LIGHT ON EXTRACTION ON LIPID FROM RETINAL RODS. R. G. A d a m s ( N a t . I n s t . A r t h r i t i s a n d Metabolic Diseases, B e t h e s d a , Md. 20014). J. Lipid Res. 8, 245-8 (1967). CMorof o r m - m e t h a n o l ( 2 : 1 ) removes a significantly g r e a t e r q u a n t i t y of lipid f r o m bleached bovine retinal rods t h a n f r o m a darka d a p t e d c o u n t e r p a r t . The e x t r a c t s contain p h o s p h a t l d y I serine, p h o s p h a t i d y l choline, p h o s p h a t i d y ] ethanolamine, sphingomyelin, a n d an u n k n o w n s u b s t a n c e which m a y be a c o m b i n a t i o n of p h o s p h o l i p i d and retinaldehyde. The difference between e x t r a c t s of l i g h t a n d d a r k - a d a p t e d rods is q u a n t i t a t i v e r a t h e r t h a n qualitative. The d a t a t e n d to confirm a model of rhodopsin in which isomerization of the r e t i n a l d e h y d e chromophore causes its d i s p l a c e m e n t a n d opens a p a t h to the interior of the molecule. BIOSYNTHESIS

OF

RETINOIC

ACID BY

INTESTINAL

PNZYSIES

OF

THE RAT. F. D. Crain, F. J. L o t s p e i e h a n d R. F. K r a u s e ( W e s t V i r g i n i a Univ. School Med., M o r g a n t o w n , W. V. 26506). J. Lipid l~es. 8, 249-54 (1967). The i n c u b a t i o n of fl-cnrotene~C with the soluble f r a c t i o n of the i n t e s t i n a l nmcosa resulted in the f o r m a t i o n of small a m o u n t s of acidic material. The a d d i t i o n of N A D or N A D H to the soluble f r a c t i o n caused a t e n f o l d increase in this material. I n c u b a t i o n of retinal-152~C with the soluble f r a e t i o u of the i n t e s t i n a l mucosa plus X A D or N A D H resulted in the conversion of 8 0 - 9 0 % of the retinal to acidic m a t e r i a l , which h a s been shown to contain retinoic acid. In vivo studies on the f o r m a t i o n of retiuoic acid in the i n t e s t i n a l m u e o s a a f t e r the a d m i n i s t r a t i o n of fl-carotene-~'C revealed t h a t an appreciable a m o u n t of fl-carotene was co~v e t t e d to acidic compounds. W h e n retinal-15-~dC was adm i n i s t e r e d , p o r t a l blood contained 3 0 - 4 0 % of the absorbed r a d i o a c t i v i t y ; 2 4 % of this r a d i o a c t i v i t y was f o u n d in acidic m a t e r i a l , which h a s been shown to contain retinoic acid. It is s u g g e s t e d t h a t enzymes in r a t i n t e s t i n e cleave ~-carotene to r e t i n a l a n d oxidize the l a t t e r to retinoie acid, which is then t r a n s p o r t e d v i a the portal circulation to the liver. R E L A T I O N S H I P OF LIPOPROTEIN LIPASE 3,CTIVITY TO TRIGLYCERIDE

UPTAKE IN ADIPOSE TISSUE. Arlene S. Garfinkel, N. B a k e r and M. C. Schotz (Dept. Biol. Chem., U C L A School Med., L()~ Angeles, Calif. 90024). J. Lipid Res. 8, 274-80 (1967). F a s t e d r a t s injected with a e t i n o m y e i n or f e d glucose show increased lipoprotiu lipase activity o f e p i d i d y m a l adipose tissue. D a t a f r o m the a e t i n o m y c i n - t r e a t e d a n i m a l s showed a direct corre]a~ tion between the lipoprotein ]ipase activity a n d the u p t a k e of lipoprotein triglyeeride by the e p i d i d y n m l f a t p a d i~ ritro

502A

AND NUTRITION

a n d in ri~'o. D a t a f r o m tile a n i m a l s f e d glucose confirmed these findings in vitro. These d a t a s t r o n g l y s u g g e s t t h a t lipoprotein lipase p l a y s a m a j o r role in triglyeeride deposition in adipose tissue. INFLUENCE OF CALCIUM, CHOLESTEROL, A~NrD UNSATURATION ON LECITHIN NIONOLAYERS. D. O. Shah a n d J. H. S e h u h n a n ( S t a n l e y - T h o m p s o n Lab., School of Eng., C o h m b i a Univ., N. Y. 10027). J. Lipid Res. 8, 215 26 (1967). S u r f a c e p r e s s u r e s a n d potentials of m i x e d m o n o l a y e r s of dicetyl phosphatecholesterol, d i p a h n i t o y l leclthin-eholesterol were m e a s u r e d . The s u r f a c e potential is shown to be a more reliable p a r a m e t e r for the s t u d y of inte,'aetions in m o u o l a y e r s t h a n the s u r f a c e pressure. Monolayers of dieetyl phosphate-cholesterol follow the additivity rule for a r e a / m o l e c u l e w h e r e a s lecithin-cholesterol monolayers deviate f r o m it. The reverse is true for the ,~dditivity rule with r e g a r d to s u r f a c e p o t e n t i a l / m o l e c u l e . T h u s , the s u r f a c e potential indicates t h a t there is no interaction (or complex f o r m a t i o n ) between leeithin a n d cholesterol, b u t t h a t there is ion-dipole i n t e r a c t i o n between dicetyl phosp h a t e and cholesterol, as ~-ell as between p h o s p h a t i d i e acid and cholesterol. ~UTRITIONAL VALUE OF REFINED OR HYDROGENATED RAPESEED OILS AND TFIEIR PRINCIPAL COMPONENTS. STUDY ]VITH }.[ALE GROWING RATS. T. Cheniti, G. B o u r d e l and R. J a c q u o t (Center for Res. on N u t r . of C.N.R.S., Bellevue ( H a u t s - d e - S e i n e ) , F r . ) . Rec. Franc. Corps. Gras 1 4 ( 3 ) , 151-166 (1967). R a t s were fed balanced diets, ad libit~m, in which only the n a t u r e of the lipid was varied. The following f a t s were f e d at 20% level: sunflower oil, refined rapeseed oil a n d h y d r o g e n a t e d rapeseed oil. I n addition, diets with 20% h y d r o g e n a t e d rapeseed oil s u p p l e m e n t e d with 7 g of various other oils were also fed. The v a r i o u s oils were sunflower seed oil, linoleic acid, a n d the ethyl esters of oleic, erueic and behenic acid. The tests showed t h a t high f a t diets are n e c e s s a r y to reveal deficiencies in the use of rapeseed oil. The slight depressing effect of rapeseed oil m a y be corrected by the addition of linoleic acid. The d e p r e s s i n g effect of rapeseed oil d i s a p p e a r s when the r a t becomes an adult. No pathological s y m p t o m s were noted with either rapeseed oil, behenic acid or erueie acid. TWO PARTICULAR ASPECTS OF THE UTILIZATION OF FATS, INTRAVENOUS AND ORAL FEEDING. M. T. J u i l l e t ( I n s t . of F a t s a n d Oils, P a r i s , F r . ) . Rev. Franc. Corps Gras 1 4 ( 2 ) , 99-109 (1967). T h i s p a p e r is a review of the use of f a t s and oils for i n t r a v e n o u s and oral feeding. 71 references. STUDIES OF MEMBRANE FORMATION IN TETRAHY~IENA FYRIFORMIS. I. :RATES OF PHOSPHOLIPID BIOSYNTHESIS. G. A. Thompson, Jr. (Dept. of Biochem, Univ. of W a s h i n g t o n , Seattle, W a s h . 98105). Biochemistry 6, 2015-22 (1967). Characterization of the p r i n c i p a l s t r u c t u r a l lipids of Tetrahymena pyriforints W discloses a unique p a t t e r n . L e c i t h i n of the classical t y p e is replaced to a significant degree by the glycerol e t h e r analog, and the lipid r e s e m b l i n g p h o p h a t i d y l e t h a n o l a m i n e also c o n t a i n s considerable a m o u n t s of b o u n d glycery] ethers as well as 2 - a m h m e t h y l p h o s p h o n i c acid. The f o r m a t i o n of these lipids f r o m a n m n b e r of radioactive p r e c u r s o r s h a s been studied. The n m s t active p r e c u r s o r s e x a m i n e d are p a l m l t l e acid, acetic acid, and ehimyl alcohol. I t is entirely feasible to use these c o m p o u n d s in labeling lipids s y n t h e s i z e d d u r i n g a brief period in the cell cycle. The effects of several experim e n t a l variables are assessed in p r e p a r a t i o n for an e v a l u a t i o n of m e m b r a n e i n t e r r e l a t i o n s h i p s within the cell. The action of a p o t e n t s y s t e m of lipolytic enzymes is m e a s u r e d . ]?IOSYNTHESIS OF CARDIOLIPIN IN ESCHERICHIA COLI. N. Z. Stanaeev, K i n g - Y i n g C h a n g a n d E. P. K e n n e d y (Dept. of Biological Chem. H a r v a r d Med. School, Boston, Mass. 02115). J. Biol. Chem. 242, 3018-19 (1967). Cell-free p a r t i c u l a t e f r a c t i o n s f r o m Eseheriehia coil have been f o u n d to catalyze the s y n t h e s i s of eardio]ipin f r o m eytidine d i p h o s p h a t e diglyceride a n d L-glycerol 3-phosphate. Evidence is p r e s e n t e d t h a t p h o s p h a t i d y l g l y c e r o l is the i m m e d i a t e p r e c u r s o r of cardiolipin in a reaction involving the t r a n s f e r of a phosp h a t i d y l moiety f r o m CDP-diglyeeride. TURNOVER

AND

UTILIZATION

OF

ESTERIFIED

FATTY

ACIDS

IN

EHRLICH ASCITES TUMOR CELLS. A . A. Specter a n d D. Steinb e r g (Lab. of Metabolism, N a t i o n a l H e a r t Inst., N a t i o n a l Inst. of H e a l t h , B e t h e s d a , M a r y l a n d 20014). J. Biol. Chem. 242, 3057-62 (1967). N e t utilization of esterifled f a t t y acids was d e m o n s t r a t e d in E h r l i e h aseites t u m o r cells i n c u b a t e d i~ t'itro. ('ells in which the lipids had previously been labeled by i n c o r p o r a t i o n of f a t t y acid-l-~C lost lipid ester radioactivity progressively d u r i n g incubation. The f r a c t i o n a l loss of such radioactivity f r o m ester stores exceeded net loss of (Continued on p a g e 514A) J A~L O~L CH~:_~ISTS' SOC., OCTOBER

][967 (Vol,. 44)

ABSTRACTS: BIOCHEMISTRY AND N U T R I T I O N (Continued from page 502A) chemically determined lipid esters, showing t h a t the endogenous esters m u s t include more t h a n one kinetically distinguishable pool. Phospholipids, predonlinantly lecithin, provided most of the ester f a t t y acid utilized. P a r t of the f a t t y acid hydrolyzed from endogenous esters was oxidized to CO,_,, and the remainder was released into the medium as free f a t t y acid. Incubation in a medium containing a high concentration of free f a t t y acid did not prevent net depletion of lipid esters. On the other hand, incubation with free f a t t y acid plus glucose produced a highly significant net increment in lipid esters. B u t even in the face of this net increase in total lipid ester, radioactive f a t t y acid previously incorporated was released, indicating a true dynamic state. The primary effect of glucose and free f a t t y acid in the medium appears to be the stimulatlon of ester formation, not the suppression of lipid ester breakdown. LONG-TERM REDUCTION OF SERUM CHOLESTEROL LEVELS OF PATIENTS WITH ATHEROSCLEROSIS BY SMALL DOSES OF NEOMYCIN.

P. Samuel, C. M. Holtzman and J a n e Goldstein (Dept. of Med., The Long Island Jewish Hosp. and L o n g Island Jewish Hosp.Queens Hosp. Center Affiliation, New Hyde Park, N. Y., and Jamaica, N. Y . ) . Circulation 35, 938-946 (1967). The effect and tolerance of long-term oral administration of small doses of neomycin as a serum cholesterol reducing agent has been investigated. Sixteen patients were given neomycin sulfate orally for periods varying from 12 to 40.1 months, following control periods of 2.6 to 14.6 months. A f t e r an initial daily dose of 2 g of neomycin, ttle daily dose was varied between 0.5 and 2 g according to response. Average total serum cholesterol concentrations decreased in each of the 16 patients by 15 to 3 2 % ; the average decrease for the group was 22%. The difference was statistically significant in each patient at the 0.1% level. Serum cholesterol concentrations were mainrained at the lower plateau as long as the drug was given. I n an additional patient, after administration of neomycin for 2 months there was no change in serum cholesterol concentrations and the study was discontinued. Another developed severe diarrhea, nausea, and abdominal cramps during the first week of study. F A T T Y ACID COMPOSITIO~ AND WEIGHTS OF ORGANS FROM ESSENTIAL FATTY ACID-DEFICIENT AND NONDEFICIENT l I E N S .

H. Menge (U. S. Dept. of Agr., Beltsville, Maryland). J. N~ttr. 92, 148-52 (1967). F a t t y acid analyses and relative weights of organs from hens severely depleted of linoleic acid were made and compared with those obtained from corresponding organs f r o m nondeficient hens. Group 1 was fed a purified EFA-deficlent diet, and group 2 was given the same diet supplemented with corn oil calculated to supply 4% linoleic acid (18:2). The control group (group 3) was cmnposed of 20 birds selected at random from pullets fed a practicaltype diet hatching. At 23 weeks group 3 was given a practicaltype diet containing sufficient corn oil to supply 4% 18:2. The spleen, pituitary, pineal, thyroid and adrenals of the EFA-deficient hens weighed significantly more than corresponding organs from non-deficient hens (groups 2 and 3). This increase in weight was regarded as a reflection of the severe dietary stress imposed on the hens. The f a t t y acid composition of the tissue lipids from group 2 differed only slightly from t h a t of group 3, even though egg production, egg weight, and hatchability of fertile eggs were significantly lower in group 2 as compared with t h a t of group 3. These results demonstrated t h a t the purified diet lacked a f a c t o r ( s ) other than 18:2 t h a t was necessary for optimal reproduction. THE

EFFECT

OF

PROLACTIN

ON

LIPOGENESIS

IN

THE

PIGEON.

A. G. Goodridge and E. G. Ball (Dept. of Biol. Chem., H a r v a r d Med. School, Boston, Mass. 02115). Biochemistry 6, 1676-82 (1967), The effect of prolactin on lipogenesis in the pigeon was examined by injecting glucose-U?~C and tristearin-9,10-zK into birds which had been untreated or injected daily with 1 mg of bovine prolactin for 5 days. Radioactivity in p l a s m a g h c a s e and in liver, plasma, and adipose tissue total f a t t y acids (~*C and 8H) was deternfined 0.5, 7, 15, and 30 min after injection of the labeled substances. In those birds receiving prolactin the rate of accumulation of labeled f a t t y acids was three-to fourfold faster per g r a m of liver and the liver was nearly double the normal size. Accunmlation of ~*C f a t t y acids in plasma and adipose tissue was negligible at 7 rain bat increased rapidly and linearly with time thereafter. Tile rate of aecmnulatlon in both plasma and adipose tissue of the birds receiving prolaetin was markedly accelerated, the increase over the normal being of nearly the same m a g n i t u d e as seen for the total liver. The fate of the tritiated f a t t y

acids indicates t h a t the liver of birds receiving prolactin h a d a markedly enhanced capacity to process preformed f a t t y acids. The results are consistent with the hypothesis t h a t in both normal and prolactin treated pigeons f a t t y acids were synthesized predominantly ill the liver and released to the blood for t r a n s p o r t to adipose tissue where they were picked up and stored. Treatment with prolaetin produced an increase in the rate of hepatic f a t t y acid synthesis and turnover which was reflected in an increased level of plasma f a t t y acids and deposition of f a t t y acids in peripheral depots with an increase in body weight. RELATIVE FAILURE OF SATUR3.TED FAT IN THE DIET TO PRODUCE ATHEROSCLEROSIS IN THE RABBIT. W . E . C o l l n o r , J . J . R o h w e d -

der, and M, L. A r m s t r o n g (Dept. of Internal Med., Univ. of Iowa College of Med., Iowa City, Iowa 52240). Circ. Res. 20, 658-63 (1967). Three "saturated" f a t s of vegetable origin were fed to different groups of rabbits for periods up to 1 year. Cocoa butter and a hydrogenated vegetable oil shortening produced no hypercholesterolemia. Coconut oil feeding increased the serum cholesterol concentrations for 4 months, b u t a decline to baseline values occurred after 6 months. No gross atheroselerosis occurred in any animal fed coconut oil or the hydrogenated vegetable oil shortening. Slight atherosclerotie lesions were found in 50% of the rabbits fed cocoa butter. Aortic cholesterol content was slightly increased in animals fed coconut oil and cocoa butter. Dietary fats, even when highly saturated, had only a minimal capacity to produce atherosclerosis in the rabbit, a species usually highly susceptible to the induction of atherosclerosis. W h e n a moderate amount of cholesterol was added to the diet, the serum cholesterol levels increased greatly and considerable atherosclerosis resulted. VITAMIN

E

ACTIVITY

AND

METABOLISM

OF

N-METHYLTO-

COPHERA.*ZINES. J. G. Bieri and E. L. Prival (Nat. Inst. of Arthritis and Metabolic Diseases, Nat. Inst. of Health, Bethesda, Maryland 20014). Biochemistry 6, 2153-8 (1967). The synthesis of new tocopherol derivatives has initiated reconsideration of structure-activity relationships of vitamin E active couipounds. I n two different bioassays with the chick, dl-a-tocopheramine, dl-N-methyl-/~-tocopheramine, and dl-Nnlethyl-'~-tocopheramine were as active on a molar basis as dl-a-tocopherol. Considerably less active were dl-fl-tocopheramine and dl-7-toeopheramine. W h e n the compounds were fed to rats, blood levels of N-methyl-/9-and N-methyl-'ytocopheramines were one-half t h a t of a-tocopherol but in liver there was twice the concentration of the N-methyltocopheranfines as a-tocopheral. The amounts of /~- and 7-toeopheramines in blood and liver were considerably lower t h a n those of atocopheramine and the N-methyl derivatives. The distribution of a-tocopherol, fl-tocopheramine, and N-methyl-fl-tocopheramine in liver cellular fractions was sinfilar. Neither the tocopheraniines nor N-methyl-tocopheranlines, when administered to rats, gave rise to detectable amounts in the tissues of their corresponding toeopherols. The compounds were recovered f r o m liver and identified by their ultraviolet absorption spectra and gas chromatographic retention times. N-Methyl-t~tocopheramine had antoxidant activity equal to t h a t of atocopherol in stabilizing methyl linolenate emulsions, while fltocopheramine was one-half as active. E S S E N T I A L FATTY ACID DEFICIENCY AND ITS EFFECT UPON REPRODUCTIVE ORGANS OF MALE RABBITS. B . Ahluwalia, G. Pincus

and 1~. T. Holman (The Worcester Found. for Experimental Biol. Shrewsbury, Mass.). J. Nutr. g2, 205-214 (1967). To study the effects of essential f a t t y acid deficiency upon rabbits, especially upon spernmtogenesis, five immature, male, New Zealand rabbits were fed a purified diet devoid of f a t for 14 weeks. The f a t t y acids of the testes showed a marked increase of 5,8,11-eicosatrienoic acid and a decrease in the members of the linoleate family of f a t t y acids. Gross evidence of essential f a t t y acid ( E F A ) deficiency included diminished growth and feed efficiency, and toss of hair. Total lipids, phospholipids, and free cholesterol of testes were found to be decreased, whereas triglycerides followed the reverse pattern. Testes of deficient animals showed an extensive degenerative change in the senIiniferous tubules; no stage beyond secondary spermatocyte was evident. Glueose-6phosphate dehydrogenase and Aa-3fl-hydroxysteroid dehydrogenase activity of Leydig cells in both groups showed t h a t these enzymes were present. These observations suggest t h a t the degeneration of gonads observed during essential f a t t y acid deficiency may be due to primary impairnIent of anterior hypophyseal function. (Continued on page 516A)

ABSTRACTS:

BIOCHEMISTRY

( C o n t i n u e d f r o m p a g e 514A) CI~USTACEAN LIPOVITELLIN. ISOLATION AND CHARACTERIZATION OF THE ~AJOI~ tlIGH-DENSITY LIPOPROTEIN ~ROM THE EGGS OF DECAPODS. ]:~. A. Wallace, S u s a n L. W a l k e r , and P. V. H a u s c h k a (Biol. Div., Oak R i d g e N a t . Lab., Oak Ridge, T e n n . ) . Biochemistry 6, 1582-90 (1967). A simple procedure is described by which the p r i n c i p a l p r o t e i n c o m p o n e n t of the e g g s a n d m a t u r e ovaries of six decapod c r u s t a c e a n s was isolated in relatively p u r e f o r m a n d in large amounts. The component, in all cases, was a lipoprotein ( 3 0 % lipid) which lacked p r o t e l n - b o u n d p h o s p h o r u s a n d h a d an a v e r a g e molecular w e i g h t of 3.5 • 105. T h e relatively intense c h r o m a t i c properties of the c r u s t a c e a n lipoproteins were due to the presence of a carotenoid noncovalently bonded to the lipid a n d / o r protein. Those p r o t e i n s d i s p l a y i n g colors (purple, blue, a n d g r e e n ) associated with shorter wave l e n g t h s of the visible s p e e t r m n u n d e r g o spectral c h a n g e s d e p e n d e n t upon solvent conditions. A l t h o u g h these c r u s t a c e a n p r o t e i n s m a y not be h m n o l o g o u s to the v e r t e b r a t e lipovitellins, they a p p e a r to serve in the same capacity, a n d generic use of the t e r m "lipovitellin" is t h u s s u g g e s t e d for the m a j o r h i g h - d e n s i t y lipoprotein f o u n d within a n i m a l eggs. The c r u s t a c e a n lipovitellins a p p e a r to offer several a d v a n t a g e s for studies of lipoproteins in general a n d lipoprotein s y n t h e s i s in p a r t i c u l a r . ISOLATIOR" OF A PHOSPHOLIPID RENII~r INHIBITOR FROM K I D N E Y . S u b h a Sell, R. R. Smeby, a n d F. M. B u m p u s (Res. Div., Cleveland Clinic F o u n d . , Cleveland, Ohio 44106). Biochemistry 6, 1572-81 (1967). The reactivity of r e n i n a d d e d to p l a s m a f r o m nephrectoInized dogs increases i n d e p e n d e n t of increase in renin s u b s t r a t e concentration. A d d i t i o n of p l a s m a proteins f r o m n o r m a l dogs to p l a s m a f r o m a n e p h r e e t o m i z e d dog reduces the reactivity of renin. This s u g g e s t s the presence o f a r e n i n i n h i b i t o r in n o r m a l dog's p l a s m a of renal origin. The inhibitor was isolated f r o m dog's kidney a n d shown to be a p h o s p h o l i p i d similar to bovine p h o s p h a t i d y l s e r i n e b u t differs in f a t t y acid c o n t e n t a n d the s t r u c t u r e of the a m i n o acid. The phospho]ipid completely inhibits the reaction of dog r e n i n with dog renin s u b s t r a t e in vitro and single, daily i n t r a m u s c u l a r i n j e c t i o n s of the c o m p o u n d reduces the blood p r e s s u r e of chronic r e n a l h y p e r t e n s i v e rats. THE USE 0F ROASTED SO~x'BEAN I~.IEAL AS ANI-XIAL FEED AND EQUIPMENT FOR ITS PRODUCTION. F. G a i m a r i (Biih]er Co., Milan, I t a l y ) . Riv. Ital. Sostanze Grasse 44, 169-71 (1967). E q u i p m e n t used to n m n u f a c t u r e s o y b e a n meal is reviewed. INSULIN-LIKE ACTIVITY OF A MICROBIAL PROTEASE ON ISOLATED FAT CELLS. J. F. Kuo, C. E. H o h n h n d , I. K. Dill a n d N. Bohonos (Lederle L a b . ) . Arch. Biochem. Biophys. 117, 269-74 (1966). A p r o t e a s e p r o d u c e d by Streptomyces griseus h a s been f o u n d to display insulin-like effects on the m e t a b o l i s m o f isolated f a t cells f r o m r a t epididynlal tissue. These effects include e n h a n c e d conversion of glucose to carbon dioxide a n d lipid, a n d repression of the lipolysis s t i m u l a t e d by corticotropin a n d norepinephrine. G r e a t e r t h a n 9 5 % of the proteolytic activity could be abolished w i t h o u t significantly a l t e r i n g the insulin-like activity of the protease. T h e significance of these observations is discussed. STUDIES ON LIPOGENESIS IN VIVO. COMPARISON OF CHOLESTEROL AND FATTY ACID SYNTHESIS IN RATS AND MICE. G. R. J a n s e n , M. E. Z a n e t t i a n d C. F. H u t c h i s o n (Merck I n s t . for T h e r a p . Res.). Biochem. J. 102, 864-9 (1967). The i m p o r t a n c e of f a t t y acid s y n t h e s i s as a p a t h w a y for the disposal of i n g e s t e d glucose h a s been e v a l u a t e d in r a t s and mice given a purified high-glucose, l o w - f a t diet. U n d e r the conditions employed f a t t y acid s y n t h e s i s a p p e a r e d to be a more i m p o r t a n t p a t h w a y f o r glucose disposal in mice t h a n in rats. Ill mice 15.3% of i n g e s t e d glucose-U-~dC was converted into f a t t y acid a n d in r a t s the c o r r e s p o n d i n g value w a s only 8.6%. I n c o n t r a s t , t h e conversion of glucose-U-a~C into cholesterol, as a p e r c e n t a g e of dose, was twice as h i g h in r a t s as in mice. Mice given diets c o n t a i n i n g 1% or 20% of corn oil converted 14.5% or 7.0% respectively of d i e t a r y glucose-U :4C into f a t t y acid over a 24-hr period. There was no effect of f a t on the i n c o r p o r a t i o n of the isotope into cholesterol. I n mice given diets c o n t a i n i n g 1% or 2 0 % of corn oil approx. 10% a n d 2c~, respectively, o f newly s y n t h e s i z e d f a t t y acids were f o u n d in the liver. H e p a t i c f a t t y acid s y n t h e s i s a p p e a r s to be more sensitive to d i e t a r y f a t t h a n is e x t r a h e p a t i c synthesis. STUDIES ON LIPOGENESIS IN VIVO. FATTY ACID AND CHOLESTEROL SYNTHESIS IN HYPERGLYCEMIC-OBESE 5IICE. Ibid, 870-7. Lipogenesis h a s been s t u d i e d in i n t a c t genetically obese mice by meas u r i n g the incorporation of a single oral dose of 250 m g of glueose-12-adC into f a t t y acid a n d cholesterol in the liver a n d ext r a h e p a t i c tissues. Studies were also carried out with labelled ~]6A

AND NUTRITION

glucose a d d e d to the diet and f e d for 24 hr. W i t h either method, the conversion into f a t t y acid was g r e a t l y elevated in the livers of the obese mice. B y contrast, conversion of the single dose of glucose into f a t t y acid in e x t r a h e p a t l c tissues of obese mice was only h a l f t h a t occurring in the non-obese litter mates. Conversion of the single dose of glucose-l'C into liver cholesterol was comparable in obese a n d non-obese mice f e d on a purified low-fat diet. However, obese mice given this diet for 12 weeks a e c u n m l a t e d 1.54% cholesterol ill the live," vs. 0.29% ill tile non-obese litter mates. This a c c u m u l a t i o n a p p a r e n t l y resulted f r o m a decrease in removal of cholesterol f r o m the liver, r a t h e r t h a n an increased synthesis. Conversion of the glucose into e x t r a h e p a t i c f a t t y acid was decreased by 18-hr s t a r v a t i o n , p r o p o r t i o n a t e l y as m u c h in obese as in non-obese mice. The decrease in liver f a t t y acid s y n t h e s i s caused by s t a r v a t i o n also was considerable in obese mice, a l t h o u g h s o m e w h a t less m a r k e d t h a n ill the non-obese. THE OXIDATION AND UTILIZATION OF PALMITATE, STEARATE, 0LEATE AND ACETATE BY THE MAMMARY GLAND OF THE FED GOAT IN RELATION TO THEIR OVERALL METABOLISM. E. F. Annison, J. L. Linzell, S. F a z a k e r l e y and B. W. Nichols (Unilever Res. Lab., S h a r n b r o o k , E n g l a n d ) . Biochem. J. 102, 637-47 (1967). M e a s u r e m e n t s were m a d e of milk yield, m a m m a r y blood flow a n d arteriovenous differences of each p l a s m a lipid fraction, a n d their specific radioactivities, d u r i n g the i n f u s i o n of stearate-U-~'C, oleate-L'-~C, p a l m i t a t e - U - u C a n d acetate-1a~C into f e d l a c t a t i n g goats. A c e t a t e accounted for 2 3 % of the total CO2 produced by the aninml a n d c o n t r i b u t e d to the m e t a b o l i s m of the m a m m a r y g l a n d to a b o u t the same extent. C o r r e s p o n d i n g values for each of the long chain acids were less t h a n 1%. There were no significant arteriovenous differences of phospholipids, sterols or sterol esters, and their f a t t y acid composition showed no n e t c h a n g e s d u r i n g p a s s a g e t h r o u g h the m a m m a r y gland. T h e r e were l a r g e arteriovenous differences of p l a s m a triglycerides a n d their acid composition c h a n g e d m a r k e d l y across the gland. The levels of p a h n i t a t e a n d s t e a r a t e fell, a n d t h a t of oleate increased. A r t e r i o v e n o u s differences of p l a s m a F F A were small a n d variable, b u t a large fall in the specific radioactivity of each of the long chain acids h~dicated a s u b s t a n t i a l u p t a k e of p l a s m a F F A , a c c o m p a n i e d by r o u g h l y equivalent F F A release f r o m m a m m a r y tissue. The u p t a k e of F F A was confirmed by the extensive t r a n s f e r of r a d i o a c t i v i t y into milk. R e s u l t s confirmed t h a t C~-C~ milk f a t t y acids arise largely f r o m blood acetate, while p a h n i t a t e is derived p a r t l y f r o m acetate and p a r t l y f r o m p l a s m a triglyeeride, the latter f r a c t i o n being almost the sole p r e c u r s o r of oleate a n d stearate. ~NHIBITION OF ..LIPOXYGENASE I~Y ..SATURATED ~IONOHYDRIC ALCOHOLS THROUGH HYDROPHOBIC BONDINGS. H. M i t s u d a , K . Y a s u m o t o a n d A. Y a m a m o t o ( N y o t o Univ., K y o t o , J a p a n ) . Arch. Biochem. Biophys. 118, 664-9 (1967). A series of s a t u r a t e d m o n o h y d r i c alcohols h a s been e x a m i n e d in search of evidence p e r t a i n i n g to h y d r o p h o b i e b o n d i n g s d u r i n g the reaction of l i p o x y g e n a s e f r o m d e f a t t e d s o y b e a n meal. The alcohols produce a reversible inhibition of the enzymic reaction, the degree of which increases with i n c r e a s i n g chain l e n g t h of the alcohols. V a n ' t Hoff plots for the inhibition indicate a positive e n t r o p y c h a n g e for the c o m b i n a t i o n of the alcohols with the enzyme. H y d r o p h o b i c b o n d f o r m a t i o n between alcohols a n d enzyme is not only accounted for by these f a c t s b u t also a n t i c i p a t e d f r o m close r e l a t i o n s h i p s e s t a b l i s h e d between the i n h i b i t o r y activity of the alcohols and their physicochemical properties. F r o m L i n e w e a v e r - B u r k plots it follows t h a t the inhibition is of a m i x e d type. The alcohols are unable to p r e v e n t the enzyme f r o m the i n a c t i v a t i n g action of h y d r o g e n peroxide, which destroys the catalytic site in the enzyme. The possibility t h a t the alcohols combine with tile enzyme at a h y d r o p h o b i e region which serves as b i n d i n g site for the s u b s t r a t e is discussed. .

.

OXIDATION OF FATTY ACIDS IN GUINEA PIG EPIDERMIS. J. H. H e r n d o n a n d J. S. McGuire (Yale Univ. School of Med.). Arch. Biochem. Biophys. 119, 583 5 (1967). Evidence is presented to the effect t h a t both short and long chain f a t t y acids are r a p i d l y oxidized in g u i n e a p i g e p i d e r m i s a n d t h a t the r a t e s of glucose a n d p a h n i t a t e oxidation are similar. Conc e n t r a t i o n s of f a t t y acids insufficient to produce toxic sin.face effects reduce the rate of glucose oxidation, while f a t t y acid oxidation is itself depressed by glucose. A d d i t i o n to the incubation m e d i u m of d/-carnitine, a s u b s t a n c e whose r e g u l a t o r y role in lipid oxidation in other tissues h a s been d e m o n s t r a t e d , s t i m u l a t e s f a t t y acid oxidation in epidermis. T h e evidence s u g g e s t s t h a t the oxidative capacity of e p i d e r m i s is at l e a s t as g r e a t for f a t t y acids as it is for glucose. J. AM. Oil, CHEMISTS' SOC., OCTOBER 1967 (VoL. 44)

ABSTItACTS: CHANGES IN

BIOCHEMISTRY

LIPID SYNTHESIS

IN

AND NUTItITiON

RAT LIVER

DURING

DEVELOP-

I~IENT. 1~. J. Ballard and It. W. Hanson (Temple Univ. School of Med.). Biochem. J. 102, 952-8 (1967). Lipogenesis, as measured by the incorporation of glucose-1'C oi' acetate into f a t t y acids in liver slices, is h i g h in foetal and a d u l t rat liver b u t is low in the liver of the suckling rat, especially with glucose as s u b s t r a t e . The rate of s y n t h e s i s of nonsaponifiable lipids f r o m glucose is a b o u t 15 times as g r e a t in the liver of the 18-day foetus as in a d u l t liver. Activity in the newborn is negligible. Glucose incorporation into f a t is s t r o n g l y c o n c e n t r a t i o n - d e p e n d e n t in liver slices f r o m the adult and the 2-week old rat, b u t less m a r k e d l y so in liver slices f r o m the foetus. C h a n g e s in the activity of hepatic citratecleavage enzyme occur in parallel with the c h a n g e s in the e x t e n t of f a t t y acid f o r m a t i o n , s u p p o r t i n g the p a r t i c i p a t i o n of this enzyme in lipogenesis. THE MEI~IBRANE SYSTEMS OF THE ~IITOCI~0XDRION, IV. THE CALIZATION OF T H E F A T T Y ACID OXIDIZING SYSTE~I. D . W .

L0All-

m a n n , L. Galzigna, R. E. M c C a m a n a n d D. E. Green (Univ. of Wisconsin, Madison, W i s e . ) . Arch. Biochem. Biophys. 117, 413-22 (1966). T h e localization of tile enzymes concerned in the v a r i o u s steps of f a t t y acid oxidation h a s been d e t e r m i n e d by the enzymic analysis of the isolated inner and outer m e m b r a n e f r a c t i o n s of b e e f h e a r t mitoehondria. The e n z y m e s t h a t activate f a t t y acids, the c a r n i t i n e d o n g chain acyl transferase, a n d tile e n z y m e s of the fl-oxidation, have been f o u n d to be localized exclusively in the outer m e m b r a n e . None of the activities associated with these enzymes could be detected in the p r e p a r a t i o n of the inner m e m b r a n e . The e n z y m e s for the complete oxidation of p a h n i t a t e are localized in the crater m e m b r a n e . The r e q u i r e m e n t f o r the e a r n i t i n e - m e d i a t e d transf e r of the aeyl g r o u p across the outer m e m b r a n e f r o m exterior to interior was also d e m o n s t r a t e d . This finding established the outer m e m b r a n e as the carnitine "barrier." A t r a c t y l o s i d e ( a n inhibitor of several m i t o c h o n d r i a l reactions) is a p o t e n t intfibitor of f a t t y acid oxidation. T h i s inhibition is exerted on e n z y m e s associated with the n ~ e m b r a n e - f o r m i n g sector of the outer m e m b r a n e . The a t r a c t y l o s i d e "barrier" for f a t t y acid oxidation has been e s t a b l i s h e d as the outer m e m b r a n e . LIPID OTHER

offers 102 cata/og ~terns for... THIN LAYER CHROMATOGRAPHY

t Camag Model 12B T L C StaPter K i t

COb[POSITION OF AOt~TI.O I N T I M A P L U S I N N E R ~MEDI.k AND TISSUE FRACTIONS FRO.~I FETAL AND ADULT ]~HESUS

MONKEYS. 0. W. Porhnan and M. Alexander (Univ. of Oregon Me(]. School). Arch. Biochem. Biophys. 117, 357-65 (1966). Lipids of the intlma and inner media of aortas fronl adult rhesus monkeys and fronl a series of fetuses of about 75, 125 a n d 150 d a y s of g e s t a t i o n a l age were characterized as to m a j o r lipid classes, t y p e s of phospholipids a n d f a t t y acid s p e c t r a of the lipid classes a n d subclasses. P l a s m a lipids a n d the t y p e s of phospholipids of erythrocytes, total liver a n d of h e p a t o c y t i e organelles were also studied. The free a n d ester eholesterol concentrations of a d u l t a o r t a were h i g h e r t h a n comp a r a b l e f r a c t i o n s in the fetuses. Triglyceride a n d total phospholipid c o n c e n t r a t i o n s of f e t a l a n d a d u l t a o r t a were not different. T h e s p h i n g o m y e l i n concentration of a d u l t a o r t a was three t i m e s t h a t of the fetal aorta. The p h o s p h a t i d y l serine was also h i g h e r a n d p h o s p h a t i d y ] choline lower in tile a d u l t aortas. The d i s t r i b u t i o n s of different phospholipids were h i g h l y specific to the other tissues or subeellular organelles in question, b u t these p a t t e r n s were m u c h less affected by age of the donor a n i m a l t h a n were the phospholipids of aorta. T h e h e p a t o c y t i c organelles h a d low c o n c e n t r a t i o n s of sphingomyelin a n d p h o s p h a t i d y l seriue while these phospholipids were p r o m i n e n t in the erythrocytes. F a t t y acid d i s t r i b u t i o n s were specific as to lipid classes a n d subclasses of aorta, a l t h o u g h there were also differences between comparable f r a c t i o n s from the f e t a l a n d a d u l t series. ]:~EASSOCIATION OF PURIFIED LIPOPOLYSACCHARIDE AND PHOSPHOLIPID OF THE BACTEI~IAL CELL ENVELOPE: ELECTKON MICROSCOPIC AND MONOLAYER STUDIES. L . :Rothfield and It. W .

H o r n e (Dept. of Molec. Biology, Albert E i n s t e i n Coll. of Med., Y e s h i v a Univ., New York, N . Y . ) . J. Bacteriol. 93, ] 7 0 5 - 1 7 2 ] (1967). P h o s p h a t i d y l e t h a n o l a m i n e ( P E ) and lipopolysaecharide ( L P ) were purified f r o m Escherichia eoli a n d Salmonella typhi~urium cell envelopes. By electron microscopy L P f r a c t i o n s showed u n i f o r m hollow s p h e r e s ( d i a m e t e r 500 to 1000A) b o u n d e d b y a continuous leaflet (30A t h i c k ) ; P E f r a c t i o n s showed a r e g u l a r ]ame]lar structure. W h e n L P a n d P E were m i x e d the leaflet of lipopolysaccharide spheroids extended directly into the P E structure. M o n o l a y e r experinlents indicated t h a t L P p e n e t r a t e d a m o n o m o l e e u l a r fihn of P E at an a i r - w a t e r interface. T h e r e s u l t s indicate a common leaflet c o n t a h f i n g P E a n d L P m a y be f o r m e d in vitro and a s i m i l a r leaflet m a y exist in the i n t a c t cell envelope.

a. A.,,. o-, CHE.,,~S~S'SOO..O0roBE~ 1~67 ~VoL.44~

M a l l i n c k r o d t T L C Teaching and Trial K i t

In 1960, Thomas learned of a new European analytical technique termed "Dtinnschichtchromatographie". Investigation convinced our R.&D. staff that Thin Layer Chromatography - - a s it was translated--offered a novel method of separating mixtures to which paper chromatography was inapplicable. We now offer four complete Kits as well as coating materials from Camag, Mallinekrodt, and Schleicher & Schuell. Individual components of Kits and many accessory i t e m s - several developed by Thomas--are listed separately to permit selection for specific needs. Pre-Coated Plates provide the ultimate in convenience.

Camag Bibliography Service. A periodic review of new techniques and applications. Copies are available from Thomas free upon request. Detailed descriptive literature sent upon request

ARTHUR H. THOMAS COMPANY Scientific Apparatus and Reagents VINE STREET AT 3RD PHILADELPHIA, PA. 19105 More and more laboratories RELY Oh/THOMAS

517A

ABSTRACTS:

BIOCHEMISTRY

FATTY ACID SYNTHETASE OF SACCHAROI~IYCES CEREVISIAE. H. P. Klein, Carol M. Volkmann aud F. Chao (Exobiology Div., A m e s Res. Center, N.A.S.A., Moffett Fld., Calif. 94035). J. Bacteriol. 93, 1966 (1967). A l i g h t particle f r a c t i o n of crude ribosonial m a t e r i a l f r o m Saccharomyces cerevisiae cont a i n e d the f a t t y acid s y n t h e t a s e . By use of g r a d i e n t d e n s i t y a n a l y s i s this enzyme was located in the 47 S eonIponent. The particles were 3 0 0 2 in d i a m e t e r , were considerably flatter t h a n ribosomes a n d consisted entirely of protein. I N F L U E N C E O F CULTURE CONDITIONS ON T H E GLYCERIDE COMPOSITION OF FATS OBTAINED FR01~I T H E ~IOLD F U S A R I U M ,

J. Salmonowicz, J. Marcinkiewiez a n d H. Niewiadiowski ( P o l y t e e h n i e a l School of Gdansk, P o l a n d ) . Rev. Fra~w. Corps Gras 1 4 ( 5 ) , 311-31~ (1967). Fusarium c~tlmor~tm E54 was g r o w n u p o n identical m e d i a except f o r the source of carbon. One culture w a s g r o w n on a m e d i a u s i n g glycerine as the carbon source, the other u s i n g lactose. A difference exists between the two cultures not mIly in the b i o s y n t h e s i s of f a t t y acids b u t also in the composition of the triglycerides formed. The culture g r o w n w i t h glycerine produced f a t t y acids with less u n s a t u r a t i o n t h a n the culture g r o w n on lactose. F r o m 30 to 4 0 % of t h e u n s a t u r a t e d f a t t y acids of the culture g r o w n on glycerine were C20:2, while the culture grown on lactose h a d C18:1 a n d C18:2 f a t t y acids at levels of 40 to 50%. A B O U T T H E FATE OF AFLATOXIN DU~ING R E F I N I N G BY DISTILLATION 0~' PEANUT OIL. N. V e l a n a n d J. R e y n a r d ( L a b . of Res.

of the Society S a l a d o r ) . Bey. Franc. Corps Gras 1 4 ( 5 ) , 305-310 (1967). Aflatoxin is renIoved d u r i n g the alkali refining of p e a n u t oil. I t is shown in this s t u d y t h a t cont i n u o u s refining followed by a n e u t r a l i z a t i o n distillation or s t e a m refining is also effective in r e m o v i n g aflatoxin. E F F I C I E N T E L UT IO N OF RABBIT LIVER AND PLASZIA P H O S P H O LIPIDS F R 0 5 i T H I N - L A Y E R PLATES, J . J . Biezenski (Depts. of

O b s t e t r i c s a n d Gynecology, M a i m o n i d e s Med. Center, a n d S t a t e Univ. of N e w York, D o w n s t a t e Med. Center, Brooklyn, N. Y. 11219). J. Lipid Res. 8, 409-10 (1967). The efficient recovery ( 9 6 . 3 - - 9 9 . 6 % ) of phospholipids by elation f r o m t h i m l a y e r plates is documented. The conIposition of phospholipids f r o m r a b b i t liver a n d p l a s m a is reported. 1,2fill-CHOLESTEROL

AS

A

TRACER,

IN

STUDIES

OF

HU.~IAN

CHOLESTEROL METABOLIS),I. P. D. S. Wood, D. Myers, Y u e n L i n g Lee, Ryuzo Shioda a n d L. W. I(insell (Inst. for Metabolic Res., H i g h l a n d General Hosp., Oakland, Calif. 94606). J. Lipid Res. 8, 406-8 (1967). 1,2-an-Cholesterol was f e d to a s u b j e c t t o g e t h e r with 4-~'C-cho]esterol a t a known aH/~*C ratio. The ratio was s a t i s f a c t o r i l y p r e s e r v e d in cholesterol recovered f r o m p l a s m a , red cells, a n d bile, a n d in acids of bile. I s o t o p i c f r a e t i o n a t i o n was seen d m ' i n g thin-layer e h r o n m t o g r a p h i e isolation of cholesterol. I n work with 1,2-all-cholesterol or its m e t a b o l i t e s care should be t a k e n to recover c h r o m a t o g r a p h i c b a n d s in their entirety. C O MP OS IT IO N OF NEUTRAL LIPIDS FROM ERYTHROCYTES OF COM-

~ION ~IA~*ALS. G. J. N e l s o n (Bio-Medical Div., L a w r e n c e R a d i a t i o n Lab., Univ. of Calif., L i v e r m o r e , Calif. 94550). J. Lipid Res. 8, 374-9 (1967). The n e u t r a l lipids of the e r y t h r o c y t e s were i n v e s t i g a t e d in several c o m m o n m a m m a l s : cow, dog, goat, horse, pig, rabbit, r a t a n d sheep. Cholesterol content was deternfined by gas-liquid, thin-layer and colmnn c h r o m a t o g r a p h y the last in c o n j u n c t i o n with the I R spcct r o p h o t o m e t r y . T h e three m e t h o d s yielded similar results. I n every species i n v e s t i g a t e d , cholesterol was the m a j o r n e u t r a l lipid; cholesteryl esters, triglycerides a n d free f a t t y acids were detected only in trace a m o u n t s . I t is concluded t h a t these s u b s t a n c e s n m y have been e o n t a n f i n a n t s f r o m p l a s m a lipoproteins or leukocytes r a t h e r t h a n true c o n s t i t u e n t s of the erythrocyte. I n the e r y t h r o e y t e s of all species, cholesterol c o n t e n t was close to 3 0 % of the total lipids e x t r a c t e d f r o m the cells, a n d the nlolar ratio of cholesterol to phospholipid was a p p r o x i m a t e l y one. The significance of the d a t a is discussed in relation to c u r r e n t concepts of the s t r u c t u r e of the cell m e m b r a n e involving cholesterol-polar lipid conIplexes. METABOLIS31 OF LYSOPtIOSPttATIDYL ETHANOLAMINE AND L Y S O P K O S P H A T I D Y L CHOLINE BY H O ~ O G E N A T E S OF R,ARBIT POLY~iORFHONU CLEAI~

LEUKOCYTES

AND

AL~r

MACROPHAGES,

P. E l s b a c h (Dept. of Med. of N e w Y o r k Univ. School of Med., New Y o r k 10016). J. Lipid l~es. 8, 359-65 (1967). A con> p a r i s o u h a s been m a d e between the conversion of a~P-labeled lysophosphatidyl ethanolamine (LPE) and lysophosphatidyI choline ( L P C ) to their respective acylated a n d deacylated derivatives by h m n o g e n a t e s of r a b b i t p o l y m o r p h o n u c l e a r leukocytes a n d alveolar m a c r o p h a g e s . S y n t h e s i s of P E h y

518A

AND NUTRITION

b o t h h o m o g e n a t e s a n d of PC by m a e r o p h a g e h o m o g e n a t e s proceeded to a b o u t the sanie e x t e n t and is a t t r i b u t e d to direct acylation of the lyso compounds. A t higher L P C concentrations f o r m a t i o n of P C by leukocytes is f a r g r e a t e r t h a n by m a e r o p h a g e s . The m e c h a n i s m of this e n h a n c e d s y n t h e s i s of PC, which is b r o u g h t out by h i g h e r s u b s t r a t e concentrations, is believed to be a t r a n s f e r of the aey] g r o u p of one L P C molecule to another. U n d e r optinial conditions m a c r o p h a g e h o m o g e n a t e s deacylated L P E to a g r e a t e r extent t h a n L P C , while the reverse was true f o r leukocyte l m n m g e n a t e s . A l b u m i n inhibited deacylation of L P C a n d its conversion to PC by leukocytes, p e r h a p s by b i n d i n g the s u b s t r a t e (2 moles of L P C per mole of a l b u m i n ) . Other effects of a l b u u f i n - s t i n m l a t i o n of deacylation a n d a c y l a t i o n of L P E by m a e r o p h a g e s , iuhibitiml of deaeylation a n d aeylation of L P E by l e u k o c y t e s - - r e m a i n unexplained. PROPERTIES AND METABOLISM OF 2-ALKYLALKANOATES. I I I : ABSORPTION OF METHYL AND ETHYL 2-AIETHYLPALMITATE. T. A. Saladin a n d E. A. N a p i e r , Jr. (Dept. of I n t e r n a l Med. Univ. of Mich. Med. School, A n n Arbor, Mich.). J. Lipid Res. 8, 342-9 ( ] 9 6 7 ) . The recovery f r m n r a t a n d r a b b i t tissues of f e d methyl-~'C a u d ethyl-2-~*C 2 - m e t h y l p a h n i t a t e with unaltered specific activity h a s d e m o n s t r a t e d the existence of m e c h a n i s m s for the absorption and deposition of both m e t h y l a n d ethyl esters of f a t t y acids, at least for 2 - m e t h y l p a h n i t a t e . I n thoracic d u e t - c a n n u l a t e d rats, a p p r o x i m a t e l y 9% of the f e d conlpounds was recovered f r o m the l y m p h d u r i n g the first 24 hr, the rate of recovery r e a c h i n g a n I a x i n m m between 6 a n d 8 hr. I n the r a b b i t , the fed, u n a l t e r e d esters in p l a s m a were t r a n s p o r t e d principally by m e a n s of the low d e n s i t y lipoproteins. Only trace a m o u n t s of the u n a l t e r e d esters were s u b s e q u e n t l y detected in the blood a n d tissue lipids a f t e r feeding, however, even d u r i n g the period of m a x i m a l absorption; moreover, in c o n t r a s t to at least one r e p o r t by others, f u r t h e r a n a l y s e s for niethyl or ethyl esters of other f a t t y acids h a s shown t h a t such esters of s h o r t - c h a i n alcohols cons t i t u t e no more t h a n a trace a n l o u n t ( 0 . 0 0 4 - 1 . 0 3 % ) of the lipids e x t r a c t e d f r o m a wide variety of m a u l m a l i a n tissues. The possibility r e m a i n s t h a t even these trace anIounts of esters arose as a r t i f a c t s of autolysis, extraction, or assay. INCORPORATION OP ACETATE INTO FATTY ACIDS AND LECITHIN BY LUNG SLICE~ FROM FETAL AND NEWBORN LA*X[BS. N, Chida and F. H. A d a m s (Div. of Cardiology, Dept. of P e d i a t r i c s , Univ. of Calif. at Los Angeles, School of Med., Los Angeles, Calif. 90024). J. Lipid Res. 8, 335 41 (1967). I n c o r p o r a t i o n of acetate-l-l~C into p h o s p h o l i p i d s a n d f a t t y acids by l u n g slices f r o m f e t a l a n d n e w b o r n l a m b s a n d f r o m ewes was s t u d i e d in ritro. The d i s t r i b u t i o n of radioactivity in tim f a t t y acids of n e u t r a l lipids, pbospholipids, a n d lecithin was determined. Acetate-l-~*C was i n c o r p o r a t e d into m y r i s t i e , p a h n i t i c , a n d C~s f a t t y acids. Of the lecithin f a t t y acids, m y r i s t i c a n d p a l m i t i c were the m a j o r radioactive f a t t y acids. The results indicate t h a t the l u n g of f e t a l l a m b s is able to synthesize lecithin c o n t a i n i n g s a t u r a t e d f a t t y acids, a m a j o r c o n s t i t u e n t of p u h I m n a r y s u r f a c t a n t . A m a r k e d increase in the rate of acetate incorporation into lecithin was observed d u r i n g n m t u r a rich, and these r a t e s were h i g h e r t h a n those obtained in the ewes. A possible relationship between developmental c h a n g e s in lecithin b i o s y n t h e s i s and p u h n o n a r y s u r f a e t a n t is discussed. DISTRIBUTION OF RADIOACTIVE GLYCEROL AND FATTY ACIDS A~IONG ADIPOSE TISSIfE TRIGLYCERIDES AFTER ADMINISTRATION OF aL~;COSE-U-*~C. C. H. t t o l l e n b e r g (McGitl Univ, Med. Clinic, Montreal Gen. Hosp., Montreal, Quebec, C a n a d a ) . J. Lipid Res. 8, 328-34 (1967). Adipose lipid obtained f r m n f e d r a t s 15 or 60 nfin a f t e r i n j e c t i o n of radioactive glucose was s e p a r a t e d into 10 triglyceride classes of differing f a t t y acid compositions. The d i s t r i b u t i o n a m o n g these classes of total and radioactive triglyccride-glycerol was determined a n d f o u n d to be the same. T h u s newly s y n t h e s i z e d adipose triglyeerides resemble in kind a n d p r o p o r t i o n the triglycerides which exist in the tissue. This finding is in accord with the concept t h a t the s t r u c t u r e s of adipose t r i g l y e e r i d e s are stable over long periods a n d t h a t the t u r n o v e r rate of the several triglyeeride species are similar. A f t e r a d m i n i s t r a t i o n of radioactive glucose, the specific activity of s a t u r a t e d f a t t y acids was h i g h e r in the nmre s a t u r a t e d triglyeeride species. These d a t a indicate t h a t newly fornied s a t u r a t e d acids do n o t mix completely with all adipose tissue f a t t y acids available f o r esterification. F a t t y acids derived f r o m p l a s m a triglyeeride influenced the composition of newly s y n t h e s i z e d adipose tissue triglyceride and t h u s constitute an i m p o r t a n t source of adipose tissue lipid. a A.~t. OIL CttE51ISTS' SOr OCTOB~:R1967 (Vot~. 44)

A B S T R A C T S : B I O C H E M I S T R Y AND N U T R I T I O N L I P I D COl~IPOSITION OP THE VASCULAR SYSTEM DURING INFANCY~

CHILDHOOD, AND YOUNG ADULTHOOD. Hilda F. Wiese, E. Coon, W. Yamanaka, Shirley Barber, and P. Johnson (Bruce Lyon Menmrial Res. Lab., Children's Hosp. Med. Center, Oakland, Calif. 94609). J. Lipid Res. 8, 312-20 (1967). The object of this study was to determine the changes in lipid composition t h a t occur in blood vessels f r o m infancy to young adulthood. Analyses included levels of total cholesterol, total triglyceride, phospholipid and cholesteryl ester f a t t y acids, and the distribution of saturated and u n s a t u r a t e f a t t y acids. Triglyeeride, total and monoenoic f a t t y acids, and linoleic acid were lower in the ascending, thoracic, and abdominal aorta than in the pulmonary artery and inferior vena cava. Phospholipids and arachidonic acid were higher in aortic segments than in the other two vessels. Aortic ]ipids showed significant changes with increasing age: total cholesterol and total f a t t y acids decreased fronl 1 wk to 5 yr, then increased to 22 yr of age. Triglycerides decreased whereas eholesteryl esters increased from 10 to 22 yr of age. Saturated f a t t y acids decreased from 1 wk to 10 yr, then remained relatively constant. Linoleie acid (3.7-9.8% of total f a t t y acids) and arachidonie acid (15.8-21.7%) both increased with age; the increase in cholesteryl linoleate was highly significant. After 10 yr of age, total cholesterol and total f a t t y acids were significantly higher in abdominal t h a n in ascending and thoracic segments of aorta. OCCURI~ENCE O1~ POSITIONAL ISOMERS OXP OCTADECENOIC HEXADECENOIC ACIDS IN H U M A N DEPOT tSAT. J . Jacob

AND

and G. Grinlmer (Univ. H a m b u r g , H a m b u r g , Germany). J. Lipid Ees. 8, 308-11 (1967). Positional isomers of hexadecenoie and octadecenoie acids of h u m a n adipose tissue have been separated by gas-liquid chromatography and their amounts determined by oxidative cleavage (MnO~ and IO,). The following isomeric octadecenoic acids were present: 7-octadecenoie acid (0.4%), 8- (1.9%), 9- (73.0%), 10- (2.5%), 11- (19.0%) and 12(3.2%). The hexadecenoie acids have also been shown to be a mixture of positional isomers, in which the cis 9dsomer predominates. 10-Hexadecenoie and 12-octadeeenoic acids could conceivably be precursors of linoleic acid. The following branched f a t t y acids have also been determined in h u m a n depot f a t : 13-methylpentadecanoic, 12-methyltetradecanoic, 14-methylpentadecanoic, 14-methylhexadecanoie, and 16-methylheptadecanoic acid. They were present in percentages of 0.020.6% and their identification rests solely on comparison of their gas-liquid chromatographic retention times with those of synthetic compounds.

phosphatidyl inositol. Plasmalogen was found mainly as phosphatidal ethanolamine. The neutral lipid fractions contained free cholesterol and various amounts of triglyeeride, but little esterified cholesterol. Normal lymphocytes contained about half as much total lipid per cell as normal polymorphonuelear leukoeytes, with a similar cholesterol:-lipid-P ratio but relatively more lecithin and less elhanolamine glycerophosphatide. Normal mature leukocytes, compared with immature cells of the same morphological series, had a higher total lipid content per cell, more cholesterol and a higher ratio of cholesterol to lipid-P. Little difference was found in total lipid-P per cell, but mature cells contained relatively less lecithin and more sphingomyelin. DETERMINATION OF MOLECULAR SPECIES OF LECITHIN FROM ERYTHROCYTES AND PLASMA. L. M. G. Van Golde, V. Tomasi and L. L. M. Van Deenen (Lab. Organic Chem., Dept. of Biochem., Univ. of Utrecht, Utrecht, The Netherlands). Chem. Phys. Lipids 1, 282 93 (1967). The molecular species of lecithin fronl erythrocyte and plasma of man and rabbit were determined after conversion of the lecithins into diglycerides by means of hydrolysis with phospholipase C. The resultant dig]ycerides were separated by thin-layer chromatography on silica impregnated with silver nitrate into 6 or 7 fractions differing with respect to their degree of unsaturation. The positional distribution of the f a t t y acids in these fractions w a s determined by hydrolysis with pancreatic lipase and w a s found to be in agreement with the positional distribution of the f a t t y acids in the lecithin as ascertained by means of phospholipase A hydrolysis. Using these techniques about 20 nmleeular species accounting for about 90% of the total lecithin, could be evaluated in the erythrocyte and p l a s m a of man and rabbit. I t became clear t h a t qualitatively the molecular species of lecithin in the red blood cell and the plasma are similar. Quantitatively, however, there were some striking differences to be noted: in man the amount of (dipahnitoyl)- and (di-oleoyl)-lecithin was higher in the corpuscles when compared with plasma. On the other hand (1pahnitoyl-2-linoleoyl)- and (1-pahnitoyl-2-arachidonoyl)- lecithin were more a b u n d a n t in plasma. In rabbit similar differences were found in the make-up of the molecular species of lecithin between the erythrocyte membrane and the surrounding plasma.

I{INETIC ANALYSIS 01~ THE OXIDATION 0P PALlXIITATE-IfitC IN 1MAN DURING PROLONGED HEAVY I~USCULAR EXERCISE. R. J.

Havel, L. G. Ekeluud, and A. H o h n g r e n (Dept. of Clin. Phys. and the K i n g Gustav V Res. Inst., Karolinska Inst. Stockhohn, Sweden). J. Lipid Res. 8, 366-73 (1967). Two healthy men with high working capacities were injected intravenously with pahnltate-l-~4C and NaH~4COa on two occasions while they were performing strenuous exercise on a bicycle ergometer. F r o m analysis of a~CO.~ in expired air after injection of NaH~*COs, rate constants and compartment size describing a three-compartulent system for CO._, were determined algebraically. These data were combined with those of a separate study in which ~C in free f a t t y acids of arterial blood plasnm and in expired CO2 were measured after injection of pahnitate1-~C to construct an eight-cmnpartment model with an analogue computer t h a t described precisely the observed d a t a in each subject. The results indicate t h a t under these conditions almost half of the free f a t t y acids leaving the blood are oxidized directly (i.e., are transferred to mitochondria] oxidative sites through small internlediate compartments). The remainder enters larger compartments apart from the direct p a t h w a y ; most of these fraction reenter the direct oxidative pathway within 30 min. LIPIDS

OF

HUMAN

LEUKOCYTES :

I~ELATION

TO

CELL

TYPE.

E. L. Gottfried (Dept. of Med. and the Unit for Res. in Aging, A. Einstein College of Med., Yeshiva Univ., Bronx, N. Y. 10461). J. Lipid Res. 8, 321-7 (1967). Significant differences in lipid composition have been found between normal h u m a n lymphocytes and polymorphonuclear ]eukocytes, abnormal ]eukoeytes from patients with acute and chronic leukemia, and leukocytes from peritoneal exudates. Lipid extracts of isolated leukocytes were analyzed for total lipid, phosphorus, cholesterol, and plasmalogens. Individual phospholipids and neutral lipids were separated by thin-layer chromatography. The major phospholipids and neutral lipids were separated by thin-layer chromatography. The major phospholipids were phosphatidyl choline, ethanolamine, glycerophosphatides, sphingomyelin, phosphatidyl serine, and J. k~f. OIL C]=[E~fISTS' SOC., OCTOBER 1967 (VoI,. 44)

$1ll)IIIM < IVl l!'l'l,IYl.,+l'l'l! (Sodium Methoxide)

Spec 101. Packaged in airtight steel drums of 10, 25, 50 and 200 pounds net. Free flowing white powder. Formula NaOCH3. Bulk density 4.15 pounds per gallon. Molecular weight 54.03. Write today for full information.

@ HARSHAW Division of Kewanee Oil Company

THE HARSHAWCHEMICALCOMPANY 519A

ABSTRACTS: THE

BIOCHEMISTRY

ISOLATION AND CHARACTERIZATION OF PHOSPHATIDYLGLYC-

EROL AND A STRUCTURAL ISOME~ FROM PIG LE-NG. D. R. Body a n d G. M. G r a y ( L i s t e r I n s t . of P r e v e n t i v e Medicine, L o n d o n , E n g l a n d ) . Chem. Phys. Lipids 1, 254 63 (1967). Two minor phospholipid c o m p o n e n t s were isolated f r o m a lipid e x t r a c t of p i g lungs. One was identified as phosphatidylglycerol. The results of alkaline hydrolysis, periodate oxidation a n d aeetolysis showed t h a t the other was a s t r u c t u r a l isomer of p h o s p h a t i d y l glycerol with the s t r u c t u r e of a lyso-bis-phosphatidic acid. I t s c h r o m a t o g r a p h i c c h a r a c t e r i s t i c s on thin-layer plates of silica gel a n d on silicic a c i d - i m p r e g n a t e d p a p e r were quite distinct f r o m those of phosphatidylglycerol. Both of these phospholipids were also p r e s e n t in lipid e x t r a c t s of rat l u n g s a n d r a b b i t lungs. OSI~OTIC

PROPERTIES AND V(ATER PERMEABILITY OF PHOSPHO-

LIPID LIQUID CRYSTALS. n . D. B a n g h a m , J. De Gier a n d G. D. Greville ( A g r i c u l t u r a l Res. Council I n s t . of A n i m a l P h y s i o l o g y , B a b r a h a m , Canibridge, E n g l a n d ) . Chem. Phys. Lipids 1, 225246 (1967). A smectic m e s o p h a s e (myelin-like s t r u c t u r e , layerlatticed liquid c r y s t a l ) of c h a r g e d phospholipid behaves as an a h n o s t p e r f e c t o s m o m e t e r when alkali nietal salts, glucose, sucrose or m a n n i t o l are used as solutes. Other solutes show g r a d e d p e r m e a b i l i t i e s (ethyl-urea, m e t h y l u r e a , ethylene glycol, a m m o n i u m acetate, p r o p i o n a m i d e , glycerol ~ u r e a ~ malonamide ~ e r y t h r i t o l ) . Osmotically driven swelling a n d s h r i n k a g e were followed by nleans of the c h a n g e s in optical e x t i n c t i o n ; the validity of this was confirmed by d e t e r m i n a t i o n of the volumes a n d i n t e r s t i t i a l spaces of c e n t r i f u g e d pellets. The r a p i d volume changes, d e t e r m i n e d optically, combined with the Ineasured total e x t e r n a l s u r f a c e a r e a s of the phospholipid dispersions, were used to calculate osmotic w a t e r p e r m e a b i l i t y coefficients (0.8-16 t~sec-~). The c o m p l e m e n t a r y effects of s u r f a c e c h a r g e a n d electrolyte concentration on the equilibrimn volumes of smeetic m e s o p h a s e s were exalnined optically and by c e n t r i f u g a t i o n . The volume of the particles decreased with i n c r e a s i n g c o n c e n t r a t i o n of the electrolyte solution in which they formed. The i n t r a m e l l a r s p a c i n g s were not consistent with a single H a m a k e r c o n s t a n t over the r a n g e of the electrolyte c o n c e n t r a t i o n a n d a r e a - c h a r g e ratio studied. The c o n s t a n t was h i g h (10 -u e r g s ) with low electrolyte concentrations and lower by a f a c t o r of a b o u t 100 with a h i g h electrolyte concentration. T H E SOLUBILIZATION OF SO~IE STEROIDS BY PHOSPHATIDYL CHOLINE AND LYSOPHOSPHATIDYL CHOLINE. I . W. K e l l a w a y

AND

NUTRITION

in the oxidation of both isomers. Tile oxidation of unifornlly l~C-labeled oleic acid exceeded t h a t of m l i f o r m l y 1*C-labeled elaidie acid at all s u b s t r a t e c o n c e n t r a t i o n s ( 4 ' 1 0 5 to 40" 10 -~ M) a n d at all i n c u b a t i o n t i m e s (5 to 160 lniu) examined. D a t a o b t a i n e d with the specifically labeled acids d e m o n s t r a t e d t h a t the difference in oxidation rates was due to a slower oxidation of the alkyl chain on the m e t h y l side of the tra~s double bond of elaidic acid. DETERMINATION OF .MUSCLE LIPIDS. S. O. F r o b e r g ( K i n g G u s t a f V t h Res. Inst., Stockhohn, Sweden). Biochim. Biophys. Acta 144, 83-93 (1967). Methods have been devised to s e p a r a t e red muscle tissue f r o m white in the rat g a s t r o c n e m i u s muscle a n d to determine the content of cholesterol, phospholipids and triglycerides in these lnuscle types. No difference was observed in the concentration of cholesterol, phospholipids or triglyeerides between r i g h t a n d l e f t g a s t r o c n e m i i of either muscle type. I n f e d a n i m a l s cholesterol a n d phospholipid c o n c e n t r a t i o n s were about 50(/c h i g h e r in red nmsele, whereas the a m o u n t of triglycerides was only slightly higher. T H E LIPIDS OF SOME RUMEN HOLOTRICH PROTOZOA. I . K a t z a n d M. K e e n e y (Dept. of D a i r y Sci., Univ. of M a r y l a n d , College P a r k , Md. U S A ) . Biochim. Biophys. Acta 144, 102-112 (1967). The lipids f r o m r m n e n holotrich protozoa were isolated a n d p a r t i a l l y identified. The lipid consisted of 70c/~ phospholipids a n d 307~ non-phospholipids. The phospholipids contained phosp h a t i d y l e t h a n o l a m i n e ( 2 1 ~ ) , p h o s p h a t i d y l e t h a n o l a m i n e plasm a l o g e n (22c~), p h o s p h a t i d y l choline (289"r), a n d u n k n o w n phospholipids (29r/~). All the phospholipid f r a c t i o n s contained significant a m o u n t s of b r a n c h e d chain and u n s a t u r a t e d f a t t y acids. D e g r a d a t i o n of the p h o s p h a t i d y l ethanolalnine and p h o s p h a t i d y l choline with phospholipase A revealed t h a t the b r a n c h e d chain and u n s a t u r a t e d acids were located in the b e t a position. Chemical d e g r a d a t i o n of the p h o s p h a t i d y l ethanolamine p l a s m a l o g e n indicated t h a t the vinyl ether linkage was its the alpha position. The non-phospholipids consisted of a m i x t u r e of waxes, hydrocas'bons, aliphatic alcohols, diglyeerides, monoglycerides, h y d r o x y a c i d s , unesterified f a t t y acids and sterols. The sterols a n d miesterified f a t t y acids comprised 50% of the fraction. The low concentration of stearic acid in the unesterified f a t t y acids (8..3c/~) raises a question as to the q u a n t i t a t i v e i m p o r t a n c e of holotrich protozoa in r u m e n hydrogenation.

a n d L. S a u n d e r s ( P h y s . Chem. Labs. The School of Biochim. P h a r n l a c y , The Univ. of London, E n g l a n d ) . Biophys. Acta 144, 145-8 (1967). Q u a n t i t a t i v e estilnations of the a m o u n t s of some steroids solubilized by ultrasonic dispersion with p h o s p h a t i d y l choline in water, have indicated t h a t m o n o p o l a r steroids are solubilized to a g r e a t e r e x t e n t t h a n m u l t i p o l a r steroids. Also, of the nIonopolar steroids studied, those p o s s e s s i n g a 5-en structure, were solubilized to a lesser e x t e n t t h a n the 4-en-3-one steroids a n d those with a s a t u r a t e d nucleus. The effect of c h a i n l e n g t h of the acid p r e s e n t in a series of cholesterol esters on the q u a n t i t y solubilized by p h o s p h a t i d y l choline was examined. I t was f o u n d t h a t as the series was ascended so the q u a n t i t y solubilized decreased, a l t h o u g h the t r e n d was reversed for h i g h e r nIembcrs of the series. Dispersion with l y s o p h o s p h a t i d y l choline in the presence of p h o s p h a t i d y l choline resulted in an increase ill the q u a n t i t y of p r o g e s t e r o n e solubilized in ultrasonically i r r a d i a t e d aqueous sols.

F A T FEEDING AND CHOLESTEROL SYNTHESIS. ~V. M . Bortz (Div. of Res., The L a n k e n a u Hosp., P h i l a d e l p h i a , Pa., U S A ) . Bioehim. Biophys. Acta 137, 533-9 (1967). The f e e d i n g of f a t h a s previously been shown to result in a decrease in f a t t y acid s y n t h e s i s and an increase in cholesterol s y n t h e s i s by the liver. F u r t h e r m o r e , it h a s been proposed t h a t f a t t y acids s y n t h e s i s is controlled by the inhibition of the r a t e - l i m i t i n g acetyl-CoA earboxylase by long-chain f a t t y acyl CoA derivatives with a consequent build-up of aeetyl CoA in the liver. The p r e s e n t e x p e r i m e n t m e a s u r e s the effect of f a t f e e d i n g on aeetate-l-~*C conversion to ~CO~, f a t t y acids, cholesterol, and acetoaeetate by rat-liver slices. The r e m a i n d e r of the lives' was a s s a y e d for levels of the f a t t y acyl-CoA derivatives, acetyl-CoA, a n d =g l y c e r o p h o s p h a t e . I t was shown t h a t f a t f e e d i n g produces an early a c c u m u l a t i o n of the acyl-CoA derivatives a n d acetyl-CoA with a decreased f a t t y acids s y n t h e s i s and increased ketone body synthesis. No alteration in cholesterol s y n t h e s i s was seen u n t i l a later time interval, however.

MECHANISI, I

ESTERIFICATION IN RAT-LIVER CELL SAP. Masako Akiyama, Osamu Minari and Toshio Sakagami (Dept. of Chem. Sapporo Medical College, Sapporo, Japan). Biochim. Biophys. Acta 137, 525-532 (1967). The existence of a cholesterolesterifying enzyme was investigated with sap from liver cells. After subfraetiouation of liver homogenates, cholesterol esterifieation was checked with p a r t i c u l a t e a n d cell sap f r a c t i o n s a n d c o m p a r e d with the activity in plasnla. Cholesterol was esterified on i n c u b a t i o n with cell sap. The enzyme of cell sap esterified cholesterol in the same m a n n e r as t h a t of p l a s m a ; it did not require A T P , CoA or Mg ~'. The f a t t y acids esterified were derived f r o m the a d d e d phospholipids, lecithin a n d cephalin. P r e t r e a t m e n t with p h o s p h o l i p a s e A or the addition of N - e t h y h n a l e i m i d e caused a m a r k e d lowering of the esterifieation. The o p t i m a l p H (6.5) was lower t h a n t h a t (7.3) of plasma. F r e e linoleie aeid-l-~C a d d e d to reaction m i x t u r e s was n o t i n c o r p o r a t e d into cholesterol ester w h e t h e r or not A T P , CoA a n d Mg ~§ were present. I t is concluded t h a t , in cell sap, cholesterol ester was synthesized by a t r a n s f e r of the f a t t y acids f r o m lecithin, a n d in the p a r t i c u l a t e s by a t r a n s f e r of the f a t t y acids f r o m acyl-CoA.

OF SIDE-CHAIN DEGRADATION

OF Cm STEROIDS BY

SPORES Or SEPTOHYXA AFPINIS. K. S i n g h a n d S. R a k h i t ( A y e r s t L a b o r a t o r i e s , Montreal, C a n a d a . ) Biochim. Biophys. Acta 144, 139-144 (1967). Side chain cleavage of C~ steroids by spores of Septomyxa affinis h a s been investigated. The spores t r a n s f o r m e d 17a-deuteroprogesterone to 17a-deuterotestosterone i n d i c a t i n g t h a t the side chain was d e g r a d e d via a p a t h w a y a n a l o g o u s to the non-enzymic B a y e r - V i l l a g e r oxidation of ketones by peracids. 20a-Hydroxypregn-4-en-3-one was p r o b a b l y t r a n s f o r m e d by a n a l t e r n a t i v e p a t h w a y . The possibility of 20fl-hydroxypregn-4-en-3-one b e i n g all i n t e r m e d i a t e in the sidechain cleavage reaction is ruled out since the spores were i n c a p a b l e of cleaving its side chain a n d the only p r o d u c t obt a i n e d fronl this steroid was the c o r r e s p o n d i n g 1-dehydro analog. OXIDATION OF THE GEOMETRIC ISOMERS OF -~9-OCTADECENOIC ACID BY RAT-LIVER ]~IITOCI-IONDRIA. R . L. A n d e r s o n (The P r o c t e r

a n d Gamble Co., M i a m i Valley Labs., Cincinnati, Ohio, U S A ) . The oxidation of the geometric isomers of Ag-octadeeenoic acid by rat-liver m i t o e h o n d r i a was e x a m i n e d u s i n g the acids labeled at C-1 or C-10 or unifornfly labeled with ~C. The mitochossdria oxidized these acids to CO2, acetoaeetie acid a n d fl-hydroxybutyric acid, t h u s e s t a b l i s h i n g the f u n c t i o n i n g of the fl-oxidation sequence

Bioehim. Biophys. Acta 144, 18-24 (1967).

,-,i/~

CHOLESTEROL

A

~

la~7

(VOT,

A,I)

ABSTRACTS: B I O C H E M I S T R Y AND N U T R I T I O N PORTAL

ABSORPTION

OF

FATTY

ACIDS

IN

LYMPH-

AND

PORTAL

VEIN-CANNULATED RATS. S. A. Hyun, G. V. Vahouny and C. R. Treadwell (Dept. of BiochenL School of Med. The George Washington Univ., Washington, D.C.). Biochim. Biophys. Acta 137, 296-305 (1967). The route and the rate of the intestinal absorption of oleic-l-~4C, caprylic-l-a~C and 2-ethyl-~4C-n-caproic acids have been studied using lymph and portal vein-cannulated rats. I t was found that 85% of absorbed oleic acid was transported directly via the portal system. With short-chain fatty acids, between 94-98% of the absorbed acids were transported via the portal system. Studies on the rate of the intestinal absorption of these acids indicated that 2-ethyl-n-caproie acid was absorbed less completely and subsequently nletabolized less effectively than the corresponding straight-chain fatty acid, caprylic acid. Studies on the distribution of radioactivity in lymph lipids showed that most of the radioactivity (85%) was present as triglycerides when oleic acid-~C was administered to lymph and portal vein fistula rats. However, when the ~Clabeled short-chain f a t t y acids were given, 96 102% of the radioactivity was present as free f a t t y acids. Studies on the distribution of radioactivity in lipid fractions of portal vein blood showed that 50 and 98-100% of the radioactivity present were in the form of free f a t t y acids when oleic acid2~C and ~C-labeled short-chain f a t t y acids, respectively, were administered to lymph and portal vein fistula rats. MECHANISltI

OF

STIMULATION

OF

CHOLESTEROL

ABSORPTION

BY

2-ETHYL-N-CAPROIC ACID IN VIVO. Ibid., 306-14. Studies on the mechanism of stimulation of (7 a-all) cholesterol absorption of 2-ethyl-n-caproic acid have been carried out in lymph and portal-vein cannulated rats. About 15% of administered cholesterol was absorbed in 8 h when the sterol was given with oleic acid alone. The administration of 2-ethyl-n-eaproic acid together with oleic acid and cholesterol significantly increased the absorption of cholesterol to 23%. Simultaneous determination of f a t t y acid absorption and esterification showed that 44% of the fed oleic acid-l-~4C was recovered in thoracic duet lymph in 8 h, and about 15% of the long-chain acid was transported directly via portal blood. However, in the presence of 2-ethyl-n-caproic acid, only 22% of the administered o]eic acid-l-~C was recovered in lymph, while 40% was transported directly into portal system. This effect of the branched-chain f a t t y acid was most pronounced 4 8 h after feeding. In this group there was a reduction in total lymph trlglycerides and a slight increase in lymph free fatty acids. These data support the earlier suggestion that the primary effect of 2-ethyl-ncaproic acid is inhibition of triglyceride synthesis in intestinal mucosa, resulting in increased transport of free fatty acids via portal blood and increased availability of f a t t y acids for cholesterol esterification and absorption. THE

R O L E OF P L A C E N T A

IN

LYSOLECITtIIN

I~IETABOLISI~I I N

RATS

A~I) MICE. S. Eisenberg, Y. Stein and O. Stein (Dept. of Medicine B and Lipid Research Laboratory, Hadassah Univ. Hospital, Jerusalem ( I s r a e l ) ) . Biochim. Biophys. Acta 137, 115-20 (1967). I n 16-20-days pregnant rats a 50% fall in serum ]ysolecithin level was found. Following intravenous injection into p r e g n a n t rats and mice there was an extensive uptake of palmitoyl-l-~C-lysolecithin by the placenta followed by a rapid conversion of the labeled lysolecithin to lecithin. During the first 10 min after injection of pahnitoyl-l-~C lysolecithin-~2P, the ~4C/a2P ratio in the newly fornied lecithin was the same as the injected lysolecithin, indicating that the conversion of lysolecithin to lecithin in the placenta was accomplished through the acylation pathway. I t is concluded that the fall in serum lysolecithin is due to a selective uptake of ]ysolecithin by the placenta and this additional source of placental lecithin could be of importance in an organ with a pronounced tronsport function. THE

RESOLUTION

OF

('+')-CARNITINE

AND

THE

SYNTHESIS

OF

ACYLCARNITINES. K. Brendel and R. Bressler (Dept. of Biochem. and Med., Duke Univ. Medical Center, Durham, N.C.). Biochim. Biophys. Acta 137, 98-106 (1967). Procedures are described for the resolution of ( _ ) - c a r n i t i n e nitrile chloride into its optical isonlers by salt formation with (§ sulfonic acid and (+)-dibenzoyltartaric acid. Procedures for the acylation of carnitine are described employing large excesses of the acylating agent in a homogenous reaction. The acylation of the carnitine benzyl ester can be carried out using lower ratios of acylating agent to earnitine. METABOLISI~[

BY of

OF

I-PAL~IITOYL

DIOLEIN

AND

3-PALI~IITOYL

DIOLEIN

ADIP0SE TISSUE. W. R. Wright and S. B. Tove (Depts. BiochenL and Animal Sci., North Carolina State Univ.,

Swedish Symposium on Metal Catalyzed Lipid Oxidation The Swedish I n s t i t u t e of F o o d P r e s e r v a t i o n Research ( S I K ) in O5teborg is o r g a n i z i n g a s y m p o s i u m on M e t a l Catalyzed L i p i d Oxidation on Oct. 9 a n d 10, 1967. M e t a l catalyzed lipid o x i d a t i o n - - a s metal catalysis in g e n e r a l - - p l a y s a n i m p o r t a n t role in t e r m s of quality a n d stability in various b r a n c h e s o f food technology. I t therefore a p p e a r e d desirable to g a t h e r experts with different lines of interest w i t h i n this s p h e r e at a s y m p o s i m n in o r d e r to pronIote scientific research a n d technical development. I n v i t a t i o n s were m a i n l y sent to scientists engaged in research within this complex of p r o b l e m s a n d p r e p a r e d to take a n active p a r t in the symposium. The idea of this s y m p o s i m n has been accepted with g r e a t i n t e r e s t a n d scientists r e p r e s e n t i n g 15 countries were represented at S I K . The symposiuni will be i n t r o d u c e d by Dr. I n g o l d from the N a t i o n a l Research Council, Ottawa, Canada, who will deliver a review on the s u b j e c t in question. There was a section on a n a l y t i c a l techniques, a section on f u n d a m e n t a l research, a n d a section on the p r o b l e m s in various sectors of' food technology a n d i n d u s t r y . F i n a l l y p a c k a g i n g p r o b lems were discussed. O r g a n i z i n g secretary of' the s y m p o s i m n was Dr. R e i n h a r d Mareuse, S I K , GSteborg.

Basic Statistics and Evolutionary Operation Courses Basic Statistical Methods for the Chemical and Process Industries A two-day s h o r t course will be co-sponsored by the Chemical Division of A S Q C a n d the Section on P h y s i c a l a n d E n g i n e e r i n g Sciences of A S A . This course will cover two days of practical, easy-to-learn statistical methods f o r the e n g i n e e r a n d the a p p l i e d scientist in i n d u s t r y - - i n the p l a n t or in the l a b o r a t o r y . P r i n c i p a l topics to be covered are concepts, f r e q u e n c y distributions, control charts, comp a r i s o n of means, c o m p a r i s o n of variances, test precision a n d a n a l y s i s of variance, regression, e x p e r i n i e n t a l desig~ a n d e v o l u t i o n a r y operation. The i n s t r u c t o r s are D. S. Chambers, P r o f e s s o r of Statistics at the U n i v e r s i t y of Tennessee, a n d Mr. H. O. H e h n e r , M a n a g e r of Quality Control of M o n s a n t o ' s Organic Chemicals Division. The r e g i s t r a t i o n fee is $100, dates are N o v e m b e r 3 a n d 4, a n d place is the M i d l a n d H o t e l in Chicago. F o r f u r t h e r i n f o r m a t i o n a n d a p p l i c a t i o n forms, contact Mr. Charles Ferczok, O p e r a t i o n s Research D e p a r t m e n t , S w i f t & Con> p a n y , 115 W . J a c k s o n Blvd., Chicago, Illinois 60604. Telep h o n e n u m b e r is 312-431-2777.

Evolutionary Operation A t h r e e - d a y s h o r t course on Evolutionam" O p e r a t i o n will be co-sponsored by the Chemical Division of A S Q C a n d the Section on P h y s i c a l & E n g i n e e r i n g Sciences of A S A . Cost reduction, quality i m p r o v e u I e n t a n d increased c a p a c i t y are d e m o n s t r a t e d results of E V O P . This method of process i m p r o v e m e n t h a s been so successful because it is a p p l i e d directly to o p e r a t i n g processes a n d designed to be used by r e g u l a r p l a n t personnel. This method of process i m p r o v e m e n t does not i n t e r f e r e with n o r n m l p r o d u c t i o n . The r e g i s t r a t i o n fee is $140, which includes all course m a t e r i a l s a n d lunches. Dates are N o v e m b e r 16, 17 a n d 18, in the M i d l a n d Hotel, Chicago, Ill. F o r f u r t h e r i n f o r m a t i o n a n d a p p l i c a t i o n forms, contact G. R. W a g n e r , O p e r a t i o n s R e s e a r c h Dept., S w i f t & C o m p a n y , 115 W. J a c k s o n Blvd., Chicago, Illinois 60604, Telephone 312-431-2777.

(Continued on page 522A) ,]'. ~ M

O H . (7. E I . I S T S , S 0 C

OCTO ~"

5967

('Vm

A~,)

591A

ABSTRACTS: BIOCHEMISTRY AND N U T R I T I O N (Continued from page 521A) Raleigh, N.C.). Biochim. Biophys. Acta 137, 54-8 (1967). Stereospecific metabolism of triglycerides was investigated by incubating homogenates of adipose tissue with 1-palmitoyl diolein and 3-pahnitoyl diolein, each labeled with ~C at the carboxyl group of the palmitic acid. No evidence for stereospecific hydrolysis was obtained from the specific activity of the fatty acids, monoglycerides and diglycerides. However, approximately twice as much label was incorporated into the 2-position of the tissue triglycerides from 1-pahnitoyl dlolein as from 3-palmitoyl diolein, suggesting a stereospecific transfer of a fatty acid from the 1-position of a triglyceride to the 2position of a triglyceride precursor. STUDIES OIq THE PHOSPHOLIPIDS OF RAT BRAIN W H I C H CONTAIN

GLYCERYL ETHERS. L. A. Horrocks and G. B. Ansell (Dept. of Exptl. Neuropharmacology, The Med. School Birmingham, Great Britain). Biochim. Biophys. Acta 137, 90-7 (1967). The phospholipids of rat brain which are stable to mild alkaline and acid hydrolysis were examined quantitatively. The glyceryl ether form of phosphatidyl ethanolamine (acyl alkyl glycerylphosphorylethanolamine) contains 3.1% of the rat-brain lipid phosphorus and accounts for most of the glyceryl ethers present in the phospholipids. The presence of the acyl group was confirmed by acetolysis of the purified ethanolamine phospholipids. Some evidence for the presence of dialkyl glycerylphosphorylethanolamine and alkyl glycerylphosphorylcholine in small amounts was also obtained. The methods used for mild hydrolysis in these studies are suitable for determination of labelled phosphorus, ethanolamine or choline incorporation into diacyl, acy] alkyl types of glycerophospholipids. T H E BIOSYNTHESIS O~~ GLYCERIDES AlqD GLYCEROPI~OSPHATIDES RY RABBIT RETICULOCYTES. H . A . S l o v i t e r a n d S. T a n a k a (Har-

rison Dept. of Surgical Res. School of Medicine, Univ. of Penn., Phil., Pa.). Biochim. et Biophys. Acta 137, 70-9 (1967). When rabbit reticulocytes were incubated with glyeerol-l-~C, radioactivity was incorporated into glycerides and glycerophosphatides but no radioactivity was present in their fatty acid moieties or in cholesterol. Lecithin and ethanolamine phosphatide together contained about 70% and the neutral lipids about 20% of the total radioactivity. The triglyceride, which comprised less than 2% of the ]ipids, had the highest specific activity of all the lipids. Experiments with other radioactive precursors of the phosphatides gave results which indicate that the minor phosphatides are metabolically much less active than lecithin and that the formation of lecithin from serine phosphatide or ethanolamine phosphatide is quantitatively unimportant in these cells. Incubation of rabbit reticulocytes with inositol-2-3H resulted in the formation of radioactive phosphoinositides. Most of this radioactivity was present in a monophosphoinositide. K . Schubert, Rose and Clare Horhold (Deutsche Akademie der Wissenschaften zu Berlin, Institut fur Mikrobiologic und experimentelle Therapie, Abteilung fur Steroidforschung, Jena). Biochim. Biophys. Acta 137, 168-71 (1967). Cholesterol has been isolated as the only sterol present in Streptomyces olivaeeus, a species of the order Actinomycetales--which belongs to the bacteria. The demonstration of the occurrence of sterols in bacteria by means of adsorption ehronmtography, gas-liquid chromatography and by mass spectrometric and infrared spectral photometric methods, refutes the general assumption according to which bacteria are incapable of synthesizing sterols. S. olivace~ts synthesized cholesterol and also has the capacity of degrading it, A~-androstene-3, 17-dione and A~'~-androstadiene-3,17-dione occurring as intermediary products. CHOLESTERIN I N STREPTOMYCES OLIVACEUS.

B I O P H Y S I C S OE LIPIDIC ASSOCIATIONS. I I . T H E TERNARY SYSTEMS CHOLESTEROL-LECITHIN-WATER. M . Bourges, D. M. Small and

D. G. Dervlchian (Service de Biophysique, Institut Pateur, Paris ( F r a n c e ) ) . Biochim. Biophys. Acta 137, 157-67 (1967). Mixtures containing different proportions of lecithin, cholesterol and water have been prepared and their separation into different phases has been determined. The structure of these systems has been analysed with the polarising microscope and by X-ray diffraction. A ternary triangular phase diagram has been constructed showing the regions of composition in which single phases and mixtures of 2 and 3 phases exist. A paracrystalline hydrated phase with a lamellar structure exists which can contain variable amounts of cholesterol up to a maximum of 1 molecule of cholesterol per nlolecule of lecithin. The maximum quantity of water in this phase varies from 45 to 35% according to the quantity of incorporated cholesterol. With larger quantities of water the paracrystalline phase is

522A

dispersed in the form of anisotropic particles in the excess of water. ON THE SYNTHESIS OF PLASMALOGENS. A . ,[. Slotboom, G. H. De Haas and L. L. M. Van Deenen (Dept. of Biochem., Lab. of Organic Chem., Univ. of Utrecht, Utrecht, The Netherlands). Chem. Phys. Lipids 1, 192-208 (1967). The chemical synthesis is described of (rac)-traas-l-(n-hexadec-l'-enyloxy)2-oleoyl-glycerol-3-phosphoryleholine (plasmalogen). This synthesis made use of a specific degradation of (rac)-trans-l-(nhexadec-l'-enyloxy), 2,3-dioleoyl glycerol with pancreatic lipase (EC 3.1.1.3). The latter compound was converted into a plasmalogen by a reaction with 2-bromoethyl-phosphoric acid dichloride and trimethylamine. A partial synthesis of cis-l-(nalk-l'-enloxy)-2-oleoyl-glycerol-3-phosphorylcholine was developed by application of this method to cis-l-(n-alk-l'-enyloxy)2,3-dioleoyl glycerol. The preparation of cis-l-(n-alk-l'enyloxy)-2,3-dioleoyl glycerol was made by acylation of cis1-(n-alk-l'-enyloxy) glycerol obtained from ox-heart plasmalogen after degradation with phospholipase C (EC 3.1.4.3) and alkaline hydrolysis. The I.R. spectra of both plasmalogens were completely identical with each other and differed from the spectra of lecithins only by the presence of a vinyl ether absorption at 1660 cm -~. The N.M.R. spectrum of the acetylated synthetic (rac)-l-(n-hexadec-l'-enyloxy)glycerol as well as of the synthetic plasmalogen revealed a tra~s configuration of the vinyl ether linkage. FACTORS INFLUENCING THE PATTERN OF FATTY ACIDS SYNTHESIZED BY CELL-FREE PREPARATIONS OF LACTATING RAT MAMMARY GLAN]). J. C. Bartley, S. Abraham and I. L. Chaikoff

(Dept. of Clinical Sci., School of Veterinary Med. Univ. of Calif., Davis). Biochim. Biophys. Acta 144, 51-60 (1967). The pattern of fatty acids synthesized from acetate-l-~C, acetyl-l-~'C-CoA, citrate-l,5-'C2 and malonyl-l,3-1~C2-CoA by various homogenate preparations of mammary glands of lactating rats was studied with the aid of gas-liquid chromatography. Addition of microsomes to the 100,000 x g supernatant fraction significantly decreased the incorporation of labeled acetate into C~o and C~2 fatty acids and increased that into C~ and C~s acids. When aeetate-~C or aeetyl-CoA were the substrates in experiments with the 100,000 • g supernatant fraction, the isotope was incorporated predominantly into C~,, fatty acid. The labeled malonyl-CoA was predominantly converted to C~ fatty acid. The pattern of incorporation of the ~'C of citrate-l,5-~C~ was intermediate between these two. When an ammonium sulfate fraction of the 100,00 • g supernatant fluid, precipitating between 0 and 40% saturation, was used as the source of acetyl-CoA carboxylase (EC 6.4.1.2) and fatty acid synthetase, the pattern of conversion of all labeled substrates to fatty acids was the same, i.e., predominantly to C~,, acids. Addition of fractions precipitating at higher saturations of ammonium sulfate had no effect on the pattern of conversion. ESTERIFICATION OF FREE FATTY ACIDS BY SUBCELLULAR PREPARATIONS OF RAT ADIPOSE TISSUE. D . A. K. Roncari and C. H.

Hollenberg (McGill Univ. Med. Cliu., Montreal General Hosp. Montreal, Quebec, Canada). Biochim. Biophys. Acta 137, 446-463 (1967). The intracellular location of the enzymes responsible for catalyzing the esterification of pahnitate-~C with a-glycerophosphate was studied with enzyme fractions prepared by centrifugation of adipose tissue homogenates. Esterifying activity was confined to mitoehondrial and mierosomal fractions, the mitochondria being the more active. ATP and CoA were obligatory requirements. With either particulate fraction, phospholipids were the principal ester products; phosphatidic acid was tentatively identified as being the major phospholipid formed. The soluble fraction (109,000 • g supernatant fluid) when used alone did not stimulate esterification. However, addition of this fraction to particulate preparations, produced a consistent alteration in ester products so that tri- and diglyceride became the major products, while net formation of ester bonds was only modestly increased. The soluble fraction was found to exert its effect after binding of free f a t t y acids to subcellular particles. The factor(s) responsible for the activity of the soluble fraction could also be bound by these particles. The soluble fraction activity persisted after heating to 58C and was slowly dialyzable. Its effect could not be replicated by a variety of proteins and ions. I t is suggested that the effect of the soluble fraction was due to stimulation of particulate phosphatidate phosphohydrolase activity. H E P A T I C LIPID METABOLISM IN EXPERIMENTAL DIABETES. I I . INCORPORATION OF P A L M I T A T E - I - l t C INTO LIPIDS OF THE LIVER AND OF THE D ~ 1 . 0 2 0 PERFUSATE LIPOPROTEIR*S. M . Heimberg,

D. R. Van Harken, and T. O. Brown (Dept. of Pharmacol., Vanderbilt Univ. School of Med., Nashville, Tenn.). Biochim. J. A3I. OIL CItEMIST$' SOC,, OCTOBER 1967 (VOL. 4 4 )

ABSTRACTS: B I O C H E M I S T R Y AND N U T R I T I O N Biophys. d c t a 137, 435-45 (1967). Livers from normal rats, from rats treated 48 hours before use with alloxan, and from alloxan-diabetic animals treated with insulin, were perfused in vitro with a medium containing palmitic acid-l-~C. I t was observed under our experimental conditions that hepatic release of triglyceride, phospholipid, and cholesterol into the d ~ 1.020 lipoprotein was depressed by alloxan diabetes and was restored to normal by pretreatment of the animal with insulin. During these perfusions of livers from diabetic animals with small loads of pahnidc acid, hepatic triglyceride concentration was diminished, whereas it appeared to be unchanged in livers from normal rats. Incorporation of 1~C into triglycerides and phospholipids of the d ~ 1.020 lipoprotein was depressed by alloxan diabetes, perhaps, in part, a result of decreased release of these lipids into the lipoprotein. The rate of hepatic biosynthesis of phospholipid also appears to be inhibited in alloxan diabetes since the incorporation of ~C and the specific activity of liver phospholipid was depressed. Although the incorporation of ~*C into hepatic triglyceride did not appear to be depressed in these experiments as a result of the alloxan diabetes, we can not say that rates of esterification of non-esterified f a t t y acid to triglyceride were normal; this reservation is necessary since these data were obtained at the termination of the perfusion experiment during which time the hepatic concentration of triglyceride was declining, f a t t y acid was being oxidized and triglyceride was lint being released at normal rates.

INCORPORATION OF GLUCOSE-6fl~C AND PALI~IITIC ACID-9,10aII IN VITRO INTO LIPIDS OF ADIPOSE TISSUE FRO},[ ESSENTIAL FATTY ACID-DEFICIENT RATS. A. Solyom, E. Muhlbachova and Lina Puglisi (Inst. of Pharmacology, Univ. of Milan, Milan, Italy). Bioehim. Biophys. Acta 137, 427-34 (1967). The simultaneous incorporation of labelled glucose and pahnitic acid into lipide has been investigated in vitro in epididymal fat pads of rats fed essential f a t t y acid-deficient diet, in order to obtain information on possible metabolic differences brought about by essential f a t t y acid-deficiency in adipose tissue. It has been found that the incorporation of both precursors, but especially of glucose, is greater into adipose tissue lipids (mostly triglycerides) in rats fed essential f a t t y acid-deficient diet than in controls, indicating a greater triglyceride synthesis in these animMs. Lipid synthesis in the adipose tissue of essential f a t t y acid-deficient animals, however, does not seem to differ qualitatively from that of controls. The distribution of radioactivity among the lipid components suggests that no change in the metabolic utilization of essential f a t t y acids for the synthesis of neutral lipids occurs. Also the incorporation of pahnitic acid and glucose into glyeerides is sinfilarly affected in control and essential f a t t y acid-deficient animals during fasting or nicotinic acid or theophylline treatment. THE STRUCTURE AND ABUNDANCE OF RAT TISSUE CARDIOLIPINS.

S. Courtade, G. V. Marinetti and E. Stotz (Biochem. Dept., Univ. of Rochester School of Med., Rochester, N. Y.). Biochim. Biophys. Acta 137, 121-134 (1967). Cardlolipins of rat tissues were isolated by c o h m n chronmtography and analyzed. The P content ranged from 2.61% to 3.64%. The ester :P ratio varied from 1.63 to 2.09, and the glycerol:P ratios varied from 1.34 to 1.68. The f a t t y acid spectrum of the tissue cardiolipins showed some, llke heart, kidney and liver to be highly unsaturated and others like brain, lung and testis to be highly saturated. Analysis of the f a t t y acids released by plv)spholipase A demonstrated that certain f a t t y acids are l)referentially fl-linked, but on the whole, the f a t t y acid distribution is much more random than that of other phospholipids. like the lecithins. All the rat tissue cardiolipins are degraded by hot acetic acid to yield diglycerides, very small amounts of monoglycerides, and other P-containing products. However, only with rat-liver cardiolipin, beef-heart cardiolipin, and a synthetic cardiolipin are appreciable mnounts of water-solub!e P released. On treatment with sodium methoxide at 0C all rat tissue cardlolipins gave rise to 4 6-1yso-derivatlves resulting from the sequential loss of one or more fatty acids. All cardiolipins are eventually completely degraded to fatty acid methyl esters, a water-soluble P con~pound and smaller amounts of other products including free f a t t y acids and vitamin A. I n the case of rat-liver cardiolipin, alkaline hydrolysis yields vitamin A but not in stoichiometric amount.

9

Literature

B E C K M A N I-N~STR.L'MENTS, I N C . , has released bulletin 7119, dealing with a complete u l t r a v i o l e t - i n f r a r e d " s p e e t r o s c o p y l a b o r a t o r y " in one compact unit. The u n i t includes Beekm a n ' s D B U l t r a v M e t S p e e t r o p h o t o n l e t e r a n d the Microspec I n f r a r e d S p e c t r o p h o t o m e t e r with 7-speed recorder. (Technical h l f o r m a t i o n Section, Scientific h l s t r m n e n t s Division, 2500 H a r b o r Blvd., F u l l e r t o n , Calif. 92634.)

" H e a l t h Aspects of C a s t o r B e a n D u s t " is a p a r t of the E n v i r o n m e n t a l H e a l t h Series, established to r e p o r t the results of seientific a n d e n g i n e e r i n g studies of m a n ' s enviromuent. I n c l u d e d are reviews of A g r i c u l t u r a l a n d Commercial Aspects, Toxicity a n d Allergenieity, Occupational Illness, C o n m m n i t y Illness a n d Control Measures. ( R e q u e s t P H S P u b l i c a t i o n No. 999-AP-36, f r o m U S D e p a r t m e n t of H e a l t h , E d u e a t i o n a n d W e l f a r e , Public H e a l t h Service, B u r e a u of Disease P r e s e n t i o n a l a n d E n v i r o n m e n t a l Control, Cincinnati, Ohio 45202. A new technical bulletin on a preset batch counter with s t a r t - s t o p controls f o r use with flowmeters of' flow measuring devices has been p r e p a r e d by BROOKS INSTRUMENTS I)1VISION of E m e r s o n Electric Co. Designated the Brooks Model 4801 B a t c h counter, this i n s t r u m e n t has a m a x i n m m pulse rate of 600 e o u n t s / m i n u t e . ( B u l l e t i n DS-4801, Brooks I n s t r u m e n t Division, E m e r s o n Electric Co., Hatfield, Pa., 19440.) LACH-~T CHEMICALS INCORPORATED has e x p a n d e d t h e i r listing of p u r e chemicals, l a b o r a t o r y aids a n d testing services. T h e i r Catalog No. 7 lists chemicals alphabetically, a n d again, by class of compound, usually according to ascending carbon content. Facilities f o r new gas chromat o g r a p h y analyses a n d o t h e r analytical services a n d labo r a t o r y aids, are shown following the a l p h a b e t i c a l listing. Cross-indexing of c o m p o u n d s by the most commonly used s y n o n y m s is continued. (20200 A s h l a n d Ave., Chicago Heights, Ill. 60411.)

I)URKEE F a c t o r s Fo(ms has p r e p a r e d a guide to bulk h a n d l i n g of s h o r t e n i n g and oils, f r o m the p l a n n i n g of such facilities to t h e i r maintenance. A n a d d i t i o n a l b r o c h u r e details the technical a n d p e r f o r m a n c e characteristics of high stability oils p r o d u c e d t h r o u g h D u r k e e ' s new F r a c tional Crystallization process. A new p r o d u c t sheet outlines the applications, a d v a n t a g e s a n d other details of D u r k e e ' s S a t i n a coating b u t t e r , which is designed specifically f o r use in pastel coatings. ( D u r k e e h i d u s t r i a l Foods Division, 2333 L o g a n Blvd., Chicago, Ill. 60647.) ALDRICH CHEMICAL COMPANY, I x c . , has p u b l i s h e d its most comprehensive catalog, a d d i n g a b o u t 1,500 new listings for a total of a h n o s t 9,000 different chemicals. These chemicals are in stock a n d available for immediate shipnient. The new listings include chenlieals listed t h r o u g h KARDINDEX S E T No. 105, dated S e p t e m b e r 20, 1966. ( A l d r i c h Chemical Conipany, Inc., 2371 N. 30th St., Milwaukee, Wis. 53210.) \*ARIAN ANALYTICAL INSTRUMENT DIVISION is offering a new mass s p e c t r o m e t e r / g a s c h r o m a t o g r a p h interface. The V-5500 M S / G C Accessory t r a n s f e r s in real time, organic materials in gas c h r o m a t o g r a p h i c effluents f r o m the GC flow stream to the source of a nmss s p e c t r o m e t e r while a t the same time p r e v e n t i n g a n y a p p r e c i a b l e flow of c a r r i e r g'as into the mass spectrometer. (611 H a n s e n W a y , P a l o Alto, Calif. 94303.)

HYD&OLYSIS OF PHOSPHOLIPIDS AND GLYCERIDES BY RAT-LIVrR

PREPARATIONS. M. Waite and L. L. M. van Deenen (Dept. of Biochem., Lab. of Org. Chem., The State Univ., Utrecht, The Netherlands). Biochim. Biophys. Acta 137, 498-517 (1967).

tg

DALLAS TEXARKANA FORT WORTH MIDLAND HOUSTON BEAUMONT

(Continued on page 524A) a. a.,L o~L CHE~,~S~S' SOC., Oe,oBER i967 (VoL. 44)

523A

A B S T R A C T S : B I O C H E M I S T R Y AND N U T R I T I O N (Continued from page 523A) Rat-liver honmgenates were found to hydrolyze phospholipids, giving rise to both the 1-acyl and 2-acyl lysoderivatives. Subcellular fractionation of the homogenate separated the phospho]ipase A~ (specific for the 1-aeyl ester), the phospholipase A~ (specific for the 2-acyl ester) and the lysophospholipase(s) to a large extent. The phospholipase A~ was found to be located mainly ill the mierosomes, the phospholipase A._, in the nlitochondria and the lysophospholipase(s) in the soluble fra(> tion. Lipase activity, determined using sonicates of a triglyceride and phosphatidyl ethanolamine mixture, was found to be associated with the particulate fractions, mainly the mitochondrial fraction. The triglyceride on hydrolysis gave rise to free f a t t y and diglyceride. SURFACE PROPERTIES AND H Y S T E R E S I S OF DIPALlUITOYLLECITHIN IN RELATION TO T H E ALVEOLAR L I N I N G LAYER. .~,[. Galdston

and D. O. Shah (Dept. of Med. New York Univ. School of Medicine, New York). Biochim. Biophys. Acta 137, 255-63 (1967). Investigations using surface pressure and surface potential measurements and observations of changes in the fihn state were undertaken to account for the factors which determine the surface properties and hysteresis of L-a-dipalmitoyllecithin fihns which have been reported to resenlble lung extract fihns and to be mainly responsible for the capacity of the alveolar lining to maintain lung stability. When a film of L-a-dipalmitoylleeithin is compressed intermittently to an area short of fihn collapse, hysteresis increases with the extent of fihn compression and it is associated with parallel changes in surface pressure and surface potential and is reproducible in successive cycles. Lecithin fihns are in the liquid state below surface pressure of 35 dynes/era, in the gel state between 35 and 40 dynes/era and in the solid state above 40 dynes/cnl. When compression is continued beyond fihn collapse (about 44 d y n e s / c m ) , surface pressure rises sharply unaccompanied by a parallel increase in surface potential. Here hysteresis results from fihn solidification and loss of material from the surface and probable entrance of saline solution into gaps in the fihn during expansion. I f the alveolar lining layer responds to eonlpression and expansion during respiration as a L-a-dipahnitoylleeithin film responds ill a fihn balance, then it's stable during expiration only when surface tension is above 32-28 dynes/era. Below this surface tension level, the lining layer would collapse and the nmterial displaced would have to return to the alveolar surface or be replenished during inspiration to m a i n t a i n a tmalthy alveolar lining layer. T H E E F F E C T OF C~s UNSATURATED F A T T Y ACIDS ON M E T H A N E PRODUCTION I N VITRO BY 5IIXED R U M E N BACTERIA. D , I . Demeyer

and H. K. Henderickx (Dept. of Nutr., Faculty Agr. Sci., Ghent, Belgium). Biochim. Biophys. Acta 137, 484-497 (1967). C~ u n s a t u r a t e d f a t t y acids inhibit methane production frmn various substrates by mixed rumen bacteria in vitro. This inhibition is not due to a competition for available hydrogen, b u t to a toxic effect towards methanogenic bacteria. Cisu n s a t u r a t e d f a t t y acids are much more active than trans isomers or saturated f a t t y acids. W i t h cis isomers, toxicity increased with the number of double bonds. Various esters were inactive, indicating the importance of the free carboxyl group. These findings can be explained by assuming a physiochemical mechanism of inhibition. W i t h pyruvate as substrate, inhibition of methane production is accoulpanied by stimulation of propionic acid production. T H E CONTROL OF F A T T Y ACID ESTERIFICATION IN A SUBCELLULAR

PREPARATION OF RAT ADIPOSE TISSUE. Aubie Angel and D . A. K .

Roncarl (McGill University Medical Clinic, Montreal General Hospital, Montreal, Quebec, Canada). Biochim. Biophys. Acta 137, 464-474 (1967). A cell-free preparation of rat adipose tissue fortified with A T P , CoASH, Mg 2§ F - and GSH was used to determine the kinetics of f a t t y acid esterification to L-a-glycerophosphate. The principal product was triglyceride. tleducing the incubation temperature to 20C permitted accurate measurement of initial velocity. The Km for a-glycerophosphate was found to be 8.6 9 10 -4 (pH 7.0, 20C) and t h a t for palmitate 1.68-10-4 M (pH 7.0, 20C). The activity of esterifying enzymes was reduced with fasting. Refeeding augmented esterification in the cell-free system to levels greater than control probably through the mechanism of enzyme induction. Adipose tissue is potentially capable of esterifying cholesterol since addition of cholesterol to the enzyme preparation resulted in incorporation of pahnitic aeid-l-~'C into cholesterol ester. A B S O R P T I O N AND I%IETABGLISI%I OF L E C I T H I N AND L Y S O L E C I T H I N

BY INTESTINAL SLICES. Ake Nilsson and Bengt Borgstrom (Dept. of Physiol. Cheul., Univ. of Lund, Lund, Sweden). s Eiophys. Acta 137, 240 54 (1967). Intestinal absorp-

524A

tion and metabolism of lysoleeithin and lecithin has been studied using hamster amid rat intestinal slices and inverted sacs, and (eholine-Me-:~H - ( a e y l y H ) lysolecithin and lecithin as substrates. Lysoleeithin is well absorbed and metabolized mainly to lecithin. Tile uptake and mnetabolism of lysolecithin is not influenced by the presence of sodimu taurodeoxycholate in the medium. The absorption and metabolism of lysoleeithin is the same in sIices from all levels of the small intestine except the most distal part. No definite evidence could be obtained t h a t lecithin is absorbed intact. LIPASE IN T H E RAT. ,l. R. Carter, .Jr. (Lab. of Metabolism, Nat. Heart Inst., Nat. Inst. of Health, Bethesda, Md. USA). Biochim. Biophys. Acta 137, 147-56 (1967). Whole homogenates of rat liver are capable of hydrolyzing artificial triglyceride emulsions in ritro at a pH of 7.4. The products of tile reaction are primarily free f a t t y acids and glyeeroh The lipolytie activity is progressively inactivated after 30 rain at 37C. Hydrolysis is inhibited by divalent cations. The lipolytic activity studied differs ill several respects from previously described intraeellular lipases. Direct transesterifieation of triglyeeride f a t t y acids to new complex lipids was not observed. The addition of A T P and COA pron/oted incorporation of the hydrolyzed triglyceride f a t t y acids into phospholipids; under the conditions of tim experiment significant reincorporation into new triglyeerides was not seen. Microsomes, mitochondria and soluble fraction all contain some "triglyeeride lipase'" activity with the highest specific activity in the microsonles. Partial glycerides are hydrolyzed more rapidly than triglycerides. Maximal rates of hydrolysis for mono-, di- and triolein are given for each of the subcellular fractions. In tlme :soluble fraction, triglyceride and monoglyceride lipases are separable on the basis of heat inactivation and D F P inhibition. Intraeellular hydrolysis is probably tile first step ill the lnetabolism of triglyeerides taken up by the liver. The exact site at which this occurs is not certain. HEPATIC

THE

PROPERTIES

OF T H E LIPOPROTEIN L I PA SE S

OF RAT J:IEART~

LUNG AND ADIPOSE TISSUE. Margaret Brady and Joan A. Higgins (Bioehenl. Dept. Univ. of Liverpool, Liverpool, Great Britain). Biochim. Biophys. Acta 137, 140-6 (1967). A study of time properties of lipoprotein lipases of rat heart, lung and adipose tissue has been made, using enzymes prepared by extraction of acetone powders with 0.025 M NH~OH, and by induction fronl the fresh tissue with heparin. Lipase activity was not released from fresh heart tissue by heparin, although activity was found ill extracts of acetone powders of the tissue. The enzyme preparations have similar " K ~ " values in the range 4.28 • 10 -~- 4.8 • 10 -4 M, and pH optima in the range 8.2-8.4. However, differences were found in the "activation energies," the enzylne from heart lmving a value of 13.5 keal compared with 19.1 and 18.9 keal for those from adipose tissue and lung. S E X DIFFERENCES IN* T H E I~IETABOLISM ON P H O S P H A T I D Y L CHO-

LINES IN RAT LIVER. R . L. Lylnan, J. Tinoco, P. Bouehard, G. Sheehan, R. Ostwald and P. Miljanich (Dept. of Nutritional Sciences, Univ. of Calif., Berkeley, U S A ) . Biochim. Biophys. Acta 137, 107-114 (1967). Mature male and female rats were injected intraperitoneally with tracer doses of methionine-Me~'C, then were killed 20, 40, 60 and 120 rain afterwards. Liver phosphatides from both sexes were separated by thin-layer chronlatography and the phosphatldyleholine (PC) divided into 3 subfractions. Determinations of f a t t y acid composition and measurenlents of radioactivity of the phosphatide fractions were made. The f a t t y acid composition of the fastest-moving PC subfraction resembled that of the phosphatidylethanolamine fraction and had a higher proportion of stearic and arachidonic acids t h a n did the other slower moving fractions. Female rats had a higher proportion of stearic and arachidonic acids in their f a s t moving PC than did males and the specific activity of this fraction was also higher in females. The results indicated that methylation of phosphatidylethanolamine produced PC having a high proportion of stearic and arachldonic acids. The sex difference in these f a t t y acids in the liver PC appeared to have resulted f r m n the higher rate of PC synthesis via methylation in female rats than in males. CONTROLLING EFFECTS OF A T P , Ma e+ aND CTP IN THE BIOSYNTHESIS OF LIPIDS. J. F. Erbland, M. Brossard and G. V. Marinetti (Dept. of Biochem., School of Med. and Dentistry, The Univ. of Rochester, Rochester, N. Y.). Biochim. Biophys. Acta 137, 23-32 (1967). The main ainl of this work was to test the controlling effects of essential cofactors on lipid biosynthesis. The effects of A T P , Mg ~*, CTP, CMP, phosphoryl choline and cytidine diphosphate choline on the incorporation of glyceral-'C into lipids of rat-liver holnogenates have been a

AM, OIL CItEMISTS' SOC., OCTOBER 1 9 6 7 (u

44)

ABSTRACTS: B I O C H E M I S T R Y AND N U T R I T I O N studied. A T P proniotes glycerol-~'C incorporation into all lipids and this incorporation is preferentially directed into phosphatidyl ethanolamine and lecithin when Mg 2§ is added. The effect of CTP, in the presence of A T P and Mg'-'-, is concentration dependent; 0.001 M CTP does not affect phosphatidyl ethanolamine and lecithin labeling but stimulates incorporation into diglyeerides and triglycerides, whereas 0.01 M CTP supresses phosphatidyl ethanolaniine and lecithin labeling an,l promotes incorporation into diglycerides and triglycerides. The effects of 0.01 M CTP are Mg2+-dependent. CMP has effects sinfilar to those of CTP. Phosphoryl choline and cytidinc diphosphate choline inhibit the labeling of phosphatidyl ethanolamine and lecithin in the rat-liver system studied. RETROCONVElgSION OF POLYUNSATURATED FATTY ACIDS BY PARTIAL DEGRADATION AND HYDROGENATION. H.

IN

VIV0

Schlenk, Joanne L. Gellerman and D. M. Sand (Hormel Inst., Austin, Minn.). Biochim. Biophys. Acta 137, 420-6 (1967). 4,7,10,13,16Docosapentaenoate, randomly labelled with ~C, was given to f a t deficient rats. After 10 hours about 13% of the radioactivity of all liver f a t t y acids was located in 5,8,11,14eicosatetraenoie (arachidonic) acid. Degradation of the arachidonic acid by decarboxylation and by ozonization showed that randonI labelling has been maintained in the course ~f the conversion. Therefore, the reetroconversion of the pentaenoie into the tertaenoic acid must imply, besides degradation by not more than two carbon atoms, the biohydrogenation of the double bond closest to the earboxy] group. T H E EFFECT OF TUBE FEEDING OF GLUCOSE CORN OIL ON ADIPOSt: T I S S U E LIPOPROTEIN L I P A S E ACTIVITY AND UPTAKE 0 P llC_ LABELED P A L M I T I C ACID O:P CHYLE TBIGLYCERIDES IN VITRO,

N. Pokrajae and W. J. Lossow (Dept. of Physiol. Univ. of Calif. Berkeley, Calif.). Biochim. Biophys. Aeta 137, 291-5 (1967). The feeding of pure glucose or fat loads to fasted rats increased both the amount of ]ipoprotein lipase released from adipose tissue by heparin and the uptake i~t ritro of the "~C of triglycerides of very low-density chyle lipop,'otcins by that tissue. I n both instances feeding glucose had a greater effect than feeding fat. Feeding a combination of glucose and f a t had an effect sinlilar to feeding glucose alone. S I T E SPECI~'ICITY OF BOVINE ADRENAL HYDROGENASE AND ~5-3-KETOSTEROID

3~-HYDROXYSTEROID DEISOMER~SE. Sarah G.

Cheatum, A. W. Douville and J. C. Warren (Univ. of Kansas School of Med., Kansas City, Kan.). Bioehi~. Biophys. Acta 137, 172-8 (1967). The 3fl-hydroxysteroid dehydrogenase and As-3-ketosteroid isomerase activities from the microsomal fraction of bovine adrenal cortex have been studied with emphasis on the site specificity for dehydrogenation and isomerization of the natural C~ and Cm steroid substrates. The data indicate a distinct isomerase site each of which is capable of utilizing both C19 and C~ substrates as shown by the following parameters: activity ratios during purification, pH curves, inactivation rates, and the kinetics of equimolar nfixtures. These observations are sinlilar to results with the same activities front bovine corpora lutea. I N H I B I T I O N OF HE P AT IC STEROL OXIDATION BY CHOLANIC

(BILE)

ACIDS AND THEIR CONJUGATES. P. D. G. Dean and M. W. Whitehouse (Dept. of Biochem., Univ. of Oxford, Oxford, G,'. Brit.). Biochim. Biophys. Acta 137, 328-334 (1967). Evidence is presented that conjugated bile acids (50-200 nM) inhibit each of the following steps in sterol oxidation in ritro by ratand mouse-liver preparations: (i) Transformation of cholesterol to trihydroxycoprostane. Oxidation of 26-hydroxycholesterol to the corresponding C~-carboxylic acid. Catabolism of 3~-hydroxycholest-5-en-26-olc acid to 3fl-hydroxy-chol-5-en-24oic acid and propionate. These bile salts did not inhibit the oxidation of propionate of an aliphatic analogue of a sterol C~-carboxylic acid, namely 2-methyloctanoate, when added in concentrations smaller or equal to concentrations which inhibit mitochondrial A T P biosynthesis. The results are discussed in relationship to current theories of negative feedback control of hepatic cholesterol oxidation by bile salts in the enterohepatic circulation. I t is suggested that bile salts may exert control at nmltiple sites, rather than at a unique site, in the overall sequence of sterol oxidation and bile acid fornlation. COMPARATIVE STUDIES ON T H E TURNOVER AND FATE OF PLASMA CHOLESTEROL I N T H E CHICKEN. Michihiro Sugano a n d M a s a f u t o

Wada (Lab. Nutr. Chem., Dept. of Food Sci. and Techn., Kyushu Univ. School Agr., Fukuoka, J a p a n ) . Bioehim. Biophys. Acta 137, 315-327 (1967). Differences in the rates of turnover and excretion of p]asnia cholesterol between male and (Continued on page 526A) ,]-. AM. OIL CIIEMISTS' S a c . , OCTOBER 1 9 6 7

(VOL. 4 4 )

Call for Papers for Microwave Symposium The 1968 S y m p o s i u m on .~[icrowave Power, s p o n s o r e d by the h l t e r n a t i o n a l Microwave P o w e r h i s t i t u t e , will be held at the S t a t l e r H i l t o n H o t e l in Boston, Mass., M a r c h 21-23, 1968. The S y m p o s i u m will be concerned with the a p p l i c a t i o n of microwave p o w e r to processes within the food, a g r i c u l t u r a l f o r e s t product, textile, chemical, a n d other industries a n d to a d v a n c e d concepts in scientific a p p a r a t u s a n d p o w e r t r a n s m i s s i o n systems. P a p e r s are being solicited. To he considererl, a b s t r a c t s should be subnlitted not later t h a n J a n u a r y 1, 1963. Abstracts should be a p p r o x i m a t e l y 250 words in le-g'~h a n d should be mailed to : 1968 S y m p o s i u m on Mierowave Power, Box 342, Weston, M a s s a c h u s e t t s 02193.

Canadians Plan First Sessions on Biological Engineering The first C a n a d i a n technical sessions dealing with biochemical e n g i n e e r i n g will be p r e s e n t e d d u r i n g the 17th C a n a d i a n Chemical E n g i n e e r i n g Conference in N i a g a r a Falls, Ontario, Oct. 16-18, 1967. This new f r o n t i e r on chenlieal e n g i n e e r i n g is p a r t i c u l a r l y i n l p o r t a n t to the beverage, food, a n d metallurgical industries. P r o g r e s s in the field will be explored in 11 p a p e r s at the Conference. A n invited lecture, ' : E n g i n e e r i n g P r o b l e m s Associated with the F e r m e n t a t i o n of H y d r o c a r b o n s " will tie given by A. E. H u m p h r e y , U n i v e r s i t y (if P e n n s y l v a n i a . The c u r r e n t a n d f u t u r e needs of C a n a d i a n indust~3~ f o r biochemical engineers will be estimated by M. Moo Young, U n i v e r s i t y of W a t e r l o o , W a t e r l o o , Ont., who a r r a n g e d the Bioehenfical E n g i n e e r i n g sessions. I n a d d i t i o n to these sessions on Biochemical E n g i n e e r i n g , the Conference will include a total of 116 o t h e r p a p e r s covering the entire r a n g e in chenlical engineering. P r o g r a m details can be o b t a i n e d f r o m The C a n a d i a n Society f o r Chemical E n g i n e e r i n g , 151 S l a t e r Street, Ottawa 4, Ontario, Canada.

Found-One Author! The writer of "The Chromatogra.pher's Lament," published in, the J~dy J A O C S , has bee~ .found, and all of those who~ grimly or good-n.aturedly, identified with him in his sentiments~ now know whom to thank for putting their own reflections into verse. The a u t h o / s letter follows: Dear Sir: I was both s u r p r i s e d a n d pleased to find m y poeni " T h e C h r o m a t o g r a p h e r ' s L a m e n t " in the J u l y issue of y o u r j o u r n a l . However, siuce it is signed as " A u t h o r U n k n o w n , " I felt p r o m p t e d to write you s o m e t h i n g as to its origin. These verses were first w r i t t e n in May, 1966, while I was still employed b y Shell D e v e l o p m e n t Co., H o u s t o n , Texas. A t t h a t time, I was w o r k i n g on a " S p e c i a l A n a l y t i c a l P r o b l e m s " p r o j e c t u n d e r Dr. R. D. Schwartz, now with U n i t e d Gas Corp., S h r e v e p o r t , La., with whoni I s p e n t m a n y p l e a s a n t hours p r o b i n g the intracacies of' c a p i l l a r y eolunln GC. I am c u r r e n t l y a staff m e m b e r of the C h e m i s t r y Dep a r t n i e n t , University of H o u s t o n , where I am still engaged in GC research raider P r o f . A l b e r t Zlatkis. T h a n k vou a g a i n f o r p r i n t i n g m y verse m~d f o r y o u r kind wordsI~ODERIC G . ~ [ A T H E W S Research A s s i s t a n t

525A

ABSTRACTS:

BIOCHEMISTRY

( C o n t i n u e d f r o m p a g e 525A) l a y i n g chickens have been s t u d i e d u s i n g cholesterol-4-uC in lipoproteins as tracer substance. I n the plasnla of l a y i n g hens, free cholesterol was removed f r o m the blood s t r e a m more r a p i d l y t h a n in male birds. The half-life for the l a y i n g hen was 24.1-33.1 hours, a n d t h a t for the male b i r d s was 45.5-58.2 hours. The l a y i n g also i n c o r p o r a t e d considerable a m o u n t s (up to 5 4 % of the dose) of the cholesterol-4-~*C into e g g yolk, and the excreted r a d i o a c t i v i t y was twice t h a t observed in the males. The body pools of cholesterol w h i c h were most r a p i d l y equilibrated with p l a s m a cholesterol a p p e a r e d to be of similar m a g n i t u d e in both the l a y i n g hen a n d the male bird. The differences between male a n d f e m a l e b i r d s a p p e a r e d to be g r e a t e r t h a n could be accounted for on the basis of cholesterol t r a n s p o r t into the e g g yolks of the l a y i n g hen. The h o r m o n a l action of e s t r o g e n s on cholesterol t r a n s p o r t m a y have been a c o n t r i b u t i n g f a c t o r in these p h e n o m e n a . SUBCELLULAR SITES INVOLVED IN LIPID SYNTHESIS IN SACCHAROMYCES CEREVISIAE. H. P. Klein, Carol M. V o l k m a n n a n d M. A. Leafier. (Exobiol. Die., A m e s Res. Center, N A S A , Moffett Field, C a l i f o r n i a 94034). J. Bacteriol. 94, 61-65 (1967). The crude ribosomal f r a c t i o n of Saccharomyces cerevis~iae was s e p a r a t e d into l i g h t a n d h e a v y f r a c t i o n s by c e n t r i f u g a t i o n . The l i g h t f r a c t i o n contained the f a t t y acid s y n t h e t a s e activity, the h e a v y f r a c t i o n the acetyl-Coenzyme A s y n t h e t a s e , f a t t y acid d e s a t u r a s e a n d squalene oxidocylase activities. The a u t h o r s conclude t h a t the f a t t y acid s y n t h e t a s e particles are freely s u s p e n d e d ; t h a t the f a t t y acid d e s a t u r a s e s y s t e m is a lipoprotein conlplex b o u n d to the r i b o s o m e s ; t h a t the acetyl-CoA s y n t h e t a s e a n d squalene oxidoeyelase are att a c h e d to or p a r t of the i n t e r n a l m e m b r a n e systems.

9 D r y i n g Oils and P a i n t s A

CONTRIBUTION

TO

THE

STUDY

OF

THE

CREATION

OF

CONJUGATED

SYSTEMS IN FATS BY INDIRECT DEHYDROGENATION. J. Denise (Univ. of B e s a n c o n ) . Oleagine~x 2 2 ( 6 ) , 389-394 (1967). W h e n safflowerseed oil is reacted with t e r t i a r y b u t y l hypochlorite, t h e n d e h y d r o h a l o g e n i s e d , dieuic, trienic a n d t e t r a e n i c conj u g a t e d s y s t e m s are obtained. B e s t results are obtained when the q u a n t i t y of t e r t i a r y b u t y l hypochlorite is equivalent to 0.7 to 1.0 equivalent per u n s a t u r a t e d f a t t y acid, the reaction p e r f o r m e d at 20C a n d p r o t e c t e d f r o m light. L i m e plus heat is used to d e h y d r o c h l o r i n a t e the c h l o r i n a t e d oil. The end p r o d u c t contains more t h a n 37% of c o n j u g a t e d acids. THIN LAYER CftROMATOGRAPHIC IDENTIFICATION OF FATTY ACIDS OF 0IL COMPONENTS Ol~ ALKYD RESINS AND PAINTS. M. F. P. L o p e s de Castro ( N a t . Lab. of Civil E n g . , P o r t u g a l ) . Paint Technol. 31, No. 6, 12-16 (1967). A m e t h o d h a s been developed for the identification of oil c o m p o n e n t s of alkyd resins and p a i n t s b a s e d on the t h i n - l a y e r c h r o m a t o g r a p h y of their f a t t y acids on silieic acid a n d p l a s t e r of P a r i s . The s p o t s are made visible with a 70% aqueous solution of s u l f u r i c acid s a t u r a t e d with p o t a s s i u m dichromate. A f t e r s p r a y i n g the plates are h e a t e d to 180C to visualize the spots. COLOUR STABILITY OF FILMS FROI~[ CONVENTIONAL AND EMULSION PAINTS CONTAINING LINSEED OIL. G. E. MeManis, L. E. Gast a n d J. C. Cowan. J. Paint Tech. 38, No. 503, 740-5 (1966). F i h n s of white enmlsion p a i n t s p r e p a r e d f r o m 5 bodied linseed oils, senli-gloss a n d flat oil p a i n t s a n d acrylic latex p a i n t s have been aged at three different indoor sites for 18 m o n t h s and the degree of yellowing m e a s u r e d . F i l m s f r o m the linseed emulsion p a i n t s showed b e t t e r colour s t a b i l i t y t h a n those f r o m the oll p a i n t s a n d were s o m e t i m e s as good as the latex paints. Addition of a wide v a r i e t y of chemicals affected the yellowing rate b u t none gave an overall i m p r o v e m e n t u n d e r all couditions. T h u s , a t r i a l d e h y d e oil (triglyceride of azela-aldehydic a c i d ) , 5 - 1 0 % , increased the yellowing of the oil p a i n t s b u t at 1 % reduced t h a t of the enlulsion paints. A c e t a l d e h y d e , acetone a n d acetonitrile i m p r o v e d the oil p a i n t s , e t h a n o l a m i n e s g e n e r a l l y i n c r e a s e d yellowing, a n d aldehydes and ketones had variable effects, tRey. C u r r e n t Lit. P a i n t Allied Ind. No. 300. Established 1904

HOUSTON LABORATORIES Analytical and Consulting Chemists 311 Chenevert Street P.O. Box 132 H o u s t o n , Texas 77001 CA 2-1319

526A

AND NUTRITION

9 Detergents DETERGENT COMPOSITION. ]~. H. Chaffee a n d L. E. Meyer ( P r o c t e r & Gamble Co.). U.S. 3,324,038. A quick-dissolving detergent tablet consists essentially of a core of compressed d e t e r g e n t particles inside a s u b s t a n t i a l l y u n i f o r m coating. Tile c o a t i n g m a t e r i a l is either a solidifed m e l t or a dried aqueous m i x t u r e of u r e a a n d either a polyethylene glycol or a water soluble s u r f a c t a n t , with a ratio of u r e a to s u r f a c t a n t of f r o m 1:1 to 9:1, a n d a ratio of w a t e r to u r e a + s u r f a e t a n t f r o m 3:1 to 1:2.5. The a q u e o u s m i x t u r e is dried while p r e s e n t on the s u r f a c e of the d e t e r g e n t tablet in an a m o u n t to give a c o a t i n g of f r o m a b o u t 0.005 to a b o u t 0.1 g r a m s per square centimeter of tablet s u r f a c e on an a n h y d r o u s basis.

PROCESS FOR PRODUCTION OF SODIU.~ PERBORATE. W. K e g e l a r t (Solvay & Cie). U.S. 3,311,4~6. A n i m p r o v e m e n t is claimed in the process for the m a n u f a c t u r e of s o d i u m p e r b o r a t e stabilized by an alkaline e a r t h m e t a l silicate by crystallization of a supers a t u r a t e d solution of sodium p e r b o r a t e p r o d u c e d by c o n t a c t i n g s o d i u m m e t a b o r a t e and h y d r o g e n peroxide a n d ill which the ratio between the weight of sodium p e r b o r a t e p r e s e n t a n d t h a t which would n o r m a l l y be soluble at 20C is b e t w e e n 4 a n d 12. The i m p r o v e m e n t consists in m i x i n g tile d a m p crystallized perborate obtained by s e p a r a t i o n f r o m the reaction m e d i u m and which contains, besides water of crystallization, 4 0 - 6 0 % by wt. of m o t h e r liquor, with 40 to 150% by wt. of dry sodium perborate, and d r y i n g the r e s u l t i n g m i x t u r e in a fluidized bed drier. DETERGENT COMPOSITIONS. G. J. M c E w a n ( M o n s a n t o Co.). U.S. 3,311,563. A d e t e r g e n t composition h a v i n g s y n e r g i s t i c a l l y e n h a n c e d d e t e r g e n c y is claimed, consisting essentially of an alkali m e t a l n m n o hexene dimer a l k y l a r o m a t i c s u l f o n a t e and an alkali m e t a l mono hexene t r i m e r a l k y l a r o m a t i c s u l f o n a t e , in which the alkyl p o r t i o n of tile first m a t e r i a l is s t r a i g h t chain in c h a r a c t e r with b r a n c h i n g on 2 5 - 5 0 % of its alpha C a t o m s and tile alkyl p o r t i o n of the second m a t e r i a l is also s t r a i g h t chain with b r a n c h i n g on 5 - 5 0 % of its a l p h a C atoms. The a m o u n t of the dimer m a t e r i a l is 2 0 - 8 0 % by wt. b a s e d on the total w e i g h t of the d e t e r g e n t mixture. DETERGENT COMPOSITION. E. W. L u n g a n d H. W. McCune ( P r o c t e r & Gamble Co.). U.S. 3,313,734. An aqueous deterg e n t composition especially a d a p t e d for use in s h a m p o o i n g hair consists essentially of (a) 0.1 to 7.0% of a watersoluble p o l y m e r h a v i n g a molecular w e i g h t f r o m a b o u t 1,000 to a b o u t 5,000,000, at least 3 0 % of whose nloleeular s t r u c t u r e is composed of m o n o m e r i e u n i t s consisting of q u a t e r n i z e d vinylimidazole, q u a t e r n i z e d d i m e t h y l a m i n o e t h y l m e t h a c r y l a t e , q u a t e r n i z e d d i e t h y l a m i n o e t h y l m e t h a e r y l a t e or q u a t e r n i z e d pd i m e t h y l a m i n o m e t h y l s t y r e n e , the balance of the p o l y m e r b e i n g conlposed of m o n o m e r i c u n i t s derived f r o m m o n o e t h y l e n i c a l l y u n s a t u r a t e d g r o u p s ; (b) 0.1 to 10% of a water-soluble salt of a h i g h e r f a t t y acid or an anionic o r g a n i c s u l f u r i c reaction p r o d u c t c o n t a i n i n g an alkyl g r o u p with 8 to 20 C a t o m s a n d a sulfuric acid or sulfonic acid ester r a d i c a l ; (c) 5 to 2 0 % of certain n i t r o g e n c o n t a i n i n g polar nonionic or a m p h o l y t l c d e t e r g e n t s ; a n d the balance (d) water. The w e i g h t ratio of c o m p o n e n t ( b ) to c o m p o n e n t (a) should be no g r e a t e r t h a n a b o u t 10 to 1. SHAMPOO COMPOSITION. H. W. McCune ( P r o c t e r & Gamble Co.). U.S. 3,313,735. A s h a m p o o composition is claimed, cons i s t i n g essentially of (1) 10-30% of a water-soluble d e t e r g e n t salt of organic sulfuric reaction p r o d u c t s c o n t a i n i n g a n alkyl g r o u p with 8 to 18 C a t o m s a n d a sulfonic acid or sulfuric acid ester radical, a n d acyl s a r c o s i n a t e s with f r o m 10 to 18 C a t o m s in the acyl g r o u p ; (2) 0.2 to 5% of at least one p h o s p h o n o c o m p o u n d h a v i n g the f o r m u l a IRN(CH~.POaMz)_~, or the f o r m u l a RC(X)(Z)PO:~M_~, where R is an alkyl radical with 6 to 18 C atoms, X is either H or CHa, Z is either OH, COOM or PO.~M.~ a n d M can be H, N a , K , NH~, mono-, di- or t r i e t h a n o l a m m o n i u m ; (3) the balance is s u b s t a n t i a l l y water. The s h a m p o o composition h a s a p H in the r a n g e between 6.0 and 10.0. D~TERGENT COMPOSITIONS. ]:I. M. P r i e s t l e y a n d J. H. W i l s o n (Lever B r o t h e r s Co.). U.S. 3,317,430. A n i m p r o v e d d e t e r g e n t composition comprises an organic s y n t h e t i c d e t e r g e n t selected f r o m the g r o u p consisting of anionic non-soap d e t e r g e n t s a n d nonlonic d e t e r g e n t s and, as a f o a m stabilizer, an a m i n e oxide selected f r o m the g r o u p consisting of N , N - b i s ( 2 - h y d r o x y e t h y l ) dodecylamine oxide a n d N - b e n z y l - N - m e t h y l - d o d e c y l a m i n e oxide, the a m i n e oxide b e i n g p r e s e n t at a level r a n g i n g f r o m 2 to 100% by wt. of the s y n t h e t i c detergent.

a.A.~I. OIL CI{EMISTS' SOC., OCTOBER 1967 (VoI. 44)

ABSTRACTS: DETERGENTS SOME

NOTES

ON AMINE

OXIDES

AND AMINO

9 N e w Members Active

POLYCARBOXYLIC

ACIDS. A. Coeur and J. Alary (Univ. of Grenoble, France). Tenside 4, 65-9 (1967). The sequestering properties of anfino polycarboxylic acids have ]o~g been known aa~(t used to neutralize the undesirable effects due to the presence of alkaline earth and heavy metal salts in aqueous solutions, as well as to stabilize hydrogen peroxide and persalts. These sequestering agents can be oxidized by the hydrogen peroxide, especially at high temperatures. The niechanism of the reaction between hydrogen peroxide and amino polycarboxylic acids is discussed, and the changes in the sequestering properties of these acids, through their transformation into amine oxides, are explained. Methods are given for the preparation of these amine oxides ill both alkaline and acid uiedia, as well as analytical methods for their detection. The decomposition of amine oxides in aqueous solutions is also exanfined. GERMICIDAL DE'I~ERGENT COMPOSITIONS CONTAINING AI~IIDES AND HALOGENATED AI~IIDES OF SULFUR-CONTAINING PHENOL CAR-

Frank Bradley, SeeretalT General, International Society for Fat Research, Ruislip, Middlesex, England Sanmel Cohen, President, Lipo Chenfieals, Inc., New York, N.Y. John Cornelius Friend, Assistant Chief Chemist, Swift & Co., Kankakee, Ill. Lowton L. Gentl3,~, Refinery Superintendent, Cargill, Inc., Des Moines, Iowa. Dale Norman Kinsey, Project Leader, Riviana Foods, Inc., Houston, Texas. Klaus Robert Lange, Research Quartz Co., Primos, Pa.

Associate,

Philadelphia

Geolge David Lee, Gas Chromatographic Specialist, Swift & Co., R & D Center, Chicago, Ill.

BOXYLIC ACIDS. H. C. Stecker. U.S. 3,311,562. A germicidal detergent eoniposition consists essentially of an anionic, cationic, non-ionic or ampholytic surfactant, and about 0.01 to 1.0% by wt. of a sulfur-containing compound having the general formula: R(AH)X~C=ANH--RXb, where: II is a phenyl or naphtbyl group, A is oxygen or sulfur, X is F, C1, Br or I, a is a numeral between 0 and 2 and b is a numeral between 0 and 3.

K. T. Louis, Group Leader, Tap Research & Application Laboratories, CIBA Cheroical & Dye Co., Roms River, N.J.

T H E USE OF FLUORESCENT BRIGHTENERS IN MODERN DETERGENTS, THEIR INCORPORATION AND WHITENESS MEASUREMENT. E, E.

Gray Tillman Maleohn, Instructor, L. S. U. Medical School, New Orleans, La.

Lindermer (Ciba S.p.A., Basel, Switzerland). Riv. Ital. 8ostanze Grasse 44, 79-85 (1967). Current developments are reviewed on the use of fluorescent dyes in detergent products. T H E POSITION 0E THE DETERGENT PROBLEM IN EUROPE. I-t. Spohn (Stmlicht G.m.b.H., Hamburg, Germany). Tenside 4, 74-9 (1967). The current status is reviewed of affairs in 22 European countries with regard to the problem of detergent degradabiIity in water systems. T H E USE OF CATIONIC SURFACTANTS IN INDUSTRY, I . A. Chwala. Tenside 4, 69-74 (1967). A review is given of the various types of cationic surfactants currently available and their industrial uses in road construction and the protec,tion of buildings, in corrosion protection, flotation, leather finishing, in paints and varnishes, in disinfectants, in the preparation of polishes and in other applications. T H E USE OF DETERGENTS IN COMMERCIAL LAUNDRIES. A . L u s e t t i

Harold Ogden Locke, Analytical Che,uist, General Aniline & Fihn Corp., Easton, Pa.

Donald George Manly, Research Manager, Glyeo Chemicals, Williamsport, Pa. Saito Minoru, Technical Director, Jap an Oil and Vitamin Inspection Institute, Minato-ku, Tokyo, Japan. Stephen Edward _Nebraska.

Mitchell,

Kellogg

Company,

Omaha,

Abdel Kader Naggar, President, and Bulk Oils and Draught Surveyor, Alexandria Superintending Co., Alexandria, Egypt, and Philadelphia, Pa. ~oger E. Nelson, Cheufist, Lever Brothers, Co., Edgewater, -N.J. Dale Frances O'Connell Research Chemist, Assistant Laboratory Manager, Stamford Cheufieal Industries, Inc., Staniford, Conn.

(Milan, Italy). Riv. Ital. Sostanze Grasse 44, 86-8 (1967). The technical and economical principles of operation of commercial laundries are reviewed.

Alberto Piaggio, Manager, 01cotee nice, S. A. Callao, Peru

T H E TESTING 0E DETERGENTS AND W A S H I N G PROCESSES BY ~IEANS OF ARTIFICALLY SOILED AND UNSOILED TEST FABRICS.

Francois Pouillaude, Technical Director, Societe Georges Lesieur et Fils, Paris, France

H. Bruschweiler (Empa Co., St. Gallen, Switzerland). Rit:. (1967). Soiled and unsoiled test fabrics can be used for the evaluation of detergents and washing processes. Artifically soiled Empa fabrics and suitable optical measurements enable studies to be carried out on washing and bleaching effects, as well as soil redeposition. Since each type of soil exhibits characteristic washing and bleaching behavior, it is suggested that tests be carried out with several types of artlfically soiled cloths. Mechanical and chemical damage to fabrics can also be evaluated by using unsoiled test fabrics subjected to repeated washings. ItaL Sostanze Grasse. 44, 25-33

STANDARD

PROCEDURES

FOR

TESTING

LAUNDRY

DETERGENTS.

K.

J. Nieuwenhuis

(Inst. for Text. Cleaning, Delft, Netherlands). Riv. Ital. Sosta~ze Grasse 44, 13-24 (1967). The general concepts used in testing detergents for both home and institutional use are discussed in detail, with special reference to : mechanisms of soil and stain removal; effects on cloth, such as shrinkage, discoloration, whiteness maintenance, ash content, chemical damage to fibers and mechanical wear. Standa.rd washing procedures used in testing and nIininmm performance requirements expected of a commercial detergent are given. ACTIVITY OF THE TEST ~IETIcIODS COI~I~IITTEE OF THE S P A N I S H COI~IMITTEEON DETERGENCY. R i v . Ital. Sostanze Grasse 44, 11-2

(1967). The organiza.tlon and activities of the Test Methods Connnittee of the Spanish Committee on Detergency are discussed. I N H I B I T I O N OE HYDROLYSIS OF FATS. ~ . A . Norris and D. P. Grettie (Swift & Co.) U.S. 3,800,524. A process for inhibiting the hydrolysis of fats derived from oil bearing fruits to free fatty acids consists of treating the fats with an aqueous solution of an active chlorine-containing material.

s A~, o,L c ~ . . , ~ s ~ s ' s o o , o o . ~ o . ~ ,0~7 ( v o L 44)

BarIT B. Rein, Market Development Representative, Continental Oil Co., Peterboro, N. M. Donald MacFarland Small, Instructor in Medicine, Boston University School of Medicine, Boston, Mass. Per Sten Stensby, Technical Development Manager, Geigy Chemical Corporation, (Saw Mill River Road) Ardsley, N.Y. Robert Earle Wing, Director, Research and Dcvelopnicnt, Tasty Baking Compank, Philadelphia, Pa. Hani F. Zoumut, Research Chemist, Simoniz Co., Division of Morton International, Woodstock, Ill. Individual Associate

Bir Bal Sharnm, Chief Chemist, Britania Lard Refining Co., Ltd., Slough, Bucka., U. K. Active

Junior

Suhadi Hardjo, Graduate Student, Department os Food Science & Technology, University of California, Davis, Calif. Paul Cornell Taylor, Bayonne, N. J.

Food

(Tech.),

Corn

Products,

John Cheairs Porter, Manager Detergent Processes, Engineering Sales Department, Monsanto Co., St. Louis, Mo.

527A