ABSTRACTS...

' R. A. REINERS, Editor

ABSTRACTORS: Lenore Petschaft Africk, R. R. Allen, S. S. Chang, Sini'tiro Kawamura, F. A. Kummerow, Louise R. Morrow, and E. G. Perkins

9 Fats

and

Oils

is studied in relation to the eolorimetrie deternfination of weak organic acids in alkaline solution. Certain organic solvents are classified according to wave length eharaeteristie and intensity.

CHROMATOGRAPHIC SEPARATION OF FATTY ACIDS BASED ON CttLORO,PHENACYL ESTERS. A. C. Kibriek and S. J. Skupp (Biochemistry Section, L a b o r a t o r y Service, New York V e t e r a n s A d m i n i s t r a t i o n Hospital, New York, N. Y.). J. Anal. Chem. 31, 2057-60 (1959). 4'-BroIno-2-chloroacetophenone has been synthesized f r o m aeetyl chloride and monochlorobenzene. E s t e r s of deeanoie, laurie, myristie, pahuitic, stearic, oleic, linoleic, and linolenie acids have been p r e p a r e d with this reagent, and melting points and absorptivities at 257 ni/~ are reported. The separation of the eight f a t t y acid esters by c h r o m a t o g r a p h y on a column of polyethylene and celite and chillon with various proportions of alcohol are presented.

VAPOR PI~ESSURES ON PATTY OIL SOLUTIONS. Kgzuhito Kusano. Yzd~agal:u ( J . J a p a n Oil C~hemists ' See.) 8, 8-14 (1959). The vapor pressures ( P ) were measured for solutions of soybean oil in n-hexane, benzene, or CC1, at various concentrations at 20 50 ~ (at intervals of 5~ The results showed t h a t there were negative deviations f r o m the values expected f r o m the Raoult rule on ideal solutions chiefly owing to tile differences of molecular volume of soybean oil and t h a t of the solvent (the latter being 1/7 to 1 / 1 0 ) . There were s t r a i g h t line relations between log P and 1 / T , where T was absolute temperature.

DETERMINATIOig OP HYDI~OXYL VALUl~ OF ALCOHOLS BY NEARINFIgARED SPECTROSCOPY. R. O. Crisler and A. M. Burrill (The P r o c t e r & Gamble Co., Cincinnati 31, Ohio). Anal. Chem. 31, 2055-2057 (1959). The hydroxyl-stretching overtone band at 1.4 microns in the n e a r - i n f r a r e d region is used to determine hydroxyl values of aliphatie alcohols. Favorable results are indicated in comparison with the acetic anhydride-pyridine method. Tile method allow.s differentiation of hydroxyl types. EVALUATION OF A COMMERCIAL ALKYL ARYL SULFONAT~ DETERGENT AS A COLUMN PACKING lot)R GAS CHI~O~M'Aq?OGI~APttY. D. ]5[. Desty and C. L. A. H a r b o u r n (The British Petroleum Co., Ltd., Sunbury-on-Thames, Middlesex, E n g l a n d ) . Anal. Chem. 31, ]965-1970 (1959). A solid anionic household detergent cont a i n i n g a b o u t 17% of an alkyl aryl s u l f o n a t e has wide application, especially f o r analysis at high operating tenlperatures. (}AS UHR.OMATOGRAPttY~ GUIDE TO BLOTTEREXTRACTION PROCESSES. (}. W. W a r r e n .tad R. R. Y a r b o r o u g h (Union Carbide ChemieMs Co., South Charleston, W. V a . ) . Ind. Eng. Chem. 51, 1475-6 (1959). Previous investigators have compared gas chrom a t o g r a p h i c separations to those obtained by conventional distillations. Gas c h r o m a t o g r a p h i c separations c~nl be correlated only with extractive distillation separations. Tile ratio of partition coefficients obtained f r o m the chromatographic data is eompared to relative voh~tiliti~ obtained from equilibrium still data. INFLUENCE O?0' AC'IDS AND BASES ON TIIE EF~'IC'IENCY OP INFEIBITORS. K. U. I n g o l d and I. E. P u d d i n g t m i (Division of Applied Chemistry, N a t i o n a l Research Council, Ottawa, C a n a d a ) . Ind. Enq. Chem. 51, 1319-24 (1959). The en~tioxidant efficiency of 2,4-dimethylaniline in white mineral oil can be iuereased by addition of the oil-soluble bases N,N-dimethylaniline and benzylamine. There is a synergistic effect between the inhibitors 1-naphthol and 2,4-dimethylaniline and N-phenyl-2-naphthylamine, the induction period for the mixed inhibitors being greater than the stun of tile two i~dividual induction periods "~t the same concentration. These two w n e r g i s t i c effects suggest new ways by which the 'n~tioxidant efficiency of other inhibitors aright be improved. MAS,N SPEC:TROME'I'RIC ANALYSIS. AROMATIC ACIDS AND E:STEI~S. F. W. McLafferty "rod R. S. GoMke. (Spectroscopy L a b o r a t o r y , The Dew Cheniical Co., Midland, Mich.). Anal. Chem. 31, 2076-82 (1959). Correlation of the spectra of 50 aromatic acids and esters shows usefulness of the m a s s spectrometer in identification, structure determination, and analysis. A summ a r y of some common m a j o r ions facilitates molecular structure determination. POLAROGRAPHIC DETEUMINATION 010 ALIPI~ATIO ALDEHYDES .aND !KETONES AS IM]NES. M. E. Hall (The Chemstrand Corp., Deca.tur, Alabama.). Anal. Chem. 31, ~007-2009 (1959). Polarog r a p h i c methods are used to determine aldehydes and ketones as imines. Diamines react with the earbonyl g r o u p to f o r m imines. The imino g r o u p is reduced at the d r o p p i n g mercury electrode. The imines of aldehydes and ketones reduce at different voltages. SOLVENT EFFECTS IN THE SPECTROPtIO.TOMETRIC DEWElgMINATIO'N 0/~ WEAK ORGANIC ACIDS IN ALKALINE SOLUTION. ]qJ,. Wa.wieki, T. R. H a u s e r , a n d T. W. Stanley. Anal. Chem. 31, 20'63-5 (1959). The effect of the solvent on the a b s o r p t i o n m a x i m u m 104

ENTROPY OF MIXING FATTY OIL WITH SOLVENTS AND THE' PHYSIOOCI~EMICAL PROPERTIES OF THESE SYSTEMS. THE SYSTEMS OF SOYBEAN OIL-BENZENE AND SOYBEAN OIL-CARBON 'rE~AeHLOalI)~. K a z u h i t o Kusano. Ibid. 15-21 (1959). The theory of E. A. Guggenheim (1944) was f o u n d applicable. When solvents were mixed with soybean oil, tile main interaction between molecules of solvent and oil occurred in the alkyl p a r t of oil and t h e solvent. The changes of energies and volume due to mixing were the functions of the n u m b e r of contacts of both molecules, and the viscosity coefficients of the solutions could be calculated f r o m the s u r f a c e area f r a c t i o n and the viscosity coefficient of the components. When soybean oil was mixed with benzene or CGh, about one-third and two-thirds of the alkyl g r o u p of oil was dispersed and contacted with the solvent. The free energy by mixing was due to entropy. VOLUMES OF MIXING PATTY OIL WITI-I VARIOUS SOLVENTS. g a z u hito K u s a n o (Miyazaki Univ.). Yukagalcu ( J . J a p a n Oil Chemi s t s ' Sot.) 7, 400-6 (1958). Refined soybean oil was mixed with various solvents and the volume change due to mixing was calculated by m e a s u r i n g the densities of the soybean oil, the svlvent, and the mixtures accurately. The value of volume change due to m i x i n g was highest at about 1.'1 mixture of oil and solvent. The volume increased by mixing in the case of CS~, CH~C1CH._,C1, CHaCOOCsHs, cyclohexane, and benzene (in decreasing o r d e r ) , while the volume decreased by mixing in the ease of acetone, CHCI~CHCI._,, CC],, CHCI:CCle, CHCI.~, and n-hexane (in increasing order). HEATS OF MIXING FATTY OIL WITI-I VARIOUS SOLVENTS. Kazuhito K u s a n o . Ibid. 406-14 (1958). The change of heat due to mixing soybean oil with solvents was measured at 30 ~ I n general heat was absorbed in ease of solvents where volume due to mixlug increased, while heat was evolved in case of solvents where volume due to mixing decreased. Exceptions were n-hexane and acetone. The highest or lowest value of heat of the mixing was as follows (cal./g.) : CHCL, +1.57, CHCI: CCh +0.81, CCh +0.20, C , H , , - 0 . 3 6 , n-hexane --0.48, eyelohexane --1.16, C1CH~UH~C1 --0.86, CHaCOOC,aH.~ --1.04, CH~ -1.16, and acetone --2.05. DFVELOPMENT OF THE THEORY OF CATALYTIC tlYDROGENA~IO,N. T o m i n a g a Keii (Tokyo Inst. Teehnol.). Y ~ k a g a k u ( J . J a p a n Oil Chemists' See.) 8, 224-31 1959). A review with 37 references. THE STUDIES ON COPPER-NICKEL ALLOY CATALYSTS. Toyosaburo Takeuchi ( T o y a m a Univ.). Ibid. 231-6. A review with 31 references. PRODUCTION OP HIGHER FATTY ALCOHOLS BY THE CATALYTIC HYDROGENATION. Zen-iehi Miyagawa ( K a 5 Soap Co., Ltd., Tokyo). Ibid. 236-40. A review with 30 references. REDUCTION OF FATS, OILS~ AND E'STEIgS WITH METALLIC SODIUM. Masatoshi F u k u s M m a ( N i p p o n Soda Co., N~ka-Kubiki-gun, N i i g a t a ) . Ibid. 240-9. A review with 77 references. PATENTS ON THE HYDROGENATION CATALYSTS. Shizuo Takumi (Nikki Chem. Co., Niitsu, N i i g a t a ) . Ibid. 262-6. A list of 190 patents. THE RELATION BETWEEN PF~TR~LEUM CHEMISTI~Y AND PAT C~HETvrISTRY. Ryohei Oda ( K y o t o Univ.). Yulcagalcu ( J . J a p a n Oil Chemists' Sot.) 8, 30.7-10 (1959). A review. PETROLEUM CHEMISTRY AND PAINTS. Saburo Toyota. Ibid. 323-7. A review.

FEBI~UARu

1960

ABSTRAC'rS: F A T S AND O~;~S

PETROLEUM CHE:~IISTRY A N D SYNTHETIC GLYCERIDES.

Wada (Ind. Research Inst. Osaka Pref.). review w i t h 33 references.

Nobuaki

IbCd. 327-33.

A

Weruzo A s a h a r a a n d K e i r y o M i t s u h a s h i (Univ. T o k y o ) . Ibid. 339-50. A review with 46 references. V I N Y L OOMPOUNDS DEI~IVEO FKOI~[ FATS.

ALKYLENE OL'(IDES AND SURFACE ACTIVE AGENTS. O s a m u N a k a h a r a ( D a i i c h i K S g y 6 S e i y a k u Co., Ltd., K y S t o ) . Ibid. 361-8. A review with 20 references. ALKYLBENZENES AND ALKYLPHENOLS AND THEIR APPLICATIONS.

K o i c h i I s o d a (San-y6 Y u s h i K S g y 6 Co., Ltd., K y C t o ) . 368-72. A review with 29 references. DIFFFARENTIAL

TttElg.MAL

ANALYSIS.

Ibid.

PRINCIPLES AND APPLIC'A-

TIONS IN 0IL CHEMIS~Y. H i r o t a r o K a m b e ( U n i v . T o k y o ) . Yulcagaku (J. J a p a n Oil C h e m i s t s ' Soc.) 8, 267-72 (1959). A review with 16 references. RADIOCHEMISTRY GF FATS. Saburo K o m o r i ( O s a k a U n i v . ) . Y~lcagaku ( J . J a p a n Oil C h e m i s t s ' Soc.) 8, 9 ] - 9 (1959). A review with 25 references. ISOLATION AND ESTIMATION OF PARTIALLY HYDROGENATED FATTY

ACIDS. K . Schilling ( D a n i s h F a t R e s e a r c h Inst., C o p e n h a g e n ) . Fette Sci/en Anstrichmittel 61, 765-768 (1959). The a u t h o r describes a m e t h o d b a s e d on c o u n t e r c u r r e n t f r a c t i o n a t i o n to s e p a r a t e sufficient q u a n t i t i e s of t h e test s u b s t a n c e f o r c a r r y i n g o u t s t r u c t u r a l analyses. I n order to increase the differences in solubilities of different u n s a t u r a t e d f a t t y acids t h e y are conv e r t e d into m e r c u r y salt adducts. The m e t h o d m a k e s it possible to s e p a r a t e t h e lower u n s a t u r a t e d f a t t y acids d e p e n d i n g u p o n the degree of u n s a t u r a t i o n a n d c h a i n length. Configuration a n d positionM i s o m e r i s m seem to have little influence on the p a r t i a l distribution. The q u a n t i t a t i v e d e t e r m i n a t i o n of t h e f r a c t i o n s is done with t h e aid of dithizon. QUALITATIVE AND QUANTITATIVE ANALYSIS OF FATTY ALDEHYDES WITH THE AID OF PAPER CHI~0MATOGI~APHY. H . P . K a u f -

n m n n a n d H. K i r s c h n e k (Deut. I n s t . F e t t f o r s c h u n g , M u n s t e r , W e s t f . ) . Fette Seifen Anstriehmittel 61, 750-764 (1959). I t h a s been possible to s u b j e c t f a t t y a l d e h y d e s to p a p e r chrom a t o g r a p h i c a n a l y s i s a f t e r their conversion to 2,4-dinitrop h e n y l h y d r a z o n e s . T h e selection of s t a t i o n a r y a n d mobile p h a s e s d e p e n d s u p o n the chain l e n g t h a n d t h e degree of u n s a t u r a t i o n . The s e p a r a t i o n of the critical p a i r s a n d the e s t i m a t i o n of u n s a t u r a t e d aldehydes is done t h r o u g h t h e f o r m a t i o n of m e r c u r y salt adducts. P o l a r o g r a p h y h a s been u s e d f o r t h e q u a n t i t a t i v e d e t e r m i n a t i o n of small a m o u n t s of s u b s t a n c e s s e p a r a t e d f r o m pape:' eh;'(:nlutog:ap:ic,~i~y. A SEMI-MICRO METHOD FOR THE COLORIMETRIC DETERMINATION OF THE PttOSPI{OI~US CONTENT IN LIPIDS. I . K o r p a e z y ( I n s t .

Food Research, B u d a p e s t ) . Fettc Seifen Anstrichmittcl 61, 748-750 (1959). T h e a u t h o r h a s improved u p o n T h a l e r ' s m e t h o d for t h e d e t e r m i n a t i o n of p h o s p h o r u s c o n t e n t of lipids. H e ext r a c t s t h e blue colored r e a c t i o n product ( f r o m t h e reaction of silver nlolybdate a n d h y d r a z i n e s u l p h a t e ) f r o m the a q u e o u s m e d i u m w i t h n - b u t a n o l a n d m e a s u r e s it with the help of a s p e e t r o p h o t o m e t e r . T h e sensitivity of t h e m e t h o d m a k e s it possible to d e t e r m i n e one m i c r o g r a m of p h o s p h o r u s in one g r a m of f a t . INVESTIGATION GF F A T ADULTERATION I!Sr CACAO PRODUCTS. 5 I . A CRITICAL EXAMINATION OF THE COMMON METHODS USED FOR THE INVESTIGATION 0~F CACAO BUTTER AND CHOCOLATE ADULTERANTS. A. P u r r ( I n s t . F o o d Tech., M u n i c h ) . Fette Scifen

Anstrichmittel 61, 6 7 5 - 6 8 2 (1959). T h e a u t h o r describes ilve d i f f e r e n t m e t h o d s "for t h e a n a l y t i c a l detection of a d u l t e r a n t f a t s in cacao b u t t e r . The, l i m i t a t i o n s of t h e different m e t h o d s r e q u i r e proper selection. The best nlethods f o r t h e detection o f a d u l t e r a n t f a t s of t h e cacao f a t group, of h y d r o g e n a t e d f a t s , of v e g e t a b l e f a t s , a n d of f a t s h a r d e n e d b y physical m e t h o d s of h a r d e n i n g are s u g g e s t e d . DETERMINATION OF SMALL AMOUNTS OF ADULTERANTS OF THE CACAO F A T GR0~P IN CHOCOLATES AND OTHER CO'NFECTIONEIgIES BY PAPEI~ CHR0MATOGI%APHY. E . P i e t s c h m a n n (Chemical R e -

search I n s t : , N u r m b u r g ) . Fette Seifcn Anstrichmittel 61, 6 8 2 686 (1959). T h e a u t h o r e n u m e r a t e s different f a t c h a r a c t e r sties which are i m p o r t a n t f o r the detection o f a d u l t e r a n t s in chocolates a n d other confectioneries. H e describes in detail a p a p e r c h r o m a t o g r a p h i c m e t h o d b a s e d on the conversion of the f a t s into t h e i r c o r r e s p o n d i n g h y d r o x a n i i c acids a n d t h e i r s u b s e q u e n t s e p a r a t i o n into c o m p o n e n t acids. STUD5; OF A FOOD ANTIOXIDANT. C. P ~ q u o t a n d Mlle J. Mercier

(Lab. Lipid Chemistry,

C.N.R.S., B e l l v u e ) .

Oleagineux

14,

105

591-592 (1959). A s t u d y of t h e a n t i o x i d a n t p r o p e r t i e s of t h e t i o x a n s w a s m a d e u s i n g tile ethyl esters of linseed oil as a test oil a n d c a r r y i n g out the o x i d a t i o n a t 30 ~ A control cons i s t i n g of linseed oil-ethyl esters gave a p e r o x i d e i n d e x (I.P.---millimoles of O2 a b s o r b e d by a kg. of oil) of 20 a f t e r 16 h o u r s a n d 100 a t 100 hrs. The following m e a s u r e m e n t s were t a k e n a n d a r e respectively: c o n c e n t r a t i o n of a n t i o x i d a n t in p e r c e n t ; h o u r s required to reach an I. P. of 20 a n d 100; organoleptic s t a b i l i t y in h o u r s ; i n d u c t i o n period in h o u r s ( u s i n g t h e accele r a t e d s t a b i l i t y t e s t of S w i f t ) . T i o x a n RC8, 0.03, 160, 240, 144, 190; T i o x a n RC8, 0.05, 216, 372, 200, 322; T i o x a n RC10, 0.03, 200, 320, 183, 270; T i o x a n RC10, 0.05, 296, 470, 280, 420; a-tocopherol, 0.05, 160, 610, 144, 560; p a l m i t o y l d-ascorbate 0.01, , ., 1, 6; a-tocopherol 0.01, ---, - - , 99, 186. SPREADING PROPERTIE'S OF TABLE [~'[ARGARINE. I V . SUBJECTIVE ~[EASUI~E:MENTS OF SPREADING AND HARDNESS. A. V z z a n a n d

E. S a n b u e (I.T.E.R..G., Marseille). Rev. Franc. Corps Gras 6, 531-537 ( 1 9 5 9 ) . M e a s u r e m e n t s of m a r g a r i n e s p r e a d a b i l i t y a n d h a r d n e s s p r e f e r e n c e s were c a r r i e d out u s i n g t h e c o m p a r i s o n of g r o u p s m e t h o d . Cubes of m a r g a r i n e were held a t 12.5, 17.5, a n d 22.5 ~ a n d compared as to h a r d n e s s a n d s p r e a d a b i l i t y in g r o u p p a n e l tests. F r o m the results o b t a i n e d a coefficient of correlation b e t w e e n the s u b j e e t i ? e m e a s u r e m e n t s a n d the ease of s p r e a d i n g a n d h a r d n e s s of m a r g a r i n e h a s b e e n calculated. The a u t h o r s i n d i c a t e d t h a t t h e coefficient so o b t a i n e d i n d i c a t e d not only a n i e a s u r e m e n t of s p r e a d a b i l i t y a n d h a r d n e s s b u t also t h a t a sufficient distinction b e t w e e n the two p r o p e r t i e s could n o t be established. R e s u l t s of t h i s s t u d y are of v a l u e f o r calculation of coefficients of correlation in order to c o m p a r e p h y s i c a l t e s t s with s u b j e c t i v e evaluations. THE

POLYMORPHISM OF DI- AND TETrA-FATTY ACID ESTEI~S OF

PENTAFA~YTHI~ITOLS. T. M a l k i n a n d A. G u p t a (Dept. of Chem., Univ. o f B r i s t o l ) . Fette Sei/en Anstrichmittel 61, 868-871 (1959). The a u t h o r s have i n v e s t i g a t e d the p o l y n m r p h i s m in case of the di- a n d t e t r a - e s t e r s of p e n t a e r y t h r i t o l s by m e a n s of capillary m e l t i n g point, h e a t i n g a n d cooling curves, a n d x-ray diffraction techniques. B o t h g r o u p s of t h e esters sbow the m o n o t r o p i c p o l y m o r p h i s m which is a t y p e very similar to the 1,3-glycerides. T h e y exist in t h r e e f o r m s , a, fl, a n d fl', a n d show a n increase in m e l t i n g p o i n t s in the s a m e order. U n d e r specific conditions of cooling the m o l t e n t e t r a - e s t e r gives a solid p r o d u c t which a p p e a r s blue in reflected l i g h t b u t colorless in t r a n s m i t t e d light. AbrALYTIOAL DETERMINATION OF THE

STAGE 0P

OXIDATION OF

OLEFINIC FATS. K . T a u f e l a n d R. Z i m m e r m a n n (Deut. A k a d a m i e der W i s s e n s c h a f t e n ) . Fette Seifcn Anstrichmittel 61, 836-41 (1959). T h e a u t o x i d a t i o n a n d s u b s e q u e n t r e a c t i o n s t a k i n g place s i m u l t a n e o u s l y lead to the f o r m a t i o n of h y d r o p e r o x i d e s a n d their s e c o n d a r y p r o d u c t s in t h e firs$ s t a g e s of a u t o x i d a t i o n . The a u t h o r s a p p l i e d the peroxide value on one h a n d a n d t h e benzidine a n d t h i o b a r b i t u r i c acid reactions on the other h a n d for the a n a l y t i c a l e x a m i n a t i o n of t h e s t a g e of a u t o x i d a t i o n reached. D u r i n g the a u t o x i d a t i o n of some m o n o - u n s a t u r a t e d a n d s a t u r a t e d acids b r o u g h t a b o u t by the U V - r a d i a t i o n s , some p r o d u c t s are f o r m e d whose a b s o r p t i o n m a x i m a c o r r e s p o n d to those o b t a i n e d in the case of some s a t u r a t e d aldehydes a n d with c r o t o n a l d e h y d e a n d acrolein. The i n v e s t i g a t i o n s show t h a t in case of edible f a t s p o s s e s s i n g different acidities, t h e a u t o x i d a t i o n pvovided by U V - r a d i a t i o n s gives a s t e a d y increase in peroxide value as well as t h e i n t e n s i t ~ of color in case of t h e benzidine a n d t h i o b a r b i t u r i c acid reactions. DETERMINATION OF STRUCTUKI~ AND ANALYSIS 0~F THE HYDROPEROXIDE ISOMERS OF AUTOXIDIZED METHYL 0LEATEI. O. S. P r i v e t t

a n d E. C. Nickell ( T h e H o r m e l Inst., Univ. o f Minn., A u s t i n , M i n n . ) . Fette Scifen Anstrichmittel 61, 842-845 (1959). A procedure is described d e m o n s t r a t i n g the f o r m a t i o n of f o u r h y d r o p e r o x i d e i s o m e r s in t h e a u t o x i d a t i o n of m e t h y l oleate in accordance with the free radical c h a i n reaction concept of a u t o x i d a t i o n . E x p e r i m e n t a l p r o o f is also g i v e n f o r the location of t h e h y d r o p e r o x i d e g r o u p in t h e a l p h a position relative to t h e double bond. N e w m e t h o d o l o g y is r e p o r t e d in t h e use of the Ldndlar C a t a l y s t f o r the q u a n t i t a t i v e e s t i m a t i o n of peroxides. T h e q u a s i s i x - m e m b e r e d r i n g t h e o r y of o x i d a t i o n as a p p l i e d to the a t m o s p h e r i c oxidation of f a t s is shown to have no f a c t u a l basis. T H E OCCURRENCE OP EICOSATETRAE,N@IC, DOCOSAPENTAENOICj AND DOCOSAHEXAENOIC AC'IDS IN FISH 0ILS. Y . T o y a m a , Y. I w a t a ,

a n d K . F u j i m u r a ( N a g o y a Univ., N a g o y a , J a p a n ) . Fette Sei/en Anstrichmittel 61, 846-49 (1959). T h e a u t h o r s have isolated eicosatetraenoic acid f r o m s a r d i n e oil a n d docosapentaenoic acid a n d docosahexaenoic acid f r o m t h e s a u r y fish oil, in t h e f o r m of their m e t h y l esters. On t h e b a s i s of ozonolysis

106

T H E JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY

the authors assign the following configuration to these acids: 5, 8,11,14- tetra- eieosanoic acid, 4, 7,10,13,16 - docosapentaenoic acid, and 4,7,10,13,16,19-docosahexaenoic acid. Q U A N T I T A T I V E P A P E R C~HR0ikIATOGR,APHY O F F ~ T T Y ACIDS. II. T H E PHOTOMETRIC METHOD. A. SeAm" (Deut. Inst. fiir P e t t f o r s c h u n g , Munster, W e s t f . ) . Forte Seifen Anstriehmitte~ 61, 55-59 (1959). The method for the quantitative evaluation of paper chromatograms, described in a n earlier publication, has been put to a thorough theoretical a n d experimental investigation. The attention is drawn to the possible sources of error a n d the methods are suggested to avoid them.

DETE:CTIOLN AND QUANTITATIVE DETER.MINAT[oN 0 F POLYUNSATURATED FATTY ACIDS. T. Miyakawa (Osaka Industrial Research

Inst., Osaka, J a p a n ) . Forte Seifen Anstrichmittel 61, 850-55 ( 1 9 5 9 ) . The author has demonstrated that it is possible to determine quantitatively the polyunsaturated f a t t y acids through photometric evaluation of the paper chromatograms on which the f a t t y acids have been analyzed, using an undecane/acetonitrile: acetic acid system. The results obtained by this method are in agreenmnt with those obtained through the lithium salt acetone fractionation method. Hydrogenation of the unsaturated f a t t y acid spots lead to f u r t h e r conclusions. THE

INI~LUENCE OF B I U R E T O N

THE

FORMATION

0F UREA

FATTY

ACID ADDUCTS. R. Rigamonti and V. Riccio (Inst. Chem. Ind., Torino, I t a l y ) . Fette Seifen Anstrichmitte~ 61, 864-867 (1959). The authors have investigated the various proportions of biaret-urea mixtures for the formation of urea f a t t y acid adducts. The general conclusions arrived at are t h a t the addition of biuret reduces the yield of the addition compounds and t h a t the crystals are smaller in size. The addition of biuret to urea however results in an increased formation of the adducts in the case of s a t u r a t e d f a t t y acids. The presence of biuret in the addition products can be proved qualitatively although the quantitative deternfination has not yet been possible. ACTION OF IONIZING RADIATIONS ON FAT. I. P~RMATION OF PEROXIDE DURING UV-RADIATION OF I~ATS. H . K i i h n a n d H . L i i c k

(Deut. Porschungsinstit. fiir Lebensmittelchemie, Munich). Fette Seifen Anstriehmittel 61, 860-64 (1959). Ethyl oleate, olive oil, and lard have been exposed to the action of ultraviolet rays in the presence of air. Peroxide, acid, iodine, and hydroxyl values as well as spectroscopic determination of trans-isomerism were employed to follow the course of the reaction. The authors have discussed their results exhaustively. STRUCTURE ANALYSIS 0 F NATURAL GLYC~RIDES. P . Desnuelle and P. Savary (I.T.E.R.G., Marseille). Fette Seifen Anstrichmittel 61, 871-76 (1959). The structure analysis of mixed n a t u r a l glycerides leads to the following conclusions: The structure of animal and vagetable mixed glycerides is not random; the position of f a t t y acids in the glyeerides appears to be dependent on the chain length of the saturated acids as well as the degree of u n s a t u r a t i o n of the u n s a t u r a t e d acids. In vegetable oils the s a t u r a t e d acids occur mainly at the 1 and 3 positions and the u n s a t u r a t e d acids at the 2 position in the glyceride molecule. The principle of distribution is however not so rigid in the case of animal fats. The manner in which the location of f a t t y acid rests in the glyceride molecules affects the biological and physical properties of the glyceride is discussed. P'I%EPARATION OF LONG CHAIN FATTY ACID'S AND 10-KETO ACIDS.

F. L. Breusch, P. Baykut, and S. Ozeris (Chem. Inst. Univ. I s t a m b u l ) . Pette Seifen Anstrichmittet 61, 891-93 (1959). The 10-keto f a t t y acids with 24, 25, 26, 27, and 28 carbon atoms have not until now been completely described. They have been prepared through the condensation of sebacyl chloride monomethyl esters with n-alkyl iodides in the presence of a Cu-Zn reagent. The n - f a t t y acids which are otherwise difficult to obtain have been prepared by the Clemmensen reduction ~of the keto acid. A N A L Y S I S OF LIPIDS W I T H

THE

HELP OF THE RADIO REAGENT

METHOD. L. K. Mangold (Hormel Inst., Univ. of Minn., Austin, Minn.). Pette Seifen Anstriehmittel 61, 877 81 (1959). Mixtures of ]iplds can be analyzed with the help of a radio reagent method. P a t t y acids can be esterified with radioactive diazomethane and lipids containing amino or hydroxy groups can be acetylated with radioactive acetylation mixtures. The author describes in detail the reaction conditions for the separation of the lipid derivatives and gives an example of the application of the radio reagent method and working details of the chromatographic analysis procedure. ~OLUMN CHROMATOGRAPHY OF LIPIDS : O D D N U M B E R E D STI%AIGHT CHAIN FATTY ACIDS 0.F MENHADEN OIL. Joanne L. Hellerman and

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H. Schlenk (Hormel Inst., Univ. of Minn.). Experientia 15, 387-388 (1959). The occurrence of normal CI:J, Ci~, C1~, and C1~ carboxylic acids in menhaden oil was determined using paper chromatography in an acetic acid/peracetic acid system with silicone treated paper, at 30 ~. The acids were isolated by column chromatography using silicone treated columns and acetonitrile as the developing agent. E I G H T E E N CAR~ON" POLYHYDIC0XY FATTY ACIDS AND ALDE,HYDES.

H. P. K a u f m a n n and H. J a n s e n (Deut. Inst. fiir P ettforschung). Chem. Per. 92, 2:789-97 (1959). Polyhydroxy f a t t y acids were prepared from the corresponding conjugated f a t t y acids by osmium tetroxide oxidation. These products gave with alde* hydes and ketones the corresponding substituted 1,3-dioxolane f a t t y acids. Simple hydroxylated f a t aldehydes were prepared f r o m the diazoketones according to the G r u n d a m a n n synthesis. I f the hydrazide of a polyhydroxy acid is condensed with acetyl acetone, an acetylated 3,5-dimetbylpyrazolene results which when hydrogenolyzed yields the polyhydroxy f a t t y aldehyde. A. V. Roncero, P. R. Ayerbe, and M. A. Romero ( P a t Inst. Seville, Spain). Fette Seifen Anstrichmittel 61, 900-904 (1959). The alkali fusion of oleic acid gives rise to palmitic acid, acetic acid, and hydrogen as the products of the reaction. The investigations on V a r r e n t r a p p s Reaction shows t h a t in polyunsaturated f a t t y acids, alkali fusion gives rise to as m a n y molecules of acetic acid as the number of double bonds in the reacting acids m a y be. Linoleic and linolenic acids yield two molecules of acetic acid and myristic acid, and three molecules of acetic and laurie acids, respectively. The authors also point out the economic potentialities of the reaction for the m a n u f a c t u r e of short chain f a t t y acids. A L K A L I FUSION O*F UNSATURATED FATTY ACIDS.

APPLICATION OF MOLECULAR DISTILLATION TO TH]~ DETE!%MINATION O]~ THE I~ATTY ACID COMPOSITION OF C P ~ M B E ABYSSINICA SEED

0IL. H. Niewiandomski, B. Drozdowski, and W. Zwierzykowski (Inst. of P a t Technology, Gdansk Technical Institute, Poland) Fette Seifen Anstrichmittel 61, 897-99 (1959). The authors have studied and reported the physical and chemical properties of the Crambe Abyssinica seed oil a n d its f a t t y acids. A f t e r a preliminary fractionation of the f a t t y acids with the help of molecular distillation, they were subjected to polarographic-paper-chromatographic analysis in order to determine the f a t t y acid composition, qualitatively as well as quantitatively. The f a t t y acid composition was found to be as follows: myristic, 4.7% : palmitic, 9.7% ; arachidic, 2.7% ; behenic, 0.1%; oleic, 18.7%; linoleic, 12.7%; and erucic, 51.4%. ISOLATION AND DETERMINATION METHODS FOR BRAIN C'EREBR0SIDES~ HYDROXY FATTY ACIDS, AND UNSATI/I%ATED AND SATURATED FATTY ACIDS. Yasuo Kishimoto and Norman S. Radin

(Biochem. Dept., Northwestern Univ. Medical School, Chicago). J. Lipid Research I, 72-78 (1959). A new method is described for the isolation of nearly pure total cerebrosides from the fresh brain. Plorisil colunms are used to separate the cerebroside hydroxy and normal acids, in the form of their esters, and to separate the saturated a n d u n s a t u r a t e d esters of each group. The esters within each group are determined by gas chromatography, the hydroxycsters being run as the methyl esters. Yields in the various steps are close to theoretical. The presence of lower homologues in all four classes ,of r a t brain cerebroside acids was discovore~L Particularly large a m o u n t s of C~, and C~2 saturated acids were found. Devyatnin a n d I. A. Solunina. Med. Prom. S.S.S.R. 13(2), 38-42 (1959). A method of determination of a-tocopherol and selfn i t r a t i n g tocopherols f r o m the same extracts was developed. The method is given in detail. (C. A. 53, 19412) DETEI~MINATION 0 P TOCOPHERO15S IN P L A N T O I L S . V . A .

T H E ]~FFECT 0P AIR, TEMPERATURE~ A N D STOI%AGE TIME ON THE PEROXIDE C O N T E N T IN U N S A T U R A T E D P A T ACIDS. C. Pietrzyk. Rocz~idi Teehnol. i Chem. Zywnosci 3, 77-91 (1958). The content of active oxygen in the process of autoxidation is a function of peroxide production and utilization. I t depends on the type of f a t t y acid, air access, temperature, a n d time of storage. A straight-llne relation exists between the logarithms of the time of m a x i m u m peroxide content and temperature and also between the logarithm of time of m a x i m u m rate 'of peroxide f o r m a t i o n and temperature of storage. (C. A. 53, 19412) COMPONENT PATTY ACIDS OF THE SEED P A T OF ALBIZZIA LEBBEK.

A. Sen Gupta and M. M. Chakrabarty (Univ. Calcutta). Indian J. Ap~l. Chem. 21, 227-9 (1958). The composition of the seed f a t of Albizzia lebbek grown in the desert area of R a j a s t h a n

FEBRUARY, 1 9 6 0

ABSTRACTS: FATS AND OILS

(saponification equivalent 290.2, iodine value 114.3, unsaponifiable content 1.6%, n 4~ 1.4683) was ]inolenic 1.5, lino]eie 57.6, o]eic 10.3, and s a t u r a t e d acids 30.6%. (C. A. 53, 19411) DISTILLATION OF FATTY ACIDS AT THE VOLGODON COMBINE. FOR SYNTHETIC FAT SUBSTITUTES. G. B. A l ' t e r m a n a n d M . G. Morkovin. Maslobogno-Zhirovaya Prom. 25(6), 38-43 (1959). The process for distillation of f a t t y acids is described, with diagrams. (C. A. 53, 19411) ~ECENT WOrK OF THE INSTITUT DES C(~RPS ~RAS, PARIS, 0'N THE EEC:OV~EY OF STEROLS ]~ROI%fI[{.EPINERY WASTE I~ J.P. Sisley and A. Uzzan. Grasas y aceites (Seville, Spain) 9, 310-15 (1958). A review with 7 references. (C. A. 53, 19411) I~0DE OP ACTION 0F NATURALANTIOXIDANTS OF FATS. K. T~ufe], C1. Franzke, and G. Gehlert (Humbolde Univ., B e r l b 0 . Nahrung 2, 853-67 (1958). The antioxidant effects of the nonsaponiffable fractions of rapeseed and sunflower oils were probably due to tocopherol. (C. A. 53, 19411) A N E W LABORAT0'ICY A P P A R A T U S FOR T H E OIL A N D F A T INDUSTRIES. G. B. Martinenghl. Olearia 13, 114-17 (1959). A n especially designed laboratory-scale a p p a r a t u s for decolorizlng, esterifying, deodorizing, and distilling oils and f a t s in the process of refining is described. (C. A. 53, 19411) SAFONIFICATION COLOR VALU~ OF ~kNIMAL FATS. A. Mirna ( B u n d e s f o r s e h u n g s a n s t a ] t Fleischwirtschaft, Kulmbach, Ger.). Fleischwortschaft 11, 669-712 (1959). The increases in saponification value a n d peroxide value during saponification of f a t are closely related to the u n s a t u r a t e d character of the fat. Mono-unsaturated f a t t y acids behave differently from multiu n s a t u r a t e d f a t t y acids. T r e a t m e n t with bleaching earths reduces peroxide value more intensely t h a n saponification value. Saponification color values markedly above 0.10 with low peroxide value (below 4.0) indicate unaccepted methods of treatmont. (C. A. 53, 19411) DETEI~MINATION OF THE IODINE VALUE 0LF FATS IN AQUEOUS MEDIUM WI~H0~T E;~ULSIFIEES. P. P. Suprun (Control Anal. Lab., Konotop). Aptechnoe Deto 7 ( 3 ) , 48-51 (1958). Pla~e 0.15-0.25 g. of f a t of iodine number up to 130, or 0.05-0.08 g. of iodine number over 130, in a glass-stoppered flask of 300500 cc. capacity; add 100 ec. hot water (80 ~) and 25 ec. 0.1 normal ICI.HC1, carefully stir for 10-15 minutes, depending on the iodine n u m b e r ; c0ol, add 15 co. 10% K I , and titrate the liberated iodine in the usual way. (C. A. 53, 19411) Two-STEP ]kTEUTRALIZATIONOF PEANUT OIL. ~4-. Naudet, J. C. Drap, a n d S. Bonjour. Grasas y aceites (Seville, Spain) 9, 292-5 (1958). (C. A. 53, 19415) SPECTROPHOTOMETRIC EXAMINATION OF OLIVE OILS. A. FabbiettL Boll. lab. chain. Provinciali (Bologna) 9, 287-96 (1958). Extinction coefficients E at 8 wave lengths are determined for olive oils subjected to L i e b e r m a n n ' s reaction. The quality and p u r i t y of the olive oll is determined by the value of E~eo/E~65. (C. A. 53, 19414) R.HODONATION OP OLEIC AND ELAIDIC ACIDS AND THEIR ES~'ERS. L. A. Zhila. Pratsi Odcs'k. Dcrzhav. Univ. ira. L I. Mech. nikova, Prirodnich,~ N a ~ i 148(3), 161-6 (1958). The rhodo-ation rates fev oleic acid and its esters were much higher t h a n for e]aidic acid and its esters. Rates for esters were lower t h a n for acids. Chain lengthening of alcohol radicals a n d their b r a n c h i n g reduced reaction rates of esters in cis forms stronger t h a n in trans. (C. A. 53, 18852) DECOMPOSITION 0F PEROXIDES IN FATS WITH PARTICULAI~REFERENCE TO THOSE: IN SAURY OIL. Hisashi W a t a n a b e and Yoshiyuki Toysma. Mere. Fac. Eng., Nagoya Univ. 10, 95-104 (1958). Peroxides in oxidized marine animal oils decompose more readily t h a n do those of vegetable oils. Rate of decomposition of peroxides in vegetable oils is not alike for all samples. Peroxides in a viscous oxidatively polymerized vegetable oil decompose more rapidly t h a n do peroxides in less deteriorated oil. The addition of 10% of a highly u n s a t u r a t e d methyl ester prepared from unoxidized saury oil to oxidized vegetable oils tends to accelerate the decomposition of peroxides. The addition of 0.2% pro-oxidants (copper or iron soaps) to oxidized saury o~1 markedly accelerates the peroxide's decomposition. The addition of 0.01-0.06% antloxidants, such as nordihydroguaiaretic acid, b u t y l a t e d hydroxyanisole, and propyl gallate to oxidized saury oil does not noticeably affect the decomposition of peroxides. W i t h a combination of pro- and antioxidants in the oxidized saury oil, tile accelerafing effect of pro-oxidants on the peroxide's decomposition is not suppressed. The over-all decomposition of peroxides in oxidized saury oil is allied to a 1st-order type rather t h a n a 2nd-order type. (C. A. 53, 19409)

]07

CHEMICAL DETERI%fINATION OF THE ~r OF O,O-DIMETHYL DITHIOPH0,SPHOI%YLACETIC ACID IN OLIVE OIL. B. Bazzi and i~. Senti (Ist. Ricerche Agr. Soc. Montecathfi, Florence). Olivicoltura 1958(4), 1-4. The title substance is the active principle of a commercial insecticide. I t is extracted from the oil by ethanol, chloroform, and s a t u r a t e d aqueous sodium chloride. Tile colorimetric determination is made from the chloroform solution. The method does not produce a chemical t r a n s f o r m a t i o n in the insecticide. (C. A. 53, 19414) COLOR DETE~fINATION OF OLIVE OILS. J. M. R. de la Borbolla y Alcal~, R. de Castro Ramps, and R. Vazquez Ladr6n (Inst. Grasa y sus Derlvados, Seville, Spain). Grasas y aceites (Seville, Spain) 9, 302-5 (1958). A colorimeter using 2 filters having t r a n s m i t t a n c e between 400 and 700 mtL is used to measure the color of olive oil. The 2-filter system characterizes the oils as well as does the complete absorption spect r u m determined with a spectrophotometer. Other color methods are discussed. (C. A. 53, 19414) FATTY OILS CONTAINED IN THE. SEEDS O'F SO'ME SPECIES OF MALVA. V. M. Shelud'ko and N. G. GoIkhman (Pharm. Inst., Odessa). Nekotorye Voprosy Fa.rmatsii, Sborni?~ Na~ch. Trudov Vyssh. Fa~'m Ucheb. Zavedeni~ UI~r. S. S. R. 1956, 190-2. The following constants (density, index of refraction, saponification number, iodine number, Reichert-Meiss] number, % unssponifiable residue) were determined, respectively, for f a t t y oils of: Malva sylvestris 0.992, 1.4722, 181.5, 107.6, 4.4, 0.28: M. neglecta 0.929, 1.4728, 182.1, 103.5, 1.9, 0.37; M. moschata 0.928, 1.4726, 180.2, 107.8, 3.3, 0.36; M. meluca 0.928, 1.4726, 178.3, 108.7, 2.8, 0.28. The last 3 m a y be classified as drying oils, the first as a semi-drying oil. These m a y be used like linseed oil in pharmaceutical practice. (C. A. 53, 19414) UTILIZATION OF COT'TONSEEDOIL REPINING FOOTS. K. T. Achaya, B. Bhushan, and S. R. Rap (Regional Research Lab., Hyderabad). Papers Symposium Cottonseed and By-Products, ttyder abad India, Sect. VI, 1958, 40~50. Results are reported on the potential uses of I n d i a n cottonseed oil toots, such as recovery of f a t t y acids by distillation and urea-adduct methods. Experiments are described on the p~rolysis of toots with the aim of obtaining synthetic liquid fuel. (C..4. 53, 19414)

WORLD COTTONSEED AND OIL. A. Ferrara. Olearia 13, 73-85 (1959). The origin, world production, a n d use of cottonseed and oil are discussed. Comparative figures are given for the U. S., South America, Asia, Russia, Africa, E,urope, and Oceania. (C. A. 53, 19413) SOLVI~NT FRAC'TIONATION 0]~ DEHYDRATED CASTOR OIL. V. R. Ambekar a n d I(. K. Dole (Fergusson Coll., Poona). Indian J. Appl. Chem. 21, 193-8 (1958). Dehydrated castor oll was fractionated by isopropyl alcohol into 3 fractions. F r a c t i o n 1 contains polymerized castor oil; fraction 2 contains a mixture of semi-polymerlzed and monomerie castor oil; both produce tack-free films superior to films obtained f r o m castor oil. Fraction 3 contains partially hydrolyzed glycerides, free f a t t y acids, undehydrated castor oil, and decomposition products having low molecular weights; its films show after-tack and dry slowly: Dehydration in the presence of 0.2% anthraqulnone-l:8-disulfonic acid at 250 ~ for 20 m~nutes yielded the lowest amount of fraction 3. (C. A. 53, 19413) SEED OILS. Yoshit0 K o y a m a , Tadayoshi Hisatsune, Hisashi W a t a n a b e , a n d Yoshiyuki Toyama. Mere. Pac. Eng., Nagoya Univ. 10, 88-94 (1958). Seed oils f r o m Viburnum odoratissimum, Elaeagnus umbellata, Eurya japonica, Cleycra ochnacea, Ampelopsis heterophy~la, Cissus japonica, Parthenocissus tricuspidata, Acer ginnale, Acer trifidaem, Euphorbia heterophylla, Amelanchier axgatica, Kadsura japonica, Celtis sinensis variety Japonica, Alnus firma, and Alnus multimervis were studied. Linoleic acid is present in each of the oils and linolenic, acid in E. umbeUata, A. ginnalc, A. trifidum, and E. h~t~ro~)'hylIa oils. The unsaponifiable m a t t e r from K. japonica was almost completely soluble in cold methanol, without yielding a crystalline solid. (C. A. 53, 19412) T H E HYDR0~XYL N U M B E R 0F CASTOE 0IL. M. Naudet and IV[.J. P e r r o t (Natl. Lab. Oils a n d F a t s , Marseille, F r a n c e ) . Peintures, pigments, vernis 35, 239-41 (1959). The quality of dehydrated castor oil is a function of the hydroxyl number of the original castor oil. Improper refining methods of the castor oil m a y lead to low hydroxyl numbers. Laboratory tests indicate t h a t countercurrent extraction with petroleum ether yields the d e s k able increase in hydroxyl n u m b e r s of 8-10 points. (C. A. 53, 19412) BEHAVIOR OF FATTY OILS DUEING STER.ILIZATI0,N. CI. Franzke (Humboldt Univ., Berlin). Deut. Apoth.-Ztg. 97, 465-6(1957).

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No chemical changes occur d u r i n g normal sterilizing. F a t t y oils are affected only on prolonged h e a t i n g at 200 ~ (C. A. 53, 19412) REFININO 0F VEOI~TABLE OILS WITH UREA. W. N. Metha a n d M. S. M u r t y (Univ. N a g p n r , I n d i a ) . Grasas y aceites (Seville, S p a i n ) 9, 316-17 (1958). Acidic components ( f a t t y acids) and mona- and diglycerldes f o r m e d during storage of raw oils are removed by t r e a t m e n t with u r e a moistened with water. More t h a n the theoretical a m o u n t of urea is required, a n d the ratio of urea to w a t e r is 2:1. The mixture becomes an emulsion which can be broken by centrifuging. (C. A. 53, 19412) DEODORIZATION OP OILS IN THE ~ILOT PLANT OF TI-IE INSTITUT0 DE LA GRASA. F. Ramos Ayerbes ( I n s t . Grasa y sus Derivados, Seville). Grasas y aceites (Seville, Spain) 9, 318-21 (1958). The energy consumption f o r deodorizing oils in a pilot p l a n t is measured. (C. A. 53, 19412) ~ATALYST STUDIES OF VAPOR PHASE ESTER.IFICATION OF OCTYL ALCOHOL AND ACETIC' ACID. Y. V e n k a t e s h a m (Ohio State Univ., Columbus). Univ. Microfilms ( A n n Arbor, Mich.). L. C. Card No. Mic. 59-2330, 174 pp.; Dissertation A b s t r . 20, 240-1 (1959). (C. A. 53, 19857) WAX OF THE LEAVES OF PICEA PUNGENS (COLORADO SPRUCE) 9 E. v. Rudloff (Natl. Research Council, Can., Saskatoon). Can. J. Chem. 37, 1038-42 (1959). The chloroform soluble n e u t r a l wax isola.ted f r o m the leaves of Picea p u n g e n s was shown to contain sabinic, 14-hydroxytetradecanoic, and juniperie acids with m i n o r a m o u n t s of nonsaponifiable substances and n - f a t t y acids. I n f r a r e d spectra of the neutral wax showed no free hydroxyl g r o u p s a n d it was suggested t h a t the neutral wax was composed mainly of a cyclic polymer of the ~-hydroxy acids and that the seasonal changes in acidity were caused by ring opening or closure. Since the 1,14-tetradecanolide had a musk-like odor, it could be used for production of compounds having such odor. (C. A. 53, 19862) APPLICATIONS OF PROTON MAONETIC RESONANC~ SPECTRA IN FATTY ACID CHEMISTRy. C. Y. H o p k i n s and H. J. Bernstein, Can. J. P h y s . 37, 775-82 (1959). I n t r o d u c t o r y study of f a t t y acids, their esters, and glyceride oils indicates t h a t s t r u c t u r a l questions can be solved by use of nuclear magnetic resonance ( N M R ) . Spectra obtained for chloroform solutions permit the identification of terminal methyl, CHf, C:C, OH, divinylmethane, and other g r o u p s with characteristic p r o t o n configurations. The keto and enol f o r m s of diker ones cast be differentiated by NMR. On the basis of its NMR spectrum the f o r m u l a I I CH:, (CH~) ~CH. CH [ CH : CH (CH._,) 7CO2H ]- CH._, f o r stereulic acid is j u d g e d incorrect, and the f o r m u l a

F CH:,(CH,.,) 7C : C[ (CH_o)TCO.~H] "CH~ is favored, but not positively proved. (C. A . 53, 199]8) LENTISaUS OIL AS DETECTOR OF OLIVE HUSK OIL. G. Condroelli (Univ. Catania, Sicily). Boll. i n f o r m a z , ind. olearia e saponiera 4, 119-20 (1958). Lentiscus oil is proposed instead of cottonseed oil as an additive to olive husk oil because of the easy and sensitive chromatographic reaction f o r determining lentiscus oil in a commerci:fl mixture, and of the similarity between olive oil and lentiscus oil. (C.A. 53, 20605) DETECTION OP ANTIOXII)ANTS Ih~ LARD, ESPECIALLY O.P BUTYLH'YDROXYANISOLE ( B H A ) . J. B. Roos. F l e i s c h w i r t s c h a f t 11, 667-8 (1959). The occurrence of antioxidants is detected either by the phosphomolybdic acid or open-dish test. A more precise test f o r B H A is achieved by inactivating other antioxid'~nts with active carbon followed by a determination with phosphomolybdic acid. Other methods are mentioned. (C. A. 58, 20604) CHOLESTEROL IN MILK. F. K a y s e r and D. Tachkova. Congr. sac. pharm. France, 9 ~, Clcrmont-Ferrand 1957, 135-8. A liter of cow milk contains a b o u t 170 mg. cholesterol of which 119 are f o u n d in the cream and 16 in the casein (average content 0.55 m g / / g . ) . (C. A. 53, 20602) CHEMICAL COMPOSITION O~ THE FATTY 0~L OF THE FRUIT OF PIMPINELLA ANTISETUM. YU. G. Borisyuk and G. V. Makarova ( P h a r m . Inst., K h a r k o v ) . N e k o t o r y e V o p r o s y Farm., S b o r n i k N a u c h . Trudov Vyssh. F a r m . Ucheb. Zavedeni~ Ut;r. S . S . R . 1956, 179~84. The f r u i t o f P i m p i n e l l a a n i s e t u m contains 8.2% f a t t y oil, the glyeerides of which contain oleic 61, petroselinic 26, linoleic 9.6, and palmitic acids 3.4%. E x c e p t for differences in the a m o u n t s of aliphatie acids this oil is similar to coriander oil, and the solid p a r t of the oil m a y be usable as cacao oil s u b s t i t u t e in pharmaceutical practice. (C. A. 53, 20844)

VOL. 37

CHROMATOGRAPHIC ISOLATION OF SISTOSTEROL PROM COTTONSEED 0IL. A. L. M a r k m a n and A. U. Umarov. Uzbek. K h i m . Zhur., A k a d . N a u k Uzbek. S . S . R . 1959, No. 1, 63-5. Two kg. of cottonseed oil was dissolved in 20 liters of ether and passed t h r o u g h a l u m i n u m oxide columns. The u n a d s o r b e d f r a c t i o n was a colorless oil. Elution with ether yielded an orange oily substance f r o m which 9.3 g. (0.47%) of sistosterol was extracted with methanol. Distillation of the methanol-insolubles gave ~ crystalline solid. (C. A. 53, 20843) CHEMICAL E:XAMINATION OF THE OIL FR0,]~ THE SEEiDS 0F CITRULLUS F~STULOSUS. S. I~. Agarwa], D. R. Dhingra, and G. N. Gupta (Muslim Univ., A l i g a r h ) . I n d i a n Soap J. 24, 257-60 (1959). E x t r a c t i o n of the powdered seeds 4 times with petroleum ether gave 25.39% of a clear light yellow oil having the following characteristics: d~ 0.9146, n 2~ 1.4704, acid value 9.2, iodine value 120.15, saponification value 181.4, acetyl value 11.09, diene value 6.55, H e h n e r value 94.8, and unSaponifiable 1.91%. The f a t t y acids in the all were myristic 0.64, palmitic 5.66, stearic 12.50, oleic 33.89, and linolenie 47.31%. The unsaponiflable m a t t e r contained sitosterol and a yellowish g u m m y substance. (C. A. 53, 20843) I~CREAS]5IN THE STABILITY OF REFINED VEOETABLE OILS BY THE USE 0IF ANTIOXIDANTS. Z. K. Levedeva. Maslobo~no-Zhirovaya Prom. 2 5 ( 7 ) , 24-8 (1959). Sunflower and cottonseed oils were effectively stabilized a g a i n s t oxidative deterioration at 90 ~ by propyl gallatc ( 0 . 0 1 % ) , or dibutylmethylpheno] (0.01%) and citric ac'd (0.002%) as a synergist. Other suitable antioxidants are betaine hydrochloride (0.05%) and ascarbyl palm i t a t e ( 0 . 0 2 % ) . I n contrast to this, butylated hydroxyanisole (0.02:%) and tocopherols (0.05%) caused a slight destabilization of sunflower ,~nd cottonseed oils. (C. A. 53, 20842) SCOPE FOR THE UTILIZATIONOF NONEDIBLE 0ILS IN INDIA. T . V . Subba Rao ( T a t a Oil Mills Co., B o m b a y ) . IndOan Soap J. 24, 71-91 (1958). (C. A. 53, 20842) MICRODETERMINATION O,P CITRIC ACID IN OILS AND PATS. Shinroku M a s u y a m a (Municip:~l Ind. Research Inst., Osaka). K a g a k u ~o K d g y d (Osaka) 33, 224-6 (1959). A calorimetric method w a s developed f o r determining citric acid in oils or fats. (C. A. 53, 2084]) SEPARATIC'N OF FATTY ACIDS WITH FRACTIONAL DISTILLATION. J. Per~di (NSv~nyolaj 4s H h z t a r t S s i Vegyipari K u t a t 6 Int~zet, B u d a p e s t ) . Rlelmez~si I p a r 11, 189 94 (1957). Relative evaporation, equilibrium curves, n u m b e r of plates, and reflux ratio for the separation of f a t t y acids by fractional distillation were determined. A 20-plate l a b o r a t o r y f r q c t i o n a t i n g column was constructed on the basis of these data. F a t t y acid mixtures (coconut oil, rice oil, and hardened sunflower oil) were separated and the results are given. ( C. A. 53, 20841)

DETERIOI~ATION OF PATS ; ANTIOXIDANTS USED IN THE, FOODINDUSa'RY. J. Pcr~di (N5v~nyolaj 5s Hhztart/~si Vegyipari K u t a t 5 Int~zet, B u d a p e s t ) . ~lelmesdsi I p a r 12, 97-103 (1958). A review with 34 references. (C. A. 53, 20841) DEVELOPMENT OF NONEDIBLE FATS FOR EDIBLE PURPOSES. M. Chakrabarty, M. K. C h a k a r a b a r t y , and N . K. Sen (Univ. Calcutta). I n d i a n S o a p J. 24, 283-7 (1959). A review o f chemical methods "tnd economics. (C. A. 53, 20841) GAS-LIQUID CHROMATC.ORAPIIIC DETERMINATION OF TH]5 FATTY ACID COMPOSITION IN O*IL FROM SEEDS OF ULMUS. I b S6rensen and P. S01toft (Dan. tekn. H6jskole, Copenhagen). A c t a Chem. Scand. 12, 814-22 (1958). The seeds f r o m various Ulmus spp. on crushing and petroleum ether extraction gave a mixture of f a t t y acids having the composition Cs 3.6, C~o 65.2, C~2 4.7, C~ 3.4, C~,, 6.4, and C~ 16.7%, fully confirming the literature t h a t a high C~,) f a t t y acid content is particularly characteristic of ehn seed oil. The f a t t y acid comp'osition was determined b y low-pressure gas-liquid c h r o m a t o g r a p h y of methyl esters. (C. A. 53, 20845) ABSOLUTE CONFIGURATION 0.F C-(24) ETtIYL OF STIGMASTEROL. K. T s u d a (Univ. of Tokyo), R. H a y a t s u , and Y. Kishida (Sankyo Co., Ltd., Shinagawa, Tokyo). Chem. ~" Ind. 1959, 1411-2. I t is concluded t h a t the C-(24) ethyl group of stigmasterol is 'of the alpha configuration when it is expressed in P l a t t n e r ' s convention. ~]r CONTENT AND THE SMOKE POINT 0P SOME FATS. Belle Lowe, S a r a l a P r a d h a m , and J. Kastelic ( I o w a State Univ., A m e s ) . J. H o ~ e Econ. 51, 778-9 (1958). V a r i o u s f a t s were used, in 2100-g. amounts, f o r f r y i n g doughnuts at 185 ~ Following the f r y i n g , the: h e a t i n g of the f a t s w a s continued until a 540-minute period had elapsed since the h e a t i n g b e g a n . A

FEBRUARY, 1 9 6 0

ABSTRACTS: F A T S AND OILS

relation was observed between the initial free f a t t y acid content and the smoking point of the fat, the f a t s with higher a m o u n t s of free f a t t y acid having the lower smoking points. (C. A. 53, 22587) DECOLORATION 0F RAPE OIL. I l l . BROWN PIGMENTS. E t s u j i Yuki and Chuta H a t a ( H i r o s h i m a F o o d Ind. Expt. Sta.). N 6 s a ~ K a k 6 Gyqitsu K e n ~ y f t K a i s h i 6, 48-50 (1959). B r o w n p i g m e n t s in rape oil were composed of the following components: (1) iron salts of f a t t y acids, (2) colored oxidized f a t t y acid, (3) water-insoluble, nitrogen-containing colored substance, (4) water-soluble, nitrogen-containing colored substance. The last seems to be an aldehyde-amine condensed substance. (C. A. 53, 22587) SPEC'TROPHOTOMETI~Y OF THE EDIBLE 0ILS. I I . F. D. Francesco. Olii minerali, grassi e saponi, colori e vernici 36, 73-6 (1959) ; cf. Boll ~ab. chim. provinciali 9, 76-89 (1958). The fluorescence d i a g r a m s ~obtained in the exanlination of several oils are discussed. (C. A. 53, 22587) ANALYTICAL STUDY OP EDII~LE OILS USED IN SPAIN, 1955-56. R. F u e n t e and R. Garcla Olmedo (Univ. M a d r i d ) . Anales bromatol. ( M a d r i d ) 11, 213-43 (1959). The chemical and physical constants of olive oil of various origins, cottonseed oil, pork fat, and b u t t e r are determined. (C. A. 53, 22587) CttANGES IN STABILITY OV OIL DURING DEEP-FAT FRYING. Yoshiko Yanmmoto, F u t a r a On0, and K i m i Tanaka. K a s e i g a ] c u Zasshi 10, 57-60 (1959). Ohanges in iodine, peroxide, a n d acid values were studied during deep-fat f r y i n g of fish meats and vegetables. (C. A. 53, 22587) THE CAUSE 0P DETERIORATIONAND THE ~ECHANICAL PR(~T~CTI0'N OP PATS FROM ENVIRONMENTAL FACTORS. A. P u r e n a s , J. Venskevi~ius, and L. Bernatoniene ( K a u n o Politech, Inst., K a u r n a s , L i t h u a n i a ) . K a u n a Politech. I n s t . Darbai 9, 19-24 (1958) ( R u s s i a n s u m m a r y ) . U n d e r identical p a c k a g i n g and storage conditions, tallow oxidized f a s t e r t h a n lard. The oxidation of f a t s packaged in casein-enamelled wooden boxes proceeded slightly f a s t e r t h a n in tin-coated metal cans. (C. A. 53, 22586) EFFECT OF LIPIDES 0~ LIP0'PROTE~IN FORMATION DURING DOUGHING OF FLOUm t t i r o m u Kisaki (Doshisha W o m e n ' s Coll.). Doshisha JoshidJaigaku 8, 79-92 (1957). The addition of soybean oil to flour made the a m o u n t of extractable gluten and also the a m o u n t of glutenin increase; this m i g h t be due to the f o r m a t i o n of lipoprotein with protein and oil, while this effect was only observed by the addition of oil below 10% a g a i n s t flour. The addition of lecithin and some detergent to flour also increased the gluten yield. (C. A, 53, 22561) ]=~HOSPHATIDIC ACIDS. I V . A n n a Candela and G. J a c i n i (Staz. sper. olii e grassi, Milan). Olii minerali, grassi e saponi, colori e verniei 36, 110-]3 (1959). The methods of Baer and of Verkade for the p r e p a r a t i o n of dipahnitoy]phosphatidie acid are modified in order to o b t a i n greater yields. The phosphatldic acids f r o m soybean and linseed oils were extracted, and the antioxidizing power of the phospholipides was determined. (C. A. 53, 23009) ~ATTY ACIDS CO3fPONGNTS OF GLYCERIDES IN THE DISTILLATE FRO~f THE MOLECULAR DISTILLATIC~N 0,F SHARK LIVEI~ OILS. Seiichi I s h i k a w a and Atsuko K o j i m a ( J i s s e n W o m e n ' s Coll.). J i s s e n Joshidaiga]cu K i y o 5, 1-4 (1958). Myristic, palmltic, and stearic acids, as s a t u r a t e d f a t t y acid components, and oleie, zoSmalir (C~H~O_,), and shark ~oleie a~ids, as u n s a t u r a t e d acds, were identified in the f a t t y acids m i x t u r e of the distillate of shark liver oil by molecular distillation. (C. A. 53, 230'08) ~ROCESSING SUNPL0WER SEED AND SOYDEANS BY ~ SINGLE-STAGE PRESSING AND AN UNINTERRUPTED EXTRACTION. M. A. M i n a s y a n and E. Z. Plyushkin. Maslobo~no Z h i r o v a y a P r o m . 1954(5), 29-31. The kernel (with a husk of 1.7-3.9%) is g r o u n d and roasted; the pulp (with a moisture of 4.5-5.5%) is pressed at 100-105 ~ at 12 revolutions per minute. The yield of oil is 83.8%. The oil cake is g r o u n d ; the g r o u n d cake, with a moisture of 5.5-7% and a n oil content of 13-14%, is extracted a t a rate of 6-7 cu. m . / h o u r ; the concentration o f ligroine in the outgoing solution is 10-11%. The amount of sediment is small, and the consumption of ligroine is 7.1 k g . / t o n of seed. The oil content o f the residual oil cake is 0.46-0.56%, b u t the oil content of the first oil cake a f t e r pressing is 9.06-9.75%. This method provides better results t h a n the method of a 2-fold pressing and a 1-stage extraction. (C. A. 53, 2 3 0 0 7 ) CHROI~IATOGRAPI~Y OF S0~s PHOSPHOLIPIDES SOLUBLE, IN ALCOrraL. G. De Zotti (Staz. sper. olii e grassi, M i l a n ) . Olii minerali, grassi e saponi, colori e vernici 36, 114-17 (1959).

109

The mixture of phospholipides obtained f r o m the soybean oil by precipitation with acetone and extraction with absolute ethanol was c h r o m a t o g r a p h e d on a column of cellulose powder and eluted with a mixture of ethanol ( 2 0 ) - c h l o r o f o r m (80)water (2.5) at 22 ~, or on silicon dioxide using chloroform containing 10% methanol. The leeithins isolated were at p u r i t y of about 95%, and the cephalins at 84%. The total yield is about 40% o f the weight of s t a r t i n g material. (C. A. 53, 230'07) APPLICATION OP SPECTR0.PHOTOMETRY TO THE ANALYSIS OP OLIVE 0ILS. I. THE USE OF THE ULTRAVIOLET SPECTROPHOTO,METER FOR THE IDENTIPICATION O1~ THE SUPERFINE OLIVE. OILS. A. Montefredine and L. La P o r t a (Lab. ehim. provinc. Pescara, I t a l y ) . Olii m~nerali, grassi e saponi, colori e vernici 36, 31-6 (1959). EXPEaIMENTAL PART. Ibid. 64-72. A f t e r a detailed review, speetrophotometrie d a t a of 206 samples of olive oil are tabulate& The ratio between the extinction value at 232 mg and 270 mt~ in the " s u p e r f i n e " olive oils is generally higher t h a n 10 and may reach 20; the average values of olive oils of various ages are discussed. (C. A. 53, 23006) CONTRIBUT~(~N TO THE DIF:FERENTIATION OF B-RECTIFIED OLIVE OILS. V. Sissi. Olii m~nerali, grassi e saponi, colori e vernici 36, 214-16 (1959). Some analyses are tabulated, and the criteria for the classification of several types of oils are discussed. (C. A. 53, 23006) IDENTIFICATION O'I~ OLIVE OIL ]~y 0LEUROPE.IN tCEACTION. H. Schmidt-Hebbel (U~iv. Chile, S a n t i a g o ) . Colegio f a r m . (Santiago, Chile) 16(190), 2-3 (1959), A eolorimetric method for detecting 10% or more of olive oil is described. (C. A. 53, 23006) CURRENT PROBLEMS IN THE PRODUCTION OP OLIVE OIL. M. Th. Francois. Bull. soc. pharm. N a n c y 38, 5-11 (1958). Discussed are mechanical and other procedures for preventing putrefactive changes leading to r a n c i d i t y in the off. The use of para~ thiGh and malathion as insecticides is undesirable, since they contaminate the oil. Methods of disposing of residues a f t e r expression ,of the oil are discussed. Oil which is rancid or otherwise of low quality m a y be renovated by saponification with alkali, followed by re~sterification with glycerol at high t e m p e r a t u r e s in the presence of a catalyst, b u t the p r o d u c t obtained does not have the flavor of good quality olive oil. The peroxide index is of limited value in determining quality. (C. A. 53, 230'06) THEI IODINE NUMBER O;P THE UNSAPONIF'IABLE MATTER, IN THE DIFPEI~ENT'IATION OF OLIVE OIL PROM OTHER 0~LS. ~I. L. F r o n t e r o . Olii minerali , gras~i e saponi, colori e vernici 36, 154-6 (1959). The determination of the iodine n u m b e r of the unsaponifiable m a t t e r p e r m i t s differentiation o f olive oil f r o m other oils. This value is lower f o r animal oils t h a n for vegetable oils. The method does not p e r m i t differentiation of the esterified olive oil f r o m the esterified oil obtained f r o m the f a t t y acids of p e a n u t ,oil. (C. A. 53, 23006) A I~EVIEW OF THE ~IETIKODS OF ANALYSIS OP OLIVE GILS~ WITH SPECIAL ]~XAMINATION OF SOME COLOR REACTIONS. S. Anselmi ( I s t , super sanifft, R o m e ) . Olii minerali, grassi e saponi, colori e verniei 36, 210-13 (1959). An accurate technique is proposed for the Fitelson reaction f o r the detection of tea oil in olive oil. The reaction is positive in the presence of 5% tea ~oil, and the color reaches a m a x i m u m within 4 minutes. (C. A. 53, 23006) RES]~ARCH OIP GRAI:~E SEED 0IL I N OLIVE OIL BY PAPE/~ CHR0'MATOeRAP~Y. G. Petruccioli ( I s t . Olivicolt., Spoleto, I t a l y ) . Olii minerali, grassi e saponi, colori e vernici 36, 260-3 (1959). By analytical methods it is not possible to detect g r a p e seed oil in some B-rectified olive oils. Use of p a p e r c h r o m a t o g r a p h y to detect the presence of linolenic acid is recommended. This procedure detects 5% of g r a p e seed oil in olive oil. (C. A. 53, 23006) PREPARATION OP SEBACIC ACID AND CAPI~YL ALCOHOL FROM CASTOR OIL. S h u - K u n g Chu and W e n H s i Lin ( U n i o n I n d . Research Inst., F o r m o s a ) . C h e m i s t r y ( T a i p e i ) 1959, 69-78. Castor oil was hea~ed 5 hours at 800 lb./sq, in. in a nickel-chromium stainless steel autoclave with the same weight of 50% aqueous sodium hydroxide at 310 +__5~ to give sebacic acid in 44.6:% yield and eapryl alcohol in 28.2% yield. W h e n 3% cadmimn oxide was added in the above reaction f o r 1 hour, it gave 45.6% sebacie acid and 26.7% eapryl alcohol (C. A. 53, 2300'5)

II0

THE

JOUaNAn

o ~ THE

AMERICAN

CHEMICAL COMPOSITION OF THE OIL OF EUONYMUS YE'P~UCO.SA. N. I. Simonova ( I n s t . M o t i o n P i c t u r e Ingrs., L e n i n g r a d ) . Zhur. PriIAad. K h i m . 32, 1637-40 (1959). Ethyl ether extraction of seeds of E u o n y m u s verrucosa f r o m the N o r t h e r n Caucasus and f r o m the L e n i n g r a d region yielded 4 5 - 7 % oil ( d r y b a s i s ) . The composition 'of this oil was as follows: s a t u r a t e d acids 19.3, oleic 55.8, linoleic 19.3, and linolenic 5.6%. (C. A. 53, 23005) ESTIMATION OP EPOXIDES IN 0ILS AND FATS. L. I~rull (MargarineUnion Akt.-Ges., H a m b u r g - B a h r e n f e l d , Ger.). Farbenchemiker 61, 23-7 (1959). A new" method for the estimation of epoxides, based on a r g e n t o m e t r y , has been developed and critically investigated. (C. A. 53, 23005) D]~TECTI0,N OF SlVIALL &MOUNTS OF CASTO~ 0IL IN THE VEGETABLE OK ANIMAL OILS AND FATS. S. Anselmi, L. Boniforti, and R. Monacelli ( I s t . super, sanitY, Rome). Olii m~nerati, gravsi e 8aponi, eolori e vernivi 36, 253-5 (1959). A m i x t u r e of the oil with paraffin is extracted with 90% alcohol; the alcohol is evaporated, and the residue is dissolved in petroleum ether and ethyl ether (9: 1). The f a t t y acids are eliminated by adsorption on silicic acid; and the castor oil is identified a f t e r condensation with p-dimethylaminobenzaldehyde. An orange-red color develops a n d (in chloroform) shows a m a x i m u m adsorption at 532 mt~. ( C . A. 53, 23005) PREPARATION O~ AZ.ET~AIC ACID FI~OlYi CASTOR OIL BY T~HEIACT~I0'N OF NITEIC ACID. Shigen'obu K a w a h a r a . N a r a Gakugei Daigaku K i y o 5, 57-60 (1955). Castor oil was heated with nitric acid and with m a n g a n e s e dioxide as the catalyst. B y this about 15% of azelaic acid f r o m castor :oil could be obtained. (C. A. 53, 2.3005) DETEKMINATION OF ISOOLEIC ACIDS IN I~YDRDGENATED EATS. J. Pokorn2 a n d B. Kak55 (Vysok~ w chem. technol., P r a g u e ) . Pr~tmsyl pvtravin 10, 19-20 (1959). D e t e r m i n a t i o n b y means of the lead salts method gives results t h a t are 1 - 9 % lower than those of the spectral method. A calibration curve f o r the correction of results of the f o r m e r method is given. (C. A. 53, 2300'4) FFP~CT OP LIGHT ON AUTOXIDATION OF :~ATS. ~. ]~L~AC'HING, FLUOl~ESC~NCE, AN]) YELLOWING. H. P. K a u f m a n n and M. Vogelmann (Deut. Inst. F e t t f o r s c h u n g , Miinster/Westf., Ger.). Farbenchemiker 61, 6-10 (1959). Fluorescent spectra of crude linseed oil and ultraviolet a b s o r p t i o n spectra of crude linseed oil a n d B-carotene in different stages of exposure to sunlight a n d scattered light are given. Absorption maxima of chlorophyll lie at 660, 614, 576, 532, 529, 410 m~, of pheophytin a at 665-70, 608-10, 559, 532, 505, 470, 410 m~, and pheophytin b at 653, 599, 558, 523, 433, 413 m~. The absorption m a x i m u m of B-carotene and p h e o p h y t i n a are to be f o u n d in linseed oil. On exposure to light B-carotene in oil seems to be more stable t h a n in methanol solution (1 rag./100 ml.), whereas the absorption b a n d s of pheophytin a are shifted to those of pheophytin b. (C. A. 53, 230:04) ~'I~EA COI~IPLEXES--PREPARATION OF FATTY ACIDS AND ESTE]~S I~I~OM COTTONSEED OIL. N. A. Khan (Fast Regional Labs., Dacca). Pal~istan J. Sci. Research II, 9-12 (1959). Formation of the u r e a complex was utilized f o r s e p a r a t i n g oleic and linoleie acids f r o m cottonseed oil acids. (C. A. 53, 23003)

VAI~IATIONS IN THEI C(~I~IPOSITION O1~ ~gO0*L FAT. I. ACID NUI~IBEE AND LIGHT REFRACTION. G. Nitschke ( F o r s c h u n g s i n s t . Textiltech., K a r l - M a r x - S t a d t , Ger.). Faserforsch. u. Textiltech. 10, 380-7 (1959). A review with 25 references. (C. A. 53, 23003) DETERMINING TH~ ACETYL VALUE O'F DEE.PLY COIA)BED ]~ATS. A. 1%. S. K a r t h a ( M a h a r a j a ' s Coll., E r n a k u l a m ) . J . Sc/. In.d. Research ( I n d i a ) 18B 217-19 (1959). A method u s i n g acetic anhydride is described. (C. ,4. 53, 23003) CATALYST IN FAT CHEI~IISTRY. J. E. W. Coenen (Unilever Research Lab., Vlaardingen, N e t h . ) . Chem. Weekblad 54, 715-18 (1958). An address. (C. A. 53, 2.300.1) E,FF~CT OF C'OBALT-60 "y-IZAY RADIATION O,N THE, FATTY CONSTITUENT O~ t ~ KAMABOKO. ~ ~ Chieko Urakaml and Hiroko Tanaka. Kasei-gak~ Zassi 10, 70-3 (1959). A marked increase in peroxide value w a s observed when f a t extracted f r o m kamaboko and fish meat paste is irradiated in the presence of air, b u t no increase occurs in the absence of air. (C. A. 53, 230.01)

~UTOREACTIONS O]~ RICINOLEIC ACID. I. REACTION AT 180 c, 147 ~ 122--3 ~ AND AT ~00~ TEMPERATUKE. F. Hawke and E. A. Kohll ( A f r i c a n Explosives Chem. Inds., Ltd. T r a n s v a a l ) . J. S. A f r i can Chem. Inst. 12, 1-16 (1959). When ricinoleic acid is heated or kept at room t e m p e r a t u r e in an inert atmosphere, the m a i n

OIL CHEMISTS'

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reaction is the f o r m a t i o n of estolides, this reaction being of the second order. P u r e ricinoleic acid is very reactive, there being a m a r k e d drop in its hydroxyl value if it is kept at room temp e r a t u r e f o r more t h a n a few hours. I t m u s t be stored as a solid below 4 ~ The autoreactions of ricinoleic acid are intramolecular dehydration, the hydroxyl g r o u p reacting with either neighboring h y d r o g e n atom to give m i x t u r e of linoleic acids, and intermolecular dehydration, the hydroxyl group condensing with a free carboxyl g r o u p of another molecule to f o r m estolides. The reaction can be repeated, giving long-chain polyco ndensates. I I . CA'I~ALYZI~DI~I~HYDR~TION OF RICINOLEIC AGID. Ibid. 17-25. Chemical dehydration of rieinoleic acid at 180 ~ in the presence of anhydrous sodium acid sulfate proceeds in two stages. The first stage f o r m s short-chain estolides and diethenoid acids tog e t h e r with some enantbal and 10-undecenoic acid. I n the second stage as the hydroxyl value approaches zero, r u p t u r e of estolide chains commences, f o r m i n g f u r t h e r quantities of diethenoid acids, mainly c o n j u g a t e d 9,11-octadecadienoic acid. Chemical dehydration is a first-order reaction with respect to hydroxyl value, while estolide f o r m a t i o n is second-order with respect to neutralization and hydroxyl values. (C. A. 53, 19863) PKEPARATION OF UNSATURATED FATTY ACIDS FI~0,M THE FATTY ACIDS OBTAINED IN THE OXIDATIONOF PARAFFIN. I. V. Nicolescu, P. Vasilescu Em. Angelescu, and P. Antonescu (Univ. C. I. P a r h o n , Bucure~ti, R o m a n i a ) . Analele univ. " C . I. P a r h o n ' " Bueure~.ti, Ser. stiint, nat. 1958, No. 18, 57-62. The a u t h o r s have obtained u n s a t u r a t e d acids with an iodine n u m b e r 112 f r o m the fraction C~4-C~o and with an iodine number 82 f r o m the f r a c t i o n Cv-CI~. This latter f r a c t i o n h a d not been studied before. The s a t u r a t e d acids were chlorinated up to a chlorine content of 2-2.5/mole. A higher chlorine content produced decomposition and polymerization when dechlorination of the acid was attempted. The dehydrochlorination was achieved in an autoclave in about 5 hours at 170-180 ~ and 13-15 atmospheres in the presence of calcium hydroxide. An excess of about 15% calcium oxide had to be present. The u n s a t u r a t e d acids thus obtained were used in the p r e p a r a t i o n of u n s a t u r a t e d alcohols a n d epoxides. (C. A. 53, 19856) QUALITY EVALUATIONOF LARD. J. W u r z i g e r and E. Lindemann. Fleisehw~rtschaft 10, 599-605 (1958). Measurement of quality of lard by acid number, extinction at $ 4 7 E of sample treated with alkali according to W u r z i g e r and Lindemann, Lea number, a n d quotient e x t i n c t i o n / L e a n u m b e r ( Q p ) is studied in r e g a r d to effect of storage of raw material before rendering, rendering temperature, and time, and of f r y i n g . I n general very sound lard has a Qp of about 0.10 or less; a value above 0.15 occurs with excessive rendering temperatures, and poor quality of r a w materials. A t extinction above 0.45 the lard has poor stability and should be excluded f r o m importation. I f extinction is 1.0 or more, independent of acid n u m b e r and L e a number, it should be considered spoiled. W i t h calculated Lea value ( m u l t i p l y i n g extinction by 10) the w a r n i n g value should be 3. A s t u d y of imported lards show t h a t those f r o m the U. S. A. had very low Q p ' s (usually below 0.10), those f r o m Holland had Qp 0.15-0.20, while lards f r o m Poland and Sweden were intermediate. (C. A. 53, 22586) STUDIES ON THE KtCEIS TEST. I I I . I~REIS TEST FOI~ SUBSTANCEIS I~ELATED TO SYNTHESIS OI~ VITAMIN A. Seiichi Ishikawa, Toseko Asano, and Ikuo Iizuka ( J i s s e n W o m e n ' s Coll.). Jissen Joshi Dwigaku K i y o 3, 1-3 (1955). IV. PEROXIDE VALUES OF ALDE:HYDES. Seiichi Ishikawa and Luko Itorikawa. Ibid. 4-8. V. COMPAKISON AMONG T~STS OF RANCIDITY IN FATS AND OILS. Seiichi Ishikawa, Keiko Terasaki, and Nobuko K a n b a r a . Ibid. 4, 1-4 (1957). VI. INDOLE, KREIS, AND THIORARBITUF~IC ACID TESTS. Seiichi Ishikawa and Akiko Matsunaga. Ibid. 5, 5-9 (1958). The indole test was found to be the most stable one to aldehydes and thiobarbituric acid tests. In the indole test I ml. of petroleum ether, 1 drop of aldehydes (I~0 ml.) were placed in a test tube, and the mixture was shaken 30 seconds. Then, 1 ml. iof 0.05% indole-methanol solution was added, and the tube was shaken f o r 30 seconds. The lower layer of this mixture was used f o r colorimetry. (C. A. 53, 23009)

THE USE. 01~ HYDBOGE]~I PE~0XIDE FOR OXIDATION O'F BIVALENT IRON IN SOLUTIONS OF A NICKEL CATALYST. A. G. KoblyanskH a n d N. Kh. K a m e n e v a . T r u d y Krasnodar. Inst. Pishchevo~ P r o m . 1956, No. 13, 3 - 7 ; Referat. Zhur., K h i m . 1957, A b s t r . No. 33974. Oxidation by h y d r o g e n peroxide of bivalent iron was investigated in " s o l u t i o n s of a nickel catalyst ~ t h a t con-

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t a i l e d 8.37 g . / l i t e r nickel a n d 0.72 m i l l i e q u i v a l e n t b i v a l e n t iron in the f o r m of s u l f a t e s , as well as s u l f u r i c acid a n d occasionally c e r t a i n o r g a n i c m a t e r i a l s o b t a i n e d in the f a c o r y in the process of h y d r o g e n a t i o n Of f a t s . I n this case, o w i n g to t h e presence of organic m a t e r i a l , the q u a n t i t y of h y d r o g e n peroxide used was 1.5-2.0 t i m e s t h a t n e c e s s a r y for t h e oxidation of b i v a l e n t iron. T h e n e c e s s a r y a m o u n t of h y d r o g e n per,oxide decreased with i n c r e a s e d c o n c e n t r a t i o n of s u l f u r i c acid up to a c e r t a i n l i m i t ; it also decreased when s o d i u m c a r b o n a t e or c u p r i c s u l f a t e was a d d e d to t h e liquid; the a m o u n t of h y d r o g e n peroxide i n c r e a s e d with increased t e m p e r a t u r e . The use of h y d r o g e n peroxide for oxidation of b i v a l e n t iron can s i m p l i f y the process a n d save labor on r e g e n e r a t i o n of nickel a n d copper f r o m u s e d catalysts. (C. A. 53, 23004) HYDROGENATION O| FATS AT LO~V~ r TEMPERATURE,S. B. N. Wyuty u n n i k o v a n d I. I. N o v l t s k a y a . Trudy Khar'tcov Politekh. Inst. im. V. I. Lenina., Set. Khim.-Tel~hnol. 1 3 ( 4 ) , 97-104 (1957). F a t s o b t a i n e d t h r o u g h h y d r o g e n a t i o n of oils a t 100 ~ have a f a i r l y s h a r p odor. L o w e r i n g of t e m p e r a t u r e below 100 ~ lessens the odor. T h e recovery of t h e c a t a l y s t f r o m 100 ~ h y d r o g e n a t i o n is m a n y t i m e s less t h a n the recovery a f t e r 200 ~ h y d r o g e n a t i o n : W i t h t h e increase of the q u a n t i t y of c a t a l y s t a t a c o n s t a n t t e m p e r a t u r e , its recovery decreases. I n c r e a s i n g t h e h y d r o g e n s u p p l y p e r m i t s i n c r e a s e d c a t a l y s t recovery. T h e selectivity of h y d r o g e n a t i o n of sunflower a n d cottonseed oil a t 100 ~ with the u s e of 0.5% nickel is lower t h a n at 200~ w i t h 0.15% nickel. W h e n the c a t a l y s t q u a n t i t i e s are f u r t h e r i n c r e a s e d the hydrogen a t i o n selectivity increases. I n t h e 100 ~ tests, t h e f o r m a t i o n of isohleic acids is low, especially in t h e h y d r o g e n a t i o n of whale f a t . Cottonseed oil develops less isohleie a c i d s than does sunflower oil. I n c r e a s e s in c a t a l y s t i n d u c e s i n c r e a s i n g developm e n t of isohleic acids. T h e p h y s i c a l p r o p e r t y of f a t s obtained f r o m cottonseed a n d sunflower oils a t 100 ~ are similar. The consistency differs s h a r p l y f r o m t h e consistency of whale f a L (C. A. 53, 23001) Co!~IPOSITIOlq o,P A PARAFFIN WAX IVRACTION FR0.~ TOBACC'OL15AF AND TOBACC;O SMOKEI. W. C a r r u t h e r s a n d R. A. W. J o h n s t o n e

( M e d i c a l l~es. Council Carcinogenic S u b s t a n c e s Res. Group, Univ. of E x e t e r ) . Nature 184, 1131-1132 (1959). M a s s spectroscopic a n d gas-liquid c h r o m a t o g r a p h i c a n a l y s e s of p a r a f f i n w a x isolated f r o m g r e e n tobacco leaf, f r o m the black f e r m e n t e d tobacco of a v a r i e t y o f A r g e n t i n i a n cigarettes, a n d f r o m the smoke of these e i g a r e t t e s i n d i c a t e d t h a t t h e w a x f r o m each w a s a complex m i x t u r e of s i m i l a r composition, n - t I e n t r i a c o n t u n e (C.n) w a s the m a i n i n d i v i d u a l component, b u t a p p r e c i a b l e q u a n t i t i e s v f t h e Ce9 a n d t h e C~s a n d small a m o u n t s of the Cso a n d C:~..,h o m o l o g u e s were also present. Relatively h i g h concent r a t i o n s of t h e b r a n c h e d i s o m e r s of C29-C~ a l k a n e s were also found. A n a l y s e s of the m e t h y l esters of f a t t y a c i d s f r o m fluecured tobacco o f a v a r i e t y of B r i t i s h c i g a r e t t e s showed t h e m a j o r c o m p o n e n t to be m e t h y l p a l m i t a t e a c c o m p a n i e d b y some s t e a r a t e a n d s m a l l e r a m o u n t s of other h i g h e r a n d lower homologues. Considerable a m o u n t s of C~s u n s a t u r a t e d esters were also p r e s e n t with m e t h y l linolenate predoming~ing. PttOCE.SS FOIl pREPARII'IG A WATEI~-DISPEI~SIBLE. ALC(~H0,L-S0~UBLE PHOSPHATIDE CO~[POSITION. P. F . Davis a n d tI. T. Iveson (Glidden Co.). U. S. 2,910,362. A liquid triglyceride oil is a d d e d to a n alcohol-soluble e x t r a c t (still wet w i t h the extracti n g alcohol) of whole p h o s p h a t i d e s so t h a t the m i x t u r e c o n t a i n s 65 to 73% p h o s p h a t i d i c material: T h e m a s s is t h e n dried u n d e r conditions which will expel m o s t of the residual alcohol without d a m a g i n g t h e p h o s p h a t i d e , deodorized, a n d diluted with 5 to 15% of a n edible polyol such as p r o p y l e n e glycol or glycerine. METHODS FOIr TI-IE F!~ACTIONAL CRYSTALLIZATION 0F COTTONSEED OIL. L. J. l%ubin, B. F. Teasdale, a n d W. G. M e r t e n s ( C a n a d a Packers, Ltd., Toronto, Ontario, Can.). U. S. 2,910,363. A process f o r w i n t e r i z a t i o n of cottonseed oll consists of m i x i n g t h e oil w i t h 15% or less of a low-molecular w e i g h t ketone, acetate, or ether, r a p i d l y chilling the solution to 2 8 ~ h o l d i n g at t h a t t e m p e r a t u r e r a n g e f o r n o t m o r e t h a n 8 h o u r s to crystallize t h e h i g h e r - m e l t l n g triglycerides, a n d finally separ a t i n g the crystallized f r o m t h e liquid f r a c t i o n . PROCess OF P~EPA~ING STABLE rAT'rY ~ONO~LYCERmES. J. G. B a l d i n u s ( C o l g a t e - P a l m o l i v e Co.). U. S. 2,910,491. A n unstable f o r m of a solid p o l y m o r p h i c f a t t y m o n o g l y c e r l d e of a s a t u r a t e d f a t t y acid c o n t a i n i n g m o r e tha~l 12 caxb`on a t o m s is s u b j e c t e d to m e c h a n i c a l w o r k i n g to b r i n g a b o u t a solid-solid t r a n s i t i o u to t h e stable p o l y m o r p h i a f o r m . T h e m e c h a n i c a l process m a y be extrusion, compression, m a s t i c a t i o n , k n e a d i n g , or m i l l i n g a n d is p e r f o r m e d at a t e m p e r a t u r e a p p r o a c h i n g the m e l t i n g p o i n t of the monoglyceride.

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PEANUT BUTTER PRODUCT. G. I-L R o w l a n d a n d C. W. W i l l i a m s , J r . ( S a f e w a y Stores, I n c . ) . U. S. 2,911,303. The p r e p a r a t i o n of a stabilized p e a n u t b u t t e r which is n o t s u b j e c t to oil separation, a n d which h a s good p a l a t a b i l i t y , smoothness, a n d spreada b i l i t y over a wide t e m p e r a t u r e r a n g e is described. T h e s p r e a d c o n s i s t s of particles of p e a n u t s h o m o g e n e o u s l y m i x e d with p e a n u t oiI t o g e t h e r with I0 to 2 5 % o f a n edible stabilizer which is a blend of 80 to 9 0 % ,of a n u n s a t u r a t e d liquid oil a n d 20 to 10% of a s a t u r a t e d v e g e t a b l e f a t . GRINDING AND RENDF~ING OF t~AT-CONTAINING TISSUE. C. Greenfield. U. S. 2,911,421. A n i m a l f a t - c o n t a i n i n g proteinaceous tissue is finely g r o u n d a n d t h e n h e a t e d a t reduced p r e s s u r e at a t e m p e r a t u r e sufficient to melt a t least a p o r t i o n of the f a t b u t below the c o a g u l a t i o n t e m p e r a t u r e of the protein. The w a t e r is s u b s t a n t i a l l y r e m o v e d as vapor a n d the liquir f a t c a n t h e n be easily s e p a r a t e d f r o m t h e solids in the r e s u l t a n t slurry. ]~ECOVERY 0.F S'FEARIC AND 0LEIC ACIDS. G. Greenfield. U. S. 2,911,423. A m i x t u r e of stearic a n d oleic acids is cooled to 75 ~ to 100~ The cooled m i x t u r e is p r e s s e d at 250 to 4,0'00 p.s.i. to s e p a r a t e the crystalline stearic acid. F u r t h e r cooling of the residual liquid s e p a r a t e s liquid oleic acid f r o m the r e s u l t i n g crystals. TRIGLYCEI~IDE C~)MPOSITIONS ESPECIALLY F01~ USE IN SALAD 0ILS. T h o m a s t t e d l e y & Co. L t d . Brit. 316,343. Glyceride oils cons i s t i n g of esters o f f a t t y acids c o n t a i n i n g 8-24 carbon a t o m s J molecule a n d n o r m a l l y n o t suitable f o r use in m a y o n n a i s e s a n d s a l a d oils a r e m a d e s u i t a b l e for u s e b y r a n d o m interesterificalion with glycerol t r i e s t e r s of acetic, propionic, b u t y r i c or caproic acid, or t h e i r m i x t u r e s . Oils h a v i n g m i n i m u m iodine values of 80, a n d derived f r o m a n i m a l f a t s , f r o m m a r i n e oils. or t h e i r h y d r o g e n a t e d p r o d u c t s , a n d f r o m oils which a r e l a r g e l y e s t e r s of oleic, li~mleic a n d linolenie acids, a n d their h y d r o g e n a t e d products, are interesterified with glycerol t r i e s t e r s in a glycerol t r i e s t e r s : o i l mole ratio of 1.0:0.5-4:.0. The combined acids in desired p r o d u c t consist o f 5 - 2 5 % b y w e i g h t of the acids derived f r o m glycerol triesters. Oils c o n s i s t i n g l a r g e l y of esters .of laurie acid, a n d of no specified iodine value, are similarly interesterified with glycerol t r i e s t e r s in a glycerol t r i e s t e r s : o i l mole ratio of 1:05.-2.0. The c o m b i n e d acids in t h e p r o d u c t consist of 2 5 - 3 0 % b y w e i g h t acids derived f r o m glycerol triesters. T y p i c a l oils t h u s used a r e p a r t i a l l y h y d r o g e n a t e d cottonseed a n d s o y b e a n oil a n d uIfllydrogenated coconut oil. Brit. 816,344. The p r o d u c t is similar with respect to the m e t h o d of interesterification a n d t h e r e a c t a n t s , b u t a m i n i m u m iodine v a l u e of 55 is p e r m i s s i b l e f o r t h e first oil. P r o p o r t i o n of glycerol t r i e s t e r s a n d 'oils are chosen to o b t a i n a h i g h yield of p r o d u c t c o n t a i n i n g 2 acid radicals of t h e glycerol t r i e s t e r s g r o u p a n d 1 acid f r o m the oil g r o u p s per glycerol-ester molecule. (C. A. 53, 22610) RECGVEttY 0~F WOOL WAX. L. F. E v a n s , W. E. Ewers, a n d C. S i m p s o n ( C o m m o n w e a l t h Scientific a n d I n d u s t r i a l R e s e a r c h O r g a n i z a t i o n ) . Get. 962,630. See A u s t r a l i a n 160,602. (C. A. 53, 20850) FR&CTIO~AL EXTt~ACTIO'N O~ LIPIDES I~RDIv~ NATURAL PRODUCTS. H. P. K a u f m a n n . Get. 1,000,225. Lipide f r a c t i o n s with increased iodine n u m b e r a n d free of p b o s p h a t i d e s are o b t a i n e d by e x t r a c t i n g the crude p r o d u c t s at --30 ~ to --60 ~ with hexane, ethyl chloride, or liquefied p r o p a n e c o n t a i n i n g 3 0 % b u t a n e . ( C. A. 53, 23011) SAPONIFICATION 0P WOOL FAT. S. D. ROSSOUW a n d E. v. Rudloff ( S o u t h A f r i c a n Council f o r Scientific & I n d u s t r i a l R e s e a r c h ) . Ger. 1,001,787. T h e wool f a t is saponified at 80-150 '~ b y m e a n s of calcium h y d r o x i d e a n d (or) m a g n e s i u m h y d r o x i d e a n d in t h e presence of other a d d i t i v e s w h i c h accelerate t h e saponification addition. S u i t a b l e a d d i t i v e s are s y n t h e t i c d e t e r g e n t s , e.g., alkyl s u l f a t e s , a r y l s u l f o n a t e s , or q u a t e r n a r y a m m o n i u m c o m p o u n d s ; solvents f o r wool f a t a n d water, e.g., ethylene glycol m o n o e t h y l ether, b u t y l alcohol, or dipropyl k e t o n e ; caustic alkalies; a n d calcium or m a g n e s i u m soaps. (C. A. 53, 23010) OILY eASE FOR LIQUID FGODS. N a o t o N a k a o k a , S h i n j i Mitsun a g a , S h u j i A r a i , a n d J u n K a w a i ( N i p p o n l % t s & Oils Co.). Japan. 3733('59). S o d i u m p a l m i t a t e (0.1 kg.) ~ o n t a i n i n g 80% w a t e r is dissolved in 23 kg. w a t e r w i t h h e a t i n g . A m i x t u r e of 0.5 kg. m o n o g l y c e r i d e o f f a t t y acid, 0.1 kg. ester of f a t t y acid w i t h s o r b i t a n , a n d 50 kg. s o y b e a n oil i s a d d e d g r a d u a l l y , s t i r r e d a t 50 '~ a n d 23 kg. s u g a r is a d d e d to give a p r o d u c t which is stable, h a s a p l e a s a n t t a s t e , a n d is soluble in w a t e r or in liquid foods. (C. A. 53, 20616) POWDERED FATS AND OILS. S h i n s h i r o Ohtaki. Japan. 6~77('58). H y d r o g e n a t e d cottonseed oil, m e l t i n g a t 40 ,~ is h e a t e d with

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0.02% a n t i o x i d a n t u n t i l molten. Then, it is cooled to 35 ~ with a g i t a t i o n . This p r o d u c t is s p r a y e d in a cooling c h a m b e r at 5 ~ to o b t a i n t h e powdered oil. (C. A. 53, 23010) P R E V E N T I O N 0,I~ COL01~ATION AND DEVELO,P~IENT OF AN 0DOI%0PUS S U BS TA NC E IN REFINE]) 0 I L I)URING ST0~I~AGE. M i t s a i N a k a m u r a

a n d Akiri Suzuki ( S u g i y a m a I n d u s t r i a l Chem. R e s e a r c h Inst., I n c . ) . Japan. 6766('58). Deodorized s o y b e a n oil (4 kg.) is t r e a t e d with 8 g. of a 3 0 % a q u e o u s solution of (NaO,CCHf).~ NCI-IfCH,N(CfH~OH)C:H_oCO~Na a n d stirred f o r 2 h o u r s in nitrogen. T h e n t h e oil is w a s h e d with w a t e r to o b t a i n a t r e a t e d oil. P r o p e r t i e s of t r e a t e d a n d u n t r e a t e d oil are g i v e n : acid n u m b e r 0.03, 0.08; s m o k i n g p o i n t 238 ~, 230~ iron c o n t e n t 0.02 p.p.m., 0'.38 p.p.m.; odor agreeable, rancid. (C. A. 53, 23010) A . I . Skipin. U. S. S. R. 118,933. The p r e p r e s s e d cake is g r o u n d to a flour a n d t h e n s p r a y e d with atonfized w a t e r u n t i l it c o n t a i n s 7-13% water. (C. A. 53, 23010)

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sebacate. T h e b l e n d is t h e n h e a t e d above 100 ~ with 0.1 to 2.0% of a g u a n i d i n e c a r b o n a t e to give t h e desired lubricant. AI)IPIC AOID DIAMIDE. K . Merkel a n d A. P a l m ( B a d i s c h e Ani]in- & S o d a - F a b r i k Akt.-Ges.). Ger. 1,014,097. Adipie acid 1460 p a r t s was m e l t e d a t 152 ~ the t e m p e r a t u r e t h e n raised to 170 ~ a n d a s t r e a m of a m m o n i a i n t r o d u c e d d u r i n g 3 hours, u n t i l t h e f o r m a t i o n of t h e a m m o n i u m s a l t w a s complete. T h e mixt u r e was t h e n h e a t e d 4 h o u r s at 225 ~ w i t h distilling of aqueous a m m o n i a , t h e r e s u l t i n g d i a m i d e removed f r o m the reaction vessel, a n d allowed to solidify to give colorless adipic acid d i a m i d e 142'0 p a r t s . A l t e r n a t e l y t h e reaction can be carried o u t in the presence of C6HsCh. (C. A. 53, 19'892)

P R E P A R I N G PREPI~ESSEI) 0 I L CAKE FOR. EXTRACTION.

R achinskil, A. S. Mozzhukhin, N. M. S l a v a c h e v s k a y a , a n d L. I. Taifli. U. S. S. R. 118,935. A l i p h a t i c polyamines, a n d p a r t i c u l a r l y water- a n d fat-soluble p o l y e t h y l e n e p o l y a m i n e s a n d fat-soluble derivatives of e t h y l e n e d i a m ! n e a n d p o l y e t h y l e n e p o l y a m i n e s , are a d d e d to f a t s to a r r e s t oxidation, t o lower the peroxide n u m b e r , a n d to i n a c t i v a t e t h e m e t a l s w i t h i n the f a t . (C. A. 53, 23010) I N C R E A S I N G T H E STABILITY OF FATS.

F.

Yu.

oFatty Acid Derivatives FATTY AMIDES. I . PRE,PAtCATION AND PROPEBTIES. H . P. K a u f m a n n a n d K . J. Skiba (Deut. Ins. F e t t f o r s e h u n g , Miinster, W e s t f a l e n , Get.). Fette, Seifen, Anstriehmittel 59, 340-4 (1957). The a u t h o r s describe the p r e p a r a t i o n of f a t t y amides by d e h y d r a t i o n of a m n m n i u m salts of f a t t y acids b y reaction o f glycerides with a m m o n i a a n d by a F r i e d e l - C r a f t s reaction with NH.~COCI. (C. A. 53, 19857) P R E P A R A T I O N 0~P C ~ YSTALLI NE TRANS-TRANS I~[ETHYL LINOLEATE

HYDROPEROXID~5. A. B a n k s , S. F a z a k e r l e y , J. N. K e a y , a n d J. G. M. S m i t h ( T o r r y Res. Station, Dept. of Sci. a n d Ind. Res., A b e r d e e n ) . Nature 184, 816 (1959). M e t h y l linoleate, p r e p a r e d b y d e b r o m i n a t i o n of t e t r a b r o n l o s t e a r i c acid, w a s oxidized in p e t r o l e u m ether solution with oxygen gas, t h e r e s u l t i n g peroxide b e i n g c o n t i n u o u s l y e x t r a c t e d f r o m solution b y finely dispersed 85% aqueous m e t h a n o l s a t u r a t e d with p e t r o l e u m ether. P u r i f i c a t i o n was accomplished by f u r t h e r p a r t i t i o n of the peroxide a n d the u n c h a n g e d ester between m e t h a n o l a n d p e t r o l e u m ether. Two c r y s t a l l i z a t i o n s f r o m p e t r o l e u m ether at --35 ~ a n d two f r o m ethqnol at --76 ~ gave p u r e c o n j u g a t e d trans-trans m e t h y l linoleate hydroperoxidc. ESTERIFICATION MI~TH0,D. G. R. B o n d , J r . ( H o u d r y P r o c e s s Corp.). U. S. 2,910,489. A carboxylic acid such as oleie a n d an alcohol h a v i n g at least 6 carbon a t o m s arc reacted in the presence 'of c a t a l y t i c a m o u n t s of t i t a n i u m dichloride diacetate. The r e s u l t i n g ester h a s a n exceptionally low t~cid n u m b e r a n d a color as l i g h t as the original acid. H ~ A T - S E N S I T I V E COPYING PAPER. It,. Owen ( M i n n e s o t a M i n i n g & M f g . Co.). U. S. 2,9~0,377. The heat-sensitive l a y e r of a c o p y i n g - p a p e r contains, in i n t i m a t e association, one tool of silver b e h e n a t e , a b o u t one tool o f behenic acid, a n d a b o u t oneh a l f tool of protocatechule acid. Silver salts o f o t h e r organic acids such as stearic, oleic, laurie, a n d h y d r o x y s t e a r a t e m a y also be used.

PROCESS FOR paEPARING G L Y C O L MONOESTE,RS OF ORGANIC CARBOXYLIC AC'II)S. J. D. M a l k e m u s ( J e f f e r s o n Chemical Co.). U. S. 2,970,490. A glycol m o n o e s t e r o f a f a t t y acid is p r e p a r e d by the reaction of a carboxylic acid h a v i n g f r o m 6 to a b o u t 24 carbon a t o m s with a n alkalene oxide (ethylene, propylene, or glycidol) at t e m p e r a t u r e s of a b o u t 75 ~ to 175 ~ in the presence o f a n ammonium halide catalyst. Q u a t e r n a r y ammoniuni catal y s t s are p a r t i c u l a r l y effective. LOW-TEMPEtCATUICE S T ABI LI TY O1~ S Y N T H E T I C LUBRICANTS. B .

W.

Fowler, M. F. Hoare, a n d H. G. K r i s c h a i ( E s s o Res. a n d E n g . Co.). U. S. 2,911,368. A process f o r i m p r o v i n g t h e low-temperature viscosity of a s y n t h e t i c l u b r i c a t i n g composition is described. T h e l u b r i c a n t consists of a complex-ester, di-ester b l e n d p r e p a r e d f r o m nonyl alcohol, sebacic acid, a n d polyethylene glycol of molecular w e i g h t of a b o u t 200. T h e h a l f ester of t h e polyglyeol a n d t h e acid is f o r m e d a n d the acid p r o d u c t is t h e n esterified with t h e m o n o h y d r i c alcohol to f o r m t h e complex-ester. The all-ester consists essentially of di-nonyl

9 Biology and N u t r i t i o n ATHEROSCLEir IN TIiE BANTU. J. P . Strong, J. W a i n w r i g h t , a n d H. C. McGill, J r . ( D e p a r t m e n t s of P a t h o l o g y , L o u i s i a n a S t a t e U n i v e r s i t y School of Medicine, New Orleans, L a . ) . Circulation 20, 1118-27 (1959). The n a t u r a l h i s t o r y of aortic atherosclerosis in t h e B a n t u , of D u r b a n , South A f r i c a , ages 1 to 40 years, is c o m p a r e d to t h a t of t h e N e w Orleans N e g r o a n d white m a n in t h e same age group. F a t t y s t r e a k s arc p r e s e n t u n i v e r s a l l y in all 3 g r o u p s to some e x t e n t a f t e r the first decade. T h e a v e r a g e s u r f a c e i n v o l v e m e n t w i t h f a t t y s t r e a k s is n o t a p p r e c i a b l y different in the 3 groups. The prevalence a n d q u a n t i t a t i v e e x t e n t of fibrous p l a q u e s are m u c h less in the B a n t u t h a n in t h e N e w Orleans N e g r o a n d New Orleans w h i t e m a n . T h i s difference does n o t a p p e a r to be due to s a m p l i n g bias b y selection of autopsies. The degree of aortic f a t t y s t r e a k i n g in early life is n o t correlated with reported g r o u p differences in d i e t a r y f a t intake, s e r u m cholesterol levels, a n d tl~e incidence of clinical m a n i f e s t a t i o n s of atherosclerosis in l a t e r life. T h e degree of aortic fibrous plaques in the f o u r t h decade does parallel the r e p o r t e d racial a n d g e o g r a p h i c differe~mes in t h e s e factors. DIETAI~y FAT AND PROTEIN AND SERUm[ CttOLESTEI~OL.

I. ADULT

SWINE. R. H. B a r n e s , E v a K w o n g , Grace Fiala, M. Reehicigi, R u t h L u t z , a n d J. Loosli ( G r a d u a t e School of N u t r i t i o n a n d t h e D e p a r t m e n t s of A n i m a l H u s b a n d r y a n d F;ood a n d N u t r i tion, Cornell U n i v e r s i t y , I t h a c a , N e w Y o r k ) . J. Nutrition 69, 261-268 (1959). A d u l t swine were f e d either a h u m a n - t y p e diet of m i x e d f o o d s or a purified diet with c h a n g e s in the n m o u n t a n d t y p e of f a t or the a m o u n t of protein. I n both t y p e s of diet, f a t caused the s e r u m cholesterol to rise with the g r e a t e s t increase r e s u l t i n g f r o m t h e m o s t s a t u r a t e d fat. T h e h u m a n - t y p e diet consistently gave h i g h e r s e r u m cholesterol values, b u t the response to different f a t s paralleled t h e results obtained with the purified diet. l I . YOUNG SWINE. :R. H. B a r n e s , E v a K w o n g , W. P o n d , R. Lowry, a n d J. K. Loosli. Ibid. 269-273 (1959). F o u r g r o u p s of weanling p i g s were f e d either high- or low-protein a n d either high- or l o w - f a t diets for 36 weeks. Evidence of p r o t e i n mall m t r i t i o n w a s nlost m a r k e d in t h e low-protein, h i g h - f a t group. These aninlals exhibited s i g n s t h a t have been i n t e r p r e t e d as r e s e m b l i n g the h u m a n i n f a n t disease, kwasMorkor. F a t in t h e f o r m of beef tallow in the diet c a u s e d a r a p i d rise in s e r u m cholesterol. L o w - p r o t e i n i n t a k e s also resulted in a n increase in s e r m n cholesterol. EFFECTS OF t i l G H PI%OTEIN I N T A K E S ON CHOLESTEa(~LE:MIA AND ATHEI~OGENESIS I N GF~OWING AND M A T U R E CHICKENS F'FAD HIGHFAT, HIGH-CHOLESTEI~OL I)IE,TS. R. Pick, J. Stamler, a n d L. N. K a t z ( C a r d i o v a s c u l a r D e p a r t m e n t , Medical Research I n s t i t u t e , Michael Reese H o s p i t a l a n d Medical Center, Chicago, Ill.). Circulatio~ Research 7, 866-9 (1959). H i g h p r o t e i n i n t a k e s u p p r e s s e s hypercho]esterolemia a n d a t h e r o g e n e s i s in y o u n g cockerels on high-cholesterol, h i g h - f a t diets. This h a p p e n s with s u p p l e m e n t a t i o n b y a n y n u t r i t i o n a l l y good protein a n d is m a n i f e s t irrespective o f source of cholesterol a n d type of f a t . I n n m t u r e roosters or h e n s - - as in y o u n g g r o w i n g cockerels--low p r o t e i n i n t a k e intensifies, a n d a d e q u a t e p r o t e i n i n t a k e suppresses h y p e r c h o l e s t e r o l e m i a a n d atherosclerosis o c c u r r i n g with high-cholesterol, h i g h - f a t diets. However, inhibition of coronary a t h e r o g e n e s i s i n d u c e d in hens b y e n d o g e n o u s e s t r o g e n secretion continues to supervene, despite low p r o t e i n intake. Oviduct l i g a t i o n p r e v e n t e d intensification of hypercholesterolemia a n d atherosclerosis with low p r o t e i n intake. EXTICACTION METHOI)S AND AN INVESTIGATION 0]~ DRKI~SOPFI:ILA LIPII)S. J. J. W r e n a n d H. K. Mitchell ( K e r c k h o f f L a b o r a t o r i e s of the Biological Sciences, C a l i f o r n i a I n s t i t u t e o f Technology, P a s a d e n a , C a l i f o r n i a ) . J. Biol. Chem. 234, 2823-27 (1959). The

FEBRUARY,

1960

flxBSTRACTS:

BIOLOGY AND NUTRITION

113

general problem of extractions of lipids w i t h o u t degradation is discussed and details of a s a t i s f a c t o r y procedure are presented. A m o n g lipids obtained front Drosophila were hydrocarbon, wax ester, cholesterol ester, triglyeeride, cholesterol, glyeerophosphatidic acid, phosphatidylglycerol, inositol phospho]ipids, phosphatidylethan01amine, ethanolamine plasmalogen, phosphatidylserine, cerebroslde, lysophosphatidylethanolamine, lysophosphatidylserine, phosphatidylcholine, choline plasmalogen, a n d lipids containing b o u n d amino acids. Twelve different b o u n d amino acids and p e r h a p s peptides were f o u n d in lipid fractions, but no f r a c t i o n contained more t h a n 0.1 mole of amino acid per kg. of lipid.

107 normal men for 7 years. A m o n g these 11 developed infarction and 6 a n g i n a peetoris. Little change in lipid levels was associated with these events. Eleetrophoretie p a t t e r n s early a f t e r infarction showed eertain relatively characteristic changes, especially, increase in a-2 and fl-globulins and fibrinogen. Lowdensity lipoprotein also increased. WMle a-2 globulin was usually greatest in p a t i e n t s with the most extensive myocardial damage, there was little over-all correlation between lipoprotein p a t t e r n and severity of infarction. The " c o r o n a r y p r o f i l e " can be more sharply delineated by repeated lipid m e a s u r e m e n t s because as a g r o u p those with atherosclerosis and i n f a r c t i o n exhibit slightly elevated values.

~ATTY ACID DISTRIBUTION IN EGG YOLK AS INFLUE:NCED BY TYPE AND LEVEL OF DIETARY FAT. Pricilla Wheeler, D. W. PetersDn, and G. D. Miehaels ( I n s t i t u t e for Metabolic Research, Highland-Alameda County Hospital, Oakland, California). ' J . Nutrition 69, 259-60 (1959). H e n s were fed diets r 5, 10, 15, 22.2, or 30% of safflower oil; 22.2 or 30% linseed oil; and 10% of cottonseed, corn, or soybean oil. The total f a t t y acids of the yolk f s t were determined by alkaline isomerization and by gas-liquid c h r o m a t o g r a p h y and their distribution eonlpared with t h a t of eggs produced on a stock diet or on a low-fat diet. I n eggs f r o m hens fed diets containing linolenic acid, linoleic acid was not deposited as efficiently as in those f r o m hens fed safflower oil or cottonseed oil suggesting an antagonistic or inhibitory effect of linolenic acid t o w a r d incorporation of ]ino]eic acid into yolk fat.

RELATION BETWEEN DIETARY FAT, FAT CONTENT 0F' MILK AND CONO~N~A~ON OF CERTAIN ENZYM]SS IN HUMAN MILK. M. G. Karmarkar and C. V. Ramakrishnan (Biochemistry Department, Faculty of Science, Maharaja Sayajirao University of Baroda, Baroda, I n d i a ) . J. Nutrition 59, 274-6 (1959). D i e t a r y fat, milk f a t and the ]ipase, esterase, acid and alkaline phosp h a t a s e contents of milk of 60 lactating women were estimated a n d i t w a s f o u n d t h a t up to a certain limit increases in dietary f a t were accompanied by increases in milk f a t as well as in lipase, esterase, and alkaline p h o s p h a t a s e contents o f milk.

HYPOCHOLESTEREMIC ]SFFECT OF BENZMALACENE. I, H. P a g e and R. E. Sehneckloth. (Research Division, Cleveland Clinic Foundation, Cleveland, Ohio). CircMation 20, 1075-8 (1959). Benznlalacene iN- (1-methyl- 2, 3 - di- p- ehloro-phenylpropyl-maleantic a c i d ) ] effectively lowers blood cholesterol levels in most hypertensive p a t i e n t s b u t with some weight loss. Cholesterol was lowered in some hypercholesteremic patients b u t not in all and this occurred without weight ]oss. I n 2 hypercholesteremic patients a s h a r p rise in triglycerides occurred while the ehol e s t e r o l : p h o s p h o l i p i d ratio fell and the free: total cholesterol ratio rose. Liver f u n c t i o n as m e a s u r e d by bromsulfa]ein a f t e r 4 m o n t h s ' t r e a t m e n t had deteriorated in 8 ~of the 12 p a t i e n t s studied. Nausea, epigastric discomfort, and diarrhea were on Occasion sufficiently discomforting to require discontinuing the drug. D r u g s t h a t interfere with cholesterol hynthesis should be studied with great care for ]ong periods before their widespread use in an a t t e m p t to p r e v e n t atheroselerosis. INFLUENCE 0,F HIGH LEVELS OF DIETARY PATS AND C'HOLESTEI%0L ON ATHBI~O.SCLEROSISAND LIPID DISTRIBUTION IN S~'INE.. R. Relser, Mary F. Sorrels, and M a r y C. Willimns ( D e p a r h n e n t of Biochemistry a n d Nutrition, Texas Agricultural E x p e r i m e n t Station, College S t a t i o n , T e x a s ) . Circulation Research 7, 833-45 (1959). The degree of incorporation of injected 1-C~*-aeetate into tissue cholesterol on cholesterol free diets w a s much higher in the liver and plasma of swine ingesting s a t u r a t e d t h a n uns a t u r a t e d fat. The levels of cholesterol in all tissues increased with the presence of f a t or cholesterol in the diet. The levels of cholesterol in all tissues increased with the presence of cllolesterol, a n d cholesterol levels were highest in the presence of u n s a t u r a t e d fat. The combination of u n s a t u r a t e d f a t with cholesterol in the diet produced the greatest degree of typical a t h e r o m a t o s i s and the highest levels of cholesterol in the tissues, while s a t u r a t e d f a t w i t h cholesterol produced diffuse atypical lesions. INTERMEDIATE~S IN THE CONVERSION 0F MEVALONIC ACiD TO SQUALENE BY A I~AT LIVE]~ ENZYME SYSTEM. L. h . W i t t i n g and J. W. P o r t e r (Radioisotope Unit, Veterans A d m i n i s t r a t i o n Hospital, Madison, Wisconsin). J. Biol. Chem. 234, 2841-46 (1959). An a m m o n i u m s u l f a t e precipitated f r a c t i o n of the water-soluble, s u p e r n a t a n t enzyme system f r o m r a t liver, h a s been f o u n d to f o r m at least nine intermediates between mevalonie acid and squatene. Three of these have been identified as 5-phosphomevalonic acid, 5-pyrophosphomevalonic acid, a n d isopentenyl p y r o p h o s p h a t e (pyrophospho-3-metbyl-but-3-ene-l-ol). The other six are water-soluble, acid-labile derivatives of higher terpenoid compounds, l%rnesol has been identified as a component of one of these compounds. LIPOPROTEINS, CI~OLESTE~OLAND SERUM PROITEINS AS PI~EI)ICTORS OF MYOCARDIAL INFARCTION. I. H. P a g e and L e n a A. Lewis (Research Division, Cleveland Clinic Foundas Cleveland, Ohio). Circulation 20, 1011-27 (1959). The normal variability of lipoprotein and cholesterol ]cvels was established f o r 6 women over a period of 5 m o n t h s for comparison with levels in people who develop myocardial infarction. We have studied

TtlE INI~LUENC[E 0IF SELECTED VEGETABLE FATS ON PLASMA LIPID CONCNNTtCATIONS AND AORTIC ATttEEOMATOSIS IN C~HDLESTEBI)LFED AND DIETHYLSTIBESTROL-ISIPLANTEDCOCKEI~ELS. D. M. Tennent, M a r y E. Zanetti, H. Siegel, G. W. K u r o n , and W. H. Ott (Merck I n s t i t u t e f o r Therapeutic Research, Rahway, New J e r s e y ) . J. N~trition 59, 283-8 (1959). I n cockerels fed diets containing 8.2% of vegetable f a t and 2% of cholesterol, there was a close connection between p l a s m a lipid p a t t e r n and the composition of the f a t fed. P l a s m a cholesterol concentrations were inversely p r o p o r t i o n a l to the percentage of polyenoie acids in the f a t (or directly p r o p o r t i o n a l to s a t u r a t e d plus monoenoie). P l a s m a lipid p h o s p h o r u s concentrations were inversely p r o p o r t i o n a l to the total a m o u n t of u n s a t u r a t i o n . Aortic lesion scores were not closely related to the composition of the f a t f e d . I t a p p e a r s t h a t a given p l a s m a cholesterol concentration in birds fed some f a t s m a y not be so injurious as the concent r a t i o n would be in birds fed other fats. VITAMIN-A CONTENT OF TI-IE FKOG EYE DURING LIGHT AND DARK ADAPTATION. Ruth H u b b a r d and A. D. Cohnan (Biological L a b o r a t o r i e s at H a r v a r d University, Cambridge, Mass.). Science 130, 9.77-8 (1959), Rhodopsin is synthesized f r o m l l - c i s retinene ( v i t a m i n A aldehyde), b u t releases all-trans retinene when bleached in light. I n the frog, both isomers of vitamin A are stored in the eye. Total ocular vitamin A, including t h a t b o u n d as retinene in rhodopsin, remains constant during light and dark adaptation. Stores of l l - c i s vitamin A, however, diminish in the light and are replenished in darkness. COMPOSITION OF CERE,BROSIDE ACIDS AS A ~UNCTIO.N OF AGE. Yasuo Kishimoto and N. S. Radin (Bioehem. Dept., Northwestern Univ., Medical School, Chicago). J. Lipid Research I, 79-82 (1959). The b r a i n s of f r o m 11 to 30 r a t s of various age g r o u p s (23 to 418 days old) were pooled and analyzed f o r total lipids, total cerebrosides, and the individual cerebroside acids. Cerebroside deposition is evident over the r a n g e of ages studied, and its contribution to the total depostion becomes increasingly i m p o r t a n t with increasing age. Cerebronie acid is by f a r the m a j o r cerebroside acid, b u t appreciable a m o u n t s of the alpha h y d r o x y C~ and C~ acids are also present. The uns a t u r a t e d acids constitute a nfinor element, and t h e contribution of the h y d r o x y u n s a t u r a t e d acids is least. The odd n u m b e r e d acids show the g r e a t e s t increases with age, comp a r e d to the other acids, while the h y d r o x y u n s a t u r a t e d acids show little accumulation except d u r i n g the earliest period studied. D e g r a d a t i o n experiments w i t h the s a t u r a t e d hydroxy acids show t h a t the hydroxyl g r o u p s are in the a l p h a position. OXIDATION O~F C'HOLESTEROL BY RAT LIVEI~ MITOC'HOINDRIA: EFFI~0T 0.P DIETARY FAT. D. Kritehevsky, Ruth R. Kolman, M. W. Whitehouse, M a r t h a C. Cottrell, a n d E. Staple (The W i s t a r Inst. of A n a t o m y and Biology, Philadelphia, P e n n . ) . J. Lipid. Research 1, 83-89 (1959). R a t s were m a i n t a i n e d on n o r m a l diets or on diets containing 20% corn oil or on commercial shortening for 40 days. The liver mitochondria of the r a t s fed s a t u r a t e d f a t oxidized eholesterol-26-C ~ to C~O_~ to a much greater extent t h a n did liver mitochondria f r o m r a t s fed u n s a t u r a t e d fat. I n general, liver mitochondria f r o m control rats also oxidized more eholesterol-26-C ~4 t h a n did mitoehondria f r o m rats fed u n s a t u r a t e d fat, b u t this difference was not as consistent. The results were the same with r a t s of either sex. Oxidation of sodium pyruvate-2-C~4 did n o t vary with diet. The results could not be a t t r i b u t e d to differences in liver lipid

]]4

T H E J O U R N A L OF THE AMEI%ICAN 0 I L

or cholesterol content. I t h a s been shown t h a t t h e homologous c o m b i n a t i o n of liver m i t o c h o n d r i a a n d boiled s u p e r n a t a n t f r o m t h e livers of t h e u n s a t u r a t e d f a t f e d r a t s g r e a t l y i m p a i r s cholesterol oxidation. A d d i t i o n of boiled s u p e r n a t e front the livers o f t h e other d i e t a r y g r o u p s to liver m i t o c h o n d r i a f r o m the r a t s f e d u n s a t u r a t e d f a t restores t h e cholesterol oxidation to nmunal levels as does s u b s t i t u t i o n of a ] 0 % sucrose solution f o r the boiled s u p e r n a t e . A d d i t i o n of the boiled liver superh a t e f r o m t h e a n i m a l s f e d u n s a t u r a t e d f a t to liver mitoc h o n d r i a f r o m the n o r m a l or s a t u r a t e d f a t f e d r a t s h a s no a p p r e c i a b l e i n h i b i t o r y effect. INDEPENDENCE OF AaTERIAL PI-IOSPHOLIPID SYNTTIE,SIS FI~OM ALT~I%ATIONS IN BLOOD LIPIDS. D. B. Zilversmit and E. L. McCandless (Dept. of Physiology, Univ. of Tenn., Memphis 3, Tenn.). J. Lipid Research i, 118-124 (1959). Rabbits fed cholesterol for 1 to 5 months showed gradually increasing amounts of aortic phospholipid preceded by increases in plasma phospholipld concentration. Cholesterol feeding appeared to increase the turnover of plasma as well as aortic phospholipid. Curtailment of p~asma phespholipid synthesis to one-tenth of normal by evisceration did not diminish the incorporation of p32 into aortic lipids. In these animals the aortic phospholipid specific activity was ]5 to 90 times as great as that of plasma, so that practically all of the labeled aortic phospholipid must have been synthesized in situ. Lowering the plasma lipid levels by removal of cholesterol f r o m the diet did n o t d i m i n i s h the choleserol c o n t e n t of t h e aortic lesion or alter its phospbo]ipogenesis. THE ISOLATI0~N A N D IDENTIFICATION OF L Y S O L E C I T H I N PROM LIPID E X T R A C T S OF N O R M A L HUMAN S E R U M . E. Gjone, J. F.

B e r r y a n d D. A. T u r n e r (Dept. of Medicine, J o h n s H o p k i n s Univ. School o f Medicine). J. Lipid Research I, 66-71 (1959). C h r o m a t o g r a p h y 'on silicic acid w a s employed f o r t h e separation of phospholipid c o m p o n e n t s of h u m a n serum, u s i n g diethyl ether, a n d c h l o r o f o r m - m e t h a n o l solutions as e l u t i n g a g e n t s . The c o m p o n e n t s identified b y p a p e r c h r o m a t o g r a p h y were cephalins, lecithin, s p h i n g o m y e l i n , a n d lysolecithin. Chemical a n a l y s e s a n d i n f r a r e d s p e c t r a were employed to confirm t h e identification of the c o m p o u n d s isolated. The q u a n t i t i e s of t h e phospholipid c o m p o n e n t were also determined. FATTY ACID OXIDATION BY CARP LIVER MITOCHONDRIA. W. D. B r o w n ( I n s t . of M a r i n e Resources, Univ. of Calif. Berkeley, Calif.) a n d A. L. Tappel. Arch. Biochem. Biophys. 85, 149158 (1959). The n a t u r e of the f a t t y acid-oxidizing s y s t e m in fish is similar to t h a t in m a m m a l s . Carp liver m i t o c h o n d r i a were s h o w n to c o n t a i n a n e n z y m e s y s t e m t h a t will Oxidize f a t t y acids in the presence 'of adenosine t r i p h o s p h a t e , eytochrome c, a n d M g ~+. B u t y r i c , octanoic, palmitic, olelc, linoleic, ]iuolcnic arachidonic, eicosapentaenoic, a n d docosahexaenoic acids were readily oxodized. TRA(~ER STUDIES ON THE BIOSYNTHESIS O~i~ CI.IOLESTE]%OL ~I~OM Cs pI%EC'URSORS IN ACTIVE BULLFROG SCIATIC NERVE. J. F. Saunders (Dept. of Chem., Georgetown Univ., W a s h i n g t o n , D. C.) a n d S. L. F r i e s s . Arch. Bioche~t. Biophys. 85, 234-244 (1959). The levels o f a s s a y a b l e total cholesterol in s h e a t h e d a n d d e s h e a t h e d p r e p a r a t i o n s of b u l l f r o g sciatic nerve have been f o u n d to be u n a f f e c t e d by i n c u b a t i o n with h i g h concentrations of u n l a b e l e d acetylcholine ion. However, i n c u b a t i o n with tr'tcer a m o u n t s of choline or a c e t a t e ions labeled with C ~4 results in i n c o r p o r a t i o n of isotope into cholesterol w i t h o u t i n c r e a s i n g t o t a l e n d o g e n o u s cholesterol levels of the tissue. These d a t a h a v e been i n t e r p r e t e d in t e r m s of possible processes l e a d i n g to t h e s y n t h e s i s of cholesterol in the nerve. SPECIpIC INHIBITI0~N OF CHOLESTEROL BI0'SYNTHE:SIS BY A SYNTHETIC CO,MPOUND ( M E R - 2 9 ) . T. R. B l o h m a n d R. D. MacK e n z i e (Dept. of B i o c h e m i s t r y , Scientific Div., T h e W m . S. Merrell Co., Cincinnati, Ohio). Arch. Biechem. Biophys. 85, 245-249 (1959). MER-29 is 1 - [ ( 4 - d i e t h y l a m i n o e t h o x y ) p h e n y l ] ]- (p-tolyl) -2- (p-chlorophenyl) ethanol. I n p r e l i m i n a r y t e s t s this c o m p o u n d w a s f o u n d to p r o d u c e a p r o f o u n d lowering of blo:od cholesterol in rats. F u r t h e r s t u d i e s i n d i c a t e d t h a t it i n h i b i t e d t h e b i o s y n t h e s i s of cholesterol in liver a n d i n t e s t i n e of t h e int a c t rat. T h e inhibition is specific f o r cholesterol a n d occurs at a late s t a g e in t h e s y n t h e t i c p a t h w a y , since i n c o r p o r a t i o n of acetate-]-C ~4 into total d i g i t o n i n - p r e c i p i t a t e m a t t e r of r a t liver is not affected, b u t i n c o r p o r a t i o n into cholesterol purified via t h e d i b r o m i d e is reduced. ]~PFECTS OF MER-29, A CHOLESTEROL SYNTHESIS INHIBITOR, O~N iVfA:I~IMALIAI~TISSUE LIPIDES. T. R. Blohm, T. K a r i y a , a n d M a r i e W. L a u g h l i n (Dept. of B i o c h e m i s t r y , S c i e n t i f c Div., T h e W m . S. Merrell Co., Cincinnati, Ohio). Arch. Biochcm. Biophys. 85, 250-2'63 (1959). T h e effects of MER-29 on t h e blood a n d

CHEMISTS'

SOCIETY

VOL. 37

tissue lipides of the r a t a n d m o n k e y were studied. Chronic a d m i n i s t r a t i o n significantly reduced t h e cholesterol levels of the following t i s s u e s in t h e r a t : p l a s m a , erythrocytes, liver, skeletal muscle, lung, a d r e n a l , a n d aorta. T h e cholesterol of b r a i n a n d adipose tissue was n o t reduced. L i v e r total lipide w a s unchanged, a n d liver a n d p l a s m a unsaponifiable m a t t e r were reduced. P l a s m a phospholipide Was also reduced, b u t less t h a n cholesterol. A linear relationship exists between the l o g a r i t h m ,of the dose a n d t h e r e d u c t i o n of p l a s m cholesterol a n d phospholiplde in t h e rat. I n m o n k e y s , oral a d m i n i s t r a t i o n of MER-29 over a 6 - m o n t h period r e d u c e d p l a s m a total a n d a- a n d fl-lipoprotein cholesterol, e r y t h r o c y t e cholesterol, a n d p l a s m a uunsaponifiable m a t t e r . I t h a d no effect on p l a s m a phospholipide or a- a n d fl-lipoproteins s t a i n a b l e with Oil R e d O. INVOLVEMENT OF ]%IETHIONINE IN BACTERIAL LIPID SYNTHESIS. W. M. O ' L e a r y (Div. of Biological a n d Medical Res., A r g o n n e N a t l . Lab., L a m o n t , Ill.). J. Bactcriol. 78, 709~713 (1959). The possible i n v o l v e m e n t of m e t h i o n i n e in bacterial, f a t t y acid s y n t h e s i s was i n v e s t i g a t e d . Lactobacillus arabinoius a n d a m e t h i o n i n e - s t i m u l a t e d m u t a n t of Escherichia coli were shown to i n c o r p o r a t e a p p r e c i a b l e a m o u n t s of m e t h y l carbon f r o m exogen o u s methionine-methyl-C~t I n each species, 20 to 2 5 % of the total r a d i o a c t i v i t y in the cells was c o n t a i n e d in the m i x e d cellu l a r f a t t y acids. C h r o m a t o g r a p h i c a n a l y s i s showed t h e r e was a selective a c c u m u l a t i o n of m e t h i o n i n e m e t h y l carbon in the C~s-~9 f r a c t i o n of L. arabinosus a n d in the c h r o m a t o g r a p h i c fraction of E. co~i acids t h a t is u s u a l l y f o u n d to c o n t a i n palmitic acid. The possible i n v o l v e m e n t of one-carbon t r a n s f e r s in the bacterial s y n t h e s i s of certaSn u n u s u a l f a t t y acids is discussed. BACTERIAL tIYDROCAR~0,N 0XIDATIO~. I I . ESTEI% POI%MATI0.N 1~1%O1~ALKANES. J. E. S t e w a r t a n d R. E. Kallio (Dept. of Bacteriol., S t a t e Univ. of Iowa, Iowa City, I o w a ) . J. Bactcriol. 78, 726-730 (1959). O x i d a t i o n of paraffins by a g r a m - n e g a t i v e coccus resulted in the a c c u m u l a t i o n of relatively h i g h molecular w e i g h t esters ( w a x e s ) . Octadecane yielded a 1 : 1 m i x t u r e of octadecyl s t e a r a t e a n d octadecyl p a l m l t a t e . T e t r a d e c a n e yielded tetradecyl ( m y r i s t y l ) p a l m i t a t e . The ester produced f r o m the dodecane was n o t completely identified b u t was shown to possess a p a l m i t y l moiety. The w a x e s p r o d u c e d always h a d a n alcohol with the same c a r b o n skeleton as the paraffin f r o m which it was derived, while the acid moiety was palmitic except in the case of octadecane where h a l f of t h e total ester was m a d e up of octadecyl s t e a r a t e . A CONCAVE CONCENTRATION GKADIENT OF i~IETHANOL IN C'HLOR0PO!%M EMPLOYED IN ELUTIO,N OF LIPIDS FROM SILICIC ACID. J. J. W r e n ( L y o n s Labs., H a m m e r s m i t h Road, London, W. 14). Nature 184, 816-817 (1959). A n a p p a r a t u s p e r m i t t i n g cont i n u o u s concave g r a d i e n t elution of lipids f r o m a silicic acid c o l u m n is described. E l u t i o n curves showed t h a t continuous g r a d i e n t elution gave s h a r p e r p e a k s a n d less tailing, avoided the spurious p e a k s produced b y t h e a b r u p t c h a n g e s of e h e n t in d i s c o n t i n u o u s g r a d i e n t elution, a n d improved resolution of t h e c o n s t i t u e n t lipids. PRESENCE 0P BEHENIC ACID IN SPI-IINGOMYELIN FI~OM I.IOI%SE SPINAL CO~D. Y. F u j i n o a n d T. N e g i s h i (Dept. of D a i r y Sci., Obihiro Zootechnieal Col., Obihiro, Hokkaido, J a p a n ) . Nature 184, 817-818 ( ] 9 5 9 ) . Crude s p h i n g o m y e l i n was purified by t r e a t m e n t with dilute alkali, column c h r o m a t o g r a p h y on alum i n a , a n d several recrystallizations f r o m ethyl acetate. A f t e r refiuxing with s u l f u r i c acid in m e t h a n o l , three f r a c t i o n s of m e t h y l esters were isolated. The f a t t y ~lcid of f r a c t i o n 1 (0.5 g.) was identified as nervonic, f r a c t i o n 2 (0.7 g.) as a m i x t u r e of stearic a n d palmitic acids, a n d f r a c t i o n 3 (1.4 g.) as behenic acid. HYDI~OGENATION OF LIPIDS BY KUMEN FROTOZOA. D. E. W r i g h t ( P l a n t Chem. Div., Dept. of Sci. a n d Ind. Res., P a l m e r s t o n N o r t h , N e w Z e a l a n d ) . Nature 184, 875-876 (1959). T h e ability of protozoa f r o m cow r u m e n to h y d r o g e n a t e various dietaxy u n s a t u r a t e d f a t s was studied. I n c u b a t i o n with a s u s p e n s i o n of r u m e n protozoa caused h y d r o g e n a t i o n of both linoleic acid a n d linseed oil. A s u s p e n s i o n of chloroplasts p r e p a r e d b y g r i n d i n g f r e s h l y picked r e d clover leaves was also incubated. T h e r e was considerable conversion of the C~s triene acid to diene a n d the nlonoene to stearic acid; tufty s l i g h t conversion of diene t,o m o n o e n e a p p e a r e d to have occurred. The non-saponifiable m a t e r i a l exhibited a s p e c t r u m t y p i c a l of a c a r o t e n e - x a n t h o p h y l l mixture. Little h y d r o g e n a t i o n fof t h e h i g h l y - u n s a t u r a t e d pigm e n t s h a d occurred, however. D I E T A R Y PROTEIN A N D SEKU~f CIIOLESTER0,L IN I~ATS. A. P. de Groot (Central Institute for Nutrition & F o o d Research, T.N.O.,

Utrecht).

Nature 184, 903-904 (1959).

Newly w e a n e d male

FEBRUARY, 1 9 6 0

ABSTRACTS: BIOLOGY AND NUTRITION

a n d f e m a l e r a t s were f e d a hypercholesterolemic diet w i t h supp l e m e n t s of different p r o t e i n c o n c e n t r a t e s or ami~o a c i d s ( a t 5 % of r a t i o n ) . L o w e s t levels of s e r u m cholesterol were obt a i n e d with d r i e d whole egg, w h e a t gluten, fish meal, a n d m e a t meal. Casein, gelatin, a n d s o y b e a n p r o t e i n were less active. Low cholesterol levels were also o b t a i n e d w h e n a mixture of a m i n o acids b a s e d on t h e composition of w h e a t g l u t e n w a s s n b s t i t u t e d f o r the i n t a c t protein. The a d d i t i o n of differe n t c o m b i n a t i o n s of 3 a m i n o acids ( a t c o n c e n t r a t i o n s of 0,2, 0.4, a n d 0.6% r e s p e c t i v e l y ) l o w e r e d t h e cholesterol level i f m e t h i o n i n e was one of t h e acids. E~FECT OF DIETARY I~AT AND EXTENT OF BLOOD SAMPLING ON THE LEVEL OF PLASMA CHOLESTEROL IN THE. t~AT. I. Coleman ( D e f e n s e R e s e a r c h Board, K i n g s t o n Labs., Barriefield, Ontario, C a n a d a ) a n d J. M. R. Beveridge. Nature 184, 1041-1042 (1959). R a t s were f e d h i g h f a t diets (58.5% of calories supplied b y corn oil), m o d e r a t e f a t diets (28.4% of calories supplied b y oil), a stock diet of ' ~ P u r i n a ~' f o x chow, a n d f a t free diets. The h y p e r c h o l e s t e r o l e m i a p r o d u c e d was a produ c t of both d i e t a r y f a t a n d the degree of h e m o r r h a g e to which the a n i m a l s were subjected. U n d e r conditions of low bleeding s t r e s s a h i g h f a t diet caused no c h a n g e in p l a s m a cholesterol. W h e n bleeding w a s increased to 1 to 1.5% of t o t a l blood on a l t e r n a t e d a y s f o r 6 days, a h i g h corn oil diet p r o d u c e d a significant increase in p l a s m a cholesterol a l t h o u g h a n i m a l s on a f a t free diet showed no change. W h e n bleeding w a s i n c r e a s e d to 2.5 to 4 % of blood volume, h i g h l y significant i n c r e a s e s in p l a s m a cholesterol occurred in b o t h t h e h i g h - f a t a n d t h e f a t free groups. T h e a u t h o r s s u g g e s t t h e effect of h e m o r r h a g e as a possible e x p l a n a t i o n f o r some of the conflicting r e p o r t s on t h e effect of d i e t a r y f a t s on t h e p l a s m a cholesterol level of rats. STEI~OL GLYCOSIDES IN OILSEED PtIOSPHOLIPIDS. F. A y l w a r d a n d B. W. Nichols (Dept. of C h e m i s t r y a n d F o o d Technology, B o r o u g h Polytechnic, L o n d o n , S.E. 1). Nature 184, 1319-1320 (1959). A c e t o n e p r e c i p i t a t i o n of a n ethereal solution of commercial rapeseed lecithin yielded a crude p h o s p h o l i p i d which c o n t a i n e d 2.1% of a sterol glycoside. A similar s u b s t a n c e isolated f r o m linseed p h o s p h o l i p i d c o n t a i n e d 2.9% of a sterol glycoside. I t is probable t h a t in each case fl-sitosterol is the m a j o r sterol component, b u t m i n o r p r o p o r t i o n s of other phytosterols m a y also be present. TOCOPHEROLS IN MIC~RO-OR.GANiS]~IS. J, Green, S. A. Price, a n d L. Gare ( W a l t o n Oaks Exptl. Station, Res. L a b s . o f V i t a m i n s , Ltd., D o r k i n g Rd., T a d w o r t h , S u r r e y ) . Nature 184, 1339 (1959). The occurrence of tocopherols in t h e lipid f r a c t i o n ~)f a r a n g e of m i c r o - o r g a n i s m s was i n v e s t i g a t e d . Of some 11 o r g a n i s m s studied, a-tocopherol was detected in Chlorobium thiosulphatophilum, Ochromonas malhamensi~, a n d F~uglena gravilis. W h e n g r o w n in the d a y l i g h t Ochromonas c o n t a i n e d a b o u t six t i m e s as m u c h tocopherol as did the s a m e o r g a n i s m g r o w n in t h e dark. The results t o g e t h e r with t h e o b s e r v a t i o n t h a t tocopherol occurred only in o r g a n i s m s c o n t a i n i n g chlorophyll s u p p o r t t h e s n g g e s t i o n t h a t t h e r e is a close r e l a t i o n s h i p between tocopherol a n d chlorophyll s y n t h e s i s a n d t h a t tocopherol m i g h t be f o r m e d f r o m t h e same p h y t o l p r e c u r s o r as chlorophyll. ISOMERS 0,P VITAMIN A IN" FISH LIVER OILS. P a t r i c i a S. B r o w n , W . P . B l u m , a n d M. H. S t e r n (Biol. Labs., H a r v a r d Univ., Cambridge, a n d the Res. L a b s . of Distillation P r o d u c t s I n d u s tries, Div. of E a s t m a n K o d a k Co.). Nature 184, 1377-1379 (1959). The occurrence of iso-a a n d iso-b, the 6-c@ a n d t h e 2,6-di-c/s i s o m e r s of v i t a m i n A, in a n u m b e r ~of fish liver oils h a s been i n v e s t i g a t e d b y m e a n s of reaction with t h e r e t i n a l protein, opsin. These isomers were f o u n d to c o n s t i t u t e a b o u t 20% of the v i t a m i n A in t h e cod, shark, a n d m i x e d fish liver oils ekamined. A s m e a s u r e d by r a t bioassay, the isomers have only a b o u t o n e - f o u r t h t h e g r o w t h - p r o m o t i n g a c t i v i t y of alltrans v i t a m i n A. T h e possibility of the isomers o r i g i n a t i n g f r o m in vivo i s o m e r i z a t i o n of all-trans or n e o v i t a m l n A to f o r m a n equilibrium m i x t u r e is discussed. EI~!~EC'T OF ~AMIN0-AC~D IMRALANC'E~ ON GI~OWTI-I AND VITaMIN A STORAGE IN THE WHIT~ RAT. M. Rechcigal, J r . ( L a b . of Biochim., N a t i o n a l C a n c e r Inst., N a t i o n a l I n s t i t u t e s of H e a l t h , B e t h e s d a , M d . ) , S. B e r g e r , J. K . Loosli, a n d H. H. W i l l i a m s . Nature 184, 1404 (1959). W h e n t h e i n t a k e of v i t a m i n A is controlled, r a t s are able to store a n a m p l e a m o u n t of v i t a m i n A in t h e liver despite a m i n o - a c i d i m b a l a n c e or in complete absence of d i e t a r y protein. I f t h e v i t a m i n i n t a k e is n o t controlled, however, t h e lack Of or i m b a l a n c e in t h e d i e t a r y p r o t e i n m a y result in a lower s t o r a g e of Y i t a m i n A b e c a u s e u n d e r these conditions t h e a n i m a l s u s u a l l y lose a p p e t i t e which will result in lowered c o n s u m p t i o n of v i t a m i n A.

115

ELECTROPHOKETIC I~/IIGRATIONOF SERUM LIPOPROTEINS IN STARCH GEL. H. K u t t , F. McDowell, a n d J. H. P e r t ( N e u r o l o g i c a l Service, Cornell Med. Div., Bellevue H o s p i t a l a n d Dept. of Med., Cornell Univ. Medical Col., N. Y.). Proc. Soc. Exptl. Biol. Med. 102, 38-40 (1959). H u m a n s e r u m ]ipoproteins were f r a c t i o n a t e d b y s t a r c h g r a n u l e electrophoresis a n d by sediment a t i o n in the p r e p a r a t i v e u l t r a c e n t r i f u g e , a n d t h e isolated fractions s u b m i t t e d to eleetrophoresis in s t a r c h gel. Alpha-2 a n d b e t a ]ipoproteins m i g r a t e d close to t h e ~origin, w h e r e a s alpha-1 l i p o p r o t e i n s m i g r a t e d in the p o s t a l b u m i n r e g i o n . EXPERIMENTS ON CHOLESTEROL ATHERD~SCLEROSIS IN RABBITS. E. Schwenk, D. F. Stevens, a n d R. A l t s e h u l ( W o r c e s t e r F n . f o r Exptl. Biol., S h r e w s b u r y , Mass., a n d L a b . of Gerontology, Univ. of S a s k a t c h e w a n , Saskatoon, C a n a d a ) . Proc. Soe. Exptl. Biol. Med. 102, 42-45 (1959). T h e f e e d i n g of h i g h l y purified cholesterol to r a b b i t s f o r 12 weeks resulted in h i g h s e r u m cholesterol a n d atherosclerotic lesions which a p p e a r e d m o r e severe t h a n those o b t a i n e d with commercial cholesterol, i m p u r i t i e s isolated f r o m m o t h e r liquors a f t e r t r e a t m e n t of commercial cholesterol with a n h y d r o u s oxalic acid in o r g a n i c solv e n t s did not produce atherosclerotic lesions, b u t w h e n given t o g e t h e r with cholesterol caused less e x t e n s i v e lesions t h a n those o b t a i n e d with p u r e or commercial cholesterol. CHANGES IN HUMAN LUNG COLLAGEN AND LIPIDS WITH AGE. A. M. Briscoe, W. E;. L o r i n g , a n d J. H. M c C l e m e n t (Depts. of Biochem. a n d Med., Columbia Univ., College of P h y s i c i a n s a n d Surgeons, C h e s t Service, Bellevue H o s p i t a l , a n d Dept. of P a t h ology, N. Y. Univ. Col. of Medicine, N. Y . ) . Proc. Soc. Expt. Biol. Med. 102, 71-74 (1959). The lipid c o n t e n t of t h e h u m a n l u n g decreases w i t h age. I t is a p p a r e n t l y not a f u n c t i o n of b o d y size ~or n u t r i t i o n a l state. SERUM LIPID ANALYSES IN RATS FED NATURAL AND ttYDROGENATF/D COTTONSEED OIL WITH CHOLESTEROL AND CHOLATE.. C . R . Seskind, V. R. W h e a t l e y , R. A. R a s m u s s e n , a n d R. W. W i s s l e r ( D e p t s . of P a t h o l o g y a n d Medicine, Univ. of Chicago School of Medicine, Chicago, Ill.). Proc. Soc. Exptl. Biol. Med. 102, 90-95 (1959). D i e t a r y cholate with cholesterol a d d e d to n a t u r a l a n d h y d r o g e n a t e d cottonseed oil r a i s e d s e r u m cholesterol a n d phospholipid. T h i s effect was a u g m e n t e d with s a t u r a t e d f a t . D i e t a r y lipid s a t u r a t i o n or cholate alone h a d no effect on s e r u m cholesterol. T h e s e r u m c h o l e s t e r o l / p h o s p h o l i p i d ratio w a s elev a t e d only w h e n b o t h d i e t a r y cholate a n d cholesterol were a d d e d to h y d r o g e n a t e d f a t . I n t h e r a t , h i g h l y s a t u r a t e d f a t ( I o d i n e No. 43) f e d with cholesterol r e v e r s e d the a l p h a to b e t a l i p o p r o t e i n ratio with b e t a b e c o m i n g d o m i n a n t . C o m b i n a t i o n of d i e t a r y cholate w i t h cholesterol p e r m i t t e d reversal of a l p h a to b e t a lipoprotein with m o d e r a t e ( I o d i n e No. 78) or no hydrog e n a t i o n ( I o d i n e No. 107) o f d i e t a r y f a t . The s e r u m cholesterol ester f a t t y acid composition c h a n g e d w i t h g r e a t e r s a t u r a t i o n of d i e t a r y f a t a n d a d d e d cholate a n d cholesterol. H i g h oleic acid levels were n o t e d in s e r u m cholesterol ester f r a c t i o n of r a t s f e d s a t u r a t e d f a t ( I o d i n e No. 78) w i t h cholate a n d cholesterol. The a u t h o r s conclude t h a t n o t only s e r u m cholesterol level b u t also q u a l i t a t i v e a n d q u a n t i t a t i v e c o m p o s i t i o n of cholesterol esters, as influenced b y d i e t a r y f a c t o r s , is likely to b e signific a n t in u n d e r s t a n d i n g elevation of s e r u m lipids a n d deposition of lipids in arteries. EFFECT OF DIETARY FAT ON EXCRETION AND DISPOSITION O1~ C 14 FROM CHOLESTEROL-4-C'-14 IN RATS. J. m. A n d e r s o n , J r . (Dept. of Med., Vanderbil~ Univ. School of Med., Nashville, T e n n . ) , J . G. Conigli0, a n d P r a n k R. Blood. Proc. Soc. Exptl. Biol. Med. 102, 155-157 (1959). The influence of a purified diet cont a i n i n g 20% f a t as h y d r o g e n a t e d c o t t o n s e e d oil (Crisco, iodine no. 73), corn oil (Mazola, iodine no. 123), or coconut oil (iodine n,o. 1O) on fecal excretion a n d tissue deposition of C1~ h a s been s t u d i e d in r a t s i n j e c t e d with cholesterol-4-C 14. T h e r e w a s no significant difference b e t w e e n the t h r e e g r o u p s in a m o u n t of C 1~ excreted f r o m feces or deposited in liver a n d in pooled i n t e r n a l :organs ( h e a r t , l u n g s , aorta, a n d k i d n e y s ) . EFFECT OF NEOM'YCIN~ PARA-AMINOSALICYLIC-ACID AND OTHER ANTIBACTERIAL DRUGS ON SERUM CHO~STEROL LEVEL OF MAN. P. S a m u e l (Dept. of Med., N. Y. U n i v . - - B e l l e v u e Medical Center, P o s t - G r a d u a t e Medical School, N . Y. C i t y ) . l~roc. Soc. Exptl. Biol. Med. 102, 194-196 (1959). N e o m y c i n was given orally to 18 p a t i e n t s at daily dose of L 5 to 2 g. f o r 4 to 20 weeks. M e a n s e r u m c h o l e s t e r o l levels were decreased signific a n t l y in each p a t i e n t b y 17 to 29%, a n d were m a i n t a i n e d 1,ow f o r d u r a t i o n of a d m i n i s t r a t i o n of neomycin. I n t r a m u s c u l a r a d m i n i s t r a t i o n to 5 p a t i e n t s f o r 3 w e e k s failed to alter s e r u m chOlesterol levels. Oral a d m i n i s t r a t i o n of 12 g. of p a r e - a m i n o salicylic acid to 2 p a t i e n t s l o w e r e d s e r u m cholesterol concent r a t i o n s significantly, while doses o f 6 g. h a d no effect. N o

]16

T H E JOUtCNAL OF THE AMERICAN O I L C H E M I S T S '

appreciable c h a n g e s in s e r u m cholesterol resulted w h e n phthalylsulfathiazole, isoniazid, d i h y d r o s t r e p t o m y c i n , oxytetracycline, p o l y m y x i n B s u l f a t e , b a c i t r a c i n , a n d novobiocin were given orally. EXTENT OF TOTAL HYDROLYSIS OF DIETARY GLYCEEIDE'S DURING DIGESTION AND ABSORFTIO'N IN THE ~IIUMAN. R. B l o m s t r a n d , B. B o r g s t r S m , a n d O. D a h l b a c k (Depts. Of Clinical Chem., Physiol. Cimm., a n d Thorac~c S u r g e r y , Univ. of L u n d , S w e d e n ) . Proe. Sac. Exptl. Biol. Meal. 102, 204-206 (1959). S u b j e c t s were f e d a doubly labeled triglyceride s y n t h e s i z e d f r o m linoleic acid-l-C ~'~ a n d glycerol-l-C ~4. A n a l y s i s of thoracic duct l y m p h lipids i n d i c a t e d t h a t w h e n d i e t a r y glycerides reach the thoracic d u c t l y m p h in m a n ~ to ]~ have been completely hydrolyzed. W i t h i n t h i s r a n g e , the e x t e n t of h y d r o l y s i s varies considerably with a t e n d e n c y to lower h y d r o l y s i s d u r i n g the e a r l y period of digestion a n d a b s o r p t i o n . INTgACELLULAR DISTRIBUTION OF GLYCFA%IDE SYNTKESIZING SYSTEMS. B. Shapiro a n d Y. S t e i n ( H e b r e w U n i v . - H a d a s s a h Med. School, J e r u s a l e m , I s r a e l ) . Radioisotopes Sei. Research, Proc. Intern. Conf., Paris, 1957 I I I , 185-91 ( P u b . 1958). B y t h e use of 1-C~4-palmitie acid in rat, glyceride s y n t h e s i s w a s s h o w n to occur c o n c u r r e n t l y in microsomes a n d m i t o c h o n d r i a , a n d t h a t t h e t u n m v e r of glycerides at these sites is m u c h more r a p i d t h a n over-all t u r n o v e r in the liver. (C. A. 53, 20361) CI:[YLOMICRONS AND LIPIDE TRANSP(~RT. J. H. B r a g d o n (Natl. H e a r t Inst., B e t h e s d a , M d . ) . Ann. N. Y. Acad,. Sci. 72, 845-50 (1959). T h e chylomicron consists of t r i g l y c e r i d e s with small a m o u n t s of cholesterol, phospholipides, a n d protein. Cholesterol c o n t e n t c a n be increased in t h e chylomicron o f r a t chyle by f e e d i n g i n c r e a s e d a m o u n t s , b u t phospholipide c o n t e n t cannot. T o t a l lipide c o n t e n t is the s a m e a f t e r f e e d i n g lecithin as a f t e r olive oi[, which shows t h a t lecithin is h y d r o l y z e d in the i n t e s t i n e a n d the f a t t y acid is i n c o r p o r a t e d into chylomicron triglycerides a n d p h o s p h o r u s - m o i e t y a b s o r b e d via t h e p o r t a l vein. Chylom i c r o n p r o t e i n is synthesized, at least in p a r t , in t h e i n t e s t i n a l wall. The rate of clearance of chylomicron is i n d e p e n d e n t of n u t r i t i o n a l state. However, t h e C~402 excretion d u r i n g 90 minutes a f t e r i n j e c t i o n of chylomicron c o n t a i n i n g C~ in palmitic acid, is 4 5 % in c a r b o h y d r a t e f e d a n d only 5 % in f a s t i n g rats. (C. A. 53, 2'0379) TItE MECP~A~ISM OF CHOI.ESTEEOL ABSORPTION. L. Swell, E. C. Trout, Jr., J. R. H o p p e r , H. Field, Jr., a n d C. R. Treadwell ( V e t e r a n s A d m i n . Center, M a r t i n s b u r g , W. V a . ) . Ann. N. Y. Aead. Sci. 72, 813-25 (1959). The p r e s e n t r e s u l t s s u g g e s t e d t h a t the free cholesterol pool of m u c o s a in r a t s e x p a n d s with l a r g e a m o u n t s of f e d cholesterol. I t is a p p r o x i m a t e l y 5 to 6 mR., a n d t u r n s over once in 24 h o u r s in the f a s t i n g a n i m a l . E x a m i n a t i o n of tim d a t a i n d i c a t e d t h a t a complex of cholesterol a n d bile s a l t s is f o r m e d in t h e l u m e n a n d e n t e r s t h e i n t e s t i n a l wall. A t e n t a t i v e scheme for t h e m e c h a n i s m of cholesterol absorption is presented. (C. A. 53, 20378) Et~FECT OF FAT INFUSIONS ON EXPERIMENTAL RABBIT ATHEROSCLEROSIS (~VITH REFERENCE TO THE ME'CttANISM OF GLUCOCORTICOID ACTION ON EXPERIMENTAL ATHEROSCLEROSIS). V. Felt, D. Reiehl, S. Roehling, a n d S. V o h n o u t ( I n s t . C a r d i o v a s c u l a r Research, P r a g u e ) . Gerontologia 2, 247-52 (1958). Bloodlipide c h a n g e s r e s e m b l i n g those induced by glucocorticoids were elicited b y i n t r a v e n o u s i n f u s i o n s of n e u t r a l f a t a n d phospholipides. R e t r o g r e s s i o n of e x p e r i m e n t a l atherosclerosis w a s effected b y i n f u s i o n s of phospholipide emulsions. (C. A. 53, 20352) THE CI=[OLESTE.ROI~ CONTENT OF RAT LIVER AFTE~ NUTRITION ON COMMEECIAL FATS. H. Sch5n a n d E. L. K r S b e r ( U n i v . E r l a n g e n , Get.). Naturwissenschaften 44, 43 (1957). The following values were o b t a i n e d f r o m r a t s f e d a hypolipotropic diet containi n g 2 0 % t e s t f a t for the f a s t s ( d i e t a r y f a t , liver f a t c o n t e n t in % of wet weight, total cholesterol in m g . / 1 0 0 g. l i v e r ) : control, 3.9, 130.3; b u t t e r , 10.2, 147.9; olive oil, 9.4, 273.3; cod-liver oil, 4.3, 150.6; cocoa b u t t e r , 6.8, 136.7; sunflower seed oil, 6.5, 177.0. (C. A. 53, 20.352) RELATION OF DIETARY EAT AND CHOLESTEROL TO TISSUE AND SERUM CHOLESTEEOL AND POLYUNSATURATED I~A~TY ACIDS IN RATS. V. S. P a t i l a n d N. G. M a g a r ( I n s t . Sci., B o m b a y ) . Indian J. Med. Research 47, 448-55 (1959). F e e d i n g of cholesterol to r a t s was shown to h a v e a g e n e r a l a d v e r s e effect on the m e t a b o l i s m of p o l y u n s a t u r a t e d f a t t y acids. (C. A. 53, 20349) D'I]~TARY FATS AND THE DIABETIC PATIENT. L. W. Kinsell, G. W a l k e r , G. D. Michaels, a n d Florence Olson ( H i g h l a n d Alam e d a C o u n t y Hasp., Oakland, Calif.). N e w Engl. J. Med. 251, 4 3 1 - 4 (1959). Recent o b s e r v a t i o n s indicate t h a t s u b s t i t u t i o n

SOCIETY

VOL. 3 7

of p o l y - u n s a t u r a t e d f a t for s a t u r a t e d - m o n o s a t u r a t e d f a t is also associated w i t h b e t t e r diabetic m a n u g e m e n t in t e r m s of blood s u g a r levels. W h e n a s y n t h e t i c triglyceride c o n t a i n i n g 5 0 % each of p a l m i t i c a n d oleic acid w a s s u b s t i t u t e d f o r a calorically e q u i v a l e n t a m o u n t of ethyl linoleate, there was a s t r i k i n g rise in blood lipides a n d i a blood s u g a r , a n d i n c r e a s e d a m o u n t s of i n s u l i n were needed to control t h e diabetes in t h e p a t i e n t tested. W i t h s u b s t i t u t i o n of safflower oil for the s y n t h e t i c triglyceride, t h e r e was a fall in lipides a n d a decreased insulin requirement. (C. A. 53, 20348) ESSENTIAL FATTY ACIDS IN TttE ALIMENTATION IN EARLY CHILDHOOD. A. Sinios, G. Nass) a n d W. Schliiter (Allgem. K r a n k e n h a u s St. Georg, H a m b u r g , GEL). Monatsschr. Kinderheillc. 107, 309-13 (1959). T h e f a s t i n g lipide c o n t e n t of t h e s e r u m of very y o u n g i n f a n t s is a l m o s t t h e s a m e as in older children. The p o s t - p r a n d i a l l i p e m i a a f t e r a m e a l enriched with u n s a t u r a t e d f a t t y a c i d s w a s a p p r o x i m a t e l y t h e same as a f t e r p u r e b u t t e r f a t a l i m e n t a t i o n . I n p r e m a t u r e a n d very y o u n g n u r s l i n g s , who have a relative intolerance to c o w ' s milk f a t , the f a t absorption w a s i m p r o v e d b y the a d d i t i o n of essential u n s a t u r a t e d f a t t y acids. (C. A. 53, 20347) MILK, CHOLESTEROL, AND ARTERIOSCLEROSIS. W. H o l d e n (Univ. Gatz, A u s t r i a ) . Intern. Dairy Congr., Proc., 15th CanEr., London 1, 27-33 (1959). Milk c o n t a i n s 12 reg./liter of cholesterol, t h e lowest of all f o o d s t u f f s of a n i m a l origin. The body synthesizes 10-20 t i m e s the i n t a k e of cholesterol on a n o r m a l milk diet. Lecithin, a n d v i t a m i n A i n h i b i t to some extent t h e deposition of cholesterol on the a r t e r i a l walls. The lecithin content of milk is 20 t i m e s t h a t of cholesterol. The essential amino acids a n d v i t a m i n s o f milk c o n t r i b u t e to the resistance of the a r t e r i a l wall to d e g e n e r a t i v e diseases. Milk f a t (50 g.) in a b a l a n c e d diet l e a d s to a significant decrease of cholesterol in t h e blood of h u m a n s . T h e m e t a b o l i s m o f cholesterol is established by e q u i l i b r i u m of s a t u r a t e d a n d certain u n s a t u r a t e d acids in t h e presence of sufficient a m o u n t s of lecithin. Milk with its essential n u t r i e n t s , is h e l p f u l in the p r e v e n t i o n of arteriosclerosis. (C. A. 53, 20'342) INFLUENCE OF DIETARY FAT ON ENERGY CONSUMPTION AND DIGESTION UTILIZATION OP WEANLING RATS..~. P. Bowland, I. R. Sibbald, R. T. B e r g , a n d N. H u s s a r (Univ. Alberta, Edmont o n ) . Can. J. Anir Sci. 38, 187-93 (1958). F a t a d d i t i o n to the diet resulted in a significant i m p r o v e m e n t in n i t r o g e n digestibility a n d g r o s s n i t r o g e n retention. N i t r o g e n levels pe se did not influence digestible e n e r g y consumption, b u t a n interaction existed b e t w e e n f a t a n d n i t r o g e n levels in t h e diet in relation to digestible e n e r g y intake. Efficiency of food utilization i m p r o v e d as either f a t or n i t r o g e n levels in the diet increased. (C. ,4. 53, 20339) SERUM-CI-IOLESTEROL LEVELS AND ATttEROSCLEROSIS: EFFECTS O~ COMPOSITION OF DIET AND TRIIODOTHYRONINE ON THE I~AT. W . F . J . ( ~ t h b e r t s o n , P. V. Elcoate, D. M. Ireland, D. C. B. Mills, a n d P a t r i c i a Shearley (Glaxo Labs., Ltd., Greenford, E n g l . ) . Brit. J. Nutrition 13, 227-42 (1959). T h e a d d i t i o n of cholesterol to a stock diet i n c r e a s e d the c o n c e n t r a t i o n of cholesterol in the s e r u m b y 1/~ a n d in the liver 2-5 times. Addition of p e a n u t oil to t h e stock diet g r e a t l y i n c r e a s e d s e r u m a n d liver cholesterol. I n a h i g h f a t diet c o n t a i n i n g cholesterol, cholic acid, choline chloride, a n d p e a n u t ,oil, cholic acid a n d choline chloride were both n e c e s s a r y to produce m a x i m u m c o n c e n t r a t i o n s o f cholesterol in t h e s e r u m a n d liver. H y d r o g e n a t e d p e a n u t oil was more effective t h a n t h e raw oil in p r o d u c i n g hypercholesterole m i a ; p e a n u t oil was likewise more effective t h a n e a r n oil. (C. A. 53, 20446) SE:I~U~V~LIPIDES AND LIPOPEOTEINS IN HYPEETENSION. Eliel W a r i s (Univ. T u r k u , F i n l a n d ) . A e t a Med. Scand. 161, Suppl. No. 337, 7-79 (1958). The lipide a n d lipoprotein levels were determ i n e d in the s e r u m s of 101 p a t i e n t s s u f f e r i n g f r o m h y p e r t e n sive disease a n d of 60 h e a l t h y controls. The results were discussed. (C. A. 53, 20436) NUTRITIVE VALUE OF CRUDE, ICEFINED, AND HYDROGI~NATEDCOTTONSEED OIL. M. N a r a y a n a RaG, S. K u p p u s w a m y , M. S w a m i n a t h a n , D. S. B h a t i a , a n d V. S u b r a h m a n y a n ( C e n t r a l F o o d Technol. Research Inst., M y s o r e ) . Papers Symposium Cottonseed wad By-Products, Hyderabad, India. Sect. V I I , 1958, 8-15. No significant difference w a s o b s e r v e d between t h e growth-pram o t i n g value of diets c o n t a i n i n g 1 0 % of crude, refined, a n d h y d r o g e n a t e d cottonseed oil or refined p e a n u t oil or c o w ' s ghee in r a t m e t a b o l i s m studies. The cottonseed ~oils were digestible to t h e e x t e n t of 9 5 - 8 % in the rat. A b o u t 7 0 - 5 % o f c a l c i u m a n d 6 5 - 7 0 % of p h o s p h o r u s was u n t i l i z e d by r a t s f e d diets containi n g 10% of t h e cottonseed oils. (C. A. 53, 20605)

FEBRUARY, 1 9 6 0

ABSTRACTS: P A I N T S AND DRYING OILS

THE BIOLOGICAL ACTIVITIES OF e- AND ~-TOCOPHEROLS. R. J. W a r d (Univ. Cambridge, E n g l . ) . B r i t . J. Nutrition 12, 226-31 (1958). N a t u r a l e-tocopherol had less t h a n 7.5% of the activity of a-tocopherol, while ~-tocopherol had about 45%. (C. A. 53, 20337) FAT CONTENT IN THE. DIET. L. K r z h i k a v a and K. Oshantsova ( I n s t . P e o p l e ' s Nutrition, P r a g u e ) . Voprosy Pitaniya 1 7 ( 6 ) , 12-18 (1958). F a t consumption in Czechoslovaki~ was investigated in relation to the cholesterol content in blood serum. The results indicated that men consuming meals with f a t contents over 30% of the total calories were overweight. F a t consumption in a m o u n t s equaling 30% of the total calories is considered good f o r women up to 40 years old; f a t consumption b y women over 40 years old should be decreased to 25% of the total calories. The serum cholesterol depends on sex and age. I n women f r o m 10-80 years old, the serum cholesterol increased continuously with age f r o m 149 to 212 rag. %. I n men f r o m 10-40 years old, s e r u m cholesterol increased front 146 to about 200, then dropped continuously with the age ( f r o m 40 to 80 years) to a b o u t 146 rag. %. Obese persons and persons doing mental work had a somewhat higher serum cholesterol. (C. A. 53, 20355) STRUCTURE AND HOMOGENI~ITYOF THE LOW-DENSITY SERUM LIPOPROTEINS. F. T. Lindgren, A. V. Nichols, T. L. Hayes, N. K. F r e e m a n , and J. W. G o f m a n (Univ. of California, Berkeley). Ann. N. Y. Acad. Sci. 72, 826-44 (1959). The average lipide composition of the 3 broad lipoprotein classes in the s e r u m of 9 f a s t i n g adults was determined. Great variations were f o u n d in glyceride, free cholesterol, and cholesteryl esters due to differences in lipoprotein distribution. I n the S~ 20-400 b a n d the dominant lipide was glyceride. Analysis of n a r r o w b a n d S~ 6-7 lipoprotein fractions showed g r e a t e r u n i f o r m i t y of composition although considerable variability remained. Lipoproteins of high S~ (400-75,000) are a p p a r e n t l y converted to those of lower S~ values by glyceride hydrolysis and f a t t y acid removal. A l o w density lipoprote!n model with a simple glyceride core containing small a m o u n t s of cholesterol, cholesteryl ester, and phospholipides is proposed. Electron microscope studies indicate t h a t these lipoproteins (S~ 6-8) are composed of 2 or 3 asymmetrical subunits a p p r o x i m a t e l y 350 A. in length with molecular weights f r o m 2.8 to 3.1 • 106. Calculations f r o m dissymmetry data yield prolate ellipsoids a p p r o x i m a t e l y 160 • 360 A. r a t h e r t h a n the spherical shape given for chemically isolated l i p o p r o t e i n (S~ 2-10). (C. A. 53, 20379) SUPPLEMENTARY VALUE OF LOW-FAT COTTONSEED FLOUR TO POOR VEGETARIAN DII~TS BASEn ON CERTAIN CEI%EALS. g . g r i s h n a m u r t h y , A, J. P a n t u l a , 3/[. N a r a y a n a Rao, M. S w a m i n a t h a n , Y. K. R a g h u n a d a Rao, and V. S u b r a h m a n y a n (Central Food Technol. Research Inst., Mysore). Papers Symposium Cottonseed and By-Products, Hyderabad, India 1958, Sect. V I , 51-7. The s u p p l e m e n t a r y value of alcohol-extracted cottonseed flour to poor vegetable diets based on wheat, ragi, rice, and j o w a r as determined by the r a t - g r o w t h m e t h o d showed t h a t cottonseed flour, when incorporated at a 10% level in the diet, had a m a r k e d value to diets based ,on r a g i and j o w a r and only a moderate value to rice and wheat diets. The protein efficiency ratio of the p r o t e i n s of alcohol-extracted cottonseed flour at a 10% level was f o u n d to be slightly superior to those of expeller pressed meal. The proteins of cottonseed flour supplemented to a m a r k e d extent the proteins of wheat and j o w a r a s m e a s u r e d by r a t growth. (C. A. 53, 20325) DIETARY FAT AND CHOLESTEROL METABOLISM: EFFECTS OF UNSATURATION OF' DIETARY PATS ON LIVER. AND SEI%UlcILIPIDES. Bath Okey, 3/[. 3/[. L y m a n , Anne G. H a r r i s , B e t t y Einset, and W. H a i n (Univ. of California, Berkeley). Metabolism, Clin. and Exptl. 8, 241-55 (1959). The following f a t s were fed 7 weeks to weanling r a t s at a concentration of 10% in a n adequate synthetic diet: menhaden, safflower, corn, soy, s t r a i g h t and h a r d e n e d cottonseed, peanut, olive, lard, coconut, and b u t t e r oils, b u t t e r f a t , a n d s h o r t e n i n g . Each f a t was given to 2 g r o u p s of 10 males a n d 10 females; in addition, ,one g r o u p also received 1% cholesterol in the diet. No significant effects on g r o w t h were noted a m o n g these fats. I n general lower liver cholesterol contents were f o u n d in r a t s fed f a t s of low iodine number, and vice versa. F e m a l e s fed cholesterol tended to have higher serum cholesterol levels a n d lower liver cholesterol concentrations t h a n did males. V e r y high serum cholesterols were seen only in females fed safflower, cottonseed, olive, and cocon u t oils. The f a t t y acid moiety of the liver cholesterol esters reflected the composition of the dietary fat, though the % of cholesterol linoleate was always lower t h a n t h a t of linoleate in the diet; oleic acid was always an i m p o r t a n t constituent of the ester. (C. A. 53, 20351)

117

RAPESEED OIL MEAL AS A PROTEIN SUPPLEMEINT FOR SWINE: AND RATS. I. RATE OF GAIN~ EFFICIENCY OF FOOD UTILIZATION, CARCASS CHARAC:TERISTICS~ AND THYROID ACTIVITY. N. H u s s a r and J. P. Bowland (Univ. Alberta, Edmonton, Can.). Can J. Animal Sci. 39, 84-93 (1959). Diets containing 0, 2, and 10% expeller-extracted A r g e n t i n e - t y p e rapeseed oil meal were fed to swine f r o m 3 weeks of age to m a r k e t weight of 195 lb. and to r a t s f r o m 3 weeks to 6 m o n t h s of age. The 10% level depressed the rate of weight gain and, in some cases, the efficiency of feed utilization in both species. Total weight, histological sectioning, and I ~1 t u r n o v e r rate of the t h y r o i d gland indicated h y p e r t r o p h y and other abnormalities on animals fed the 10% rapeseed oil meal ration. Animals fed tile 2% rapeseed oil meal showed no clear-cut toxic effects. I I . ENEI%GY AND NITROGEN DIGESTIBILITY AND NITROGEN RE~TENTION. Ibid. 94-101. The 10% rapeseed oil meal depressed app a r e n t digestibility of the dry m a t t e r , energy, and nitrogen with significant effects occurring only in rats. The 2% level did not affect digestibility. Retention of digestible nitrogen was not altered by the level of rapeseed of oil meal in diet. Female r a t s are more susceptible to toxic s y m p t o m s of rapeseed oil meal than males. (C. A. 53, 20340) 4.

9 Paints and Drying Oils TOBACCO OIL IN THE PRODUCTION OF VARNISHES. G. BalbL Olearia 13, 118-27 (1959). A m o n o g r a p h reviewing and discussing the distribution of NicotCana tabacum, chemical and physical p r o p e r t i e s of the oil, and the oil's use as a standoil and in the m a n u f a c t u r e of varnishes, alkyd resins, and inks. (C. A. 53, 20833) SYNTHETIC RESIN PAINTS. Teikichi Y a m a d a (Cashew Co., Ltd., T o k y o ) . Y u k a g a k u ( J . J a p a n Oil Chemists' Soc.) 8, 435-41 (1959). A review. GLYCERIDE 0IL GEL PAINTS. J. Rinse ( J . W. Ayers & Co.). U. S. 2,911,316. Thixotropic p a i n t and v a r n i s h bases are produced by gelling a hydroxylated glyceride d r y i n g oil by reacting it with a small a m o u n t of a l u m i n u m compound. Bodied linseed oil, f o r example, is heated with 3% of h y d r o x y isopropoxy a l u m i n u m stearate solution in mineral spirits. REACTING PHENYLALKOXY SILOXANES WITI-T HIGtIE]~ FATTY ALCOHOLS. M. 3/[. Olson and R. 3/[. Christenson ( P i t t s b u r g h Plate Glass Co.). U. S. 2,911,386. Liquid coating m a t e r i a l suitable f o r baked finishes is p r e p a r e d by h e a t i n g a liquid phenylalkoxypolysiloxane (alkoxy g r o u p containing 3 to 6 carbon a t o m s ) with a high molecular weight alcohol (11 to 18 carbon atoms) until ester interchange is complete. The material m a y also be used as a modifier f o r an alkyd resin. PI~EPARATION OF DRYING OIL BY MODIFICATIONAND C0~POLYMERIZATION OF SOYBEAN OIL WITH A VINYL I~0NOME'E. A. Schwa.rem a n (Spencer Kellogg and Sons, I n c . ) . U. S. 2,912,396. The film f o r m i n g characteristics of soybean oil are improved by first h e a t i n g the oil with p e n t a e r y t h r i t o l ( 1 % to 7% on weight of oil) at a t e m p e r a t u r e of 400 ~ to 500~ W h e n aleoholysis is complete, a like a m o u n t of maleic anhydride is added and heating is continued until an oil of low acid n u m b e r and a GardnerHoldt viscosity in the r a n g e of H to Z2 is produced. The modified oil (40 to 60 p a r t s by weight) is then heated with 60 to 40 p a r t s by weight of vinyl toluene a t t e m p e r a t u r e s of 300 ~ to 600~ in the presence of a catalytic a m o u n t of an organic peroxide until copolymerization is effected and a f a s t drying oil is produced.

9

"

Detergents

SURFACE-ACTIVE SUBSTANCES IN FOOD PROCESSING--SOl~IE BIOCHEMIC'AL AND PHARMACOLOGICAL ASPECTS. F. A y l w a r d (Borough Polytech., L o n d o n ) . Chem. ~ Ind. ( L o n d o n ) 1959, 524-30. A review with 40 references. (C. A. 53, 14363) WETTING 0P L0iW-ENERI]Y SOLIDS BY AQUEOUS SOLUTIONS OF HIGHLY FLUORINATED ACIDS AND SALTS. M a r i a n n e K. B e r n e t t and W. A. Zisman (U. S. N a v a l Research Lab., W a s h i n g t o n , D. C.). J. Phys. Chem. 63, 1911-16 (1959). W e t t a b i l i t y studies of aqueous solutions of several series of pure, highly fluorinated, aliphatic acids and salts were carried out on two low-energy organic solids, polyethylene and Teflon. As anticipated, the fluorinated compounds were able to depress the surface tension of w a t e r below the critical surface tension of

118

T H E JOURNAL OF THE AIVIERIChN OIL CHEMISTS' SOCIETY

Teflon, and were therefore capable of completely wetting it. In contrast, conventional hydrocarbon wetting agents do not depress the surface tension of water to this extent. DETFJt~,MINATION OP LAUNDERING PROPERTIES OF DETERGENTS BY COLLOIDAL-UNE~IICAL ~IETHODS. P . A , Demcbencko. Maslobo{no-

Zhirovaya P~+om. 25(7), 36-9 (1959). A comprehensive review of literature a~.'d some of the experimental d a t a are presented to show the interrelationship between the critical micelle concentration (CMC), solubilization, and laundering properties of Na soaps of natural and synthetic f a t t y acids, alkyl sulfates, alkylarenesulfonates, a n d nonionic detergents. There is a direct relationship between the solubilization properties of a detergent and its activity as ~n emulsifying and thickening agent. 16 references. (C. A. 53, 20848) APPLICATION OF P-TOLUIDINE ~IETHOD ]Y0~R THE DETE~.MINATION OF SO,DIU~,~ SALTS. OF ALKYL SULFATES IN SYNTH]~TIC LAUNDErING AGENTS. I . t~. G e t m a n s k i i . Maslobo~no-Zhirovaya P r o m .

25(7), 29-31 (1959). Application is described of p-toluidine titration method of Stupel and Segesser to the determination in synthetic pastes and powders of alkyl sulfate salts of secondary synthetic alcohol fractionated from synthol at 275-320 ~ or sperm whale fat. (C. A. 53, 20848) T H E USE OP ION-EXCHANGE RESINS FOR TItE SEPARATION OF SURFACE-ACTIVE SUBSTANCES WITH SPECIAL I~E,FERF~NC~ TO CATIONIC AND NCfNIO,NIC COb[POUNDS. H . I-tempel and H. Kirschnek.

Fette, SeifeTt,, Anstrichmittel 61, 369-74 (1959). The new porous cation-exchange resins Lewatit CN 206, based on polyacrylic acid, can be used for the quantitative separation of cationactive and nonionic eonlpounds. I t can also be used to separate some anionic and nonionic compounds. (C. A. 53, 20846) MECHANISM OF I)ETERGE.NCY. A. S. C. Lawrence (Univ. Sheffield, Engl.). Nature 183, 1491-4 (]959). The author suggests t h a t detergency is not brought about by free surface-energy phenomena b u t by eryoseopic forces only. This is interpreted by means of phase diagrams of soap-water-amphiphile systems, microphotographs, etc. (C. A. 53, 20848) SODILTM ALKYLARENESULFONATES AS ST~&NDARD SUBSTANCES IN

DETERGENT CHE]UISTRY. E. Q. Laws a1~d W. Hancock (C~ov~t Lab., London). Nature 183, 1473-4 (1959). To establish stand9Jrds for detergent testing, Na sulfonates of straight-chain substituted benzeDe hydroca.rbons from butylbenzenc to tctr~decylbenzene were synthesized from the f itty acids with even number of C' atoms. The branched-chain a-dimethyldeeylbenzenesulfate was also prepared. Their behavior in solutions was studled by using the methylene blue method and by paper chromatography. Optical density multiplied by molecular weight gave a result of approximately 346, in the series from n-octylbenzene upwards. Values of Rf for paper chromatography of the octyl, decyl, dodecyl, and tetradecyl derivatives in various alcoholwater mixtures are tabulated. (C. A. 53, 20848) SILICATES IN DET:E]CGENTS, W . L . Sehlcyer (Philadelphia Quartz Co., Philadelphia, P a . ) . Soap Chem. Specialties 35(11), 51-4; (12) 66-7, 146 (1959). Alkali silicates are effective detergents by virtue of their surface activity and their high negative electric charge. This can be demonstrated by testing their soil suspending power, their capacity to remove soil from test swatches, their :~bility to prevent deposition and redeposition, their emulsifying and wetting action, and other specific functions encountered in the washing process. Alkali silicates are also detergent builders because, in addition, they provide alkalinity, buffer capacity, and corrosion protection. Although silicates do not form soluble complexes with water hardness, they m a y be used in major portion as builders 'of spray-dried household detergent products to furnish equal detergency at lower cost. Spray-dried products containing sodium tripolyphosphate are s;lid to be more easily produced in acceptable form in the presence of silicate. I n both liquid and spray-dried heavy duty detergents, stability is improved by more nearly equalizing silicate solids and phosphate contents. 25 references. THE

COaI~OSION

OF ZINC CAUSED BY ]ViOI)ERN DETER~ENTS,

H.

Stupel (Dutch Shell, Hague, Holland). Soap, Perfumery, Cosmetics 32, 1111-18 (1959). The corrosive effect on zinc of various detergents has been studied. In hard water the corrosion of zinc is less t h a n in soft water, since calcium clearly counteracts corrosion. T h e effects of the various detergent

VOL. 37

components also vary. Silicates are protective substances; sulfates, carbonates and orthophosphates, inert; chlorides and chlorites mildly corrosive; while polymeric phosphates and perborates are actively corrosive and the active detergent component itself h a s little corrosive action. DETET~MINATI01~- OF ALKYLA]CENESTJLF(}NATES BY PHOTO~IETRIC+ TURBII)ITY TI'I~ATIO,N. ]~. W i c k b o l d . Sei/en-Ole-Fette-Waehse

85, 415-16 (1959). When a dilute solution of a cationic surfaceactive agent is added to a similar solution of an anionic surfaceactive agent, a turbidity appears which, in case of alkylarenesulfonates ( I ) and sulfosuecinic acid esters ( I I ) , reaches a maximum at the equivalent point. I n titration of I or I I with a cationic surface-active agent, photometric determination of the turbidity maximuni offers a means for end-point detection. Thus, I was determined by placing the titration vessel, contaiidng f r o m 25-30 rag. I in 70-100 ml. H~O, in a specially designed titration photometer, and titrating with 0.04 N hexadeeylpyridinium chloride solution with an ultramicro pistontype buret of 3 ml. capacity. The method is accurate within • 0.2% and very fast. I t is limited to I and I I because f a t t y alcohol sulfates do not show a turbidity maximum, and with alkyl sulfonates no turbidity develops. Organic solvents and nonionic surface-actlve agents interfere. Inorganic salts c a u s e low results (addition of 100 rag. Na~SOd/30 mg. I. resulted in a 3% negative error). (C. A. 53, 20846) T H E INTERACTION BETWEEN COLORS AND SUR,VACTANTS. Wamotsu Kondo (Musashi Univ., Tokyo). Y u k a g a k u (J. J a p a n Oil Chemists' Soc.) 8, 181-5 (1959). A review with 11 references. EFFECT OF SURFACTANTS ON LUBRICATION. Y a s u k a t s u T~mai (Aeronautical Research Inst., Univ. Tokyo). Yul~agaI~u (J. J a p a n Oil Chemists' Soe.) 8, 2-7 (1959). A review with 28 references. THE

LIQUII) SOAP C0~IPOSITION. Lillian L. Golub and H. S. Sylvester (Colgate-Pahnolive Co.). U. S. 2,912,385. 2-Mercaptobenzothiazole or an alkali metal salt thereof is incorporated in potassium liquid soaps to render them non-corrosive to copper and copper base alloys. DETERGENT COMPOSITION. ~ . N. F i n e m a n and C. G. Gebelein (Rohm & H a a s Co.). U. S. 2,9~3,416. A liquid dishwashing detergent t h a t has a high cloud point and t h a t exhibits excellent detergency on glass, metal and plastic, with little or no f o a m consists of about 10% of the benzyl ether of oetylphenoxypolyethoxyethanol containing sixteen ethoxy units, about 15% of the sodium salt of a f a t t y acid containing twelve to eighteen carbon atoms, about 7% tetrapot,~ssium pyrophosphate, and water to make up to 100%. LIQUID

I)ETERGmNCY COMPOSITION. L. E. Weeks (Monsanto Chem. Co.). U. S. 2,913,~17. A surprising synergistic effect has been produced in the detersive efficiency of detergent compositions consisting of the combination of alkylolamides of tall oil f a t t y acids and the condensation products of ethylene .oxide and an alcohol produced by the Oxo process, particularly tridecy] alcohol. HEAVY DUTY DETERGENT. M. K o p p (General Aniline & Film Corp.). U. S. 2,914,482. The combination of a nonionic surf:~ctant together with appropriate quantities of carboxymethyl cellulose and an alkanolamine produces '~ heavy duty liquid detergent which yields a small a n m u n t of suds to prevent overflow from a dishwasbing machine and at the same time a more powerful cleansing effect. SURI~ACE-AC~IVE Ah~PIIO~FlhRIC COIvEPOUNDS+ I~. F r a n k (Farbwerke Hoechst Akt.-Ges. vorm. Meister Lucius & B r u n i n g ) . Gcr. 1,013,289. The condensation products of 3-30 moles ethylene ,oxide (1) with alcohols or phenols containing at least 6 C atoms are treated with aminocarboxylic acids after substitution of the terminal OH groups of the condensate with halogen, t h u s preparing amphoterie surface-active compounds. Thus, 1 mole of the w-chlorocompounds 'of the condensation product of iso-AmOH with 5 moles I was treated with 1 mole N-methyltaurine and heated to 150-5 ~ until 1 mole C1 was removed from the waxlike reaction product, which is a good deemulsifyiag agent. Similar products were obtained with sarcosine as the amino acid and a chlorinated polycondensate of triisobutylphenol and I. (C. A. 53, 20850)