JUNE, 1959

Hu~uxna:

I,ETTER TO T H E EDITOR

h = peak height a = attenuation factor M = molecular weight of the corresponding unacety]ated component Using this formula, the calculated composition of the glyeeride mixture is compared in Table I with that found in several GLPC determinations at several temperatures. It may be seen that the results are in reasonably good agreement with each other. It is hoped that these preliminary experiments will

263

serve to increase interest in the quantitative estimation of mono- and diglyeerides by gas chromatography. V. 1~. HUEBNEI~ Armour and Company Chicago, Ill. REFERENCE 1. Mclnnes, A. G., Tattrie, N. H., and Kates, M., "The Application of Gas-Liquid Partition C!hrom~tography to the MicroestimatiGn of ~Ionoglyc~rides," presented ~ the 32nd F~ll Meeting, American 0il Chemists' Society, Chicag% Ill. Octobm- 20-22, 1958. [Received M a r c h 2, 1959]

Report of the Examination Board, 1958-1959 UmNG the year ended May 31, 1959, among their various active members, 40 commercial laboratories were granted referee certificates from the A.O.C.S. Examination Board, as follows: 7--Cottonseed, 0il Cake and Meal, F a t t y Oils, and Tallow and Grease 14--Cottonseed, Oil Cake and Meal, and F a t t y 0i]s 7--Cottonseed, Oil Cake and Meal 2--Oil Cake and Meal, F a t t y 0ils, and Tallow and Grease 1 - - 0 i l Cake, Meal and F a t t y Oils 6 - - 0 i l Cake and Meal 2 - - F a t t y 0ils 1--Tallow and Grease

D

AB S TRA

All laboratories certified for Oil Cake and Meal were automatically certified for Protein Concentrates. During the certificate year C. E. Worthington of Barrow-Agee's Decatur, Ala., laboratory was trans. ferred to Memphis, Tenn., O. M. Bakke of Houston Laboratories, Houston, Tex, and R. M. Dillard, Texas Testing Laboratories, Dallas, Tex., have retired from active chemical participation. The chairman extends his thanks to all members of the Examination Board and to R. W. Bates and his efficient Smalley Committee for their excellent cooperation. R. T. DOUGHTIE R. R. KING F~. R, HAHN R,. C. ~ L L M A N N. W. ZIELS, chairman

CT S

. . . .

R.A.

R E I N E R S , Editor

ABSTRACTORS: Lenore Petschait Africk, R. R. Allen, S. S. Chang, Sini'tiro Kawamura, F. A. Kummerow, and Dorothy M. Rathmann

9 Fats

and

Oils

A SIMPLIFIED PI~0,CEDURE :POP~ SYNTt{ESIS OF OLEIC-I-~~4 ACID.

S u s a n n e yon S c h u c h i n g a n d E. S t u t z m a n ( R a d i o i s o t o p e Ser. a n d General ivied. Research, V e t e r a n s ' Ad.ministration Cez~ter, M a r t i n s b u r g , W. Va. a n d Dept. of Biochem., T h e George W a s h i n g t o n Univ. School of !V[ed., W a s h i n g t o n 5, D.C.). J. Org. Chem. 24, 345-6 (1959). B e r g s t r 5 m ' s m e t h o d f o r t h e i n t r o d u c tion of a CX
14-)/[ETHYL PENTADE~ANOIC

(Is0~PAL~ITIC) ACID. R. P. H a n s e n , F. B. Shorland, a n d N. J. Cooke ( F a t s R e s e a r c h Lab., Dept. o~ Scientific & Ind. Research, W e l l i n g t o n , N e w Z e a l a n d ) . Chemistry and Industry 1959, 124. ~6 iso acid 14-methyl p e n t a d e c a n o i c acid w a s isolated f r o m u n h y d r o g e n a t e d b u t t e r f a t a n d identified. EVIDENCE FOI~ A N E W OXYGENATED FATTY ACID IN TtI~I SEED OIL OF Cttl~YSANTHE:MUIM: CORONARIU]Y[. ~, R. S m i t h , Jr., K . F .

Koch, a n d I. A. Wolff ( N o r t h e r n R e g i o n a l Reseaxch Lab., :Peoria, Ill.). Chemistry a~d I~dustry 1959, 259-60. A new epoxy f a t t y acid occurring in t h e seed oil of Chrysanthemwm coronarium ( f a m i l y compositae) w a s n a m e d coron~ric acid a n d its chemical s t r u c t u r e p r o v e d to be ~is-9:lO-epoxy-cisoctadee-12-enoic acid. ][NKLUENCE OP THE EXTRACTION OF LIPIDS FRO~ FLOUR ON GLUTEN DI~VEL0.PMENT AND BP~AKDOWN. A. H. B l o k s m a ( I n s t . for Cereals, Flour, a n d B r e a d T.N.O., W a g e n l n g e n , T h e N e t h e r l a n d s ) . Chemistry and Industry 1959, 253-4. T h e flour lipids p l a y a role in t h e g l u t e n d e v e l o p m e n t a n d breakdown. T h a t t h e original d o u g h p r o p e r t i e s are n o t r e s t o r e d completely u p o n r e c o n s t i t ~ t i o n m a y be e x p l a i n e d by either of th~ fefilowlng t h r e e a s s u m p t i o n s , n a m e l y (i) t h e c o n t a c t with t h e solvent c h a n g e s other flour c o n s t i t u e n t s , e.g. t h e p r o t e i n f r a c t i o n ; (ii) the flour lipids p a r t l y lose t h e i r essentiaJ p r o p e r t i e s d u r i n g isolation, or (iii) u p o n r e c o n s t i t u t i o n t h e y do n o t reach t h e a r e a s w h e r e t h e y ea~ exert t h e i r beneficial influenc~ or reach t h e s e a r e a s only a f t e r a long m i x i n g time. E x p e r i m e n t s als0 i n d i c a t e d t h a t t h e m i x i n g tolerance o.f a flour d e p e n d s heavily upon t h e s t a t e of t h e flour lipids. UNSATUt~ATED FATTY ACIDS OF BUTTERFAT. W. E. Scott, S. F. H e r b , P . M a g i d m a n , a n d I~. W. R i e m e n s c h n e i d e r ( E a s t e r n U t i l i z a t i o n R e s e a r c h a n d D e v e l o p m e n t Div., A g r . R e s e a r c h Ser., U.S.D.A., P h i l a d e l p h i a 18, P a . ) . J. Agri. Food Chem. 7, 125-9 (1959). T h e pre.~ence of C~o to C~,~m o n o e t h e n o i d acids in butt e r f a t was confirmed; t h e C~ ~nd C~ a c i d s we,re p r e d o m i n a n t l y the c/s-form, while t h e C~ a n d C~s a c i d s h a d b o t h cis a~d trans double bonds. The n o n c o n j u g a t e d dienoic acids, were f o u n d to be a m i x t u r e of cis-cis a n d either cis-trans or tran~trans isomers. C o n j u g a t e d dienoie a c i d s were identified as

264

T H E J O U R N A L OF T H E A}IERICAN O I L C H E M I S T S ' SOCIETY

cis-~rans a n d tra~s-trans isomers. The trienoic, tetraenoic, a n d p e n t a e u o i c acids h a d the all-cis configuration. PREPARATION O~ OLEIC ACID~A I~EAGENT FOI~ DETE~MINATION OP THE J:[ARDNESS OF WATER. G. I. Mikha~lov a n d R. M. Levina. ~ rudy Vsesoyuz. Nauch.- Issledovatel. Inst. Khi~n. Reaktivov 1 9 5 6 ( 2 1 ) , 90-2; Referat. Zhur., Khim. 1956 abstr. No. 54824. Oleic acid p r e p a r e d f r o m a p r i c o t ( p e a c h ) kernel oil with a yield of 80 5 % is applicable f o r t h e d e t e r m i n a t i o n of the h a r d n e s s of w a t e r b y the oleic m e t h o d of Technical Specifications of t h e M i n i s t r y of Chemical I n d u s t r y of t h e U.S.S.R. No. 2501-51. (C.A. 53, 4773) ANALYTICAL CON22~OL OF THE DEGt~EE 0'F OXIDATION IN FATS. G. Wode. T V F 29, 141-50 (1958). D e t e r m i n a t i o n of the peroxide a n d t h e a l d e h y d e n u m b e r s p e r m i t s suitable e v a l u a t i o n of the degree of o x i d a t i o n in f a t s . The aldehyde n u m b e r provides i n f o r m a t i o n r e g a r d i n g the t a s t e - r e t a i n i n g ability of deodorized f a t s . E x a m p l e s are given of t h e e m p l o y m e n t of the a n a l y t i c a l m e t h o d in t h e p r o d u c t i o n of oils, in storage, h a r d e n i n g , a n d refining of oils a n d in m a r g a r i n e m a n u f a c t u r e . (C.A. 53, 26~5) INFRARED ABSORPTION SPECTRA O]~ SOME VEGETABLE OILS. Y v o n n e F a v i e r ( E ' e o l c n a t i o n a l e s u p e r i e u r e chhn., P a r i s ) . Compt. rend. 247, 295 7 (1958). A b s o v p t l o n s p e c t r a b e t w e e n 6 a n d 15 ~ of a b o u t 15 v e g e t a b l e oils a n d derivatives are discussed in r e g a r d to i n t e r p r e t a t i o n s of s t r u c t u r e s , adulteration, etc. C h a r a c t e r i s t i c b a n d s of i n d i v i d u a l oils or struct u r e g r o u p s a r e m e n t i o n e d , b u t detailed d a t a are n o t presented. (C.A. 53, 3527) DETECTION

OP PISTACIA

LENTISCUS

OIL IN OLIVE

OIL.

G. Con-

dorelli (Univ. Catania, Sicily). Boll. inform, ind. olearia e sapon. 4, 49 52 (1958). The u l t r a v i o l e t s p e c t r u m of t h e u n s a ponifiable m a t t e r of the oil of t h e f r u i t of Pistacia lentiscus showed two c h a r a c t e r i s t i c p e a k s a t 270-290 m~. The followi n g color r e a c t i o n is also s u g g e s t e d : s h a k e 10 g. oil w i t h 15 cc. e t h a n o l ; to 1 ca. of t h e alcohol e x t r a c t a d d 1 drop of diazoie r e a g e n t ( p - n i t r o a n i l i n e 0.5% solution in 2 % hydrochloric acid, s o d i u m n i t r i t e 0.5% solution) a n d 3-5 drops 10% s o d i u m c a r b o n a t e solution; a red color is o b t a i n e d if at l e a s t 0.5% lentiscus oil is a d m i x e d with olive oil. The t e s t can also be c o n d u c t e d by p a p e r c h r o m a t o g r a p h y (ethanol, 75% solution, as the mobile p h a s e ) , the s p o t s being" s p r a y e d with diazotized p-nitroaniline a n d s o d i u m carbonate. (C.A. 53, 3527) EPFECT O}~ UNTREATED AND CHL0]~INATED WATER 0'N THE KEEPING QUALITY OF BUTTER. J. Lewis, C. Allison, R. G. Drnce, G. George, a n d S. B. T h o m a s (Univ. Coll. Wales, A b c r y s t w y t h ) . J. Soc. Dairy Technol. 11, 186-93 (1958). B u t t e r w a s h e d with c o n t a m i n a t e d w a t e r developed r a n c i d i t y w i t h i n 21 d a y s a t 3 7 41~ w h e r e a s w a t e r f r o m t h e same source c o n t a i n i n g 5 p a r t s per million residual chlorine gave b u t t e r which r e t a i n e d good flavor f o r six weeks. N o chlorine t a i n t w a s detected in t h e b u t t e r washed with w a t e r c o n t a i n i n g as n m c h as 200 p a r t s per million. (C.A. 53, 3525) ADDITION BUTTER.

OF EXTRANEOUS FATS AND THEIR DETECTION IN M. Vitagliano and A. D'Ambrosio (Univ. Naples).

Ann. fae. agrar, univ. Napoli Portici ( N a p l e s ) 22, 35-68 ( 1 9 5 6 - 7 ) . M a n y m e t h o d s are c o m p a r e d : volatile acidity ratio, t e s t with N H : O H - H C 1 (Nelson, C.A. 50, 11550i), tocopherols d e t e r m i n a t i o n ( M a h o n , et al., C.A. 49, 9 1 8 1 f ) , the melti n g p o i n t of sterol a c e t a t e s (Cannon, C.A. 49, 9833d), a n d the W o l l n y n u m b e r . The f r a c t i o n a t i o n of t h e b u t t e r b y m e a n s of a b s o l u t e alcohol according to P h a l e r a o , et al. (C.A. 50, 14136c), a n d of t h e f a t acids with u r e a according to Shipe (C.A. 50, 2189i) are criticized. S i x t y - t h r e e references. (C. A. 53, 3524) PHOSPHOLIPIDES IN NEW ZEALAND DAIRY PRODUCTS. I I I . EFFECT OF STC~RAGE ON THE PHOSPttOLIPIDES AND ON TId]~ PARTITION O,P PHOSPHORUS IN BUTTER. A. K. R. MeDowell ( D a i r y R e s e a r c h I n s t . P a h n e r s t o n N o r t h , N. Z.). J. Dairy Reseaveh 25, 475-9 (1958). A v e r a g e values f o r the total p h o s p h o r u s c o n t e n t of s e r u m s f r o m u n s a l t e d b u t t e r s a m p l e s a n d f o r the p h o s p h o r u s c o n t e n t of the v a r i o u s f r a c t i o n s of t h e s e r u m s a f t e r p a r t i t i o n with CChCO~H were: Total p h o s p h o r u s , 83.6 m g . ; acid-soluble p h o s p h o r u s , 32.4 mR.; i n o r g a n i c p h o s p h o r u s , 28.8 mR.; acid-insoluble p h o s p h o r u s , 51.2 m g . ; a n d phospholipide p h o s p h o r u s , 33.6 m g . / 1 0 0 gin. T h e r e was no evidence t h a t decomposition of the phospholipides or other o r g a n i c phosp h o r u s c o m p o u n d s occurred in salted or u n s a l t e d sweet c r e a m b u t t e r s d u r i n g s t o r a g e a t 10 ~ f o r e i g h t m o n t h s . (C.A. 53, 3522) NOMOGEAPH FOE DETERMINING PERCENT CONCENT~ATION OF FAT IN BAKERY PE0~DUCTS. G. A. K o c h a r y a n ( B r e a d B a k i n g T r u s t , B a k u ) . Khlebope~ar. i Konditer. Prom. 3 ( 1 0 ) , 12-3 (1958). A h o m o g r a p h is g i v e n f o r use with a r e f r a c t o m e t r i c

VOL. 36

m e t h o d f o r d e t e r m i n i n g f a t in b a k e r y products. (C.A. 53, 3520) INOSITOL AND SCYLLITOL IN FOOD PLANTS. P. M a l n g e a u (School P h a r m a c y , P a r i s ) . Qualitas Plant. et Materiae Vegetabiles 3-4, 393-404 (1958) ( i n F r e n c h ) . A review with f o r t y - t h r e e references. (C.A. 53, 3519) CHROMATOGRAPHY OF SPEI~I-HEAD OIL. H i r o s h i S a k u r a i a n d M a s a o F t Q i w a r a ( O s a k a U n i v . ) . Mere. Inst. Sci. and Ind. Research, Osaka Univ. 15, 229-34 (1958) (in E n g l i s h ) . S p e r m whale h e a d oil was s e g r e g a t e d into w a x a n d glyceride b y elution c h r o m a t o g r a p h y . i~V[OLECULARDISTILLATION OF SPEI~M-HEAD OIL. t t i r o s h i S a k u r a i a n d Y a s u t a k a Tozaki ( O s a k a U n i v . ) . Ibid. 15, 235-40 (in E n g l i s h ) . S p e r m whale h e a d oil was s e p a r a t e d into w a x a n d glyceride by a molecular p o t still a p p a r a t u s . S e p a r a t i o n was i m p r o v e d by s t i r r i n g the distilland. (C.A. 53, 3739) PEANUT OILS 0P DOMESTIC PRODUCTION. I I . PI~ECIPITATION TEMPERATURES (BELLIEtr AND FATTY-ACID COMPOSITIO.N. t ). Cattaneo, R. Gimenez, a n d Alicio L. Colombo ( U n i v . B u e n o s A i r e s ) . Anales asoe. quire, arg. 46, 179-95 (1958). The prec i p i t a t i o n t e m p e r a t u r e (Bellier n u m b e r ) of p e a n u t oils is rel a t e d to the s a t u r a t e d f a t t y acid (C~,, to C~) c o n t e n t (the arachidic-behenic-lignoceric acid composition) a n d the iodine value of the oils. R e s u l t s are b a s e d on a c o m p a r i s o n of I.R.A.M. ( I n s t i t a e A r g e n t i n a de Racionaliza~ion de M a t e r i a l e s ) a n d A.O.A.C. techniques. D e t e c t i o n of p e a n u t oils in olive oils is discussed. (C.A. 53, 3739) DETERMINATION OF GOSSYPOL BY THE LUMINESCENCE METHOD. S. N. V i l ' k o ~ a a n d A. L. M a r k m a n . Zhur. Priklad. Khim. 31, 1548-53 (1958). Gossypol, n o t l u m i n e s c e n t in itself, quenches the luminescence of chloroform a n d acetone a n d t h e degree of q u e n c h i n g i n c r e a s e s with the c o n c e n t r a t i o n of gossypot. However, the relation is not proportional. T h e luminescence of fluorescein, excited b y t h e 336 m ~ line ( m e r c u r y l a m p t h r o u g h a blue filter), is quenched b y gossypol in p r o p r t i o n to i t s c o n c e n t r a t i o n so t h a t the log ( I / I o ) versus c o n c e n t r a t i o n gossypol curves are linear f u n c t i o n s . (C.A. 53, 3737) DETERMINATION OF SMALL QUANTITIES 01~ SOAP IN I~EF'INED OILS. M. S. Levit, L. G. Bliner, a n d T. K. L oseva. Maslobo~no. Zhirovaya Prom. 2 4 ( 1 1 ) , 35-6 (1958). S t a n d a r d a n d bromophenol blue in acetone solution t i t r a t i o n m e t h o d s for the estiniatio~ of small q u a n t i t i e s of soaps in refined oils are compared. (C.A. 53, 3738) ~DENTIFICATI(}N OF FATTY ACIDS BY FUNC'TIONAL DEEIVATIVES. D. L e f o r t . Ol~agineux 12, 685-90 (1957). A review with twenty-five references. (C.A. 53, 3738) CARBAMIDE ME.THOD FOR FRACTIONATION OF FATTY-ACID MIXTUNES. A. L. M a r k m a n a n d B. A. K a t s . Maslobo~uo-Zhirovaya Prom. 2 4 ( 1 1 ) , 12 6 (1958). E f f e c t s of u r e a concentration, c r y s t a l l i z a t i o n time, a n d t e m p e r a t a r e on t h e f r a c t i o n a t i o n of a f a t t y - a c i d m i x t u r e a n d yields o~ f r a c t i o n s f r o m cottonseed soap stock a r e discussed. (C.A. 53, 3738) APPLICATION O~ URE:A-ADDUCT SEGREGATION METHOD TO FATS CONTAINIIqG CONJUGATED FATTY ACIDS. S. Sinha, S. R. Chakr a b a r t y , a n d M. M. C h a k r a b a r t y (Univ. Coll. of Sci. & Technol. C a l c u t t a ) . J. Indian Chem. Soc. Ind. ~ News Ed. 20, 104-5 (1957). I n u r e a - a d d u c t f o r m a t i o n t h e influence of m e l t i n g p o i n t a n d solubility appeaxs to s u b o r d i n a t e to t h e influence of u n s a t u r a t i o n . W i t h d e c r e a s i n g u n s a t u r a t i o n t h e c o n j u g a t e d acids have a m a r k e d t e n d e n c y t o w a r d f o r m i n g a d d u c t s with u r e a at less c o n c e n t r a t i o n s of t h e latter. T h e f i n d i n g s indicate t h a t s e p a r a b i l i t i e s c a n n o t be b a s e d on the m e l t i n g p o i n t s a n d solubilities, b u t t h e detailed s t r u c t u r e of f a t t y a c i d s m u s t also be considered in each case. (C.A. 53, 3738) COl~IPONENT FATTY ACIDS FRO,~Vl THE SEED FAT OF CAESALPINIA DIGYNA. D. K . Gupta, B. T. R. I y e n g a r , a n d M. M. C h a k r a b a r t y (Univ. C a l c u t t a ) . J. Indian Chem. Soc. Ind. ~ News Ed. 20, 112-6 (1957). L o w - t e m p e r a t u r e crystallization a n d ultraviolet a b s o r p t i o n s p e c t r o p h o t o m e t r i e a n a l y s e s of t h e f a t t y acid f r o m t h e seed f a t of Caesalpinia digyama show m y r i s t i c 0.6, palm i t i c 20.42, s t e a r i e 8.24, a r a e h l d i c 1.4, b e h e n i e 0.19, oleic 30.25, linoleic 37.12, ethyl linolenate 1.68, a n d nonsaponifiables 0.13%. The composition of t h e seed f a t shows t h a t the oil, if axailable in commercial q u a n t i t i e s (there is a possibility in t h e b y - p r o d u c t i n d u s t r y ) , should be very suitable as a raw m a t e r i a l f o r t h e soap a n d edible-fat i n d u s t r i e s . (C.A. 53, 3737) OBTUSILIC ACID. I. SYNTKESIS OF TRANS-4-DECENOIC ACID. Mituo I w a k i r i ( K i n k i Univ., F u s e , O s a k a ) . Nippo~ KaRakul. Zassi ( J . Chem. Soc. J a p a n , P u r e Chem. Seet.)78, 1460-3 (1957). Obtusilic acid (4-decenoic acid) f o u n d in the seed oil of Lindera obtusiloba h a s n o t y e t been synthesized. The newly s y n t h e s i z e d acid w a s f o u n d to be trans isomer by i n f r a r e d spec-

Ju~E,

1959

ABSTRACTS

troscopy. The n a t u r a l obtusilie acid differed f r o m the s y n t h e sized acid in m.p. of p - b r o m o p h e n a c y l ester. T h u s obtusilie acid was a s s u m e d to be t h e cis isomer. SEPAI~ATION O~ A gE'vV EICOSATIClENOIC ACID OIL OF PODOCAEPUS NAGI. Y0shito Koyama

FR0lVi THE SEED and Yoshiyuki

T o y a m a ( N a g o y a U n i v . ) . Nippon Kagau Zessi ( J . Chenl. Soe. J a p a n , P u r e Chem. Sect.) 78, 1223 4 ( t 9 5 7 ) . T h e seed of this p l a n t yielded 39.2% (on dry seed) yellow oil, d ~''~ 0.9228, n '-'~ 1.4774, acid no. 1.2, sapon, no. 187.0, iodine no. 158.8, u n s a p o n i fiable m a t t e r c o n t e n t ( % ) 0.55. This oil c o n t a i n e d ]inoleic acid and, besides, a new eicosatrienoie acid, which was free of a triple bond, a double bond a t the end, a n d c o n g u g a t e d double bonds. This new acid did n o t f o r m c o n j u g a t e d trienoic acid b u t only c o n j u g a t e d dienoic acid by alkaline isomerization. I t was nanled podocarpic acid. FATTY OIL OF INCILLAEIA CGNI~USA AND ITS STE~0L COJMPONEN~J. T a t s u o T a n a k a a n d Y o s h i y u k i T o y a m a ( N a g o y a U n i v . ) . Nippon Kagc~;u Zassi (J. Chem. Soe. J a p a n , P u r e Chem. Sect.) 78, 1101 (1957). The oil f r o m slugs, Incillaria eonfusa ( 9 % of d r y m a t t e r ) h a d n ~~ ].4817, acid no. 47.9, sapon, no. 184.6, iodine no. 85.0, a n d nnsaponifiable m a t t e r c o n t e n t ( % ) 23.23. The sterol consisted raainly of fl-sitosterol a n d only 0.3% of /V~. 7-sterol" SEPARATION OP OCTADECADIENOIC AND OCTADECATRIENOIC ACIDS FEOh/[ TIlE OIL OF CYPRINIS AURATUS. T o r u T a k a g i , T s u t o m u Shimooka, a n d Y o s h i y u k i T o y a m a ( N a g o y a U n i v . ) . Nippon Kaqal~u Zassi (J. Chem. Soe. J a p a n , P u r e Chem. Sect.) 78, 1690-4 (1957). The viscera, eggs, a n d body ( e x c l u d i n g viscera a n d e g g s ) of this f r e s h - w a t e r fish c o n t a i n e d 23.7, 3.0, a n d 3.2% oil (ether e x t r a c t ) , respectively, with the following characteristics: d ~~ 0.9238, 0.9462 ( a t 3 0 ~ 0.9242; n 2~ 1.4766, ].4750 (at 30~ 1.4774; acid no. 4.14, 4.25, 0.36; sapon, no. 186.6, ] 69.6, 189.5; iodine no. 154.2, 145.1, 161.3; unsaponifiable niatter 1.67, 9.25, 0.42%. F a t t y acids of viscera a n d egg oils were s u b j e c t e d to u r e a - a d d n c t f o r m a t i o n , the p a r t s rich in dienoie a n d trienoic acids were cmnbined, a n d t h e y were converted to m e t h y l esters, which were distilled to o b t a i n m e t h y l esters corr e s p o n d i n g to C~s. Silica-gel c h r o m a t o g r a p h y , b r o m i n a t i o n , a n d ozone decomposition showed t h a t the acids in this fish oil cont a i n e d linoleie a n d linolenie aids. THE WAX AND HYDROCARBONS Ilk' SAWA-MILLET BRAN OIL. M i t s u 0 K i t a m u r a a n d T e t s u j i r o O b a r a (Tokyo Univ. E d u c a t i o n ) . Nippon Ndgei-kagaku Kaishi ( J . A g r . Chem. Soc. J a p a n ) 32, 946 7 (1958). T h e b r a n oil f r o m the s e e d s of Panicum cr.~sgalli vat. frumentaeeum c o n t a i n e d 1.1% w a x y solid, which w a s s e p a r a t e d into hot-alcohol-soluble p a r t ( A ) a n d insoluble p a r t (B). A was w a x c o n s i s t i n g of eeryl alcohol, a-hydroxy-n-docosanoic acid, a n d eerotie acid, while B was h y d r o c a r b o n s c o n s i s t i n g of C~H~o a n d C~,H~. PAFF~R CHR0'~ATOGRAPtty OF PATTY ACIDS. X X u SEPARATION OP THIOCYANOGEN ])EI~IVATIVES. I~. P. I s and M. Arens. Fette, Seifcn, Anstrichmittcl 60, 803 6 (1958). T h e Rf values of t h i o c y a n o g e n derivatives of ~'criticaU ~ p a i r s of f a t t y acids are, owing to their h i g h e r polarity, g r e a t e r than1 the free acids a n d their broDm derivatives. Thus, in lauric a n d linolenie acid with Rf values of 0.52 a n d 0.55, m y r i s t i c a n d linoleic a c i d s 0.48 a n d 0.49, a n d palnlitie a n d oleic 0.37 a n d 0.35, the t h i o e y a n o g e n derivatives of t h e u n s a t u r a t e d acids are 0.94, 0.89, 0.79, a n d p e r m i t c h r o m a t o g r a p h i c s e p a r a t i o n by d i l u t i n g acetic acid to 70%, t h u s r e d u c i n g t h e m o b i l i t y of the s a t u r a t e d acid. (C.A. 53, 3737) PHYSICAL-CHE'MICAL METIIODS OP ANALYSIS Of' PATT~g ~ATERIALS AND THEIR I)ERIVATIVES. J. :P. Wolff. Inds. aliment, et a.qr. ( P a r i s ) 75, 639-48 (1958). A review with t h i r t y - s i x references. (C.A. 53, 3737) THE VARIATION OlP THE PAT CONTENT OF SAU~u CI~LOLABIS SAIRA, OR THE NOETHEASTEICN SEA AREA OP JAPAN. K a t s u o N a g a k u r a ( T o h o k u K a i k u Suiken, S h i o g a m a , M i y a g i P r e f e c t . ) . Tdholcu-kai~;u Suisan-kenl~yujo Ken~'yu-hdl~oku No. 7, 54-9 (1956). The seasonal v a r i a t i o n of the f a t c o n t e n t of s a u r y was e x a m i n e d d u r i n g 1953-1955. The relation b e t w e e n the oil e x t r a c t e d by boiling a n d p r e s s i n g a n d the total fish oil was f o u n d to be linear according to u = 1.44X + 46.9, where X is the a m o u n t of e x t r a c t e d oil a n d Y the t o t a l oil. (C.A. 53, 3737) REFINING FAT BY

O,P GLYCE~0L IoN-EXCHANGE

WATER FROM CONTACT SPLITTING OF RESINS. T. A. Chernushkina, N. I.

P l y a s u n k o v a , a ~ d N. Ya. Vetrova. Maslobo~no-Zhirovaya Prom. 2 4 ( 1 1 ) , 37 9 (1958). Only m u l t i p l e ion-exchange c o l u m n s can be used successfully to refine glycerol w a t e r s f r o m t h e cataIytic s p l i t t i n g of f a t s . The related properties of several resins are discussed. (C.A. 53, 3737)

265

USE O1~ HYDROGENATED FAT FOR THE MANUFACTURE OF C~COAI. P o k o r n y l , E. M a r e s h , a n d A. Makha~lichek ( R e s e a r c b I n s t . V e g e t a b l e Oils a n d P a t s , U s t i n a d L a b e m , Strekov, Czech.). Maslobo~no-Zhirovaya Prom. 24 (11), 17 19 (1958). M a n u f a c t u r e of cocoa-butter s u b s t i t u t e f r o m h y d r o g e n a t e d p e a n u t , sunflower, a n d r a p e oils b y t h e use of c r y s t a l l i z a t i o n m e t h o d is discussed. (C.A. 53, 3737) TECHNOLOGY O F PATS. L I I 1 . DISINTEGRATIO,N OF RAW ~IATE~ RIALS. H. P. K a u f m a n n a n d J . G. Thieme. Fette, Stitch, Anstriehmittel 60, 852-9 (1958). (C.A. 53, 3736) P/gOPEI~TIES OP OLIVE-KElCNEL OILS :PRODUCED BY DIFFERENT METHODS. M a r i e T. F r a n c o i s a n d S u z a n n e H e i n r i c h . Compt. rend. 247, 222-5 (1958). (C.A. 53, ~ EFFECT OP THE DEGREE OF RIPENESS OF RAPESEED ON THE STABILITY O F THE ~AFES~ED OIL. A. R u t k o w s k e a n d Z. M a k u s . Oldagineux 13, 203-5 (1958). The lipase a c t i v i t y a n d w a t e r c o n t e n t o f r a p e s e e d w a s d e t e r m i n e d daily f o r a period of sixteen days p r i o r to h a r v e s t i n g . The lipase a c t i v i t y is a f u n c t i o n of t h e w a t e r c o n t e n t of the seed a n d i t decreases d u r i n g the r i p e n i n g process. Oil f r o m f u l l y ripe seed iS m o r e stable. The chlorophyll c o n t e n t of t h e r a p e s e e d decreases duri n g r i p e n i n g while the tocopherol c o n t e n t increases. D u r i n g five m o n t h s ' s t o r a g e u n r i p e rapeseed show a g r e a t e r increase in free f a t t y acid a n d peroxide c o n t e n t t h a n t h e f u l l y ripe seed. (C.A. 53, 2649) OIL OF SESAI~'IE. K. R. V a r m a ( T a t a Oil Mills Co. IAd., Bomb a y ) . Oldagineux 13, 793-801 (1958). A review with fortynine references. (C.A. 53, 2649) ALEURITE,S MOLUC:CANA. }I. F. K. D i t t n m r . Pharm. Zentralhalle 94, 393-400 (1955). T h i s tree is widely dispersed t h r o u g h t h e tropical a r e a s o~ t h e world. Oil c o n t e n t of the kernel ( a v e r a g e 6 4 % ) is h i g h e s t of a n y m e m b e r of the genus. P h y s i cal p r o p e r t i e s a n d chemical c o n s t i t u t i o n of the n u t oll were determined. (C.A. 53, 2649) EXPERIMENTS WITH" AUTO-IGNITION. S. B e r g m a n a n d B. Lindberg. Fiirg och Fernissa 2 2 ( 3 ) , 6-8 (1958). A u t o - i g n i t i o n e x p e r i m e n t s were m a d e in a M a c k e y a p p a r a t u s in which the cotton h a d been replaced by 30 g. s a w d u s t ( > 0 . 4 ram.) soaked with 30 ml. of t h e oil sample. Cooked or d r i e r - c o n t a i n i n g linseed oil i g n i t e d earlier t h a n did r a w oil. L i n s e e d oil f a t t y acid n o t c o n t a i n i n g driers i g n i t e d j u s t as well a s t h e raw oil. T h e f a t t y acid of d e h y d r a t e d castor oil i g m t e d as easily as linseed oil f a t t y acid a n d raw linseed oil a n d m o r e readily t h a n d e h y d r a t e d castor oil. The i g n i t i o n time decreases with increase in iodine n u m b e r of t h e sample. (C.A. 53, 2649) NEW UTILIZATIO.NS OF SYNTHETIC PAT'r~r ACIDS PREPARED BY OXIDATION OF PARAFFIN. I. V. Nicolescu, E. Angelescu, a n d :P. Varsilesco (Univ. B u c a r e s t , R o m a n i a ) . Rev. franf, corps gras 5, 384-91 (1958). A n entirely new class of c o m p o u n d s c o r r e s p o n d i n g to f o r m u l a

BUTTER SUBSTITUTE.

I--

I

O' ( R ) CH" CH (CH~),,COOCft~CH : CH: was o b t a i n e d b y esterification of u n s a t u r a t e d f a t t y alcohols p r e p a r e d f r o m two f r a c t i o n s c o n t a i n i n g , respectively, C~-C~, a n d C~-C~o s a t u r a t e d f a t t y acids f a b r i c a t e d by a t l o m a n i a n f a c t o r y with allyie alcohol l e a d i n g to esters with iodine n u m b e r of, respectively, 156 a n d 141, followed by e p o x i d a t i o n with acetic a c i d - h y d r o g e n p e r o x i d e - s u l f u r i c a e i d n l L , : t u r e in b e n z e n e solution. The s i m u l t a n e o u s presence of the reactive epoxy a n d allylic g r o u p allowed the p r e p a r a t i o n of h i g h - m o l e c u l a r comp o u n d s b y p o l y m e r i z a t i o n or p o l y e o n d e n s a t i o n with a n d w i t h o u t ulaleic acid; some e x a m p l e s of such c o m p o u n d s a r e given, a n d it is s h o w n by e n u m e r a t i o n of p h y s i c a l d a t a t h a t t h e y can be utilized in order to m o d i f y a d v a n t a g e o u s l y the m e c h a n i c a l p r o p e r t i e s of v a r n i s h e s or f o r t h e p r e p a r a t i o n of p r o d u c t s f o r m i n g h i g h l y r e s i s t a n t f l m s . A s i m i l a r p r o d u c t was obt a i n e d by e m p l o y i n g cotton oil f a t t y acids f o r the p r e p a r a t i o n of such a compound, a n d c o n d e n s i n g it with maleic acid at 150-180 ~ (C.A. 52, 21168) PHYSICAL AND ~HEI~ICAL CHAEACTERISTICS O F OILS AT I)IFFE~ENT STAGES OF MATUEITY OF THE SEED O F SEVERAL PLANT SPECIES. A. A. Vidal (Univ. L a P l a t a , A r g . ) . Hey. fac. agron. L a Plata 32, 159-71 (1956). A n a l y s e s of the seed oils of Brassiea campestris, flax, Carthamus tinetorius, sunflower, sesame, a n d s o y b e a n a t t h r e e s t a g e s d u r i n g a m o n t h ' s g r o w t h showed a n increase in oil content, decrease in f r e e acid, a n d increase in iodine n u m b e r . The c h a n g e s were small in the oils of Brassica campestris, sesame) a n d soybean. The acidity of Carthamus tinetorius oil increased, possibly because of increase in c o n c e n t r a t i o n of t h e acidic colored component. C h a n g e s in index of r e f r a c t i o n were slight. (C.A. 53, 2649)

266

T H E JOUlCNAL OF THE A M E R I C A N O I L C H E M I S T S ' SOCIETY

ADDUCT FORMATION OF LONG-CHAIN FATTY ACIDS WITH UREA. K . Taiifel, G. Miiller, a n d C1. F r a n z k e . Nahrung 2, 255-67 (1958). A difference in c h a i n l e n g t h of snore t h a n two carbon a t o m s is n e e d e d f o r s a t i s f a c t o r y s e p a r a t i o n b y f o r m i n g u r e a adducts. M e t h y l e s t e r s can be s e p a r a t e d as r e a d i l y as t h e i r f a t t y acids. A l o n g e r r e a c t i o n period w i t h o u t s t i r r i n g , such as o v e r n i g h t s t a n d i n g of t h e f a t t y - a c i d solution w i t h urea, gives better separatio~ than a few hours with stirring. Methyl alcohol is b e t t e r t h a n solvents such as e t h y l ether, ethyl alcohol, p r o p y l alcohol, b u t y l alcohol, or chloroform. T h e a d d i t i o n of u r e a in several small p o r t i o n s r e s u l t s in smaller yields b u t more selective separation. T h e h i g h e r t h e c o n c e n t r a t i o n of a g i v e n f a t t y acid in t h e m i x t u r e , t h e more complete is its s e p a r a t i o n . (C.A. 53, 2648) PAPER CH!~OMATOGRAPHY OF HIGHER SATURATED FATTY ACIDS. Sobeslav F i k e r a n d V~clav H ~ j e k ( U s t a v h y g i e n y , P r a g u e ) . Chem. listy 52, 549-51 ( ] 9 5 8 ) . 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 for h i g h e r s a s f a t t y acids was modified f o r the s e p a r a t i o n of a c i d s c o n t a i n i n g m o r e t h a n 24 c a r b o n atoms. (C.A. 53, 2647) FLAVOMATICS PRO2~I FAT. J. J. B r o d e r i c k ( L e v e r Bros. Co., N e w York, N . Y . ) . Am. Perfumer Aromat. 7 2 ( 5 ) , 49, 52-2, 56 (1958). F a t s c o n t a i n i n g low-molecular-weight f a t t y acids in t h e i r triglyeerides (e.g., milk f a t , coconut oil) are i m p o r t a n t flavorwise. Some flavomatics derived f r o m fas a r e u s e d in s t r a w b e r r y a n d other flavors, a l t h o u g h those f r o m p r o t e i n s a n d c a r b o h y d r a t e s are more i m p o r t a n t . T w e n t y - e i g h t references. (C.A. 53, 2502) R,EACTION 0P METHYL RICINOLEATE AND TERT-]3UTYL CH~O~IATE. S e n j i r o M a r u t a a n d Yoshihito Suzuki ( Y a m a n a s h i Univ., K o f u ) . Kdgy6 Kagaku Zasshi 60, 31-3 (1957). M e t h y l rieinoleate w a s oxidized b y t e r t - b u t y l c h r o m a t e to give an o x i d a t i o n p r o d u c t in 71% yield. The r e s u l t s showed t h a t t h e o x i d a t i o n of h y d r o x y l radicals in m e t h y l ricinoleate f o r m s m e t h y l 12-oxo5etadecenoate a n d t h a t p a r t of m e t h y l ricinoleate is p o l y m e r i z e d or condensed while other p a r t s decompose into e n a n t h i e acid, e s m n t h a l d e h y d e , u n d e c y l e n i c acid, a n d caproie acid. Cis-methyl ricinoleate is p a r t l y c h a n g e d to transm e t h y l rieinoleate. (C.A. 53, 4126) THE SYNTHESIS 0,E LONG-CHAIN FATTY ACIDS. I I . STRAIGHT CHAIN ALKANO~C ACIDS. H. P. K a u f m a n n a n d W. S t a m m (Univ. of Miinster, Ger.). Chem. Ber. 91, 2121-6 (1958). C h a i n - l e n g t h e n i n g of f a t t y acids is achieved b y a d d i n g t h e acid chlorides to C~H~, d e h y d r o e h l o r i n a t i n g t h e r e s u l t i n g 2-chloroethyl alkyl ketones, oxidizing the v i n y l k e t o n e s with potass i u m p e r m a n g a n a t e to a-oxo acids, a n d reducing, or b y t r e a t i n g t h e 2-ehloroethyl alkyl k e t c h e s w i t h p o t a s s i m n cyanide or with NaCH(CO,~C-2HG)2 a n d h y d r o l y z i n g t h e c o n d e n s a t i o n p r o d u c t s to fl- a n d 7-oxo acids, respectively, which are finally reduced to t h e f a t t y acids. (C.A. 53, 4118) THE ESTIMATION OP FAT IN RICE. J o s e p h a M. M. ]suykx. Intern. Tijdschr. Brouw. en Mout. 17, 222-3 (1958). T h e rice meal is e x t r a c t e d in a Soxhlet a p p a r a t u s with carbon tetrachloride. The l a t t e r is distilled a n d the residue dried at 105-7 ~. (C.A. 53, 4603) THE SUR]PACE ]SAYERS OF MILK-FAT GLOBULES. IV. THE CHOLESTEROL CONTENT (FREE AND ESTERIFIE'D CHOLESTEROL) O~ THE SURFAC~ LAYERS. H. M u l d e r a n d T. A. Z u i d h o f ( A g r . Univ., W a g e n i n g e n , N e t h . ) . Neth. Mille Dairy J. 12, 173-9 1958). Cholesterol c o n t e n t s of milk f a t , m i l k - f a t globules, a n d milk sesmm were: 286 ~ 7, 322 _+ 9, a n d 2.2 ___ 1.2 rag./100 g., respectively. A b o u t a~ of t h e t o t a l cholesterol in milk was in t h e f a t , ]/~o in t h e m e m b r a n e s , a n d t h e r e s t in the serum. A b o u t 1 5 % of t h e cholesterol was esterified. (C.A. 53, 4509) CUI~RENT IDEAS ON THE' DETERMINATION OF FATS IN MILK. 5. P i c a . Mises au point chiT. anal. pure et appl. et anal. bromatoL 3, 85-132 (1955). A review with s e v e n t y references. (C.A. 53, 4509) ]:~.ECENT R.]SSEARCH ON THE ORIGIN OP MILK FAT. 1~. F. Glascock (Natl. I n s t . R e s e a r c h D a i r y i n g , Shinfield, E n g l . ) . Proc. Roy. Soc. ( L o n d o n ) B149, 402-13 (1958). A review c o n c e r n i n g t h e nonlipide a n d the lipide p r e c u r s o r s of t h e f a t t y a c i d s of b u t t e r f a t , a n d t h e origin of its glycerol. Forty-five references. (C.A. 53, 459.8) I)ETI~CTION O~ ~/[USTARD OIL IN OTHER EDIBLE OILS. S. N. M i t r a , ]3. R. Roy, a n d P. N. S e n g u p t a ( C e n t r a l F o o d L a b o r a tory, C a l c u t t a 16). Current S~. ( I n d i a ) 27, 221 (1958). The t e s t proposed is e s s e n t i a l l y t h e m e t h o d in Methods of Analyais A.O.A.C., 8 t h ed., p. 517, 1955, f o r volatile oil o f m u s t a r d in which a]lyl i s o t h i o c y a n a t e is detesmained. A d a r k color on a d d i t i o n of silver n i t r a t e to t h e distillate, which c a n be q u a n t i t a t i v e l y e s t i m a t e d , is considered positive evidence of

VOL. 3 6

allyl i s o t h i o c y a n a t e . T h i s c o m p o u n d is n o t f o u n d in significant a m o u n t s in other oils. (C.A. 53, 4595) COSTUs-~RoOT OIL AND LACTONIC CONSTITUENTS THEREFROM. Govind R a m a e h a n d r a K e l k a r a n d S a s a n k a C h a n d r a B h a t t a c h a r y y a (Council of Scientific a n d I n d u s t r i a l R e s e a r c h ) . Indian 59,853. Costus-root oil w a s e x t r a c t e d f r o m eostus~root powder with a yield of 6.2%. A total of 250 g. of '~eons t a n o l i d e ' ~ a n d ' ' n e o c o s t a n o l i d e " were isolated a n d s e p a r a t e d f r o m 450 g. of oil. (C.A. 53, 4779) SOLVENT EXTRACTION 0F COTTONSEED OIL. N. K . Roy Chaudh u r i a n d S. K . N a n d i ( I n d . I n s t . Teehnol., K h a r a g p u r ) . J . Indian Chem. Soc., Ind. ~" News Ed. 19, 8 7 - 9 4 (1956). Cottonseed a f t e r d e l i n t i n g a n d d e h u l l i n g w a s e x t r a c t e d with benzene, alcohol, a n d solvent oil u n d e r d i f f e r e n t o p e r a t i n g conditions. E x t r a c t i o n w a s done b y m e c h a n i c a l m i x i n g of t h e solvent with dehulled seed a n d also in a n a t t r i t i o n mill to have s i m u l t a n e o u s p u l v e r i z a t i o n a n d extraction. ]3enzene w a s t h e b e s t solvent, a n d 98% e x t r a c t i o n h a s been obtained. (C.A. 53, 4775) THE SELECTIVITY 0,P HYDROGENATI0,N OF SUNFLOWEIr OIL WITH FORlk~ATE NICKEL CATALYST. G. L Kolesnikov. Trudy Kras. nodars]~. Inst. Pishehevo{ Prom. 1 9 5 5 ( 1 1 ) , 8 1 - 2 ; Referat. Zhur., Khim. 1955, A b s t r . No. 56473. T h e effect of t e m p e r a t u r e (180-220 ~ on t h e "radical '~ selectivity of h y d r o g e n a tion of sunflower oil (iodine n u m b e r 121.9; c o n t e n t of acids [in % ] : s a t u r a t e d 9.8; oleic 39.5; linoleie 50.7) with t h e u s e of 0.075% ( b a s e d on nickel c o n t e n t ) f r e s h a n d depleted form a t e nickel c a t a l y s t , w i t h o u t a carries', w a s studied. T h e speed of the h y d r o g e n flow w a s 3 liters per m i n u t e ; s a t u r a tion of oil was to a n iodine n u m b e r of 88-90. The degree of selectivity (ratio of h y d r o g e n a t i o n of linoleic a n d oleic acids) did n o t d e p e n d on t h e t e m p e r a t u r e . The depleted c a t a l y s t a c t e d m o r e selectively u n d e r the s a m e conditions of hydrog e n a t i o m (C.A. 53, 4775) ANALYSIS OF TRICHILIA QUADRIVALVIS SEED, OLEAGINOUS PLANT PaOM THE KWANGO PLAIN. J. P. J. Casier (Univ. cathol. L e u v e n , B e l g . ) . Bull. agr. Congo Belge 49, 1301-5 (1958). Triehilia quadrivalvis seed c o n t a i n e d 4 6 - 5 6 % of clear g r e e n viscous oil with iodine n u m b e r 33.5, saponification n u m b e r 221, n~ 1.48435, n ( b u t y r o ) 84.45. T h e oil cake c o n t a i n e d a b o u t 2 0 % protein. (C.A. 53, 4775) EXTRACTION OP SOYBEANS. MECHANISM WITH ~ARIOUS SOLVENTS. D. F. O t h m e r a n d W. A. J a a t i u e n ( P o l y t e c h n i c I n s t . of Brooklyn, Brooklyn, N e w Y o r k ) . Ind. Eng. Chem. 51, 543-6 (1959). T h e m e c h a n i s m of v e g e t a b l e oil e x t r a c t i o n is u n c l e a r ; a n d e q u i p m e n t d e s i g n is empiric. E a r l i e r s~udies gave a theory f o r one s y s t e m a n d d e m o n s t r a t e d a m e t h o d for e q u i p m e n t design b a s e d on simple l a b o r a t o r y d e t e r m i n a t i o n s . S o y b e a n flakes o f different t h i c k n e s s e s were e x t r a c t e d in n i n e solvents. P h y s i cal t e s t i n g requires only a balance, l a b o r a t o r y glassware, a n d shaker. T h e single solvent, hexane, previously used, e x t r a c t e d a t t h e same r a t e s w h e n c o n t a i n i n g u p to 2 0 % oil. M o s t p r e s e n t solvents e x t r a c t e d m o r e slowly w h e n c o n t a i n i n g m o r e t h a n 1 0 % oil, with less residual oil in flakes w h e n solvent c o n t a i n e d less oil. T h i s is a f u n c t i o n of d e n s i t y t i m e s s u r f a c e t e n s i o n divided b y viscosity, a t e r m which a p p e a r s in a modified H a g e n Poisenuille e q u a t i o n defining t h e m a e h a n i s m . T h e t h e o r y a n d d e s i g n m e t h o d s were g e n e r a l i z e d ; simple c o n t a c t i n g w a s as effective as c o u n t e r c u r r e n t o p e r a t i o n at low miscella concent r a t i o n s . These s i m p l y d e t e r m i n e d l a b o r a t o r y d a t a allow imm e d i a t e design of p l a n t extractors. THE USE OP HIGH EEFICIENCY CAPILLARY COLU~INS ~0.1r THE SEPARATION OP CERTAIN CIS-TRANS ISOMERS O]o ]50NG (~HAIN" FATTY ACID ESTERS BY GAS CHROMATOGRAPHY. S. ]:~. L i p s k y , J. E. ]5ovelock, a n d R. A. L a n d o w n e ( D e p a r t m e n t of Medicine, Yale Univ., N e w H a x e n , Conn.). J. Am. Chem. Sop. 81, 1010 (1959). P r e l i m i n a r y e x p e r i m e n t s e m p l o y i n g capillary c o l u m n s c o n t a i n i n g c e r t a i n polyesters as s t a t i o n a r y ]iqnids pvovlded t h e r a p i d resolution of m o s t c o m p o n e n t s i n c l u d i n g linoleate a n d lino]enate w i t h good s e p a r a t i o n f a c t o r s b u t low theoretical plate efficiencies. THE EPFECT OP UREA AND ETT1ANOL ON SELECTIVITY 0~ THE FRACTIONATION PI~0CESS FOR FATTY ACIDS 0P COTT0~NSEED OIL. ]3. A. K a t s a n d A. ]5. M a r k n m n . Doklady AIca& Nauk Uzbek. S.S./~. 1957(4), 45-9 (in R u s s i a n ) . T h e influence of v a r y i n g a m o u n t s of u r e a a n d solvent ( e t h y l alcohol) on f r a c t i o n a t i o n of cottonseed oil f a t t y acids is studied. T h e v a r i o u s distributions of t h e i n d i v i d u a l f a t t y acids b e t w e e n precipitas and solution a r e t a b u l a t e d . A complete s e p a r a t i o n of s a t u r a t e d a n d oleic acid ( p r e c i p i t a t e ) f r o m linoleic acid ( i n solution) was n o t a t t a i n e d . (C.A. 53, 4773) KINETICS I~O'R THE OXIDATION OF FATS. D. G. K n o r r e , Yu. N. L y a s k o v s k a y a , a n d N. M. E m a n u e l . Bull. Avad. Sci. U.S.S.R.,

JUNE, 1959

Div. Chem. Sci. 1957, 693-8 (E1)glish translation).

ABSTRACTS

(C.A. 53,

4773) DEGI~EI~ OF POLYMERIZATION 0P LINSEED OIL. M. Taniewski and L. Bulczyfiska (Inst. Dyes and Lacquers, Gliwice, P o l a n d ) . Przemys~ Chem. 35, 324 5 (1956) (English s u m u m r y ) . Linseed oil was polymerized by heat alone at 265, 285, and 305 ~ and polymerized by heat and air (4-5 liters p~r minute) ut 100, 150, and 285 ~ Determination of iodine nunfber ( A ) , bromine number ( B ) , and application of 1 . 5 8 B - A - - X , gave a measure of degree of oil polymerization, ttowever, the differences in X of oil polymerized to 3-30 poises were small. (C.A. 53, 4768) SEED OILS OP P01)OCARPUS NAGI AND 1NTINE OTHE~ JAPANESE PLANTS. Y. K o y a m a and Y. Toyama. Mere. Fac. Eng., Nagoya Univ. 9, 14o-6 (1957). The oils of Viburnum erosum, Lig~s-

tram japonieum, Hibiscus mutabilis, Ilex integra, llex macropoda, flex svrrata ear. sievoldii, Pourthiaea vil~osa, Smilax china, and Smilax nipponica were analyzed. The bromination test on the f a t t y acids of each oil showed the presence of linoleic acid and the absence of linolenic acid. The presence of oleic acid in the f a t t y acids of V. erosum, H. mutabilis, L. setrata, a n d P. vi~osa oils was demonstrated by separating elaidic acid from the elaidinized product of the liquid fatty-acid fraction. The fatty-acid composition for each oil except P. nagi was estimated by ultraviolet absorption measurements of the alkall-isomerized f a t t y acids; these results checked satisfactorily for a few oils with the lead salt-ethyl alcohol method. The f a t t y acids consisted of approximately 90% linoleic and oleic acids and 10% saturated acids. The oil of P. nagi was found to contain, besides linoleic acid, a new eicosatrienoic acid named podocarpic acid. (C.A. 53, 2649) THE SILPARATIONOF ~ATURATEDAND UNSATURATED~'~ATTY ACID ESTERS BY GAS-L~QUID CHROMATOGRAPHY. B. M. Craig and N. L. M u r t y (Natl. Research Council Cazt., Saskatchewan). Can. J. Chem. 35, 1297-1301 (1958). Gas-liquid Chromatography has been applied to the anMysis of f a t s and oils in synthesized plasticizers which release stearic, olelc, linoleic, and linolenic acid esters, and which do not bleed. The columns, nmde of copper tubing (12 ft. x 0.25 in.) were packed with 1 : 4 silicone grease on 20-40-mesh fireb~ick. Plasticizer columns were constructed of the same copper tubing 6 ft. long packed with 1 : 4 diethylene glycol ~dil~te or diethylene glycol succinate on the firebrick; these plasticizer columns being coupled in series, the succinate column being first. The succinate column separated the stearic and oleic acid esters; the adipate column, the linoleic and arachidic acid esters. The methyl esters of soybean oil were separated with the plasticizer c01umn into palmitic, stearic, oleic, linolelc, and linolenie acids. Tallow esters with a silicone column were separated into the s a t u r a t e d even-number carbon atom acids C~-C~8, also the C~:. and C~7 s a t u r a t e d acids were observed; likewise peaks between C~ and C~ and also between C~s and C~7, which m a y have been branched-chain acids. The plasticizer column showed additional peaks probably due to u n s a t u r a t e d acids of various chain lengths. Herring-oil esters showed odd-number f a t t y acids from C, to C~ a n d the expected even-number carbon acids with a silicone column. L a r d esters showed even-number f a t t y acids C~o-C_~o on a silicone column, and some u n s a t u r a t e d acids on plasticizer column. (C.A. 53, 2647) ANALYTICAL STUDY OF THE ALKALINE NEUTRALIZATION0V OILS. M. Naudet, C. Drap, and S. Bonjour (Fac. sei., Marscille). Rev. fran~, corps gras 5, 557-65 (1958). The neutralization at 60-80 ~ of 10-kg. samples of edible oil was studied by two methods: (a) in a single stage with theoretical quautities of sodium hydroxide; and (b) in two stages beginning with 60-70% of the theoretical and then, after separation of the layers by centrifugation, completing with an additional portion of sodium hydroxide. Three oils of 7.0, 6.8, and 3.8 acidity, treated according to a, showed, respectively: residual acidity of 0.12, 0.19, 0.14%; nonglyeerides 0.51, 0.69, 0.57; the " i n evitable l o s s e s " 7.70, 6.75, 4.15%; and the glyceridic losses 5.0, 4.35, 2.50%. W i t h the first-stage t r e a t m e n t of b there was an economy of 10-15% of sodium hydroxide, and the final acidities varied between 0.09 a n d 0.13%, monoglycerides 0.240.52%, glyceridic losses 2.25-4.25%. W i t h the completion of the second stage of b, monoglycerides were 0.19-0.27. Glyceridic losses were similar to t h a t of the a, b u t the color of the neutralized oils expressed in trichromatic figures was superior. (C.A. 53, 4595) WAX CI%YSTAL STRUCTURE VERSUS WATER-VAPoR TRANSMISSION. B. C. Fox (Califormnia Research Corp., l~ichmond). Modsrn Pac]~aging 32(2), 141-149, 196 (1958). Microscopic and x-ray diffraction measurements indicate t h a t water vapor

267

does not penetrate wax crystals on the surface of waxed cellophanes, b u t r~ther passes between them. Large wax plate crystals, oriented parallel to the base sheet, give a low watervapor transmission rate. Formation of these large oriented plate crystals is aided by air cooling of the wax film or by recrystallization and reorientation of the water-cooled wax film during storage. An increase in storage temperature accelerates the rate of reerystallization and reduces the water-vapor transmission rate. (C.A. 53, 2650) WAXES. X I I L RE~INING SUGAR-CANE WAX BY FRACTIONATION FROm SOLVENTS. H. H. t t a t t and A. H. Redeliffe (C.S.I.R.O., Die. Ind. Chem., Melbourne). Australian J. Appl. Sci. 9, 380403 (1958). Aqueous and anhydrous solvents and solvent mixtures were compared in refining the crude sugar-cane wax recovered from the filter cake of sugar mills of Australia. This wax can be resolved by certain solvents in two simple steps into fat, hard-wax and pitch fractions. The hard-wax fraction can then be bleached readily by air alone. The f a t fraction m a s t be removed from sugar-cane wax, otherwise more than two separations are needed. Of various solvents investigated a 4 : 1 mixture of ethyl alcohol: C~It~ (or an equivalent petroleum fraction) is the most suitable for Australian conditions. (C.A. 53, 4777) WAXES. V. Charrin. Peintures, pigments, vernis 34, 513-14 (1958). Compositions of commercial synthetic waxes are discussed. (C.A. 53, 4777) 5s I%EFI~ING. R. O. Schmitt (Buckeye Cellulose Corp.). U.S. 2,878,275. I n the refining of vegetable oils, a solution of the crude oil in a volatile solvent is mixed with toots, and then treated with alkali. TRANSEST~BIFICAT~0N OF TRIGLYCERIDES BY MEANS OF PLURAL ME~AL C~TALYS~. G. u Brokaw ( E a s t m a n K o d a k Co.). U.S. 2,379,Z81. In a continuous process, a mixture of higher f a t t y acid triglycerides and lower f a r t s acid triglyceridcs is transesterifie4 by h e a t i n g in the presence of a plural metal soap catalyst. The c2:talyst contains at least one alkali or alkaline earth metal soap and a t least one saop of an ampho~eric metal. The reaction mixture is fractionated by thin fibn vacoum distillation so as to separate a mixed triglyceride containing at least one higher acyl radical and at least one lower acyl r a d i c a l SEPARATION OF ~0I~IP0.NENTS OF OLEAGINOUS MIXTUI~ES BY FRACTIONAL ~I%YSTALLIZATION. I n t e r n a t i o n a l Research and Development Corp. Brit. 801,102. A continuous and (or) batch process provides for the removal of undesirable high-freez,ing stearins from vegetable and animal oils and fats, by treating a miseella of approximately 45% by weight of oil and 55% suitable solvent, e.g., hexane. The m i x t u r e is cooled in thirty minutes to the temperature at which t u r b i d i t y first appears, then more slowly to a temperature intermediate between the temperature of turbidity and the gelling temperatnre. A low viscosity permits rapid separation of solute crysCMs frown the miseella. Small amounts of moisture present in the oll crystallize to f o r m tiny nuee]i which promote the crystallization of the stearins. (C.A. 53, 4778) PURIFICATION 01~ GLYO0PLS, ]~SPECIALLY ETHYLENE GLYCOL. Norvik Aekroyd and Wm. A. O'Neill (Imperial Chemical Industries Ltd.). Brit. 801,723. Addition of water to a crude glycol prior to distillation results in a product of high purity and stability towards heat. (C.~. 53, 4778) WAX PASTES. W. Hessler (Werner & Mertz Akt.-Ges.). Get. 936,Z28, and Get. 938,146. Stable wax pastes which do not dry and have good plasticity are: obtained by mixing and homogenizing waxes, paraffins, and coloring materials with the solvent at room temperature or a little above. Waxes and solvents can be used of the same type as before, but heating energy, coo!: ing energy, and time for stabilizing are decreased. More material of low quality can be used to give pastes of equal quality to those produced by melting and cooling more expensive raw materials. (C.A. 53, 4779) DEHYDRATIOI'r OF LO~W-]~C[OLECULARFATTY ACIDS. C. Contor (Lambiotte & Cic. S. h. r. 1.). Ger. 957,122. (C.A. 53, 4778) LIGHT-COL0'RED WAXES "WITH A HIGH CONTENT OlS MOSNTANIC ACID. W. P r e s t l n g a~ld G. Walther. Ger. (East) 11,873. Upon t r e a t i n g mixtures of m o n t a n wax and solid paraffins with both nitric acid and another mineral acid (phosphoric acid or sulfuric acid) the resins settle, the esters are hydrolyzed, and the resulting alcohols are oxidized to montanie acid. A hard yellow-white wax, acid number 90, saponification number 115, melting at 80 ~ was obtained by this method. (C.A. 53, 4779) I:~ARI) POLISHING WXXES. O. Klein, W. Presting, and G. Walther. Ger. (East) 1~,543. Addition to Get. (East) 7997. Mixtures of equal amounts of resin-free or resinous crude m o n t a n

268

T H E J O U R N A L OF THE A M E R I C A N 0 I L C H E h I I S T S ' SOCIETY

waxes with maeroparaffins f r o m F i s c h e r - T r o p s c h s y n t h e s i s or with h i g h e r - m e l t i n g h a r d - w a x f r a c t i o n s a r e h o t refined b y use of at l e a s t 7 0 % s u l f u r i c acid. The e x t r a c t i o n of r e s i n f r o m the crude m o n t a n w a x is accomplished b y m e a n s of n i t r i c acid or by t r e a t m e n t with selective solvents in t h e presence of h a r d portions of t h e macroparafifins. Refined w a x e s of excellent h a r d n e s s , good oil-binding capacity, a n d a l i g h t color are obtained. (C.A. 53, 4779) RECLAMATION OP OIL AND BLE&CHING CLAY. V e n k t r a m a n Set h u r a m a n , R a j e n d r a I~. B h a t n a g a r , a n d N a r a s i n g R. K u l o o r ( S h r i R a m I n s t i t u t e f o r I n d u s t r i a l R e s e a r c h ) . Indian 61,257. F i l t e r - p r e s s m u d f r o m v a n a s p a t i f a c t o r i e s or semi-tar industries is e x t r a c t e d with a n o r g a n i c solvent to remove f a t t y a n d oily m a t t e r f r o m s p e n t b l e a c h i n g clay, a n d t h e b l e a c h i n g clay t h u s o b t a i n e d is a c t i v a t e d b y h e a t i n g at 400-600 ~ f o r 1-60 m i n u t e s . The o r g a n i c solvent u s e d is a n azeotropic m i x t u r e of b e n z e n e a d d alcohol or a n azeotropie m i x t u r e of alcohol with benzene, toluene, or trichloroethylene. (C.A. 53, 4779) REFINING 0E SUGAE-C!ANEWAX. R a m S. D u b e y a n d W a l c h a n d s u g a r I n d u s t r i e s L t d . Indian 61,413. C r u d e s u g a r cane w a x (10 g.), m e l t i n g a t 63 ~ was t a k e n u p with 25 ml. water, heated, a n d m a i n t a i n e d at 75-80 ~ A s t r e a m of chlorine w a s p a s s e d in. A f t e r a b o u t six hours, the blackish g r e e n w a x b e c a m e yellowish brown. I t was w a s h e d several t i m e s w i t h h o t w a t e r a n d dried. I t m e l t e d a t 65 ~ a n d c o n t a i n e d 7.5% chlorine. (C.A. 53, 4779) CONTINUOUS I-~u OF FATTY P]~ODUCTS. G. Mazzoni S.p.a. Ital. 550,134. A two-step process a n d a p p a r a t u s is described for t h e h y d r o l y s i s a n d for recovery of the reaction products. The fa.tty m a t e r i a l is h y d r o l y z e d with w a t e r a t h i g h t e m p e r a t u r e s a n d p r e s s u r e s a n d i n t r o d u c e d into a distilling c h a m b e r u n d e r v a c u u m to recover m o s t of the liberated acids; the residue is t h e n c a r r i e d t h r o u g h a second h y d r o l y s i s a n d distillatiml. F a t s p l i t t i n g ix 98-99.5% complete. (C.A. 53, 4778) EXTI~ACTION OF FAT FROM PALMETTO. R. M. Morales. Span. 237,471. T h e p a l m e t t o in a m o r e or less size-reduced s t a t e is s h a k e n in a t i g h t l y closed c o n t a i n e r w i t h carbon disulfide for 60-75 m i n u t e s , a f t e r which time t h e carbon disulfide is d r a w n off a n d placed in a n o t h e r container, where it is distilled with steam, so t h a t t h e f a t remains. (C.A. 53, 3741) DEMULSIFIER. V. Ya. M a s u m y a n a n d M. K . D a n i e l y a n . U.S.S.R. 1~3,860. A demulsifier is obtained b y air o x i d a t i o n of the g a s oil-solar oil f r a c t i o n at 140-50 ~ in the presence of caleimn n a p h t h e n a t e as catalyst. (C.A. 53, 3741) R.EMOVAL 0F BITTER TASTE AND ODOR FROM WHALE OIL. Seiji T a d a a n d Ohki N a k a y a m a . Japan. 2841 ('58). W h a l e oil (10 kg.) is h o m o g e n i z e d with 100 g. casein in 1.5 1. w a t e r a n d s o d i u m h y d r o x i d e to neutralize. The emulsion is s e p a r a t e d by c e n t r i f u g i n g to o b t a i n 9.8 kg. odorless oil. (C.A. 53, 4607) APPARATUS F(}R DIGESTION OF WHEAT OIL. Worao M u r a k a m i ( N i p p o n F i s h e r y Co.). Japan. 9987 ('58). (C.A. 53, 4779) FATTY

ACID DERIVATIVES

SYNTHESIS OE FATTY ACID NITRILES. P. V. N a u m e n k o and B. A. K h a s k i n ( A l l - U n i o n Sci.-Research I n s t . F a t s , Moscow). MasloboD~o-Zhirovaya Prom. 2 4 ( 1 0 ) , 13-15 (1958). A review with eight references. (C.A. 53, 2082) REACTIONS OF UNSATURATED FATTY ALCOHOLS. IV. OXIDATIVE DEGRADATION OF LAURYL ISO'PROPYL ETHER. L. E. Gast, C. B. Coleman, a n d H. M. Teeter ( T h e N o r t h e r n U t i l i z a t i o n Research a n d D e v e l o p m e n t Div., Agr. R e s e a r c h Ser., U . S . D . A . ) . J. OrE. Chem. 24, 160-5 (1959). L a u r y l isopropyl ether conr a i n i n g catalytic a m o u n t s of cobalt n a p h t h e n a t e was d e g r a d e d with o x y g e n at 150 ~. I s o l a t e d oxidation p r o d u c t s indicate a t t a c k at both carbon a t o m s a d j a c e n t to the ether oxygen. D e g r a d a t i o n p r o d u c t s isolated were laurie acid, acetone, isopropyl lnurate, lower f a t t y acids f r o m C2 to C~ a n d their esters, carbon dioxide, isopropyl alcohol, a n d polymerized acidic products. Laramie acid a n d isopropyl l a u r a t e were oxidized u n d e r the s a m e conditions as l a u r y l isopropyl ether. L a u r i e acid gave small a m o u n t s of lower acids in the hontologous series as deg r a d a t i o n products. I s o p r o y l l a u r a t e was oxidized to f a t t y acids f r o m C~. to CA~ in a b o u t one t h i r d the q u a n t i t i e s f m m d f r o m lauryl isopropyl ether. AN IMFI~0VED PI~OCEDURE P0R PREPARING GLYCEROL ETHERS. S. C. G u p t a a n d F. A. K u m m e r o w (Dept. of F o o d Technology, Univ. of Illinois, U r b a n a ) . J. Org. Chem. 24, 409-11 (1959). B u t y l alcohol, a n a t u r a l occurring glycerol ether f o u n d in the liver of various Elasmobranchii (shark, rays, etc.), w a s f o u n d to be identical with 1-stearyl glycerol ether. The 1- a n d 2s t e a r y l glycerol ethers were s y n t h e s i z e d with a modified procedure. S y n t h e s e s of 2-oleyl a n d 2-1inoleyl glycerol ethers did

VOL. 3 6

n o t produce s a m p l e s pure m m u g h for a c c u r a t e carbon and h y d r o g e n values. SYNTHESES OF UNSATUI~ATED FATTY ALDEHYDES. H. K. Mangold ( T h e H o r m e l Inst., Univ. of M i n n e s o t a ) . J. Org. Chem. 24, 405-7 (1959). Oteyl-, linoleyl-, a n d linolenyl-aldehydes were p r e p a r e d b y a modified G m n d m a n n synthesis. T h e procedure can be u s e d f o r t h e p r e p a r a t i o n of r a d i o a c t i v e aldeh y d e s on a m i l l i g r a m scale. THE PEEPARATION OF HIGHER FATTY ALDEHYDES. H. P. K a u f m a n n a n d D. B. S p a n n u t h . Chem. Ber. 91, 2127-9 (1958). E s t e r s of selenious acid a n d f a t t y alcohols yield u p o n p y r o l y s i s f a t t y aldehydes a n d selenium. (C.A. 53, 4118)

oBiology and Nutrition THE EXPERIMENTAL PRODUCTION OF ATHEROSCLEROSI8 IN SWINE FOLLOWING THE FEEDING OF BUTTER AND MARDAEINE. H. C. Rowsell, H. G. Downle, a n d J. F. M u s t a r d ( O n t a r i o , Vet. Coll., Guelph). Can. Med. Assoc. J. 79, 647-54 (1958). W h e n divided into t h r e e g r o u p s , tifirty-three swine, f e d either a l o w - f a t diet or isocaloric diets rich in b u t t e r or m a r g a r i n e , showed some atherosclerosis on l o w - f a t diet, little increase with a highf a t m a r g a r i n e diet, b u t a considerable increase w i t h a h i g h - f a t b u t t e r diet. Blood cholesterol a n d phospholipide levels did n o t increase with either m a r g a r i n e or b u t t e r diet. The evolution of t h e disease a n d t h e g r o s s a n d microscopic findings of tile ather o m a r e s e m b l e d t h a t f o u n d in h u m a n s . I t w a s s u g g e s t e d f r o m the data. t h a t t h e activity of clotting s y s t e m is r e l a t e d to tile development o f atheros~lerosis in t h e swine a n d t h a t the t y p e of f a t is a n i m p o r t a n t f a c t o r in d t e r m i n i n g t h e s e changes. (C.A. 53, 4460) COMPARATIVE SOLUBILITY OF PKOTEIN IN COTTONSEED FLAKES EXTRACTED BY HEXANE AND BY ETHANOL. L. K . A r n o l d a n d Beverly J. Schriver ( I o w a E n g . E x p t . Sta., A m e s ) . Proc. Iowa Acad. Sci. 55, 230 3 (1958). A h i g h e r p e r c e n t a g e of protein in the meal e x t r a c t e d b y e t h a n o l tllaal in t h a t e x t r a c t e d by h e x a n e is indicated. A p p a r e n t l y the ethanol e x t r a c t e d some n o n p r o t e i n c o n s t i t u e n t s not dissolved by hexane, t h u s r e s u l t i n g in a h i g h e r p e r c e n t a g e of p r o t e i n in the meal. W a t e r - s o l u b l e p r o t e i n in tim h e x a n e - e x t r a c t e d meal w a s 63.6% m o r e t h a n in the ethanol product. P r o t e i n in t h e h e x a n e - e x t r a c t e d meal, soluble in s o d i u m chloride solution, w a s 39.2% g r e a t e r t h a n t h a t in tim e t h a n o l - e x t r a c t e d meal. P r o t e i n soluble i n dilute s o d i u m h y d r o x i d e solution in the h e x a n e - e x t r a c t e d meal wax 13.7% more t h a n in t h a t f r o m ethanol. (C.A. 53, 2498) DEBITTEEING SOYBEANS IN THE FOOD INDUSTRY. G. J a n i ~ e k (Vysokh w chem. technol., P r a g u e ) . Sbornik vysokd ~koly eh~m.-technol, v Praze; Oddil potravinarskd teehnol. 1957, 197213. D e b i t t e r i n g (deodm-ization) of s o y b e a n s b y d i g e s t i o n with h o t w a t e r is effective a n d p r e s e r v e s f a v o r a b l e organoleptic properties. N u t r i m e n t s a n d biologically effective s u b s t a n c e s are p a r t l y renmved. The i n c r e a s e d c o n t e n t of w a t e r in the final p r o d u c t causes microbial decay. Removal of w a t e r by d r y i n g is expensive, a n d t h e so.ybeans d a r k e n a n d acquire a n u n d e s i r a b l e taste. D e b i t t e r i n g b y m e a n s of live s t e a m is effective, no u n d e s i r a b l e c h a n g e s occur, t h e e n z y m e s which m a y cause oxidation of t h e oil a n d carotenoids are destroyed, t h e biological value is u n c h a n g e d , a n d t h e thermolabile protein soyin is destroyed. D e b i t t e r i n g b y i n f r a r e d r a y s is ineffective a n d causes u n d e s i r a b l e c h a n g e s in t h e so~bean f a t . Biological process gives a debittered p r o d u c t due to t h e d i g e s t i o n b y t h e w a r m water. D e b i t t e r i n g b y e x t r a c t i n g with organic solvents ix due p a r t l y to t h e e x t r a c t i o n a n d p a r t l y to t h e h e a t d u r i n g t h e s t e a m - d i s t i l l a t i o n of t h e solvents. (C:A. 53, 2499) EFFECT OF DIETARY PROTEIN, FAT, AND CHOLINE ON THE SERUM LIPIDES AND LIPO.PROTEINS OF THE RAT. R. Olson, J. R. J a b ]onski, a n d E. T a y l o r (Univ. of P i t t s b u r g h , P i t t s b u r g h , P a . ) . Natl. Kitamin Foundation, Nutrition Symposium Ser. 1 9 5 8 ( 1 6 ) , 22-9. Choline deficiency in t h e y o u n g a d u l t r a t caused a m a r k e d a l t e r a t i o n in f a t t r a n s p o r t with a decrease in the level of cholesterol a n d phospholipides, a r e d u c t i o n in t h e h i g h - d e n s i t y a-lipoproteins, a n d v i r t u a l d i s a p p e a r a n c e of t h e low-density fl-lipoproteins. T h e s u b s t i t u t i o n of casein f o r soy p r o t e i n entirely p r e v e n t e d the hypocholesterolemia a n d m i n i m i z e d t h e hypolipoproteinenfia seen on t h e soy p r o t e i n diets even t h o u g h it did not, a t all levels of d i e t a r y f a t , completely p r e v e n t f a t t y infiltration of the liver. A p p a r e n t l y , for t h e rat, t h e w i t h d r a w a l of choline a n d other labile m e t h y l donors f r o m the diet w a s a more effective m e a n s of lowering t h e s e r m n cholesterol a n d fl-lipoprotein c o n c e n t r a t i o n t h a n v a r y i n g t h e k i n d a n d a m o u n t of d i e t a r y f a t . The level a n d t y p e of d i e t a r y f a t did not m o d i f y the effect of choline on s e r m n lipides. The liver elaborates the fl-lipoproteins which p r o m o t e atherogenesis, a n d this process is

JUNE, 1959

ABSTRACTS

sensitive to a l t e r a t i o n of d i e t a r y protein, lipotropic factors, a n d f a t . (C.A. 53, 4464) EFFECTS 0'P DIETARY FREE C~s SATURATED AND UNSATURATED FATTY ACIDS AND DL-METHIONINE-CHOLINE CHLORIDE MIXTUlCE ON PLASMA CItOLESTEROL OF THE MALE ALBINO RAT. E. T, J a n s s e n ( W a r t b u r g Coll., W a v e r l y , I o w a ) . Proe. Iowa Aead. Sei. 55, 234-40 (1958). T h e f e e d i n g of 15% free acids ( s t e a r i c a n d linoleic acid, respectively) caused a rise in the p l a s m a cholesterol levels, t h e significant rise b e i n g in a n i m a l s on t h e 15% linoleic acid diet. W h e n a s u p p l e m e n t of D L - m e t h i o n i n e a n d choline chloride was fed, it p r o d u c e d a g r e a t e r rise in t h e cholesterol levels t h a n w a s p r o d u c e d b y only t h e 15% linoleic acid. T h e liver cholesterol level showed only s l i g h t v a r i a t i o n s f r o m t h e v a l u e s of the control group, except in t h e case o f t h e a n i m a l s f e d t h e 1 5 % linoleic acid. The u n s u p p l e m e n t e d 1 5 % acid diet showed a h i g h e r liver cholesterol ester c o n t e n t t h a n the diet c o n t a i n i n g a d d e d methionine-choline. I n d i c a t i o n s were t h a t on a 15% linoleic acid diet t h e a d d i t i o n of methionine-choline decreases t h e ester c o n t e n t of t h e liver while r a i s i n g t h e p l a s m a cholesterol ester content. (C.A. 53, 2387) FAT METABOLISM STUDIES IN EARLY CHILDHOOD. THE ABSORPTION O1~ FATS WITH A HIGH CONTENT OF UNSATURATED FATTY ACIDS. K . Sehreier (Univ. Heidelbergi Get.) Z. Kinderheilk. 81, 442-7 (1958). The a b s o r p t i o n of v e g e t a b l e f a t s a d d e d to cow milk, is g r e a t e r t h a n t h a t of a d d e d b u t t e r f a t . (C.A. 53, 4490) NUTRITIVE VALUE OF LIPIDES. X I I I . SEBOI~RHEA FORMATION DY ADMINISTRATION 01~ LARGE AMOUNTS OF ESTERS OF FATTY ACIDS WITH HIGHER ALCOHOLS IN ]:~ATS. 2. PRI~VE'NTIVE METHODS AGAINST S]~BORRHEA. T a k a s b i K a n e d a , H i s a e Sakai, a n d Seinosuke I s h i i ( T o k a i R e g i o n a l F i s h e r i e s Lab., T o k y o ) . Ndppon Snisangalcu Kaishi 23, 324-30 ( 1 9 5 7 - 5 8 ) . R a t s f e d w i t h s p e r m whale oil or f a t t y acid esters of h i g h e r alcohols such as oley] oleate c o n t a i n e d in t h e bodies 150 t i m e s as m u c h h y d r o c a r b o n a n d 5 t i m e s as m u c h sterol as did n o r m a l r a t s . S u p p l e m e n t a tion of t h e f e e d s by s o y b e a n phospholipide p r e v e n t e d t h e occurrence of t h e s e b o r r h e a b u t s o y b e a n a n d egg-yolk lecithins were n o t effective. Crude s o y b e a n cephalin also p r e v e n t e d t h e s e b o r r h e a a l t h o u g h the h y d r o c a r b o n a n d sterol c o n t e n t s were still high. E t h a n o l a m i n e h a d no p r e v e n t i n g activity. Sitasterol p r e p a r e d f r o m the unsaponifiable m a t t e r of s o y b e a n oil r a t h e r a u g m e n t e d t h e seborrhca f o r m a t i o n . (C.A. 53, 4459) FAT ACCUMULATION AND STORAGE. E. W e r t h e i m e r ( H e b r e w Univ., J e r u s a l e m , I s r a e l ) . Miinch. reed. Woehschr. 100, 115360 (1958). The recent l i t e r a t u r e c o n c e r n i n g the i m p o r t a n c e of adipose t i s s u e f o r f a t metabolisnl is reviewed a n d discussed. T h i r t y - t h r e e references. (C.A. 53, 4498) DIET, BLOOD LIPIDES, AND HEALTII OF ITALIAN MEN IN BOSTON. D. C. Miller, M a i ~ h a F. Trulson, Mary ]3. M c C a n n , P. D. W h i t e , a n d F. J. S t a r e ( H a r v a r d U n i v . ) . An.n. Internal Med. 49, 1178-1200 (1958). A s t u d y w a s m a d e of 189 h e a l t h y Bost o n men, whose p a r e n t s h a d been born in N a p l e s b u t who b a d t h e m s e l v e s lived all their a d u l t lives in t h e U n i t e d States. T h e y were f o u n d to have a m e a n blood s e r u m total cholesterol level a n d d i e t a r y f a t i n t a k e similar to other A m e r i c a n s , b u t this was considered h i g h e r t h a n t h a t of n a t i v e Neopolitans. (C.A. 53, 4460) CHOLESTEROL ME.TABOLISM. CHANGES IN BLOOD AND LIVER DURING A ]rIIGH-~HOLESTEROL DIET. A. Catolla-Cavalcanti (Univ. T u r i n , I t a l y ) a n d F. F. Ferrero. Ormonologia ( T u r i n ) 17, 477-98 (1957). I n albino r a t s f e d a diet c o n t a i n i n g pork f a t 40 a n d cholesterol 2 % , a r e m a r k a b l e increase of cholesterol in blood a n d liver ( b u t no connection b e t w e e n the two levels) was observed. (C.A. 53, 4461) INFLUENCE OF A FINE COCONUT OIL EMULSIO,N (EDIOL) ON SOME BLOOD AND TISSUE CONSTANTS. EXPERIMENTAL RESEARCH ON ALBINO RATS. F. G r i g n a n i (Univ. Cagliari, I t a l y ) a n d V. B e r n a r d i n i . Bass. reed. sarda 8, 635-56 (1957). The presence of Ediol in the diet caused a b e t t e r tolerance of the diet, avoided a b n o r m a l values for c o n s t i t u e n t s of blood a n d tissues, a n d provoked a n evident increase of the weight curve, especially at the lowest doses. (C.A. 53, 4461) ROLE OF [~IPIDES IN ATHEROSCLEBOSIS. ~ . Coppo (Univ. Modeua, I t a l y ) , G. P. Vechi a n d R. Lorenzini. Bull. sc.hweiz. Akad. reed. WiNs. 13, 179-91 (1957) (in I t a l i a n ) . ~Iypercholesterolemia w a s observed in 60 cases of m y o c a r d i a l infarction. A rich diet w a s c h a r a c t e r i s t i c of t h i s t y p e of atherosclerosis, with 3 4 % of the caloric equivalent c o m i n g f r o m f a t s . H e p a r i n o i d s u b s t a n c e s ( N - o c t y l a m i n e precipitable) in p l a s m a a p p e a r e d to be significantly lower t h a n in t h e control s u b j e c t s . C h a n g e s in the d i s t r i b u t i o n of blood lipides a n d p r o b a b l y c h a n g e s in t h e g e n e r a l lipide m e t a b o l i s m are involved in the p'~thogenesis. (C.A. 53, 2430)

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LIPIDE AND LIPOPROTEIN RELATIONS IN SFA~UM. F. W. F i s c h e r (Allgenl. K r a n k e n h a u s , H a m b u r g - ] 3 a r m b e k , Ger.). Klin. FVoehsehr. 35, 1112-17 (1957). A lack of dependence of lipoproteiu d i s t r i b u t i o n of the absolute a m o u n t s of lipide or lipoprotein in the s e r u m of n o r m a l mlbjects was observed due to m a r k e d i n d i v i d u a l v a r i a t i o n s in t h e level of the a-lipop r o t e i n f r a c t i o n . D i s t r i b u t i o n of oil r e d s t a i n on the lipoprotein f r a c t i o n s exhibited t h e s t r o n g e s t dependence on t h e d i s t r i b u t i o n of cholesterol. (C.A. 53, 2402) SITES OF INTESTINAL FAT ADSORPTION IN DOGS. D. F. A n n e n t o (Cleveland Clinic Hosp., Cleveland, O.). Bull. Georgetown Univ. Med. Center 11, 158-61 (1958). D o g s were f e d 11alabeled triolein or oleic acid, a n d f o u r to five h o u r s later were sacrificed. T h e i r g a s t r o i n t e s t i n a l t r a c t s were cut into 10 g. aerial s e g m e n t s a n d t h e r a d i o a c t i v i t y of t h e s e pieces m e a s u r e d . The distal d u o d e n u m a n d the p r o x i m a l j e j u n u m were f o u n d to be t h e sites of m a x i m a l a b s o r p t i o n of n e u t r a l f a t , a n d the distal ileum f o r f a t t y acids. (C.A. 53, 2405) CONJUGATED LIPIDES. V I I I . CONSTITUENTS OF PHRtJNOSIN. OBTAINED FROM BEEF SPINAL CORD. u F u j i n o (Obihiro Zootech. Coll., Obihiro, H o k k a i d J ) . Nippon N6gei-kagalcu Kaishi ( J . Agr. Chem. Soc. J a p a n ) 31, 43-5 (1957). The h y d r o l y s a t e of p h r e n o s i n f r o m b e e f spinal cord with H~S04 in m e t h a n o l c o n t a i n e d cerebronic acid, s p h i n g o s i n , a n d galaetose. S e p a r a t i o n a n d identification are described in detail. Sphingosin s u l f a t e , m. 248 50 ~ t r i a c e t y l - s p h i n g o s i n , m. 99-100 ~ tribenzoyl-sphingosin, m. 121 ~ a n d g a l a c t o s e m e t h y l p h e n y l h y drazone, m. 190 ~ were prepared. I X . ACID HYDROLYSIS 0.P DIHYDROPHRENOSIN. Ibid. 46-8. The h y d r o l y z a t e of d i h y d r o p h r e ~ o s i n with HfSO4 in m e t h a n o l c o n t a i n e d both erythro- a n d t h r e o - t y p e s of d i h y d r o s p h i n g o s l n . T h u s it w a s proved t h a t d i h y d r o p h r e n o s i a ( e r y t h r o - t y p e ) was stereoisomerized d u r i n g acid h y d r o l y s i s as was phrenosln. T r i b e n z o y l d i h y d r o s p h i n g o s i n ( e r y t h r o - t y p e ) , m. 92-6 ~ a n d the same ( t h r e o - t y p e ) , m. 63-5 ~ were p r e p a r e d . X. ALKALINE HYDROLYSIS OF DIHYDROPHRENO'SIN. Ibid. 48-52. The h y d r o l y z a t e of d i h y d r o p h r e n o s i n with ]3a(OH)2 in dioxane did n o t cause stereoisomerization at C 3 of s p h i n g o s i n . Only a b o u t 2 0 % of d i h y d r o p h r e n o s i n w a s h y d r o l y z e d with Ba(OH)._,, while 95% of p h r e n o s i n could be hydrolyzed. I n f r a r e d s p e c t r a were g i v e n f o r d i h y d r o p s y c h o s i n , t r i a c e t y l - d i h y d r o s p h i n g o s i n (erythro-type), and tribenzoyl-dihydrosphingosin (erythrotype). ToxIcITY O,F ~ISH OIL. I I I . N o b o r u M a t s u o (Tokyo Med. Coll.). Seikagal~u (J. J a p a n . ]3iochem. Soc.) 29, 769-72 (195758). E t h y l esters of h i g h l y u n s a t u r a t e d f a t t y a c i d s f r o m cuttle-fish oil were distilled in vacuo. The first distillate (the least u n s a t u r a t e d ) , boiling below 180 ~ at 2 m m . H g (iodine no. 232.3), w a s autoxidJzed in the air to p r o d u c e oxidized ester (iodine no. 156.6, peroxide 1461 rag. % ) . T h e oxidized ester w a s toxic w h e n g i v e n per os to albino r a t s at 5 % to the b a s a l diet. F r o m this e x p e r i m e n t it was p r e s u m e d t h a t n o t only h i g h l y u n s a t u r a t e d f a t t y acids b u t also linoleic a n d ]inolenic acids m i g h t become toxic a f t e r oxidation. Oxidized ethyl esters of h i g h l y u n s a t u r a t e d f a t t y acids (peroxide 1716 mg. % ) were toxic ~dso w h e n applied on the skin of albino rats. Such rats died a f t e r 7-10 days. ]%ts died a f t e r 14-19 d a y s which received nonoxidized e s t e r s ; the esters were a s s u m e d to have been autoxidized on the skin. Oxidized esters were toxic also f o r rabbits. IV. ACTIONS OF THE ETHYL ESTERS OE HIGHLY UNSATURATED FATTY ACIDS O'N PROTEINS AND AMINO ACIDS. Ibid. 773-7. A q u e o u s 2% egg-whlte solution f r e e d f r o m ovoglobulin produced b r o w n c u r d y p r e c i p i t a t e a t 37 ~ when a d d e d with oxidized esters of h i g h l y u n s a t u r a t e d f a t t y acids (peroxide 1800 rag. % ) , while it showed no c h a n g e when a d d e d with nonoxidized esters. I n the fox,her case t h e p H of t h e filtrate from c u r d y p r e c i p i t a t e dropped f r o m 6.7 to 3.5 a f t e r 290 hrs., this filtrate p r o d u c e d no p r e c i p i t a t e u p o n a d d i t i o n of trichloracetic acid. T h u s p r o t e i n was completely d e n a t u r e d by a d d i t i o n of oxidized esters. The lowering of p H was att r i b u t e d to the oxidation of t e r m i n a l a m i n o acid; p a p e r c h r o m a t o g r a p h y of h y d r o x a m i e acids showed t h e presence of formic, acetic, propionic, butyric, oxalic, malonie, oxalacetic, a n d adlpic acids in the filtrate f r o m the c u r d y precipitate. A d d i t i o n of oxidized esters to glycine or g l y c y l g l y c i n produced b r o w n resinous p r e c i p i t a t e a n d a m m o n i a at 37 ~ Oxidized esters acted on eystine to p r o d u c e cysteic acid. V. SOME CONSIDEI~ATIONS ON THE OXIDATION OF HIGHLY UNSATURATED FATTY ACIDS. Ibid. 807-12. W e i g h t i n c r e a s e was m e a s u r e d of t h e esters of h i g h l y u n s a t u r a t e d acids (iodine no. 338.7) at room temp. f o r a year, a d d e d with n o t h i n g or i0 -~ M a n t i o x i d a n t . A s t h e a n t i o x i d a n t , h y d r o q u i n o n e was the

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T H E JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY

most effective, aseorbic acid was medium, and a-tocopherol acetate was the least effective: a-tocopherol was slightly effective. Copper, hemin, and iron accelerated the oxidation of the esters in this order. I n f r a r e d spectra of autoxidized esters showed absorption at 3 ~ due to hydroperoxide and hydroxyl groups. Ultraviolet absorption spectra showed a weak peak at 274 m# in the esters of highly u n s a t u r a t e d f a t t y acids, boiling at 210-221 ~ at 4 mm. Hg, and a distinct peak at 234 mt~ (due to diene linkage) in oxidized esters. V I . TOXICITY 0F OXIDIZED COMMERCIAL LIVER OILS. Ibid. 812-15. Commercial cod-liver oil (iodine no. 168.9, peroxide none) was oxidized in the air to produce oxidized cod-liver oil (iodine no. 117.8, peroxide 775 rag. % ) . Feeding experiments with albino rats showed sufficient growth with commercial oil and toxicity with oxidized oil. Highly u n s a t u r a t e d f a t t y acids were separated from commercial liver oil and the properties of distillate of u n s a t u r a t e d f a t t y acids were given. V I I . PRODUCTI0,N OF THE SO-CALLED SEBORKI~IEA. Ibid. 816-18. Oleyl oleate produced seborrhea on rats fed a t 15% to the basal diet. OleyI alcohol did not produce seborrhea, but it had higher toxicity t h a n oleyl oleate. VIII.

TOXICITY OF F I S H

OIL POLYMERIZED BY HEATING IN

CARBON DIOXIDE. Ibid. 885-91. Feeding experiments with r a t s were carried out. Cuttle-fish oil at 20% to the basal diet produced normal growth. The oil heated for 120 hrs. at 95 ~ at 20% to the basal diet produced a little worse growth. The oil heated for 10 hrs. at 250 ~ when fed at 20% of the basal diet, reduced the weight of rats. The same oil produced moderate growth when fed at 5% to the basal diet. By the urea adduct method the heat-polymerized oil was separated into addact-forming ethyl esters of linear structure and nonadduct-forming esters of cyclic structure. The former produced good growth, while the latter was very toxic. IX.

T o x i c I T Y 0E F I S H OIL POLYMERIZED BY HEATING IN THE

AIR. Eiyd to Shokury5 (J. J a p a n . Soc. Food Nutrition) 10, 255-9 (1957-58). Chltfle-fish oil was heat-polymerized at 225 + 10 ~ for 10 hrs. This polymerized oil contained no peroxide, b u t was toxic to rats when given at 20% to the basal diet owing to cyclic ethyl esters, as proved by urea adduct separation and testing. A SIMPLE ~ E T t t O D FOR THE SEPARATION OF UI'~SATURATED ACIDS EKOM SMALL AMOUNTS 0 F LIPIDES. F . Leupold and D.

Eberhagen (Univ. Cologne, Ger.). Fette, Seifen, Anstrichmittel 50, 809-11 (1958). Polyene f a t t y acids ean be separated from s a t u r a t e d and weakly u n s a t u r a t e d f a t t y acids by dissolving 10-100 mg. of the mixture in a flat-bottom glass tube in 3 ml. ethyl alcohol-urea, freezing 30 minutes each at 0 and --10 ~ holding 3 hours a t --20 ~ removing s u p e r n a t a n t solution, washing the precipitate, decomposing the urea inclusion compounds in dilute hydrochloric acid, and extracting 5 times with 5 ml. ethyl ether-petroleum ether mixture. The method is applicable for the separation of f a t t y acids in blood serum. (C.A. 53, 3738) ESSENTIAL FATTY ACIDS AND THE PROBLEM OF ATHERgSCLE-

RosIS. L. W. Kinsell, G. D. Michaels, Priscilla Wheeler, P. F. Flynn, and G. Walker (Highland-Alameda County Hosp., Oakland, Calif.). Am. J. Clin. Nutrition 6, 628-31 (1958). The lowering of plasma ]ipides is associated with favorable effects upon either formation of plaques or resorption of existing plaques in patients with known atherosclerosis. (C.A. 53, 3438) TRANSPORT OF FATTY ACIDS ACROSS THE CELL WALL.

J.

F.

Mead (Univ. of California, Los Angeles). Am. J. Clin. Nutrition 6, 611-12 (1958). Experiments were carried out in the W a r b u r g a p p a r a t u s with washed cells. Substrates used were carboxy-labeled palmitic acid in buffer or its albumin complex and biosynthetic albumin from ascitic fluid of mice fed phenylalanine-3-C~t W h e n palmitic acid was added alone to the incubated cells, it was metabolized, since C~O: appeared in the center cells. This oxidation was incomplete and irregular, ceasing a f t e r 30% oxidation of palmitic acid occurred. (C.A. 53, 3402) CHANGES IN TISSUE LIPIDE.S AND TISSUE HISTO~LOGY RESULTING FROM ESSENTIAL FATTY ACID DEFICIENC~s IN RATS. Roslyn B.

AlfimSlater and S. Bernick (Univ. of S. California, Los Angeles). Am. J. Clin. Nutrition 6, 613-24 (1958). The deficiency state was induced by withholding added f a t in the diet. Animals on such a diet showed testicular degeneration and histological changes in bone. Liver sections from animals fed fat-free diets showed various degrees of f a t infiltration, and this irregularly distributed. I n the adrenals there was evidence of atrophy. Sections of thyroid gland gave the appearance of a hyperactive gland. (C.A. 53, 3402)

VOL. 36

FAT ABSOI%PTI0,N. J. F. Mead (Univ. of California, Los Angeles). Am. J. Clin. Nutrition 5, 606-8 (1958). Absorption of hydrocarbons such as highly emulsified mineral oil and the carotenes was found to depend on simultaneous absorption of fat, the presence of bile and other factors important in absorption of f a t and cholesterol. (C.A. 53, 3402) ESSENTIAL FATTY ACIDS IN RELATION TO, H U M A N NUTRITION.

A. E. Hansen (Univ. of Texas School of Med., Galveston). Am. J. Clin. Nutrition 6, 625-7 (1958). A discussion of the importance of linoleic acid in the diet (C.A. 53, 3402) LIPIDES 0F BIOLOGICAL I]~iPORTANCE. PEROXIDATION PRODUCTS AND INCLUSION CO1V[POUNDS GP ~IPIDES. W . 0 . L u n d b e r g

(Univ. of Minnesota, Minneapolis). Am. J. Clin. Nutrition 6, 601-3 (1958). A discussion of oxidation products of lipide materials, especially the peroxidation products of f a t t y acid esters and the so-called lipide inclusion compounds: (C.A. 53, 3402) EFFECT OF COI%N OIL ON THE METABOLISM O15 CALCIUM AND

PHOSPHORUS BY SHFJEP. A. D. Tillman and J. R. Brethour (Univ. of Tennessee, Oak Ridge). J. Animal Sci. 17, 782-6 (1958). The effects of corn oil on the utilization of calcium and phosphorus by lambs was studied by comparative balance and isotope dilution procedures. The inclusion of 7.5% dietary corn oil did not affect significantly the a p p a r e n t digestibility, fecal endogenous excretion, true digestibility, or n e t retention of dietary phosphorus. Neither did it affect the fecal endogenous or u r i n a r y excretion of dietary calciunL This level of fat, however, significantly reduced a p p a r e n t digestibility calcium from 21.6 to 11.8% and true digestibility of calcium from 62.7-54.7. (C.A. 53, 3403) DIETARY FATS AND BLO,0D COAGULATION. S. A. H a s h i m and R. E. Clancy ( H a r v a r d School of Public Health, Boston, IV[ass.). New Engl. J. Med. 259, 1115 23 (1958). A review with eighty-five references. (C.A. 53, 3406) EPPECT OF PyRIDOXINE DEPICIENCY ON CHOLESTEROL AND POLYENOIC FATTY ACIDS IN CHICKS. U . D~m, G. Kristensen,

G. K. Nielsen and E. SOnderga.ard (Polytech. Inst., Copenh a g e n ) . Acta Physiol. Scand. 44, 67-69 (1958). The influence of pyridoxine deficiency on chicks fed fat-free and 10% peanut oil diets with a~d without 1% cholesterol was studied. Pyridoxine deficiency resulted in increased plasma and aorta cholesterol, no change in liver cholesterol, a n d decreased heart cholesterol. W i t h a fat-free, pyridoxine-deficient diet a marked content of tetraenoie acid was found in heart and liver, whereas, the trienoic acid was proportionally decreased. Feeding of 10% peanut oil without pyridoxine caused less deposition of tetraenoic acid in heart and especially in liver t h a n feeding of 10% p e a n u t oil with pyridoxine. Addition of 1% cholesterol to the diets resulted in a decrease in amount of tetraenoic acid in heart and liver (C.A. 53, 3406) ~ETABOLISM

OF PLASMA UNESWERIFIED FATTY

ACID.

D.

S.

Goodman and R, S. Gordon (Natl. Insts. of Health, Bethesda, Md.). Am. J. Clin. Nutrition 5, 669-80 (1958). Normal unesterified f a t t y acid level in h u m a n beings is of the order of 0.5 meq./1., and represents a mole ratio of unesterified f a t t y acid to albumin of less t h a n one. W i t h normal lipoprotein concentrations, less t h a n 2% of the total unesterified f a t t y acid is bound to low-density lipoproteins. I t appears t h a t albumin is well constructed to serve as a t r a n s p o r t vehicle for unesterified f a t t y acid. (C.A. 53, 3409) ORIGINS OF PLASMA CHOLESTF-~ROL. S. A . Byers (Mr. Zion Hosp., San Francisco, Calif.). Am. J. Clin. Nutrition 6, 638-41 (1958). There is a small positive correlation between the plasma cholesterol concentration and development of clinical diseases ascribed to atherosclerosis. Cholesterol eaters the plasma either by absorption or by synthesis and release from the tissues. (C.A. 53, 3409) PttOSPHOLIPIDES AND BLOOD COAGULATION. G. Rouser (City of Hope Med. Center, Duarte, Calif.). Am. J. Clin. Nutrition 6, 681-7 (1958). A significant inaroase in the in vivo coagulability of blood a f t e r a f a t meal h a s not been demonstrated with certainty, nor has the presence of an increased amount of lipide in an available form t h a t ann promote clotting been demonstrated after f a t feeding. I t m u s t be borDe in m i n d t h a t the methods of study are crude and t h a t no reliable teehnique for the evaluation of the in vivo status of the coagulability of the blood is available. (C.A. 53, 3409) DETERMINATION

OF UNESTERIFIED

FATTY

ACIDS

IN

NORMAL

HUMAN PLASMA. A. Svanborg and L. Svennerholm (Univ. Ghteborg, STeal.). Clin. CAirn. Acta 3, 443-9 (1958). A method for the determination of unesterified f a t t y acids in plasma is described. (C.A. 53, 3414)

JUNE, 1959

ABSTRACTS

EFPECT OF SUPPLEMENTAL I~AT ON DIGESTION AND THE RU~INAL CALCIUI~ l~EQUIRl~IvIENTGP SHEEP. W. W. White, R. B. Grainger,

F. H. Baker, and J. W. Stroud (Kentucky Agr. Expt. Sta., Lexington). J. Animal Sci. 17, 797-803 (1958). Three balance trials were conducted with 80-lb. crossbred wethers. Corn oil fed at 5% of the ration progressively decreased cellulose digestion during the first 40 days of trial 1. Recovery of cellulose digestion was not complete until 17 days after the omission of corn oil. In trials 2 and 3, 30 g. of alfalfa ash or 4.4 g. of calcium or 0.86 g. of phosphorus and 4.4 g. of calcium restored cellulose digestion in a i~tion containing 5% corn oil. The same amount of phosphorus alone or a trace mineral mixture containing Cu, Mo, Mu, Co, Fe, Zn, and B was ineffective. (C.A. 53, 4452) ]~ATTY ACIDS. J. 1~. Mead (Univ. of California, Los Angeles). Am. J. Clin. Nutrition 6, 656-61 (1958). Polyunsaturated f a t t y acids of the animal body are formed by successive additions of double bonds in the divinyl methane relative to the existing double bonds of unsaturated fatty acids ingested or synthesized from saturated acids in the body. The new double bonds are introduced between the existing double bonds and the carboxy groups of the acids which m a y be lengthened by addition of acetate when the double bond system approaches to within 3 or 4 methylenes of the carboxy group. There thus arises 3 families of polymlsaturated f a t t y acids, not readily interconvertible and possibly serving different functions in the body. (C.A. 53, 3409) METABOLISM 01~ THE ESSENTIAL

FAT METABOLISM IN H1GHE]~ PLANTS. X I . THE CONVEI~SION O]~ FAT INTO CAF~BOHYDI~A~I~IN PEANUT AND SUNFL()WE.R SEED-

LINGS. C. Bradbeer and P. K. Stumpf (Dept. of Agr. Biochem., Univ. of California, ]~erkeley, Calif.). J. Biol. Chem. 234, 498-501 (1959). Carbon-14 from both acetate-I- and -2-C~ was rapidly incorporated into free sugars and intei~ediates of tile tricarboxylic acid cycle by excised cotyledons from etiolated peanut and sunflower seedlings. The observed distributions of the carbon-14 within malic acid and the glucose moiety of sucrose are consistent with the operation of the glyoxylate cycle in the conversion of f a t into carbohydrate in these tissues. Some of the enzymes of the glyoxylate cycle, malic synthetase, isocitritase, condensing enzyme, and fumarase, were demonstrable in soluble enzyme preparations from the peanut and sunflower cotyledons. TOXICITY STUDIES O N TH]~ ANTIOXIDANT 6-ETHOXY-1,2-DIHYDRO-

2,2,4-TPAIv[ETHYLQUINOLINE. R. H. W i l s o n a n d F. D e E d s (Agricultural Res. Service, U. S. Department of Agriculture, Albany, Calif.). J. Agr. and ]Food Chem. 7, 203-6 (1959). The effect on rats of the antioxidant 6-ethoxy-l,2-dihydro-2,2,4trimethylquinoline have been investigated. The following aspects are emphasized: acute toxicity, chronic toxicity, skin toxicity, weight of vital organs, and reproductive ability. ABSORPTION, METABOLISM, AND EXCRETI0.N OF THE ANTIOXIDANT,

6-ETHOXY-1,2-DIHYDRO-2,2,4-TRIMETHYLQUIN(~LINE. R. H. Wilson, J. O. Thomas, C. R. Thompson, H. F. Launer, and G. O. Kohler (Agricultural Research Service, U. S. Department of Agriculture, Albany, Calif.). J. Agr. and Food Chem. 7, 206-9 (1959). Metabolism and excretion of tagged cthoxydihydrotrimcthylquinoline (EMK-C~, Santoquin-C~4) was studied in rat and cow. EMQ is rspidly and nearly completely excreted in urine and feces. Ttlere is little breakdown to carbon dioxide, indicating stability of the ring system. Distribution in tissues suggests a modification of the molecule to make it more watersoluble. Traces of radioactivity remain in tissues for as long as 4 weeks. Continued ingestion by the rat of a diet containing 0.00.5% EMQ for 10 days produced tissue concentrations, as EMQ, ranging from 0.04 to 0.3 p.p.m, in muscle to 2.1 to 4.8 p.p.m, in kidney and liver. Milk from rats eating the 0.005% EMQ diet for 10 days contained 0.12 to 0.19 p.p.m, of activity as EMQ. ~SSENTIAL ~ATTY ACID ACTIVITIES OF I:IYDI~0CARBONS AND ALCOHOLS ANALOGOUS TO LINOLEATE AND LIN0.LENATE. E.

Aaes-Jorgensen, O. S. Privett, and R. T. tIolman (The Hormel Inst., Univ. of Minnesota, Austin). J. N u t r i t i o n 67, 413-21 (1959). The effect of linoleyl and linolenyl alcohols, octadecadiene and octadecatriene upon EFA-deficient male rats has been tested. Only ]inoleyl alcohol relieved the symptoms of E F A deficiency. Octodecadiene and octadecatriene, hydrocarbon analogs of linoleie and linolenie acids, acted as severe skin irritants and induced fatty livers in the rats. These compounds also caused changes in the polyunsaturated f a t t y acid pattern of the heart lipides indicating that they absorbed and metabolized to some extent. Linoleyl and linolenyl alcohols stimulated growth and induced changes in the polyunsatu-

271

rated f a t t y acid content of heart tissue Mmilar to those induced by the corresponding acids. THE SYNTHESIS AND BIG.LOGICAL AVAILABILITY OF SPREE LOWER HOMOLOGS 0P CHOLESTE~0L. E. D. Bergmann, M. Rabinovitz, and Z. H. Levinson (Dept. of Organic Chemistry, Hebrew University, Jerusalem, Israel). J. Am. Chem. Soc. 81, 1239-43 (1959). Several analogs of cholesterol containing shorter sidechains have been synthesized from the chloride of 3-acetoxyetioehol-5-enie acid (I1) and di-n-butyl-, di-n-pentyl- and diphenylcadmium and from pregnenolone acetate ( I I I ) and n-butyl-, n-pentyl- and phenylmagnesium bromide. In the former ease, the ketones obtained were reduced, in the latter the tertiary carbinols dehydrated and subsequently hydrogenated. The structure of these dehydration products and the configuration of the hydrogenation products has been established, the latter by the observation that the analogous series of reactions with 4-methylpentylmagnesium bromide Ieads to cholesteryl acetate. Ttmse " u n n a t u r a l " sterols show an effectlveness of at most 43% of that of cholesterol, as growth promoters of housefly larvae. No pupation occurred when these " u n n a t u r a l " sterols were added to the sterile medium in which tile larvae were reared. CHOLESTEI%OL BIOSYNTHESIS IN PREPARATIONS Ol~ LIVER FROM NORMAL, I~ASTING, X-IRRADIATED, CHOLESTEI~0L-FED, TRITON, Ol~ ~%C~ItOLESTI~N-3-ONE-TREATED RATS. Nancy Bucher, K a t h -

leen MeGarrahan, Elizabeth Gould, and A. V. Loud (Massachusetts General Hospital, Boston, Massachusetts). J. Biol. Chem. 234, 262-67 (1959). The capacity to synthesize cholesterol from C~4-1abeled acetate, mevalonic acid, and squalene h~ts been studied in cell-free preparations of liver from rats subjeered to x-rays, Triton WR 1339, food deprivation, administration of a cholesterol-rich diet, and Atcholesten-3-one. In each experimental group, large deviations from the normal level were found in all segments of the reaction sequence, but the extreme changes appearing before the point of entry of nlevalonic acid f a r outweighed those occurring at later stages. Tissue frac~ionation sudies showed that the activity of the system was determined principally by the mierosomes. The soluble components were also affected, but to a lesser extent. GLYCERIDE-GLu

PRECURSORS IN THE INTESTINAL MUCOS.&.

G. C. Buell and R. Reiser. (Dept. of Biochemistry and Nutrition, Texas Agricultural Experiment Station, College Station, Texas). J. Biol. Chem. 234, 217-9 (1959). Ceil-free homogenates of the intestinal mucosa of swine were incubated with pahnitic acid, C~t]abeled fructose diphosphate, and appropriate cofactors. The label ~ppeared in the glycerides isolated from the reaction mixture. The addition of either unlabeled dihydroxyacetone phosphate or L-a-glycerophosphate diluted the activity of the resultant glyceride, but free glycerol did not. The activity was in the mitochondria-free fraction of the homogenate. I t is concluded, therefore, that the intestinal mucosa does not contain glycerol kinase, or that it is not demonstrable by the conditions used, and the L-a-glyeerophosphate is the immediate precursor of glyceride-glyeerol. SOME INTERRELATIONSHIPS B]STWEEN VITAMIN E AND VITAMIN

A IN HOLSTEIN CALVES. Mal~ha Dicks, J. E. Rousseau, Jr., H. D. Eaton, R. Teichman, A. P. Grifo, Jr., and H. A. Kernmeter, Jr. (Agricultural Experiment Station, Storrs, Connecticut). J. Dairy Sci. 42, 501-11 (1959). Thirty-slx Holstein male calves, 64 days of age and partially depleted of their tocopherol and vitamin A stores, were fed, in addition to a basal ration low in tocopherol and vitamin A, one of three levels of tocopheryl acetate, equivalent to 1, 5, or 25 ms. of free tocopherol per pound live weight per day and one of three levels of vitanain A palmitate equivalent to 10, 100 or ]000 of vitamin A alcohol for a 4-wk. period. Upon completion of a 28-day tocopherol-vitamin A supplementation period, onehalf of the calves were slaughtered and the other ][8 calves were nmintained OR tile basal ration until plasma vitamin A decreased to 4.0 7/100 nil. Based on plasma and liver vitamin A concentrations at the termination of supplementation and OR vitamin A depletion time, tocopherol resulted in an increase in utilization of vitamin A at the highest intake of vitamin A, decreases at the lowest intake of vitamin A, and inappreciable change at the middle intake. Across all levels of tocopherol intake, the tocophero] concentration of the tissues decreased with increasing intake of vitamin A. This decrease was greater between the 10 and 100 7 intake of vitamin A than between the 100 and 1,000 7 intake. These results indicated a need to establish levels or ratios of intakes of vitamins A and E. COUI~TERCURRENT

DISTRIBUTION

O~ MILK F A T

TRIGLYCERIDES.

W. Haab, L. M. Smith, and E. L. Jack (Dept. of Dairy Industry, Univ. of California, Davis). J. Dairy Set. 42, 454-67

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T H E JOURNAL OF THE AMERICAN OIL CHEMISTS ~ SOCIETY

(]959). The purpose of tiffs study was to investigate the application of countercurrent distribution to the separation of milk f a t triglycerides. Of the solvent systems tested, the most satisfactory was a 12:7:5 mixture of pentane, 2-nitropropane, and nitrometlmne. The distributions were followed gravimetrieally and by determination of iodine values and saponification equivalents of selected fractions or groups of fractions. The fractionation was influenced by degree of u n s a t u r a t i o n and molecular weight of the triglycerides. Although useful separations were obtained with 100 stages, better resolution was achieved by applying the technique to samples previously separated from milk f a t by crystallization from pentane at low temperatures. The §176 precipitate and --53~ filtrate were fractionated by countercurrent distribution, and the f a t t y acids in selected fractions were dete~Tained by ultraviolet spectrephotometry and gas-liquid chromatography. STUDIES ON THE INHIRITION

OF GI%OWTH O'F AN IMPLANTI~]D

FIBROSAI~CO~IA tN RATS. THE EFFECT OF FAT IN THE DI~I' WITH AND WITHOUT INJECTIONS OF GUINEA P m SERUM. Eloise Jameson, R. M. Ryan, and P. I. K r a m e r (Department of Medicine, Univ. of Southern California, Los Angeles). J. Nutrition 67, 469-82 (1959). Five experiments were conducted to study the effects of inhibiting growth of an implanted fibrosarcoma in randomly bred and inbred Irish gray r a t s by (1) ~dding essential f a t s to otherwise ineffective diets, and by (2) giving intraperitoneal injections of guinea pig serum. Statistical analysis revealed t h a t cottonseed oil in the diet, without guinea pig serum injections had significant effects in (1) reducing the number of tumor " t a k e s , " (2) slowing tumor growth or (3) bringing about regressions, unless the tumor was too rapidly growing to allow sufficient time for the production of possible immunologic inhibitory ~lgents. Considering all experiments together the results were significant at the 5% level. R~LATION OF I~ATURAL COPPER IN M I L K TO INCIDENCE OF SPONTANEOUS OXIDIZED FLAVOR. R. L. K i n g and W. L. Dunk]ey

(Dept. of Dairy Industry, Univ. of California, Davis). J. Dairy Sci. 42, 420-7 (1959). Milk as it is produced by the cow conrains a low but variable concentration of copper (natul~l copper). Results are presented t h a t show a relatively high concentration (ca. 0.2 p.p.m.) of natural copper in early lactation milk, and a level of about 0.01-0.04 p.p.m, for most cows during the remainder of a lactation period. These results are similar to others reported recently. No difference was observed between pasture and dry feed in the natural copper concentration in the resulting milk. W h e n cows on dry feed were drenched with large (10-g.) doses of copper sulfate, there was an increase in the n a t u r a l copper content of their milk and in the incidence and intensity of spontaneous oxidized flavor. For cows on an a l f a l f a hay-grain concentrate ration, and not in early lactation, a highly significant correlation was observed between the concentration of natural copper in milk and the intensity of spontaneous oxidized flavor. I t is concluded t h a t the copper present in milk as it comes from the cow is an i m p o r t a n t catalyst of oxidized flavor. T H E STRUCTURE OF BEEF HEART IDLASMALOGENS, G. V . M a r l netti, J. Ergland, and E. Stotz ( D e p a r t m e n t of Biochemistry, School of Medicine, Univ. of Rochester). J. A m . Che~t. Soc. 81, 861-4 (1959). The total phosphatides a n d the lecithin and phosphatidylethanolamine fractions of beef heart were isolated and reduced with hydrogen. These lipids were degraded to give a 68-72% yield of long-chain a-glycerol ethers. Hence the m a j o r p a r t of the plasmalogens of beef heart have the aldehyde attached to the a-position and the f a t t y acid attached to the fl-position of glycerol. The unreduced beef heart lecithin fraction was hydrolyzed by snake venom lecithinase A to yield nfixture of the typical monoester type lysoleeithin and the monoether type lysoplasmalogen. These lysophosphatides were reduced with hydrogen and hydrolyzed with acid. A 68% yield of long-chain a-glycerol ether was obtained from the lysoplasmalogen. These data demonstrate t h a t snake venom locirhinos A can hydrolyze the fl-linked f a t t y acid on the plasmalogem D a t a on the reactivity of the plasmalogens and tysoplasmalogens toward the Schiff reagent and methanolic iodine are given. POSSIBLE TOXIC FACTOR OF TI~ICHLORETHYLENE-ExTRACTED SOY-

BEAN OIL M ~ L . L. L. MeKinney, J. C. Picken, Jr., F. B. Weakley, A. C. Eldridge, 1%. E. Campbell, J. C. Cowan, and H. E. Biester (Northern Utilization ICes. and Development Division and the Veterinary Medical Res. Inst., Iowa State College). J. A m . Chem. Soc. 81, 909-15 (1959). T r e a t m e n t of anfino acids and peptides with t~ichloroethylene, under conditions known to produce the bovin aplastic anemia-causing factor in soybean oil meal and other proteins, showed t h a t tri-

VOL. 36

chloroethylene reacted readily with the sulfhydryI groups of cysteine and reduced glutathione. The S-dichlorovinyl derivatives of L-cysteine and L-glutathione were synthesized and found to produce the aplastic anemia syndrome in calves typical of t h a t produced by trichloroethylene-extracted soybean oil meal. The stability and properties of the S-diehlorovinyl derivatives are in agreement with known properties and mode of formation of the toxic principles in the meals. ]~nzymie hydrolysis of a toxic protein from trichloroethylene-extraeted soybean oil meal resulted in tbe loss of a large portion of its toxicity. Chromatographic studies on the hydrolyzate indicated the presence of products resembling the synthetic compounds, and giving tests for the S-dichlorovinyl group. T H E EFFECT OF CONCENTRATES O1v POLYUNSATURATED ACIDS I~R011V[ TUNA OIL UPON ESSENTIAL FATTY _A~CID DEFICIENCY.

O. S. Privett, E. Aaes-Jorgensen, /%. T. Holman, a n d W. O. L u n d b e r g (Hormel Inst., Univ. of Minnesota, A u s t i n ) . J . Nutrition 57, 423-32 (1959). H i g h l y u n s a t u r a t e d ac.ids from t u n a oil were concentrated a n d their esters were separated according to chain length by fractional distillation. Each chain-length fraction was fed as a supplement to fat-deficient rats and the effects were compared with those induced by ethyl linoleate. None of the fractions containing f a t t y acids of 16, 18, 20 or 22 carbon atoms in length relieved the dermal symptoms of E F A deficiency. I-Iowever, all the fractions except the 16carbon fraction showed marked stimulation of growth. Only the 16-carbon fraction allowed the deposition of abnormally high amounts of trienoic acid in heart and testis tissue. NUTI~ITIONAL STUDIES WITI=I THE GUINEA ~ I G . V . EF)~E'C'TS OF DEFICIENCY 0 P F A T 0Ir UNSATUl~ATED FATTY ACIDS. Mary R e i d

and Mary Matin (Lab. of N u t r i t i o n and EndocrinologY, U. S. Dept. of Health, Education, a n d Welfare, Bethesda, Md.). J. N u t r i t i o n 67, 611-22 (1959). Purified diets containing all of the nutrients known to be required by the g u i n e a pig except f a t were fed to guinea pigs placed on the diet a t two to five days of age. Comparable animals were given the same type of diet to which 7.3% of corn oil h a d been added. As previously found in this laboratory, lack of dietary f a t caused retarded growth, dermatitis, skin ulcers, loss of fur, and some mortality. CATAROLISi'~ IN VITRO OF ~HOLESTEROL. I. OXIDATION 0'i~ THE TEI~MINAL METHYL GROUPS O1~ ~HOLESTEROL TO ~.~-ICBON DIOXIDE BY RAT LIVER PtCEPAtCATIONS. M. W . Whitehouse, E .

Staple and S. Gurin (Dept. of Biochemistry, Univ. of Pennsylvania, Philadelphia, P a . ) . J. Biol. Chem. 234, 276-81 (1959). R a t liver nfitachondria are able to oxidize the terminal methyl groups of the cholesterol side chain to carbon dioxide in the presence of a soluble cofactor prepared from either liver tissue or heart muscle. Glutathione, adenosine 5-monophosphate, adenosine 5'-triphosphate, diphosphopyridine nucleotide, magnesium ions, a n d sodium citrate r~ust be added for optimal activity. Evidence is presented t h a t this oxidation requires the functimfing of the tricarboxylie acid cycle. EXAMINATION OF LIPIDS IN I-IuMAN SEBU)s B~z~ D I S K CHROMATOGRAPHY. J. Horaaek and Marie Cernikova (Masaryk Univ.,

Brno, 0zechoslovakia). Biochem. J. 71, 417-19 (1959). Paper chromatography of lipids of sebum obtained from the forehead skin of healthy white adults showed the presence of phosphatides, triglyeerides, cholesterol and its esters, and plasmalogens. KETOSIS IN THE RAT ON A FAT DIET. P. A. Mayes (Royal Veterinary College, London, N.W. 1). Biochem. J. 71, 459-66 (1959). The coarse of ketosis was investigated in rats fasted 24 hr. and subsequently fed various levels of butter. Ketenaemia persisted under all diets which were deficient in calories but was reduced markedly, or even abolished, when the calorie requirement was met entirely from exogenous fat. The amount of liver f a t and glycogen increased in proportion to the quantity of f a t fed. u A~ ALDEHYDE IN TH~ EGGS O1~ TI~IE HE~RING (C~LUPEA HAICENGUS L . ) AND OTHEI~ ]V[AEINE TELE0STS. 1~ A . P l a c k ,

S. K. Ken, a n d S. Y. Thompson (Natl. I n s t i t u t e for :Research in Dairying, Ulfiv. R e a d i n g ) . Biochem. J. 71, 467-76 (1959). The biological vitamin A activity of herring eggs i s about ten times greater t h a n the chemically determined content o f vitamin A~ ester and alcohol. Most of this activity is accounted for by vitamin A~ aldehyde. A similar distribution was found in the eggs oY seven other species of marine teleost fishes. T H E FATTY ACIDS 0 ~ PHOSPHATIDYLETI-IANO~LAMINE AND P H O S PHATIDYLCttOLINE FROM HEN'S EGG. J. C. Hawke ( F a t s Research Lab., Dept. S c i . & Indus. Research, Wellington, New Zealand). Biochem. J. 71, 588-92 (1959). Gas-liquid chromatography of f a t t y acids f r o m phosphatidylethanolamine and phosphatidyleholine from egg yolk revealed, respectively, C~

JUNE, 1959

ABSTRACTS

s a t u r a t e d 39.5 and 14.2%, and C~s unsaturated, 20.1 and 44.7%. Most of the u n s a t u r a t e d C~s acid in phosphatidylcholine was oleie acid. Mere C~ and O_~.,u n s a t u r a t e d acids were present in phosphatidylet]mnolamine t h a n in phosphatidylcholine. GEOWTH-PI%oMOTtNG ACTIVITY OF BUTTERFAT ACIDS l~Olg LACTO~ BACILLUS CASEI. M. N. Camien and M. S. D u n n (Univ. Califorrda., Los Angeles). Proc. Soc. F~xptt. Biol. Med. 100, 433-6 (1959). The L. easel growth-promoting factor in butter f a t was shown to be myristie acid a n d traces of an unidentified contaminant. Purified commercial myristic acid was essentially inactive. PHOSPHOLIPIDS OP I~IuMAN R.~D BLOOD CELLS. G. B. Phillips and N. S. Bourne (College of Physicians and Surgeons, Columbia Univ., N. u City). Proc. Soc. Exptl. Biol. Med. 100, 48992 (1959). Phospholipids f r o m h u m a n red blood cells were ehromategraphed on silicic acid a n d found to consist chiefly of ethanodamine- add serine-containing phospholipids, lecithin, sphingomyelin and ]ysolecithin. EI~I~CTS OP DIETHAN0,LAI~IINE (DEA) oN RATS FED ATHEI%OGENIC DIETS. T. B. Clarkson and H. B. Lofland (Bogyman Gray School of Medicine, Wake Forest College). Proe. Soc. Exptl. Biol. Med. 100, 525-6 (1959). Ilt rats fed hypercholesterolizing diets, DEA significantly reduced liver lipides, liver cholesterol, am'tie cholesterol, and serum cholesterol when the dietary f a t was hydrogenatel coconut oil. There was no effect of D E A when dietary f a t was corn oil. Serum cholesterol levels were lower in the corn oil-fed group. EpVI~OTS UP DIETARY FAT UPON POLYUNSATURATED FATTY AcII~S up BLOOD IN PATIENTS WITH MULTIPLE SCLEIgOSIS. B. Gerstl, W. E. Davis, Jr., J. K. Smith, E. Athineos, and G. Herold (Vet. Admin. Hosp., Oakland, and School of Medicine, Univ. Calif., San Francisco). Proc. Soc. Exptl. Biol. Med. 100, 534-8 (1959). Diets containing soybean oll and lecithin decreased the cholesterol/total lipid ratio in the blood of both a control group of normal individuals a n d a group of patients with m u l t i p l e sclerosis. The p o l y u n s a t u r a t e d f a t t y acid ( P U F A ) / l i p i d ratio increased in both groups but the t r i e n e / P U F A ratio decreased mdy in the controls. DIGESTIRILITY OF CORN GEP~M AS FACT0'1% IN ITS APPAR~ENT HYPOCHOLESTEROLEI~IC EFPECTS. I'i. A. N a s h and H. Wolff (Pitman-Moore Co., Indianapolis, Ind. and A. E. Staley Mfg. Co., Decatur, Ill.). Proe. Soc. Exptl. Biol. Med. 100, 622-5 (1959). Digestion of whole corn germ by chicks not receiving grit is poor. This e~plains to a large extent the apparent effects of whole corn germ in m a i n t a i n i n g low cholesterol levels and preventing atherosclerotic lesions. SEEU~f LIPID LEVELS IN RATS FED VEGETABLE OILS WITH AND WITHOUT CHOL~ST~ROL. C. R. Seskind, M. T. Sehroeder, R. A. Rasmussen, aa~d R. W. Wissler (Univ. Chicago School of Medicine, Chicago). Proe. Sue. Exptl. Biol. Med. 100, 631-4 (1959). Rats were tube fed diets containing one of the following fats,. with or without cholesterol: soybean oil, olive oil, an olive oilpalmitic acid mixture, hydrogenated cottonseed oil. Results suggest t h a t serum cholesterol contents are elevated by increasing saturation of the dietary f a t a n d t h a t dietary cholesterol a u g m e n t s this effect for the more s a t u r a t e d fats. The phospholipid/cholesterol ratio was elevated in rats receiving the most s a t u r a t e d f a t samples. PROCESS Or MAKING GEa~r FLAKES. F. Grandel. U.S. 2,879,167. Cearal seed germ material, of an oil content not exceeding about 4%, is pasted in water, is spread in a thin layer and dried.

9 Paints and D r y i n g

Oils

IDENTIFICATION OP PIGMENTS IN PAINT PRODUCTS I~y IN~I~.~I~lgD SPBCTtg(~SCOPY. T. I~. I.iarkins, J. T. tIa.rris, and O. D. Shreve (E. I. du P o n t de Nemours & Co., Inc., Philadelphia, P c . ) . Anal. Chem. 31, 541-5 (1959). An i n f r a r e d spectroscopic method is devised for the qualitative deternfination of pigments iu paint products. Inorganic a n d organic pigments are classified according to the number and shape of the absorption bands in the i n f r a r e d spectrum. Chief disadvantage is t h a t several inorganic pigments do not exhibit characteristic i n f r a r e d absorption bands. COATINGS. M. It. Swann, M. L. Adams, and G. G. Esposito (Aberdeen Proving Ground, Md.). Anal. Chem. 31, 674-8 (1959). This biennial review covers the period from October 1956 and represents the a u t h o r s ' choice of the i m p o r t a n t contributions in coating "malysis.

273

(~OPOLYZvIERS up THE FATTY ACID ESTI~I% O,F h PHENOXY ETHANOL-FOI%MALDEHYDE CONDENSATION PtC0DUCT AND AN ETHYLE:~IC A'IONOXcBm J. E. Hurtle, A. IvI. Tringali a n d H. Yuska (Interchenfical Corp.). U.S. 2,880,187. A resin is prepared by heating, in the presence of an organic peroxide, a mixture of styrene or methyl methacrylate and a drying oil f a t t y acid ester of the alcohol obtained by reacting phenoxy ethanol with formaldehyde. CAN CO'ATINGVARNISHES CONTAINING ~ANGANESE SOAP DRIEP~ AND STEAM-C~ACKED DISTILLATE P~ESINS. J. F. McKay (Esso Research & Engineering Co.). U.S. 2,880,188. A baked coating for a metallic surface is formed from a mixture of d r y i n g oil ( t u n g oil, oitieica oil, fish oil, or dehydrated castor oil), another vegetable oil such as linseed, perilla or soybean oil, a manganese carboxylate soap drier and an olefin-diolefin resin obtained by heat polymerization of a steam-cracked petroleum fraction which contains piperylene.

9 Detergents SURFACTANTS IN VISCOSE PROCESSING. ~qV. 5. Alexander and 1~. D. K r o s s (Rayonier, Inc., Whippany, N. J . ) . Ind. Eng. Chem. 51, 535-8 (1959). Chemical celluloses treated with selected s u r f a c t a n t s were carried through the viscose process to show the beneficial functions surface active additives can perform in viscose processing. I m p o r t a n t benefits are reduction in power requirement to shred alkali cellulose, improved accessibility in xanthation with a resultant higher level of viscose filterability, prevention of spinnerette enerustation, and improved f a t i g u e life of the resultant tire cord. S u r f a c t a n t s tested which were effective in bring about these improvements include Igepal CO 630, Nopco 2265 a n d sodium oleate, showing t h a i nonionic, cationic or anionic types may be used. AMPHOTEI~IO SURFACE ACTIVlg AGENTS. D. B a s s (Cyclo Chemicals Ltd., Manfield House, Strand, London W C 2, EngL). Mfg. Chemist 30, 105-6 (1959). Amphoteric or ampholytic surface active agents cmnbine anionic and cationic chemical groups and properties. Almost any anionic compound can be turned into an amphoteric by introducing an amine group into the molecule, while eationics can be converted by the introduction of an anionic group, or groups in a variety of positions. The balanced amphoteric with an isoelectric point of pH 7 is the most versatile showing particular a d v a n t a g e s in cosmetics, pharmaceuticals and metal cleaning, The preparation, properties and uses of Miranol C2M are described as being typical of the amphoteries. EVALUATING THE E.t~FECTIVENESS OF FLUORESCENT W[4:ITE.NERS AND OXIDIZING BLEACHES ON COTTON. ~I. S. Furry, P. ]~. Bensing, and ft. L. Kirkley (U. S. Dept. of Agr., Washington, D. C.). Am. Dyestuff Reptr. 48(8), 59-73 (1959). Using refleetometers, the fluorescent and nonfluorcscent whitening effects o~ laundering repeatedly with different fluorescent whiteners and peroxygen- and chlorine-containing bleaches were measured in a bleached cotto~ percale sheeting. Results were f o u n d to conform well with visual ratings of whiteness. The extent of chemical and physical damage produced in the fabric by the various washing solutions was also determined. Based on these laboratory evaluations using small samples of the unsoiled fabric washed in a Lauder-Ometer and dried on plate glass, one syndet (with whitener) and one peroxygen bleach were selected f o r f u r t h e r study. Unsoiled swatches a n d naturally soiled pillowcases made from t,he test fabric were laundered in a nmdified-agitator household washer and dried by four different methods. The whitening effects produced in the fabric washed in the Launder-Ometer and in the household laundering equipment were emnpared for similar washing solutions. Fluidity a n d breaking strength results indicated the a m o u n t of damage to the fabric caused by laundering and by use. ~N~cV COLU:MNAI%AND MIXED BED IoN EXCHANGE METHODS FOR SUI%:PACTANT ANALYSIS AND PUI%IFICATION. M. E. Ginn and C. L. Church (Monsanto CSem. Co., Dayton, Ohio). Anal. Chem. 31, 551-5 (1959). Analysis of mixed anionic and nonanionic detergents by sorption of the anionic portion on an ion exchange resin is described. The nonionic portion is recovered f r o m the effluent, after which the anionic portion is eluted from the resin and recovered. This two-stage method is applicable to common anlonics and nonanionics except those t h a t are cleaved by acid or base-ester sulfates and sulfoaates. A mixed-bed, batch method is given also for the rapid purification and anlysis-of nonionic surfactants.

274

THE

JOURNAL

OF THE

AMERICAN

HIGH-EXPANSION FOAMS FOR CONTROLLING EXPERI]~IENTAL COAL MINE FI~ES. I. Hartmann, J. Nagy, R. W. Barnes, and E. M. MuYphy (U. S. Bur. of Mines, Pittsburgh, Pc.). U. S. Bur. Mines, Bept. Invest. 5419, 18 pp. ( ] 9 5 8 ) . The f o a m was f o r m e d b y spra:~ing a dilute solution of a f o a m i n g a g e n t in HfO on a lace-knitted cotton n e t s t r e t c h e d across t h e entire m i n e entry. Generally f o a m s produced with c o m p o u n d s of the lauryl s u l f a t e t y p e h a d a h i g h e r s t a b i l i t y a n d lower rate of liquid loss t h a n did those produced with alkyl aryl sulfo~mte, a m i n o f a t t y acid, a m i d e of f a t t y acid, a l k y l a t e d phenol, a l k y l a t e d phenol ether, a n d a l k y l a t e d ester. (C.A. 53, 2626) INVESTIGATIONS O1~ SURFACE-ACTIVE AGENTS. I I . PI~EPAICATION AND SUI~PACE ACTIVITY OF THE SODIUIv[ SALTS OF SULPATE'S OF I~r OF SYNTHETIC FATTY ACIDS. Zb. J e d l l n s k i a n d M. H a m p e l (Dept. Technel. F a t s , Gdansk, P o l a n d ) . Prezmysl. Chem. 1 2 ( 3 5 ) , 47-51 (1956) ( E n g l i s h s u m m a r y ) . C~-~ a n d O , ~ f r a c t i o n s , respectively, of s y n t h e t i c f a t t y acids were converted into monoglycerides, s u l f o n a t e d , a n d converted to t h e N a salts. The original f a t t y - a c i d f r a c t i o n s c o n t a i n e d small a m o u n t s of unsaponifiable m a t t e r , carbonyl compositions, a n d u n s a t u r a t i o n . T h e d e t e r g e n t p r o d u c t s were ~ ' b u i l t ~ ' with Na~PO~ a n d c o m p a r e d with c o m p a r a b l e commercial products. T h e y f o a m e d b e t t e r a n d h a d w a s h i n g p r o p e r t i e s e q u i v a l e n t to a c o m p a r a b l e p r o d u c t p r e p a r e d f r o m laurie acid. (C.A. 53, 5709) DETElCGENTS AND REDEPOSITION 0E SOIL. ,]-. Stawitz a n d P . H o p f n e r . Seifen-Ole-Fette-Wachse 84, 711-13 (1958). Redeposit.ion of soil on cotton was s t u d i e d d u r i n g the w a s h cycle as a f u n c t i o n of time, with a n d w i t h o u t a d d i t i o n of earboxymethylcellulose ( I ) . The redeposition b e g i n s s i m u l t a n e o u s l y with t h e removal of soil f r o m fabric, a n d it c o n t i n u e s at the s a m e r a t e t h r o u g h rinsing. A d d i t i o n of I r e s u l t s in a signific a n t r e d u c t i o n of redeposition rate, b u t only a f t e r a n " i n h i b i tion p e r i o d " of a p p r o x i m a t e l y 15 m i n u t e s . T h i s period is reduced b y a n i n c r e a s e d a m o u n t of I. A p p l i c a t i o n of I in d e t e r g e n t f o r m u l a t i o n is discussed. (C.A. 53, 4777) THE PI:~EPARATION OF SULFONAPHTHENIC ACIDS AND THEIK USE IN THE M~KING OF DETERGENTS. B. 1~. T y u t y u n n i k o v a n d Yu. M. Volkov. Khim. i Te~hnol. Topliv i Masel 3 ( 1 2 ) , 49-52 (1958). T h e photochemical s y n t h e s i s of s u l f o n a p h t h e n i c acids w a s carried out in a l a b o r a t o r y t r a i n whose m a i n f e a t u r e is a reactor provided with a h e a t i n g element a n d a source of light. SO.., a n d CI~ e n t e r a t a rate of 0.44 1./minute a n d 0.40 1./minute, respectively, per kg. of h y d r o c a r b o n to provide a d e t e n t i o n period of 3 h o u r s at a t e m p e r a t u r e of 25 ~ T h e s u l f u r y l chloride conversion is 2 7 - 3 0 % . The conditions given are o p t i m u m f o r m i n i m i z i n g t h e f o l z n a t i o n of d i s u l f u r y l chlorides a n d the subs t i t u t i o n of C1 in the h y d r o c a r b o n ring, which m a k e s it hydrophylic a n d lowers t h e d e t e r g e n c y of the N a salt of the sulfah a t e d product. R e s i d u a l C1 p r e s e n t in the s u l f o n a p h t h e n i c acid c a n be removed b y the m e t h o d of B a g involving a catalytic h y d r o g e n a t i o n at 180 ~ a n d 10-12 a t m . T h e d e t e r g e n c y of th~ n a p h t h e n i c s u l t a n a t e ( 0 . 2 % ) is 310-325, which c o m p a r e s favora b l y with other synthetics. (C.A. 53, 5709) APPLICATION OF ION EXCHANGEI~S IN DETEEGENT ANALYSIS. P. Voogt. ( U n i l e v e r R e s e a r c h Lab., V l a a r d i n g e n , N e t h . ) . Rec. tray. chim. 77, 889-901 (1958). P r o c e d u r e s are described f o r s e p a r a t i n g m i x t u r e s of N a salts of a l k y l s u l f u r i c or sulfouic acids, f a t t y acids, a n d nonionics. Three f r a c t i o n s s t r o n g l y acldie, weakly acidic,and nonionie, respectively, are obtained b y p a s s i n g a n E t O H solution t h r o u g h the acidic f o r m of Dowex-50 ( 8 % cross-linked), the a c e t a t e f o r m of Dowex-1 ( 2 % cross-linked) a n d t h e basic f o r m of Dowex-2 ( 8 % crosslinked). The acids are d e t e r m i n e d by p o t e n t i o m e t r i c t i t r a t i o n , a n d the nonionics are d e t e r m i n e d gravimetrically. (C.A. 53, 5709) SYNTHETIC DETERGENT FORI~ULATIONS CONTAINING I~-ACYL Tx~raA~S. H. Y. Low ( C a l i f o r n i a R e s e a r c h Corp.). U.8. 2,874,225. T h e f o a m i n g a n d s u d s i n g p r o p e r t i e s of s y n t h e t i c d e t e r g e n t compositions containi~lg water-soluble N-acyl t a u r a t e s p r e p a r e d f r o m tallow, or t a u r a t e m i x t u r e s with other deter-

O I L CHEMISTS'

SOCIETY

VOL.

36

gents, are i m p r o v e d b y the a d d i t i o n of f r o m a b o u t 1 to 5 % of a C~r-C,s s a t u r a t e d s t r a i g h t c h a i n alcohol such a s hexadecanol. SULI~ONATE DI~TERGENT COMPOSITIONS O]~ I~PROVED FOAM CttARAC~r~STICS. tI. Y. L e w a n d R. D. S t a y n e r ( C a l i f o r n i a Research Corp.). U.S. 2,874,127. The f o a m of dilute a q u e o u s solutions of b r a n c h e d - c h a l n C,-C15 m o n o a l k y l b e n z e n e s u l f 0 n a t e d e t e r g e n t s can be improved b y c o m b i n i n g t h e m with f r o m 2 to 2 0 % b y weight of a s u l f o n a t e d CirCus s a t u r a t e d f a t t y a~id anilide such as N--acyl s u l f a n i l a t e a n d t h e n c o m b i n i n g with f r o m 2 to 2 0 % of a s a t u r a t e d aliphatic alcohol or 1,2-glycol. DETERGENT COMPOSITIONS. P. B. D a l t o n (Colgate-Palmolive Co.), U.S. 2,875,153. I t h a s been f o u n d t h a t a n i m p r o v e d det e r g e n t gel with u s e f u l p r o p e r t i e s m a y be f o r m e d by se]ectlng the proportion of a water-soluble soap to liquid nonionic polyalkylene oxide d e t e r g e n t f r o m t h e r a n g e of a b o u t 4 : 1 to 1 : 1 b y weight, with total weight of the two d e t e r g e n t s f r o m a b o u t 4 0 - 6 0 % , the rest b e i n g water. N0,N-CAKING SOLID PAI~TICULATE DETEI~GENTS. A. H. Lewis ( C a l i f o r n i a R e s e a r c h Corp.). U.S. 2,875,15~t. C a k i n g tendencies of d e t e r g e n t compositions which c o n t a i n s o d i u m s a l t s of alkyt benzene sulfonic acids or alkyl toluene s a l f o n i c acids h a v i n g f r o m 9 to 18 carbon a t o m s in the alkyl c h a i n can be reduced or coulplete]y e l i m i n a t e d by a d d i n g a b o u t 3 to 5 % by w e i g h t of boric acid. DETEI~GENT BRIQUETT~ AND PROCESS FOR THE PlCODUCTION THEgEOI% G. D. Miles (Colgate-Palmolive Co.). U.S. 2,875,155. P a r t i c l e s of d e t e r g e n t c o n t a i n i n g h y d r a t a b l e i n o r g a n i c salt are l i g h t l y compressed to a f o a m - r e t a i n i n g condition, a n d t h e n the s u r f a c e s of the r e s u l t i n g b r i q u e t t e are m o i s t e n e d to h y d r a t e t h e salt a n d increase t h e s t r e n g t h a n d a b r a s i o n resistance of the product. MAKING PEttBORATE CONTAINING DETERGENTS. B. Strain, S. L. E a t o n , a n d K. R. E r i c s o n ( T h e P r o c t e r & Gamble Co.). U.S. 2.876,200. A g r a n u l a r d e t e r g e n t - p e r b o r a t e w a s h i n g conIposition h a v i n g b l e a c h i n g p r o p e r t i e s is p r e p a r e d ill which the perborate is e n t r a i n e d in the porous s t r u c t u r e a n d is n o t s u b j e c t to g r a v i t a t i o n a l s e p a r a t i o n d u r i n g h a n d l i n g . D~TERGI'~NT COMPOSITION. P. F e l d m a n n ( D a n River Mills I n c . ) . U.S. 2,376,201. The d e t e r g e n c y value of ethylene oxide cond e n s a t i o n p r o d u c t s is i m p r o v e d b y t h e a d d i t i o n of a base such as a m m o n i a or a n organic amide, a ~ d a builder which is t h e s o d i u m salt of styrene-maleic a n h y d r i d e copolymer k n o w n as S t y m e r S. CLEAtr LIQUID DETERGENT CaM'POSITION. K . C. K r u m r e i , B r u c e S t r a i n , a n d H. J. P e d d i c o r d ( P r o c t e r & Gamble Co.). U.S. 2,$77,185-6. A h e a v y - d u t y clear liquid d e t e r g e n t is p r e p a r e d which c o n t a i n s a n a]kyl glyceryl e t h e r s u l t a n a t e , a solubilizer such as sodium toluene s u l t a n a t e , l a r g e a m o u n t s of pyro- or t r i p o l y p h o s p h a t e a n d silicate of soda to protect a g a i n s t tarn i s h i n g or corrosion of a l u m i n u m . DETEKGENT CONTAINING B,B'-DECYLA~IINOBISETHANOLPI%OPIONAMIDE. L. F. H e n d e r s o n a n d C. H. S c h r s m m ( L e v e r B r o t h e r s Co.). U.8. 2,377,137. A l i g h t - d u t y powdered or liquid aniouic or nonionie d e t e r g e n t c o n t a i n s a small a m o u n t of B,B'-decyla m i n o b i s - e t h a n o l p r o p i o n a m i d e to i m p r o v e t h e s u d s i n g a n d det e r g e n c y of the composition. DETEI%GENTS CONTAINING SUCCINIC COMPOUNDS. V. Dvorkovitz, N. W. Berst, a n d G. G. L e i s t (Diversey Corp.). U.S. 2,878,190. A non-acid, n o n - i r r i t a t i n g d e t e r g e n t consists of a m i x t u r e of sodium h i g h e r alkylbenzene s u l t a n a t e s a n d h i g h e r alkylphenyl ethers of polyethylene glycol a n d a t ]east 0.1% of a skini r r i t a t i o n r e d u c i n g additive such as suceinic acid or its salts. CONTINUOUS SOAP MANUFACTUICE. G. Mazzoifi S.p.a. Italian 550,133. P r o p o r t i o n a l a m o u n t s of pro-heated f a t t y acids a n d alkalies are i n t r o d u c e d in a series of reaction c h a m b e r s which continuously h e a t a n d blend the reaction p r o d u c t s u n d e r controlled p r e s s u r e s a n d t e m p e r a t u r e s . The process is a u t o m a t i c a n d provides t h o r o u g h l y saponified p r o d u c t s of a c o n s t a n t degree of alkalinity. (C.A. 53, 4781)