A B S T R A C T S R.A.REINERS,Editor.ABSTRACTORS: J.G.EndreJ.Iavicoli, K. Kitsuta, F. A. Kummerow, C. C. Litchfield, Louise R. Morrow, E. G. Perkins, and T. H. Smouse

• Fats

and Oils

A HIGHLY SENSITIVE METHOD i~l~ ~EASUEE~ENT OF LIPID !4YDROFE~OXIDES BY IODII~IETaY AND AX'~IPE%%(~i~IE'I'~IC~ENDFOINT. K . Oette, M. L. P e t e r s o n a n d R. L. M c A u l e y ( T h e Rockefeller Inst., N e w Y o r k 21, N. Y . ) . J. Lipid Res. 4, 212-215 (1963). A simple, accurate, a n d h i g h l y sensitive m e t h o d is described f o r m e a s u r e m e n t of lipid h y d r o p e r o x i d e s , u t i l i z i n g s t a n d a r d iodimetrie r e a c t i o n s a n d a n a m p e r o m e t r i c e n d p o i n t . Measurem e n t of 10 '-s e q u i v a l e n t s o f h y d r o p e r o x i d e s is feasible in s a m p l e s o f m i l l i g r a m size. Several p a r a m e t e r s of t h e a n a l y s i s have b e e n defined. DIELS ALDE~ REACTION I1~ THE FIELD 0F FATS. H. P. K a u f m a n (Deut. I n s t . F e t t f o r s c h , M f i n s t e r ) . Fette Seifen Anstriehm%ttel 64, 1115-1126 (1962). T h e Diels Alder r e a c t i o n in t h e field of f a t s is discussed in a s y s t e m a t i c order. T h e significance of t h e diene r e a c t i o n f o r f a t analysis, s t r u c t u r e research, a n d for p r e p a r a t i v e work is discussed. PRO- AND ANTI0~IDANTS II~ FATS.

VIII.

THE SYNTHESIS OF

C H O L E S T E R O L ESTERS O F I:fYDI~OXY A N D K E T 0 FATTY ACIDS. H . P . Kaufman, G. Garloff, a n d F. Diecke (Deut. Inst. Fettforsehung, IVIiinster). Fette Se~fen A~vstr~eh~aitte~ 64, 1104-

1109 (1962). T h e a u t h o r s a t t e m p t to characterize t h e p r o d u c t s of a n a q u e o u s r e a c t i o n of cholestrol linoleate a n d haemoglobin. A p p a r e n t l y d i h y d r o x y f a t t y acids a r e a m o n g t h e products. T h e effects, o f ~-toeopherol a n d b i l l i r u b i n u p o n the oxidation were s t u d i e d as well. CARBONYL FOR)/IATION IN AUTOXIDIZ~D FATTY ACID E S ~ S . K. T a u f e l a n d G. H e d e r (Deut. I n s t . L e b e n s m i t t e l c h e m . u n d Technol., H u m b o l d t Univ., B e r l i n ) . Fette Seifen Anstriehmittel 65, 85-9'1 (1963). E s t e r s of olei~ acid a n d linolelc acid were oxidized to peroxide v a l u e s of 14G-200, a n d s u b j e c t e d to t h e a c t i o n of b l e a c h i n g e a r t h in t h e presence of acid. A n i n c r e a s e d f o r m a t i o n of s t e a m volatile m o n o c a r b o n y l comp o u n d s was noted. T h e 2 , 4 - d i n i t r o p h e n y l h y d r a z o n e s were p r e p a r e d a n d c h a r a c t e r i z e d with t h e a i d of p a p e r chromatography. ~-~¥DROGENATI0,N 01~ ACID 0ILS AN]) TE~IINICAL OILS A T V A T E D PRE:SSURE. H. W i s s e b a c h ( O h w e r k e G e r m a n i c ,

ELE-

Emmerich). Fett~ Seifen Anstrichmitte~ 54, 9'67-970 (1962:). The a u t h o r r e p o r t s t h a t h y d r o g e n a t i o n o f acid oils a n d technical oils (recovered f r o m s p e n t b l e a c h i n g e a r t h ) c a n be c a r r i e d out m o r e quickly a n d with lower c a t a l y s t cons u m p t i o n b y a p p l y i n g i n c r e a s e d h y d r o g e n p r e s s u r e , 30 atmospheres i n s t e a d of 3 a t m o s p h e r e s . The cycle t i m e is reduced by 70-80% a n d nickel c o n s u m p t i o n lowered, b y 30~-50%. IS0ff~ATION 0,~

~[ETH:YL KETONES FI¢O~ t~ATS A.ND PAPF~R Dn~'I~'EI%ENTIATION llq THE F~)I~lY[ OF 2,JzDINITI%OFHENYLHYDRAZONES. K . T a u f e l , K . Sehmidt, a n d C1. F r a n z k e ( I n s t . L e b e n s m i t t l e c h e m i e , H u m b o l d t Univ., B e r l i n ) . Fette Seifen An~richmittet 54, 957-961 (1962). H e a t t r e a t e d b u t t e r c o n t a i n s t h e h o m o l o g e o u s series of odd n u m b e r e d m e t h y l k e t o n e s f r o m C.~ to C~s. I n u n h e a t o d b u t t e r only acetone is detected. E v i d e n c e is p r e s e n t e d which i n d i c a t e s the possible presence o f even n u m b e r e d a n d b r a n c h e d chain c o m p o u n d s which also m a y be ketches. C HI%0~1%I ATOGI~AGH

IC

M]SCHANIS~ 0F ACYL- MIGI%ATION IN P A R T I A L L Y ACYLATED GLYC~IDE.S. D. B u c h n e a ( B e a t i n g a n d B e s t , Dept. o f IVied. Research, Univ. of Toronto, C a n a d a ) . Fette Seife~ Anstrichmittel 54, 887-892 (1962). T h e a u t h o r outlines seven schemes in detail which m a y e x p l a i n t h e m i g r a t i o n o f acyl g r o u p s in p a r t i a l glyeerides, l~ost of t h e r e a c t i o n c o n d i t i o n s u n d e r which these r e a c t i o n s occur a r e included in t h e schemes. T h e acyl m i g r a t i o n in recap a n d d i g l y c e r i d e s is s h o w n to be a two s t a g e reaction. T h e a u t h o r shows t h a t in s a c h m i g r a : tions a n e x c h a n g e of t h e aey] g r o u p s b e t w e e n two molecules t a k e s place.

SISCONDARY C O N V E R S I O N S OF AUTOXIDIZED F A T T Y ACID ESTERS. K . T a u f e l , G. Heder, a n d CI. F r a n z k e ( I n s t . L e b e n s m i t telchemie, H u m b o l d t Univ., B e r l i n ) . Fette Seifen Anstrichmittel 6~, 6-13 (1963). The influence o f cupric, ferric, f e r r o u s a n d p l u m b o u s ions, a n d of sulfuric, hydrochloric, phosphoric, oxalic, monochloroacetic, citric, a n d benzoic a c i d s on autoxidized m e t h y l oleate a n d ]inoleate was i n v e s t i g a t e d . CUpric ion h a s a s t r o n g e r peroxide d e s t r o y i n g a c t i o n on concent r a t e s of m e t h y l o]eate h y d r o p e r o x i d e t h a n f e r r o u s ion. This w a s shown b y a decrease in a b s o r p t i o n at 232 m/~. JOURNALA.O.C.S., JvnY 1963 (Von. 40)

M i n e r a l a c i d s a n d lesser o r g a n i c acids (especially when w a r m e d ) lead to decomposition of h y d r o p e r o x i d e s in m i x t u r e s of esters a n d to a d e e p e n i n g of color. Decrease in peroxide value, decrease in the extinction coefficient a t 232 m~, and color d e e p e n i n g were parallel to the s t r e n g t h a n d concent r a t i o n of m i n e r a l acids. STUDIES OF THE U V SPECTRA OF ANTIOXIDANTS. I I . A NEW DIR.ECT U V SPECTROSCOPIC METHOI) FOR THE DETEt~MINATION OF ANTIG~XIDANTS IN' FATS. B. A. J . Sedlacek (Inst. Ernahningforch., Prague). Fette Seifen Anstri:ehmittel 54, 962-967 (1962). A new U V m e t h o d f o r the d e t e r m i n a t i o n of g a l l a t e esters, B H A , a n d N D G A is reported. Chloroform h a s been shown to be a b e t t e r s o l v e n t t h a n toluene in this method. S t a t i s t i c a l c o m p a r i s o n s of t h i s m e t h o d with others are included. NEW POSSIBILITIES OF AFPLICATIONS OF VEGETABLE~ 0ILS IN THE FIELD 0F (~OATING :~ATE~IALS. J. E. Wiff, P. H. M a r t i n a n d A. R. B a l d w i n ( T h e Cargill Corp., Minneapolis, Minnes o t a ) . Fette Seife~ An.~trichmittel 55, 117-121 (1963). I n v e s t i g a t i o n s were c a r r i e d o u t w i t h f i l m s of zinc oxide conr a i n i n g linseed oil of v a r i o u s viscosities with r e g a r d to t h e i r r e s i s t i v i t y to t h e f o r m a t i o n of bubbles, v a p o r p e r m e a b i l i t y , and water absorption. The r e s u l t s o b t a i n e d are c o m p a r e d with t h o s e o b t a i n e d f r o m l i n s e e d oil emulsions. PItEPAKATION O F ERUOIC ACID B Y L O W LIZATION. I~[. Taufel~ K . O. H e e m s

TE'.MPF~ATUI%~ CI~YSTALa n d C. F r a n z k e (Inst.

L e b e n s m i t t e l c h e m i e , H u m b o l d t Univ., B e r l i n ) . Fette Seifen Anstriehmittel 64, 10.23-1026 (1962). Low temperature c r y s t a l l i z a t i o n of r a p e s e e d o i l f a t t y a c i d s or m e t h y l esters f r o m acetone s o l u t i o n yields erucie acid o f over 9 5 % p u r i t y in one f r a c t i o n , l~epeated c r y s t a l l i z a t i o n s give a p u r e product. Y i e l d s are a b o u t 2 0 % b a s e d on t h e t o t a l acids. II¥DROGENATION 0F CASTOR OIL IN ETHANOL. ,]-: G. K a n e a n d K . ~ . M a n e r k a r ( D e p t . o f Chem. Tech., U n i v . o f B o m b a y , Bombay, India). Fette Seifeu Anstr£chm~ttel 64, 102.6-1030 (1962). T h e c o u r s e of h y d r o g e n a t i o n o f castor oil in e t h a n o l was studied. The influence of t e m p e r a t u r e , pressure, alcohol:oil ratio, a n d t h e c o n c e n t r a t i o n o f alcohol a n d catal y s t w a s i n v e s t i g a t e d . I n t h e presence of alcohol as solvent, t h e h y d r o g e n a t i o n of castor oil is r a p i d a n d little d e h y d r o x y l a tion w a s observed. INTEIC~STERIFICATION OF FATS V : DETECTION OF METI-Y~A-NOL IN FATS BY INTERESTERIFICATION WITH SODIUM "ME.TTIYLATE. H. P. K a u f m a n a n d B. G r o t h u e s (Deut. I n s t . F e t t f o r s c h . , M i i n s t e r ) . Forte Seifen Anstriehmittel 64, 805-80'7 (1962). T h e a u t h o r s have shown t h a t a d e t e r m i n a t i o n o f the m e t h y l esters of f a t s as m e t h a n o l b y t r a n s e s t e r i f i c a t i o n is n o t possible. A direct m e t h o d f o r t h e detection o f m e t h y l esters in f a t s u t i l i z i n g p a p e r c h r o m a t o g r a p h y h a s b e e n developed. GLYCEI~YLETHEI~S OF COD LIVEK OIL. A. E m m e r i e a n d C. E n g e l (Lab. Mikrobiologie, Univ. U t r e c h t ) . Fette Set,fen Anstrichmittel 54, 813-816 (1962). A new chromatographic method ( c o l m n n ) is described f o r t h e p r e p a r a t i o n of t h e unsaponifiable p o r t i o n of cod liver oil. P u r i f i c a t i o n a n d s e p a r a t i o n of f r a c t i o n s o b t a i n e d b y c h r o m a t o g r a p h y a n d t e s t i n g of t h e m b y microbiological m e t h o d s a i d e d in the isolation of f r a c t i o n s w i t h h i g h b a c t e r i o s t a t i e activity. The activity w a s s h o w n to. be confined to t h e u n s a t u r a t e d a-glyeeryl ethers. O t h e r glyceryl ethers, a p a r t f r o m selachyl alcohol, were isolated. ISOMEt~IZATIOI~ FATTY

ACIDS

O1~ I~IGHLY UNSATURATED NONCONJUGATED

BY

H~AT

TR]~ATMENT

0F

SEA-ANImAL

OILS.

T.

M i y a k a w a a n d H. N o m i z u ( G o v e r n m e n t Ind. Res. Inst., Osaka, Japan). 2~ette Seifen Anstriehmgttel 64, 593-599 (1962). H e a t i n g the m e t h y l e s t e r s of cuttle fish oil a t 200 to 2 5 0 C causes f o r m a t i o n first of eis-cis-traus a n d t h e n trans~cis-trans triene compounds. These m a t e r i a l s t h e n u n d e r g o p a r t l y inter- a n d i n t r a - m o l e c u l a r cyclisation. T h e f o r m a t i o n of cyclic c o m p o u n d s w a s followed b y u r e a f r a c t i o n a t i o n , a n d UV and IR measurements. MGLEC-~ULAK WEIGHT FOLYI~ERS

IN T H E

DETEKI~IINATION OF

ULTRACENTRIFUGE.

FATS

AND

FAT

II. I~OLECULAI% W E I G H T

DETE~]~INATION OF PATS I~P~O:M: ' THE APPROXIMATION OF THE SEDI"M]!~NTATION EQUILIBRIUM. H. L u c k a n d E. Rickerl (Deut. I n s t . L e b e n s m i t t e l c h e m i e , M u n i c h ) . Fette Seifen Anstrichm~t( C o n t i n u e d on p a g e 28) 25

_A_BSTRACTS: F A T S AND 0 I L S ( C o n t i n u e d fronl p a g e 25) tel 64, 8.25-831 (1962). U s i n g g r o u n d n u t oil as a n example, it w a s s h o w n t h a t a m o l e c u l a r w e i g h t d e t e r m i n a t i o n of f a t s is possible u s i n g t h e u l t r a c e n t r i f u g e . T h e molecular w e i g h t s o b t a i n e d in p o l a r a n d non-polar solvents show no significant differences. A t h i g h e r oil c o n c e n t r a t i o n ( 5 - 1 0 % ) a s s o c i a t i o n p h e n o m e n a are observed. ~TUDI~S 0,N r£':H~ UV-SPECTglY~ O~ A N T I O X I D A N T S I : INF~UEN'CE OF SOLVENTS AND FAT O N TH]~ UV-SP]!IOT~UM. B. A. J . Sedlacek ( I n s t . E r n a h n i n g s f o r s c h u n g , P r a g u e ) . Fette Seifen Anstriehm~ttel 64, 683-687 (1962). T h e U V s p e c t r a of m e t h y l , ethyl, propyl, octyl, a n d dodecyl g a l l a t e ; B H A , B H T , N D G A , ascorbyl p a l m i t a t e a n d ascorbic acid were s t u d i e d in a q u e o u s a n d e t h a n o l i c solutions. T h e spectra, w i t h f a t s a d d e d in solution a n d w i t h o u t a n t i o x i d a n t s were d e t e r m i n e d . Chlorof o r m a n d t o l u e n e were s u i t a b l e solvents. F a t r a n c i d i t y reduces the e x t i n c t i o n values of a n t i o x i d a n t a b s o r p t i o n m a x i m a .

EVALUATION O~ THE KNOWN METHODS OP CHgOi~[ATOGgAPHIC S~IFAR.ATION OF LOV~rE~ PATTY ACIDS. ,I. C h u r a c e k ( I n s t . A n a l . Chem. Chcmish-Technolog. Itochschule, P a r d u b i c e / C S S R ) . Fette Seifeu Anst~ichmittel 54, 679-682 (1962). The l i t e r a t u r e is reviewed. M e t h o d s a r e described b r i e f l y a n d e v a l u a t e d f r o m the p o i n t of simplicity, speed, a n d sensitivity. LINS]gED OIL OF I~UMANIAN 01~IGIN. CL A l e x a a n d G. Caraeulacu. Studii Cere. et Sti. CAirn., Iassy 12, 237-55 (1961). T h e oil o b t a i n e d f r o m t h e seed of a linen flax of t h e Conc u r r e n t v a r i e t y was s h o w n to be very similar, in i t s physical a n d chemical properties, to oil o b t a i n e d f r o m linseed g r o w n p r i m a r i l y f o r its oil content. The oil c o n t e n t o f t h e Conc u r r e n t linseed v a r i e d f r o m 34: to 35.2%. (!~ev. C~Irrent Lit. P a i n t Allied I n d . ) YAglATION OF I~EF~AC'TIVE INDEX AS A I~APID M]~THOD FOR M~ASUI%ING FAT OXIDATION. G. J a n i b e k a n d J. P o k o r n ~ ( I n s t . of Chem. Tech., P r a g u e ) . Papers of the Inst. of Chem. Tech. Prague 4-I, 157-83 (1960). T h e r e f r a c t i v e i n d e x of oils i n c r e a s e s with their degree of oxidation, even t h o u g h t h e r e m a y be a c o r r e s p o n d i n g decrease in iodine value. The r e l a t i o n s h i p b e t w e e n r e f r a c t i v e index a n d degree of oxidation is d e p e n d e n t on t h e t y p e of oil, h e a t i n g time a n d t e m p e r a ture. D u r i n g t h e i n d u c t i o n period, however, t h e r e f r a c t i v e i n d e x does n o t c h a n g e a t all even t h o u g h t h e peroxide value is g r a d u a l l y i n c r e a s i n g . I n t h e second s t a g e of oxidation, the r e f r a c t i v e i n d e x b e g i n s to i n c r e a s e a t the same time as t h e rate of peroxide f o r m a t i o n also s u d d e n l y increases. I n t h e t h i r d s t a g e of oxidation the peroxide c o n t e n t is d e c r e a s i n g while the r e f r a c t i v e index c o n t i n u e s to increase t h o u g h a t a slower rate. T h e r e f r a c t o m e t r i c m e t h o d allows the end of the i n d u c t i o n period to be a c c u r a t e l y d e t e r m i n e d a n d provides a n e a r l y linear relationship b e t w e e n r e f r a c t i v e index a n d peroxide value in the r e g i o n f r o m 100 to 1,000 m c q . / K g . (second s t a g e ) . Tile a d v a n t a g e of the refractom e t r i c m e t h o d over t h e peroxide wflue d e t e r m i n a t i o n a p p e a r s to be in the f a c t t h a t the f o r m e r m e a s u r e s more t h a n j u s t one of t h e o x i d a t i o n p r o d u c t s of t h e oil. I n addition, it is both rapid, inexpensive a n d accurate. A STUDY OF TH15 AUTOXIDATION 0F SOME VE~ETABLL 0'ILS AT EL]bY&TED TIhMP~]gATUI~ES. V I I I . THE. INKLU~NCE OF IZE:ACTION CONDITIONS ON THE FlgEPAIZATION O1~ OXIDIZED LINSEED 0IL WITH OPTIMUM D~YING PI~OFE~TIES. J . P o k o r n # ( I n s t . of Chem. Teeh., P r a g u e ) . Papers of the Inst. of Chem. Teeh. Praflue 4-II, 223-37 (1960). T h e d r y i n g t i m e of linseed oil c a n be s h o r t e n e d b y s u b j e c t i n g the oil to a previous p a r t i a l oxidation, w i t h t h e r e s u l t a n t d e s t r u c t i o n of n a t u r a l antioxid a n t s a n d f o r m a t i o n o f peroxides. T h e m a x i m u m decrease in d r y i n g t i m e ( a b o u t 4:0%) corresponds to t h e s t a g e of o x i d a t i o n in which the peroxide c o n t e n t of t h e oil reaches a m a x i m u m , while f u r t h e r oxidation causes t h e d r y i n g t i m e to increase s l i g h t l y once more. T e m p e r a t u r e of oxidation ( b e t w e e n 65C a n d 130C) h a s no g r e a t influence on d r y i n g time. However, d r y i n g r a t e is n o t a simple f u n c t i o n of peroxide level, b e i n g also d e p e n d e n t on t h e r a t e at which o x y g e n is blown t h r o u g h the oil d u r i n g t h e oxidation period. T h i s i n d i c a t e s t h a t other o x i d a t i o n p r o d u c t s beside peroxides also affect d r y i n g rates. T h e viscosity increase up to t h e p o i n t of n l a x i m u m peroxide level is small a n d n o t reproducible, t h e r e f o r e it is n o t a suitable m e t h o d f o r following the course of the reaction. KINE,TICS OF T H E E;STES~IFICATION OF DIGLYCE~0,L WITII STEAXIO ACID. E. Mare§ a n d J. Pokorn:~ ( I n s t . of Chem. Tech., Prague). Papers of the Inst. of Chem. Teeh. Prague 4-I, 275-93 (1960). The c a t a l y z e d esterification reaction b e t w e e n 28

diglycerol a n d stearic acid is f o u n d to be a second order reaction, with t h e r a t e c o n s t a n t g r e a t l y affected b y temperature (there is a 17-fold i n c r e a s e in rate g o i n g f r o m 175C to 250C). P o t a s s i u m h y d r o x i d e is u s e d as a catalyst. A c a t a l y s t level of 0.5% ( b a s e d on t h e stearie acid) is o p t i m u m with r e s p e c t to r a t e of esterifieation, h i g h e r c a t a l y s t levels not yielding any rate advantage. D u r i n g esterification, the m o n o e s t e r c o n t e n t increases to a m a x i m u m a n d a f t e r w a r d s decreases due to esterification of the r e m a i n i n g free h y d r o x y l g r o u p s a n d interesterification. The m a x i m u m a m o u n t of m o n o e s t e r s i n c r e a s e s with d e c r e a s i n g ratios of f a t t y acid to diglycerol a n d d e p e n d s on t h e reaction t e m p e r a t u r e . The activation e n e r g y of the r e a c t i o n is calculated at 17,400 cal. THE DETEIZlVLINATION OF THE PE]g0XIDI~ VALU]g OF OOSIvH~TIO CRIDAMS CONTAINING VFJGETABLE OILS. J. Pokorn~, J. Cmollk, V. P o k o r n ~ a n d G. J a n i b e k ( I n s t . of Chem. Tech., P r a g u e ) . Papers of the Inst. of Chem. Teeh, Prague 4-II, 297-310 (1960). T h e o p t i m u m conditions f o r t h e a n a l y s i s o f peroxide value in cosmetic c r e a m s c o n t a i n i n g 20~25% o f vegetable oils ( s u c h as l i n s e e d oil, sunflower seed oil a n d s o y b e a n oil) are discussed. B o t h t h e w e i g h t o f sample used in t h e analysis a n d t h e a m o u n t of w a t e r p r e s e n t d u r i n g t h e reaction are f o u n d to affect results, p r o b a b l y because of a s y n e r g i s t i c effect of t h e other c o m p o n e n t s of the c r e a m on t h e oxidation of p o t a s s i u m iodide. Details of t h e m e t h o d are given. THE DEq~A~MINATION OF THE PI~ES]~NCE OF HARDENFbD FATS IN COCOA BUTTE~. J . Pokorn:~, J. Smi~ek, B. K a k £ 5 a n d G. J a n i b e k ( I n s t . of Chem. Tech., P r a g u e ) . Papers of the Inst. of Chem. Tech. Prague 4-II, 313-24: (1960). T h e presence of h y d r o g e n a t e d f a t s in cocoa b u t t e r c a n be detected by a n a l y s i s o f t h e trans f a t t y acid content, p r e f e r a b l y b y m e a s u r e m e n t of t h e optical d e n s i t y of a solution o f t h e f a t , since p u r e cocoa b u t t e r c o n t a i n s no m o r e t h a n 2 % of trans acids. T h e a d d i t i o n of 5 % or nlore of h y d r o g e n a t e d f a t s to cocoa b u t t e r can be a s c e r t a i n e d b y this m e t h o d , with an accuracy of 100%. A_ STUDY OF TIlE CHI!IMISTI~Y OF OATS AND ITS PaoDucTs. III. CHANGE.S IN THE CONTENT AND PI~OPEJ~TIES OF OAT F~LAKE:S I,IFIDS CAUSED BY TItEI~MAL TgEATMENT. G. J a n i b e k a n d J . Pokorn:~ ( I n s t . of Chem. Tech., P r a g u e ) . Papers of the Inst. of Chem. Teeh. Prague 4-II, 32:7-39 (1960). The chemical c h a n g e s c a u s e d in t h e lipids of oat flakes b y h e a t i n g to 100-200C f o r 90-300 rain. are described. The amount of c h l o r o f o r m e x t r a c t of oat flakes h e a t e d to 135C or h i g h e r decreases l i n e a r l y w i t h t h e h e a t i n g t e m p e r a t u r e . T h e spectral c h a n g e s of t h e o a t lipids a r e r a t h e r complicated, i n d i c a t i n g the d i s a p p e a r a n c e of chlorophyll a n d the f o r m a t i o n of new color bodies. T h e d e t e r m i n a t i o n of r e f r a c t i v e index is not suitable as a n l e a s u r e m e n t of the degrees of oxidation. THE COMPOSITION OF WAXY SUBSTANGE.S FgOM OAT IIULLS. 2. THE COMPOSITIO,N OF THE GLYCFiB.II)F. F0gTION OF THE EXTgACT. J. Pokorn:~, 2. Z e m a n a n d G. J a n i b e k ( I n s t . of Chem. Tech., P r a g u e ) . Papers of the Inst. of Chem. Tech. Prague 4-II, 343-54: (1960). E x t r a c t i o n of oat hulls with l i g h t p e t r o l e u m f r a c t i o n s or c h l o r o f o r m yields a b o u t 1% of a g r e e n i s h - b r o w n paste-like extract. Tile e x t r a c t c o n t a i n s only a s m a l l a m o u n t ( 5 % ) of unsaponifiables, m o s t l y h i g h e r alcohols, a b o u t 2 5 % f a t t y acids, p r o b a b l y h y d r o x y a c i d s , a n d a b o u t 2 5 % of even more h i g h l y polar compounds, soluble only in ethanol. T h c glyceride f r a c t i o n of t h e e x t r a c t cont a i n s 5 0 % oleic acid, 25% p a l m i t i c acid a n d 1 7 % linoleic acid. ESTlgl~IFICATI0,N O]a EI~UCIC ACID WITH HIGHEg ALCOIKOLS. J. Zajic a n d M. Bure~ov5 ( I n s t . of Chem. Tech., P r a g u e ) . Papers of the Inst. of Chem. Tech. Prague 4-II, 275-94 (1960). T h e esterification of erucic acid ( p r e p a r e d f r o m rapeseed oil, w i t h a n I.V. of 73 a n d a 30C m e l t i n g p o i n t ) with cetyl, s t e a r y l a n d oleyl alcohols w a s studied. T h e reaction w a s c o n d u c t e d u n d e r v a c u u m (180 ram. H g ) , a t 160, 200, a n d 24:0C in t h e presence of catalyst. The o p t i m u m reaction conditions were f o u n d t o b e : c a t a l y s t , 0.5-2.5% p h o p h o r i c a c i d ; t e m p e r a t u r e , 24:0C; cetyl alcohol to erucic acid m o l a r ratio, 1:1. F i n d i n g s relative to rate c o n s t a n t s , a c t i v a t i o n e n e r g y , effect of t y p e a n d a m o u n t of c a t a l y s t a n d m o l a r r a t i o o f r e a c t a n t s are r e p o r t e d upon. The cetyl a n d stearyl esters a r e solid s u b s t a n c e s (m.p. respectively 40 a n d 48C) while the oleyl ester is liquid a t 20C. D i l a t a t i o n curves a n d p e n e t r a t i o n r e s u l t s of t h e cetyl a n d s t e a r y l esters show g r e a t s i m i l a r i t y to those o f beeswax. These m a t e r i a l s a p p e a r t h e r e f o r e to be s u i t a b l e f o r the p r o d u c t i o n of synthetic waxes. JOUR."qALA.O.C.S., JULY 1963 (VOL. 40)

ABSTRACTS: F A T S AND 0 I L S ANALYSIS OF /~IXTUI~ES OF HIGHE~ ALIPHATIC NITI%ILES BY GAS-LIQUID OHRO]~ATOGI%AFtt'Y. 3. P o k o r n ~ a n d I. Z e m a n ( I n s t . o f Chem. Tech., P r a g u e ) . Papers of the InsL o/ Chem. Tech. Prague. 4-II, 255-71 (1960). M i x t u r e s of a l i p h a t i e ~fitriles p r e p a r e d f r o m palmitic, oleic, s t e a r i c a n d coconut f a t t y a c i d s were a n a l y z e d b y vapor p h a s e c h r o m a t o g r a p h y u s i n g a microflame detector, iqitriles were f o u n d to h a v e elation t i m e s a p p r o x i m a t e l y c o r r e s p o n d i n g to those of t h e respective m e t h y l esters. T h e h i g h t e m p e r a t u r e (265C) of the a n a l y s i s does n o t affect t h e r e s u l t s a n d t h e correction f o r c o m b u s t i o n h e a t s h a s only negligible influence on t h e values of t h e c o n s t a n t s f o r the i n d i v i d u a l c o m p o n e n t s . T h e Cs a n d the C~o c o m p o n e n t s e v a p o r a t e d p a r t i a l l y d u r i n g t h e reaction a n d t h e i r m e a s u r e m e n t s were n o t q u a n t i t a t i v e . STUDY OF CAST01% 0IL HYDROGENATION AT LOW TLMFEI%ATURES. J. H l a d l k a n d J. Z a j i c ( I n s t . of Chem. Tech., P r a g u e ) . Papers of the Inst. of Chem. Teoh. Prague 4 - I I , 241-52 (1960). T h e h y d r o g e n a t i o n of castor oil was studied, a t t e m p e r a t u r e s b e t w e e n 12.0 a n d 180C. T h e o p t i m u m conditions, f r o m t h e s t a n d p o i n t of t h e s t a b i l i t y of the hydro.xyl g r o u p a n d o f t h e f o r m a t i o n of t h e l ~ - h y d r o x y s t e a r i c acid, are: 160C a n d 0.5% N i catalyst. I n two h o u r s of hydrog e n a t i o n u n d e r these conditions, the I.V. w a s reduced f r o m 83 to 14 a n d t h e h y d r o x y l value f r o m 171 to 149. H i g h e r t e m p e r a t u r e s a n d h i g h e r a m o u n t s of c a t a l y s t f a v o r a l a r g e r loss of h y d r o x y l groups. COLGRIMETRIC DETERMINATION 0F FAT PEI%OXID]LS BY 1V[EANS OF TITANIUM CHLOI~ID~, I. G. JaniLek a n d J. P o k o r n ~ ( I n s t . of Chem. Technology, P r a g u e ) . Papers of the Inst. of Chem. Teeh., Prague 3, 2 3 3 - 5 5 (1959). & m e t h o d of eolorime.tric d e t e r m i n a t i o n of peroxides in f a t s b y t i t a n i u m chloride in glacial acetic acid is described. I n c o m p a r i s o n to t h e t i t a n i u m s u l f a t e m e t h o d ( b y Strohecker et al.) t h e t i t a n i u m chloride m e t h o d is 30~50 t i m e s m o r e sensitive, r e q u i r i n g very small a m o u n t s o f f a t ( a s little as 0.1 g) for t h e d e t e r m i n a t i o n . The m e t h o d h a s good r e p r o d u c i b i l i t y a n d is simple a n d rapid. One single c a l i b r a t i o n curve is sufficient for all t h e m o r e c o m m o n oils, while special c a l i b r a t i o n c u r v e s are required f o r such oils as castor oil, c o n j u g a t e d linseed oil a n d t u n g oil. T h e only d i s a d v a n t a g e is t h a t it is n e c e s s a r y to observe t h e r e a c t i o n t i m e (20~40 seconds) strictly, since the color i n t e n s i t y of t h e p e r t i t a n i c complex h a s a s h a r p m a x i m u m a t t h i s time. I I . DEqFERI~INATION IN A OHL0aOFtOI~M-PI%OPIONIC ACID MEDIUM. J. Pokorn:~, J . Cmolik a n d G. Jani~ek Ib$d, 4-II, 197-2.07 (1960). T h e preYious m e t h o d f o r colorimetrlc peroxide det e r m n i a t i o n w a s modified b y r e p l a c i n g acetic acid with propionic acid. A directional a d v a n t a g e o f this m e t h o d is t h a t f a t s are more soluble in propionic t h a n in acetic acid a n d also t h a t t h e colored t i t a n i u m complex is s o m e w h a t more stable in this m e d i u m , t h u s m a k i n g t h e previous requirenlent for o b s e r v i n g t h e r e a c t i o n time a c c u r a t e l y (2:0 to 40 seconds) slightly less s t r i n g e n t . I I I . INPLIFE;NCE 01~ LACTIC ACID ON RESULTS IN A FROPIGNIC ACID MEDIU1V[. Ibid, 211-20. T h e a d d i t i o n of lactic acid to a c h l o r o f o r m - p r o p i o n i c acid m i x t u r e g r e a t l y i n c r e a s e s t h e s t a b i l i t y of t h e colored p e r t i t a n i c complex f o r m e d d u r i n g eolorimetric d e t e r m i n a t i o n of f ~ t peroxides., T h e o p t i m u m reaction t i m e is t w e n t y m i n u t e s . The peroxide values o b t a i n e d b y t h i s m e t h o d are up to 50,% h i g h e r t h a n in the m e t h o d w i t h o u t lactic acid a n d correlate quite well with t h e r e s u l t s o b t a i n e d b y t h e iodometric m e t h o d , t h u s s h o w i n g t h e reaction to be q u a n t i t a t i v e . D e t a i l s o f t h e m e t h o d a r e discussed. DETEI%:~INATIGN OF ACTIVE OXYGEN IN SOM~ COSMEITIC PRODUCTS. J. P o k o r n # , M. K a r v ~ n e k , V. P o k o r n £ a n d G. J a n i ~ e k ( I n s t . o f Chem. Technology, P r a g u e ) . Papers of the Inst. of Chem. Teeh. Prague 4-I, 319~30 (1960). A s e m l m i c r o colorimetric m e t h o d f o r t h e a n a l y s i s o f active o x y g e n in cosmetic p r o d u c t s is proposed. T h e m e t h o d e m p l o y s t i t a n i u m chloride as t h e color-forming r e a g e n t . Special p r o c e d u r e s f o r p r e p a r i n g t h e sample b e f o r e t h e a n a l y s i s are r e c o m m e n d e d a n d details o f the m e t h o d are discussed. The iodometric m e t h o d can also be u s e d f o r cosmetic p r o d u c t s , while the m a n g a n o m e t r i c m e t h o d w a s f o u n d u n s a t i s f a c t o r y in s o m e cases. SOLVENT EXTRACrI'ION Or GLYCF~INE FROM "WATFA~ SOLUTIONS. J. Dyr, V. K r u m p h a n z l a n d J. C h u d # ( I n s t . of Chem. Teeh., Prague). Papers of the Inst. of Chem. Tech. Prague 4-II, 145-64 (1960). The t e r n a r y equilibrium d i a g r a m s of t h e systems: n-butanol-water-glycerine, isobutanol-water-glyeerine a n d eyclohexanol-water-glyeerine h a v e b e e n s t u d i e d a t 25-5075C. The e x t r a c t i o n coefficient i n c r e a s e s w i t h i n c r e a s i n g JOURNAI~A.O.C.S., JULY 1963 (VOL. 40)

t e m p e r a t u r e a n d w i t h i n c r e a s i n g glycerine c o n c e n t r a t i o n in the initial solution, while it decreases with t h e choice of solvent in t h e f o l l o w i n g o r d e r : n-butanol, i s o b u t a n o l , benzyl alcohol a n d cyetohexanol. T h e two-phase r e g i o n in t h e t e r n a r y d i a g r a m is l a r g e s t with cyclohexanol a n d decreases with i s o b u t a n o l a n d n - b u t a n o l . THE RE~INING OF 0~LS WITH HIGH ~ FATTY ACID CONTE~qT. J. Zajle, J . Z a ] u d a n d J. H l a d i k ( I n s t . of Chem. Tech., Prague). Papers of the Inst. of Chem. Tevh. Prague 4-I, 253-70 (1960'). W h e n oils c o n t a i n i n g h i g h ( 2 0 % or m o r e ) levels o f F F ~ a r c refined by conventional m e t h o d s , excessive losses o f n e u t r a l f a t t h r o u g h saponification are encountered. Refining b y s o l v e n t e x t r a c t i o n of the F F A was s t u d i e d u s i n g 9 6 % e t h a n o l a s a solvent. The optimum conditions for e x t r a c t i o n a r e f o u n d to b e : e t h a n o l to f a t ratio, 1:1, or as little as 1 : 2 i n t h e lower r a n g e of F F A levels; temperature, 30 to 40C. L o s s e s t h r o u g h solubilization of t h e f a t in e t h a n o l a v e r a g e 0.35%. I n m o s t cases, a s e v e n - s t a g e e x t r a c t i o n is required to e l i m i n a t e 9 7 - 9 8 % o f t h e original F F & content. DETERMINATION OF OARBONYL GROUPS IN OXIDIZED !~ATS IN THE PRESENCE :OF PEROXIDES. 3. P o k o r n ~ , J. Smi§ek a n d G. JaniLek ( I n s t . of Chem. Tech., P r a g u e ) . Papers of the Inst. of Chem. Teeh. Prague 4-I, 187-201 (1960). The d e t e r m i n a t i o n of earbonyl g r o u p s ( a l d e h y d e s a n d ketones) in oxidized f a t s is a n i m p o r t a n t c o m p l e m e n t to peroxide value d e t e r m i n a t i o n in r a n c i d i t y studies. T h e h y d r o x y l a m i n e m e t h o d g e n e r a l l y u s e d is s u b j e c t to i n t e r f e r e n c e b y t h e peroxides p r e s e n t in t h e oxidized f a t s , which c a n also oxidize h y d r o x y l a m i n e a n d t h u s cause r e s u l t s to be b i a s e d in excess. The m e t h o d of c a r b o n y l g r o u p d e t e r m i n a t i o n in glacial acetic ~cid m e d i u m ( a c c o r d i n g to H i g u e h i a n d B a r n s t e i n ) w a s f o u n d to require no correction, since none o f t h e various o x i d a t i o n p r o d u c t s e x a m i n e d (peroxides, h y d r o p e r o x i d e s , esters, free f a t t y acids) i n t e r f e r e with t h e a n a l y s i s . A modification of t h e m e t h o d a i m e d a t o p t i m i z i n g i t s accuracy is proposed. D~TF~I:~IVIINATI0.N O.P THE' IODINEq VALUE OF EDIBLE OILS BY A ]~iODII~IED ]-IYPOCHLOR.ITE METHOD. M. K a r v ~ n e k a n d J. P o k o r n # ( I n s t . o f ~ Chem. Teeh., P r a g u e ) . Papers o/ the Invt. of Chem. Tech. Prague 3, 413-425 (1959). A p r e v i o u s hypochlorite m e t h o d f o r iodine v a h e d t e r m i n a t i o n ( b y M u k h e r j e e ) w a s modified b y u s i n g a s o d i u m a c e t a t e solution in glacial acetic acid a n d c a r b o n t e t r a c h l o r i d e as a solvent. T h e modified m e t h o d h a s b e t t e r r e p r o d u c i b i l i t y a n d lower a n a l y t i c a l error, while y i e l d i n g r e s u l t s in good a g r e e m e n t w i t h o t h e r m e t h o d s (e.g., t h a t of Won M i k u s c h a n d F r a z i e r ) . Use of the m e t h o d is n o t r e c o m m e n d e d in t h e case of d r y i n g oils, where c o n s i s t e n t l y low r e s u l t s are obtained. ]:{ELATION B]~TWE~N TH]~ PATTY ACID ~0]YfPOSITION OF HAI%DENED FATS AND THEII~ PHYSICO-0HEIV[ICAL AND TECHNICAL PROPERTIE:S. J. P o k o r n ~ ( I n s t . of Chem. Tech., P r a g u e ) . Papers of the Inst. of Chem. Teeh. Prague 3, 347-40.7 (1959). Hydrog e n a t i o n of p e a n u t oil a n d s o y b e a n oil is described in relation to its e f f e c t s on m e l t i n g point, dilatation, p e n e t r a t i o n , ref r a c t i v e index, isoleic a c i d f o r m a t i o n , stability, specific g r a v i t y . T h e r a t e o f h y d r o g e n a t i o n of s o y b e a n oil is f o u n d to be a p p r o x i m a t e l y twice as h i g h as t h a t of p e a n u t oil, all other conditions b e i n g equal. T h e d e t e r m i n a t i o n of ref r a c t i v e index or iodine value as indices o f d i l a t a t i o n c h a n g e s is v a l i d only i f selectivity a n d rate of iso~eic acid f o r m a t i o n are c o n s t a n t a n d t h e initial f a t t y acid c o m p o s i t i o n of the off does n o t v a r y . 2~ STUDY OF TH]~ PI%EPARATION 0P I~ATS "WITH PROP:E~TIES SIMILAI% T O THOSE O~ COCOA BUTTER. I. HAI%IYENING OF VE(~ETA]~LE FATS. G. JaniLek a n d J. P o k o r n # ( I n s t . of Chem. Tech., P r a g u e ) . Papers o~ the Inst. of Chem. Teeh. Prague 3, 301-42: ( 1 9 5 9 ) . Simple h y d r o g e n a t i o n of coconut oil, p a l m oil or p a l m kernel oll is n o t suffÉcient to p r o d u c e a s a t i s f a c t o r y cocoa b u t t e r s u b s t i t u t e . H y d r o g e n a t e d coconut oil h a s t h e s t e e p e s t d i l a t a t i o n curve of t h e t h r e e oils e x a m i n e d , c o m i n g close to m a t c h i n g cocoa b u t t e r in this r e s p e c t ; however, i t s m e l t i n g p o i n t r e m a i n s lower, even a f t e r full hydrog e n a t i o n , t h a n t h a t o f cocoa b u t t e r . Hydrogenated pahn kernel oil h a s a less s t e e p dilatation curve b u t a m e l t i n g p o i n t (37.9C) closer to cocoa b u t t e r . P a l m oil is definitely u n s u i t a b l e as a cocoa b u t t e r s u b s t i t u t e because of its m u c h flatter d i l a t a t i o n curve a n d excessive c o n t e n t of glycerides m e l t i n g above 100F.

~k STUDY 01~ AUTOXIDATION 0,i~ SOLVE VEGE.TABLE OILS AT EL~VA~q~D T]~3LPEI%ATURES. V I . AUTOXIDATION 0F BLOWN LINSF~D OIL IN FIL~S. J . P o k o r n ~ ( I n s t . of Chem. Tech.,

29

ABSTRACTS: FATS AND OILS Prague). Papers of the Inst. of Chem. Teeh 3, 261-293 (1959). The kinetics of the autoxidation reaction of blown linseed oils was studied. Blown oils are so deeply oxidized t h a t their peroxide content is relatively high a n d there is not a sufficient a m o u n t of f a t t y acids capable of being oxidized to fully utilize the ability of hydroperoxides to initiate the chain reaction. Consequently, oxidation velocity cannot increase proportionally to peroxide content a n d autoxidation proceeds as a first order reaction. W h e n blown oils are heated to 65-130C in inert atmosphere to decompose their peroxides and subsequently caused to autoxidize, the reaction proceeds as an autocatalytic second order reaction with a lower initial rate. Once a sufficient a m o u n t of peroxides has been formed, the reaction changes again to the first order a n d the reaction course loses its autocatalytic character. VII.

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RELATION

TO

REACTION COhV])ITIONS AND METHOD OF MEASUK]~M~T. Ibid, 4-I, 205-2.47 (1960). The color changes of refined and nnrefined linseed oil during autoxidation at 70, 100, 130C were measured by colorimetric and spectrophotometric methods. The dominant wavelengths were practically unaffected by oxidation (less t h a n 8 m~). The optical density at 450 m~ increases sharply at the beginning, reaching a m a x i m u m during the induction period, after which it falls rapidly to a value lower t h a n in the original oil at the end of t h e induction period: F u r t h e r oxidation causes the optical density to increase again. A STUDY OF THE CHE;MICAL COMPONENTS OF OAT AND ITS P~O])UCTS. I. OA~' LIPn)s. G. JaniLek and J. Pokornj; (Inst. of Chem. Tech., P r a g u e ) . Papers o f Inst. o/ Chem. Tevh. Prague 3, 50,3-20 (1959). The properties of lipid fractions of oat extracts were examined after successive extractions with petroleum ether and methanol, before hydrolysis, and with petroleum ether a n d chloroform after it. A total of approximately 5% f a t t y acids was found in the f o u r extractions, about 70% of t h e total being found in the first extraction of oatmeal with petroleum ether. The p e t r o l e u m ether extract contained 55.6% oleic acid, 33.1% linoleic acid and 12.1% palmiti¢ acid. Only a small percentage of f a t t y acids came f r o m the hulls, the bulk being found in the hull-free grain. Stability of the oat extracts was comparable to t h a t of rapeseed oil. II. T H F A % ~ A L L Y S T A B L E A N T I O X I D A N T S IN OAT. ~. SupovS, ft. Pokorn:~ and G. Jani~ek, Ibid, 535-44, The antioxidant effect on lard of various oat extracts was studied. Extractions were carried out with methanol, petroleum ether, water and benzene, and the extracts added to lard at the 0.5-1.0.% ]eve]. Rate of f a t oxidation was measured b y the increase in peroxide number with time of aeration a t 100C.. All of the oat extracts e x h i b i t e d some antioxidant properties increasing the stability of lard by 50 to 100%. The highest activity was f o u n d with the lipid-free methanolie extract of oatmeal. The antioxidant effect of these oatmeal extracts is however only one fifth as large as t h a t of propyl gallate. PARTIAL OXIDATION OF UNSATURATEDFATTY ACIDS BY PE~IODIC ACIBS AN]) O~HE~ PERACIDS. F. D. Gunstone and P. J. Sykes ( U n i v . of St. Andrews, F i f e ) . Riv. Ital. Sostanze Grassy 11, 561-7 (1962). P a r t i a l oxidation of u n s a t u r a t e d f a t t y acids by m e a n s of peracids h a s been studied with two m a i n objectives: as an improved method for determining the position of double bonds in p o l y u n s a t u r a t e d acids and as a m e a n s for distinguishing methylene-interrupted polyene acids (such as linolMc) f r o m monoethenoid acids, such as oleie. The a t t a i n m e n t of the first objective and some interesting results in connection with the second are described. QUANTITATIVE GAS OI{ROMATOGRAFH'YOF BUTTF~ I~ATTY XOI])S WlTI{ PR00RA:~:~D FLOW. S. Valussi a n d G. Cofleri (Trieste). l~iv. Ital. Sostanze Grassc 12, 617-9 (1962). Gas chromat o g r a p h y of b u t t e r f a t t y acids with linearly increasing prog r a m m e d flow (from 10-30 to 60-i10 co./rain:) is f o u n d to give good results in the quantitative analysis of low molecular weight f a t t y acids whose peaks are thus well separated and nearly equidistant. CYCLOTRITEI%PENIC ALCOHOLS, MINOR CONSTITUENTS OF VE(]ETA~L~. OILS. G. J a c i n i and P. ~ p e l l a (Staz. Sperim. Oli e Grassi, Milan). Riv. Ital. Sostanze Gra~se 12) 620-3 (!962). The substances responsible for the F peak in the chrom a t o g r a m of the unsaponifiable of several vegetable oils have been f o u n d to consist of two parts, one of w h i c h is precipitated by digitonin and one is not. The digltonin JOURNALA.0.C.S., JULY 1963 (YOn. 40)

precipitate, t h a t was previously t h o u g h t to be a mixture of sterols, was analyzed a n d f o u n d to be a mixture of eyclotriterpenic alcohols. HYDRATION OF SOYBEAN PHOSPHATIDES. A. 5akubowski ( I n s t i t u t Przemyslu Tluszczowego, Warsaw, P o l a n d ) . /~iv. Ital. Sostanze Grasse 10, 512-6 (1962:). A s t u d y of phospholipid h y d r a t i o n (the process through which phospholipids are precipitated f r o m crude oils) confirms the hypothesis of f o r m a t i o n of a double monomolecular layer m a d e u p of water a n d phospholipids plus glycerides, provided the minim u m amount of water necessary for the process is used. This m i n i m u m q u a n t i t y of water necessary to hydrate the phosphollpids depends on the type of phosphatide present, in the case of lecithin being approximately eight moles for each P atom. THE EFFECT OP REPINING ON THE VISIBLE SPECTRUM 01~ EOIBLE OILS. M. T. Giordano and V. P e n n a t i (Enologic Bureau, Genoa). Olearia 5-6, 168-70 (1962). R e f i n i n g of edible oils induces alterations in the coloring substances t h a t can be observed by spectrophotometry. I n particular, the absorption m a x i m u m of chlorophyll in the visible spectrum is shifted f r o m 670 m/z to lower values. This effect is always encountered a f t e r deodorizing b u t not after neutralization of the oil's acidity. CHP*~)~[ATOGRAPHIC STUDIES ON EST~nI~IED' OLIVE OILS. G. Bigoni (Gaslini S.p.A.,. Genoa). Riv. ][tal. Sostanze Grasse 9, 428-31 (1962). Bromination of the methyl esters of olive oil is f o u n d to increase the structural differences between c/s a n d trans isomers of oleic acid, thus affording the possibility of quantitatively determining the tranS acid content of olive oil by g a s ehronmtography. B y applying this method, the conclusion is reached t h a t trans acid content cannot be used as an index of esterification of the oil, since u n t r e a t e d solvent-extracted olive oil contains approximately the same a m o u n t of trans acid as esterified oils. IDENTIPIOATION BY G&S CHROMATOGRAPH~ r OF ~IIN01~ P & ~ ACIDS PRESEiNTIN OLIVE 0IL. D. Grieco (Chem. Lab. of Grain Association, l~ilan). Riw. Ital. S,asta~ze Grasse 9, 432-8 (1962). Gas chromatograms of olive oils of different origins indicate t h a t the presence a n d concentration of minor f a t t y acids m a y vary with the sample a n d the analytica ! technique employed. Linolenie, arachidic and eicosenoic acids are always present, in m a x i m u m concentrations, respectively, of 0.9%, 0.5% a n d 9.1%. Laurie, myristic, beheni¢ a n d lignoceric acids are sometimes present as traces. The presence of two f a t t y acids with 17 C atoms h a s been established: the heptadecanoic acid is present up to the 0.1% level and the heptadecenoie acid up to t h e 0.2% l e v e l . CHANGES 117 THE LIPID CONTENT 0F ALMONDS DURING THE RIPENING OP THE FI~UIT. C. Galoppini e G. Lotti (Univ. of Pisa, I t a l y ) . Olearia 5-5, 16.4-7 (1962). D u r i n g maturation of the Prunus Amygalus S (a variety of almond) the saponification number remains practically constant, while the I.V, diminishes gradually f r o m about 106 (April) to about 94 (September) a n d the refractive index also becomes lower. Oleie acid constitutes about 80~% of the total lipids a t the end of the period, while linoleic a c i d , initially present at the 35% level, drops to approximately 15:~o. STUDY o~ GREEK OLIVE OIL. VI. OLIVE OIL CROP, 1961-1962. Anon. (Ministry of Commerce, K i n g d o m of Greece, Special Experimental Lab., Canningos Sq., Athens, Greece). 85 pp., 35 tables (1962). Analyses are given for 518 samples of olive oil f r o m all producing districts in Greece. Oil from short-sized kernel olives was of lower iodine value t h a n oil f r o m larger-slzed kernel olives. Yariations in climatic conditions h a d no effect on oil properties. COL0a 1%EVERSION IN SAPONII~ICATION. ELIMINATION OF REVEESION PRODUCTS BY S_~LTING OUT. IV[. G. Lechartier (Lab. J e a n Ripert, Paris, F r . ) . Rev. Franc. Corps Gras 10, 19-23 (1963). I t has been shown t h a t by salting out, using a suitable salt concentration, and the successive washing of the different phases used in the m a n u f a c t u r e of soap (saponification, cooking, liquidation, etc.) an improvement in the color of finished soap can be accomplished. Oxidized acids which are responsible for color reversion are removed with the salting out procedure. COI%{PAR3~TIVE S T U D Y OF TI{E INFLUENC]~ OF O E E T A I N P H Y S I O A L AND CHEMICAL PACTORS UPON THE PEROXIDE AND CARBONYL VALUE. F. Birden, Y. L a u c h a r d and M. Loury (Lab. J. Ripert, Inst. Corps Gras, Paris, F r . ) . Rev. Franc. Corps (Continued on page 34)

31

ABSTRACTS: F A T S AND 0 I L S ( C o n t i n u e d f r o m p a g e 31) Gras 10, 1~o. 2, 79~85 (1963). I n order to b e t t e r u n d e r s t a n d t h e p r a c t i c a l significance of t h e c a r b o n y l value, t h e a u t h o r s h a v e b e e n able to d e m o n s t r a t e b y t h i s s t u d y t h a t t h e variation of t h e carbonyl v a l u e u n d e r t h e influence of v a r i o u s chemical a n d p h y s i c a l f a c t o r s is m u c h s m a l l e r t h a n t h a t of t h e peroxide v a l u e u n d e r t h e s a m e conditions. T h e earbonyl v a l u e c o n s e q u e n t l y r e p r e s e n t s to a b e t t e r degree t h e alteration of f a t t y m a t e r i a l s .

• Fatty Acid Derivatives S~REOIS0~E~ I ~ 0 R ~ T I O N oN TH~ (~ZONIZA~ON OF ~SI"~RS OP I~ONOUNSATURATRD FATTY 2~CIDS. O. S. P r i v e t t a n d E. C. Iqickell ( U n i v . of M i n n e s o t a , T h e H o r m e l Inst., A u s t i n , M i n n . ) . J. Lipid Res. 4, 208-211 (1963). The formation of stereoisomers of ozonides on t h e ozonization of m e t h y l esters of m o n o u n s a t u r a t e d f a t t y acids i n p e n t a n e a t --70C was demonstrated by thln-layer chromatography, infrared spectra, a n d other analyses. T h e c~s- a n d trans-isomers of ozonides of vis- a n d trans-methyl 9-octadecenoates ( m e t h y l oleate a n d m e t h y l elaidate) were isolated a n d characterized. THE SYNTHESIS Ol~ KETONES ~ROI~I ACID C'HL01%ID]~S WITI~ THE H~LP OP ALUI~IINUI~ ALKYLS. H . B e r t s c h a n d H . Relnheckel ( I n s t . F e t t c h e m i e , Deut. A k a d . W i s s e n s c h a f t e n , Berlin-Adlers h o f ) . Fette Seifeu Anstrichmittel 54, 881-886 (1962). A n u m b e r of a l i p h a t i c a n d s o m e a r o m a t i c acid chlorides were t r e a t e d w i t h ethyl a l u m i n u m - s e s q u i c h l o r i d e in a l i p h a t i e hydroc a r b o n s as t h e solvent. T h e c o r r e s p o n d i n g ethyl ketones were f o r m e d in yields of 80 to 85%. T h e behavior of diearboxylie acid h a l f - e s t e r chlorides a n d dicarboxylic acid dichlorides a n d the influence of other r e a c t i o n conditions as well a s other ethyl a l u m i n u m c o m p o u n d s were i n v e s t i g a t e d . T h e s y n t h e s i z e d c o m p o u n d s were: hexanone-3, octananone-3, decanonane-3, dodecanone-3, teradeeanone-3, hexadecanone-3, oetadecanone-3 a n d eicosanone-3. T h e following keto esters were s y n t h e s i z e d : 10-ketolaurate, a n d 6-ketocaprate ( m e t h y l esters). Tetradecadione-3,12,- w a s also p r e p a r e d . Complete p h y s i c a l c o n s t a n t s a n d c o n s t a n t s of derivatives are given. T h e p r e p a r a t i o n of v a r i o u s a l u m i n u m alkyls is also given. DIELS

ALDER

REAC~TIONS

IN

THE

FIELD

01~ FATS"

II:

THE

REACTION O1~ DRYING OILS WITI-I ETtI:YLEN]~ A N D ITS H01~OLOGFES. H. P . K a u f m a n n a n d F. J. B u s c h e r (Deut. I n s t . F e t t f o r s e h , M i i n s t e r ) . Fette Seifen AnsSrichmittel 55, 105108 (1963). M e t h y l esters of c o n j u g a t e d acids were r e a c t e d with ethylene, propylene, a n d b u t y l e n e a t h i g h p r e s s u r e a n d high temperature. T h e Diels Alder a d d u c t was t h e n t r a n s f o r m e d into t h e c o r r e s p o n d i n g a r o m a t i c s y s t e m s . C o n j u g a t e d polyene oils were also s u b j e c t e d to these r e a c t i o n conditions. I n f r a r e d s p e c t r a are given. The a d d u e t s p r e p a r e d were: l-carbomethex'y-4-methyl-cyclohexene 5, t h e 2,4-dimethyl acid; the 2-ethyl-4-methyl d e r i v a t i v e ; 1-(carbomethoxy-n-heptyl)(4-n-hexyl) -cyclohexene-5, the 4-n-hexen-l-yl, 2-methyl-4( n - h e x e n - l - y l ) - , a n d t h e 2 - e t h y l - 4 - ( n - h e x e n - l - y l ) - derivatives. I~IGI:[LY UNSATURATED ~ATTY ACID CHLORIDES. ~I. P. I ~ a u f m a n n a n d E. G u l i n s k y (Deut. I n s t . F e t t f o r s c h u n g , M i i n s t e r ) , F e t t e Seifen Anstrivhmittel 64, 599-601 (1962). The chlorides of linolenic acid, a- a n d fl-elaeostearic acid, a n d a - p a r i n a r l c acid were p r e p a r e d u s i n g p h o s g e n e a n d p y r i d i n e with app r o p r i a t e solvents. The r a t e s of a u t o x i d a t i o n o f these comp o u n d s were d e t e r m i n e d a n d c o m p a r e d to those of the corr e s p o n d i n g a c i d s a n d m e t h y l esters. BIS-CYANOETHYLA.TION OF I~ATTY A.MINES. I. SYNTHEiSIS OF BIS(fl-CYANOE~YL)C~YL.~IN~. Seimei N i t a n a i a n d ¥ a s u o Saito ( T o y o K o a t s u Co., I t o k k a i d o ) . Y u k a g a k u 12, 154-8 (1963). T h e c y a n o e t h y l a t i o n r e a c t i o n of e c t y l a m i n e was investigated. The velocity of f o r m a t i o n of m o n o c y a n o e t h y l c o m p o u n d w a s v e r y rapid. The reaction f o r f o r m a t i o n of bis(cyanoethyl) c o m p o u n d took place a f t e r t h e monoc y a n o e t h y l a t i o n reaction. T h e f o r m a t i o n of t h e b i s - c o m p o u n d was very slow w i t h o u t t h e solvent. T h e velocity f o r f o r m a tion of b i s - c o m p o u n d in p o l a r solvents, such as m e t h a n o l or ethanol, w a s very r a p i d a n d the* yield w a s q u a n t i t a t i v e in some cases. The r e a c t i o n in the non-polar solvent, such as benzene or toluene, gave t h e m o n o - e o m p o u n d only a n d little or no bis-compound. T h e reaction in m e t h a n o l in t h e presence of s o d i u m h y d r o x i d e gave q u a n t i t a t i v e yield of m o n o - c o m p o u n d . T h e r e a c t i o n in m e t h a n o l was n o t influenced b y the a d d i t i o n of acetic acid. 34

~IYDROXYI~ETHYLATIOI~ OF TALL OIL ROSIN. Choiehiro Hirai, K a z u m i t s u Suzuki, a n d T a r o M a t s u m o t o ( N i h o n Univ., " Tokyo). Y u k a g a k u 12, 149-53 (1963). A b i e t i c acid conc e n t r a t e d f r o m tall oil rosin w a s m a d e to r e a c t with f o r m a l d e h y d e f o r 30=60 m i n u t e s in acetic acid or propionic acid to give 8 , 9 ~ b i s ( m e t h y l e n e a c e t o x y ) - a b i e t i c acid; t h e cyelohexylam i n e salt, m. 180C. H y d r o l y s i s of t h i s c o m p o u n d gave 8,9d i h y d r o x y m e t h y l a b i e t i c acid, m. 1 9 2 - 3 C . T h e r e a c t i o n of tall oil r o s i n w i t h f o r m a l d e h y d e in t h e absence of carboxylie acid or i n e r t solvent such as dioxane a n d b e n z e n e did n o t occur, b u t t h e c o n d e n s a t i o n of tall oil rosin w i t h formaldeh y d e w a s p r o m o t e d in the presence of a s m a l l a m o u n t of acetic acid, or even i n h i g h e r f a t t y acid. T h e above reaction w a s also c a r r i e d o u t in the presence of hydrochloric acid, b u t this yielded l a r g e a m o u n t s of ether-insoluble m a t t e r .

• Biology

and N u t r i t i o n

ENZYMATIC SYNTHESIS OF OYCLOPROPANEI FATTY ACIDS CATALYZED BY BACTERIAL ]gXTRAGTS. H . Zalkln, 3. I-I. L a w , a n d tI. Goldfine ( J a m e s B r y a n t C o n a n t Lab., H a r v a r d Univ., C a m b r i d g e 38, M a s s . ) . J. Biol. Chem. 238, 1242=1248 (1963). E x t r a c t s of either Serratia m arceseenv Or Clostridium butyrieum a r e capable of f o r m i n g labeled cyclopropane f a t t y acids w h e n t h e y are i n c u b a t e d with S - a d e n o s y l m e t h i o n i n e labeled in t h e m e t h y l g r o u p . M e t h i o n i n e itself is n o t a n effective p r e c u r s o r ; n e i t h e r are other 1 c a r b o n donors such as f o r m a t e , f o r m a l d e h y d e , a n d serine. T h e e n z y m e s y s t e m of Serratia marcescens c o n t a i n s endogenous l i p i d s u b s t r a t e s for t h i s rea c t i o n which c a n n o t be removed or replaced b y simple m a n i p u lations. V a r i o u s u n s a t u r a t e d f a t t y acid derivatives f a i l to e n h a n c e t h e r a t e of the reaction. O p e r a t i o n s w h i c h are o r d i n a r i l y e m p l o y e d to remove s m a l l cofactor molecules f r o m e n z y m e s do n o t d i m i n i s h the r a t e of r e a c t i o n catalyzed b y these e x t r a c t s . RAPID APPBARANCE OP INJECTI~D FAT IN THE GUT O1~ A RAT. D. J. W i l k i n s ( N e w E n g l a n d I n s t . f o r Med. Res., Ridgefield, Coral.). t~roc. Soc. Exp. Biol. Med. 112, 953-955 (1963). Oil e m u l s i o n s c o n t a i n i n g a fluorescent dye were g i v e n intravenously to r a t s . R a t e of r e m o v a l f r o m t h e blood s t r e a m w a s t y p i c a l f o r reticuloendothelial clearance of a colloid. The emulsion a c c u m u l a t e d in t h e liver b u t a p p e a r e d i n t h e bile d u c t a n d d u o d e n u m w i t h i n m i n u t e s a f t e r injection. A p p r o x i m a t e l y one-half of the dye was f o u n d in the i n t e s t i n a l contents. CARCINOGE~NIC EFFECT OP EGG WHITE:~ EGG YOLK AND LIPIDS IN ~ICE. J. Szepsenwol (Dept. of A n a t o m y , Univ. of P u e r t o Rico School of Med., S a n J u a n ) . l~roc. Soe. Exp. Biol. Me& 112, 1073-10'76 (1963). Mice of the T. M. S t r a i n were m a i n t a i n e d f r o m t h e a g e of 4 weeks on t h e Rockland r a t diet ( G r o u p 1) s u p p l e m e n t e d w i t h h a r d boiled e g g white ( G r o u p 2), r a w e g g yolk (Group 3) or with cholesterol a n d lard (Group 4). I n one series of e x p e r i m e n t s m a l e s a n d f e m a l e s were c a g e d separately, while in the other one t h e y were b r e d a n d t h e i r o f f s p r i n g m a i n t a i n e d on the s a m e diets. Each of the g r o u p s of the second series of e x p e r i m e n t s consisted of mice f r o m 3 to 4 successive g e n e r a t i o n s . T h e r e s u l t s were: The mice of Groups 2 a n d 3 developed a very h i g h incidence of l y m p h o s a r c o m a a n d l u n g a d e n o c a r c i n o m a . The mice of G r o u p 3 developed, also a relatively high incidence of m a m m a r y cancer (33% of t h e b r e e d i n g f e m a l e s ) which did n o t a p p e a r in t h e a n i m a l s of Group 2 nor in the controls. I n c i d e n c e of m a m m a r y cancer was p a r t i c u l a r l y h i g h in the mice of G r o u p 4. F r o m these r e s u l t s it a p p e a r s t h a t b o t h e g g white a n d e g g yolk are carcinogenic, b u t t h a t their c a r e i n o g e n i c i t y differs. A carcinogenic s u b s t a n c e c a u s i n g the d e v e l o p m e n t of l y m p h o s a r e o m a s a n d l u n g a d e n o c a r c i n o m a s , would be p r e s e n t in both, while a m a m m a r y carcinogen, lipid in n a t u r e , is p r e s e n t in the yolk only. RUMINANT FAT I~ETAROLISI~ WITIt PAI~TICIILAI~ REIqVE~ENCE TO FACTORS AFF'ISCTING LOW I~ILK I~AT AND FREED EIPFICIEN:CY. A ltEVIEW. P. J. V a n Soest ( A n i m a l H u s b a n d r y Res. Div., Agr. lies. Service, U S D A , Beltsviile, M d . ) . J. Dairy Scg. 45, 204-216 (1963). U p to t h e p r e s e n t time, r u m i n a n t n u t r i t i o n research h a s followed two p r i n c i p a l lines of development. On the one h a n d , t h e r e are f e e d i n g e x p e r i m e n t s t u d i e s which deal with i n p u t - o u t p u t m e a s u r e m e n t s , digestibility, a n d effieiencies. On t h e o t h e r h a n d , t h e r e a r e n u m e r o u s biochemical studies d e a l i n g w i t h rumen, r u m e n a b s o r p t i o n , a n d intermediary metabolism. The biochemical a p p r o a c h offers a m e a n s of e x p l a i n i n g a n d u n d e r s t a n d i n g t h e o b s e r v a t i o n s m a d e f r o m f e e d i n g e x p e r i m e n t s , b u t r e s e a r c h in this a r e a h a s really JOURNAL A.0.C.S., JULY 1963 (VoL. 4O)

~kBSTRACTS:

BIOLOGY AND ~UTRITIOI~

only begun. Certain phenomena, such as low milk f a t on various rations, offer opportunities to learn more a b o u t littlek n o w n aspects of r u m i n a n t metabolism. The i n t e r m e d i a r y steps involved in the p r o d u c t i o n of milk solids represent one area in which f u r t h e r research is badly needed. I t is proposed here to review the literature on low milk f a t and certain environmental a n d physiological factors known to affect the f a t content of milk, a n d to compare these conditions in light of their a p p a r e n t effects on the over-all efficiency and p e r f o r m a n c e of cattle. ESSENTIAL FATTY ACSD DEFIC~EIqCY AND RAT LIVE~ H01MOGISNATE 0xn)~Tm~s. 5. Smith and H. ]~. DeLuca (Dept. of Biochem., Univ. of Wisconsin, Madison). J. 2iutr. 79, 416-42'2 (1963). Essential f a t t y acid deficiency ( E F A ) in rats, whether induced b y a diet containing no f a t or a large q u a n t i t y of s a t u r a t e d fat, results in an increased oxidation of practically all of the citric acid cycle intermediates, pyruvate, and eaprylate b y liver homogenates. This increase was detectable a f t e r r a t s were fed a high f a t diet f o r two weeks, and a f a t - f r e e diet f o r f o u r weeks. These elevated oxidative rates were reduced to the normal r a n g e within one week a f t e r feeding a source of E F A . F r a e t i o n a t i o n of liver homogenates revealed t h a t the greatest effect of E F A deficiency is associated with the debris fraction. However, the isolated mitoehondria f r o m deficient r a t s showed an increased oxidation rate when the results were expressed on an equivalent n i t r o g e n basis. PURIt~ICATION 0t~ HUMAN PLASMINOGE:N AND PLASMIN BY GEL FILTRATION ON SE~'HABEX AND tYIROMATOGRAPHY ON I)IE~HYLAMINOETttYL-SEPHADEX. K. 0. B o b b i n s and L. S u m m a r l a (Biochem. Res. and Development Dept., Michael l~eese Res. F o u n d a t i o n , Chicago 16, Ill.). J. Biol. Chem. 238, 952-962 (1963). P l a s m i n o g e n can be p r e p a r e d in a highly purified f o r m f r o m h u m a n p l a s m a F r a c t i o n I I I : . 8 b y a modification of the Kline method followed by either gel f i l t r a t i o n t h r o u g h Sephadex columns or c h r o m a t o g r a p h y on D E A E - S e p h a d e ~ columns, with s t a r t i n g agent development conditions. The m a j o r modification of the Kline m e t h o d was to precipitate the plasminogen, in the final step, at p H 6.0, with NaH2POd. Plasminogen, of the same purity, can also be p r e p a r e d by directly c h r o m a t o g r a p h i n g extracts of p l a s m a F r a c t i o n III2.3 on D E A E - S e p h a d e x columns.

~Tl~UCTURE AND' SYNTHESIS 0]P MILK I~AT. IV. ROLE OF THE MAMMARY GLAND WIll{ SPI~CIAL I~EI°EI%E;NC~I5TO THE. ~tt0L~STEROL ESTERS. S. P a t t o n a n d R. D. McCarthy (Dept. of D a i r y Sei., Penn. State Univ., University P a r k ) . J. D a i r y Sci. 46, 396-400 (1963). The extent to which milk lipids are synthesized within the m a m m a r y gland is not known. The objective of the research w a s to provide a b e t t e r definition of w h a t the gland accomplishes, as distinguished f r o m w h a t m a y be contributed by lipid metabolism in the rest of the body. U s i n g i n t r a m a m m a r y i n f u s i o n of both labeled a n d unlabeled f a t t y acids, it w a s demonstrated t h a t cholesterol esters, glycerides, and phospholipids of milk are all made f r o m f a t t y acids within the gland. Diverse evidence f r o m this and other studies s u g g e s t s t h a t most, if not all, of the ester lipids of milk are synthesized front a common pool of f a t t y acids within the m a m m a r y gland. A r e m a r k a b l y active metabolic role is indicated for the cholesterol esters of milk. I n the case of both labeled (pa]mitate-l-C ~) and unlabeled (linoleate) infusates, u p t a k e by the cholesterol ester fraction w a s more intense and, by tracer, more r a p i d t h a n f o r the glycerides or phopholipids. Some compositional d a t a on cholesterol esters of milk are also presented. MACE0- AND 1VfIC'~ROM~ETtIODS I~OR Tt{]5 DETERMINATION OF SEEUI~ ¥ITAMII~ A USING TI%IPLUOROACETIC ACID. ~. E. Neeld, J r . a n d W. lXl. P e a r s o n (Div. of N u t r i t i o n , Dept. of Bioehem. and Med., V a n d e r b i l t Univ., School of Med., Nashville, T e n n . ) . J. N u t r . 79, 454-462 (1963). A new m e t h o d f o r the determination of p l a s m a or serum v i t a m i n A levels which uses trifluoroacetic acid ( T F A ) as the chromogen is described. This r e a g e n t produces a typical Carr-Price color b u t does not exhibit the t u r b i d i t y or f i l m - f o r m i n g properties of SbCls in the presence of moisture. The new procedure gives values t h a t agree well with those obtained b y the Carr-Priee method when rat, porcine, or h u m a n sera are analyzed. Significantly higher values are obtained with T F A , however, when bovine sera were analyzed. A micro- modification of the method p e r m i t t i n g the analysis of 50 ~1 of serum is described and its a d v a n t a g e s over existing methods are discussed. VITAMIN A AND CtIOL~STEEOL ABSORPTION IN THE C'HICKE~'~. B. E. March and J . Biely (Dept. of P o u l t r y Sci., Univ. of 36

British Columbia, Vancouver, C a n a d a ) . J. N u t r . 79, 474-478 (1963). The a d m i n i s t r a t i o n of large a m o u n t s of vitamin A to 6- to 7-week-old chickens reduced the increase in serum cholesterol level resulting f r o m the inclusion of 1% of cholesterol in the diet. V i t a m i n A did not, however, moderate the hyper]ipemia and hyperclmlesterolemia produced in birds f e d a low cholesterol diet and treated with diethylstilbestrol. L a r g e doses of v i t a m i n A reduced the level of cholesterol in the intestinal wall and in the liver of b i r d s fed 1% of cholesterol. Conversely, birds receiving large a m o u n t s of vitamin A and 1% of cholesterol in the diet did not store as much v i t a m i n A in the liver as birds receiving the same a m o u n t of v i t a m i n A in conjunction with a diet low in cholesterol. I t is concluded t h a t there is m u t u a l interference between v i t a m i n A and cholesterol during the course of a b s o r p t i o n across the intestinal wall. M~TABOLISM 0P GLYC~I~OLIPIDS. I I I . REACTIVITY 0P VARIOUS ACYL ESTERS O1~ COEI'TZYM]~ A WITH a'-ACYLGLYCERO-Pt-I0'SPHOI%YLCHGLINE~ AND POSITIONAL SPEC'IFICITIES IN LECITHIN SYN~H~.SIS. W. E:. M. L a n d s and L Merkl (Dept. of Biol. Chem., Univ. of Michigan, A n n A r b o r ) . J. Biol. Chem. 238, 898-903 (1963). R a t liver nficrosomes catalyze the t r a n s f e r of acids f r o m their aeyl coenzyme A derivatives to the fl-hydroxyl group of a'-acylglycerophosphorylcholine to f o r m lecithin. The u n s a t u r a t e d acyl coenzyme A esters react more rapidly t h a n the s a t u r a t e d derivatives. H y d r o l y s i s of acyl coenzyme A in this system does n o t a p p e a r to be due to t r a n s f e r of the acyl g r o u p to water b y the aeyl t r a n s f e r a s e , b u t r a t h e r to a s e p a r a t e hydrolytic enzyme with different kinetic properties. This microsomal system can be used to estimate the relative content of the positional isomers in acylglyeerophosphorylcholine p r e p a r a t i o n s . Results with mixed acylglycerophosphorylcholine aceeptors indicate t h a t the acyl t r a n s f e r occurs with a p r e f e r e n t i a l esterification of s a t u r a t e d f a t t y acids with the a'-hydroxyl group a n d u n s a t u r a t e d acids with the fl-hydroxyl group. IV. SYNTHiESIS OF Pt{OSPt{ATIDYLETHANOLAMIN~. I. Merkl and W. E. M. Lands. I b i d , 905-906. Stereospecifically labeled radioactive diacylglyeerophosphorylethanolamine may be synthesized f r o m either a'- or fl-acylglycerophosphorylethanolamine b y use of a r a t liver microsomal p r e p a r a t i o n . Linoleate was a b e t t e r s u b s t a r t e t h a n stearate in e s t e r l f y i n g a'-acylglycerophosphorylethanolamine, whereas the reverse was true with the fl-acyl precursor. INITIAL REACTIONS IN THE M]~TABOLISM OF D- AND L-GLYCEI~ALDEHYDE BY RAT LIVER. B. R. L a n d a u a n d W. Merlevede (Dept. of 3/fed. and Bioehem., W e s t e r n Reserve Univ., Cleveland 6, Ohio). J. Biol. Chem. 238, 861-867 (1963). Marked activity in carbon a t o m s 3 a n d 4 of glucose f r o m glycogen was observed when D-glyceraldehyde-3-C 14 was a substrate. This indicates t h a t an initial step in D-glyceraldehyde metabolism is reduction to glycerol. With D-fructose-6-C 14 as substrate, activity w a s p r i m a r i l y in carbon a t o m s 1 and 6 of the glucose, indicating the if D-glycera]dehyde is f o r m e d f r o m f r u c t o s e within the liver, it is not reduced to glycerol b u t r a t h e r enters the Embden-Meyerhof p a t h w a y via glyceraldehyde phosphate. B o t h L-sorbose-6-C~ and L-glyceraldehyde3-C~ yield glucose labeled p r i m a r i l y in carbon atoms 1 and 6 with more activity in carbon 6 t h a n carbon 1. This suggests t h a t L-glyceraldehyde presented to the liver and t h a t f o r m e d f r o m L-sorbose within the liver traverse the same p a t h w a y s . M]~]TABOLISM A~ND BIOLOGICAL AC'TIVITY O1~ VITAMIN A AC~D IN TH]~ CHICK. S. I { r l s h n a m u r t h y , J. G. Bieri and E. L. A n d r e w s (Lab. of N u t r . and Endocrinology, N a t ' l I n s t . of A r t h r i t i s a n d Metabolic Diseases, N I t t , Bethesda, M d . ) . J. N u t r . 79, 503-510 (1963). The a m o u n t of vitamin A acid required to p r e v e n t vitamin A deficiency s y m p t o m s in chicks depended u p o n the time dosing b e g a n relative to the onset of symptoms. The acid was f o u n d to have a s p a r i n g action on vitamin A in the body. W h e n vitamin A acid was the only source of the vitamin in the diet, chicks grew and developed n o r m a l l y d u r i n g a 6-week experimental period. W h e n the acid was given in daily oral doses, a m o u n t s up to 100 #g would not completely prevent development of ocular or central nervous system lesions, a l t h o u g h g r o w t h w a s normal. W h e n a l a r g e oral dose was given, the unchanged vitamin A acid could be detected in the tissue up to 18 hours, b u t not a f t e r this time. No other f o r m of v i t a m i n A was detected. The acid w a s f o u n d to be concentrated prim a r i l y in the microsomal f r a c t i o n of liver. Experiments with C~ vitamin A acid confirmed the r a p i d metabolism or destruction which b e g i n s in the digestive tract. Four JOURNAL A.O.(].S., JULY 1963 (VOIJ.40)

ABSTRACTS: BIOLOGY AND NUTRITION radioactive fractions, based on solubility, were p r e p a r e d f r o m chicken liver a f t e r a dose of C ~ vitamin A acid. Two of these represented the u n c h a n g e d acid. while a t h i r d fraction, f a t soluble, gave no reaction with antimony trichloride. A f o u r t h f r a c t i o n was w a t e r soluble. I n a rat curative assay, the third f r a c t i o n h a d biological activity b u t f r a c t i o n 4 did not. No evidence was obtained for the conversion in the body of vitamin A acid to the aldehyde or alcohol. BIOSYNTH]dJSIS 0E BRANCHED CHAIN I~ATTY ACIDS. I. ISOLATION AND IDE~Tn~ICATION O1~ FATTY ACIDS I~R0~I BAC*ILLUS SUBTILIS (A~0C 70'59). T. K a n e d a (Research Council of Alberta, Edmonton, Alberta, C a n a d a ) . J. Biol. Chem. 238, 122.2-12'28 (1963). Six b r a n c h e d chain f a t t y acids and two s t r a i g h t chain f a t t y acids have been isolated f r o m Bacillus subtil~s (ATOC 7059) g r o w n on a glucose-yeast extract-Bacto-peptone medium. The identification of the f a t t y acids was carried out by gasdiquid c h r o m a t o g r a p h y and by their i n f r a r e d spectra, x-ray diffraction, melting points, and neutralization values. The f a t t y acids identified are 12-methyltetradecanoic, 14-methylhexadeeanoie, isopentadecanoic, isopalmitic, palmitic, isoheptadecanoic, isomyristie, and myristic, in order of abundance. INPLUENCE 01~ DIETARY VITAMIN E AND SELENIUM ON DISTRIBUTION 0'V SE75 IN THE CHICK. L. S. Jensen, E. D. W a l t e r and J. S. D u n l a p (Dept. of P o u l t r y Sci. and V e t e r i n a r y Pathology, W a s h i n g t o n State Univ., P u l l m a n ) . Proc. Soc. E x p . Biol. Med. 112, 89'9-901 (1963). Three-week-old chicks f e d either a v i t a m i n E deficient or supplmented diet were intraperitoneally injected with Se 75, a n d distribution of the isotope was determined in various tissues at 24, 48, and 168 h o u r s a f t e r injection. Similarly, 2-week-old chicks fed a selenium deficient or supplemented diet were given an oral dose of Se 75 and the distribution of the isotope in several tissues was determined at 24 and 168 hours a f t e r administration. V i t a m i n E had no effect on distribution of selenium, b u t selenium itself had a marked effect on the uptake and retention of radioselenium. One-half of the dose was retained by selenium-deficient chicks at 7 days, whereas only 1/.~ of the dose was retained b y chicks fed 1 p p m selenium f r o m day-of-age. Considerable selenium was deposited and retained in the cerebellum of chicks even though this element cannot p r e v e n t encephalomalacia.

COMPOSITION OI~ DIETARY FAT AND THE ACCUMULATION OF LIVEa LIPID IN THE CHOLINE-DEFICIENT RAT. t . I w a m o t o , E. E. Hellerstein and D. M. H e g s t e d (Dept. of Nutr., H a r v a r d School of Public Health, Boston, Mass.). J. N u t r . 79, 488492 (1963). Under the conditions used, a two-week assay period and with a diet containing 12% casein, the accumulation of liver lipid in the choline-deficient r a t a p p e a r s to be inversely related to the degree of u n s a t u r a t i o n of the dietary fat. The composition of the fat, r a t h e r t h a n the a m o u n t in the diet, was th e m a j o r factor h~fluencing the a m o u n t of liver lipid. The results obtained are, however, dependent upon the basal diet used and the d u r a t i o n of the experiment. The similarity of the conclusions reached in these studies with those relating dietary oils to serum cholesterol in m a n indicate t h a t possibly similar f a c t o r s are involved. PROTEIN~ CARBOHYDRAT]~] AND ~AT CONTENT O1~ THE DIET OF THE I~AT AS REI~ATED TO GROWTH. E. E. Howe a n d E. W. Gilfillan (l~erck I n s t . f o r Therapeutic Res., Rahway, I~. J . ) J. N u t r . 79, 395-398 (1963). Addition of 9~% corn oil to the diet of r a t s receiving suboptimal protein and corn starch as a source of c a r b o h y d r a t e decreased food consumption and depressed growth. These effects were not observed if glucose replaced starch in the diet. I m p r o v e m e n t of the p r o t e i n of the diet, quantitatively or qualitatively, eliminated the difference in p e r f o r m a n c e of animals receiving starch and glucose. Replacement of corn oil b y other f a t s caused g r o w t h depression of r a t s receiving a starch diet. Linseed oil and cod liver oil also caused a g r o w t h depression in glucose low-protein diets. Addition of ehlortetraeycline eliminated the g r o w t h - d e p r e s s i n g effect of adding corn oil to the diets of low-protein starch fed rats. Oxytetraeyeline, penicillin, neomycin, streptomycin a n d sucMnylsulfathiazole were less effective or w i t h o u t effect. LIPID ANTIOXIDANT ACTIVITY IN TISSUES AND PROTEINS OF SELENIU~-~EID ANIMALS. J . W. H a m i l t o n and A. L. Tappel (DIP. of Agr. Biochem., Univ. of W y o m i n g , L a r a m i e , W y o m ing and Dept. of F o o d Sci. & Teeh., Univ. of Calif., D a v i s ) . J. N u t r . 79, 49'3-502 (1963). Lipid a n t i o x i d a n t activity of lipid-free tissue fractions, f r o m control a n d selenium-fed chickens, rats, a n d sheep was studied. Animals were fed

38

l0 or 14 p p m of selenium supplied either as sodium selenite or sodium selenate added to a nutritionally adequate basal ration. A n t i o x i d a n t activities of the tissue f r a c t i o n s were tested b y m a n o m e t r i c and p o l a r o g r a p h i e techniques. Kidney f r a c t i o n f r o m sheep contained the highest antioxidant activity. A n t i o x i d a n t activity was shown to be associated with the tissue selenoproteins. Selenium a n t i o x i d a n t s were f o u n d to possess 50,0 times the a n t i o x i d a n t activity of a-tocopherol by the p o l a r o g r a p h i c method and 50 to 100 times in the manometric method. Synergism between a-tocopherol and the tissue selenium was not large. STUDIES 01~ CHOLESTE]~0L BIOSYNTHESIS. IV. REDUCTION" OF LANOSTE~OL TO. 24, 25 -DIHYDROLANOSTEROL BY R~T LIVEI~ IIO~OOENATES. J . Avigan, D. W. S. Goodman, and D. Steinb e r g (Lab. of Metabolism, N a t ' l H e a r t Inst., Bethesda 14, Md.). J. B~ol. Chem. 238, 1283-1286 (1963). The anaerobic reduction of labeled lanosterol, biosynthetically p r e p a r e d f r o m 2-C14-mevalonic acid, to 24,25-dihydolanosterol has been denmnstrated w i t h r a t liver homogenates. E n z y m a t i c activity was associated with cell particles, mostly with mierosomes, and required reduced t r i p h o s p h o p y r i d i n e nucleotide. The enzyme was completely inhibited on addition of N-ethyhnaleimide or p-ehloromercuribenzoate, a n d did not require a divalent cation f o r activity. A t t e m p t s to demonstrate the reversibility of side chain reduction of lanosterol d u r i n g both anaerobic a n d aerobic i n c u b a t i o n s were not successful. Trip a r a n o l and two other inhibitors of cholesterol biosynthesis blocked the reduction of b o t h lanosterol and desmosterol in vitro. Unlabeled lanosterol or desmosterol added to the incubation m e d i u m caused a comparable inhibition of reduction of C~-lanosteroL I t is possible t h a t a single enzyme is responsible f o r the reduction of both sterol substrates. V. THE TIME COURSE AI~!D PATHWAY 01~ THE LATE~ STAGES OF CI~OLESTEROL BIOSYNTHESIS IN THE. LIVERS O1~ INTACT RATS. D. W. S. Goodman, J . A v i g a n a n d D. Steinberg. I b i d , 12871293. Studies have been conducted of the time course of the d i s t r i b u t i o n of radioactivity in r a t liver nonsaponifiables at several short intervals a f t e r the intravenous injection of 2-Cl~-DL-mevalonie acid. Recently developed thin layer c h r o m a t o g r a p h i c techniques were employed that p e r m i t separation of m a n y of the sterol intermediates in cholesterol biosynthesis. B o t h normal and t r i p a r a n o l - f e d r a t s were studied, and biochemical techniques were used to aid in the identification of some of the intermediate compounds. The evidence presented s u g g e s t s t h a t the radioactivity in the intermediate zone f r o m n o r m a l r a t s was contained in a Cis sterol mixture containing compounds with both s a t u r a t e d and u n s a t u r a t e d side chains. The results also indicate t h a t in normal r a t s no significant radioactivity was contained in AT"~-cholestadienol or in zymosterol, whereas m a j o r a m o u n t s of radioactivity were present in one or both of these compounds in triparanoltreated rats. THE CONDENSATION REACTION OF I~ATTY ACID BIOSYNTHESIS. II. REQUIREMENT O1~ THl~ ENZYME.S 0~~ THE CONDENSATIOI'7 REACTIOI~- F01~ FATTY ACID SYNTHESIS. P. Goldman, A. W. Alberts, and P. R. Vagelos ( E n z y m e See., Lab of Cellular Physiology, N a t ' l H e a r t Inst., N I H , Bethesda 14, Md.). J. Biol. Chem. 238, 1255-1261 (1963). Soluble bacterial synthetase s y s t e m s f r o m C l o s t r i d i u m k l u y v e r i and Escherickia coli have been shown to catalyze the synthesis of long chain f a t t y acids f r o m malonyl coenzyme A, acetyl coenzyme A, and reduced t r i p h o s p h o p y r l d l n e nucleotide. Saturated fatty acids are produced in the system f r o m C. k l u y v e r i where a requirement f o r flavin mononucleotide and an unidentified cofaetor have been found, whereas in the E. coli s y s t e m both saturated a n d u n s a t u r a t e d f a t t y acids are produced. The two synthetase systems have been fractlonated, and over-M1 f a t t y acid synthesis has been shown to be dependent on the same heat-stable and heat-labile enzymes t h a t catalyze the condensation reaction as m e a s u r e d by the malonyl coenzyme A-CO2 exchange reaction. I n contrast, the synthesis of but y r a t e in C. kluyver,~ extracts requires neither malonyl coenzyme A n o r the enzymes t h a t catalyze the condensation reaction. THE INCORP01~ATION OF LABELED PALMITIO ACID INTO THE PHOSPHOLIP~DS 09 N01~AL AND FATT~ LIVE~S. J. L. Glenn, E. Opalke, a n d K. Tischer (Dept. of Biochem., A l b a n y l~ed. College of U n i o n Univ., A l b a n y 8, ]q. Y . ) . J. Biol. Chem. 238, 1249-1254 (1963). P a l m i t i e acid-l-C ~ was rapidly incorporated into n o r m a l r a t liver phosphatides, w i t h the exception of phosphatidylserine. Phosphatidylserine was re(Continued on p a g e ~0)

JOURNALA.O.C~.S., JULY 1963 (VOL. 40)

ABSTRACTS: BIOLOGY AND N U T R I T I O N ( C o n t i n u e d f r o m p a g e 38) solved ~nd identified as a s e p a r a t e f r a c t i o n b y silicic acid c o h m n c h r o m a t o g r a p h y . A p r o n o u n c e d decrease in p a l m i t a t e i n c o r p o r a t i o n into p h o s p h a t i d y l e t h a n o l a m i n e occurred in f a t t y liver ~ f t e r cerium a d m i n i s t r a t i o n . T h i s decrease occurred a t a t i m e w h e n g r e a t e r p a l m i t a £ e i n c o r p o r a t i o n was observed into" p h o s p h a t i d y l i n o s i t o l a n d cardiolipin. INHIBITORY

AND

ACTIVATING

EFI~E;CTS

0F

POLYANIONS

0'N

LIPOPROTEIN LIPASEI. P. B e r n f e l d a n d T. F. Kelley (BioRes. Inst., C a m b r i d g e 41, M a s s . ) . J. Biol. Chem. 238, 12361241 (1963). T h e effect of m o r e t h a n 25 d i f f e r e n t s u l f a t e d p o l y s a c c h a r i d e s a n d of a f e w other p o l y a n i o n s on the activity in vitro of m o u s e h e a r t lipoprotein lipase was m e a s u r e d . All p o l y s a c c h a r i d e s u l f a t e s which c o n t a i n e d no s u l f o a m i n o g r o u p s a n d which h a d a t least 0.6 s u l f a t e ester g r o u p per r e p e a t i n g u n i t p r o v e d to be p o t e n t i n h i b i t o r s of t h e enzyme. This i n h i b i t i o n was i n d e p e n d e n t of the chemical n a t u r e of the polysaccharide, of the presence or a b s e n c e of b r a n c h i n g s therein, of the t y p e a n d configuration of i t s glycosidic bonds, of t h e presence or a b s e n c e of earboxyl or N - a c e t y l groups, as well as of its molecular weight. The s i m u l t a n e o u s occurrence of O - s u l f a t e a n d N - s u l f a t e g r o u p s in h e p a r i n a n d in other a c t i v a t o r s of l i p o p r o t e i n lipase is believed to be t h e cause f o r the coexistence of a n i n h i b i t o r y effect a t h i g h conc e n t r a t i o n s a n d of a n a c t i v a t i n g power at lower c o n c e n t r a t i o n s of the same polyanion. O - S u l f a t i o n of a p o l y s a c c h a r i d e was always a c c o m p a n i e d b y a n increase in its i n h i b i t o r y p o t e n c y ; b u t prior blocking of some of its free h y d r o x y l groups, e.g. b y n i t r a t i o n , protected it a g a i n s t O - s u l f a t i o n and, hence, prevented i t s conversion into a n inhibitor. ~TEIRILE AQUEOUS SOLUTIONS OF VITAMIN D AND CALCIUM SALT'S AND 1V~ETHOD 0 F ~ A K I N G THE SA]~[I~. J . S c h e n k ( W a n d e r Co.).

U.S. 3,089,3~2. A stable h e a t sterilizable a q u e o u s solution of a t h e r a p e u t i c a l l y active v i t a m i n D c o m p o u n d a n d a nontoxic c a l c i u m salt s u i t a b l e f o r p a r e n t e r a l a d m i n i s t r a t i o n comprises: a clear w a t e r solution of a non-toxic w a t e r soluble t h e r a p e u t i c a l l y active calcium salt a n d a t h e r a p e u t i c a l l y active v i t a m i n D ester of a f a t t y acid h a v i n g f r o m 1 to 5 carbon atoms. The solution c o n t a i n s a f a t t y acid ester of a polyoxyalkylene c o m p o u n d as a solubilizing a g e n t f o r t h e v i t a m i n D ester, the polyoxyalkylene c o m p o u n d h a v i n g b e t w e e n 20 and 50 oxyalkylene g r o u p s per molecule. AQUEOUS VITA3/IIN A OIL E3£'ULSION. R . :~. Czarnecki ( E a s t m a n K o d a k Co.). U. S. 3,089,323. A stable, a q u e o u s v i t a m i n A oil emulsion consists of a n oily v i t a m i n A-active concent r a t e a t a c o n c e n t r a t i o n of a b o u t 1-10. w e i g h t % ; 30=9'5 weight % w a t e r ; 1.55-3.5 m e t h y l cellulose; a n d g e l a t i n a t a c o n c e n t r a t i o n effective to s u p p r e s s development of coloring u n d e r n o r m a l s t o r a g e conditions b u t ineffective to cause g e l a t i o n of t h e w a t e r p h a s e of the emulsion.

• Drying ~SE

O i l s and Paints

O]~ DIME~ FATTY ACIDS IN TIIE PAINT AND THE PLASTIUS

INDUS~ZY. G. J. V a n V e e r s e n ( U n i l e v e r - E m e r y , G o u d a ) . Riv. Ital. So~tanze Grasse 10, 517-21 (1962). F a t t y acid dimers h a v e been u s e d e x p e r i m e n t a l l y to replace p h t h a l i e a n h y d r i d e or linseed oll in t h e p r e p a r a t i o n of a l k y d resins, with adv a n t a g e s b o t h in m a n u f a c t u r e a n d in finished p r o d u c t characteristics (reduced stickiness, i m p r o v e d s t a b i l i t y a n d d r y i n g ) . W h e n a d d e d to some epoxy resins, dimers increase degree of h a r d e n i n g a n d i m p r o v e stability. Other a p p l i c a t i o n s of f a t t y acid d l m e r s in t h e a r e a s of p o l y a m i d e s a n d polyuret h a n e s a r e discussed. PaOPEI~TIES, USE,S AND APPLICATION TECItNIQUE.S OF UN'MODIYIED PHENOLIC COATINGS. Anon. Materials

RAKED

Protection 1, No. 8, 8 7 - 9 0 (1962). B a k e d unmodified phenolic c o a t i n g s were t e s t e d in m o r e t h a n 500 chemical m e d i a a n d g e n e r a l r e c o m m e n d a t i o n s m a d e r e g a r d i n g t h e i r corrosion resistance to each e n v i r o n m e n t . P h e n o l i c s were less affected by solvents t h a n a n y other t y p e o r g a n i c coating. A l i p h a t i c h y d r o c a r b o n s , a r o m a t i c h y d r o c a r b o n s , alcohols, esters, ethers, k e t c h e s a n d c h l o r i n a t e d solvents h a d no effect on phenolic coatings. P h e n o l i c s also showed excellent h i g h t e m p e r a t u r e resistance ( 1 8 0 - 2 0 0 F ) to a q u e o u s s o l u t i o n s of mild acids a n d acidic a n d n e u t r a l salts. T h e y effectively resisted f e r m e n t a t i o n conditions as well as exposure to h o t a n i m a l a n d v e g e t a b l e oils. W h e n p r o p e r l y cured t h e y p r o v e d odourless, t a s t e l e s s a n d non-toxic, m a k i n g t h e m suitable for u s e w i t h food products. U s e s of h i g h - b a k e p u r e phenolics are reviewed b r i e f l y . 40

Other topics discussed include f o r m s available, c o m p o u n d i n g , s u r f a c e p r e p a r a t i o n a n d a p p l i c a t i o n techniques a n d g e n e r a l physical properties. (Rev. C u r r e n t Lit. P a i n t Allied I n d . ) t~EACTION LACQUERS DISTINGUISH THE;MSELVES. BY SUPERIOR ADH]gSION. A. Foulon. Woehbl. P a p i e r f a b r i k 1952, 90:248, 250. " R e a c t i o n lacquers ~ a r e defined as o r i g i n a t i n g on a s u b s t r a t e by a chemical r e a c t i o n b e t w e e n t h e c o m p o n e n t s of a s y n t h e t i c lacquer vehicle ( b i n d e r ) , such as a n i s o c y a n a t e a n d polyester or alkyd c o m p o n e n t s . Reaction lacquers can be f o r m u l a t e d to give either a i r - d r y i n g or o v e n - d r y i n g (baki n g ) t y p e s of coatings. B o t h t y p e s have excellent p i g m e n t b i n d i n g p r o p e r t i e s a n d superior a d h e s i o n to a v a r i e t y of s u b s t r a t e s , i n c l u d i n g f e r r o u s a n d n o n - f e r r o u s m e t a l s (such as A1 a n d Z n ) , plastics, g l a s s a n d porcelain. Solvents with reactive g r o u p s as well as water, should be avoided. S u i t a b l e c a t a l y s t s accelerate the d r y i n g t i m e of air d r y i n g lacquers a n d lower t h e b a k i n g t e m p e r a t u r e of o v e n - d r y i n g f o r m u l a tions ( f r o m 1 6 0 - 1 8 0 to 125-140C). O u t s t a n d i n g characteristics of r e a c t i o n lacquers include p e r m a n e n t a d h e s i o n a n d elasticity, a b r a s i o n resistance, h i g h dielectric properties, low i n f l a m m a b i l i t y a n d excellent r e s i s t a n c e to w e a t h e r i n g , solvents a n d chemicals. The a d d i t i o n of plasticisers m a y i m p a i r solvent r e s i s t a n c e b u t i m p r o v e a d h e s i o n a n d elasticity. Passir a t i n g p i g m e n t s provide c o r r o s i o n - r e s i s t a n t coatings. (Rev. CUrrent Lit. P a i n t Allied I n d . ) SURVEY 0F THE PROFIT ItlST0,1~Y OF TtIE BRITISH PAINT AND PRINTING INK INDUSTRIlgS AND TttE AVAILABILITY OF RAW 1VIATERIALS. A n o n . F i s k ' s P a i n t Y e a r Book 1952, 181-204. Profit histories of g r o u p s of B r i t i s h p a i n t a n d p r i n t i n g ink companies, all of which are public companies a n d p u b l i s h their accounts, a r e a n a l y s e d a n d t a b u l a t e d . P a r t 2 shows a n analysis o f t h e B r i t i s h p r o d u c t i o n a n d i m p o r t s of the m a i n raw m a t e r i a l s used by t h e p a i n t a n d p r i n t i n g ink industries. (Rev. C u r r e n t Lit. P a i n t Allied I n d . ) AND 1VIE.N. E . S u n d e r l a n d . Fisk's Paint Year B o o k 1952, 95-101. A s u r v e y of the development of technology in t h e p a i n t i n d u s t r y . T h e emergence of t h e i n d u s t r y f r o m the c r a f t state, the i m p a c t of two world w a r s a n d t h e effects of i m m e d i a t e p o s t - w a r s h o r t a g e s of technical personnel are discussed. The r e q u i r e m e n t s of t e c h n o l o g i s t s a n d the f o r m of technical service which should be available are described. (Rev. C u r r e n t Lit. P a i n t Allied I n d . ) MATERIALS

AIR

INHIBITION

OF

UNSATUI~ATED POLYESTF, R LACQUERS.

G.

Whale. C o n t i n e n t a l P a i n t s ~ Resins 1962, No. 66, 4. A short b i b l i o g r a p h y of recent p a t e n t s is given. T h e s e deal m a i n l y with a d d i t i v e s for c o n v e n t i o n a l polyesters which prev e n t air inhibition. P o l y i s o c y a n a t e s , allyl c o m p o u n d s a n d long-chain f a t t y esters are s u g g e s t e d , whilst a n improved m e t h o d u s i n g paraffin wax h a s been described. (Rev. C u r r e n t :Lit. P a i n t Allied Ind.) QUALITY C0'NTROL IN THE PAINT INDUSTI%Y. J . Hall. Austral. P a i n t J. 6, 13-16 (1961). A n outline based on t h e p a i n t technology courses conducted at t h e U n i v e r s i t y of N e w South Wales. (Rev. C u r r e n t Lit. P a i n t Allied I n d . ) PEE:P,JNG AHE;AD. P . J. Gay. F i s k ' s P a i n t Yea~ B o o k 1952, 61-8. The a u t h o r looks at c h a n g e s in a d m i n i s t r a t i o n a n d technical d e v e l o p m e n t to be expected in the p a i n t i n d u s t r y in c o m i n g years. The u n i t i n g of p a i n t m a n u f a c t u r e r s into large groups, t h e a b s o r p t i o n of p a i n t m a k i n g u n i t s into t h e chemical i n d u s t r y a n d the closer control of p a i n t c o m p a n i e s over the sales a n d use of t h e i r p r o d u c t s are the m o v e m e n t s considered. Technical a d v a n c e s f o r e s h a d o w e d are improvem e n t s in colour f a s t n e s s , i n c r e a s e d ability to control s u r f a c e c h a r a c t e r i s t i c s of p a i n t s , b e t t e r p a i n t m a k i n g m e t h o d s a n d better h a n d l i n g . CHI~I~IICALS F~I~ THE PAINT INDUSTRY : AVAILABILITY OR RIgQUII~E,MENTS? M. H. M. Arnold. Fisk's Paint Year Book

1952, 85-93. A survey is m a d e of t h e r a w m a t e r i a l s u s e d in t h e m a n u f a c t u r e of resins etc. in t h e p a i n t i n d u s t r y . The a v a i l a b i l i t y a n d economics of r a w m a t e r i a l s are discussed a n d p o t e n t i a l new m a t e r i a l s a r e assessed. (Rev. C u r r e n t Lit. P a i n t Allied I n d . ) COATING CO]YIPOSITION AND 3/IETI-IOD. D . B. Sheldahl and_ G. E n t w i s t l e ( S i n c l a i r l~efining Co.). U.S. 3,036,370. A waterin-oil emulsion consists of 50-8ff% water, 10~30% low-boiling p e t r o l e u m h y d r o c a r b o n s , 1 - 6 % p e t r o l e u m w a x h a v i n g a melti n g p o i n t of 1 2 5 - 1 4 0 F , a n d 2.0~6.5% of a m i x t u r e c o n t a i n i n g 4 - 6 % of a s u l f o n a t e selected f r o m t h e g r o u p c o n s i s t i n g of a m m o n i u m m a h o g a n y s u l f o n a t e a n d s o d i u m m a h o g a n y sulfonate, 5-50*% of a s o r b i t a n m o n o - f a t t y acid ester a n d the rest a h i g h - b o i l i n g p e t r o l e u m h y d r o c a r b o n . U. S. 3,086,37l, JOURNAL A.O.C.S., JULY 1963 (VoL. 40)

ABSTRACTS : DETERGENTS ~OATING COMPOSITION, describes a composition which consists

of 0.05-1% of a sulfonate (oil-soluble ammonium aromatic sulfonate or an oil-soluble sodium aromatic sulfonate), 0.252% sorbitan mono f a t t y acid ester, 1-10% petroleum paraffin wax having a melting point of 125-145F, 0.5-10'% boiled linseed oil, up to about 9% high-boiling petrolemn hydrocarbon, 1-80~% low-boiling hydrocarbon and 5-8% water. PROCESS 0 P CONVERTING FREE CARBOXYLIC ACID GROUPS IN LIQUID ESTEI~ COATING CO,MPOSITIOI'TS TO HALF-E~STEt¢ GROUPS WITH I%ETE2qTION OP TIIE COATIi'~'G COMPO,SITION IIq THZ LIQUID

STATE. H. W. Chatfield (Roberts & Co., Ltd.). U.S. 3,086,949. The process for inhibiting free carboxylic acidity in liquid coating compositions containing as an essential filnl-forming ingredient, acid esters of organic acids (natural resins, modified natural resins, synthetic resins) which have a free acid number of over 6, comprises mixing the liquid composition with an epoxidized f a t t y oil having internal oxirane briding 2 adjacent carbons on the f a t t y ehaln portion of the oil and heating the resulting mixture to a temperature of from 170-240C. The retained --COOH groups of the film-forming ingredient are reacted with the oxirane groups to form glyeolic half ester groups while retaining the film-forming property of the composition.

• Detergents SuaFAcE ACTIVE POLYH YDI~OXY-CO2~POUl~ns 1 8 : CONVERSION OF D~LJMANifflTOL W I T H N-OCTYL, lq'-DEC~XrL~ AND ~-DODE.C~LISOCYANATE TO ELE/C:TR0-~EUTICAL SURFAC~ ACTIVE URETHAI'TES.

E. Ulsperger and II. D. Jacobi (Deut. Akademie Wissenschaften, Berlin). Fette Seifen Anstrichmittet 54, 109310.9'8 (1962). The synthesis of nonionic surface active mono and diesters of D,L-mannitol and N-n-alkyl carbamic aicd from D,L-mannitol and n-alkyl isoeyanates of chain length Cs, C~o and C~ is reported. The structure of the products is established and their properties reported. PI~PAI~ATION

AND

PROPEB,TIES

OP

LINOLEATE, ESTERS

OF

SU-

0ROSE. E.. G. Bobalek, A. P. De Mcndoza, A. G. Causa, W. J. Collings, and G. Kapo (Case Inst. of Tech., Cleveland 6, Ohio). I # E C 1Jroduet Res. # Dev. 2, 9-16 (1963). A pilot plant process is described for production of sucrose esters by catalytic trans-esterification between the methyl esters of f a t t y acids and sucrose in dimethylformamide solvent. The process can be controlled to accomplish degrees of esterification from 1 to about 7, based upon the hydroxyl equivalents per mole of sucrose. Superior drying oil qualities develop at degrees of esterifieation exceeding 4, if the iodine value of the f a t t y acids exceeds about 140 and all unreacted methyl esters are removed by solvent extraction or absorption on silica gel. I n further chemical modification of these purified esters to produce more complex vehicles for paints and printing inks, either the hydroxyl or the olefinie reactive functions can be utilized. Examples are given where these products are converted to emulsions, urethane polymers, and styrenated oils. DETEI~GENCY OF NOIqlONIC SUKFAOTANT.

I.

E FFEOTS OF SO'ME

INOP~ANIC BUILDERS. Masaharu Kamc, Seiichiro Kishima, ¥asuhiko Danjo, and K a t s u j i Kamijo (Nippon Oils & Fats Co., Amagasaki). Yu]cagaku 12, 108-10 (1963). Tests on foaming and detergency of aqueous solutions of polyoxyethylene nonylphenyl ether (PEG-N) 0.05-0.5 g./1. and inorganic builder 0.1-1.0 g./1. were made. The result indicated that polyphosphates (hexametaphosphate, tripolyphosphate, and pyrophosphate) were more effective than the other builders (slicate, carbonate and neutral salts) in both soft and hard water. In the detergency tests carried out in water of various hardness and containing PEG-N 0.1 g./1., there was some relationship between the concentration of added builders and washing efficiency. For example, addition of 0.5 mole of pyrophosphate/mole of Ca ++ showed remarkable increase in washing power. Gomez (Instituto de la Grasa y sus Derivados, Seville, Spain). Grasas y Aceites (Seville, Spain) 13, 247-252 (1962). A review. BUILDEI~S FOR SOAPS AB!D DETERGENTS.

C.

A SIMPLE METHOD F01~ CALCULATIOI,~ SOAP FORMULAS.

]:~. C l a r a .

Afinidad 19, 458 (1962). A homograph has been developed for relating the water, caustic, and f a t t y acid content of finished soap to the saponification value of the f a t and the caustic concentration used during saponification.

ff0UI~NAL A.O.0.S., JULY 1963 (VOL. 40}

Provides values for calculation of number average molecular weights up to 5000", with an accuracy within _+1%, on single-drop samples of centimolal solutions. Usable with aqueous or non-aqueous, polar and non-polar liquids. Temperature range, without modification, 30 to 70°C; lower and higher temperatures m a y be obtained with accessory heating and cooling equipment. Serial determinations can be made in minutes following approximately 1 hour set-up period. Method is essentially that described by J. J. Neumayer in Analytica Chimica Acta, 20, 519 (1959). Principle. In an equilibrium system, condensation takes place on the surface of a solution exposed to saturated vapor of its solvent. The heat transferred causes a slight increase in temperature of the solution. In the same system an equivalent surface of liquid solvent will remain at a constant t e m p e r a t u r e because the rate of vaporization and condensation is the same. The rate of condensation and heat transfer to the solution, and thus the rise in temperature produced, is proportional to the mole fraction of solute in the solution. The t e m p e r a t u r e rise, or any proportional effect which it produces, can be used to calculate the molecular weight of solute in solutions of known concentration.

Technique. Two thermistors are used to measure t e m p e r a t u r e difference between solvent and solution in a solvent vapor chamber thermostatically controlled within _+0.003°C. Samples are applied to thermistor tips by means of micrometer syringe pipets. Provision is made for delivery of solvent to both thermistors, and for subsequent delivery of solution to the measuring thermistor. Readings made with only two dilutions of a known sample suffice to establish the molar constant for a given solvent. Change in measuring thermistor resistance is made b y means of a high-sensitivity d.c. resistance bridge. Molecular weight can be calculated directly using the resistance value obtained. Conversion to temperature units is not required. 7253. Molecular Weight Apparatus, Thomas Isothermal Distillation, as above described. Complete with six syringe pipets, and directions. For use on 115 "~olts, 50 or 60 cycles a.c . . . . . . . . . . . . . . . . . . . . . 2,200.00 *usable to 10,000 with diminishing accuracy

Bulletin 141, giving detailed information, sent upon request

ARTHUR H. THOMASCO. Scientific Apparatus VINE STREET AT 3RD PHILADELPHIA 5, PA., U. S. A.

41