ABSTRACTS • Fats

and

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

Oils

SEPARATION OF FATTY ACID ESTERS ON ACID-TREATED FLORISIL IMPREGNATED WITH SILVER NITRATE. D. Wil]ner ( N e w E n g l a n d Inst. f o r Med. Res., Ridgefield, Conn.). Chem. lnd. (London) 1965, 1839-40. Acid-treated F]orisil was mixed with a 50% aqueous solution of silver n i t r a t e and shaken until free-flowing. I t was then left overnight in an oven at 110-120C. A slurry of this m a t e r i a l in red]stilled hexane was poured into a column 2.0 x 50 cm, and the column was t a p p e d lightly to f o r m a compact packing. The packing was protected f r o m light by covering it with aluminum foil. The flow rate of the solvent could be regulated easily and was kept at 150-180 m l / h r . A mixture of myristic, pahnitic, stcaric, pahnitoleic, oleic, linolcic and ]inolenic acid methyl esters in hexane was poured on the c o h m n . The column was eluted with hexane containing increasing a m o u n t s of ether. Separation was s a t i s f a c t o r y and recovery was a h n o s t quantitative. UNSAPONIFIABLE FRACTION OF PORK FAT AS RELATED TO BOAR ODOR. L. D. Williams and A. M. P e a r s o n (Dept. of F o o d Sei., Michigan State Univ., E. L a n s i n g , Mich.). J. Agr. Food Chem. 13, 573-77 (1965). The unsaponifiab]e m a t t e r obtained f r o m pork f a t was fractionated and f o u n d to contain carbony]s, cholesterol, squalene, vitamin A, and f o u r s a t u r a t e d hydrocarbons. I n addition, cholesterol esters, a 7-ketosterol, a triterpene alcohol, and two oxidation p r o d u c t s of squalene were indicated. No evidence of p r i m a r y or secondary alcohols or of sulfur- or nitrogen-containing compounds could be found. No i m p o r t a n t differences were observed in the components f r o m f a t containing boar odor as compared to f a t free f r o m b o a r odor. MASS SPECTRA OF O-ISOFROPYLIDENE DERIVATIVES OF L~NSATUBATED FATTY ESTERS. J. Am. McCloskey and M a r t h a J. McClelland (Dept. of Biochem., Baylor Univ., College of Med., Houston, Texas). J. Am. Chem. Soc. 87, 5090-93 (1965). The mass spectra of O-isopropylidene derivatives of dio]s obtained by stereospeeifie oxidation of a n u m b e r of u n s a t u r a t e d f a t t y esters are interpreted, and are shown to be useful f o r the characterization of positional and geometrical isonmrs of the u n s a t u r a t e d esters. D e u t e r i u m and oxygen-18 labeling are used f o r the elucidation of f r a g m e n t a t i o n mechanisms. A simple p r e p a r a t i o n of oxygen-18 labeled diols is described. EFFECT OF SOLID SUPPORT AND LIQUID PHASE ON THE ACCURACY OF QUANTITATIVEGAS CHROMATOGRAPHY. V. K u s y (Chem. Works of Czechoslovak-Soviet F r i e n d s h i p , Zaluzi, Czech.). Anal. Chem. 37, 1748-52 (1965). I t was ascertained t h a t for gas chromatographic analyses the m e a s u r e d values are under certain conditions lower t h a n the actual values. This phenonmnon is nmst perceptible f o r the determination of mixtures of polar and nonpolar substances on a n o n p o l a r liquid phase and is discussed in relation to a possible s o r p t i o n of the analyzed polar substance on the solid support. I t m a y be assumed t h a t one of the causes of the irreversible sorption of polar substances is hydrogen bonding. The spatial a r r a n g e m e n t of the molecule of the analyzed substance p r o b a b l y has a large influence. I n addition to irreversible sorption, a possible interaction between the liquid phase and the analyzed substance is taken into account. Generally it m a y be assumed t h a t the presence of the nonpolar substance influences the rate of dissolution of polar substances in the liquid phase, and make the a p p r o a c h of polar substances to the solid s u p p o r t much easier. Hence, f o r gas c h r o m a t o g r a p h i c analysis, the choice of the solid s u p p o r t and the liquid phase may influence the quantitative result. CASHEW NUT PROCESSING--PART I. P. J. Hall and L. ]~anks. Trop. Sci. V I I , 12-26 (1965). Traditional methods of cashew nut processing are described, and developments in mechanical processing reviewed. An account is given of work at the Tropical P r o d u c t s I n s t i t u t e up to the end of 1964, including early work on a simple manually operated decortication device, and on c e n t r i f u g a l cracking. RELATION OF COMPOSITION OF THE AQUEOUS PHASE TO 0rXIDIZED FLAVOR DEVELOPMENT BY DIALYZED GLOBULAI~ MILK FAT. A. M. El-Negoumy (Dept. of Animal and Range Sci., M o n t a n a State Univ., Bozeman, Mont.). J. Dairy Sci. 48, 1406-12 (1965). Six per cent dialyzed milk f a t and 4 p p m copper were incorporated i n t o : 1) salt solutions containing sodium citrate, phosphate buffer, NaCI, KC1, and CaC12, and m i x t u r e s of those solutions; 2) salt solutions containing amounts of sodium ca64A

seinate r a n g i n g f r o m 0.50 to 5.0% ; 3) salt solutions containing 2 to 10% lactose; 4) the above model systems in presence of ascorbic acid. A f t e r 48 h r at 3-5C, oxidation rates and intensity were m e a s u r e d in t e r m s of the optical density ( O D ) of the 2-thiobarblturic acid test. Both rates and intensity of oxidized flavor development varied significantly in the various salt solutions and their mixtures. I n c r e a s i n g lactose concentration increased the oxidation rates significantly in all systems (OD increased f r o m 0.32 to 0.50 in phosphate and 0.14 to 0.21 in citrate). The reverse of this trend was obtained in presence of an increased concentration of sodium caselnate (OD decreased f r o m 0.25 to 0.05 in phosphate and 0.15 to 0.05 in citrate). Homogenized f a t showed much lower oxidation rates in presence of casein t h a n did nonhomogenized fat. LIPIDS OF THE FIN WHALE (BALAENTOPTERA PHYSALUS) FROM NORTH ATLANTIC WATERS. I. FATTY ACID COi~fPOSITION OF WHOLE BLUBBEI~ AND BLUBBER SECTIONS. R. G. Aekernian, C. A. E a t o n and P. M. J a n g a a r d (]#isheries Res. Board of Canada, Halifax, Nova Scotia). J. Bacteriol. 43, 1513 (1965). Oils f r o m sectioned blubber, whole b l u b b e r oils, and commercial oils f r o m the fin whale (Balaenoptera physalus) taken in Nova Scotia waters have been examined. The general properties include much lower iodine values (105-117) t h a n those conmmnly reported f o r N o r t h Atlantic (Arctic) baleen whales. The f a t t y acid composition p a t t e r n has been determined by gas-liquid c h r o m a t o g r a p h y and varies systematically with the type of acid across the b l u b b e r section, the inner section having the highest iodine value. The roles of the blubber in physiological functions other t h a n as an insulating layer are discussed in terms of f a t t y acid composition. I I . FATTY ACID COl~/IPOSITION OF THE LIVER LIPIDS AND GASLIQUID CHRO1VIATOGRAPHIC EVIDENCE FOR TIIE OCCURRENCE OF 5,8,11,14-NONADECATETRAENOIC ACID. Ibid., 1521. The f a t t y acid composition of the liver lipids of the fin whale (Balaenoptcra physalus) closely resembles t h a t of terrestrial mammals. Gas-liquid c h r o m a t o g r a p h i c evidence indicates t h a t 5,8, 11,14-nonadecatetraenoic acid is present, and the origin of this acid in association with 5,8,11,14-eicosatetraenoic acid is discussed. THE HEATS OF COl~IBUSTION, FORMATION AND ISOMERIZATION OF ISOMERIC ]YIONOGLYCERIDES. L. S. Silbert, B. F. Daubert, and L. S. Mason (Dept. of Chem., Univ. of P i t t s b u r g h , P a . ) . J. Phys. Chem. 69, 2887 (1965). H e a t s of combustion f o r the isomeric monoglyceride series r a n g i n g f r o m monocaprin to monostearin and f o r one p a i r of u n s u b s t i t u t e d benzoylmonoglycerols were determined and used f o r calculating the heat of formation, heat of isomerization f r o m the enthalpy difference of the isomers, and energy increment per CHe f o r their solid states. The heat of isomerization ranged f r o m --1.99 to --3.84 kcal. mole -~ f o r the aliphatic monoglycerides and --1.08 kcal. mole ~x f o r the aromatic series in contrast to a r e p o r t e d value of --9.52 kcal. mole -~. The kinetic equilibrium constant reported f o r the isomerization of 2-nmnoglyceride to 1-monoglyceride was compared to the equilibrium constant computed f r o m their isomerization energies. An entropy difference f o r the monopalmitin pair, AS ° = - 5 . 6 cal. deg. -~ mole -~, was derived and interpreted. The energy increnmnt per CHe r a n g e d f r o m 154.65 to 155.87 kcal. mole -1, and the possible reasons f o r the range are briefly discussed. INVESTIGATION ON THE INFRARED ROCKING BANDS OF LINEAR SATURATED~ ALIPHATIC MONO AND DIACIDS. R. P e r r o n and J. Perichon (Lab. of Lipochem. of C.N.R.S., Bellevue, F r . ) . Rev. Franc. Corps Gras 12, 381 (1965). The i n f r a r e d s p e c t r a of various linear s a t u r a t e d aliphatic monoacids (C-3 to C-22) and a-~ diacids (C-4 to C-24) have beeen determined in solid state between 700 and 900 cm% The distribution of the rocking bands of methylenic g r o u p s in this r a n g e m a y be correctly described f o r these two series of compounds by two equations of the same type as the one established by Snyder for hydrocarbons. These equations show t h a t carboxyllc groups have a certain action on the rocking vibrations of the h y d r o c a r b o n chain. The observed frequencies, as in the case of hydrocarbons, depend particularly on the difference of phase between adjacent oscillators. These angles tK,~ f o r m oscillators and J. AM. OIL CHEMISTS' SOC., FEB. 1966 (VOL. 43)

~BSTRACTS:

the k t'' n o r m a l mode, are r e p r e s e n t e d respectively b y tK.M = k T r / m + 1 (active b a n d s f o r the odd a n d even values of k) for monoacids, a n d t K , M = k ~ - / m + 2 (active b a n d s f o r even values of k) f o r diacids. F r o m this i n v e s t i g a t i o n r e s u l t s a new m e a n s of identification of these acids. D i s t r i b u t i o n of the rocking b a n d s a n d their positions in the s p e c t r a are analytically more a d v a n t a g e o u s t h a n " p r o g r e s s i o n b a n d s . " ELECTRON SPIN RESONANCE SPECTRA OF RADICALS IN "y-IRRADIATED PATTY ACIDS. H. Luck, C. U. Definer, R. K o h n (Deut. F o r e h a n s t a t t f o r L e b e n s m i t t l e c h e m , M u n i c h ) . E e t t e S e i f e n Anstrichm i t t e l 66, 665-69 (1964). Electron s p i n resonance s p e c t r a of some 7 - i r r a d i a t e d crystalline s a t u r a t e d a n d u n s a t u r a t e d f a t t y acids showed t h a t the r e s u l t i n g radicals have a relatively long life period. T h e y show very little or no reactivity t o w a r d s oxygen. T H E M E T A L C O M P L E X E S OF TRI- A N D T E T R A M E T H Y L E N E D I A M I N E NN'-TETRAACETIC ACID. F . L ' E p l a t t e n i e r a n d G. A n d e r e g g

( E i d g e n . Tech. Hoehsehule, Zfirich, S w i t z e r l a n d ) . Helv. Chim. A c t a 47, 1792-800 (1964). T h e s t a b i l i t y c o n s t a n t s of t h e complexes f o r m e d b y v a r i o u s m e t a l ions w i t h l i g a n d s of t h e t y p e ( - O O C - - C H 2 ) ~ = N - - ( C H 2 ) , - - N = ( C H ~ - - C O O - ) 2 with n : 3 or 4 have been determined. I n the case of n = 3, complex f o r m a t i o n h a s been i n v e s t i g a t e d b y five different methods, all g i v i n g identical results. The s t a b i l i t y of these complexes is lower t h a n t h a t o f the h o m o l o g u e E D T A ( n - - 2 ) , however the degree to which s t a b i l i t y is affected b y n is n o t the same f o r the v a r i o u s complexed metals. R E A C T I O N E N T H A L P Y A N D E N T R O P Y IN T H E F O R M A T I O N OF ~IETAL

COMPLEXES OF THE HIGHER HOMOLOGUES OF E D T A . G. A n d e r e g g (Eidg. Tech. Hochschule, Ziirich, S w i t z e r l a n d ) . Helv. Chim. A c t a 47, 1801-14 (1964). Complexing a g e n t s of the type discussed in the previous a b s t r a c t with values of n f r o m 2 to 8 have been i n v e s t i g a t e d . The s t a b i l i t y c o n s t a n t s a n d the h e a t s evolved d u r i n g f o r m a t i o n of the 1 : 1 complexes of Ca, M g , M n +s, F e +~, Co +~, N i +2, Cu +=, Zn +s, Cd +~, P b +e, H g ÷~ a n d L a +a have been determined. B a s e d on their behavior in complex form a t i o n these cations can be divided into two groups. I n t h e first one, i n c l u d i n g cations Ca +s, M g ÷2, M n +s, Cd ÷s, P b ÷2 a n d L a +3, t h e s t a b i l i t y c o n s t a n t s a n d - - A H of complex f o r m a t i o n decrease r a p i d l y w h e n n is increased f r o m 2 to 4. The second g r o u p c o n t a i n s all the o t h e r m e t a l ions i n v e s t i g a t e d except H g +s, a n d the drop in s t a b i l i t y is observed between 4 a n d 5, whereas --AH i n c r e a s e s slightly. The e n t r o p y g a i n by complex f o r m a t i o n is a p p r o x i m a t e l y the same if the n u m b e r of m e t h y l e n e g r o u p s in the c h a i n connecting the two n i t r o g e n s is i n c r e a s e d f r o m 2 to 4. R e p l a c e m e n t of one or two of these --CH2-g r o u p s b y --O-- or - - S - g e n e r a l l y decreases the free e n e r g y a n d the e n t h a l p y o f complex f o r m a t i o n to a g r e a t e x t e n t i f new 5 - m e m b e r e d chelate r i n g s are f o r m e d . STRUCTURE AND ACTIVITY OF CU+~-COMPLEXES IN TIIE CATALYTIC RADICAL DECOMPOSITION OF HYDROGEN PEROXIDE. tI. B r i n t z l n g e r a n d H. E r l e n m e y e r (Univ. of Basel, S w i t z e r l a n d ) . H e l v . Chim. A c t a 48, 826-9 (1965). The b i d e n t a t e N-chelates Cu+
BARROW.AGEE LABORATORIES, INC. Analytical and Consulting Chemists and Testing Engineers Main Oi~ees and Laboratories, MEMPHIS, TENNESSEE Other Laboratories: Shreveport, La. Decatur, Ala. Greenville, Greenwood and Jackson, Miss. Chattanooga and Nashville, Tenn. Little Rock, Ark.

66A

FATS

AND

OILS

PROBABLE PHENOMENA 01~ ACID ISOMERISM AND ERRORS IN THE INTERPRETATION OF GAS CHROMATOGRAMS. E. G. M o n d i n o ( S A I C A , Castelvetrano, I t a l y ) . Olearia 19, 94-7 (1965). Several p e a k s a n d shoulders p r e s e n t in f a t t y acid m e t h y l ester c h r o m a t o g r a m s are caused by oxidation of the metl%y] esters d u r i n g or a f t e r p r e p a r a t i o n a n d by the presence of u n s a p o n ifiables. T h e n a t u r e a n d the position of these p e a k s have been i n v e s t i g a t e d a n d are r e p o r t e d on in detail. CRYSTALLIZATION AND M E L T I N G BEHAVIOR OF FATS. P. W. H e n d r i k s e , J. H a n n e w i j k a n d A. J. H a i g h t o n (Unilever Res. Lab., V l a a r d i n g e n , The N e t h e r l a n d s ) . Riv. Ital. Sostanze Grasse 42, 367-84 (1965). T h e principles g o v e r n i n g the cryst a l l i z a t i o n of f a t s a n d t h e v a r i o u s c r y s t a l l o g r a p h i c f o r m s are reviewed. T h e p r a c t i c a l a p p l i c a t i o n s of d i l a t o m e t r y , calorimetry a n d D T A in t h e s t u d y of f a t solidification a n d m e l t i n g are also discussed. DETERMINATION OF THE FAT CONTENT OF CHEESES. P. A r m a n dola. I n d . A l i m . 3, 45-8 (1965). A n a l y t i c a l m e t h o d s for the d e t e r m i n a t i o n of the f a t c o n t e n t of cheeses, b o t h in good a n d in poor s t a t e of p r e s e r v a t i o n , are described a n d discussed. ESTIMATION OF THE STABILITY OF OLIVE OILS. C. Cantarelll a n d F. M o n t e d o r o (Univ. of P e r u g i a , I t a l y ) . Riv. Ital. Sostanze Grasse 42, 298-308 (1965). The a g i n g c h a r a c t e r i s t i c s of s n u m b e r of olive oil samples, b o t h u n d e r n o r m a l s t o r a g e conditions a n d u n d e r accelerated t e s t i n g , have been s t u d i e d with respect to a u t o c a t a l y t i c p e r o x i d a t i o n a n d h y d r o l y t i c acid formarion. The v a l i d i t y of t h e peroxide a n d carbonyl indices as criteria for e s t i m a t i n g s t a b i l i t y a g a i n s t r a n c i d i t y is discussed. T h e d a t a on the t r e n d of a u t o c a t a l y t i c hydrolysis show i n t e r e s t i n g differences o f b e h a v i o r with r e s p e c t to other vegetable oils. VARIATION OF THE CHEMICAL COMPOSITION OF OLIVES DURING THEIR GROWTH. G. P e t r u c c l o l l ( E x p . Olive I n s t . , Spoleto, I t a l y ) . Olearia 19, 5-13 (1965). T h e c h a n g e s in the chemical composition of v a r i o u s t y p e s of olives have been followed a t various s t a g e s of t h e i r m a t u r a t i o n over a period of e i g h t years. The f a t c o n t e n t i n c r e a s e s u p to a m a x i m u m , reached t o w a r d s the e n d o f the season, a f t e r which it r e m a i n s constant, while cellulose, p e c t i n s a n d m a n n i t e contents r e m a i n practically unchanged. The free f a t t y acid c o n t e n t becomes lower with progressive m a t u r a t i o n , a n d so does the ratio of s a t u r a t e d to uns a t u r a t e d f a t t y acids. T h e s u g a r c o n t e n t becomes s o m e w h a t lower while total n i t r o g e n (especially proteic a n d a m m i n i c N ) a n d p e n t o s a n c s decrease m a r k e d l y . These r e s u l t s confirm previous h y p o t h e s e s t h a t glucosides are the s u b s t a n c e s responsible m a i n l y f o r the f o r m a t i o n o f f a t s a n d s u g g e s t t h a t p e n t o s a n e s a n d proteic s u b s t a n c e s also m a y p l a y a role in the process. THE

F A T T Y ACID COMPOSITION OF ITALIAN A N D FOREIGN OLIVE

OILS. G. P e t r u c c l o l i ( E x p . Olive Inst., Spoleto, I t a l y ) . I n d . Alim. 3, 62-6 (1965). The f a t t y acid compositions of a b o u t 300 olive oil s a m p l e s o f d i f f e r e n t origins are reported, w i t h results g e n e r a l l y in a g r e e m e n t with previous literature. T h e existence o f r e g i o n a l differences in f a t t y acid composition is confirmed. A_ STUDY OF THE DISTRIBUTION OF FATTY ACIDS IN TRIGLYCERIDES. E. Fedeli, A. L a n z a n i , A. F . V a l e n t i n i a n d G. J a c i n l ( E x p . S t a r F a t s a n d Oils, Milan, I t a l y ) . Riv. I t a l . Sostanze Grasse 42, 67-9 (1965). T h e o p e r a t i n g conditions f o r the s e p a r a t i o n ( b y GLC a n d T L C ) of t h e glyeerides p r e s e n t in olive oil are described. Gas c h r o m a t o g r a p h y allows s e p a r a t i o n b y molecular weight b u t does n o t d i s t i n g u i s h between s a t u r a t e d a n d uns a t u r a t e d c o m p o n e n t acids. TLC, on the o t h e r h a n d , p e r m i t s s e p a r a t i o n of the t r i g l y c e r i d e s b y degree of u n s a t u r a t l o n . B y first o p e r a t i n g a T L C s e p a r a t i o n a n d s u b s e q u e n t l y d o i n g a GLC s e p a r a t i o n on the i n d i v i d u a l T L C f r a c t i o n s , one is able to characterize completely t h e glyceride c o m p o s i t i o n of an oil. B y i n c l u d i n g the technique of e n z y m a t i c hydrolysis, a v e r y complete glyeeride a n a l y s i s can be p e r f o r m e d . PRODUCTION CAPACITY AND POWER REQUIREMENTS IN OLIVE OIL PROCESSING MACHINERY. A. Chelazzi ( V e r a c i S.p.A., Florence, I t a l y ) . Riv. Ital. S o s t a n z e Grasse 42, 79-103 (1965). T h e m a c h i n e r y c o m m o n l y u s e d hi t h e first s t a g e of olive oll processing, i.e. the s t a g e p r e c e d i n g extraction, h a s been s t u d i e d for t h e p u r p o s e of e s t a b l i s h i n g t h e o r e t i c a l - e x p e r i m e n t a l form u l a s to calculate t h e h o u r l y w o r k i n g c a p a c i t y a n d the horsepower required. A m o n g t h e s u b j e c t s of this s t u d y are: r u b b e r conveyor belt f o r olives, w a s h i n g m a c h i n e r y , vertlca] screw conveyors, g r i n d i n g c r u s h e r s a n d mills. ft. AM. OIL CHEmiSTS' SOC., FEB. 1966 (VOL. 43)

_~BSTRACTS: F A T S AND OILS THE USE O~ CENTRIFUGAL SEPAI%ATORS IN CONTINUOUS REFINING PROCESSES FOR VEGETABLE OILS. Y. A r m o n i o s o ( A l f a - L a v a l , Milan, I t a l y ) . l~iv. I t a l Sostanze Grasse 42, 71-8 (1965). The v a r i o u s uses of c e n t r i f u g a l s e p a r a t o r s in v e g e t a b l e oil production, refining a n d l o o t s a c i d u l a t i o n are described. THE HYDROLYSIS AND OXIDATION OF CRUDE AND DEGUM1V[ED SOYBEAN OIL. A. Rutkowski, W. K o r z e n i o w s k i a n d J. B a t u r a (Coll. of A g r . , Olsztyn, P o l a n d ) . Riv. I t a L Sostanze Grasse 42, 63-6 (1965). U n d e g u m m e d crude s o y b e a n oil hydro]yzes r a p i d l y on storage. H i g h e r t e m p e r a t u r e a n d t h e presence of m o i s t u r e accelerate the process, w h i c h is m u c h m o r e p r o n o u n c e d t h a n in the case of d e g u m m e d oil. H y d r o l y s i s also g r e a t l y reduces the o i l ' s resistance to oxidation, espeeia]ly a t h i g h e r s t o r a g e temperatures. CHE)][ICAL AND SPECTROPHOTO~ETRIC CHARACTERISTICS OF CRUDE OLIVE OILS. R. Casillo ( C h a m b . of Comm. L a b . , N a p l e s , I t a l y ) . Olearia 19, 14-7 (1965). A t r e a t m e n t with a c t i v a t e d a l u m i n a l a r g e l y removes the free a c i d i t y a n d v a r i o u s oxidation products f r o m low q u a l i t y olive oils. These oils c a n still be identified as g e n u i n e olive oils ( r e q u i r i n g refining) b y speetrophotom e t r i c a n a l y s i s a f t e r the a l u m i n a t r e a t m e n t . COLUMN AND THIN-LAYER CHROMATOGRAPHY OF ORGANIC CO,POUNDS USING AGNOa-I)]£PREGNATED ADSORBENTS. G. J u r r i e n s ( U n i l e v e r Res. Lab., V ] a a r d i n g e n , The N e t h e r l a n d s ) . Riv. Ital. Sostanze Grasse 42, 116-21 (1965). A g N O 3 - i m p r e g n a t e d silica gel, a n a d s o r b e n t developed by D e V r i e s f o r the resolution o f h i g h e r f a t t y acid m e t h y l esters or of t r i g l y e e r i d e s w i t h cis a n d trans double bonds, is suitable also f o r t h e s e p a r a t i o n into g r o u p s of other u n s a t u r a t e d o r g a n i c s u b s t a n c e s , such as sterols, sterol esters, t r i m e t h y l sterols, sesqulterpenes, phospholipids. The specific p r o p e r t i e s of the a d s o r b e n t are especially e v i d e n t in T L C resolutions. B y u s i n g layers ] ram. thick on 2 0 x 40 cm. plates it is possible to s e p a r a t e 50-100 m g of a m i x t u r e composed of a g r e a t n u m b e r of c o n s t i t u e n t s b y a single operation. I f f r a c t i o n s of a glyceride m i x t u r e are quantitatively e x t r a c t e d f r o m t h e a d s o r b e n t , it is possible to f u r t h e r e x a m i n e a n d analyze these f r a c t i o n s . FATTY ACID COI~[POSITION OF THE BARK OF AILANTHUS GLANDULOSA. B. Chiarlo a n d E. Tacchino (Univ. o f Genoa, I t a l y ) . Riv. Ital. Sostauze Grasse 42, 122 4 (1965). One K g . o f d r y b a r k of A i l a n t h u s glandulosa, e x t r a c t e d with p e t r o l e u m ether, gave 41.5 g. residue with a 58.97% total f a t t y acid content. The m e t h y l ester g a s c h r o m a t o g r a m gave a series of 24 peaks, of which 17 were positively identified a n d t h r e e are p r o b a b l y u n s a t u r a t e d acids b e t w e e n C2~ a n d C=6. The m a i n identified c o m p o n e n t s are: behenic ( 2 7 . 7 % ) , oleic ( 1 4 . 4 % ) , ]inoleic ( 1 2 . 7 % ) a n d p a h n i t i c ( 8 . 5 % ) . T h e u n s a t u r a t e d acids represent a b o u t 3 0 % of the total. STUDIES ON POLYCYCLIC ARO~£ATIC HYDROCARBONS PRESENT IN OLIVE OIL. W. Ciusa et al. (Univ. of Bologna, I t a l y ) . / ~ v . Ital. Sostanze Grasse 42, 175-9 (1965). Several po]ycyclic a r o m a t i c h y d r o c a r b o n s have been s e p a r a t e d a n d identified s p e c t r o p h o t o m e t r i c a l l y f r o m t h e unsaponifiable f r a c t i o n o f olive oil, the p r i n c i p a l ones b e i n g : pyrene, p h e n a n t h r e n e , fluoranthene, crysene, 1,2-benzanthracene, perylene. I t h a s n o t y e t been possible to e s t a b l i s h w i t h i n w h a t limits t h e t y p e s a n d levels o f these h y d r o c a r b o n s m a y be considered typical in olive oils of v a r i o u s sources. NEW FATS AND OILS PROCESSES. G. B. M a r t i n e n g h i (Univ. o f Milan, I t a l y ) . Riv. Ital. S o s t a n z e Grasse 42, 133-7 (1965). C u r r e n t t r e n d s in oil extraction, f a t r e n d e r i n g a n d refining are reviewed. SOLVENT EXTRACTION OF OIL SEEDS. M. B e r n a r d i n i . Riv. Ital. Sostanze Grasse 42, 272-82 (1965). A review is given of t h e basic f a c t o r s involved in commercial solvent e x t r a c t i o n such as: seed p r e p a r a t i o n a n d h a n d l i n g , t y p e a n d a m o u n t of solvent, e x t r a c t i o n t e m p e r a t u r e a n d time. ~ E W CHARACTERISTIC FATTY ACID RATIOS IN BUTTER AS DETERMINED BY GAS CHROMATOGRAPHY. B. Doro a n d G. Gabueei (Prov. Chem. Lab., Trieste, I t a l y ) . Riv. Ital. Sostanze Grasse 42, 105-7 (1965), A set of ratios of f a t t y acid c o n t e n t s (Cs/

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Clo, Cs/C~, ..., Cs/Cls-) are p r o p o s e d as a criterion f o r the detection o f b u t t e r oil a d u l t e r a t i o n . THE ANALYTICAL DETERMINATION OF ANTIOXIDANTS IN FATS AND OILS. P. A r m a n d o l a . I n d . A l i m . 3, 55-6 (1965). The U . S . F . D . A . m e t h o d f o r a n t i o x i d a n t d e t e r m i n a t i o n is discussed. The m e t h o d h a s g i v e n very good r e s u l t s on B H A , B H T , N D G A a n d p r o p y l gallate, allowing a n a l y s i s of as little as 0.01%. THE NATURE OF LIPIDS PRESENT IN THE GERMINAL ORGANS AND RESERVE TISSUES OF SEEDS. G. L o t t i a n d C. Galoppini (Univ. of P i s a , I t a l y ) . Riv. l t a l . S o s t a n z e Grasse 42, 289-97 (1965). The a n a l y t i c a l values a n d acid composition o f t h e glycerides p r e s e n t in the g e r m i n a l o r g a n s a n d reserve tissue of oil-bearing seeds h a s b e e n s t u d i e d on s a m p l e s of 42 v e g e t a b l e species of 14 f a m i l i e s b e l o n g i n g to Gymnospe~mae a n d mono- a n d dicotyledon Angiospern~ae. C e r t a i n g e n e r a l r e l a t i o n s h i p s have been f o u n d b e t w e e n the t y p e a n d a m o u n t of the lipids p r e s e n t in the d i f f e r e n t o r g a n s of the seeds of t h e v e g e t a b l e species examined. GAS CHRO)~ATOGRAFHIC SEPA]~ATION OF STEROIDS AND RELATED SUBSTANCES. E. C. H o r n i n g a n d W. J. A. Y a n d e n h e u v e l (Coll. of Med., H o u s t o n , T e x a s ) . Riv. Ital. Sostanze Grasse 42, 4 1 8 29 (1965). A review is g i v e n of g a s c h r o m a t o g r a p h i c techniques as applied to the a n a l y s i s of sterols. THE BLEACHI:NG OF ~ATTY SUBSTANCES BY PHYSICAL ADSORPTION AGENTS. M. N a u d e t (Univ. of Marseille, F r a n c e ) . ~ i v . Ital. Sostanze Grasse 42, 283-8 (1965). The d i s t r i b u t i o n coefficient of p i g m e n t s b e t w e e n the t r i g l y e e r i d e s in which t h e y are dissolved a n d tim a d s o r p t i o n a g e n t s u s e d in b l e a c h i n g is s u b j e c t to the influence of several f a c t o r s , b o t h p h y s i c a l a n d mechanical (e.g., w o r k i n g t e n l p e r a t u r e , type of c o n t a c t i n g equipm e n t ) , as well as chemical. O p t i m u n l b l e a c h i n g can be expected if the oil h a s a l r e a d y been s t r i p p e d of its non-glyceride c o m p o n e n t s a n d if care h a s been t a k e n to m i n i m i z e the oxidation of the oil p r i o r to bleaching. SPECTROFLUOROMETRIC STUDIES ON OLIVE OILS. I I . G. K a d e r a v e k a n d G. Volonterio (Univ. of Milan, I t a l y ) . Riv. l t a l . Sostanze Grasse 42, 270-1 (1965). Esterified olive oil can be identified by speetrofluorometric analysis o f the residue o f nlethano] extraction. The fluorescent s u b s t a n c e to which this effect is a t t r i b u t e d h a s been isolated b u t n o t y e t identified. THE USE OF LIQUID PROPANE IN OIL EXTRACTION. ~=~.R i g a m o n t i , G. Saracco a n d A. Gianetto (Polyteeh. Inst., T u r i n , I t a l y ) . Riv. Ital. Sostanze Grasse 42, 238-40 (1965). P i l o t p l a n t results are r e p o r t e d on the e x t r a c t i o n of olive oil f r o m h u s k s in b a t c h t y p e e q u i p m e n t , u s i n g liquid p r o p a n e as the solvent. T h i s solvent h a s slightly lower e x t r a c t i n g power t h a n hexane a n d yields a m o r e deeply colored e x t r a c t w i t h lower free acidity a n d lower iodine value. T h e economic f a c t o r s involved in replacing h e x a n e with p r o p a n e are briefly discussed. OLIVE OIL TECHNOLOGY. U. A m i c u e e i (Soc. J e s i n a Macch. Agr., Jesi, I t a l y ) . Riv. Ital. Sostanze Grasse 42, 313-8 (1965). The various olive oil processing m e t h o d s c u r r e n t l y u s e d in I t a l y are reviewed. THE IDENTIFICATION OF ESTERIFIED OLIVE OILS BY INFRARED SPECTROPHOTO1V~ETRY. F. P r o v v e d l (Prov. Chem. Lab., ]~ergamo, I t a l y ) . Riv. Ital. Sostanze Grasse 42, 319-21 (1965). Esterified olive oils exhibit a c h a r a c t e r i s t i c a b s o r p t i o n I n a x i m u m at 2.5-3.5 ~ which c a n b e s t be evidenced by o p e r a t i n g on relatively thick (0.4 ram) cells. This m a x i m u m can be used f o r identification purposes. DISTINGUISHING VIRGIN OLIVE OIL FROM OTHER 0ILS BY SPECTROPHOTOMETRY. E. Synodinos ( S t a t e Chem. Lab., A t h e n s , Greece). R i v . l t a l . Sostanze Grasse 42, 325-8 (1965). A spect r o p h o t o m e t r i c m e t h o d in the visible region (450 m ~ ) is presented f o r the p u r p o s e of r e c o g n i z i n g v i r g i n olive oils f r o m f o r e i g n oils (olive h u s k oil a n d seed oils) or f r o m blends with f o r e i g n oils. THE DETEI~£INATION OF ELAIDINIC ACID IN THE OILS OF CRUCIFERAE PLANTS. U. P a l l o t t a , G. Losi a n d C. Zorzut (Univ. of Bologna, I t a l y ) . Riv. Ital. S o s t a n z e Grasse 42, 142 8 (1965). The presence of elaidinic acid in rapeseed oil is n o t directly detectable by T L C due to the i n t e r f e r i n g cis-ll-eieosenoic a n d eis-13-docosanoic acids which are p r e s e n t in s u b s t a n t i a l a m o u n t s . B y g a s p h a s e c h r o m a t o g r a p h y of t h e m e t h y l esters, s e p a r a t e d by p r e p a r a t i v e T L C technique, i t is however possible to detect the presence of about 0.3% elaidinic acid. The presence h a s also been n o t e d in rapeseed oil of small q u a n t i t i e s of two other f a t t y acids n o t previously reported, which a p p e a r to be positional i s o m e r s of cis-9-oetadecenoic a n d cis-ll-eicosenolc acids. ( C o n t i n u e d on p a g e 70A)

J AM. Oii~ CKE~fISTS' Soo., FEB. 1966 (Voh. 43)

.ABSTRACTS : F A T T Y ~_CID DERIVATIVES (Continued f r o m p a g e 68A)

• Fatty

Acid

Derivatives

ALPHA ~¢£ONOERUCATE, A NE'W E~iULSIEIER FOI~ COSI~£ETICS. J. Cyganska. 1'1. Sr. t~ior 9, 163-8 (1965). Monoerucate surpasses m o n o s t e a r a t e as an emulsifying agent f o r quality cosmetics. Monoerucate produces more stable and more homogenous emulsions t h a n monostearate. The emulsions are free f r o m odor (Rev. Franc. Corps G r a s ) . MORPHOLIDES OF EPOXIDIZED FATTY ACIDS. F. C. Magne, E. L. Skau, and R. R. Mod (Secretary of Agriculture, U.S.A.). U.S. 3,219,66& Claimed is the morpholide of epoxyoleie acid.

• Biochemistry

and N u t r i t i o n

INFLUENCE OF 1,3-BUTANEDIOL ON TISSUE LIPIDS OF COLD-EXPOSED RATS. G. S. Stoewsand, H. A. Dymsza, M. A. Mehlman and D. G. T h e r r i a u l t ( N u t r . Branch, Food Div., U.S. A r m y Natick Labs., Natick, Mass.). J. N u t r . 87, 464-68 (1965). The influence of feeding the polyhydrle alcohol 1,3-butanediol ( B D ) , on tissue liplds of n o r m a l and cold-exposed r a t s was investigated. The addition of 20% BD to a 30% f a t diet lowered adipose tissue lipids with a concomitant elevation of liver lipids at either normal or cold environments. F e e d i n g a 30% f a t diet to rats f o r 2 weeks and then exposing them to moderate cold of 5C, or severe cold --10C w i t h o u t food for 72 hours produced decreases in the total lipid content of epididymal adipose tissue, liver and muscle. Rats fed a similar diet, w i t h o u t cold exposure b u t also starved f o r 72 hours, showed no decrease in the total quality of adipose tissue lipids. CHOLESTEROL LEVELS IN THE HYPERCHOLESTEROLEi~[IC RAT : DIURNAL VARIATIONS. P. G. R a n d a n d F. W. Quackenbush (Dept. of Biochem., P u r d u e Univ., Lafayette, I n d . ) . J. Nutr. 87, 485-88 (1965). A diurnal variation in the p l a s m a cholesterol levels of r a t s fed cholesterol and sodium glycocholate in the diet was demonstrated. This variation was f o u n d to be associated with the feeding period r a t h e r t h a n with the lightdark cycle. I t was not eliminated b y altering the dietary energy source or by supplying u n s a t u r a t e d f a t t y esters in the diet. EFFECTS OF PURIFIED CIS- AND TRANS-FATTY ACID DERIVATIVES ON THE HYPERCHOLESTEROLEI~IC RAT. Ibid., 489 92. F i f t e e n compounds, derivatives of cis and trans u n s a t u r a t e d C~s f a t t y acids of high purity, were p r e p a r e d in the l a b o r a t o r y and compared f o r p l a s m a cholesterol-]owerlng effects in cholesterol-fed r a t s during an l l - d a y period. The cis-esters were more effective t h a n their non-conjugated or conjugated trans-isomers. The cis-alcohols and hydrocarbons were as effective as their corresponding esters. An acetylenic compound, ethyl stearo]ate, was inactive. I n these tests, and in 30-day tests with other compounds, effectiveness ia cholesterol-lowering was also related to degree of unsaturation. E t h y l arachidonate was the most active compound tested. Itowever, ethyl sorbate showed no activity. GLYOXYLATE IN FATTY-ACID1VIETABOLIS]Y£. R. Rabin, tl. C. Reeves, W. S. Wegener, R. E. Megraw and S. J. Ajl ( A l b e r t Einstein Med. Center, Phila., P e n n a . ) . Science 150, 1548-58 (1965). These investigations relate to the central role of g]yoxy]ate in the metabolism of f a t t y acids and other mono- and dicarboxylic acids in bacteria. Considerable p r o g r e s s has been nmde in elucidating the condensations of glyoxylate with various fattyacid CoA esters and the metabolism of these condensation products. STUDIES OF THE I~iECHANISI~ OF FATTY ACID SYNTHESIS. X I V . THE PROSTHETIC GROUP OF ACYL CARRIER PROTEIN AND THE ~£ODE OF ITS ATTACHI~ENT TO THE PROTEIN. E. L. P u g h and S. J. Wakih (Dept. of Biochem., Duke Univ., D u r h a m , N. Carolina). J. Biol. Chem. 240, 4727-33 (1965). The finding

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t h a t the prosthetic g r o u p of ACP is p h o s p h o p a n t e t h e i n e m a y account f o r some if not all of the non-CoA, protein-bound pa~ltothenic acid of the cell. This finding f u r t h e r s u p p o r t s the concept t h a t A C P functions as a coenzyme in f a t t y acid synthesis. I t essentially replaces coenzyme A in f a t t y acid biosynthesis and possibly in other metabolic systems. Acyl coenzyme A derivatives a p p e a r to be p r i m a r i l y the intermediated in catabolic reactions for f a t t y acids (with the exception of fl-hydroxy-fl-methylglutaryl-CoA synthesis and conversion to mevalonate), whereas acyl-ACP derivatives are the intermediates in f a t t y acid synthesis. One reason f o r this distinction may be t h a t there is very little choice to be made in the type of f a t t y acyl g r o u p s as intermediates in the two processes, but there is more choice at the coenzyme level. Thus, by using ACP as a eoenzyme, an o p p o r t u n i t y became available f o r the cell to distinguish catabolic f r o m anabollc substrates. COi~PARATIVE EVALUATION OE THREE SPECIES OF NEW ~VORLD MONKEYS FOR STUDIES OF DIETARY FACTORS, TISSUE LIPIDS AND ATtIEROGENESIS. O. W. P o r t m a n and S. B. A n d r u s (Dept. of N u t r , H a r v a r d School of Public Health, Boston, Mass.). J . Nutr. 87, 429-38 (1965). Cebus (Cebus albifrons), woolly (Lagothrix lagotricha) and squirrel (Saimiri sci~erea) monkeys were compared with respect to serum and other tissue cholesterol levels, serum fl-lipoprotein concentrations, f a t t y acid distributions in various tissue lipids, and severity of aortic atherosclerosis. Monkeys individually caged and f e d a semi-pui~ified diet ( b a s a l ) containing 16% of calories as corn oil were used. A s s a y s of susceptibility to hypercholesterolemia and atherosclerosis were carried out using diets which supplied 45% of calories as corn oil or coconut oil w i t h and w i t h o u t cholesterol. Cebus monkeys had the lowest m e a n serum cholesterol values of the 3 species studied with the basal diet. They also had the least spontaneous aortic sudanophi]ia. The responses of the serum cholesterol levels of the 3 species of monkeys to changes in dietary f a t or the addition of cholesterol were similar. I n the squirrel and woolly monkey the use of coconut oil ( r a t h e r t h a n corn oil) or the addition of cholesterol to either f a t resulted in a marked increase in the serum cholesterol level and severity of atherosclerosls at 6 m o n t h s ; the cebus monkey had comparable serum cholesterol levels b u t llttle atherosclerosis with the high f a t test diets. There was a high correlation in the squirrel and woolly monkey between the mean serum cholesterol levels with the test diets and extent of aortic sudanophilia, b u t the slopes of the regression lines of the cholesterol-sudanophilia plots f o r those 2 species were different. The susceptibility to diet-induced aortic sudanophilia was squirrel > woolly > cebus. B o t h diet and species affected cholesterol concentrations in several of the tissues studied. CELLULAR LIPOPROTEINS I. THE ISOLATION OF LIPOPROTEIN FRACTIONS FROM CELLULAR ~ITOCHONDRIA AND MICROSOIVfES. E. A. Napier, J r . and R. E. Olson ( Grad. School of Public Health, Univ. Pitts., Pitts., P e n n a . ) . J. Biol. Chem. 240, 424452 (1965). A procedure has been developed for the separation of lipoproteins f r o m r a t h e a r t and liver mitochondria and microsomes. The lipoproteins obtained f r o m liver mitochondria were characterized as a g r o u p with r e g a r d to physiochemical and chemical properties. Density g r a d i e n t studies of the ]ipoprotein f r a c t i o n revealed a " f a m i l y " of lipoproteins, analogous to those found in sermn, with the principal components with a density range of approximately 1.14 to 1.16. Silicic acid c h r o m a t o g r a p h y of the lipid moiety revealed 78% phospholipid, consisting p r e d o m i n a n t l y of phosphatides of ethanolamine, serine, and choline, and 22% n e u t r a l lipid, 2% of which was identified as coenzyme Q. The principal f a t t y acids in the lecithin and cephalin fractions were palmitate, stearate, ]inoleate, and arachidonic acid; the triglycerlde fraction consisted p r e d o m i n a n t l y of pahnitate, o]eate, and linoleate. INFLUENCE OF DIETARY OILS ON REPRODUCTION IN THE HEN. H. Menge, C. C. Calvert and C. A. D e n t o n (U.S. Dept. of Agr., P o u l t r y Res. Branch, Animal H u s b a n d r y Res. Div., ARS, Beltsvine, Md.). J. ~Vutr. 87, 365-70 (1965). A study was conducted to determine the effect of safflower or menhaden oil on the reproductive p e r f o r m a n c e of essential f a t t y acid-deficient hens. Single Comb White L e g h o r n pullets were reared f r o m hatching with an essential f a t t y acid ( E F A ) - d e f i c i e n t diet. A t 32 weeks of age the pullets were distributed into 6 g r o u p s o f 15 birds each. Groups 1 t h r o u g h 4 received safflower oil (calculated to supply zero, 20, 80, and 1600 m g of llnoleic acid (18 : 2 ) / h e n / d a y , respectively. I n c r e a s i n g the levels of dietary 1 8 : 2 supplied by safflower oil had a significant (Continued on page 72A)

70A

J AM. OIL CHEMISTS' See., FEB. 1966 (VOL. 43)

A B S T R A C T S : ]~IOCHEMISTRY AND ~ 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 70A) s t i m u l a t o r y effect on the reproductive c h a r a c t e r i s t i c s of t h e E F A - d e f i e i e n t hen. D i e t a r y m e n h a d e n oil f e d to E F A - d e f l c i e n t hens p r o m o t e d a significant increase in e g g production, hatchability a n d to some e x t e n t e g g size t h a t could n o t be a s s i g n e d to its 1 8 : 2 content. The d a t a i n d i c a t e d t h a t t h e p o l y u n s a t u r a t e d f a t t y acids ( P U F A ) p r e s e n t in m e n h a d e n oil were responsible f o r this stimulation. T h e a m o u n t o f 2 0 : 3 in the tissues of the E F A - d e f i c i e n t h e n was f o u n d to b e a r a definite n e g a t i v e relationship to t h e e x p r e s s i o n of the reproductive c h a r a c t e r i s t i c s of the chicken. T h e r e s u l t s of this s t u d y sugg e s t e d t h a t t h e P U F A of m e n h a d e n oil depressed t h e s y n t h e s i s of 2 0 : 3 a n d m a y have also s u b s t i t u t e d , at l e a s t in p a r t , f o r 1 8 : 2 or 2 0 : 4 , or both. THE EFFECT OF GLYCEROL 3-PtIOSPHATE ON FAT'fY ACID SYNTHESIS. C. F. H o w a r d , Jr., a n d J. M. L o w e n s t e i n (Dept. of Biochem., B r a n d e i s Univ., W a l t h a m , M a s s . ) . J. Biol. Chem. 240, 4170-75 (1965). Glycerol 3 - p h o s p h a t e s t i m u l a t e s f a t t y acid s y n t h e s i s b y cell-free p r e p a r a t i o n s of liver a n d l a c t a t i n g m a m m a r y gland. T h e c o n c e n t r a t i o n of L-glycerol 3 - p h o s p h a t e which gives one-half of m a x i m u m s t i m u l a t i o n is 0.37 raM. Comparison o f t h i s value w i t h c o n c e n t r a t i o n s of glycerol 3-phosphate in vivo u n d e r v a r i o u s conditions indicates t h a t glycerol 3p h o s p h a t e m a y exert a controlling influence on f a t t y acid synthesis in vivo. MEMBRANOUS MATERIAL OF BOVINE MILK FAT GLOBULES. 1. COMPARISON OF MEMBRANOUS FRACTIONS RELEASED BY DEOXYCHOLATE AND BY CHURNING. S. H a y a s h i a n d L. M. S m i t h (Dept. o f P h y s i c s , S a c r a m e n t o S t a t e College, S a c r a m e n t o , Calif.). Biochemistry 4, 2550-57 (1965). T h e f a t globules of milk are coated w i t h a m e m b r a n e composed of lipids a n d proteins. T h e n a t u r e of this m e m b r a n e h a s b e e n the s u b j e c t of m u c h i n v e s t i g a t i o n , b u t still is controversial. I n the prese n t work, water-soluble l i p o p r o t e i n particles a c c o u n t i n g f o r 4 5 % of the t o t a l w e i g h t of the m e m b r a n e were released f r o m the i n t a c t f a t globules b y s o d i u m deoxycholate ( D O C ) , a n d were isolated b y c e n t r i f u g a t i o n . Chemical a n a l y s e s of t h e s e lipoproteins showed t h a t lipids a n d p r o t e i n s were p r e s e n t in a p p r o x i m a t e l y equal a m o u n t s , a n d t h a t 7 6 % of the ]ipids were phospholipids. I I . SOME PHYSICAL AND ENZYMIC PROPERTIES OF THE DEOXYCHOLATE-RELEASED LIPOPROTEINS. S. H a y a s h i , D. R. Erickson, a n d L. M. Smith. Ibid., 2557-65. The lipoproteins released b y DOC have a wide r a n g e in u l t r a c e n t r i f u g a l h e t e r o g e n e i t y . S e d i m e n t a t i o n coefficients i n d i c a t e d t h a t particle i n t e r a c t i o n occurred a m o n g the lipoproteins d u r i n g t h e flotation procedure, a n d t h a t b o t h ionic s t r e n g t h of the flotation m e d i u m a n d the a m o u n t of lipid in the ]ipoproteins were f a c t o r s in particle a g g r e g a t i o n . DOC-released lipoproteins were p r e c i p i t a t e d irreversibly in a n acidic m e d i u m ; the m a x i m u m p r e c i p i t a t i o n occurred a t p i t 3.8. E x p e r i m e n t s to d e t e r m i n e t h e solubility dependence o f these lipoproteins on ionic s t r e n g t h were done a t p H 7.0, u s i n g a m m o n i u m s u l f a t e . A p p r o x i m a t e l y 93% o f the ]ipoproteins were salted o u t a t 4 5 % a m m o n i u m s u l f a t e s a t u r a t i o n ; t h e process was reversible. X a n t h i n e oxidase a n d alkaline p h o s p h a t a s e activities were a s s a y e d in f r a c t i o n s isolated, b y a m m o n i u m s u l f a t e precipitation, f r o m the DOCreleased ]ipoproteins. T h e r e was no m a r k e d p r e c i p i t a t i o n o f either enzyme, a n d it was concluded t h a t these two p r o t e i n s occur t o g e t h e r in the lipoprotein particles. FAT

METABOLISI~I IN HIGHEI% PLANTS. X X V I I I .

THE

BIOSYN-

TIIESIS OF SATURATED AND UNSATURATED FATTY ACIDS BY PREPARATIONS FRO~ BAaLEY SEEDLINGS. J. C. H a w k e a n d P. 1~. S t u m p f (Dept. of Biochem. a n d Biophysics., Univ. of Calif., Davis, Calif.). J. Biol. Chem. 240, 4746-51 (1965). A n u m ber o f carboxyl-C~tlabeled f a t t y acids .were i n c u b a t e d w i t h slices of b a r l e y seedlings. All t h e f a t t y acids f r o m octanoic t h r o u g h stearic were r e a d i l y m e t a b o l i z e d to C~40~ b u t only octanoic, decanoic, a n d dodecanoic acids served as effective p r e c u r s o r s f o r oleic acid f o r m a t i o n . B o t h p a l m i t i e a n d stearie

Established 1904

HOUSTON LABORATORIES Analytical and Consulting Chemists 311 Chenevert Street

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H o u s t o n 1, Texas

acids were ineffective. O x y g e n was required f o r the f o r m a t i o n of oleic acid. To t e s t f o r the a n a e r o b i c fl,7 e l i m i n a t i o n mecha n i s m of o]eic acid synthesis, 3-HS-labe]ed 3-hydroxy f a t t y acids were u s e d as s u b s t r a t e s . I n all cases o x y g e n w a s still required, a n d the p r i n c i p a l m o n o e n e f o r m e d was oleic acid. Therefore, while t h i s m e c h a n i s m does n o t a p p e a r operative in b a r l e y seedling s y s t e m s , these h y d r o x y acids are p r e s u m a b l y reduced to s a t u r a t e d acids which t h e n follow the p a t t e r n est a b l i s h e d p r e v i o u s l y f o r the f u r t h e r conversion of i n t e r m e d i a t e c h a i n s a t u r a t e d f a t t y acids to t h e C16 a n d C~s f a t t y acids. EFFECT OF VITAMINS h AND E ON LIPIDS IN SELECTED ]CAT TISSUES. Inez Harri]l, G]adys M i n a r i k a n d E l i z a b e t h Gifford ( N u t r . Div., H o m e Economics Section, A g r . E x p e r i m e n t Station, Colorado S t a t e Univ., F o r t Collins, Colorado). J. Nutr. 87, 424-28 (1965). To s t u d y the effect of v i t a m i n s A a n d E on ]ipids in selected r a t tissues, g r o u p s of r a t s were f e d weekly 70, 400 or 1200 I U of v i t a m i n A w i t h or w i t h o u t 10 m g o f a-tocopherol. A f t e r 12 weeks, a n a l y s e s were m a d e f o r liver a n d p l a s m a cholesterol a n d liver t o t a l lipids a n d v i t a m i n A. S t a t i s t i c a l a n a l y s i s of g r o u p m e a n s showed t h a t p l a s m a cholesterol of v i t a m i n E-deficient a n i m a l s f e d 1200 I U of v i t a m i n A was significantly h i g h e r t h a n t h a t o f c o r r e s p o n d i n g a n i m a l s f e d tocopherol. F e e d i n g tocopherol significantly decreased liver cholesterol in a n i m a l s f e d 400 or 1200 I U of v i t a m i n A. Liver cholesterol of a n i m a l s f e d 400 or 1200 I U of v i t a m i n A with toeopherol was significantly less t h a n t h a t of similar a n i m a l s f e d 70 I U of v i t a m i n A. T o t a l lipids in liver, which were n o t significantly affected by v i t a m i n A, decreased in a n i m a l s f e d v i t a m i n E w i t h 400 or 1200 I U o f v i t a m i n A. The s t o r a g e of v i t a m i n A w a s significantly i n c r e a s e d b y increased intake of d i e t a r y v i t a m i n A a n d by f e e d i n g v i t a m i n E. THE FATE OF DIETARY WAX ESTERS IN THE RAT. I. A. t t a n s e n a n d J. F. M e a d (Dept. of Biol. Chem., School of Med., Univ. of Calif., L. A., Calif.). Proc. Soc. Exp. Biol. Med. 120, 527-32 (1965). Oleyl p a l m i t a t e f e d to r a t s as 1 5 % of the diet was p a r t l y a b s o r b e d a n d p a r t l y excreted as a m i x t u r e of w a x ester, free f a t t y acid a n d free alcohol. B e c a u s e of p u r g a t i v e effects, a n i m a l s c a g e d t o g e t h e r c o n t a m i n a t e d each other's f u r with fecal lipid, g i v i n g t h e m the a p p e a r a n c e of seborrhea. A n i m a l s given oley] alcohol as 4 % of the diet did n o t show p u r g a t i v e effects b u t excreted lipid which was similar in composition to t h a t excreted b y r a t s given w a x esters. T h u s both hydrolysis a n d s y n t h e s i s o f waxes c a n occur in the intestine. Similar reactions have been carried o u t in vitro in the presence of a p a n c r e a t i c enzyme. W a x ester a n d f r e e oleyl alcohol were detected in t h e liver a f t e r f e e d i n g either c o m p o u n d a n d in both cases the p r e d o m i n a n t ester was oleyl p a l m i t a t e . The question of w h e t h e r oleyl alcohol is a b s o r b e d in the free or esterified f o r m was n o t s a t i s f a c t o r i l y resolved. METABOLISM OF OCTANOIC-]-C1~ AND PALMITIC-]-C14 ACID BY I~AT INTESTINAL SLICES. 1~. ,]-. G r e e n b e r g e r , J. J. F r a n k s a n d I~. J . I s s e l b a c h e r (Dept. of Med., H a r v a r d Med. School, Boston, M a s s . ) . l~roc. Soe. Exp. Biol. Med. 120, 468-72 (1965). Meas u r e m e n t s were c a r r i e d out on the in vitro m e t a b o l i s m of octanoic-l-C ~4 a n d palmltic-]-C ~ acid b y r a t i n t e s t i n a l slices. Significantly m o r e octanoic acid w a s catabolized to CO: a n d w a t e r soluble p r o d u c t s a n d less recovered as lipid soluble products c o m p a r e d to w h e n p a h n i t i c acid was the s u b s t r a t e . Analysis of these lipid soluble p r o d u c t s b y thin layer c h r o m a t o g r a p h y revealed t h a t more o f the p a h n i t i c acid was esterified to trlglyceride c o m p a r e d to octanoic acid. F u r t h e r a n a l y s i s of the lipid soluble p r o d u c t s b y gas-liquid c h r o m a t o g r a p h y d e m o n s t r a t e d t h a t a small b u t s i g n i f i c a n t a m o u n t ( 9 % ) of the label f r o m octanoic acid-l-C ~4 was recovered in f a t t y acids with c h a i n l e n g t h s of 10-20 c a r b o n atoms. This s u g g e s t s t h a t some of the octanoie acid-l-C 1~ m a y have been catabolized to C~-acetate which w a s t h e n i n c o r p o r a t e d into long c h a i n f a t t y acids. I n c o n t r a s t , v i r t u a l l y all of the label f r o m p a l m i t i c acid-l-C 1~ w a s recovered as such, i n d i c a t i n g t h a t v e r y little m u c o s a l c a t a b o l i s m of p a l m i t i c acid h a d occurred. IN VITRO INCORPORATION OF GLYCINE-1-C 1~ INTO TOTAL MUSCLE PROTEIN OF NORMAL AND VITAMIN E-DEFICIENT RABBITS. J. F. Diehl, C. D. F i t c h a n d G. E. N i c h o a l d s (Dept. of Biochem., Univ. of A r k a n s a s Med. Center, L i t t l e Rock, A r k . ) . Proc. Soc. Exp. Biol. Med. 120, 368-70 (1965). Skeletal muscle slices a n d h o m o g e n a t e s f r o m control a n d v i t a m i n E-deficient r a b b i t s were i n c u b a t e d in t h e presence of glycine-l-Clt I n b o t h prepa r a t i o n s v i t a m i n E deficiency resulted in a n i n c r e a s e d g]ycine i n c o r p o r a t i o n into t o t a l muscle p r o t e i n which was a c c o m p a n i e d b y i n c r e a s e d o x y g e n consumption. ( C o n t i n u e d on p a g e 74A)

72A

5 A~r. OIL CHEMISTS' Soe., FEB. 1966 (VOL. 43)

~BSTR~CTS:

BIOCHEI~ISTRY 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 72A) P A T H W A Y S OF ENZYMIC SYNTHESIS AND CONVERSION TO CHOLESTEROL OF AL'7'fa-CHOLESTATRIEN-3~-OL AND OTHER NATURALLY

OCCURRING STEROLS. M a r y E. D e m p s e y (Dept. of Biochem., Univ. of Minn. Med. School, Minneapolis, M i n n . ) . J . Biol. Chem. 240, 4176-88 (1965). A sterol h a v i n g the s t r u c t u r e A5'7'~cholestatrien-3fl-ol was s h o w n to be a n i n t e r m e d i a t e in cholesterol (AS-cholesten-3fl-ol) b i o s y n t h e s i s f r o m AT'ft5a-cholestadien 3fl-ol a n d As'2*-5a cholestadien-3~-ol. T h e s t r u c t u r e of the A5'7'~trienol w a s e s t a b l i s h e d f r o m its c h a r a c t e r i s t i c u l t r a v i o l e t absorption s p e c t r u m , c h r o m a t o g r a p h i c behavior, f o r m a t i o n of t h e epiperoxide (5a,Sa-epiperoxy-A~'ftcholestadien-3fl-ol) a n d trial (cholestan-3fl,5~,8a-triol) derivatives, a n d conversion by enzymic c a t a l y s i s to cholesterol, AL'tcholestadien-3fl-o], a n d As'ftcholes tadien-3fl-ol. These d a t a offer evidence t h a t enzymic conversion to cholesterol or n a t u r a l l y occurring sterols c o n t a i n i n g 27 c a r b o n a t o m s can t a k e place b y several a p p a r e n t l y irreversible p a t h w a y s . These r e s u l t s also show t h a t AL'7-intermediate sterols are e s s e n t i a l c o m p o n e n t s of all b i o s y n t h e t i c p a t h w a y s l e a d i n g to cholesterol. SERUM VITAMIN E DETERMINED BY THIN-LAYER CHROMATOGRAPHY.

J. G. B i e r i a n d E. L. P r i v a l ( N a t . I n s t . of A r t h r i t i s a n d Metabolic Diseases, N a t l . I n s t . of H e a l t h , B e t h e s d a , M d . ) . 2 r o c . Soc. l~xp. Biol. Med. 120, 554-57 (1965). F o r t y n o r m a l a d u l t sera were a n a l y z e d b y one-dimensional TLC. T h e a v e r a g e s in m g / 1 0 0 ml were: a-tocopherol, 0.916; combined fl + 7-tocopherols, 0.133. No 8-tocopherol was f o u n d . The p r o c e d u r e was checked b y c o m p a r i n g the GLC a n a l y s e s a n d also w i t h 2d i m e n s i o n a l TLC. INFLUENCE

OF

SOME

NONIONIC

SURFACTAh~TS ON PANCREATIC

LIPASE ACTIVITY. E. P. J o r o l a n a n d B. W. J a n l e k i ( B a s i c Microbio. Res. Lab., V. A. Hosp., W a s h . , D. C.). Proc. Soc. E x p . Biol. M e d . 120, 313-16 (1965). Two nonionic s u r f a c t a n t s , T r i t o n WR-1339 a n d Macrocyclon i n h i b i t the h y d r o l y s i s by p a n c r e a t i c lipase of t r i g l y c e r i d e s in a coconut oil emulsion ( E d i o l ) , T r i t i o n i n h i b i t i n g to a g r e a t e r e x t e n t t h a n Macrocyclon in a ratio of a p p r o x i m a t e l y 2 : 1 . HOC-60, also a nonionic s u r f a c t a n t , is n o t inhibitory. The r e s u l t s of the p r e s e n t s t u d y indicate t h a t d u r i n g its i n c u b a t i o n w i t h the s u r f a c t a n t at 37C f o r 1 hour b e f o r e a d d i n g the enzyme, the s u b s t r a t e m a y u n d e r g o a c h a n g e which would r e s u l t in a n altered s u b s t r a t e molecule t h a t is less reactive to p a n c r e a t i c lipase. Two sugg e s t e d m e c h a n i s m s of the i n h i b i t o r y action of the nonionic s u r f a c t a n t s are d i s c u s s e d : (1) f o r m a t i o n of an irreversible complex a n d (2) f o r m a t i o n of a micelle. The ability of these a g e n t s to induce h y p e r l i p e m i a in a n i m a l s was reflected by i n h i b i t i o n of e n z y m a t i c ]ipolysis in vitro. GROWTH OF A S P E R G I L L U S FLAVUS AND OTHER F U N G I IN WINDROWED PEANUTS IN G E O R G I A - - P A R T VII. C. R . J a c k s o n ( G e o r g i a

Costal P l a i n E x p . Sta., T i f t o n ) . Trop. Sei. V I I , 27-34 (1965). This p a p e r r e p o r t s r e s u l t s of e s t i m a t i o n s of p o d - s u r f a c e mycoflora a n d c u l t u r a l a s s a y s of kernels f r o m pods t a k e n f r o m windrows d u r i n g c u r i n g are t a b u l a t e d . A f l a t o x i n a n a l y s e s were m a d e on selected samples. I n one windrow e x p e r i m e n t , repres e n t a t i v e of commercial practice, A. flavus i n v a d e d kernels to a s l i g h t e x t e n t d u r i n g the excellent d r y i n g conditions which prevailed. Other f u n g i , n o t a b l y F u s a r i u m spp., P e n i c i l l i u ~ spp. a n d Dematiaceous species were more a b u n d a n t t h r o u g h o u t the w i n d r o w period. Aflatoxin was a b s e n t in kernels a n d shells f r o m w i n d r o w s a m p l i n g s . I n a second e x p e r i m e n t kernels f r o m p e a n u t s w i n d r o w e d d u r i n g cooler w e a t h e r were rarely i n v a d e d b y a n y A s p e r g i l l u s spp. a n d t o t a l n u m b e r s of other f u n g i in kernels were lower. K e r n e l s f r o m pods cured a g a i n s t the soil s u r f a c e were n o t i n v a d e d to a g r e a t e r e x t e n t t h a n those f r o m pods cured in the air, b u t e s t i m a t e d n u m b e r s of pod s u r f a c e f u n g i were larger. A . flavus w a s p r e s e n t in pod s u r f a c e mycoflora o f b o t h experiments. T H E MODE OF ACTION OF PANCREATIC LIPASE ON MILK FAT GLYC-

ERIDES. A. B o u d r e a u a n d J. M. d e M a n (Univ. of A l b e r t a , E d m o n t o n , A l b e r t a ) . J. Bacteriol. 43, 1799 (1965). Hydrolysis of t r i e a p r y l i n by p a n c r e a t i c lipase resulted in a stepwise

Ozone Research & Equipment Corp. Ozone Testing, Research, Consultation 3840 N. 40th Ave., Phoenix, Arizona

74A

hydrolysis, triglyceride to diglyceride to monoglyceride, as h a s been obtained w i t h long-chain trig]ycerides. However, hydrolysis r a t e s were m u c h f a s t e r a n d considerable a m o u n t s of free glycerol were f o r m e d . H y d r o l y s i s of a n e q u i m o l a r m i x t u r e of t r i c a p r y l i n a n d triolein i n d i c a t e d t h a t some of the s h o r t - c h a i n f a t t y acid was released f r o m t h e 2-position before all of the oleic acid was released f r o m the 1-position. H y d r o l y s i s of g e n u i n e a n d r a n d o m i z e d milk f a t r e s u l t e d in p r e f e r e n t i a l hydrolysis of glycerides c o n t a i n i n g s h o r t - c h a i n f a t t y acids. This p h e n o m e n o n was n o t d e p e n d e n t on a specific d i s t r i b u t i o n of these acids, since it also occurred with the r a n d o m i z e d fat. I t was concluded t h a t p a r t of the s h o r t - c h a i n f a t t y acids of milk f a t is located in the 2-position. The d i s t r i b u t i o n of caprylic a n d c a p r i c acids b e t w e e n t h e 1- a n d 2-positions is app r o x i m a t e l y at r a n d o m . L a u r i e , m y r i s t i c , a n d p a l m i t i e acids are p r e d o m i n a n t l y located in the 2-position, a n d stearic and oleic acids in t h e 1-position, of milk f a t glycerides. STUDIES ON THE I~APID ACCUMULATION OF TRIGLYCERIDE I N THE LIVEI¢ IN CHOLINE DEFICIENCY. S. M o o k e r j e a (Univ. of Toronto,

Toronto, O n t a r i o ) . J. Bacteriol. 43, 1733 (1965). Studies with isolated liver p e r f u s i o n p r e p a r a t i o n s showed t h a t , d u r i n g 5 to 21 days of choline deficiency ( a c u t e p h a s e ) , the livers fail to release a n y triglyceride into the p e r f u s a t e , whereas d u r i n g 1 to 2 d a y s (early p h a s e ) a n d d u r i n g 26 to 60 days of choline deficiency ( p r o l o n g e d p h a s e ) , t h e y t e n d to release triglyceride into the p e r f u s a t e a t a n e a r l y n o r m a l rate. The rate of deposition of h e p a t i c triglyceride in i n t a c t r a t s f e d a choline-deficient diet showed a p r o g r e s s i o n c o m p l e m e n t a r y to this t r i p h a s i c pattern of triglyceride release, i.e. a n early p h a s e of slow triglyceride deposition a n d a n a c u t e p h a s e of r a p i d a c c u m u l a t i o n followed b y t h e e s t a b l i s h m e n t of a h i g h e r s t e a d y - s t a t e level. I n the p e r f u s i o n e x p e r i m e n t s c h a n g e s in p h o s p h o l i p i d levels in the p e r f u s a t e followed the s a m e p a t t e r n as the triglyceride levels. I n c r e a s e d u p t a k e of free f a t t y acids by the cholinedeficient livers w a s m o s t m a r g k e d a f t e r 2 days. I n vitro additions of choline a n d several choline derivatives to the 5-day choline-deficient liver p e r f u s i o n s y s t e m were unable to restore triglyceride release. Similar s t u d i e s with blood o b t a i n e d f r o m choline-supplemented r a t s showed a very significant r e s t o r a t i o n of triglyceride release into the p c r f u s a t e . BETWEEN VITAMIN E AND POLYUNSATURATED FATTY ACIDS. H. D a m ( D a n m a r k s , Teknishe, Hijskole, Copenh a g e n ) . F e t t e S e i f e n A n s t r i c h m i t t e l 56, 899-3 (1964). The addition of polyenoie acids to food accelerates the e x h a u s t i o n of the v i t a m i n E reserve of the body. F e t a l resorption, decreasing r e s i s t a n c e to oxidative hemolysis a n d liver necrosis in rats as well as muscle d y s t r o p h y a n d e x u d a t i v e diathesis in chicken c a n arise in the absence of polyenoie acids in the food. P e r o x i d a t i o n a n d ceroid f o r m a t i o n a n d a c c o m p a n y i n g destruction of v i t a m i n A are caused by the presence of h i g h e r unsatu r a t e d f a t t y acids. The a d d i t i o n of polyenoic acids in food m u s t be a c c o m p a n i e d by the a d d i t i o n of v i t a m i n E. RELATIONSHIP

T H E EFFECT OF DIET ON THE CHANGES IN HEART LIPIDS FOLLOWING ~[USCULAR STRAIN. M. Rinetti, O. Visioli a n d L.

Colombi (Univ. of P a r m a , I t a l y ) . Riv. Ital. Sostanze Grasse 42, 322-4 (1965). The c h a n g e s in h e a r t lipid composition a f t e r an intense m u s c u l a r s t r a i n have been i n v e s t i g a t e d in r a t s f e d either a b a l a n c e d diet or a diet deficient in essential f a t t y acids ( E F A ) . I n all cases, a decrease h a s been observed in total ]ipids, nonesterified f a t t y acids ( N E F A ) a n d cholesterol esters, while t h e p h o s p h o l i p i d level was increased. The c h a n g e s have been m o r e m a r k e d in the a n i m a l s f e d an E F A deficient diet. Gas c h r o m a t o g r a p h i c a n a l y s i s h a s shown, both in the total lipids a n d in t h e phospholipids, a g e n e r a l tendency t o w a r d s h i g h e r a m o u n t s o f u n s a t u r a t e s in b o t h g r o u p s of animals. The f a t t y acid d i s t r i b u t i o n in t h e N E F A f r a c t i o n was quite diff e r e n t in the a n i m a l s f e d the r e g u l a r diet in c o m p a r i s o n to the ones f e d t h e deficient diet. T H E EFFECT OF VITAMIN A DEFICIENCY AND DIETARY a-TOCOPHERAL ON THE STABILITY OF RAT-LIVER LYSOSOMES. 0 . A . R o e l s ,

M a r i a n T r o u t a n d A. G u h a ( C o l u m b i a Univ. of N u t r . Sciences). Bioehem. J. 97, 353-9 (1965). V i t a m i n A-deficient r a t s and p a i r - f e d controls were m a i n t a i n e d on either n o r m a l or raised a m o u n t s of d i e t a r y a-tocopherol. T h e i r livers were f r a c t i o n a t e d a n d free a n d t o t a l lysosomal p h o s p h a t a s e were d e t e r m i n e d in the v a r i o u s f r a c t i o n s . The deficient livers showed i n c r e a s e d enzymic activity. P r o l o n g e d i n c u b a t i o n caused more r a p i d enzyme release f r o m the m l t o c h o n d r i a - l y s o s o m e - r i c h f r a c t i o n of the v i t a m i n A-deficient r a t s receiving t h e n o r m a l a m o u n t of d i e t a r y a-toeopherol t h a n f r o m t h e e q u i v a l e n t f r a c t i o n of their p a i r - f e d controls receiving v i t a m i n A. Raised d i e t a r y a-toeopherol reversed t h i s p h e n o m e n o n . J, AI~I. OIL CHEMISTS' SOC., FEB, 1966 (VOL. 43)

ABSTRACTS: D R Y I N G 0 I L S AND P A I N T S

• Drying

Oils and P a i n t s

TRIETHANOLAMINE BORATE CATALYZED CONDENSATION OF DISPItENOL A GLYCIDYL ETHERS ~vVITH POLYMEI%IC FAT ACIDS. J . ~:~.

Scheibli (Shell Oil Co.) U.S. 3,219,602. A process f o r prep a r i n g a linear acetone-soluble n o n - h e a t curable epoxy- containi n g condensate comprises a d d i n g a polymerized f a t t y acid prep a r e d by polynlerizlng an u n s a t u r a t e d f a t t y acid h a v i n g u p to a b o u t 20 c a r b o n a t o m s to 1.5-4 t i m e s the chemical equivalent a m o u n t of a polyepoxide c o n t a i n i n g more t h a n one vice p o x y g r o u p a n d h a v i n g no a d d i t i o n a l s u b s t i t u e n t capable of r e a c t i n g with the polynleric f a t t y acid other t h a n h y d r o x y l a n d epoxy g r o u p s in the presence of 0 . 5 - 3 % b y w e i g h t (on r e a c t a n t s ) of a t e r t i a r y a m i n e borate p r e p a r e d b y r e a c t i n g a t e r t i a r y a m i n e with m e t h y l borate at room t e m p e r a t u r e . The expression " e q u i v a l e n t a m o u n t " r e f e r s to t h a t a m o u n t needed to f u r n i s h one acidic g r o u p per epoxy group. THE

EFFECT OF ULTRASONICS ON THE DRYING PROPERTIES OF

LINSEED OIL. G. Saracco a n d E. S p a c c a m e l a M a r c h e t t i (Polytech. Inst., T u r i n , I t a l y ) . Olearia 19, 85-93 (1965). U l t r a sonic e n e r g y h a s a definite accelerating effect on the d r y i n g p r o p e r t i e s of linseed oil. E x p e r i m e n t s were r u n a t 85C on 3 0 % solutions of c r u d e linseed oil in CCL in the presence o f 1 % K I as the c a t a l y s t , with v a r i o u s i n t e n s i t i e s of supersonic e n e r g y applied. E x a m i n a t i o n of the c h a r a c t e r i s t i c s of the t r e a t e d p r o d u c t ( d r y i n g time, r e f r a c t i v e index, viscosity) indicates t h a t the oil h a s u n d e r g o n e i s o m e r i z a t i o n a n d polymerization reactions. Possible m e c h a n i s m s are discussed. TUNG OIL. Anon. Informaciones sobre Grca~as y Aceites (Buenos Aires) 3 (1), 14-17 (1965). A r g e n t l n l a n s t a n d a r d s ( I R A M ) are compared to A S T M s t a n d a r d s f o r this oil, p a r t i c u l a r l y c o n c e r n i n g r e f r a c t i v e index, viscosity a n d g e l a t i n i z a t i o n time. T H E ARGENTINIAN TUNG OIL MARKET. A n o n . Informaciones sobre Grasas y Aeeites (Buenos Aires) 3 (3 4), 53-56 (1965). The A r g e n t i n i a n t u n g oil i n d u s t r y is a n a l y z e d f r o m t h e econ o m i c view point, a n d c o m p a r e d to t h a t of other p r o d u c i n g countries (U.S.A., China, P a r a g u a y , Brazil a n d N y a s a n a l a n d ) .

• Detergents (Whirlpool Corp.). U.S. 3,213,028. A c l e a n i n g composition for soiled fibers consists of 1-10 p a r t s by w e i g h t of a d e t e r g e n t m a t e r i a l p e r 10 p a r t s of a glycerol-propylene oxide a d d u c t c o n t a i n i n g a b o u t 10 mols of p r o p y l e n e oxide p e r mo] of glycerol as a plasticizer f o r the fibers. L o w FOAMING DETERGENT. 1~. A. Grifo (General Aniline & F i h n Corp.). U.S. 3,215,633. A composition which h a s reduced f o a m i n g c h a r a c t e r i s t i c s a n d is s u b s t a n t i a l l y n e u t r a l in a q u e o u s systems consists of a cationic q u a t e r n a r y a m n i o n i u m halide s u r f a c e active a g e n t a n d f r o m 1 - 5 0 % of a n a l k y l a t e d m o n o h y d r i e phenol h a v i n g f r o m 8-18 c a r b o n a t o m s in the alkyl radical. DETERGENT FOI~ SOILED FIBERS. D . C. W o o d

C u r t i n a n d L. V. Curtin. U.S. 3,216,946. A free-flowing a n d s u b s t a n t i a l l y dustless cleaning composition consists of s o d i u m c a r b o n a t e in the f o r m of porous g r a n u l e s h a v i n g a b s o r b e d chiefly w i t h i n their capillary s t r u c t u r e s f r o m 5 to 50 p a r t s by w e i g h t of a 4 0 % a q u e o u s solution of s o d i u m h y d r o x i d e p e r 100 p a r t s by w e i g h t of u n t r e a t e d g r a n u l e s . The c l e a n i n g composition, w h e n dissolved in water, h a s a h i g h e r a l k a l i n i t y t h a n a s o d i u m c a r b o n a t e solution a n d is a n efficient cleaner. CLEANING AND DETERGENT COMPOSITION. L . P .

SURFACE ACTIVE AGENTS AND INTERFACIAL TRANSFER IN GASLIQUID CHROMATOGRAPHY. A NEW TOOL FOR MEASURING INTER-

FACIAL RESISTANCE. M. l~. J a m e s , J. C. G i d d i n g s a n d H . E y r i n g (Dept. of Chem., Univ. of U t a h , Salt L a k e City, U t a h ) . J . Phys. Chem. 69, 2351 (1965). I t is f o u n d t h a t the addition of cetyl alcohol to a c h r o m a t o g r a p h i c column, in which w a t e r is the liquid phase, g r e a t l y i n c r e a s e s the w i d t h of a n u m b e r of solute zones. B y u s i n g a g l a s s b e a d column where t h e m a j o r effects call be described by i n d e p e n d e n t c h r o m a t o g r a p h i c t h e o r y (as s h o w n h e r e ) , one can isolate the influence of interf a c i a l resistance. T h i s provides a new m e a n s f o r m e a s u r i n g the latter. The a d v a n t a g e s a n d d i s a d v a n t a g e s o f this technique are discussed. T H E INFLUENCE OF ELECTRICAL CHARGE ON INTERFACIAL ENERGY.

T. Steudel a n d R. C. M a y r h o f f e r ( I n s t . f o r the P h y s . Chem. of S u r f a c e s , M a r i e n t h a l / P f a l z , G e r m a n y ) . Tenside 2, 289-94

Correct vitamin A fortification right off your shelf The combination of vitamin A, vitamin D, vitamin E, and coloring agents you need to fortify your product may be unlike anyone else's. So we put your specific combination into batch-size cans and label them accordingly. Your label is color-coded to identify contents, has your code number to indicate batch size, and carries any special instructions you wish. You simply take the correct can off the shelf and pour. The hermetically sealed cans protect against spillage loss and inaccuracy in weighing. They guard against oxidation losses and accidental contamination. Further data and prices are quickly available from Distillation Products Industries, Rochester, N.Y. 14603. Sales offices: New York and Chicago. West Coast distributors: W. M. Gillies, Inc.

Distillation Products Industries is a division of Eastman Kodak Company

J. A~f. OIL C}IE~[ISTS' SO0., FEB. 1966 (VOL. 4 3 )

75A

ABSTRACTS : DETERGENTS

P A T T I S O N ' S L A B O R A T O R I E S , INC. C o n s u l t i n g a n d Analytical C h e m i s t s a n d Testing Engineers Since 1936 P.O. Box 346---Harlingen, Texas Telephone 512 GA 3-3196 (1965). I t has long been known that the rate of flow of water through an orifice can be increased by the presence of an electric field and that also the trajectory of a liquid jet can be deflected by electric fields. These experiments, however, do not in themselves ]end quantitative support to the theory of a possible effect of electric energy on interfaeial tension. A technique is now introduced for photographically observing changes in surface and interracial tension of ]iquid droplets on solid bodies having low surface tension (paraffins, plastics) or in immiscible liquids. By measuring the solid/liquid angle of contact it is possible to determine quantitatively the surface tension of the electrically charged liquids, assuming that the liquid surface tension and the contact angle are variable quantities and that the surface tension of the solid body is not appreciably changed by the applied electrical charges. The surface tensions of the liquids examined (water, formamide and some glycols) are lower (by 5-35%) than those of liquids that have not been electrically charged. The relationship between surface tension lowering and electrical charge is discussed and it is shown that larger drops require higher charges to attain the same effect. T H E MANUEACTURE OE I=IIGt=IEI~ ~OLECULAR ~,VEIGttT ALXYL BENZENES. A N ATTEI~PT TO DISCOVER THE REACTIOlXT MECHANISMS,

I. A. Metzger, R. Buxbaum, C. It. Uhlig and M. Gennert (Kempen/Ndrh., Germany). Tenside 2, 36 40 (1965). Phenyln-alkanes-(1) sulfonated in the para position should be extremely biodegradable, however they are too sparingly soluble in water to be useful as detergent raw materials. Starting from the consideration that the su]fonates of position isomeric phenyl-n-alkanes-(2) and -(3) are more easily water soluble with only a very slight loss in washing power, experiments were carried out to steer the alkylation of benzenes with alphan-alkenes preferentially into the (2)- and (3)- position. When aluminum chloride or bromide were used as catalysts, it was noted that under certain conditions n-alkanes were obtained in varying amounts besides alkyl benzenes, presumably formed by a side reaction, not so far understood, involving the hydration of the alpha-n-alkene used. When su]phurie acid was used as the catalyst, no alkane formation was observed. The boiling ranges and the refractive indices of the reaction products indicate that the distribution of the expected position isomeric alkyl benzenes depends largely upon the parameters of time and temperature. T H E POSSIBILITY OF PREPARING SURFACTAIqT II'TTERMEDIATES ~,VITtt THE. HELP OF ALKYL ALU]~INU]~ CO~IPOUNDS. I~. Reinheckel

and D. 5ahnke (Germ. Acad. of Sci., Berlin, Germany). Tenside 2, 249-53 (1965). Various reactions between organo-aluminum compounds and other types of organic substances, such as reduction of fatty acids, formation of ketones, etc., are discussed, as well as the possibility of using the reaction products as intermediates in surfaetant manufacture. Straight chain primary fatty alcohols are obtained by reducing fatty acid esters with dialkyl aluminum hydrides, non-terminal double bonds renmining intact in the reaction. F a t t y acid chlorides and dicarboxylie acid semi-ester chlorides or dichlorides, when reacted with ethyl aluminum sesquichloride, for the corresponding ethyl ketones, ketocarboxylic esters or diketones. The different uses of various solvents in these reactions are indicated. Triethyl aluminum and nitriles also produce ethyl ketches. Isocyanates and isothiocyanates, when reacted with trlethyl aluminum or ethyl aluminum sesquichloride, produce the corresponding N-substituted carboxy]ic and thiocarboxylic amides, respectively. T H E EFFECT OF ALKYL SULPttATES ON THE SORPTION OF PIG)/IENTS ON COTTON. E . F . Wagner (Wash R e s . I n s t . Krefeld,

Germany). Tenside 2, 173-80 (1965). The sorption on cotton of carbon black, as a prototype of spherical dirt particles, was examined by varying the chain length of the alkyl su]phates. According to the results, the course of the sorption isotherm is influenced only gradually by the presence of carbon black, since alkyl sulphates themselves adsorb according to the same type of curve on the fibre surface. The rate and absolute value of carbon black desorption from the cotton fabric increase with (Continued on page 78A) 76A

• N e w Literature UNIVERSAL 0IL PRODUCTS COMPANY has available the pamphlet, " U O P Processing Guide," containing brief descriptions of a number of the principal U O P refining processes and products. (30 Algonquin Road, Des Plaines, Ill. 60016.) CHROMATOGRAPHY CORPORATION OF A M E R I C A h a s two new bulletins available: 1) A new 6 page bulletin describes a system of flow connectors, chromatographic columns, reservoirs, needle valves and tubing f o r column chromatography. 2) A 4-page bulletin describes two new instruments for liquid c h r o m a t o g r a p h y : the Auto-Gradient, for creating predictable gradients, and the Model R forced air R e f r i g erated F r a c t i o n Collector. (60B E a s t Main St., Carpentersville, Ill. 60110.) OZONE RESEARCI-I AND E Q U I P M E N T CORPORATION h a s i s s u e d brochures 102 and 103 describing their expanded

line of L a b o r a t o r y and Process Ozonators. 40th Ave., Phoenix, Arizona.)

(3840 North

TIIE PERMUTIT COMPANY, Division of R i t t e r P f a u d l e r Corporation, has released information on their new F A V A I R F l o t a t i o n System, which makes it possible for oil, grease and suspended m a t t e r to be separated and reclainled f r o m p l a n t process waters nmre efficiently and at lower cost. The name F A V A I R is short f o r Floe Adjustment, V a r i a b l e Aeration and Ideal A i r Release, which are the m a j o r improvements of the new systenl. (Box 41, Paramus, N. J.) SKEIST LABORATORIES, INC., has compiled a bulletin called "Coatings, Prospectus f o r a Multiple-Client Study," which includes names of companies in the coatings and ink industries, developments abroad, raw materials, and many other aspects of market study on this topic. (89 Lincoln Park, Newark, N. J. 071.02.) ALOE SCIENTIFIC is distributing, free of charge, a colorful 12-page bulletin issued monthly to describe their newest laboratory equipment and supplies. ( D e p a r t m e n t RK-11, 1831 Olive Street, St. Louis, Mo. 63103.) GALLARD-SCttLESINGER

CHEMICAL

MANUFACTURING

CORP.

has published a bulletin on furoic acid, c o v e r i n g its properties, uses, complete bibliography and related data. (580 Mineola Avenue, Carle Place, Long Island, New York,

115140 UPJOHN CO~PA~Y has available for distribution new technical literature describing their carbodiimides, including di-orthoOtolyl, bis (2,6-diethylphenyl) and dicyclohexyl, and a complete bibliography of this g r o u p of chemicals. (North H a v e n , Conn. 06473.) CO]~SOLIDATED ELECTRODYNAMICS CORP., subsidiary of Bell & Howell Co., has an 8-page bulletin (21703) describing an advanced isotope-assay and atomic-research nmss spectrometer, the Type 21-703A. (360 Sierra Madre Villa, Pasadena, Calif.)

E. H. SARGENT & CO., in Bulletin SR-GC-2, describes their basic line of SR Sargent Recorders to complement any and all leading chromatographs. (4647 W e s t F o s t e r Ave., Chicago, Ill. 60630.)

PERKIN-ELMER~in a new 8-page booklet, describes the lowcost, compact Model F l l gas chromatograph, designed to place precision gas c h r o m a t o g r a p h y results within the reach of every laboratory. (Main Avenue, Norwalk, Conn.) PENNSALT CHEMICALS CORPORATION, E q u i p m e n t Division, has a 6-page bulletin (No. 2010) describing the 13 basic Sharples centrifuges for v i r t u a l l y every area of separation. (Three P e n n Center, Philalelphia, Pa. 19102.)

LAC~AT CHEMICALSINCORPORATEDhas a 2-page supplement for their Catalog No. 6, listing their stock of chemicals for research and gas chromatography. (10540 S: Western Ave., Chicago, Ill. 60643.) J. AM. OIL CHEMISTS' Soe., :FEB. 1966 (VoL. 43)

Klenle Acl/evements

.

ABSTRACTS

.

(Continued from page 50A) able p r e v i o u s l y in isolating the crystalline methylglycoside of n e u r a m i n i e acid f r o m the same material. The N-acetyl fo~ml occurs in blood s e r u m a n d t o g e t h e r with N-glycolyl, N, 0 -di a n d tri-acetyl d e r i v a t i v e s in all m u e i n s of end o d e r m a l origin. I n a d d i t i o n to his significant contrib u t i o n to the elucidation of the s t r u c t u r e of this v e r y i n t e r e s t i n g substance he showed t h a t the p r i m a r y a n d one of t h e most i m p o r t a n t f u n c t i o n s of n e u r a m i n i c acid is to serve as the d e t e r m i n a n t g r o u p of the acceptorsite f o r the m y x o v i r u s of the m u m p s - i n f l u e n z a g r o u p . H e has cont r i b u t e d f u r t h e r to the b i o c h e m i s t r y of n e u r a m i n i e acid b y showing t h a t the enzymic action o f m y x o v i r u s is the same as t h a t of the r e c e p t o r d e s t r o y i n g enzyme f r o m the culture filtrate of v a r i o u s bacteria, b y showing the role of n e u r a m i n i d a s e in v i r u s h e m a g g l u t i n a t i o n a n d p a n a g g l u t i n a t i o n reactions, a n d b y showing this acid to be the d e t e r m i n a n t g r o u p of the M N blood g r o u p system. I n the 1960's K l e n k t u r n e d his a t t e n t i o n once a g a i n to the gangliosides. P u r i f i c a t i o n of t h e gangliosides a n d det e r m i n a t i o n of t h e i r s t r u c t u r e s by p a r t i a l hydrolysis, isolation of the oligosaccharides, p e r m e t h y l a t i o n , p e r i o d a t e o x i d a t i o n a n d b y the t r e a t m e n t w i t h n e u r a m i n i d a s e , resulted in the conclusion t h a t the gangliosides are a mixt u r e of substances which are v e r y closely related in t h e i r chemical compositions. The difference in the f a t t y acid a n d s p h h i g o s i n e moieties a r e v e r y slight, the m a i n comp o n e n t of the f o r m e r b e i n g stearie acid a n d t h a t of the l a t t e r C~- sphingosine. The C~- s p h i n g o s i n e is replaced b y its C~o- hoInologue w i t h i n c r e a s i n g age. However, t h e r e is extensive v a r i a t i o n in the c a r b o h y d r a t e p o r t i o n of the molecule. The c a r b o h y d r a t e sequence in all hexosanIine cont a i n i n g b r a i n gangliosides, is glucose- (4-1) galaetose (4-1)N - a c e t y l - g a l a e t o s a m i n e ( 3 - 1 ) - g a l a e t o s e with N-acetyl- neur a m i n i c acid in a ( 3 - 2 ) - l i n k a g e a t first galactose molecule a n d the glucose molecule is glycosidically b o u n d to s p h i n gosine. A second t y p e o f ganglioside which is devoid o f the t e r m i n a l galaetose g r o u p exists in only small a m o u n t s in the n o r m a l b r a i n , b u t a p p e a r s in a b u n d a n c e in a m a u r o t i c idiocy of T a y - S a c h s type. A t h i r d ganglioside has two nmlecules of n e u r a m i n i c acid, one of which lies in the cent r a l galactose molecule a n d the o t h e r (3-2) glycosidically b o u n d to the t e r m i n a l galactose molecule. Of these two n e u r a m i n i c acids only the l a t t e r can be split off with neuraminidase. A f o u r t h t y p e of ganglioside is composed o f the same c a r b o h y d r a t e sequence but h a v i n g two molecules of N - a c e t y l - n e u r a m i n i c acid a t the first galactose molecule, linked to each o t h e r in (8-2) position. A n a d d i t i o n a l molecule o f N - a c e t y l - n e u r a m i n i c acid m a y be a t t a c h e d to the 3p o s i t i o n of the second galaetose. The existence in small a m o u n t s of a h e x o s a m i n e - f r e e ganglioside which c o n t a i n s only glucose, galaetose a n d N- a c e t y l - n e u r a m i n i c acid, was also d e m o n s t r a t e d . The configuration of the n e u t r a l s u g a r moiety c o r r e s p o n d s to t h a t of lactose. A n o t h e r hexosaminefree ganglioside consists of 3 molecules of galactose with a n N - a c e t y l - n e u r a m i n i c acid in p o s i t i o n 3 a t the c e n t r a l galactose. ( O f the extensive works of E r n s t K l e n k which h a v e been p r e s e n t e d in more t h a n 160 publications, only the events of i m p o r t a n c e could be cited.) Most of his work h a s been conducted at the U n i v e r s i t y of Cologne following his a p p o i n t m e n t as d i r e c t o r of the I n s t i t u t e f o r Physiological C h e m i s t r y in 1936. H e r e his works h a v e been accomplished in c o o p e r a t i o n with n e a r l y ]00 associates to which g r o u p the a u t h o r of this biograp h y has the h o n o r to belong. HANS ~AILLARD~ O. P R O F . D R . P H I L . I n s t i t u t fiir Physiologische Chemie d e r R u h r - U n i v e r s i t ~ t Bochum, G e r m a n y

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DETERGENTS

(Continued from page 76A) increasing chain length of the alkyl sulphates. The deposition of carbon black particles from alkyl sulphate solutions with concentrations corresponding to the ck values decreases in absolute magnitude with increasing chain length, while the change in adsorption with time remains unaffected. On the other hand, a definite increase in desorption rate was observed at the ck value of the alkyl sulphates with increasing chain length. The optimum effectiveness of the alkyl sulphates does not, according to these experiments, lle within the range of critical Inicelle concentration. CATIONIC SURFACTANTS AS LEVELLING AGENTS IN DYEING ANIONIC POLYACRONITRILE FIBERS. ]:~. R o k o h l (BASF, Ludwig-

shafen/l~hein, Germany). Tenside 2, 76-83 (1965). Cationic surfactants are effective ]evelllng agents for dyeing anionic polyacronitrile fibers with selected basic dyestuffs. The rate of uptake of the dyestuff is diminished because of the blocking effect of the agent and the ability of the dyestuff to migrate during the process is also increased. This retarding effect is dependent upon the chemical constitution of the cationic surfactant. NOTES

ON THE DOCUMENTATION OF SUREACTANT SPECTRA.

•.

Bey (Diisseldorf, Germany). Tenside 2, 105-11 (1965). The reference spectra of a large number of commerieal surfaetants have been prepared in the form of punched cards. This useful collection of spectra is an excellent aid in interpreting infrared spectra of unknown surfactants, when used in conjunction with a spectrum list similar to the Spec-Finder system by Sadtler. T H E DETERMINATION OF PERBORATE CONTENT I N SYNTHETIC DETERGENTS. E. tIeinerth (Diisseldorf, Germany). Tenside 2,

]80-1 (1965). The active oxygen content of modern detergent compositions can be determined by reaction with an arsenite solution and iodometric titration of the excess arsenite. This method is effective even in cases where the permanganate and iodine titrations faiL SPRAY DRYING EQUIPI~ENT F o a THE PRODUCTION OF SYNTHETIC DETERGENTS AND SOAP-SYNTHETIC POWDERS. E . J u r y (Lurgi

Gmbh, F r a n k f u r t / M a i n , Germany). Tenside 2, 209-16 (1965). The principles of design and construction for a detergent spray drying plant are reviewed, with special regard to slurry preparation and its effect on the end product specifications. Besides a description of the actual spray drying equipment, the after treatment of the powder, storage and transport of the finished product, automatic control equipment and economic considerations on material and labor costs are also discussed. ODORIFEROUS COMPOUNDS IN POLYPEOPYLENE BENZENE SULFONATE. I . ISOLATION AND SEPARATION OF VOLATILE OIL. W . I~.

Seifert (Calif. Res. Corp., Richmond, Calif.). Tenside 2, 150-6 (1965). Nitrogen blowing of large batches of po]ypropylene benzene sulfonate slurry and condensation of the gas in cold traps led to the isolation of 0.2% (active basis) of an odoriferous volatile oil, with no indication of decomposition during the blowing step. Separation and qualitative identification of this oil, which contains about 200 compounds were done by preparative GLC and silica gel chromatography combined with instrumental analysis. Olefins and carbonyl compounds were found to be present in the most odoriferous fractions. Isolation and analysis of the volatile oil of unsulfonated polypropylene benzene showed that all the compounds causing the sulfonate odor are produced in the sulfonation process. II. IDENTIFICATION. Ibid., 182-90. I n f r a r e d analysis of the carbonyl compounds and reduction with sodium borohydride combined with odor panel tests showed t h a t saturated ketones (less than 1 ppm) are the largest contributiors to the odor of polypropylene benzene sulfonate slurries. The second largest contributions came from about 50 ppm of substituted terpenetype diolefins, whose structure was investigated by mass spectroscopy, IR, UV, Raman Spectra and NMR before and after selective and total catalytic hydrogenation. The small odor contribution of sulfur compounds and the absence of mercaptans were demonstrated by gas chromatography combined with microcoulometrie titration and chemical microreactions combined with odor panel tests. A number of branched chain paraffins and substituted eyclohexanes were directly identified by mass spectroscopy, however the contribution of these compounds to the over-all odor was found to be negligible. III.

]~EMOVAL OF ODOI¢ BY CHEMICAL TREATMENT AND CONTROL

OF SULFONATION CONDITIONS. Ibid., 216-20. Removal of the ketone odor from polypropylene benzene sulfonate slurries is (Continued on page 81A)

78A

J, AM. OIL CHEMISTS' SOO., FEB. 1966

(VOL. 43)