ABSTRACTS •

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

Fats and Oils

THE OCCURI~ENCE OF A NATURAL ANTIOXIDANT IN CITRUS FRUIT. S. V. Ting and W. F. Newhall ( F l o r i d a Citrus Exp. Sta., Lake Alfred, F l o r i d a ) . J. Food Sci. 30, 57-fi4 (1965). Antioxidant activity was found chiefly in the flavedo of citrus fruits. Orange was f o u n d to have the highest activity with lime and lemon having almost no antioxidant activity. The a m o u n t of activity of the various fractions studied w a s measured by a nmcro-manometric a p p a r a t u s which m e a s u r e d the a m o u n t of oxygen adsorbed by d-limonene. A l u m i n a column c h r o m a t o g r a p h y was found to yield an oily f r a c t i o n rich in activity. Thin-layer ehromatograhy, a positive ferric chloridedipyridyl test and the non-polarity of the u n k n o w n active material indicate possibly a tocopherol. COLLABORATIVE STUDY ON THE QUANTITATIVE DETERMINATION OF VOLATILE FATTY ACIDS BY GAS CHROMATOGRAPHY AND BY COLUMN PAI~TITION CHROMATOGRAPHY. H. Salwin (Div. of Food Chem., F.D.A., Washington, D.C. 20204). J. Assoc. Offic. Agr. Chem. 48, 628-35 (1965). The results obtained by the gas chromatographic method were as accurate as, and possibly more accurate than, those obtained by the A.O.A.C. method. The precision of the two methods was approximately equal. The gas chronmtographie method has the advantages of a single procedure f o r formic, acetic, propionic, and butyric, improved specificity and sensitivity, a p e r m a n e n t record of the analysis and a more rapid procedure f o r some analyses. SEPARATION AND IDENTIFICATION OF SODIU~I SALTS OF ACETIC, PROPIONIC~ BUTYRIC, AND VALERIC ACIDS BY PAPER CHROMATOGRAPHY. J. A. Young, G Schwartzman and A n n a L. Melton (F.D.A., 1141 Central P a r k w a y , Cincinnati, Ohio 45202). J . Assoc. O/tic. Agr. Chem. 48, 622-24 (1965). A method is presented to confirm the identity of volatile acids a f t e r steam distillation separation by silicic acid c h r o m a t o g r a p h y and sodium hydroxide titration. The method works equally well f o r the detection of propionates in bread products. The developer

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262A

is a mixture o f two volmnes of acetone added to equal volumes of n-butanol, t-butanol, and concentrated ammonia. T h i s system was f o u n d to give more distinct separation of the acid spots and development time was reduced. ISOLATION AND IDENTIFICATION OF THE VOLATILE FATTY ACIDS PRESENT IN HICKORY SAWDUST SMOKE. H. h . Harold and R. C. Saffie ( F o o d Techno]. Dept., Univ. of Georgia, Athens, Georgia 30601). J. Eood Sci. 30, 697-702 (1965). Acetic, propionic, butyric, iso-valeric, n-valerie, iso-caproic, and n-caproie acids were identified in hickory sawdust smoke by gas chromatography, and the relative amounts of each were determined. F o r m i c acid was n o t detected since a hydrogen flame ionization detector was used and is insensitive to this acid. A total of eight columns were evaluated, three of which were used f o r identification by retention times as well as i n f r a r e d spectrophotometry. SOME EFFECTS OF HIGH LEVELS OF GAMMA IRRADIATION ON THE LIPIDS OF WHEAT. I~. H. Tipples and F. W. Noi'ris (Grain Res. Lab., Winnipeg, Manitoba). Cereal Chem. 42, 437-51 (1965). G a m m a irradiation produced small changes in the lipid fractions of irradiated wheat. Linoleie and ]inolenie acids decreased slightly and the unesterified f a t t y acids appeared to be more susceptible to irradiation damage t h a n esterified acids. Carotenoids and the tocopherols decreased with increasing radiation. Upon storage, linoleic and linolenic acids were autoxidized more slowly in the radiated samples t h a n in the control. I r r a d i a t i o n tended to cause a decrease in triglycerides, galactolipids and phospholipids and an increase in the free stcrols, monoglycerides and diglycerides. THE EFFECT OF STORAGE TIME ON THE COMPOSITIONAL PATTERNS OF RICE FATTY ACIDS. Ten-CMng Lee, Wei T. W u and V i r g i n i a R. Williams (Dept. of Biochem., La. State Univ., B a t o n Rouge, L a . ) . Cereal Chem. 42, 498-505 (1965). Significant variation occurred f r o m one sampling period to the next, but significant correlation between percentage composition and time was f o u n d in only two cases: the oleic acid and the linoleic acid of the phospholipid fraction. The oleic acid increased and the linoleic acid decreased with storage time. The same t r e n d occurred in the free f a t t y acids and mono- and diglycerides. CHANGES IN LIPID COMPOSITION IN MATURING WHEAT. R. D. D a f t a r y and Y. P o m r a n z (Dept. of F l o u r and Feed Milling Ind., K a n s a s State Univ., Manhattan, K a n s a s 66504). J. Food Sci. 30, 577-81 (1965). Changes in lipid composition during w h e a t development were followed by qualitative and quantitative thin-layer c h r o m a t o g r a p h y ( T L C ) and by fractionation on silicie acid columns. Development of the wheats was accompanied by a slight decrease of lipid content on an as-is basis, and by an almost doubling of liplds on a kernel basis. F r e e f a t t y acids in m a t u r e wheat were less than half the a m o u n t in wheat 21-23 days preceeding ripeness. A similar decrease was f o u n d in the levels of mono- and diglycerides. No consistent changes occurred with the phospholipid fractions of developing wheat b u t the carotenoid pigments disappeared as the wheat kernel developed and matured. THE FAT OF HIBERNATING ANIMALS. A. D. Popov and P. D. Mazhdrakov ( I n s t . of Org. Chem., B u l g a r i a n Acad. of Sciences, Sofia, B u l g a r i a ) . Biochem. (U.S.S.R.) 29 (4), 550-3 (1965). The composition of f a t f r o m the hedgehog was studied. The qualitative characteristics and quantitative composition of the f a t and the mixed f a t t y acids were determined. The f a t remains liquid over a wide range of t e m p e r a t u r e (M.P. ~ 0C) and is rich in u n s a t u r a t e d f a t t y acids. The hedgehog and g r o u n d squirrel f a t s are much alike and resemble f a t s of reptiles and a m p h i b i a n s r a t h e r t h a n t h a t of w a r m blooded animals. GAS CHROMATOGEAPHY OF UNSAPONIFIABLE MATTER. I I I . IDENTIFICATION OF HYDROCARBONS~ ALIPHATIC ALCOHOLS~ TOCOPHEROLS~ TRITERPENOID ALCOHOLS AND STEROLS PRESENT IN OLIVE 0ILS. J. Eisner, J. L. Iverson, A. K. Mozingo and D. F i r e s t o n e (Div. of Food Chem., S t a n d a r d s and Additives, F.D.A., Washington, D. C.). J. Assoc. O/fie. Agr. Chem. 48, 417-33 (1965). The unsaponifiable m a t t e r of both f o r e i g n and domestic olive oil was f r a c t i o n a t e d on a Florisil column. Gas c h r o m a t o g r a p h y confirmed t h a t squalene was the m a j o r component of the ~irst s A~. OIL C~EMISTS' See., JUNE 1966 (VOL. 43)

ABSTRACTS:

FATS AND OILS

two h y d r o c a r b o n f r a c t i o n s f r o m pomace oils. However, isoa n d / o r anteiso-tetratriacontane was the m a j o r h y d r o c a r b o n in olive kernel oil. Gas c h r o m a t o g r a p h y of the t h i r d Florisil fraction indicates the presence of three homologous series of norreal, iso- a n d / o r anteiso-, a n d multiple b r a n c h e d c h a i n alcohols. Triterpenoid alcohols were u s e d to d i s t i n g u i s h between pressed a n d solvent-extracted pomace oils. Campesterol a u d betasitosterol were the two sterols p r e s e n t in the olive oils. THE EFFECT Ol~ BORON ON THE LIPID CONTENT AND DISCOLORATION OF POTATOES. N. I. Mondy, A. Bourque, B. Breslow a n d L. R. M a t t i c k (Grad. School of P u r r . , N e w Y o r k Sta±e College of H o m e Econ., Cornell Univ., I t h a c a , N e w Y o r k 14850). J. F o o d Sei. 30, 420:26 (1965). Ontario, K a t a h d i n , a n d P o n t i a c p o t a t o e s g r o w n with a n d w i t h o u t boron f o l i a r s p r a y were e x a m i n e d f o r discoloration a n d lipid content. The lipid was f r a e t i o n a t e d into free f a t t y acids, n e u t r a l f a t , a n d phospho]ipids. The free f a t t y acids f r o m each of the three fractions were esterified a n d q u a n t i t a t i v e l y analyzed b y g a s chrom a t o g r a p h y . Discoloration was m e a s u r e d with a H u n t e r color-difference meter. The total lipid of all three varieties was higher in the boron t r e a t e d potatoes t h a n in the control potatoes. The p h o s p h o l i p i d f r a c t i o n of all three varieties was h i g h e r in the b o r o n t r e a t e d potatoes, a n d the n e u t r a l - f a t fraction was h i g h e r in P o n t i a c p o t a t o e s which were boron treated. P o t a t o e s receiving boron t r e a t m e n t discolored less t h a n the control potatoes. FATrlrir ACID COMPOSITION ON THE PLASMA LIPIDS 01~ NEWBORN AND MATERNAL RUI%iINANTS. W. M. F. L e a r ( I n s t . of A n i m a l Physiol., B a b r a h a m , C a n l b r i d g e ) . Bioehem. J . 98, 598-603 (1966). The f a t t y acid compositions of the p l a s m a lipids o f newborn u n s u c k l e d lambs, kids, calves a n d p i g l e t s have been d e t e r m i n e d a n d c o m p a r e d with those of m a t e r n a l p l a s m a ]ipids at p a r t u r i t i o n . The p r e d o m i n a t i n g p l a s m a f a t t y acids in the newborn o f all species are palmitic, stearie a n d oleic acids. V e r y small a m o u n t s of ]inoleic a n d linolenie acids are present, a l t h o u g h considerable a m o u n t s of these acids are contained in m a t e r n a l p l a s m a . The p l a s m a f a t t y acids of the n e w b o r n piglet c o n t a i n e d 5.5% lino]eic, those of the calf 2.0% a n d those of the lamb a n d kid less t h a n 1.0%. I n t h e l a m b a n d kid, b u t n o t in t h e calf or piglet, a C - 2 0 : 3 acid was detected in p l a s m a lipids t h a t was v e r y similar to, if n o t identical with the C - 2 0 : 3 acid t h a t a c c u n m l a t e s in the p l a s m a of anim a l s of g i v e n diets low in e s s e n t i a l f a t t y acids. The eholestery] esters of cow p l a s m a were f o u n d to c o n t a i n a h i g h e r percentage ( 4 3 % ) of ]inolenic acid t h a n those of g o a t a n d sheep plasma (5-10%). ISOMERIC METHOXY-STEARIC ACID ARTIFACTS ]~ROM SHEEP PERINEPHRIC FAT. 1:~, P. H a n s e n ( D e p a r t m e n t o f Sci. a n d I n d . Res., Wellington, N e w Z e a l a n d ) . Chem I n d . ( L o n d o n ) 1956, 288. A f r a c t i o n r e p r e s e n t i n g trace p r o p o r t i o n s of the t o t a l f a t t y acids h a s been isolated f r o m sheep p e r i n e p h r i c f a t a n d identified as a m i x t u r e of m e t h o x y - l s o m e r s ( 8 - 1 4 ) inclusive of stearic acid. The a u t h o r p o s t u l a t e s t h a t these i s o m e r s were produced as a r t i f a c t s by r i g o r o u s esterification with m e t h a n o l a n d s u l f u r i c acid of a l a r g e sample of sheep p e r i n e p h r i c f a t t y acids which c o n t a i n e d small a m o u n t s of c o n s t i t u e n t hydroxyf a t t y acids f o r m e d f r o m olelc acid by microbial or e n z y m a t i c action. FRACTIONATION AND DETERMINATION OF THE LIPID AND STEROID CONSTITUENTS OF THE ADRENAL GLANDS OP RATS BY liiEANS OF TttlN-LAYER CHROMATOGRAPHY. 1~. Angelico, G. Cavina, A. D ' A n t o n a a n d G. Giocoli ( I n s t . Superiore di Sanita, R o m a , I t a l y ) . J. Chromatog. 18, 57-68 (1965). A m e t h o d is described f o r f r a e t i o n a t i o n a n d d e t e r m i n a t i o n of the lipid a n d steriod c o m p o n e n t s in very s m a l l anlounts of s u b s t r a t e s . The sample is e x t r a c t e d with c h l o r o f o r m - n m t h a n o l (2 : 1). The total lipid e x t r a c t s were s e p a r a t e d b y thin-layer c h r o m a t o g r a p h y , the solvent s y s t e m b e i n g benzene-ether-acetic acid (70: 30: 1). Spots c o r r e s p o n d i n g to cholesterol esters, triglycerldes, f a t t y acids, cholesterol a n d p h o s p h o l i p l d s were o b t a i n e d ; corticosteroids t e n d e d to l a g b e h i n d in the least mobile f r a c t i o n , tog e t h e r with t h e phospholipids. Corticosteroids were e s t i m a t e d by a eolorimetric m e t h o d w i t h tetrazole blue a n d U. V. spectroscopy. A second c h r o m a t o g r a p h y was p e r f o r m e d on the corticosteroid e l u a t e ; the solvent s y s t e m w a s c h l o r o f o r m - m e t h anol-water ( 9 0 : 1 0 : 0 . 2 5 ) . A clear-cut s e p a r a t i o n of t h e principal corticosteroids p r e s e n t in the s u p r a r e n a l g l a n d s of r a t s was obtained. VITAIVflN E AND LINOLENIC ACID CONTENT OF HAY AS RELATED TO DIFFERENT DRYING CONDITIONS. B. T h a f v e l i n a n d H. E. O k s a n e n ( N a t . Vet. Inst., Stockholm, Sweden, a n d College of Vet. Med., H e l s i n k i , F i n l a n d ) . J . D a i r y Sci. 49, 282=6 (1966). D u r i n g t h e harvesting season of 1964 t h e c o n t e n t s o f v i t a m i n a A~

o,L c . ~ , s ~ s '

soo, s.~

1968 (vow. 43)

CUTS#i YCEBINE 91$TILLINCAN9 B£EACHIN#COSTS TENWAYS NEW W & S CONTINUOUS SYSTEM PRACTICALLY AUTOMATES ONCE ON STREAM OCrude glycerine is heated to a much lower temperature O High hydrostatic head tempera. ture rises are eliminated by spray flashing ~ C i r culating pump and external heater replace coils inside the still ~ Continuous and automatic removal of still residue (no down time between batches) ~ Less fatty acids and esters pass into condensers to contaminate final product ~ The only glycerine distillation system that uses condensate as a coolant--reduces need for cooling water O Entrainment losses are reduced to practically zero--result is an improved glycerine yield and quality O Continuous deodorizing ~ Continuous bleaching and polishing ~ Only chemically pure glycerine is produced.

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263A

ABSTRACTS: E a n d linolenie acid were d e t e r m i n e d in t h r e e different g r a s s species, viz., t i m o t h y g r a s s , red clover a n d t u f t e d hair grass. T h e influence on t h e two c o m p o n e n t s in t i m o t h y g r a s s of s t a g e of development, h a r v e s t i n g m e t h o d s a n d climatic f a c t o r s was studied. I n t i m o t h y g r a s s h a v i n g r e a c h e d t h e flowering s t a g e t h e tocopherol content w a s 108 ~ g / g r a m a n d the linolenic acid c o n t e n t of its f a t 49.1%, as c o m p a r e d to 52 ~ g / g r a m a n d 21.8%, respectively, in a late s t a g e of development. The losses of v i t a m i n E in t i m o t h y g r a s s hay, dried on h a y poles, were rem a r k a b l e even u n d e r f a v o r a b l e w e a t h e r conditions, w h e r e a s t h e f a t t y acid composition of t h e f a t r e m a i n e d l a r g e l y unchanged. I n cocked h a y a decrease in v i t a m i n E c o n t e n t could be d e m o n s t r a t e d as early as w i t h i n t e n days, in spite of favorable d r y i n g c o n d i t i o n s ; whereas, t h e linolenic acid c o n t e n t did n o t decrease u n t i l later, following a c h a n g e t o w a r d s r a i n y weather. I n hay, dried as swath, t h e r e w a s a r a p i d decrease in b o t h v i t a m i n E a n d linolenie acid c o n t e n t even u n d e r f a v o r a b l e w e a t h e r conditions. T h e rate of v i t a m i n E d e s t r u c t i o n w a s g r e a t e s t ( n e a r l y 6 0 % w i t h i n f o u r d a y s ) in hay, dried in a s w a t h a n d artificially moistened. T h e i n v e s t i g a t i o n s also included s t u d i e s on c h a n g e s in iodine value a n d degree of oxidation of t h e - h a y f a t as related to different m e t h o d s f o r haymaking. PROTON I~AGNETIC I~ESONANCE SPECTI%A OF UNSATURATED FATTY ACIDS. J. M. Purcell, S. G. Morris a n d H. Susi ( E a s t e r n Reg. Res. Lab., U. S. Dept. of Agr., 600 E. M e r m a i d Ln., Phila. P a . ) . Anal. Chem. 38, 588-92 (1966). The proton m a g n e t i c resonance ( P M R ) s p e c t r a of v a r i o u s u n s a t u r a t e d f a t t y acids were studied. The t y p e s of c o m p o u n d s s t u d i e d included those in which t h e m e t h y l e n e c h a i n is i n t e r r u p t e d by one or more carbon-carbon m u l t i p l e bonds. T h e spectral effects p r o d u c e d by t h e m u l t i p l e bonds are discussed. Chemical s h i f t s and, w h e n possible, coupling c o n s t a n t s have been determined. ANALYSIS

OF

ALCOHOLS

IN

ESSENTIAL

OILS

OF

GRAPEFRUIT,

LEMON, LL-~E, AND TANGERINE. G. L. K. H u n t e r a n d M. G. M o s h o n a s (U. S. }oruit a n d Veg. P r o d u c t s Lab., S o u t h e r n U t i l i z a t i o n Res. a n d Dev. Div., U. S. Dept. of Agr., W i n t e r H a v e n , F l o r i d a 3382). J. Food Sci. 31, 167-71 (1966). Alcohols in t h e cold-pressed essential oils of g r a p e f r u i t , lemon, lime, a n d t a n g e r i n e were e x t r a c t e d f r o m the whole oil with glycerol, isolated b y column c h r o m a t o g r a p h y , s e p a r a t e d b y g a s c h r o m a t o g r a p h y , a n d indentified b y i n f r a r e d a n d m a s s spectroscopy. N i n e t e e n alcohols were indentified in g r a p e f r u i t oil, 9 in lemon, 8 in lime, a n d 16 in t a n g e r i n e . I n addition, the fungicide, o-phynyl phenol, was f o u n d in t h e oils of g r a p e f r u i t a n d tangerine.

OXYGEN REMOVAL I~RO:~ COTTONSEED OIL BY SPARGING "WIT1=[ NITROGEN. M. L. I . i o f f m a n (Res. a n d Dev., L i q u i d Carbonic Div., Gen. D y n a m i c s Corp., Chicago, Ill., 60632). Food Technol. 20, 204-8 (1966). T h e dissolved o x y g e n c o n t e n t of cottonseed oil was reduced s u b s t a n t i a l l y b y s t r i p p i n g w i t h n i t r o g e n g a s in a n e x p e r i m e n t a l s p a r g e r designed to produce very small bubbles. The h i g h g a s velocity t h r o u g h a l ~ - i n c h s t a n d a r d p r o d u c t i o n s p a r g e r caused r a p i d coalescence o f b u b b l e s a n d t h u s reduced the i n t e r p h a s e a r e a n e c e s s a r y f o r m a s s t r a n s f e r , b u t t h e exp e r i m e n t a l sparger, w i t h a s u b s t a n t i a l l y l a r g e r relative a m o u n t of s p a r g e r surface, was able to h a n d l e h i g h g a s flow r a t e s effectively. The observed r e d u c t i o n s in dissolved o x y g e n cont e n t were f o u n d to be d e p e n d e n t on o x y g e n concentration, in c o n t r a d i c t i o n to the a s s u m p t i o n of first-order m a s s t r a n s f e r . D a t a were correlated empirically b y a s s u m i n g t h e rate of m a s s t r a n s f e r p r o p o r t i o n a l to the n-th power of t h e o x y g e n pressure, where n was f o u n d to be 1.5. CARBONYLS IN OXIDIZING I~AT. I X . ALDEHYDES ISOLATED FRO~[ METIIYL ARACHIDONATE. R. Ellis, A. M. Gaddis a n d G. T. Currie ( M e a t Lab., E a s t e r n U t i l i z a t i o n Res. a n d Dec. Div., U. S. Dept. of Agr., Beltsville, M a r y l a n d 20705). J. Food Sci. 31, 191-5 (1966). The m o n o c a r b o n y ] c o m p o u n d s developed b y oxidation of m e t h y l a r a c h i d o n a t e u n d e r mild conditions were m e a s u r e d by t h r e e m e t h o d s of isolation. A l d e h y d e s f r o m seission of hydroperoxides of the p e n t a d i e n e s y s t e m f u r t h e s t removed f r o m t h e carboxyl g r o u p a c c o u n t e d for 8 0 % of the total, a n d t h e same ones are c h a r a c t e r i s t i c of oxidized linoleate. The C6 a l k a n a l was the m a j o r aldehyde a n d C7 alkanal, a c o m p o u n d n o t readily accountable for by conventional m e c h a n i s m s of a u t o x i d a t i o n , w a s second in q u a n t i t y . The m i l d Girard T a n d Schwartz m e t h o d s broke down some p r e c u r s o r s , b u t in a qualitatively different m a n n e r . The Pool a n d K l o s e a l u m i n a c h r o m a t o g r a p h i c m e t h o d decomposed precursors, b u t n o t to the e x t e n t t h a t h a s been observed in autoxidized lard. Two u n s a t u r a t e d a l d e h y d e s isolated by t h i s m e t h o d m a y be alk-2,4,6-trienals. DETEI%MINATION

OF

CALCIUM

AND

~£AGNESIUM

IN A N I M A L

AND

VEGETABLE FAT'S BY ATOMIC ABSORPTION. R. G u i l l a u m i n a n d

}OATS A N D O I L S N. D r o u h i n ( I n s t . of }oats a n d Oils, P a r i s , }or.). l~ev. Franc. Corps Gras 12, 735-42 (1965). D e t e r m i n a t i o n of calcium a n d m a g n e s i u m by atomic a b s o r p t i o n spectroscopy is feasible for ]ipids directly dissolved in an organic solvent. Direct dissolvi n g in solvent eases p r e p a r a t i o n , reduces p r e p a r a t i o n time a n d reduces losses. The p r e f e r r e d solvent is i s o a m y l acetate methanol, 85:25. The l i m i t of detection for m a g n e s i u m is 5 p p b a n d f o r calcium is 250 ppb. A NEW FI~OCESS FOR RE~OVAL O!~ SUNFLOWER WAXES. R. Guill a u m i n a n d N. D r o u h i n ( I n s t . of }oats a n d Oils, P a r i s , }Or.). Rev. Franc. Corps Gras 12, 665-672 (1965). W i n t e r i z i n g sunflower oils is a very t e d i o u s a n d expensive process for the rem o v a l of waxes. I n t h i s p a p e r is described a new technique b a s e d on the molecular s t r u c t u r e , p o l a r i t y a n d size of the w a x molecule. The w a x molecules can be a b s o r b e d u n d e r specific conditions at t h e i n t e r f a c e s of water-oil emulsion droplets. T h u s , t h e y can be s e p a r a t e d b y c e n t r i f u g a t i o n . The best e m u l s i f y i n g a g e n t s are m i x t u r e s of t r i p o l y p h o s p h a t e or hexa m e t a p h o s p h a t e with s o d i u m lauryl s u l f a t e , sodium diisobutyln a p h t h a l e n e s u l f o n a t e or sucrose d i s t e a r a t e . The process is inexpensive a n d simple. APPLICATION OF DIFFERENTIAL THERMAL ANALYSIS TO THE STUDY OF FATS. IV. INVESTIGATION OF PRESSURE AND EXTRACTION COCOA BUTTERS. A. M a t h i e u , H. Chaveron, R. P e r r o n a n d C. P a q u o t (Lab. of L i p o c h e m i s t r y of C.N.R.S.). Rev. Franc. Corps Gras 12, 639-46 (1965). The differential t h e r m a l a n a l y s i s of p r e s s u r e a n d of e x t r a c t i o n cocoa b u t t e r s , e x t r a c t e d with different solvents with or w i t h o u t previous acid t r e a t m e n t , shows t h a t , w h a t e v e r t h e m e t h o d of o b t e n t i o n of these b u t t e r s , a p r i n c i p a l glyceride g r o u p of f a i r l y c o n s t a n t composition exi s t s in them. On t h e o t h e r h a n d , m e a s u r i n g the area of a m i n o r p e a k which a p p e a r s on cooling allows certain distinctions to be n m d e between t h e b u t t e r s studied. HYPEI~OXIDATION IN AUTOXIDATION. PART I I . SOME SPECIFIC FEATUI%ES AND UNIVERSAL NATURE IN HYDROPEROXIDATION. N. A. K a h n ( E a s t . Reg. Lab., Dacca, E. P a k i s t a n ) . Oleagineux 20, 751-755 (1965). The f o u r stages in a u t o x i d a t i o n have given a place to t h e h y d r o p e r o x i d a t i o n reaction. The electronic interp r e t a t i o n s have a d d e d i m p e t u s to t h e concepts of hydroperoxi d a t i o n a n d shown f e a s i b i l i t i e s of such reaction. The universal n a t u r e of h y d r o p e r o x i d a t i o n p r o - o x i d a n t actions, antioxygenesic a n d t h e allied reactions, e s t a b l i s h also t h e i n d e p e n d e n t n a t u r e of h y d r o p e r o x i d a t i o n t h a t occurs a h e a d of free radicals by m e a n s of a series of stepwise t r a n s i t i o n s t a t e s e l i m i n a t i n g ene r g y barriers. DETERMINATION OF SODIU~£ AND POTASSIU1Vf IN FATS BY ATOMIC ABSORPTION. A. P r e v o t a n d C. B a r b a t i ( L a b of Inst. of F a t s a n d Oils, P a r i s , }orance). l~ev. Franc. Corps Gras 12, 657-63 (1965). A m o u n t s of alkali in f a t s a n d oils are generally less t h a n detection limits of classical methods. A t o m i c absorption spectroscopy is m u c h m o r e sensitive. S o d i u m d e t e r m i n a t i o n is of i n t e r e s t as a m e a n s of controlling refining. R e g a r d i n g the g r e a t s e n s i t i v i t y of t h e method, special care m u s t be t a k e n to avoid c o n t a m i n a t i o n of solutions; for example, glass containers m u s t n o t be u s e d for s o d i u m in t h e p p m range. Two m e t h o d s have been studied. I n t h e first, s o d i u m is d e t e r m i n e d a f t e r e x t r a c t i o n by water. T h r e e e x t r a c t i o n s w i t h w a t e r removed all t h e sodium. Sodium d e t e r m i n a t i o n w a s m a d e in aqueous solutions. The w o r k i n g curve f o r s o d i u m w a s linear u p to 4 p p m . The s e n s i t i v i t y l i m i t for s o d i u m w a s 3 ppb. The second m e t h o d was by dilution of f a t s or oils solutions in an o r g a n i c solvent. The s e n s i t i v i t y l i m i t f o r t h e direct m e t h o d is ]0 p p b for s o d i u m a n d 30 ppb f o r p o t a s s i u m . DETECTION AND ESTIMATION OF ADULTERATION OF VEGETABLE OILS. T. N. M e h t a a n d M. V. Gokhale ( L a x m i n a r a y a n I n s t . of Tech., Univ. of N a g p u r , N a g p u r ) . Indian Oil Soap J. 31, 9-23 (1965). The ease w i t h which u r e a f o r m s crystalline complexes w i t h f a t t y acids is related b o t h t h e c h a i n - l e n g t h a n d the degree u n s a t u r a t i o n . - T h i s p r o p e r t y h a s been used to detect a n d e s t i m a t e a d u l t e r a t i o n of m u s t a r d , coconut a n d s e a s a m e oils w i t h p e a n u t oil a n d o f b u t t e r f a t w i t h D a l d a v a n a s p a t i . W h e n m u s t a r d seed oil is a d u l t e r a t e d w i t h p e a n u t oil, t h e iodine value of t h e f a t t y acids f o r m i n g u r e a a d d u c t s is increased a n d their n e u t r a l i z a t i o n value decreased as the prop o r t i o n of m u s t a r d oil in t h e m i x t u r e increased. A s t h e prop o r t i o n of coconut oil in a m i x t u r e of coconut oil a n d p e a n u t oil is increased, the n e u t r a l i z a t i o n value of the f a t t y acids in t h e a d d u c t p r o g r e s s i v e l y increased a n d t h e i r iodine value dropped. W h e n sesame oil is a d u l t e r a t e d with p e a n u t oil, t h e iodine value a n d r e f r a c t i v e index of t h e a d d u c t i n g acids is decreased. A d u l t e r a t i o n o f b u t t e r w i t h m a r g a r i n e ( D a l d a v a n a s t p a t i ) is easily detected. A s the level of h y d r o g e n a t e d

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CHEMICALDIVISION J. A~. OzL C~EMZSTS' Sot., J v ~ m 1966 (Yon. 4 3 )

265A

ABSTRACTS: F A T S AND OILS f a t is increased, the iodine value of the adducting acids is increased, the iodine value of the adducting acids increases. OILS F R O M FISH C A U G H T IN T H E I N L A N D SEA OF JAPAN. IV. PROPERTIES OF OILS FROM SI~ALLFISI-I, FLATHEAD~ F L A T F I S H AND

CANTHEREINS MODESTUS. Shigeru Hamada and Sei-iehi Ueno. Yukagaku 15, 30-2 (1966). The yield of liver oil from the bass and Cantherines was higher than that of body oil. Iodine numbers of these oils w_ere in the range of 160-170. There was no distinct differences in composition of body oil and entrail oil as determined by gas chromatography of methyl esters of f a t t y acids obtained from these oils. F a t t y acids were composed mainly of C~4-C2osaturated and C~-C~ unsaturated acids. Unsaponifiable matter in colorless crystals had m.p. 140-5C and iodine number 150-80. LIPIDS O~ J A P A N E S E LITTLENECK ( T A P E S JAPONICA). I . C O M POSITION OF ACETONE-SOLUBLE LIPIDS. Shigejiro Yasuda (Hire-

shima Univ.). Yukagaku 15, 50-3 (1966). The composition of acetone-soluble ]ipids in T. japonica was studied from the view point of its seasonal variation. The lipids were extracted with ethanol-ether or methanol-chloroform, and acetone-soluble ]ipids were obtained by means of acetone-precipitation and Folch-washing method. The acetone-soluble ]ipids were analyzed with counter-current distribution method. Sterols and phospholipids were separated but glycerides and esters of sterols could not be separated. These components were identified by thin layer chromatography on salicic acid. The seasonal variation of the composition of acetone-soluble ]ipids was not great. The sterol was mainly 7-dehydrostigmasterol, but the presence of another sterol was indicated by the infrared absorption spectrum and thin-layer chromatography. E F F E C T S OF THE PHOSPHATES DERIVED BY HYDROLYSIS OF THE PHOSPHATIDES ON AUTOXIDATION RATES OF THE WATER-UNSATURATED FATTY ACID ESTER SYSTEM. Chieko Urakami, Noriko

Hirosawa and Naoko Morikawa (Osaka City Univ.). Yu~aga~u 15, 7-12 (1966). All the esters in 0.0006 mM solution at p H 4 showed prooxidant activities instead of antioxidant. G]ycerylphosphorylserlne showed the strongest activity at p H 5.5, followed by phosphorylcholine (PC). Glycerophosphorylcholine (GPC) showed the activity comparable to that of glycerylphosphoric acid (GP), which is generally active in various f a t t y acid esters, whereas phosphorylethanolamine ( P E ) and glycerylphosphorylethanolamine ( G P E ) exhibited no antioxidant activity, GPC was found to be strongly active at pH 9.6 in comparison with PE, PC and fl-GP. Trimethyl and triethyl phosphates showed antioxidant activity at pH 5.5, while the pH at which tributyl phosphate showed activity was lower. The following percentages may be taken as possible optimum concentrations in the water-methyl linoleate system: fresh GP 0.03%, fresh P E 0.03-0.04%, fresh PC 0.03%, fresh GPE 0.04%, and fresh or somewhat oxidized GPC 0.03-0.05%. COLOR DEVELOPMENT OF FRYING OIL DURING HEATING. I I MECHANISI~ OF COLOR OF METHYL LINOLEATE. Akira Mukai and Shizuyuki Ota (Ajinomoto Co., Kawasakishi). Yu~aga~u 15, 58-64 (]966). Methyl linoleate was selected as a typical model component of frying oil. The sample was heated for 8 hours at 200C and the time dependence of chromaticity and characteristic changes was determined. Greater changes were observed in methyl llnoleate than in soybean oil. The highly colored sample was divided into five fractions by the urea adduct method and each fraction was tested. The composition and mean molecular weight of the compounds which did not form the urea adduct were determined and the presence of cyclic structure was confirmed. Isolated cis double bonds were isomerlzed to trans double bond on heating and this was followed by the formation of the cis-trans and trans-trans conjugation of isolated double bonds. Highly colored fractions were found to contain trans and trans-trans conjugated double bonds. Dimerization and trimerization occurred accompanied by the formation of carbonyl, hydroxyl and epoxy groups. Colored materials which were composed of partly cyclic dimers and trimers were concentrated in the fraction which did not give the urea adduct. The polar dimer containing oxygen was found to give deeper red coloration.

AUTOMATIC MEASUREMENT OF WATER CONTENT IN WATER-IN-OIL

EMULSIONS. Takeshige Fukushima and Tadatsugu Itch. Yukagaku 15, 116-17 (1966). The water content in water-inoil emulsions was measured automatically by measuring capacitance in such emulsions due to the change of water content. Accuracies are better than ± 0.1% in water content up to 5% in the usual lubricating oils. The apparatus consists of 1 kc. oscillator, transformer bridge, phase detector, Schmitt trigger circuit and relay. For recording, the measuring condenser is rotated at a constant speed. The signal from relay is also available to give an alarm or orders to control system, if the measuring condenser is previously fixed at a desired value. ANTARCTIC WHALE OILS BY GAS-LIQUID CHROMATOGRAPHY U S I N G A HYDROGEN FLAME IONIZATION DETECTOR. I I I . A N A L Y S I S OF THE FATTY ACIDS FROM F I N W H A L E BLUBBER OIL. Yoshihiko

Sano (Miyoshi Oil & F a t Co., Tokyo). Yukagaku 15, 99-108 (]966). Components f a t t y acids, obtained from the antarctic fin whale blubber oil, have been determined by gas-liquid chromatography (GL,C) using a hydrogen ionization detector. The refined oil was converted directly into methyl esters by alkali-catalyzed methanolysis, and the methyl esters were separated by silicie acid column chromatography, urea-complex fractionation and preparative silica gel thin-layer chromatography. Each fraction was then analyzed by GLC before and after hydrogenation. Qualitative or semi-quantitative evidence showed the presence of numerous f a t t y acids ranging from 12 to 24 carbon atoms in chain length in the sample oil as well as in set whale oil Of special interest were the polyunsaturated, odd-numbered f a t t y acids (19:5 and 21:5) and the existence of multi-branched chain and unsaturated branchedchain f a t t y acids. A.O.M. STABILITY OF :~ODIFIED W H A L E 0ILS. Yoshiro Abe, Hajime Seino, Twuan Yang Lee and Katsuji Suzuki (Keio Univ., Tokyo). Yu~aga~u 15, 94-9 (1966). Studies have been made on the preparation of odorless and colorless nmrine oils by means of molecular distillation. One of the problems in using this distilled oil is low stability due to its high content of double bonds. The polymerization of whale oil has been investigated as a means of increasing its stability by decreasing the number of double bonds before molecular distillation. Whale oil was polymerized by heating at 170C or 260C in the presence of activated earth under nitrogen. Polymerization proceeded at 260C and the A.O.M. stability of oil increased as the iodine value decreased, whereas the oil was not polymerized at 170C. Unsaoonifiables of vegetable oil were added to several kinds of modified oil (whale oil free from unsaponfiables by molecular distillation, refined whale oil and polymerized whale oil), and A.O.M. stabilities were determined. The addition of vegetable oil unsaponifiable matter was effective for the stabilization of whale oil, especially for the hydrogenated oil. Soybean oil unsaponifiab]e matter was more effective tha~ any other. CHEMICAL

CHANGES

OCCURRING I N

OILS

DURING FRYING.

A.

Montefredine (Prov. Chem. Lab., Pescara, Italy). Riv. Ital. Sostanze Grasse 42, 482-7 (]965). In a study conducted on several vegetable oils, as well as margarine and lard, up to 30 consecutive batches of potatoes have been deep-fried in the same batch of oil, according to a standardized procedure. Oil samples taken after the ]5th and 30th frying run and also oil extracted from the fried potatoes have been analyzed to determine what chemical modifications of the oil accompany the frying process. The most noticeable and consistent change in all of the oils examined is a very pronounced increase in the U.V. absorption at 232 m~ (dlenes), with a corresponding but smaller increase in the 268 nl~ absorption (trienes). Free acidity does not vary through the 30 frying operations and the peroxide number also remains about constant, except in the case of oils with high initial values, where there is a considerable lowering of this latter index during frying. The IV of all oils shows a definite downward trend, however, the IV drops are relatively moderate: 1-4%. I t is not yet possible, on the basis of these results, to interpret all of the chemical modifications that take place in an oil during frying. D E T E C T I O N OF ESTERFIED OLIVE OILS B Y CAPILLARY C O L U M N G A S

BARROW-AGEE LABORATORIES, INC. Analytical and Consulting Chemists and Testing Engineers Main Offices and Laboratories, MEMPHIS, T E N N E S S E E O t h e r Laboratories: Shreveport, La. Decatur, Ala. Greenville, Greenwood and Jackson, Miss. Chattanooga, Tenn. Little Rock, A r k .

266A

CHROMATOGRAPHY. L. Boniforti and R. Monaoelli (Ist. Super. di Sanita, Rome, Italy). Riv. Ital. Sostanze Grasse 42 493-6 (1965). The usefulness of the gas chromatographic method on capillary columns for detecting trans iso-oleic acid has been confirmed. A method for measuring the ration between the elaidinic and stearie acid is proposed. DETERMINATION OF ELAIDINIC ACID I N VEGETABLE OILS.

U. Pal-

lotta and G. Losi (Univ. of Bologna, Italy). Riv. Ital. Sostanze Grasse 42, 538-41 (1965). Details of a method for dej

AM. OIL CHEMISTS' SOC., JUNE 1966 (VOL. 4 3 )