NOVEMBER, 1 9 5 9

GIBBONS ET AL.:

M E T H Y L GLUCOSII)E F A T T Y ACID

mixture was held at 180~ for 1 hr. then allowed to cool to 120 ~ to 130~ and filtered through a diatomaceous earth bed to remove carbon. This method of deeolorization is not as suitable for larger-scale preparation as the hydrogen peroxide method outlined below. The quantity of carbon required tends to clog the filters, slowing down the filtration rate. With Aqueous Hydrogen Peroxide. A f t e r the desired degree of esterification was achieved, the reaction mixture was cooled to 80~ whereupon 3% of aqueous (50%) hydrogen peroxide on the weight of the ester was added slowly with stirring. The mixture was held about an hour to bleach, then the water, added with the peroxide, was removed in vacuo. In the litharge-catalyzed reactions bleaching with hydrogen peroxide was done as described above a f t e r the addition of adipic acid on the cooling cycle at 150~ The insoluble lead adipate did not interfere with the bleaching operation and was subsequently removed by filtration. Characterization of Diesters. Summarized in Table i are the experimental conditions used in the p r e p a r a t i o n of the various methyl glueoside diesters, together with some of the properties of these produets. Surface-tension measurements were made by the Du Noiiy aqueous surface-tension procedure at concentrations of 1.0, 0.1, and 0.01% of ester in water. The results of these measurements show t h a t the surface tension of water was appreeiably reduced by the addition of as little as 0.01% of the methyl glueoside diesters (Esters 1, 2, and 3). The diesters of the higher saturated f a t t y acids (Esters 4, 5, and 6) were not dispersible in water, hence no significant surface-tension data could be obtained.

ABSTRACTS

555

Summary and Conclusion Procedures are described for the p r e p a r a t i o n of methyl glucoside diesters by direct esterification, using a ratio of one mole of methyl glucoside with two moles of f a t t y acids. Rate studies indicated that lead or stannous soaps are more effective catalysts than the sodium soaps for speeding' up this esterification. With equal molar quantities of methyl glueoside and f a t t y acid, the lead and the sodium soap catalysts give products containing predominantly diester and half the methyl glueoside remaining unreaeted. Under the same conditions stannous soap catalysis gives high yields of monoesters containing only v e r y small percentages of unreacted methyl glueoside. F r o m the standpoint of speed of reaction, color of the final products, ease of removal of catalyst f r o m the ester products, and catalyst cost, litharge is the p r e f e r r e d catalyst for the p r e p a r a t i o n of m e t h y l glueoside diesters. Properties of various methyl glucoside f a t t y acid diesters, p r e p a r e d on a laboratory scale, are given. Du Noiiy surface-tension measurements indicate that small quantities of the methyl glueoside dilaurate, dicaprate, or dioleate are quite effective in lowering the surface tension of water. REFERENCES 1. 2. 260 3.

Irvine, J. C., and Gilchris% H. S., J. Chem. Soc. 125, 1-10 (1924). Wolff, n., and Hill, W. A., J. Am. Oil Chemists' Soc., 25, 258(1948). Gibbons, J. P., and Junks, R. A., ibid., 29, 467-469 (1952). [Received F e b r u a r y 18, 1959]

....

R . A . REINERS, Editor

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

9 Fats

and

Oils

T~E AUTOXIDATION OF UNSATURATED COMPOUNDS. X. IS0'LATION OF METHYL LINOLEATE HYDROPEtCOXIDES AND POLYMERIC AUTOXIDATION PRODUCTS OF )gIETttYL LINOLEATE. W. K e r n and H. W. Schneeko ( O r g a n i c Chemistry I n s t i t u t e of the Univ. Mainz). Die Malcromolelculare Chemie 32, 184-190 (1959). I t is possible to isolate pure methyl linoleate hydroperoxide f r o m autoxidized methyl linoleate by c o u n t e r c u r r e n t distribution. Application of the method to highly autoxidized oils (up to 200 mol % oxygen) yields secondary p r o d u c t s ; the content of hydroperoxide decreases rapidly. The autoeatalytic character of the autoxidation can be observed up to a conversion of 100 tool %. X I . THE CATALYSIS OF THE AUTOXIDATION OF ZVI-E~'HYL LINOLEATE WITH ]~/[ETHYL IMNOLEATE I-IYDEOPEROXIDE. W. Kern, L. Dulog, and G. Selz. 1bid., 191-196 (1959). h/[ethyl linoleate hydroperoxlde was isolated f r o m autoxidized methyl ]iI/oleute by countercurrent distribution and was ~dded to pure methyl linoleate as a catalyst for its autoxidation. The identical effect of added methyl linoleate hydroperoxide with the autocatalyst of the autoxidation reaction is demonstrated by the results of a kinetic experiment. THE CULTIVATION 0]~ PEt~ILLA OCI1~iOIDES AND PERILLA NANKINENSIS AND STUDIES OF THEIR OILS. P. Mazhdrakov and As. Popov. Compt. rend acad. bulgare sci. 11, 197 200 (1958) (in G e r m a n ) . Of the two plants, Perilla nankinensis is the better suited f o r g r o w i n g in B u l g a r i a because of the shorter g r o w i n g

season, but hardier s t r a i n s should be sought. TILe oil of Perilla nanI~inensis has ~ lower iodine n u m b e r (173 versus 178-81) b u t shows superior drying properties. I t contains 42.6% ]inoleic acid and 22.4% linolenic acid. Other usual characteristics are reported. (C. A. 53, 15593) THE COLOR OF ~[ILK FAT. L. Radema. O~c. Orgaan. Koninlcl. Ned. Zuivelbond 50, 216 17 (1958); D a i r y Sci. A b s t r . 20, Abstr. No. 1448. The color of milk f a t was determined spectrophotometrically over ~ one-year period in the mixed milk received at the experimental d s i r y of the N e t h e r l a n d s I n s t i t u t e for D a i r y Research. Converted to carotene, the lowest and highest b u t t e r f a t values recorded were 2.4 in early April and 7.8 m g . / k g , at the end of May. (C. A. 53, 15400) FATTY ACID ~OMPOSITION OF FOOD FATS AND OILS. L. R. Dugan, J r . A m . M e a t I n s t . F o u n d a t i o n , Circ. No. 36, 15 pp. (1957); D a i r y Set. A b s t r . 20, Abstr. No. 433 (1958). The f a t t y acid composition of various f a t s and oils was investigated. B u t t e r contained 57% s a t u r a t e d f a t t y acids, of which 40% were short-chain acids of less than 16 carbons. The effects of h y d r o g e n a t i o n are also g i v e n . ( C. A. 53, 15410) THE EFFECT O~F WRAPPINrG PAPER ON FAT STABILITY. Z. K w a p niewski, A. Rutkowski, and B. Kubik. Przcmys~ S p o 2 y w c z y 12, 412-15 (1958). Acid p~rchment, parchment, half-parchment, and white and g r a y cardboard accelerated the autoSxidation of fat. P o r o s i t y of the p a p e r and its content of iron and copper had the greatest effect on deterioration of fat. I m p r e g nation of the p a p e r with 0.01% octyl gallate increased considerably the stability of the fat. (C. A. 53, 15410)

556

THE JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY

USEFULNESS OF SOI~IE POLISH VEGETABLE OILS. ~ . Niewiadomski, B. Drozdowski, and W. Zwierzykowdki (Politech. Inst., Gdafisk, Poland). Przemys~ Spo~ywezy 12, 311-16 (1958). Hydrogenated oils from Camelina sativa, Helianthus annus, and Crambe abyssinica could be useful for production of margarine. Helianthus annus oil, especially, has good organoleptic properties. (C. A. 53, 15410) CHEBIICAL CONSTANTS OF VEGETABLE OILS, VANASPATIS, AND LARD. N. D. Kehar, T. S. Krishnan, S. N. Ray, :B. C. JoshJ, and B. C. Raisarkar. Studies Fats, Oils and Vanaspatis 1956, 23-30; Dairy Scg. Abstr. 19, 768 (1957). The chemical constants of vegetable oils, vanaspatis, and lard were determined and compared with those of cow ghee. The diff• of deternllning whether ghee samples were adulterated with vanaspatis or lard is discussed. The effect of heating on various chemical constants and vitamin A potency of cow ghee, bazaar ghee, crude peanut oil, and vanaspatis is given. The destruction of vitamin A was generally greatest in the ghee samples. (C. A. 53, 15416) FATTY OILS OP TH~ FRUITS OV CARAWAY (CARUI~I CARVI) AND ANISE (PIMPINELLA ANISU.~I). E. ~. Zara~skaya and Yu. G. Broisyuk. Ne~oto~'ye Foprosy Farmatsii (Kiev: Gosudarst. ~v[ed. Izdatel. Ukr. S.S.R.). Sbornik 1956, 185-9; Referat Zhur., Khim. 1958, Abstr. No. 2689. Ether extraction of eomminuted and preliminarily essential oil-freed seed of caraway and anise (oil content 19.73 and 10.76%, respectively) has the following characteristics: n :~ 1.4695, 1.4718; d :~ 0.9140, 0.9224; acid value 4.15, 3.8; saponification value 189.3, 181.4; iodine value 101.3, 98.42; thloeyanate value 84.12, 83.55; % of unsaponifiables 1.2, 2.4, respectively. The mixture of fatty acids of caraway and anise oil contains the following acids, respectively: palmitic 3.59, 3.25; petroselinic 17.0, 23.56; oleic 60.7, 56.0; linoleie 19.6, 17.16%. The oil can be utilized in soap-making, analogously to the coriander oil. Caraway oil contains 15.7% of a hard fraction, melting point 29-31.5 ~ solidification point 25-6 ~, and the anise oil 20.4% of hard fraction melting point 28.5-31 ~, solidification point 24.5-25 ~. The hard fractions of the oil can be utilized in the confectionary and pharmaceutical industries as substitutes for cacao butter. (C. A. 53, 14548) COI~IPONENT FATTy ACIDS OF THE OIL FR0~I THE SEE]) O~ CASSIA TOKA. Ram Das Tiwari and Purna Chandra Gupta (Univ. Allahabad). J. Proe. Oil Technologists' Assoc. India, Kanpu~" 10, 111-16 (1954) (Pub. 1955). The seed of Cassia torn yielded 5.5% of a nondrying, yellow oil having d~o 0.9843, n ~/D 1.4678, acid number 7.5, saponification number 173.8, aeetyl number 5.4, Hehner number 88.6, Reichert-Meissl number 0.2, unsaponifiable matter 4.6%, iodine number 92.8, and thiocyanate number 62.0. The component f a t t y acids of the oil were linoleic 37.1, oleic 38.4, pahnitic 7.5, stearic 7.3, and lignoceric 9.7%. The unsaponifiable matter consists of phytosterol and sitosterol. (C. A. 53, 12710) CARBONYLS IN OXIDIZING FAT. II. THE IDENTITY AND AMOUNTS Ol~ STEAI~K VOLATILE ~'[ONOCARBONYLS IN A RANCID FREEZER-

STORED PORK FAT. A. M. Gaddis a~d R. Ellis (Eastern Utilization Research and Development Div., U.S.D.A., Beltsville, 5{dryland). Food ges. 24, 392-400(1959). Trace amounts of acetone and methyl ethyl ketone found in more oxidized pork f a t were not observed in freezer-stored pork f a t in the early stages of rancidity, n-Alkanals C~, C~, Ca, C~, C~, three unknown carbonyls, alk-2-enals Cr, Ca, C,~, C~o, C~, and alk 2,4-dienals C~, C~,, C1o, Cn were found in unheated fat. In the 165 ~ heated fat, n-alkanals C~, Ca, C~, alk-2-enals C~, Ca, C~, C~o, C~, and alk-2,4dienals C~, C~o, C~ were observed. I-Iexanal and deca-2,4-dienals were the dominant compounds present. LARD. R. Grau and A. 5,[irna (Eundesforschungsanstalt Flelsehwirtsehaft, Kulnbach, Ger.). Fleischwirtsehaft 11, 23-5 (1959). The procedure of Kaufman, et al. for ultraviolet speetrophotometric analysis of lard treated with bleaching earth was studied in detail. Suggestions were made for improving sensitivity. (C. A. 53, 12514) OLIVE-OIL TECHNOLOGY. THE WESTPHALIA-ENFIDA PROCESS. P. Renaudet, E. Buchmann, and Y. Bagot. Oldagineux 14, 95104 (1959). The Westphalia-Enfida process for olive oil is a continuous procedure in which the olives are washed, dried, and the kernels removed; the pulp is crushed, salted, kneaded to the accompaniment of a slight increase in temperature, diluted with water, and then sieved and centrifuged to yield an oil of " e s t r a " quality. (C. A. 53, 12518) STABILIZATION 0 ~ !PITTED FRUIT OILS DURING STORAGE. E . V . Shevlyagina, A. L. Voitsekhovskaya, and E. I. Pashinina. Trudy Vsesoyuz. Nauch.-lssledovatel. Inst. Sintet. i Natural.

VOL. 36

Dushistykh Veshchestv 1958, No. 4, 119-25. Butylhydroxyanisole and diisoeugenoI have been observed to possess high antioxidative properties, thus retarding the process of self-oxidation of oils. (C. A. 53, 12517) TRANSESTEI~IFICATIO~N" AND ITS IMPORTANCE IN THai REPI~,OCESSING OP FATS. M. K. Yakubov (V. I. Lenin Polytech. Inst., Kharkov). Maslobo~no-Zhirovaya Prom. 25(3), 19-22 (1959). Transesterifieation of fats, its ]imitations and uses for practical purposes, is discussed. 9 references. (C. A. 53, 12709) ON TROPICAL VEGETABLE AND ANIMAL FAT SUBSTANCES. S. Husain Zaheer and K. T. Achaya (Regional Research Lab., Hyderabad, India). Nahrung 2, 710-18 (1958). The composition and characteristics of animal and vegetable fats as influenced by species, climate, nutrition or fertilization, etc., are reviewed. (C. A. 53, 12709) ULTRASONIC DISPERSION IN PAL?~VIITIC ACID. C. Raghupati Rao (Ist. naz. ultraeustiea, Rome). Ricerca sci. 28, 2106-11 (1958). The dispersion of ultrasonic velocities in pahnitic acid was investigated in the intensity range 0.8 X 10 -2 to 8 X 10-2 watts per square centimeter at 2 and 4 megacycle per second between 60 and 85 ~ Contrary to previously reported results, Rao finds no detectable ultrasonic dispersion in palmitic acid with either frequency or intensity of the ultrasonic beam. The determined temperature coefficient of velocity A V / A T =--3.35 meters per second degree agrees very well with other data. (C. A. 53, 12709) ~N-ATUI~E OF ACTIVE OXYGEN DETERI~INED IODOI~IETRICALLY IN THE PRODUCTS OF AUTOXIDATIVE DETERIGRATION OF FATTY ACIDS AND FATS. :~. S. Drozdov and N. P. )r (Rr. I. Pirogov 2nd State Med. Inst., Moscow). Khim. 2Va~ka i Prom. 4, 133-4 (1959). Oxygen determined in the presence of mineral acids was 1.5-2 tinies higher than the peroxide content determined by the acetic acid method. Apparently, iodine ion, in the presence of mineral acids, reacts with the epoxy compounds formed in autoxidative deterioration. (C. A. 53, 12710) SO~k[E R~CENT J~DVANCES IN THE CHE~IISTRY 01~ THE D ~V~ITA~INS. ]~. Lythgoe (Univ. Leeds. England). Proc. Chem. Soe. 1959, 141-9. A review with 56 references. (C. A. 53, 15238) QUANTUh~ ASPECTS OP CATALYSIS. THE DRYING O1~ LINSEED OIL. R. R. Myers (Lehigh Univ., t~ethlehem, P a . ) . Ann. N. Y . Acad. Sci. 79, 1-8 (1959). The oxidative mechanism is studied in the light of P a u l i n g ' s concept of resonance polymerization of linseed oil and similar organic coatings, stabilization of the free radical intermediates, and in terms of a recent vibration hypothesis. In order to explain the mechanism, the potent vibrational mode of the alpha methylene is selected as the one which leads from the tetrahedral sp ~ hybrid to the pyramidal p3 radical. The role of transition metal drier catalysts is explained on the basis of synchronization of the molecular orbital stretching frequency with the potent (vd) vibrational mode of the tetrahedron which is centered on the C alpha to a double bond. (C. A. 53, 15594) OXIDATIOffq AiqD ACTIVATION dE UNSATURATED ~ATTY ACIDS. W. S. Lynn, Jr., and Rose H. Brown (Duke Univ., Durham, N. C.). Arch. Biochem. Biophys. 81, 353-62 (1959). Small amounts of unsaturated f a t t y acids are oxidized to carbon dioxide, both in vivo and in vitro, at a rate greater than that of the corresponding saturated f a t t y acids. F a t feeding to rats stimulates the rate of oxidation of unsaturated f a t t y acids. Cholesterol feeding to rabbits, but not to rats, stimulates the oxidation of all f a t t y acids by mitochondrla, especially unsaturated f a t t y acids. Long-chain unsaturated f a t t y acids are more readily activated by mitochonda'ial enzymes than are most saturated acids. Unsaturated f a t t y acids are more metabolically active than are saturated f a t t y acids. (C. A. 53, 15280) COI~IPLEX SALTS OF HIGHER FATTY ACIDS I, II, Ill, IV. S. Fisel. Acad. rep. populate Rom{ne, Filiala Ia~i, Studii cercethri stiint., Set. I, 6, 295-327 (1955). Details are given for the preparation of 72 complex salts of palmitic and stearic acids with M H (M II = iV[n, Ni, Co, Cu, Zn, and Cd). The salts are of the type (M H X~)M~m_2 or (MHY~)X~, where X ---C~H~,CO((R ~) or C~,Hs~COC(R~); M r - - Na or K ; m = 3, 4, 6; Y = NHs(R~), Me:NH.~(R'), C~HhNH~(Rh), PrNH~(RC), and CsI-I~N(R7) ; n ----~ , 1, 2, 3, and 4. I t was found that the complex salts os formula (1V~HR~))sI have double the molecular weight and therefore their structure is suggested to be (MHI~6)]Ys u. The complexes of type ( M I I x m ) M I m _ 2 a r e supposed to have the known coordinative-type bond between the doublybonded curboxyl oxygen and the central metal. The reaction of

NOVEMBER, ] 9 5 9

ABSTRACTS: FATS AND 0ILS

NaOAc with the palmitates and stearates of Mn, Ni, Co, Cu, Zn, and Cd takes place according to the scheme: m/2 R~M ~ § (m -2) AcOM ~ = (M"R~)M~m~ -t- (m -- 2)/2(AeO)2M H. Experimental evidence suggests that R ~ or R~ derivatives of Na or K react with the R ~ or R: derivatives of Co and Zn to form the complex of type (MIIR~)MI~MII and not a mixture of 2R~MII_ +2R~M~. The long chains of the higher f a t t y acids have no effect on the number of acid molecules which co5rdinate with the metal in complexes of type (M~X~n)Mrm--_,. The effect of the metal upon the number of the aliphatlc amine molecules which add to form the complexes of the R ~ and R e derivatives is expressed in general by Ni, Co ~ Cu, Cd, Zn ~ Mn. The length of the aliphatic chain of the amine has no effect upon the number of amine molecules forming the complex. The greater the number of amine molecules in complexes of Type (M~Y~)X~, the lower the stability of the complex. For type (MIIy~)X2 complexes the stability increases with increased length of the aliphatic chain of the amine, and there is a tendency for a decrease in the number of amine molecules added, with increased chain length of the aliphatic acids. (C. A. 53, 14928) QUANTITATIVE I)ETEttMINATION

OF a, ~- UNSATURATED ~ATTY

ACIDS. A. A. Bugorkova, L. :N. Petrova, K. S. Polyakova and G. V. Meleshkina. Trudy Vsesoyuz. Nauch.-Issledovatel. Inst. Sintet, i Natural. Dushistykh Veshchestv 1958, No. 4, 73-6. Bromination of a,fl-unsaturated acids was achieved with 0.2 N bromine solution in methyl alcohol saturated with sodium bromide in 24 hours, fl,7-Unsaturated acids brominate quantitatively in 5-10 minutes with 0.1 N bromine in methyl alcohol saturated with sodium bromide. This differentiation provides a method of determining an a,fl-unsaturated in the presence of a fl,~/-unsaturated acid. (C. A. 53, 14929) CHARACTERISTIC OF a,fl-UNSATUI~ATED FATTY

ACIDS.

~.

E.

Kologrivova and V. N. Belov. Trudy Vsesoyuz. Naueh.-Issledovatel. Inst. Sintet. i Natural. DushistyI~h Veshchestv 1958, No. 4, 70-3. The reaction of CH~(CH,~),CH:CHCOOH where n = 5, 6, 7, and 9, with NH2OH in aqueous alcohol solution has been studied. Formation of respectively CH3(CI.I,),CH (NI,I-IOI.I)CHzCO21.I in 50-60% yield has been noted. I t has been shown that there are concurrently formed ketoximes having I carbon atom less than the starting acids. Heating the aqueous alcohol solution of the CH~(CH.~)nCH(NHOH)CH:CO._,H leads to complete decomposition. Because of the incomplete addition of the NH:OH to a,fl-unsaturated acids, the Posner reaction for the quantitative determination of a,fl-isomers in a mixture of unsaturated f a t t y acids cannot be applied. (C. A. 53, ]4929) SYNTHESIS OF TRIACID TItIGLYCEk%ID]~S. W. l'i. Watson (Emory Univ., Emory University, Ga.). Un,iv. Microfilms (Ann Arbor, Mich.), L. C. Card No. Mic 58-5186, 72 pp.; Dissertation Abstr. 19, 2484 (1959). (C. A. 53, 14932) SYNEI~GISTIC ACTION 0E a-AMINO ACIDS ON ANTI()XII)ANT PROPEI~TIES OF a-TocOPHERO,L. J. J a n i c k i a n d M. GogolewskL

557

CONTROLLED INTEKESTEI~IFICATION 0,E LARD. C. Placek and G. W. Holman. Chim. et Ind. (Paris) 81, 526-34 (1959). Interesterificatlon of hydrogenated vegetable f a t s in shortening increases the trlglycerlde/dlglyeeride ratio and reduces granulation. A controlled process has been developed in which chemical equilibrium is displaced by initiating crystallization of triglycerides as soon as they form. A highly reactive sodium-potassium catalyst is utilized, and a continuous process is operated. (C. A. 53, 15601) CLAY FROI~ LE:RRIJA AS A I)ECOLO!~ANT OF ~V~EGETABLE 0ILS. A. Peir6 Callizo and G. Garcla. Anales edafol, y fisiol, vepetal (Madrid) 17, 935-72 (1958). All the clays studied had good bleaching power on the samples of olive oil treated. The fractions rich ia attapulgite were the most active. (C. A. 53, 15601) GAS-LIQUID CHI~OI~IAT0~RAPHIC ANALYSIS OP HIGHER FATTY ACIDS AND FATTY-AcID METHYL ESTERS, R. K. Beerthuis, G. Dijkstra, J. G. Keppler, and J. H. Recourt (Unilever Research Lab., Vlaardingen, Neth.). Ann. N. Y. Acad. Sci. 72, 616-32 (1959). The even Dumbered free f a t t y acids C1.~ to C:e and their methyl esters were determined in menhaden oil and in Ximenia caffra oil. The alkaline isomerization of linoleic acid was ntudied by this method. (C. A. 53, 15601) COLOI~IMETRIC DETEKI~IINATION OP THE. RANCIDITY OF FATS. B. A. J. SedlfiOek and R. Rybin. Fette, Seifen, Anstriehmittel 61, 134-8 (1959). A solution, 5 ml. of 0.5 g. diphenylcarbazide, suspended in 100 ml. carbon tetraehlorlde, and 5 ml. f a t is agitated and heated to boiling, cooled, made up with carbon tetra chloride, filtered in the dark, and the red color of the filtrate is measured colorlmetrically 15 minutes after eonlpletion of the heating. For lard and talcum samples, owing to their lower solubility in carbon tetraehloride, more reagent is required. The color intensity increases with rancidity. Samples of butter rated in rancidity from 0-0.5, 1, 2-4, 4-5, and ~ 6 , showed extinction of 0.04, 0.08, 0.2-0.3, 0.3-0.5, and ~0.6. Scales for lard and oil are also given. (C. A. 53, ]5601) ZVIEASU~EI~IENT 0,F OXIDATION ON- CACAO ]~UTTER, EDIBL]~ FATS, .aND PaODUCTS CONTAINING FATS. J. Kteinert (Lindt und Spruengli Akt.-Ges., Kilchberg, Zurinch). Bey. intern, chocolat. 14, 9-11, 69-77, 114-21, 164-72 (1959). The following methods for the detection of spoilage were investigated: The Kreis test, the thiobarituric acid test, L e a ' s method, in which the peroxides are measured iodometrically, the indirect measure of the peroxides based on the spectrophotometric estimation of the conjugated double bonds, a test with the leuco base of 2,6-dichloreindophenol, and the ferrithiocyanate method. The last-named is the preferred method; it is described in detail. Measurement of oxidation in fats and f a t t y products is fully described. (C. A. 53, 15601)

Przemys~ Spo~ywczy 12, 417-20 (1958). Serlne, isoleuclne, alanlne, lysine, hlstidine, phenylalanlne, arginine, glycine, and glutamic acid increase antioxidant properties of a-tocopherol. Cysteine, valine, proline, and tryptol~han have proSxidant prop~ erties. (C. A. 53, 15602)

~ . P. Bespyatov (V. I. Lenin Po}ytech. Inst., Kharkov). Maslobo~no-Zhirovaya Prom. 25 (4), 9.-12 (]959). Tabulated data are given concerning distribution of sulfacid prepared by P e t r o v ' s contact method, sulfuric acid, soluble f a t and its acid number, and of water in the f a t intermediate, and water layers of settled acid-hydrolyzed fat. (C. A. 53, 1560])

THE CULTIVATION 0F ERUCA SATIVA AND I~EPIDIUM SATIVUM, AND CHARACTEICISTICS OP THEIR OILS. t . Poppy a n d P. Mazh-

I-~YDROGENATION AND I)EHYDROGENATION. J. T. B r a d b u r y , W.

drakov (Bulgarian Acad. Sci., Sofia). Compt. rend dead. bulgare sci. 11, 279-82 (1958) (in German). The oil obtained from the seed of Eruca sativa, as grown in Bulgaria, has an iodine number of ]02, and the f a t t y acid components comprise: oleie 35.7, erucic 40.5, llnoleie 12.2, and linolenic 6.3%. The oll obtained from the seeds of Lepidium sativum, as grown in Bulgaria, has an iodine number of 119.8 and the f a t t y acid components comprise: oleic 32.3, erucic 26.4, lino]elc 29.0, and linolenic 6.8%. The first has characteristics like beet- and rapeseed oils. The latter is llke the oils of crucifers that contain little erucic acid and, accordingly, may be useful in making soap. (C. A. 53, 15602) SUBSTANCES ~ONTROLLING THE ODOIr OP SYNTHETIC

FATTY

AciDs. N. K. Man'kovskaya, I. V. Bersegyan, N. I. Solodova. Masloboino-Zhirovaya Prom 25(4), 13-]5 (1959). It is shown that two groups of substances are largely responsible for the presence of repulsive odors in synthetic f a t t y acids. One is represented by the readily oxidizable unsaturated organic compound containing carbonyl groups with penetrating, buring odor, and the other is made up mostly of iso-acids with persistent, heavy, unpleasant specific odor. The latter can be separated from normal acids by treatment with urea. (C. A. 53, 15602)

MECHANISM OP ACID I~IYDROLYSIS OF ~AT.

M. Keely, F. J. O'Hara, and R. F. Vance (Girdler Co., Louisville, Kentucky). Ind. Eng. Chem. 51, 1111-1120 (1959). Hydrogenations with nickel catalysts have been reported for castor, corn, cottonseed, herring, sunflower, tall, tallow, train, and whale oils or f a t t y acids, ttydrogenolysis with copper catalysts has been described for cottonseed oil, mixed f a t t y acids, ethyl stearate, and synthetic spice oils. J . L. Dalton and H. L. Y[itehell (Kansas Ag. Experiment Station, Manhattan, Kan.). J. Agr. Food, Chem. 7, 570-3 (1959). Crude sorghum grain wax was also isolated by extracting the grain with Skellysolve B and precipitating the wax with acetone. The crude wax was fracttonated by adsorption on columns of trlcalcium phosphate and silicic acid. A weakly adsorbed paraffin fraction was eluted from the siliclc acid column with a small quantity of Skellysolve B. A more strongly adsorbed fraction, obtained by additional elution with Skellyso]ve B, was identified as esters. A third fraction was e]uted with 2% acetone in Skellysolve B and shown to consist of alcohols. Melting points with x-ray diffraction studies indicated that each fraction was a mixture of homologs, rather than a single compound. Of the material recovered, approximately 5% was paraffins, 49% was esters, and 46% was free alcohols. FRACTIONAT/0N OF SOI~GHUM GI~AIN WAX.

558

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

ESTEI%IFICATION. M. L. P e t e r s o n and J. W. W a y (Explosives Dept., E. I. du P o n t de N e m o u r s & Co., W i h n i n g t o n , I)e]aw a r e ) . Ind. E~g. Chem., 51, 1081-1085 (1959). Two problems of p e r m a n e n t interest in esterification technology are methods of catalysis to increase reaction rate and methods of overcoming u n f a v o r a b l e equilibria to carry a reaction to completion. The f a t s and oils industries have had much interest in recent years in the p r e p a r a t i o n of tailor-made f a t t y acid glycerides suitable for a variety of uses. A considerable volume of literature was noted on esterification and transesterification techniques for the p r e p a r a t i o n of specific g'lycerides and of f a t t y glycerides of desired properties. BUTTERI~AT OXIDATION~ EVALUATION ON LEA~S ADLEHYDE DETERSIINATION NIETH0V. A. T a m s m a and R. D. Powell. (i)'firy I n d u s t r y See., Iowa Ag, Exper. Station, Ames, I o w a ) . J. Agr. Food Chem. 7, 643-6 (1959). L e a ' s method for determination of aldehyde in f a t s is excellent f o r n-heptanaI. F o r n o r m a l aldehydes with more tlmn seven carbon atoms, recovery decreased with inereasil~g chain length and limiting values were reached with the C,,, and C,o aldehydes. F o r " a l d e h y d e s " f r o m autoxidized milk f a t the value f o u n d by L e a ' s method is arbit r a r y , because these earbonylic compounds do not behave like heptanal. Incomplete recovery can be caused by low solubility in water and low reactivity to bisulfite. Too high recovery may be obtained with u n s a t u r a t e d earbonyl compounds as a result of the double bonds. !%action products and yields were examined by isolation of the aldehyde by solvent extraction a f t e r decomposition of the bisulfite complex. " M i l k - f a t aldeh y d e " was of ketonic character; the yield was about 1~ to ~% as compared to synthetic aldehyde. FOREIGN" ~[ARKET I)EVELOPMENT AND U. S. OILSEEDS AND PRonucTS. R. J. H u d s o n ( F a t s and Oils Div., F o r e i g n Agr. Service). Soybean Digest 1 9 ( 1 1 ) , 28, 30, 32 (1959). Prospeats for the expansion of f o r e i g n m a r k e t s f o r soybeans and soybean oil are discussed. METHO~D OY FRACTIONATING TALL OIL INTO FATTY ACIDS AND I~OSIN AcIn PROm~CTS. E. F. Sisson, R. F. Cole, and J. P. K r u m b e i n ( H e y d e n N e w p o r t Chemical Corp.). U. S. 2,394,330. A method is described for the f r a c t i o n a t i o n of tall oil by p a r t i a l vaporization under reduced pressure. REMOVAL OR ODOI~ AND C0~LOI~BODIES IN ~AT SPLITTING. A . M . Ives and R. i% T h o m p s o n ( S w i f t & Co.). U. S. 2,895,975. In a continuous process, f a t is hydrolyzed with water under pressure and the reaction products are immediately passed t h r o u g h a high vacuum-distillation zone where water and color- and odor-causing bodies are flashed off'. The resultant f a t t y acids have improved color, odor, and stability. PROCESS FOR FI~ACTI0,NATION 0P FATTY ACID ~{IXT'UR)~S. S. Ka}rys, E. M. Meade, W. O. Munns, and I). A. Walder (Canada Packers Ltd.). U. S. 2,895,976. In a process for the separation of s a t u r a t e d and u n s a t u r a t e d f a t t y acid fractions, an aqueous solution of the acid soaps is aged at a t e m p e r a t u r e below 30 ~ to separate a solid fraction containing the soaps of the more s a t u r a t e d acids. METHOD 0P ~{AIKING HARD BUTTE]g. G. Barsky, V. ~ . ]3abayan, and B. J. Bahoshy (E. F. Drew & Co.). U. S. 2,898,2lL I n a process for m a k i n g a h a r d b u t t e r f r o m an u n s a t u r a t e d glyceride oil, the oil is hydrogenated to an iodine value of 40 to 60 whereby ]inoleates are t r a n s f o r m e d to oleates and some iso51eates, The product is dissolved in a volatile solvent. The solution is cooled to precipitate the highest melting constituents. The s u p e r n a t a n t liquid is removed and f u r t h e r cooled to precipitate a h a r d butter. This b u t t e r is removed. The f r s t precipitate and the glycerides f r o m the second mother liquor are combined, interesterified, and returned to the process f o r recycling. SALAD OIL .AND ~IETHOI) OF OILING TI~ PLATE. J. E. F a r b a k and E. J. K a s m e n ( S w i f t & Co.). U. S. 2,899,328. Electrolyrically produced tin plate is oiled with a mixture of an antioxidant, salad oil, and p a r t i a l glycerides derived f r o m cottonseed: oil. PHOSPtIATID55L CHOLINE CO,I~rPOUNDS. A. I)ebay and O. Saekur (See. F r a n c a i s e de Itecherches Biochimiques H. Besson & Cie.). U. S. 2,899,449. A process is described for tile production of complex compound of magnesimn sulphate and phosphatidyl choline. METs

EOIL FOOD COOKING %VRXPPER. M. Shorr. U. S. A metallic foil sheet, is coated on one side w~th a shortening which is pliable at r~om t e m p e r a t u r e and has a

2,902,371.

melting point above 140~ before cooking.

VOL. 36

and used for wrapping

foods

SOLVE:NT FRACTIONATION OF VV~INTERIZED COTTONSEEI) OIL BOTTOSIS. G. W. F a r r . U, S. 2,903,363. A process is described for the p r e p a r a t i o n of a h a r d b u t t e r f r o m winterized cottonseed oil bottoms as the sole f a t source. A solution of the winterized cottonseed oil bottoms is cooled to crystallize out a solid containing at least 75% of m o n o u n s a t u r a t e d , disaturated trlglycerides. These are separated and h y d r o g e n a t e d at 160 ~ at atmospheric pressure. A solution of the h y d r o g e n a t i o n product is chilled and tile precipitated material is separated. MateriaI remaining in solution is the desired product and has an iodine value of a b o u t 36. PIg0CESS FOR IMPROVING THE TASTE .aND FLAVOR OF ]-~[ARGARINE AND OTHER FO,ODS AND EDIBLE SUBSTANCES. N. G. Wode and U. Holm ( M a r g a r i n b o l a g e t Akt.). U. S. 2,903,364. Lactones for flavoring fat-containing foods are described. STABILIZATION 01~ ORGANIC C01~fPOUNDS. 1~.. g , Thompson (Universal Oil P r o d u c t s Co.). U. S, 2,903,363. H y d r o c a r b o n distillates and f a t t y materials normally subject to oxidative deterioration are stabilized by the addition of a 1,4-dihydroxy5,8-etbano-hydronaphthMene or a mono-ether thereof. EDIBLE OIL. G. C. t t a m p s o n and I. P. F r e e m a n (Lever Brothors Co.). U. S. 2,903~369. P r o p e r t i e s of coconut and palm kernel oils are improved by tile addition of a small a m o u n t of a Cr., ta Cls p r i m a r y amine. P a o c E s s OF HYDROGENATING GLYCERIDES. I). R. Merker ( S w i f t & Co.). U. S. 2,903,468. Plasticity and flavor stability of a partially hydrogenated f a t are improved by the addition of at least 0.05% of a naturally occurring vegetable phospholipid to the refined f a t prior to hydrogenation. ]~ECO,VERY O~ WO0~L Gt~EASE. J. ]~aoul, Marie Bevy, and E s t a b lissements Albert V. Bevy ( E T A L B O ) , S. A. Belg. 526,672. D u r i n g the process of the recovery of wool grease, the wash water which contains at least one surface active ionic or animfie agent is a g i t a t e d slighNy before the final scavenging operation. A f t e r scavenging, it is submitted at 70-80 ~ to centrifugation. (C. A. 53, 15603) ~ilXED GLYCEROL ESTEa COJVIPOSITIONS. N. I). E m b r e e and G. Y. Brokow ( E a s t m a n K o d a k Co.). Brit. 808,63& Addition to Brit. 745,566. The compositions are p r e p a r e d by reaction of a higher acylated triglyeeride with an OH-containing reactant. The latter consists of glycerol with a lower aeylated triglyceride, or a lower acylated glycerol p a r t i a l ester comprising glycerol and a u f x t u r e of lower aey]ated glyeerols. The reaction takes place in the presence of a basic tranesterification catalyst. The reaction mixture is then vacuum distilled in order to separate the remaining portion of tile O i l - c o n t a i n i n g reactant, and then the residue of this first distillation is subjected to thin-film vacuum distillation in order to separate a composition containing a substantial a m o u n t of the mixed glycerol ester. The res:_due front the second distillation and the separated remaining portions of the OH-containing r e a c t a n t are combined with additional portions of the s t a r t i n g material and the above is repeated. The glyeeride contail~.ing the lower aeyl radicals may be triaeetin or t r i b u t y r i n . The products are useful as coatings or plasticizers for foods, in cosmetics, in plastics, and as lubricants and release agents. (C. A. 53, 15603) J~EFINED SHAKK-LIVER OIL AND 3~rITAMIN A CONCEN~RATES. S. Mahdihassan, M o h a m m a d :~Ioinuddln, Syed M, Ali and Syed A. Haq. Brit. 810,643. A process is described for the simultaneous production of refined shark-liver oil and vit~lmin A concentrates as well as recovery of calcium salts of f a t t y acids. (C. A. 53, 15604) INTEI~CHANCE OF ESTEt~ I:~ADICALS IN TRIGLYCEI~II~ES. ]~. Beaker and W. Clemens ( M a r g a r i n e - U n i o n Akt.-Ges.). Get. 1,009,611. Triglycerides ( p a r t i c u l a r l y a m i x t u r e of 20% cottonseed oil, 40% coconut oil, 30% hardened whale oil, and 10% tall by weight] hardened palm oil) were submitted to ester exchange at a b o u t 120 ~ in the presence of NaOCH~. The latter was p r e p a r e d by s p r a y drying of an alcoholic NaOCH3 solution. A d r a w i n g is given. (C. A. 53, 14943) NEUTRALIZATION OF ~V~EG~TABLE OILS. J. Weiss (' ' S h a m n o n ' ' Spivak & Silberstein, Oil and Soap I n d u s t r y ) . Israeli 10,995. The complete neutralization and utilization of coconut, palm kernel, and other vegetable oils are obtained by t r e a t i n g the oil with an a m o u n t of an alkali hydroxide not exceeding the p r o p o r t i o n stoiehiometrieally equivalent to the acidity and admixing of at least 4% by weight of the acid contained in the oil of mono-, di-, or triethanolamine and an aqueous sodimn chloride solution. (C. A. 53, 15604)

NOVEMBER,

1959

ABSTRACTS:

FATTY

9 Fatty Acid Derivatives DIET~xIYLENE GLYCOL FATTY ACID ESTEt~. R. Schneider. ]?ette Seifen Anstrichmittel 5 9 ( 1 0 ) , 876-7 (1957). A review with 60 references. (C. A. 53, 15601) HYDROBOP~ATION 0F FATS. I. POSITI0,NAL ISON[ERISNI IN THE ~{ETHYL OLEATE HYDROBORATION :REACTION. Sara P. F o r e and W. G. Biekford ( S o u t h e r n Regional Research L a b o r a t o r y , New Orleans, L a . ) . J. Organic Chem. 24 (1959). I t has been found t h a t addition of deborane to the ethylenic bond of methyl oleate proceeds smoothly without significant reduction of the earbomcthoxy group. Alkaline h y d r o g e n peroxide oxidation of the tris (carbomethoxyalkyl) borane resulted in the formation of an equlmolar m i x t u r e of 9- and 10-hydroxyoctadecanoie acids, establishing t h a t the h y d r o b o r a t i o n reaction proceeded nonseleetively. Little or no isomerization occurred on heat t r e a t m e n t of these substituted trialkyl boranes.

POLYI~[ERIC FATS FRO~ STgARIC, OLEIC, AND SHORT-CHAIN DIBASIC ACIDS. R. O. Feuge and Audrey Gros (Southern Utilization Research and Development Div., U. S. Dept. of Agriculture, New Orleans 19, La.). Ind Eng. Chem. 51, 1019-1022 (1959). Mixtures of f a t t y acids, short-chain diba.sie acids and glycerol when combined in such p r o p o r t i o n s t h a t the mole ratio of f a t t y acid to dibasic acid is one or niore yield on ester ification polyesters which are niueh more viscous t h a n are edible oils and fats. On crystallization of the melt, the polyesters containing stearic acid fornl a fine-grained crystal structure and possess a h a r d n e s s at, 30~ which r a n g e s f r o m t h a t of beeswax to t h a t of completely hydrogenated cottonseed oil. OXIDATION OF ~r FATTY ACIDS AND ESTE~RS: CATALYTIC AIJTOXIBATI0.N OE METHYL N-PROPYL AND N-BUTYL PETROSELINATE. ~/[rs. J. Gold aDd J. H. Skellon (Brunel College of Technology, London, W. 3). J. Applied Chem. 9, 38995 (1959). E s t e r s of eis-octadec-6-enoates (petroselinates) were oxidized by gaseous oxygen at various t e m p e r a t u r e s in the presence of u r a n i u m petroselinate. D u r i n g the autoxidation, hydroperoxides f o r m e d initially at the 5, 6, 7, and 8 positions and subsequently decomposed. The greatest hydroperoxide concentration was obtained with the methyl esters. However, the n a t u r e of the ester g r o u p exerted little influence on the structure of the final products which included a-ketols, isomers of 6:7-dihydroxystearie acid, dicarboxyIic acids and resinous or polynierie materials derived f r o m semialdehydes. The mcehalfism of this autoxidation is a p p a r e n t l y comparable to t h a t of oleic or elaidie acid. PROCESS FOR UPGRADING POLYI~IERIZED FATTY ACID .~IIXTURES. B. L. H a m p t o n (Glidden Co.). U. S. 2,894,939. Halogen conraining substances are removed f r o m a crude polymerizcd f a t t y acid mixture by treatnient with zinc. 9,12-DIKETO-10-HYD~OXYSTEARIC ACID. J. Nichols and E. S. Schipper (Ethicon, I n c . ) . U. S. &gg~,96g. This acid is prep a r e d by the oxidation of 12-kctoe]aidie acid with either potassiuin p e r m a n g a n a t e in basic solution or h y d r o g e n peroxide in the presence of osmimn tetroxide. ACETOACETIC ACID ESTERS OF CASTOR OIL. A. R. Bader and H. A. Vogel ( P i t t s b u r g h Plate Glass Co.). U. S. 2,895,84& Nitrocellulose is plasticized with the acetoaeetic acid ester of castor oil. GELLED GLYCEROL FATTY ACID PARTIAL ESTEI{ PIIAR~IACEUTICAL CA~IEa. G. Y. B r o k a w and ~r. C. L y m a n , J r . ( E a s t m a n K o d a k Co.). [7. S. 2,395,879. A firm clear gel is f o r m e d front a mixture of 10 to 90% water, up to 15% of a medicament, and the remainder a p a r t i a l glyeeride containing less t h a n 10% of glycerides with s a t u r a t e d f a t t y acid radicals of more t h a n 11 carbon atoms and at least 75% of the monoglyeerides of C~ or higher f a t t y acids. ~ONOGLYCEI~IDE DIACETATES. W. C. Ault and R. O. Feuge (U. S. A. Secy. A g r . ) . U. S. 2,895,966. The p r e p a r a t i o n is described of epoxidized monoglyceride diaeetates f r o m cottonseed, soybean, olive, corn, fish, or tall oil. HYDaOXY ACIDS. E. N. Case (Sinclair Refining Co.). U . S . 2,895,974. Oleic acid and formaldehyde are reacted in the presence of sulfuric acid at 30 to 60 ~.

METHOD F01~ THE RE:COVER.Y OF AZELAIC ACID FROM A ~[-IXTIIRE OF OXIDIZED ACIDS. S. J. Niegowski and A. Maggiolo (The Welsbach Corp.). U. S. 2,397,23l. Oleic acid, tinoleic acid or their mixtures are ozonized and cleaved to a m i x t u r e of dicarboxylic acids. The oxidized acids are esterified and the azelate is separated by fractional distillation.

ACID

DERIVATIVES

559

DI- AND POLYCARBOXYLIC ACIDS. W. Reppe, N. v. Kutepow, and H. Detzer (Badische Anilin- & S o d a - F a b r i k Akt.-Ges.). Get. 1,006,849. Oleie acid was reacted with carbon monoxide at 270 ~ in the presence of a nickel catalyst to obtain isomeric heptadeeane diearboxylic acids in 80% yield based on oleie acid. (C. A. 53, 14945) DIAMIDE 01~ ADIPIC ACID AND ~-CYANOVALERAJV[IDE. E. N. Zil' b e r m a n and A. E. Kulikova. U. S. S. R. 115,895. Adipie diiminochloride-2HCl or the corresponding cyanovaleric irninoehloride-HC1 is t r e a t e d with an equivalent a m o u n t of w a t e r and the resulting imonium ehlorohydrin hydrolyzed with excess water in the presence of a base. (C. A. 53, 14945)

9 Biology

and N u t r i t i o n

BIOCHE~IISTRY OF HYPOGLYCINE A. I I . THE INFLUENCE OF HYPOGLYCINES ON THE OXIDATION OF GLUCO.SE AND FATTY ACIDS. C. v. Holt and I. Benedict (Physiological-Chemical I n s t i t u t e of the Univ. H a m b u r g ) . Biochem. Z. 331, 430-435 (1959). fl-Methylenecyclopropyl-a-amino-propionic acid (hypoglycine A) causes an increase in oxidation of u n i f o r m l y labeled C~*-glucose to C'402 in normal and alloxan diabetic r a t s to about twice the values observed in u n t r e a t e d animals. At the same time the oxidation of 1-C~Mabeled palmitate is decreased to a b o u t one half, while that of 1-C~4-capronate rem a i n s unchanged.

r PHOSPHATE FATTY ACID SALTS OCCURRING IN FECAL LIPIDES. J. F. Richards and K. K. Carroll (Univ. W e s t e r n Ontario). Can. J. Bioehcm. and Physiol. 37, 725-30 (1959). The presence of u n s a t u r a t e d f a t t y acids such as oleic, lino]eie, eieosenole, and erueic acid in the diet of rats causes a marked increase in lipide soluble calcium and phosphorus in the feces. A proposed structure of a calcium phosphate f a t t y acid complex salt for this material (Swell, et al., C. A. 51, 5246h) was confirmed by chemical synthesis and characterization by p a p e r c h r o m a t o g r a p h y . (C. A. 53, 15288) LINOLEIC ACID ]~ETENTION BY THE RAT OI~ANISM. I-I. W a g n e r , E s t h e r Seelig, and K. B e r n h a r d (Univ. Basel, Switz.). Z. physiol. Che~. 313, 235-43 (1958). Y o u n g nmle r a t s received a normal diet enriched with sunflower oil. They showed an increase of up to 40% in ]inoleic acid content of o r g a n and f a t deposits. W h e n these animals were put on a f a t - f r e e diet, a g r a d u a l decrease of linoleic acid occurred. Of the remaining polyenic acids, tetraenic (arachidonie) acid increased, b u t not pentaertic and hexaenic acids. Only very small a m o u n t s of the latter were present in o r g a n s and they were barely detectable in the f a t deposits, lRats on f a t - f r e e diets contained only small a m o u n t s of linoleie acid, but a moderate addition of sunflower oil to the diet caused a large increase in the llnoleic acid content of o r g a n lipides. Increases in arachidonic acid could also be determined, and the a m o u n t s f o u n d were in agreement with their possible origin f r o m linoleie acid. (C. A. 53, 15249) LINOLEIC ACID AND CHOLESTEROL ~ETABOLISI~I I~ THE RAT. I I . EFFECTS OF DIETARY CHOL~bSTER0.L O,N PLASMA AND LIVEa~ ESTER CObIPO:SITION. P. D. Klein ( A r g o n n e Natl. Lab., Lemont, Ill.). Arch. Biochem. Biophys. 81, 382:9 (1959). I n rats, addition of 0.5% cholesterol to the diets containing various levels of linoleic acid resulted in accumulation of liver cholesterol ester; the m a g n i t u d e of the accumulation was not related in an a p p a r e n t n m n n e r to the a m o u n t of linoleie acid. There was little or no increase in p l a s m a cholesterol except in animals on a f a t - f r e e diet. The m u l t i u n s a t u r a t e d f a t t y acid content of the plasma esters decreased niarkedly, and cholesterol arachidonate largely disappeared. The influx of cholesterol in the liver was accompanied by increases i n the anIounts of dienoic and trienoic ester, b u t tetraenoic and pentaenoic esters did not change. The fact t h a t feeding a diet containing 2% cholesterol f o r 28 days decreased incorporation of acetate into the octabromide f r a c t i o n o f liver lipides suggests t h a t the f o r m a t i o n of arachidonie acid f r o m linoleic acid was impaired. (C. A. 53, 15280) CO,MPARATIVE LYI~IPHA'I'IC ABSORPTION OF f~-SITOSTEtgOL AND CHOLESTEI~0L BY THE RAT. IJ. W. D u n h a m R. E. F o r t n e r , R. D. lVIoore, H. W. Culp, and C. N. Rice (Lilly Research Labs., Indianapolis, I n d i a n a ) . Arch. Bioehem. Biophys. 82, 50-61 (1959). fl-Sitosterol reduces the absorption of cholesterol via the thoracic l y m p h (Hernfindez, et al., Am. J. Physiol. 181, 523 [1955]). The percentage of fl-sitostero] absorbed is about lap that f o r cholesterol. /~-Sitosterol delays the a b s o r p t i o n of t h a t cholesterol which is absorbed. Under the conditions of

560

THE

JOURNAL

OF THE

AMERICAN

these e x p e r i m e n t s , the total a m o u n t of fl-sitosterol, r a t h e r t h a n the ratio of the 2 sterols adnlinistered, d e t e r m i n e s the effectiveness of t h e fl-sitosterol. I n 4 g r o u p s of a n i m a l s g i v e n different a m o u n t s of fl-sitosterol a n d cholesterol, l y m p h a t i c cholesterol was a b o u t 70% esterified, w h e r e a s l y m p h a t i c fl-sitosterol was only a b o u t 25% esterified. (C. A. 53, 15280) INFLUENCE 0F AGE AND RACE ON LIPIDE LEVELS IN ISRAEL. D. B r u n n e r , G. Manilis, a n d K . Loebl. Lancet 1959-I, 1071-3. T o t a l cholesterol, a- a n d fl-cholesterol, a n d other lipide fractions were e s t i m a t e d by p a p e r electrophoresis in h e a l t h y y o u n g a d u l t Y e m e n i t i s a n d A s h k e n a z i Jews. C o n t r a r y to t h e view t h a t cholesterol levels rise with age f r o m the early t w e n t i e s to middle age, no such t r e n d was f o u n d in Y e m e n i t e Jews. Y o u n g A s h k e n a z i J e w s f r o m t h e u p p e r middle social classes have h i g h e r total cholesterol levels t h a n t h e Y e m e n i t e s , b u t these are lower t h a n those of the m i d d l e - a g e d A s h k e n a z i g r o u p of m i x e d social classes. W i t h r e g a r d to low a v e r a g e values of fl-eholesteroI a n d the h i g h p e r c e n t a g e of a-cholesterol, t h e y o u n g Ashkenazis, unlike the m i d d l e - a g e d A s h k e u a z i s , are identical with Y e m e n i t e s of all ages. (C. A. 53, 15279) EFFECT OF ERUCIC ACID ON INCOI~POgATION OF ACETATE-I-Cfi4 INTO CHOLESTEROL AND FATTY ACIDS. K . K . Carroll ( U n i v . W e s t e r n Ontario, L o n d o n ) . Can. J. Biochem. and ]Physiol., 37, 803-10 (1959). Y o u n g nlale r a t s were f e d s y n t h e t i c diets c o n t a i n i n g either no f a t or v a r i o u s i n d i v i d u a l f a t t y acids f o r 3 - 4 weeks. T h e y were t h e n killed a n d t h e i n c o r p o r a t i o n of acetate-l-C ~ into cholesterol a n d f a t t y acids was m e a s u r e d in liver slices a n d in s e r a p i n g s of i n t e s t i n a l mucosa. A c e t a t e i n c o r p o r a t i o n into cholesterol b y liver slices was m u c h g r e a t e r hi a n i m a l s f e d erueic acid t h a n in those f e d no f a t , palmitie, stearlc, oleic, or linoleic acid. A m a r k e d differential w a s n o t observed in f a t t y acid incorporation, b u t values t e n d e d to be h i g h e r on the f a t - f r e e a n d erucie acid diet. E r u c i c acid did n o t s t i m u l a t e a c e t a t e i n c o r p o r a t i o n into cholesterol b y m u c o s a and, in general, m u c o s a seemed to be less sensitive to c h a n g e s in diet. (C. A. 53, 15288) BLOOD LIPIDES DURING EXERCISE. I. ARTERIAL AND VENOUS PLASMA CONCENTRATION OF UNESTEaIFIET) FATTY ACIDS. L. A. Carlson and ]3. Pernow (Karolinska Inst., Stockholm). J. Lab. Clin. Med. 53, 833-41 (1959). P l a s m a c o n c e n t r a t i o n of unesterified f a t t y acids in the a r t e r i a l blood a n d in t h e f e m o r a l veins was d e t e r m i n e d at rest a n d d u r i n g exercise in 6 h e a l t h y h u m a n s u b j e c t s . D u r i n g exercise t h e a r t e r i a l nnesterified f a t t y acids c o n c e n t r a t i o n decreased. The exercising leg e x t r a c t e d unesterified f a t t y acids f r o m plasnla. (C. A. 53, 15278) TRANSPORT OF FATTY ACIDS. D. S. F r e d r i e k s o n a n d ~ . S. Gordon, J r . (Natl. H e a r t Inst., B e t h e s d a , M d . ) . Physiol. Bevs. 38, 585-630 (1958). A review is g i v e n of recent i n v e s t i g a t i o n s into t h e problenls of the t r a n s p o r t of f a t t y acids in m a m m a l s , covering the p h y s i c a l s t a t e a n d chemical composition of the f a t t y acids in extraeellular fluids a n d also t h e t u r n o v e r a n d m e t a b o l i s m of esterified a n d unesterified f a t t y acids in extracellular fluids. 370 references. (C. A. 53, 15274) METABOLISM STUDIES WITH A MIXED GLYCERIDE OF FATTY ACIDS OF MEDIUIXI CHAIN LENGTH. I I . INVESTIGATION OF THE CHANGES OF KETONE BODIES OF BLOOD AND I~=RINE AFTER TI~EATMENT WITH THE MIXED GLYCEaIDE. I-I. Sehhn, I n g e IApach, a n d W . Gelpke (Med. Univ., E r l a n g e n , Ger.). Gastroenterologia 91, 199-213 ( ] 9 5 9 ) . R e p l a c i n g f a t s in t h e n o r m a l diet w i t h a trlglyceride of caprie, eaprylic, a n d laurie acids r e s u l t s in significantly i n c r e a s e d excretion of acetone a n d fl-hydroxybutyrie acid in t h e blood. The significance of these findings in relation to the t h e r a p y of obesity is discussed.

(c. A. 53, i527])

SERU1Vi CHOLESTEROL LEVELS IN AMEI~ICAN INDIANS. S. A b r a h a m a n d D. C. Miller (U. S. P u b l i c H e a l t h Service, W a s h ington, D. C.). Public Health Repts. (U. S.) 74, 392-8 (1959). T h e s e r u m cholesterol level of 5 tribes of A m e r i c a n I n d i a n s who were e x a m i n e d d u r i n g t h e I n d i a n H e a l t h S u r v e y w a s significantly lower t h a n t h a t of t h e Cleveland clinic group, whose m e a n level is similar to t h a t f o u n d in other s u r v e y s of A m e r i c a n n o n - I n d i a n populations. The findings of a h i g h e r s e r u m cholesterol level a m o n g one s u b g r o u p of t h e 1%avajos a n d a significantly lower m e a n level a m o n g a n o t h e r s u b g r o u p sugg e s t s i m p o r t a n t e n v i r o n m e n t a l f a c t o r s at work a m o n g this ethnic group. (C. A. 53, 15269) DIET AND CHOLESTEICEMIA: EFFECT OF 1%UTRITIONAL FACTORS ON SERUM CHOLESTEROL CONCENTRATION. 1%arindar N a t h (Univ. of Wisconsin, M a d i s o n ) . Univ. Microfilms ( A n n Arbor, Mich.), L. C. Card No. Mic 59-1420, 140 pp.; Dissertation Abstr. 19, 2741 (1959). (C. A. 53, 15251)

OIL

CHEMISTS'

SOCIETY

VOL.

36

THE 1%UTlZlTIONAL VALUE OF FATTY ACIDS ISOMERS. O. K . P a l l a d i n a , K . S. S t e p a n o v a , a n d 1%. D. B u k h m a n . Trudy Vsesoyuz. Nauch.-Issledovatel. Inst. Zhirov 1957, 1%o. 17, 7 6 82; Beferat. Zhur. Khim., Biol. Khim. 1959, A b s t r . No. 781. R e s u l t s of n u t r i t i o n a l e x p e r i m e n t s with h u m a n s i n d i c a t e d t h a i h y d r o g e n a t e d f a t s c o n t a i n i n g n o t less t h a n 3 0 % of isohleic acid were equivalent in their n u t r i t i o n a l value to b u t t e r f a t a n d sunflower seed oil. The a d d i t i o n of food p h o s p h a t i d e s to h y d r o g e n a t e d oils c o n t a i n i n g 38.5% of isohleie acids i n c r e a s e d t h e i r n u t r i t i o n a l value over b u t t e r f a t . (C. A. 53, 15245) EFFECT 0,F ]:{EDUCTION OF DIETARY FAT AND ADDITIONAL INGESTION OF CORN OIL ON HYPERCI~OLESTEKOLEMIA. D. V. R h o a d s a n d N. W. B a r k e r ( M a y o Clinic, Rochester, M i n n . ) . Proc. Staff Meetings Mayo Clinic 34, 225-9 (1959). 1%ine p a t i e n t s in a m e n t a l h o s p i t a l w i t h control p l a s m a cholesterol values b e t w e e n 247 a n d 331 rag./100 ml. were g i v e n d u r i n g successive periods a low f a t diet (57 + 10 g. d a i l y ) , t h e low f a t diet plus 90 ml. corn oil daily, the r o u t i n e h o s p i t a l diet plus 90 ml. corn oil a n d t h e r o u t i n e hospital diet w i t h o u t corn oil. I n all s u b j e c t s , p l a s m a cholesterol values decreased with the low f a t diet, decreased f u r t h e r with t h e low f a t diet p l u s corn oil, increased b u t not to control levels w i t h t h e r o u t i n e diet plus corn oil, a n d r e t u r n e d to p r e t r e a t m e n t levels w h e n t h e r o u t i n e diet w i t h o u t corn oil was resumed. T h e s u b j e c t s lost w e i g h t on the low f a t diet b u t r e g a i n e d t h i s w e i g h t when the corn oil was added. (C. A. 53, 15246) DIETARY LINOLEIC ACID A N D LINOL]~ATE. L. W. Kinse]l, G. D. Michaels, G. W a l k e r , P. Wheeler, S. Splitter, a n d P. F. F l y n n ( H i g h l a n d - A l a m e d a C o u n t y Hosp., Oakland, Calif.). Diabetes 8, 179-88 ( ] 9 5 9 ) . Linoleic acid a p p e a r s to be t h e responsible c o n s t i t u e n t of those v e g e t a b l e f a t s which, w h e n t a k e n in t h e diet, lower p l a s m a levels of cholesterol a n d other lipides. M a r k e d i m p r o v e m e n t h a s been n o t e d in c e r t a i n diabetic a n d n o n d i a b e t i c p a t i e n t s with v a s c u l a r disease when a d m i n i s t e r e d l a r g e a m o u n t s of llnoleic acid in t h e i r food. T h e f a t t y acid composition of t h e diet specifically influenced t h e composition of t h e p l a s m a cholesterol esters. H i g h linoleate i n t a k e resulted in m a r k e d l y i n c r e a s e d p l a s m a cholesterol linoleate, a n d high oleate i n t a k e resulted in m a r k e d l y i n c r e a s e d p l a s m a cholesterol oleate. (C. A. 53, 15246) BIOLOGICAL UTILIZATION OF CAROTENE FROM INDIAN EDIBLE OILS ON FRYING. Y. B. R a n g n e k a r (M. G. M. Med. Coll., I n dore, I n d i a ) . Sci. and Culture (Calcutta) 24, 330-1 (1959). A n i m p o r t a n t f a c t o r in t h e differential u t i l i z a t i o n of carotene in oils is v i t a m i n E. A n o t h e r f a c t o r is h y d r o g e n a t i o n . I n m o s t I n d i a n diets t h e edible oils are u s e d f o r f r y i n g at a h i g h temp e r a t u r e for t h e p r e p a r a t i o n of vegetable diets. I t was f o u n d t h a t f r y i n g m a r k e d l y reduced the u t i l i z a t i o n of carotene subs e q u e n t l y a d d e d to t h e f r i e d oils. F r y i n g e v i d e n t l y caused t h e development of c o m p o u n d s which i n t e r f e r e d with the proper u t i l i z a t i o n of v i t a m i n A. Coconut oil, which is devoid o f vitam i n E, gave the best response. (C. A. 53, 15243) THE CONTROL OF FAT ~{ETABOLISM. A. L. G r e e n b a u m (Univ. CoIL, L o n d o n , E n g ] . ) . Lectures Sci. Basis Med. 6, 277 96 (1956 57). A review with 26 references. (C. A. 53, 15238) ESSENTIAL FATTY ACIDS IN 1%UTRITION AND THEII~ RELATION TO VITAMINS. H. M. Sinclair (Univ. Oxford, E n g l . ) . Lectures Sci. Basis Meg. 6, 260-76 ( 1 9 5 6 - 5 7 ) . A review with 39 references. (C. A. 53, I5238 ) VITAMIN A. R. A. M o r t o n (Univ. Liverpool, E n g l . ) . Lectures Sci. Basis Mcd. 5, 143-64 ( 1 9 5 5 - 5 6 ) . A review w i t h 45 references. (C. A. 53, 15238) FAT METAB0,LISM. A. C. F r a z e r (Univ. of B i r m i n g h a m , E n g l . ) . Lectures Sci. Basis Med. 4, 311-31 ( 1 9 4 5 - 5 5 ) . A review with 67 references. (C. A. 53, 15238) INFLUENCE OF FATS ON ABSORPTION OF CALCIUM AND I~HOSPHORUS. 1%. D. K e h a r , T. S. K r i s h n a n , a n d R. C h a n d a . Studies Fats, Oils and Vanaspatis 1956, 85-90; Dairy Sci. Abstr. 19, 747 (1957). The effect of calcium a n d p h o s p h o r u s m e t a b o l i s m of ghee, vegetable oils, v a n a s p a t i s , a n d l a r d was determined. Cow ghee caused 4 5 % calcium a n d 57% p h o s p h o r u s to be retained. The other f a t s gave a p e r c e n t a g e a b s o r p t i o n of 22.6-40.7 for calcium. The v a n a s p a t i s were less efficient in p r o m o t i n g calcium a b s o r p t i o n t h a n the v e g e t a b l e oils. Phosp h o r u s a b s o r p t i o n was lower w h e n t h e oils, lard, or v a n a s p a t i s f o r m e d the d i e t a r y f a t t h a n w h e n ghee w a s used. (C. A. 53, 15240) ABSORPTION OF CAROTENE AND LIVER STOIZAOE 0'F VITAMIN A. 1%. D. K e h a r , S. N. Ray, T. S. K r i s h n a n , B. S. Joshi, a n d A. K . Pal. Studies Fats, Oils and Vanaspatis 1956, 9 - ] 0 0 ; Dairy Sci. Abstr. 19, 751-2 (1957). L i v e r s t o r a g e of v i t a m i n A

NOVEMBER, ~959

ABSTRACTS: BIOLOGY AND N U T R I T I O N

u a s h i g h e s t ~xith ghee-fed a n i m a l s a n d lowest in those receivi n g the D a l d a ( v a n a s p a t i ) . The digestibility of carotene w a s increased b y the presence of refined f a t s , v a n i s p a t i s , a n d ghee. IV. x . 53, 15240) EFFECT OP FATS AND OILS ON THE REQUIREMENTS OP THE B VITAMINS. N. D. K e h a r , T. S. K r i s h n a n , a n d B. C. Joshi. Studies Fats, Oils and Vanaspatis 1955, 1 0 1 - 6 ; Dairy Sei. Abstr. 19, 747 ( ] 9 5 7 ) . R a t s f e d ghee showed b e t t e r w e i g h t g a i n s t h a n those f e d crude or refined p e a n u t oil, or D a l d a ( v a n a s p a t i ) ; h y d r o g e n a t e d p e a n u t oil gave b e t t e r results. Riboflavin-deficient r a t s showed better g r o w t h w h e n cow ghee was t h e d i e t a r y f a t , except at h i g h i n t a k e levels, i.e. 8 ~ / d a y . (C. A. 53, 15240) THE. EFFECT 0P DIFFERENT ]OATS AND 0ILS ON PROTEIN METABOLISM. N. D. K e h a r , T. S. K r i s h n a n , a n d R. C h a n d a . Studies Fats, Oils and Vanaspatis 1956, 79-83; Dairy Sci. Abstr. 19, 746-7 (1957). W h e n f a t was a d d e d to a diet s u b o p t i m a l f o r v i t a m i n A, t h e digestibility a n d biological value of the protein was increased. Cow ghee i m p r o v e d digestibility b y 3 6 % a n d biological value b y 62%. S u p p l e m e n t a t i o n with B vitaniins did n o t affect the digestibility of the p r o t e i n b u t did i m p r o v e t h e biological value b y 1 3 - 1 4 % w h e n p e a n u t oil or D a l d a was t h e d i e t a r y f a t . (C. A. 53, 15239) SO~E EFFECTS OF FEEDING VARIOUS FILLED MILKS TO. DAIRY CALVES. I. PHYSICAL CONDITION AND WEIGHT GAINS, WITH SPECIAL RE~ERENCE TO LOW-FAT RATIONS. R. S. A d a m s , T. W. Gullickson, J. E. Gander, a n d J. H. S a u t t e r (Dept. of D a i r y H u s b a n d r y , U n i v . of M i n n e s o t a , St. P a u l ) . J. Dairy Sci. 42, 1552-61 (1959). V a r i o u s filled m i l k s a n d low-fat r a t i o n s were s t u d i e d in a n a t t e m p t to d e t e r m i n e some of the f a c t o r s responsible f o r the u n s a t i s f a c t o r y gains, poor physical condition, a n d d e a t h s which have been reported as o c c u r r i n g in calves f e d r a t i o n s c o n t a i n i n g h i g h l y u n s a t u r a t e d vegetable f a t . U n d e r the conditions of the e x p e r i m e n t , the r e s u l t s of f e e d i n g corn oil filled milk to d a i r y calves were as follows: (a) a n i m a l s appeared e m a c i a t e d a n d u n t h r i f t y , (b) a m a r k e d d i a r r h e a was observed, (c) a n i n c r e a s e d susceptibility to p n e u m o n i a a n d a h i g h m o r t a l i t y rate occurred w h e n i n f e c t i o n was n o t rigidly controlled, (d) s y m p t o m s of a n o r e x i a a n d m u s c u l a r involvem e n t were noted, (e) poor f e e d u t i l i z a t i o n a n d u n s a t i s f a c t o r y w e i g h t g a i n s were obtained. ~I. FECAL CHARACTERISTICS AND DIGI~STIBILITY DATA. Ibid., 1562-68 (1959). Y o u n g d a i r y c'dves were f e d low-fat r a t i o n s or filled nfilks c o n t a i n i n g various f a t s . One g r o u p received a corn oil filled milk which was p r e p a r e d daily r a t h e r t h a n weekly, to s t u d y effects of storage. All other diets were p r e p a r e d once each week. Differences in the color of feces were observed a m o n g t h e v a r i o u s rations. A b n o r n i a l l y large a m o u n t s of feces were voided by a n i m a l s f e d the corn oil filled milk p r e p a r e d weekly. D a i l y p r e p a r a t ' o n of the corn oil filled milk diet or t h e f e e d i n g of h y d r o g e n a t e d corn oil g r e a t l y reduced the a m o u n t s of feces excreted. III. BLOOD PLASMA TOCOPttEROL AND VITAI~IIN A LEVELS, DIET STORAGE, EI~FECTSt AND EVIDENCE OfF TOXICITY. Ibid., 1569-79 ( ] 9 5 9 ) . L o w blood p l a s m a tocopherol levels were f o u n d in calves f e d corn oil filled milk, despite a relatively h i g h tocopherol intake. B o t h p l a s m a tocopherol a n d v i t a m i n A values declined p r o g r e s s i v e l y d u r i n g t h e e x p e r i m e n t a l period in the corn oil filled milk group. Low blood p l a s m a tocophero] levels also occurred in a n i m a l s f e d lard filled milk a n d a ration c o n t a i n i n g b u t t e r oil, which was p r e p a r e d f r o m oxidized butter. Oral s u p p l e m e n t a t i o n of the corn oil a n d l a r d filled milk diets with 500 mg. of DL-alpha tocopherol or alpha tocopheryl a c e t a t e daily resulted in h i g h p l a s m a tocopherol values. IV. NECROPSY FINDINGS, ELECTI~0CARDIOGRAPI-IIC STUDIES, AND CREATINURIA RATIOS. Ibid., 1580-91 (1959). Gross and microscopic lesions were demonstrated in the cardiac and skeletal muscles of calves fed corn oil or lard filled milk. Such lesions were also found in animals receiving a similar ration containing butter oil, which had beeu prepared from oxidized butter. Both oral and intramuscular supplementation of the corn oil and lard filled milk diets with high levels of toeopherol prevented the development of muscular involvement during the course of the experiment. No evidence of muscular involvement was encountered in calves fed a low-fat, tocopherol-poor ration for periods as long as 5.6 too. The influence of certain fats in the diet on t h e p r o d u c t i o n of so-called v i t a m i n E deficiency lesions in cattle is discussed.

BILE ACIDS AND STEROIDS. L X X X I I . ON THE MECHANISM OF DEOXYCHOLIC ACID I~ORMATION IN THE RABBIT. S. B e r g s t r o m , S. L i n d s t e d t , a n d B. S a m u e l s s o n (Dept. of P h y s i o l o g i c a l Chem-

56]

istry, Univ. of L u n d , S w e d e n ) . J. Biol. Chem. 234, 2022-5 (1959). The p r e p a r a t i o n of cholic acid-7-B-H3,24-C 1~ is described. D u r i n g t h e conversion of this acid to deoxycholic acid in the r a b b i t i n t e s t i n e the t r i t i u m r e m a i n s in t h e molecule. Evidence is p r e s e n t e d t h a t the t r i t i u m is located in the 7-position in t h e deoxycholic acid f o r m e d . 7-Ketodeoxycholic acid can be t r a n s f o r m e d into deoxycholic in the r a b b i t intestine, b u t r e m a i n s l i n c h a n g e d a f t e r one p a s s a g e t h r o u g h the liver. 10-HYDROXY- ~-DECENOIC ACID, AN ANTIBIOTIC FOUND IN ROYAL JELLY. M. S. B l u m ( E n t o m o l o g y R e s e a r c h Dept., L o u i s i a n a S t a t e Univ., B a t o n Rouge, L o u i s i a n a ) , A. F. N o v a k a n d S. Taber, I I I . Science 130, ~52-453 (1959). 10-HydroxyA < d e c e n o i c a c i d , the m a j o r c o m p o n e n t o f t h e lipide f r a c t i o n of royal jelly, exhibits antibiotic~ a c t i v i t y a g a i n s t m a n y bact e r i a a n d fungi.: T h i s f a t t y : acid is 'less: than: 0 h e - f o u r t h as active as penicillin a g a i n s t Micrococcus pyogenes a n d less t h a n one-fifth as active as chlortetracycline a g a i n s t Eseheriehia coll. I t also slows t h e g r o w t h r a t e of Neurospora sitophilia a n d some unidentified molds. The salt of this c o m p o u n d is considerably less active t h a n t h e free acid. BIOCHE;MISTRy OF LONG CHAIN FATTY ACIDS. I. GENERAL OBSERVATIONS. J. C. D i t t m e r a n d D. J. H a n a h a n (Dept. of Biochem., Univ. of W a s h i n g t o n , Seattle, W a s h . ) . J. Biol. Chem. 234, 1976-82 ( ] 9 5 9 ) . The f a t t y acid composition of t h e v a r i o u s i n d i v i d u a l n e u t r a l a n d phospholipide c o m p o n e n t s of r a t liver is presented. Over a period of 4 to 18 h o u r s a f t e r f e e d i n g a single dose of corn or olive oil to a d u l t rats, the f a t t y acid d i s t r i b u t i o n in these different lipides was r e a s o n a b l y c o n s t a n t . I n a g e n e r a l s t u d y of the influence of corn a n d olive oil on the d i s t r i b u t i o n of C 1~ f r o m carboxy-labeled pa]mitic, oleic, stearie, a n d linoleic acids in the liver lipides, there seemed to be no appreciable dependence on t h e relative d i s t r i b u t i o n of these long c h a i n acids between phospholipides a n d n e u t r a l lipides. I I . METABOLIC STUDIES. Ibid., 1983-9 (1959). A f t e r oral feedi n g of p a l m i t i c aeid-l-C 1~, oleic acid-l-C~, linoleic acid-l-C ~, a n d stearic aeid-l-C ~* in corn oil to a d u l t r a t s , a s t u d y was m a d e of the i n c o r p o r a t i o n a n d d i s t r i b u t i o n of these i n d i v i d u a l f a t t y acids a t 4, 6, 10, a n d 18 h o u r s into the m a j o r lipide comp o n e n t s of t h e liver. T h e conversion of these f a t t y acids to other f a t t y acids h a s been observed a n d related to the g e n e r a l metabolic p a t h w a y s of the i n g e s t e d f a t t y acids. The p a t h w a y of the i n d i v i d u a l f a t t y acids was f o u n d to be comple x and, a l t h o u g h similar, n o t necessarily the same. PASSAGE 01~ LABELED CHOLESTEROL INTO THE AORTIC WALL 0F THE NORMAL DOG. L. E. D u n c a n a n d K a t h e r i n B u c k (Section of Clinical Endocrinology, N a t i o n a l H e a r t Inst., N . I . H . , Bethesda, M d . ) . Circulation Res. 7, 765-70 (1959). I n the norm a l dog t h e r a t e of m o v e m e n t of cholesterol f r o m t h e s e r u m into the i n n e r layer of the aortic wall is g r e a t e s t at the proximal e n d of the a o r t a a n d decreases p r o g r e s s i v e l y a l o n g the l e n g t h of t h e a o r t a u n t i l in t h e t e r m i n a l a o r t a the rate is only a b o u t one-sixth t h a t in t h e p r o x i m a l aorta. A s i m i l a r g r a d i e n t of r a t e s was previously d e m o n s t r a t e d f o r albunfin which enters the aortic wall a b o u t t h r e e t i m e s as f a s t as cholesterol. The s i m i l a r i t y of the g r a d i e n t s a n d the relative m a g n i t u d e of the r a t e s f o r cholesterol a n d a l b u m i n s u p p o r t the concept t h a t cholesterol is carried into the aortic wall of the n o r m a l dog by t h e p a s s a g e of the lipoproteins of which it is a p a r t . TOXITY OF AMII\rE-EXTRACTED S0,YREAN ~IEAL. J. Greenbueg, D. J. Taylor, H. W. B o n d , ~md J. F. S h e r m a n ( N a t i o n a l Ins t i t u t e of A l l e r g y a n d I n f e c t i o u s Diseases, N a t i o n a l I n s t i t u t e s of H e a l t h , B e t h e s d a , M d . ) . J. Agr. Food Chem. 7, 573-6 (1959). Residues of s o y b e a n meal, a f t e r e x t r a c t i o n with prim a r y , secondary, or t e r t i a r y Organic amines, were tox:c f o r t h e chick when incorporated, at levels of 20 to 4 0 % , in :m otherwise a d e q u a t e diet. A p p r o x i m a t e l y 80% of chicks f e d a m i n e - e x t r a c t e d residues o f : s o y b e a n meal died w i t h i n 10 days. Chicks f e d residues a f t e r e x t r a c t i o n with acetone, ethyl alcohol, or trichloroetbylene survived a n d a p p e a r e d normal. Those f e d t h e e x t r a c t s (except the b u t y l a m i n e e x t r a c t ) were normal. T r i e t h y l a m i n e - e x t r a c t e d cottonseed meal, black-eyed peas, soyb e a n protein, zein, a n d CereIose were toxic in v a r y i n g degrees. T r i e t h y l a m i n e - e x t r a c t e d g e l a t i n a n d casein were well tolerated. Twelve a m i n o acids f a i l e d to react with t r i e t h y l a m i n e when refluxed in the solvent f o r 24 h o u r s ; L-lysine monohydrochioride u n d e r the s a m e conditions showed evidence of c h a n g e in composition. THE NATURAL COMPOUNDS. R. Research, Univ. 234, 2169-2175

OCCURRENCE OF COENZXME q AND RELATED L. L e s t e r a n d F. L. Crane ( I n s t . f o r E n z y m e of Wisconsin, Madison, W i s . ) . J. Biol. Chem. (1959). M a n y species o f a n i m a l s , p l a n t s , a n d

562

T H E J O U R N A L OF THE A M E R I C A N 0 I L

m i c r o o r g a n i s m s have been e x a m i n e d f o r the presence of coenzyme Q a n d related lipides. I t was f o u n d t h a t coenzyme Q is w i d e s p r e a d in n a t u r e b u t n o t ubiquitous. As a rule, in h i g h l y aerobic tissues, t h e r e occur l a r g e a m o u n t s of coenzyme Q. I t is s u g g e s t e d t h a t in those t i s s u e s which are a p p a r e n t exceptions to this rule, a different electron t r a n s p o r t m e c h a n i s m , possibly utilizing other quinones such as v i t a m i n K , is operative. BILE ACIDS AND STGROIDS. L X X X I I I . ON THE INTERCONVERSION OF CHOLIC AND DEOXYCHOLIC ACID IN THE RAT. S. L i n d s t e d t a n d B. S a m u e l s s o n . (Dept. of Physiological Chem., Univ. of L u n d , Lurid, S w e d e n ) . J. Biol. Chem. 234, 2026-30 (1959). T h e t r i t i u m label in cholic acid 7fl-Ha,24-C ~ w a s a l m o s t completely r e t a i n e d in the molecule d u r i n g the conversion to deoxycholic acid b y t h e m i c r o o r g a n i s m s in the l a r g e intestine. The t r i t i u m label in t h e isolated deoxycholic acid was lost in t h e 7a-hydroxylation to cholic acid in the liver; this s u g g e s t s a s h i f t of the H~-label f r o m t h e 7fl- to the 7a-position. ALTEKATION OI~ CHOLESTEROL METABOLISI~,I IN TI-IE RAT WITYs LINOLEIO ACID, J. M. Merrill ( V e t e r a n s A d m i n i s t r a t i o n Hospital, Nashville, T e n n . ) . Circulation Res. 7, 709-11 (1959). W h e n linoleic acid is a d d e d to t h e diet of the rat, t h e r e is a n a v e r a g e increase in i n c o r p o r a t i o n of r a d i o c a r b o n into liver cholesterol of 259 per cent. B y c o n t r a s t , t h e a d d i t i o n of cocon u t oil to t h e diet does n o t increase t h e i n c o r p o r a t i o n of radioc a r b o n into liver cholesterol. T h e a d d i t i o n of linoleic acid to a stock diet is associated with a n increased fecal excretion of L i b e r m a n - B u r e h a r d chromogens, 3-fl-hydroxy sterols a n d bile acids. STUDIES ON THE BIOSYNTHESIS OF GLYCOLIPIDES AND OTHER LIPIDES OF THE BRAIN. ~I. W. Moser a n d M. L. K a r n o v s k y (Dept. of Biological Chem. a n d the B i o p h y s i c a l Lab., H a r v a r d Medical School, Boston, M a s s . ) . J. Biol. Chem., 234, 1990-7 (1959). C~'-labeled glucose or g a l a c t o s e was a d m i n i s t e r e d intraperitoneally to Swiss Albino mice r a n g i n g in a g e f r o m 3 d a y s to 6 m o n t h s . A f t e r I hour the a n i m a l s were killed by decapit a t i o n a n d the b r a i n lipides isolated. The activity p r e s e n t in eerebroside galactose e x h i b i t e d the g r e a t e s t v a r i a t i o n s w i t h age. M a x i m a l s y n t h e s i s of this c o m p o n e n t occurred in a n i m a l s 22 days old. W h e n the a d m i n i s t e r e d glucose was labeled in carbon-6, a h n o s t all of the activity of the cerebroside w a s f o u n d in t h a t carbon. GROWTH O1~ CEI~TAIN LIPOLYTIC MICROOt~GANISMS AT 4 ~ AND THEII~ INFLUENCE ON FREE FAT ACIDITY AND FLAVO~ O1~ PASTEURIZED MILK. W . W. Overcast a n d J. D. S k e a n (Dept. of D a i r y i n g , Tenn. A g r . E x p e r i m e n t Station, K n o x v i l l e ) . J. D a i r y Sci. 42, 1479-85 (1959). Twenty-five p u r e cultures of lipolytic m i e r o h r g a n i s m s s o m e t i m e s f o u n d in m a r k e t - m i l k were i n o c u l a t e d into s a m p l e s of h l g h - q u a l i t y p a s t e u r i z e d whole milk s u b s e q u e n t l y held at 4 ~ + 1 ~ for a period of 12 days. A t f o u r - d a y i n t e r v a l s d u r i n g t h e h o l d i n g period t h e s a m p l e s were e x a m i n e d f o r microbial content, free f a t acidity, a n d developed flavors. E i g h t e e n cultures grew r e a s o n a b l y well a n d b r o u g h t a b o u t i n c r e a s e s in free f a t acidity. S e v e n t e e n of these produced a r a n c i d flavor s o m e t i m e s a c c o m p a n i e d a n d / o r followed b y b i t t e r n e s s , w h e r e a s one caused the milk to be criticized as sour a n d unclean. SYNTHETIC STUDIES ON SPHINGOLIPIDS. IV. THE SYNTHESIS OF SPHINGO~IYELIN. D. Shapiro, H. M. Flowers, a n d S. SpectorS h e f e r ( D a n i e l Sieff R e s e a r c h I n s t i t u t e , W e i z m a n n I n s t i t u t e of Science, Rehovoth, I s r a e l ) . Jour. A m . Chem. Soc. 81, 4360-4 (1959). T h e s y n t h e s i s of palmitoyl-, stearoyl-, a n d lignoceroyls p h i n g o m y e l i n is described, cis-2-Phenyl-4-hydroxymethyl-5-(lp e n t a d e c e n y l ) - 2 - o x a z o l i n e is p h o s p h o r y l a t e d w i t h fl-chloroethylp h o s p h o r y l dichloride. H y d r o l y s i s , followed b y a c y l a t i o n of the a m i n o ester, leads to t h e amide. Q u a t e r n i z a t i o n of the l a t t e r with t r i m e t h y l a m i n e followed by t r e a t m e n t with alkali a f f o r d s the sphingomyelins. ANALYSIS O1~ MILK PHOSPHOLIPIDS BY CHI~O]k[AVOGEAFHY AND INFRARED SPECTROPHOTOIMETI~Y. a . M. S m i t h a n d N. K . Freem a n (Dept. of D a i r y I n d u s t r y , Univ. of Calif., D a v i s ) . J. Dairy Sc/. 42, 1450-62 (1959). Milk phospholipids were f r a e t i o n a t e d into t h e n m j o r phospholipid classes b y successive elution f r o m a silicic acid column w i t h chloroform, acetone, m e t h a n o l ( 2 0 % a n d 4 0 % ) in chloroform, a n d m e t h a n o l . E a c h f r a c t i o n was a n a l y z e d by i n f r a r e d s p e c t r o p h o t o m e t r y as well as b y chemical methods. P o t a s s i u m b r o m i d e disk s p e c t r a of milk cerebrosides, cephalins, lecitbins, a n d s p h i n g o m y e l i n s are p r e s e n t e d a n d comp a r e d with p u r e r e f e r e n c e compounds. C o n c e n t r a t i o n s of each class were calculated f r o m specific b a n d m e a s u r e d either in c h l o r o f o r m or in c a r b o n disulfide solutions. Respective w e i g h t p e r c e n t a g e s of eerebrosides, cephalins, lecithins, a n d sphingom y e ] i n s were: 6, 35, 32, a n d 24. E v i d e n c e is g i v e n f o r t h e

CHEMISTS'

SOCIETY

VOL. 36

presence of m i n o r a m o u n t s of o t h e r c o n s t i t u e n t s , i n c l u d i n g c a r b o h y d r a t e - c o n t a i n i n g phospholipids, lysolecithins, a n d unidentified lipids. A d v a n t a g e s a n d l i m i t a t i o n s of t h e m e t h o d at its p r e s e n t s t a t e of development are discussed. FAT IN TItlE DIETS OF OLDER-WOI~IEN--BODY WEIGHT AND BLOOD PRESSURE LEVELS. L i d a M. Burrill, Cecilia Schuck, a n d Alice B i e s t e r (S. D a k o t a A g r . E x p t . Station, B r o o k i n g s a n d Minn. Agr. E x p t . Station, St. P a u l ) . J. A m . Dietet. Assoc. 35, 935-7 (1959). F o r t h i s g r o u p of women, a g e d 30~97 yr., f a t calories r e p r e s e n t e d 35 to 4 1 % of t o t a l calories a n d were supplied chiefly by b u t t e r , d a i r y p r o d u c t s , m e a t s , a n d gravies. T h e r e was no a p p a r e n t r e l a t i o n s h i p b e t w e e n diastolic blood p r e s s u r e s a n d f a t c o n t e n t s of the diets. D a t a are r e p o r t e d on blood p r e s s u r e s a n d b o d y weights. REGULATION OP CHOLE,STEROL OXIDATION BY LIVE]~ Ilq VITRO. M. W. W h i t e h o u s e a n d E. Staple (School of Medicine, U n i v . P e n n a . , P h i l a d e l p h i a ) . Proc. Soc. E x p t t . Biol. Med.. 101, 4 3 9 41 (1959). B y in vitro studies with liver tissue, cholic acid c o n j u g a t e s were f o u n d to depress oxidation of cholesterol b u t n o t of s o d i u m p y r u v a t e or 3a, 7a, 1 2 a - t r i h y d r o c o p r o s t a n e . P r e p a r a t i o n s of liver m i t o c h o n d r i a f r o m livers of r a t s which h a d been deprived of bile salts by i n t e r r u p t i o n of e n t e r o h e p a t i c circulation oxidized cholesterol to a g r e a t e r e x t e n t t h a n controls. The m e c h a n i s m is discussed briefly. LIPEMIA-INDUCED ACCF~LERATION OF INTRAVASCULAt~ (,*LOTTING. It. C. Roth, W. Rosenthal, a n d E. E. M a n d e l (Chicago Medical School a n d Mt. Sinai H o s p i t a l of Chicago). Proc. Soc. E x p t l . Biol. Med. 101, 516-19 (1959). I n t r a v e n o u s a d m i n i s t r a t i o n of a cottonseed oil emulsion h a s been f o u n d to accelerate t h e f o r m a t i o n of a fibrin clot in isolated venous s e g m e n t s of a n e s t h e t i z e d dogs. LABELING OF INTESTINAL AND LYMFH CHOLE,STEI~OL AFTER AD~I INISTI~ATION OF TI~A~F~ DOSES OF ~I:s 4 L. Swell, E. C. T r o u t , Jr., H. Field, Jr., a n d C. R. T r e a d w e l l (Vet. A d m i n . Center, M a r t i n s b u r g , W. Va., a n d Geo. W a s h i n g t o n Univ., W a s h i n g t o n , D. C.). Proc. Soc. E x p t l . Biol. Med. 101, 519-21 (1959). I n studies with l y m p h fistula rats, small doses of f e d cholesteroI-4-C ~ led to l a b e l i n g of cholesterol f r a c t i o n s of m u c o s a a n d l y m p h w i t h o u t increase in level or t u r n o v e r rate of the free cholesterol pool of t h e m u c o s a or in t h e a m o u n t of cholesterol in l y m p h . S i m u l t a n e o u s f e e d i n g of s o d i u m t a u r o c h o l a t e a n d oleie acid i n c r e a s e d t h e a m o u n t of both labeled a n d u n l a b e l e d cholesterol in l y m p h . UPTAKE OF RADIOSULPHATE BY MUCOPOLYSACCHAR~DESO,F AORTA IN CHOLESTEIZOL FED C0'CKERELS. K . K o w a l e w s k i (Univ. Alberta, E d m o n t o n , A l b e r t a ) . Proc. Soe. E x p t l . Biol. Med. 101, 536-7 (1959). D u r i n g a n 8-wk. period, cockerels were f e d diets enriched with cholesterol ( 2 % ) a n d cottonseed oil ( 5 % ) . Parallel to i n c r e a s e d levels of s e r u m a n d liver lipides a n d in c h o l e s t e r o l / p h o s p h o l i p i d ratios, t h e r e was a significant increase in the S ~5 u p t a k e by s u l p h a t e d m u c o p o l y s a c c h a r i d e s in a o r t a b u t not in bones. ~O~PARATIVE EF]~ECTS O]~ BILE ACIDS ON INTESTINAL ABSORPTION OF 0HOLESTE~0L. O. V. V a h o u n y , It. M. Gregorian, a n d C. R. Treadwell (Geo. W a s h i n g t o n Univ. School of Medicine, W a s h i n g t o n , D. C.). Proc. Soc. E x p t l . Biol. Med. 101, 538-40 (1959). I n l y m p h fistula rats, cholic acid w i t h 3 free h y d r o x y l g r o u p s a n d a n u n c o n j u g a t e d carboxyi radical w a s the m o s t effective bile acid in p r o m o t i n g cholesterol a b s o r p t i o n f r o m the intestine. C o n j u g a t e d bile salts, glycoeholate, a n d tauroeholate were less effective. Cholanic, lithocholic a n d deoxycholic acids, with 0, 1, or 2 h y d r o x y l radicals, respectively, produced no increase in l y m p h cholesterol over t h e control group. TH~ RELATION BETWEEN TI~l~ ACTIVITY OF A LECITHINASE AND THE ELECTKOPHORETIC CHARGI~ OF THE SUBSTRATE. A. D. B a n g h a m a n d R. M. C. D a w s o n ( A g r . R e s e a r c h Council I n s t . of Aninlal P h y s i o l o g y , B a b r a h a m , C a m b r i d g e ) . Biochem. J. 72, 486-92 (1959). E l e c t r o p h o r e t i e m e a s u r e m e n t s of aqueous emulsions of v a r i o u s lecithin p r e p a r a t i o n s i n d i c a t e d t h a t p u r e lecithin particles have a n e t positive c h a r g e at the o p t i m u m p H for lecithinase action. A c t i v a t i n g lipids (monophosphoinositide, cardiolipin) a n d a n i o n i c a m p h i p a t h i c molecules which a c t i v a t e the e n z y m e s y s t e m s were f o u n d to confer a n e t n e g a t i v e s u r f a c e to t h e enzyme. Cationic m a t e r i a l s c a u s e d complete 'inhibition of the enzyme w h e n t h e i r c o n c e n t r a t i o n w a s sufficient to reduce t h e m o b i l i t y of the emulsion p a r t i c l e s below t h e critical a c t i v a t i o n value. Electrophoresis of Penicillium n o t a t u m phospholipase B i n d i c a t e d t h a t lysolecithinase a n d lecithinase a c t i v i t y resided in the s a m e p r o t e i n b a n d a n d t h a t t h e s e enz y m e s are identical.

NOVEMBER, 1 9 5 9

ABSTRACTS: BIOLOGY AND N U T R I T I O N

THE ACTIVATION OF SUI~FACE FILMS OF LECITHIN BY AMPKIPATttIC MOLECULES. ~:~. M. C. D a w s o n a n d A. D. B a n g h a m ( A g r . R e s e a r c h Council I n s t . of A n i m a l P h y s i o l o g y , B a b r a h a m , C a m b r i d g e ) . Biochem. J. 72, 493-6 (1959). P a t L e c i t h i n of h i g h specific a c t i v i t y was p r e p a r e d b i o s y n t h e t i c a l l y with bake r ' s yeast. Activities of Penicillium notatum p h o s p h o l i p a s e were e s t i m a t e d f r o m the rate of t r a n s f e r of counts f r o m a s u r f a c e fihn of this lecithin to a s u p p o r t i n g a q u e o u s phase. T h e enzyme h a d no effect on a film of t h e p u r e lecithin b u t did h y d r o l y z e films c o n t a i n i n g dicetylphosphoric acid. I t is concluded t h a t a n e t s u r p l u s of n e g a t i v e g r o u p s on a lecithin s u r f a c e is prerequisite f o r lecithinase attack. STUDIES ON PHOSPtt0,LIPIDS. 6. A COMPLEX PHOSPHOLIPID I~I~0!M SHEEP BRAIN. P. D. Collins ( A u s t r a l i a n N a t i o n a l Univ., Canberra, A u s t r a l i a ) . Biochem. J. 72, 532-7 (1959). Sheep b r a i n lipids were t r e a t e d with 1-fluoro-2,4-dinitrobenzene a n d t h e n with d i a z o m e t h a n e . P r o d u c t s were f r a c t i o n a t e d by counterc u r r e n t d i s t r i b u t i o n between a q u e o u s ethanol a n d p e t r o l e u m ether. A derivative of a complex p h o s p h o l i p i d was o b t a i n e d in a yield of 28% of the t o t a l phospholipids. I t h a d a molecular weight o f 2030 a n d c o n t a i n e d 2 n m l e s of glycerol 1-phosphate, 1 mole each of di~fitrophenylethano]amine, choline, a sugar, a f a t t y alcohol, 2 moles of f a t t y acids a n d two unidentified n i t r o g e n - c o n t a i n i n g m a t e r i a l s . ~OMPOSITI0JNS CONTAINING STABILIZED VITAMIN A MATERIALS. R. W. L e h m a n ( E a s t m a n K o d a k Co.). U. S. 2,895,878. A v i t a m i n A c o m p o s i t i o n is stabilized by the a d d i t i o n of toeopherol a n d 2,6-di-tert.-butyl-4-methylphenol. STABLE VITAMIN A COMPOSI~ONS. J. E. A l l e g r e t t i (Merck & Co., I n c . ) . U. S. 2,897,118. A n ester of v i t a m i n A a n d antio x i d a n t s a r c u n i f o r m l y d~spersed in t h e reaction p r o d u c t of one p a r t of f o r m a l d e h y d e with 10 to 100 p a r t s of p a r t i a l l y h y d r o l y z e d casein. STABLE POWDERED OIL SO,LUBLE VITAMIN. H. J. D u n n ( V a n C a m p Sea F o o d Co., I n c . ) . U. S. 2,897,119. T h e desired vitam i n oil c o n c e n t r a t e is h o m o g e n i z e d in a n a q u e o u s solution of lactose a n d g u m arabic or gun] g h a t t i . The m i x t u r e is s p r a y dried so as to f o r m m i e r o b e a d s in which t h e vitaufin p a r t i c l e s are e n c a p s u l a t e d in g u m a n d lactose. DRY STABLE :FEED SUPPLEMENT. A. L. W i l s o n (Corn P r o d u c t s Co.). U. S. 2,899,307. A d r y f e e d s u p p l e m e n t h a v i n g a h i g h level of f a t which is stable a g a i n s t oxidative d e t e r i o r a t i o n is p r e p a r e d b y m i x i n g 10 to 3 5 % alkaline soapstoek, 10 to 3 0 % acidic f e r m e n t a t i o n liquor, a n d a fibrous carrier. P o u L ~ Y FEED. C. M. EIy a n d J. R. F o y (Nopco Chemical Co.). U. S. 2,899,308. R a t e of g r o w t h a n d f e e d efficiency of p o u l t r y is i m p r o v e d b y t h e a d d i t i o n of 0.5 to 2.0% b y wt. of s o d i u m a n d p o t a s s i u m s o a p s of C~2 to C2~ f a t t y acids to t h e feed: METHOD O~ I:~RESERVING THE RED COLOR OF RE]) MEAT. J. E. S n y d e r a n d G. W. F e r n e r ( T h e Goodyear Tire & R u b b e r Co.). U. S. 2,900,260. The color of red m e a t is p r e s e r v e d b y packa g i n g t h e m e a t in a r u b b e r hydrochtoride film plasticized w i t h b u t o x y e t h y l laurate, b u t o x y e t h y l e p o x y s t e a r a t e or b u t o x y e t h o x y e t h y l p e l a r g o n a t e . U. S. 2,900,261. The plasticizer is a liquid dialkyl adipate.

9 P a i n t s and D r y i n g

Oils

EXAMINATION OF SA]~FL0~ER OIL FR0~M INDIGENOUS SOUI~CES ~ArITH RI~FERENCE TO ITS USE IN T~IE MANUFACTURE 01o PAINTS AND VARNISHES. M o h a m m a d A s l a m ( P a k i s t a n Council Sci. a n d Ind. Research, K a r a c h i ) . Pald~'tan J. Sol. Ind. Research 1, 312 15 (1958). Oils o b t a i n e d f r o m f o u r varieties of seeds were i n v e s t i g a t e d f o r film d r y i n g properties. Only the two oils of h i g h iodine n u m b e r (140 a n d 142) g a v e s a t i s f a c t o r y tack-free films with 0.5% lead a n d 0.1% cobalt. Oleoresinous v a r n i s h e s of 15, 25, a n d 35 gallons oil l e n g t h s were c o m p a r e d to c o r r e s p o n d i n g linseed oil varnishes. I n w a t e r resistance a n d s c r a t c h resistance t e s t s a]l t h e safflower oil v a r n i s h e s app e a r e d to be slightly superior. (C. A. 53, 15593) PREPARATION OF DRYING OILS FROM SEMIBRYING OILS BY ISOMERIZATION. G. L. Y u k h n o v s k H a n d R. R. P o p e n k e r . Trndy Khar'kov. Politekh. Inst. 4, 159-68 ( 1 9 5 4 ) ; Referat. Zhur., Khim. 1956, A b s t r . No. 52651. The effect of v a r i o u s c a t a l y s t s ( P b O , nickel on a c t i v a t e d carbon, a n t h r a q u i n o n e , iodine, bentonite, clay) on isomerization of sunflower oil was studied. A n t h r a q u i n o n e a n d iodine were the best c a t a l y s t s . (C. A. 53, 15593)

563

FATTY ACID ESTERS ~r BY ETHYLENICALLY UNSATURATED SILANE COJI~[P(~UNDS. M. M. OIson a n d R. M. C h r i s t e n s o n ( P i t t s b u r g h P l a t e Glass Co.). U. S. 2,894,922. A c o a t i n g m a t e r i m is p r e p a r e d b y h e a t i n g at 150 ~ to 350 ~ in t h e absence of o x y g e n a m i x t u r e of a n aliphatic ester of a d r y i n g oil acid a n d a h y d r o l y z a b l e c o m p o u n d such as vinyl t r i h a l o s i l a n e or vinyl t r i a l k o x y silane. The p r o d u c t is a p o l y m e r soluble in xylene a n d toluene a n d can be cured to a h a r d durable film. POLYMERIZABLE EPOXIDE GROuF-CONTAINING MODIFII~D ALKYD RESINS. M. Y u s e m ( B r a d l e y & V r o o m a n Co.). U. S. 2,895,929. A composition which c a n be cured in the presence of a n epoxy c a t a l y s t is p r e p a r e d f r o m a polymerizable polyether polyepoxide oil modified a l k y d resin a n d a m o n o m e r i c c o m p o u n d c o n t a i n i n g at l e a s t one CH2 = C--- g r o u p i n g b u t no c o n j u g a t e d double bonds. WATER EMULSION OF POLYMERIZABLE EPOXIDE GRO~UP CONTAINING OIL M(~DIFIED, ALKYD AND FORMALDEHYDE CONDENSATION RBSINS. M. Y u s e m ( B r a d l e y & V r o o m a n Co.). U. S. 2,895,930. A n a q u e o u s emulsion c o a t i n g composition is prep a r e d f r o m compositions of the t y p e described in U. S. 2,895,929 a n d a n etherified m e l a m ' n e - or u r e a - f o r m a l d e h y d e resin. ~ERTAIN ~SOFHTHALIC AND CRTHOPHTI-IALIC ACID ALKYD RESINS. IV[. J . S c h l a t t e r a n d F. G. Lure (Californi:~ R e s e a r c h Corp.). U. S. 2,895,932. Oil modified a l k y d r e s i n s are prep a r e d f r o m a f a t t y acid p a r t i a l ester of a polyhydric alcohol a n d 5-tort-butyl i s o p h t h a l i e acid or 4-tert-butyl o r t h o p h t h a l i c acid.

RUBBER-REAC'TIVE PIGMENT AND DRYING OIL PROTECTIVE CO~A.TINO COMPOSITIONS. W. E. LOX ( F o r m a n , F o r d & Co.). U . S . 2,901,447. N a t u r a l or b u t a d i e n e - s t y r e n e or butadiene-acrylonitrile r u b b e r is m i x e d with a d r y i n g oil a n d a reactive pigm e n t . The m i x t u r e is milled a n d cut back with m i n e r a l s p i r i t s a n d xylene. FILM-FoRMING AND DRYING COMFOSITIONS. H. H. B e a c h a m ( N a t i o n a l L e a d Co.). U. S. 2,901,450. A p a i n t is f o r m u l a t e d f r o m a c o n j u g a t e d d r y i n g oil, a t i t a n i u m ester (a lower alkyl t i t a n a t e or a l k o x y t i t a n i u m a l k a n o a t e ) a n d a n oil soluble resin ( p h e n o l - f o r m a l d e h y d e resin or d e h y d r a t e d castor oil modified alkyd resin). COATING CO'MPOSITI0.IqS. J. C. Cowan a n d H. M. Teeter (Secy. Agr., U . S . A . ) . U. S. 2,901,r T h e film f o r m i n g i n g r e d i e n t s in a protective c o a t i n g composition are h o m o p o l y m e r s of the vinyl ethers of linolenyl alcohol, linoleyl alcohol, or t h e m i x e d p o l y u n s a t u r a t e d f a t t y alcohols o b t a i n e d by t h e r e d u c t i o n of d r y i n g a n d s e m i d r y i n g v e g e t a b l e oils. MANUFACTURING PROCESS to0R SYNTHETIC DRYING 0ILS. C. Z. Marsel a n d J. t t a p p e l . U. S. 2,902,457. A d r y i n g oil composition of i m p r o v e d i m p a c t r e s i s t a n c e is p r e p a r e d b y h e a t i n g a t 50 ~ to 200 ~ a m i x t u r e of a polymerizable acetylenic m o n o m e r ( s u c h as m e t h y l diviny] acetylene or 2-methyl-5-hexene-3-yne2-ol) with at least one n a t u r a l l y occurring d r y i n g oil o r uns a t u r a t e d f a t t y acids f r o m such a n oil.

9 Detergents WHAT DETERGENT MARKETERS SHOULD I4~NOW AB(~T T ~ N D S IN HOUSEHOLD LAUNDI~RING. J. A l a b a c k (Whirlpool Corp., St. J o s e p h , Mich.). Soap, Chem. Spevialties 3 5 ( 7 ) , 54-5, 170-1 (1959). T h e need f o r d e t e r g e n t m a n u f a c t u r e r s to keep up to date on t r e n d s in a p p l i a n c e m a n u f a c t u r e s u c h as t u m b l e - t y p e w a s h e r - d r y e r combinations, a u t o m a t i c d i s p e n s i n g of w a s h i n g additives, dishwashers, etc., is p o i n t e d out so t h e y can p l a n p r o d u c t s in line with these developments. ELECTRICAL CONDUCTIVITY OF THE SYSTEM SoAP-WATEI~-ELECTROLYTE IN THE TRANSITION AREA FRO'M S0'L TO GEL, AND IN THE R.EVERSE Pi~0CESS. I. SODIUM STEARATE-WATEt~-SODIUM CI-ILORIDE. E. A n g e l e s c u a n d M. R a d u . Acad. rep. populare Romine, Studii ccrctari chim. 6, 403-15 (1958). T h e micellar s t r u c t u r e of N a s t e a r a t e in t h e presence of electrolyte a n d w a t e r was studied. The t r a n s i t i o n f r o m sol to gel is characterized b y a h y s t e r e s i s of the electrical conductivity, as well as by the deviation f r o m additive conductivity. L a r g e n e g a t i v e values o f t h e d e v i a t i o n were observed in t h e t e m p e r a t u r e r a n g e s corresponding, respectively, to gel a n d to sol f o r m a t i o n . The h y s t e r e s i s values a n d the deviations f r o m additive c o n d u c t i v i t y lead to t h e conclusion t h a t t h e p r i m a r y effect of t h e NaC1 is to reduce the degree of dJspersion of the s y s t e m s b y a diminution of the specific c h a r g e of t h e micelles. The effect of t h e electrolyte is m i n o r a t h i g h t e m p e r a t u r e s b u t it is very pron o u n c e d in the sol-gel t r a n s i t i o n area. A t low t e m p e r a t u r e s ,

564

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JOURNAL

OF

THE

AMERICAN

when the s t e a r a t e solution c o n t a i n i n g NaCI becomes a gel, the c o n t r i b u t i o n of t h e soap to t h e electrical c o n d u c t i v i t y of t h e s y s t e m a p p r o a c h e s zero with i n c r e a s i n g electrolyte concentration. Five tables, 16 references. (C. A. 53, 13733) BEHAVIOtr OF ]~ACTERIAL CELLS IN THE PRESENCE OF DETERGENTS, PARTICULARLY SODIUM DODECYL SULFATE. A. Bolle a n d

E. K e l l e n b e r g e r (Univ. Geneva, Switz.). Pharm. Acta Holy. 33, 379-90 (1958). A review of the action of d e t e r g e n t s on bacterial cells is offered. The s t u d y i n d i c a t e s t h a t granl-positive a n d g r a m - n e g a t i v e cells are killed by s o d i u m dodecyl s u l f a t e only in t h e presence of r e s p i r a t o r y poison, i.e., 0.01 M K C N in the case of Bacillus subtilis, Staphylococcus aurevs, E. coli, and B. megaterium. The dodecyl s u l f a t e solution ext r a c t s t h e lipoproteins f r o m the cell walls of E. coli, w h e r e a s the mucocomplexes of granl-positive a n d g r a n l - n e g a t i v e organi s m s r e m a i n u n a f f e c t e d ; cell walls of B. megaterium are completely lysed while those of B. s~r r e m a i n intact. 40 references. (C. A. 53, 12392) SYNTHETIC DETERGENTS AND ECZEI~IATOUS HAND ERUPTIONS.

E. It. F e r g u s o n a n d S. R o t h n l a n (Univ. of Chicago). A.M.A. Arch. Dermatol. 80, 300-10 (1959). A n increase in eczematous dernlatitis of t h e h ~ n d s in f e m a l e s h a s been noted. A t the p r e s e n t time, as a result of clinical studies, it is impossible to s a y w h e t h e r t h e every d a y use of the new s y n t h e t i c w a s h - d a y p r o d u c t s is h a r m f u l to t h e h a n d s or w h e t h e r or n o t the new p r o d u c t s are a n y worse or as b a d as the old s t r o n g soaps. The s y n t h e t i c d e t e r g e n t p r e p a r a t i o n s as well as soap a n d w a t e r a p p e a r clinically to a g g r a v a t e h a n d eczema, b u t so do m a n y other f a c t o r s . ]~.ELATION OF WETTABILITY BY AQUEOUS SOLUTIONS TO THE SURFACE CONSTITUTION" 0P L0w-ENERGY SOLIDS. ~ . g . G e r n e t t

a n d W. A. Z i s m a u (U. S. N a v a l Research L a b o r a t o r y , W a s h i n g t o n , D. C.). J. Phys. Chem. 63, 1241-6 (1959). C o n t a c t a n g l e s of a v a r i e t y of p u r e anionic, cationic, a n d nonionlc surface-active a g e n t s in a q u e o u s solutions of v a r i o u s concent r a t i o n s were m e a s u r e d on smooth, clean s u r f a c e s of two lowe n e r g y solids, polyethylene a n d Teflon. W e t t a b i l i t y curves were o b t a i n e d for each solid s u r f a c e by p l o t t i n g t h e cosine of the contact a n g l e v e r s u s the s u r f a c e t e n s i o n of each solution. The critical s u r f a c e t e n s i o n of each solid t h u s o b t a i n e d a g r e e s well with previous values e s t a b l i s h e d f r o m studies with various p u r e o r g a n i c liquids. A q u e o u s solutions whose s u r f a c e tensions are lower t h a n 30 d y n e s / c m , were f o u n d to s p r e a d on polyethylene, w h e r e a s no solution h a d a s u r f a c e t e n s i o n low e n o u g h to s p r e a d on Teflon. I t is concluded t h a t the m i n i m u m c o n c e n t r a t i o n s of the polar solute required to cause s p r e a d i n g on polyethylene a n d on Teflon are excellent indices of the effectiveness of the solute to f u n c t i o n as a w e t t i n g agent. A r e f e r e n c e s t a n d a r d for r a t i n g w e t t i n g effectiveness, which is less d e m a n d i n g t h a n polyethylene, would be p o l y s t y r e n e or polyvinyl chloride. SULPONATION WITH SULFUR TRIOXIDE: DERIVATIVES 01~ ACETALDEHYDE DISULFONATE. E. E. Gilbert, C a t h e r i n e J. MeGouch,

a n d J. A. Otto (Allied Chem. Corp., Morristown, N. J . ) . Ind. Eng. Chem. 51, 925-8 (1959). A c e t a l d e h y d e disulfonic acid ( A D S ) , m a d e f r o m acetylene a n d s u l f u r trioxide, was converted to new derivatives. V a r i o u s alkylbenzenes reacted at 1 : 2 mole ratio to yield surface-active a g e n t s . P h e n o l s with one reactive position c o n d e n s e d at 1 : 2 m o l a r r a t i o ; others r e a c t e d at a lower m a x i m u m ratio f o r m i n g polyulers. A l k y l a t e d phenols g a v e s u r f a c e - a c t i v e c o m p o u n d s a n d c h l o r i n a t e d phenols f o r m e d m a t e r i a l s with mothproofing a n d f u n g i c i d a l activity. E t h a n o l d i s u l f o n a t e resulted f r o m t r e a t m e n t with f o r m a l d e h y d e in a crossed Canizzaro reaction. COLORII~IETI~IC DETEI~MINATION 01~ S0'DIU~I LAURYL SULFATE~

H. D. G r a h a m a n d R. McL. W h i t n e y (Univ. of Ill., U r b a n a , Ill.). Anal. Chem. 31, 1673-6 (1959). A q u a n t i t a t i v e m e t h o d f o r the d e t e r m i n a t i o n of s o d i u m l a u r y l s u l f a t e , capable of d e t e c t i n g as little as 4 p.p.m., involves t h e development of a color produced by the action of s o d i u m l a u r y l s u l f a t e u p o n the h a l o q u i n o n e of o-tolidine in a buffered s y s t e m . The f a c t o r s a f f e c t i n g the test, influence of the available chlorine level, c o n c e n t r a t i o n of o-tolidine, n o r m a l i t y of t h e p h o s p h a t e buffer, s t a b i l i t y of t h e color developed, a n d time i n t e r v a l s b e t w e e n a d d i t i o n s of i n g r e d i e n t s have been t h o r o u g h l y i n v e s t i g a t e d . A g e n e r a l process f o r recovery of sodium l a u r y l s u l f a t e f r o m coniplexing s y s t e m s h a s been s u g g e s t e d . SOLUBILIZATIOlq. 1~. R u y s s e n ( S t a t e Univ., Ghent, B e l g . ) . Chem. Weekblad 54, 681:6 (1958). A review with 26 references. (C. A. 53, 10902)

OIL

CHEMISTS'

SOCIETY

VOL.

36

EhECTaON MIC~O~SCaPY OF SoDIU~ LAVaATE. T. H. Shuttleworth and M. Camp. Nature. 183, 535-6 (1959). The fine structure of Na laurate was investigate(] by high-resolution electron microscopy and electron diffraction. The structure of soap fibers seems to be different frmn that of soap crystals and agrees generally with that proposed by Bondi. (C. A. 53, 16561) THE COOLING OF HOUSF~HOLD SOAPS. E. T. W e b b . Soap, Perfumery, Cosmetics. 22, 477-81, 611-14, 705 7 (1959). Recently several new household soap cooling p l a n t s have been developed a n d m a r k e t e d . T h e y are capable of c o n v e r t i n g h o t liquid n e a t soap as received f r o m the soap pall into h a r d soap in the space of 30 m i n u t e s or so. These processes a r e t h e Lever P l o d d e d B a r Process, the Mazzoni a n d t h e Meccaniche M o d e r n e Processes a n d t h e y are described a n d c o m p a r e d in detail. PROCESS FOR WASHING AND ]~LEACHING COhIPOSITIONS. K. Dith-

m a r a~ld U. H o f f m a n n ( D e u t s c h e Gold- u n d Silber- Scheideans t a l t vormals R o e s s l e r ) . U. S. 2,898,18i. I t was f o u n d t h a t t h e a d d i t i o n of amides such as acetamide, f o r m a n i i d e or acrylam i d e s to w a s h i n g compositions c o n t a i n i n g o r g a n i c s u r f a c e active c o m p o u n d s a n d p e r b o r a t e b l e a c h i n g a g e n t s i m p r o v e d these compositions so t h a t t h e y have good c l e a n i n g action a n d good b l e a c h i n g a c t i o n at lower t e m p e r a t u r e s t h a n n o r m a l b l e a c h i n g a c t i o n s require. SIJLFONATED PRODUCT. A. I. Rachlin (Allied Chemical Corp.). U. S. 2,898,370. The undesirable free sulfuric acid present in a higher a]kylbenzene sulfonie acid which often causes detergent bars to become ~'frosty ~ or prevents preparation of highly concentrated aqueous solutions due to " s a l t i n g - o u t " effect can be p r e v e n t e d by c o n v e r t i n g this excess to a n o t h e r o r g a n i c sulfonic acid which is c o m p a t i b l e with the h i g h e r alkylbenzene snlfonic acid i n s t e a d of a t t e m p t i n g to renlove as i n o r g a n i c s u l f a t e . SURFACE-ACTIVE

METHOD

OF CAUSTIC

RECOVERY

IN SOAP

MANUFACTURE.

]~. V.

Owen and ]ST. A. Hurt (Lever Brothers Co.). U. S. 2,899,450. A process of neutralizing the free caustic alkali in spent lye from a soapmaking process is described in which a stream of the spent lye is mixed with a stream of fatty oil containing free fatty acid, if any, in an aulount insufficient to neutralize 9all the free caustic alkali in the lye, and the resultant mixture is vigorously agitated, and the agitation is continued until all the free alkali has reacted with the glycerides in the fatty oil. Suitable a m o u n t s of soap nlay be a d d e d to aid t h e saponification b y p r o m o t i n g more i n t i m a t e c o n t a c t b e t w e e n t h e r e a c t a n t s . M. Fowkes, W. M. Sawyer, a n d M. J. Schick (Shell D e v e l o p m e n t Co.). U. S. 2,900,346. T h e f o a m s t a b i l i t y of o r g a n i c s u l f a t e a n d sulf o n a t e d d e t e r g e n t s of all k i n d s is i m p r o v e d by t h e a d d i t i o n of the m o n o e t h e r s of glycerol a n d m o n o h y d r i e a l i p h a t i c satur a t e d alcohols h a v i n g a linear h y d r o c a r b o n c h a i n of e i g h t to sixteen carbon a t o m s such as dodeeyl glycerol m o n o e t h e r s h a v i n g p r i m a r y alkyl or s e c o n d a r y 2-alkyl g r o u p s a t t a c h e d to the ether o x y g e n atom. Iq~OlkMING DETERGE.lqT COMPC,SITIONS. F.

Ih~PEOVEMENTS IN AQUEOUS DETE!~GENT COMPOSITIONS. T. S.

~4assie (Chemical D e v e l o p m e n t s of C a n a d a , L t d . ) . Brit. 808,805. The c o m b i n a t i o n in c e r t a i n p r o p o r t i o n s of s u l f o n a t e d a n d s u l f a t e d d e t e r g e n t s with a c o n d e n s a t i o n p r o d u c t of a h i g h e r f a t t y alcohol with a n alkylene oxide, p r e f e r a b l y ethylene oxide, exhibits e n h a n c e d properties of d e t e r g e n c y a n d f o a m i n g , shows a b e t t e r b a l a n c e of detersive a n d f o a m i n g p r o p e r t i e s t h a n m o s t k n o w n liquid d e t e r g e n t compositions.

Brit. ~?08,9r A laundering agent possessing heavy-duty cleansing power with depressed s u d s i n g aetion consists of anionic s u r f a c e active a g e n t s a n d alkyl m e t a l p o l y p h o s p h a t e , a n d as a suds d e p r e s s a n t , a s y n e r g i s t i c m i x t u r e of f a t t y acids a n d / o r t h e i r alkali m e t a l soaps as " H y f a e 4 3 1 , " a n d a nonionic comp o u n d p r e p a r e d f r o m alkylphenol a n d polypropylene oxide a n d ethylene d i a m i n e such as " P l u r o n i c F 6 8 . " DETERGENT COhIPOSITION. T h o m a s H e d l e y & Co., L t d .

Brit. 809,060. The s u d s i n g c h a r a c t e r i s t i c s of d e t e r g e n t compositions c o n t a i n i n g s u l f a t e d a n d s u l f o n a t e d anionic d e t e r g e n t s w h e n used at w a s h i n g t e m p e r a t u r e s below 100~ m a y be i m p r o v e d b y the a d d i t i o n of v a r i o u s a m i d e s such as N - [ 3 - b i s ( 2 - h y d r o x y ethyl)-aminopropyl] lauramide, N-lauroyl-N-methyl gIucamine or N-keryl-D-gluconamide. DETEI~GENT C0~MP0,SITIONS. T h o m a s H e d l e y & Co., L t d .