K. L. Mikolajczak

Oxygenated fatty acids of oil from sunflower seeds after prolonged storage

AbstractsChemical analysis of a number of sunflower (Helianthus annuus) seed oil samples revealed a low and variable percentage of hydrogen bromide-reactive material. To characterize the compounds responsible for this reactivity, oil was extracted from selected introductions from Uruguay, Turkey, and Yugoslavia that had been subjected to prolonged storage. Two epoxy fatty acids and two conjugated dienolic acids were isolated from the methyl esters derived from these sunflower seed oils by using a combination of column chromatography and countercurrent distribution. The epoxy acids arecis-9,10-epoxystearic acid (0.5%) andcis-9,10-epoxy-cis-12-octadecenoic (coronaric) acid (2.2%). Characterization of the dienols revealed that they are 9-hydroxy-trans-10,cis-12-octadecadienoic acid (1.2%) and 13-hydroxy-cis-9,trans-11-octadecadienoic acid (1.3%). Fresher seed of some of these introductions contained less of the oxygenated components.Oil from recently produced seed of selected high-oil Russian sunflower varieties, including some currently grown in the United States, contained no more than trace amounts of oxygenated acids. Though the relative contributions of genetic and environmental factors toward genesis of oxygenated acids are not established, increase of those acids in some sunflower lines as a result of storage has been demonstrated.

Structure and reactions of a cyanogenetic lipid from Cordia verbenacea DC. seed oil

Abstract Cordia verbenacea DC. (Boraginaceae) seed oil consists of a mixture of cyanogenetic, nonglycerol diesters (35%) and ordinary triglycerides. The nitrogen-containing esters are composed of two ordinary fatty acid moieties (predominantly C 20 ) esterified with a five-carbon dihydroxynitrile containing a terminal methylene grouping. All attempts to isolate this diol in an unesterified form resulted in mixtures of unstable products. The diesters form hydrogen cyanide on treatment with base and also yield formaldehyde upon mild alkaline oxidation. Hydrogen uptake is erratic, and varying degrees of hydrogenolysis with formation of monoesters occur when platinum or palladium is used as catalyst. Hydrolysis of the diesters with barium hydroxide gives a mixture of products which appear to be unsaturated hydroxy lactams. γ-Lactones with one acyl group attached are generated by refluxing the diesters with glacial acetic acid containing sulfuric acid as a catalyst.

Dihydroxy fatty acids inCardamine impatiens seed oil

The oil ofCardamine impatiens L. (Cruciferae) seed includes glycerides of a series of saturated long-chain vicinal dihydroxy fatty acids, which make up 25% by weight of the mixed fatty acids. The mixture of diols, after transesterification of the oil with methanol, can be crystallized from an ether solution of the mixed methyl esters and has the following composition: methyl 13,14-dihydroxydocosanoate, 66%; methyl 15,16-dihy-droxytetracosanoate, 24%; methyl 9,10-dihydroxyoctadecanoate and methyl 11,12-dihydroxyeicosanoate, about 5% each. Chemical proof is presented showing that essentially all the diols have thecrythro configuration.

A cyanogenetic lipid fromCordia verbenacea DC. Seed oil

Cyanogenetic nonglycerol diesters, which are composed of two fatty acid moieties esterified with an unsaturated five-carbon dihydroxynitrile, constitute 35% ofCordia verbenacea DC. (Boraginaceae) seed oil.

Glyceride structure ofCardamine impatiens L. Seed oil

A group of unusual triglycerides, in which one of the acyl groups is a vicinal dihydroxy acid with one of the hydroxyl groups acetylated, has been isolated fromCardamine impatiens L. (Cruciferae) seed oil. Hydrolysis of these triglycerides with castor bean lipase facilitated isolation and identification of a mixture of C18, C20, C22, and C24 hydroxy acetoxy fatty acids. Pancreatic lipase hydrolysis data revealed that these monoacetylated dihydroxy acid residues are esterified exclusively with one of the α-positions of the glycerol moiety. The remaining acyl groups are comprised of ordinary C18 unsaturated acids (which occupy 98% of the β-position), palmitic acid, and C20, C22, and C24 monoenoic fatty acids.

Cyanolipids of kusum (schleichera trijuga) seed oil

A cyanolipid, consisting of two fatty acid moieties esterified with 1-cyano-2-hydroxymethylprop-2-ene-1-ol, constitutes 58% ofSchleichera trijuga (Kusum) seed oil.

Three new oilseeds rich incis-11-eicosenoic acid

Marshallia cacspitosa Nutt. seed oil (family Compositae) contains 44%cis-11-eicosenoic acid, and is the first oil from the Compositae found to contain a high proportion of C20-monoenoic acid. Seed oils ofAlyssum maritimum (L.) Lam. and ofSelenia grandis Martin (family Cruciferae) contain 42 and 58% of the same acid, respectively.The C20 acids from all three oils were obtained in nearly pure form by fractional distillation of the mixed methyl esters by means of a spinning band column. Permanganate-periodate oxidation of the purified methyl esters yielded predominantly nonanoic and undecanedioic acids.

13C Nuclear magnetic resonance spectroscopy of cyanolipids and cyanolipid-containing seed oils

Abstract13C nuclear magnetic resonance (NMR) signals of all carbon atoms of the hydroxynitrile moieties on which cyanolipids are based have been assigned. The four known types of cyanolipids can be conveniently distinguished and identified by13C-NMR whether they are in pure form or in unfractionated seed oils from which they are derived.

Stability of crude sunflower oils to autoxidation and to seed aging

Crude seed oils of Russian sunflower varieties, Armavirec and VNHMK 8931, are somewhat more stable to gross autoxidation than crude oils of two commercial U.S. varieties, Arrowhead and Mingren. Small amounts of oxygenated fatty acids found previously in sunflower seed oils have been shown to be produced during seed storage.

Concerning lipid composition ofSapindus mukorossi seed oil

Sir: A recent paper in this journal (A. Sengupta, S.P. Basu, and S. Saha, Lipids 10:33 [1975]) describes a s tudy of the triglyceride structure of Sapindus mukorossi (family Sapindaceae) seed oil. In their thin layer chromatographic examinat ion of this oil, Sengupta and coworkers observed the presence of a component more polar than ordinary triglycerides, and they speculate that this may be a triglyceride which contains estolide groups. Published work from our laboratory (K.L. Mikolajczak and C.R. Smith, Lipids 5:182 [1970] and earlier papers cited therein) and elsewhere (M.G. Kasbekar, R.R. Talekar, and N.V. Bring, i, Indian J. Chem. 10:244 [1972] ; D. Seigler, Phytochemistry 13:841 [ 1974] ) has established that previously unrecognized cyanolipids occur in considerable amounts in seed oils of many sapindaceous species, including S. mukorossi. Cyanolipids are not glycerides, but instead are derivatives of five-carbon hydroxyni t r i le moieties esterified with long chain fat ty acids. On the basis of previous experimental results, we feel reasonably certain that cyanolipids are responsible for the large spots below the triglycerides in thin layer chromatograms (Figs. 2 and 3) shown by Sengupta, et al., in their paper (cited above).