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9 Páginas.-- 8 Figuras, Castor beans accumulate large amounts of triacylglycerols (TAGs) in the seed endosperm. This oil contains hydroxylated ricinoleic levels close to 90%, which is unique among oil seeds. The capacity to accumulate such high levels of such an unusual fatty acids is due to its specific accumulation and channeling. Here, the ability of the castor biosynthetic machinery to accumulate unusual fatty acids in the form of TAGs was investigated, focusing on ricinoleic acid and the structurally analogous lesquerolic and coriolic fatty acids. The metabolism of different radioactive precursors in active membrane fractions from castor bean's were studied, and the rates and accumulation of these fatty acids provided evidence of the different mechanisms involved in the accumulation of hydroxylated fatty acids in this species. In particular, these studies highlighted the potential of castor to accumulate unusual fatty acids other than ricinoleic acid, showing that castor endosperm can efficiently accumulate lesquerolic acid., This work was funded by General Secretariat for Universities, Research and Technology of the Andalusian Knowledge System, within the scope of the Andalusian Plan for Research, Development and Innovation (PAIDI, 2020) with the expedient number P20_00072.

Cancer stem cells have certain characteristics, such as self-renewal, differentiation, and drug resistance, which are related to tumor progression, maintenance, recurrence, and metastasis. In our study, we targeted breast cancer stem cells (BCSCs) using a natural compound, coriolic acid, from Salicornia herbacea L. This compound was isolated by mammosphere formation inhibition bioassay-guided fractionation and identified by using NMR spectroscopy and electrospray ionization mass spectrometry. Coriolic acid inhibited the formation of mammospheres and induced BCSC apoptosis. It also decreased the subpopulation of CD44high/CD24low cells, a cancer stem cell (CSC) phenotype, and specific genes related to CSCs, such as Nanog, Oct4, and CD44. Coriolic acid decreased the transcriptional and translational levels of the c-Myc gene, which is a CSC survival factor. These results indicated that coriolic acid could be a novel compound to target BCSCs via regulation of c-Myc.

Hydroxy unsaturated fatty acids (HUFA) can function as antifungal agents. To investigate the antifungal spectrum, that is, the scope of the in vitro fungal-inhibition activities of HUFA and their potential applications, three HUFA were produced by microbial transformation or extracted from plant-seed oils; these compounds included coriolic acid (13-hydroxy-9,11-octadecadienoic acid) from Coriaria seed oil, 10-hydroxy-12-octadecenoic acid from cultures of Lactobacillus hammesii, and 13-hydroxy-9-octadecenoic acid from cultures of Lactobacillus plantarum TMW1.460Δlah. HUFA were purified by high-speed counter-current chromatography (HSCCC), characterized by LC-MS and MS/MS, and their antifungal activities were evaluated with 15 indicator fungal strains. The HUFA had different antifungal spectra when compared with unsaturated fatty acids with comparable structures but without hydroxy groups. The inhibitory effects of HUFA specifically targeted filamentous fungi, including Aspergillus niger and Penicillium roqueforti, whereas yeasts, including Candida spp. and Saccharomyces spp., were resistant to HUFA. The findings here support the development of food applications for antifungal HUFA.

The first synthesis of the fluorinated analogs of the biologically very active fatty acid metabolites (4-hydroxynonenal and coriolic acid) is reported. The key step is the regioselective fluorination of allylic acetal 3. © 1997 Published by Elsevier Science Ltd.

γ-nonanolide in the (R) enantiomeric form is obtained, close to (R) δ-decanolide, as major transformation product of (R) coriolic acid in Pichia stipitis; feeding experiments of the (S) enantiomer lead to δ-decanolide as major metabolite

Stereoselective synthesis of 15,16-didehydro coriolic acid, starting from pent-2-en-4-yn-1-ol is described.

The optimization of 13-S-hydroperoxy-9Z, 11E-octadecadienoic acid synthesis is described using lipoxygenase-1 from soybeans at high substrate concentration. The optimal values of the tested parameters are as follows: oxygen pressure 2.5 bar, temperature 5°C, pH 11, enzyme concentration 4 mg/ml and substrate concentration 0.1 M. All these values were used in a single reaction, allowing chemoenzymatic synthesis of gram amounts of (+)-coriolic acid (99%, e.e. 97%) with a 54% yield starting from linoleic acid.

In growing cultures of Cladosporium suaveolens (R) coriolic acid (3) is converted into 5-decanolide enriched in the (S) enantiomer (2) (ca. 0.4 ee), while recovered coriolic acid shows the same enantiomeric composition of the precursor, as indicated by NMR studies onto a set of (+)-MTPA derivatives.

The optimization of 13-S-hydroperoxy-9Z, 11E-octadecadienoic acid synthesis is described using lipoxygenase-1 from soybeans at high substrate concentration. The optimal values of the tested parameters are as follows: oxygen pressure 2.5 bar, temperature 5°C, pH 11, enzyme concentration 4 mg/ml and substrate concentration 0.1 M. All these values were used in a single reaction, allowing chemoenzymatic synthesis of gram amounts of (+)-coriolic acid (99%, e.e. 97%) with a 54% yield starting from linoleic acid.

An efficient and highly selective total synthesis of 13(S)-hydroxy-9Z,11E octadecadienoic (coriolic) acid is described, starting from an optically active lactol easily available through an enantioselective enzymatic hydrolysis.

The palladium catalyzed coupling of ( S )- E -1-tributylstannyl-1-octen-3-ol ( 3 ) with 2-(6-carbethoxyhexyl)-3-iodo-2-cyclopenten-1-one gave a 70% yield of the ( S )-ethyl ester of PGB 1 . Coriolic acid was synthesized in 75% yield by coupling 3 with Z -10-iododecenoic acid, demonstrating the tolerance of this coupling reaction to the carboxylic acid function.

(S)-(E)-(+)-1-Bromo-1-octene-3-ol was prepared in 85% yield and high optical purity (e.e. 97.4%) via a stereospecific reduction of corresponding bromo vinyl ketone using alcohol dehydrogenase from baker's yeast (EC 1.1.1.1) and NAD(P)H immobilized on Nucleosil 120-5 C 18 , and converted to 13(S)-hydroxy-9Z,11E-octadecadienoic (coriolic) acid.

Described herein is a convenient synthesis of coriolic acid (1) and dimorphecolic acid (2), the two natural ionophores derived respectively from bovine heart mitochondria and also shown to be self defensive substances in rice plant against rice blast disease.

Both enantiomers of coriolic acid and their geometric isomers are synthesized highly selectively. These acids are found to exhibit similar inhibition activity toward spore germination of rice blast fungus.

The total syntheses of 13(S)-hydroxy 9Z, 11E-octadecadienoic (coriolic) acid and its 13(S)-N-tosylamino analogue are reported via a short, efficient, enantiospecific route from D-mannitol.

The palladium catalyzed coupling of ( S )- E -1-tributylstannyl-1-octen-3-ol ( 3 ) with 2-(6-carbethoxyhexyl)-3-iodo-2-cyclopenten-1-one gave a 70% yield of the ( S )-ethyl ester of PGB 1 . Coriolic acid was synthesized in 75% yield by coupling 3 with Z -10-iododecenoic acid, demonstrating the tolerance of this coupling reaction to the carboxylic acid function.

Coriolic [(R)-13-hydroxy-cis-9,trans-11-octadecadienoic] acid (III, R=Z=H) was isolated as the methyl ester from twoCoriaria seed oils in 66 and 68% yields. The double bonds and hydroxyl group were located by periodate-permanganate oxidation before, and chromic acid oxidation after, hydrogenation of the double bonds. Alternatively the positions of the functional groups were indicated by a convenient micro-ozonolysis-gas-liquid chromatographic procedure. Determination of products from partial hydrolysis of theCoriaria oils with pancreatic lipase (EC 3.1.1.3) revealed a preference of the corioloyl group for the 1,3-positions in triglyceride molecules. The possible significance of coriolic acid as an intermediate in the biogenetic conversion of linoleic acid to conjugated trienoic acids is discussed.

The seed oil of Monnina emarginata St. Hill was divided by thin-layer chromatography into fractions of differing polarity. The least polar fraction (63%) contained tri-acid and tetra-acid glycerides in a 1 : 2 mole ratio, as well as the lactone of (S)-13-hydroxy-cis-9, trans-II-octadecadienoic acid [(S)-coriolic acid]. The notable structural feature of the tetra-acid glycerides was a coriolate group with its hydroxyl esteriued by long-chain acids to form estolides † . Two, more polar tetra-acid glycerides and a tri-acid glyceride with a keto acid moiety made up the fraction of intermediate polarity (5% of oil). In these glycerides, the free hydroxyl group of coriolate was esterified by 13-oxo-trans-9-octadecenoic acid or by an additional coriolic acid. The polar tri-acid glycerides contained 13-oxo-trans-9,trans-11-octadecadienoic acid. The most polar glycerides (25%) were tri-acid glycerides with one coriolate group. Pancreatic lipase (EC 3.1.1.3) was used to determine the distribution of acids esterified to the α- and β-glyceride positions. The oxygenated acids were esterified predominantly (>97%) to α-glyceride positions, whereas C18:1 and C18:1 acids accounted for more than 94% of the groups esterified to β-positions.

From the combined fatty acids of the seed oil of Central AsianArtemisia absinthium (family Compositae) we have isolated a mixture of dimorphecolic and the trans isomer of coriolic acid, found for the first time, in a ratio of 2:1.

Synthese de l'acide±hydroxy-13 octadecadiene-9,11oique a partir de l'oxydation du pentyl-2 furanne

The sorbic acid iron carbonyl complex (II) reacts selectively with the racemic alcohol (I) to give the diastereomeric esters (III).

Synthese de l'acide (±) hydroxy-13 octadecadiene-9,11oique, soit a partir de pentene-2yne-4ol-1 soit a partir de dichloro-1,4 butyne-2