- Isolation of 9-hydroxy-10E,12Z-octadecadienoic acid, an inhibitor of fat accumulation from Valeriana fauriei
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An EtOH extract of Valeriana fauriei was found to exhibit potent inhibition of fat accumulation against 3T3-L1 murine adipocytes. After performing several chromatographic steps, we successfully isolated the conjugated linoleic acid derivative, 9-hydroxy-10E,12Z-octadecadienoic acid (9-HODE). Synthesized 9-HODE and its analogs showed inhibitory activity against fat accumulation.
- Yuki, Keiji,Ikeda, Mariko,Miyamoto, Kenji,Ohno, Osamu,Yamada, Kaoru,Uemura, Daisuke
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body text
p. 1233 - 1235
(2012/10/07)
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- Unprecedented NES non-antagonistic inhibitor for nuclear export of Rev from Sida cordifolia
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Bioassay-guided separation from the MeOH extract of the South American medicinal plant Sida cordifolia resulted in isolation of (10E,12Z)-9-hydroxyoctadeca-10,12-dienoic acid (1) as an unprecedented NES non-antagonistic inhibitor for nuclear export of Rev. This mechanism of action was established by competitive experiment by the biotinylated probe derived from leptomycin B, the known NES antagonistic inhibitor. Additionally, structure-activity relationship analysis by use of the synthesized analogs clarified cooperation of several functionalities in the Rev-export inhibitory activity of 1.
- Tamura, Satoru,Kaneko, Masafumi,Shiomi, Atsushi,Yang, Guang-Ming,Yamaura, Toshiaki,Murakami, Nobutoshi
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body text
p. 1837 - 1839
(2010/07/02)
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- Synthesis and biological activity of hydroxylated derivatives of linoleic acid and conjugated linoleic acids
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Allylic hydroxylated derivatives of the C18 unsaturated fatty acids were prepared from linoleic acid (LA) and conjugated linoleic acids (CLAs). The reaction of LA methyl ester with selenium dioxide (SeO2) gave mono-hydroxylated derivatives, 13-hydroxy-9Z,11E-octadecadienoic acid, 13-hydroxy-9E,11E-octadecadienoic acid, 9-hydroxy-10E,12Z-octadecadienoic acid and 9-hydroxy-10E,12E-octadecadienoic acid methyl esters. In contrast, the reaction of CLA methyl ester with SeO2 gave di-hydroxylated derivatives as novel products including, erythro-12,13-dihydroxy-10E-octadecenoic acid, erythro-11,12-dihydroxy-9E-octadecenoic acid, erythro-10,11-dihydroxy-12E-octadecenoic acid and erythro-9,10-dihydroxy-11E-octadecenoic acid methyl esters. These products were purified by normal-phase short column vacuum chromatography followed by high-performance liquid chromatography (HPLC). Their chemical structures were characterized by liquid chromatography-mass spectrometry (LC-MS) and nuclear magnetic resonance spectroscopy (NMR). The allylic hydroxylated derivatives of LA and CLA exhibited moderate in vitro cytotoxicity against a panel of human cancer cell lines including chronic myelogenous leukemia K562, myeloma RPMI8226, hepatocellular carcinoma HepG2 and breast adenocarcinoma MCF-7 cells (IC50 10-75 μM). The allylic hydroxylated derivatives of LA and CLA also showed toxicity to brine shrimp with LD50 values in the range of 2.30-13.8 μM. However these compounds showed insignificant toxicity to honeybee at doses up to 100 μg/bee.
- Li, Zhen,Tran, Van H.,Duke, Rujee K.,Ng, Michelle C.H.,Yang, Depo,Duke, Colin C.
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experimental part
p. 39 - 45
(2010/03/31)
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- Characterization and quantification of free and esterified 9- and 13-hydroxyoctadecadienoic acids (HODE) in barley, germinating barley, and finished malt
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The analysis of (R)-9- and (S)-9-hydroxy-10E,12Z-octadecadienoic acid as well as (R)-13- and (S)-13-hydroxy-9Z,11E-octadecadienoic acid (HODE) as free acids, esterified in triacylglycerols (storage lipids), and esterified in polar lipids (phospholipids, glycolipids, etc.) in barley, germinating barley, and finished malt was performed using [13-18O1]-(S)-13-HODE isotope dilution assays with GC-MS and straight- and chiral-phase HPLC. 9- and 13-HODE occur approximately racemically in barley, indicating an autoxidation. The enantiomeric excesses increase to 78% S for free 9-HODE and to 58% S for free 13-HODE in germinating barley as a result of lipoxygenase-2 (LOX-2) catalysis, but free HODEs are at low concentration. More than 90% of HODEs in barley and malt are esterified. In the storage lipids of green malt 53 mg/kg 9-HODE and 147 mg/kg 13-HODE were detected. This ratio of 30:70 reflects the regioselectivity of the LOX-2 enzyme in malt. In the polar lipids 45 mg/kg 9-HODE and 44 mg/kg 13-HODE were characterized. The latter indicate a hitherto unknown 9-lipoxygenase activity with polar lipids as substrates. During kilning the contents of most HODEs decreased significantly due to chemical and enzymatic degradation, whereas polar-esterified (R)-13-HODE increased (43%) in the finished malt.
- Hobke, Holger,Garbe, Leif-Alexander,Tressl, Roland
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p. 1556 - 1562
(2007/10/03)
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- Enantioselective formation of (R)-9-HPODE and (R)-9-HPOTrE in marine green alga Ulva conglobata.
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When linoleic and linolenic acid were incubated with a crude enzyme of marine green alga Ulva conglobata, the corresponding (R)-9-hydroperoxy-(10E, 12Z)-10, 12-octadecadienoic acid [(R)-9-HPODE] and (R)-9-hydroperoxy-(10E, 12Z, 15Z)-10, 12, 15-octadecatrienoic acid [(R)-9-HPOTrE] were formed with a high enantiomeric excess (>99%), respectively.
- Akakabe, Yoshihiko,Matsui, Kenji,Kajiwara, Tadahiko
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p. 3171 - 3173
(2007/10/03)
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- Preparation of the enantiomers of hydroxy-C18 fatty acids and their anti-rice blast fungus activities
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In order to examine the correlation between the anti-rice blast fungus activity and the chirality of allylic alcohols 1-3, which were characterized from the infected rice plants as an enantiomeric mixture with 10% e.e., a procedure for the chemical prepa
- Kato, Tadahiro,Nakai, Toshio,Ishikawa, Rumiko,Karasawa, Aya,Namai, Tsuneo
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p. 2695 - 2701
(2007/10/03)
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- Peroxidations initiated by lignin model compounds: Investigating the role of singlet oxygen in photo-yellowing
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3,5-Di-tert-butyl-ortho-quinone, 6, and 1-(3,4-dimethoxyphenyl-2-(2-methoxyphenoxy)-1-propanone, 7, models for oxidized lignin and for lignin, were used as sensitizers of photo-oxidation. Product studies by HPLC from oxidation of methyl linoleate in solution sensitized by 6 or 7, and in sodium dodecyl sulfate (SDS) sensitized by 6, showed a product distribution of six hydroperoxides, the four conjugated 9- and 13-hydroperoxides of the geometrical isomers: trans-10, cis-12 (2), cis-9, trans-11 (3), trans-10, trans-12 (4), and trans-9, trans-11 (5)-octadecadienoates plus two nonconjugated hydroperoxides. The higher cis/trans to trans/trans (ct/tt) of geometrical isomers (2 + 3//4 + 5) compared to ct/tt from known thermal free-radical peroxidations (Type 1) indicate that singlet oxygen (Type 2) oxidation occurs in reactions sensitized by 6 or 7. Kinetic studies by oxygen uptake are reported on oxidations of hydrocarbons 1-phenyl-2-methylpropene, 8, and trans-stilbene, 9, sensitized by the quinone, 6, or by a dye, Rose Bengal. Quenching studies imply singlet oxygen reactions. Milled wood lignin undergoes self-initiated photo-oxidation in water, and oxygen uptake was quenched by sodium azide. Cellobiose, a cellulose model, undergoes sensitized photooxidation using model quinone, 6, in a mixture of tert-butyl alcohol and water or using the sensitizers benzophenone or the lignin model, 7, delivered on a solid support, silica gel, and these oxidations were quenched with sodium azide. These results implicate singlet oxygen in the photo-yellowing of high lignin content wood pulps.
- Barclay, L. Ross C.,Grandy, Jennifer K.,MacKinnon, Heather D.,Nichol, Heather C.,Vinqvist, Melinda R.
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p. 1805 - 1816
(2007/10/03)
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- Synthesis of keto- and hydroxydienoic compounds from linoleic acid
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A convenient preparative method has been developed for the synthesis of hydroxydienoic (9-HODE and 13-HODE) and ketodienoic compounds (9-KODE and 13-KODE) from natural linoleic acid. Methyl linoleate was treated with 1.25 eq. of m-chloroperbenzoic acid in alcoholic solution, giving a mixture of mono-epoxides (yield 60%), that was treated with a solution of HBr in MeOH to yield a mixture of the bromohydrins (yield 92%). The last was oxidized by Jones reagent to a mixture of bromoketones (yield 64%) and the mixture obtained was dehydrobrominated by DBU to produce a mixture of ketodienoic compounds (yield 94%). Reduction of the ketodienoic compounds by KBH4 in MeOH led to the corresponding hydroxydienoic (9-HODE and 13-HODE) methyl esters (yield 83%). The synthetic approach described is simple and gives reliable results. The keto- and hydroxy fatty acids obtained were characterized thoroughly by TLC, HPLC, UV, FT-IR, 1H-, 1H1H- and 13C-NMR.
- Kuklev, Dmitry V.,Christie, William W.,Durand, Thierry,Rossi, Jean Claude,Vidal, Jean Pierre,Kasyanov, Sergey P.,Akulin, Valery N.,Bezuglov, Vladimir V.
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p. 125 - 134
(2007/10/03)
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- Identification and quantification of the regioisomeric cholesteryl linoleate hydroperoxides in oxidized human low density lipoprotein and high density lipoprotein
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Oxidation of human LDL is implicated as an initiatior of atherosclerosis. Isolated low density lipoprotein (LDL) and high density lipoprotein (HDL2) were exposed to aqueous radicals generated from the thermolabile azo compound 2,2'-azobis(2-amidinopropane) dihydrochloride. The primary nonpolar lipid products formed from the autoxidation of LDL and HDL were the regioisomeric cholesteryl linoleate hydroperoxides. In LDL oxidations, 9- and 13- hydroperoxides with trans,cis conjugated diene were formed as the major oxidation products if endogenous α-tocopherol was present in the LDL. After extended oxidation of LDL, at the time when endogenous α-tocopherol was consumed, the two trans,cis conjugated diene hydroperoxides began to disappear and the 9- and 13-hydroperoxides with trans,trans conjugated diene appeared. At very long oxidation times, none of the primary products, the conjugated diene hydroperoxides, were present. In HDL2, which has only very low levels of antioxidants, both the 9- and 13-hydroperoxides with trans,cis conjugated diene and the 9- and 13-hydroperoxides with trans,trans conjugated diene were formed at early stages of oxidation. The corresponding alcohols were also formed in the HDL2 oxidations. A mechanistic hypothesis consistent with these observations is presented.
- Kenar, James A.,Havrilla, Christine M.,Porter, Ned A.,Guyton, John R.,Brown, Spencer A.,Klemp, Keith F.,Selinger, Elizabeth
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p. 737 - 744
(2007/10/03)
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- High-Performance Liquid Chromatographic Analysis of the Products of Linoleic Acid Oxidation Catalyzed by Pea (Pisum sativum) Seed Lipoxygenases
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An HPLC method is discussed for the analysis of the products formed by the pea (Pisum sativum) lipoxygenase catalyzed oxidation of linoleic acid.The results demonstrate the feasibility of analyzing all of the hydroperoxides, hydroxides, and keto fatty acids in a single chromatographic step and show that it will be possible to analyze the product profile from the lipoxygenase activity contained in a portion of a seed, which will permit the remainder of the seed to be grown on for subsequent generations.The chemical structures of the products have been identified by HPLC analysis and GC-MS. Keywords: Lipoxygenase; hydroperoxides; chromatography
- Wu, Zecai,Robinson, David S.,Domoney, Claire,Casey, Rod
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p. 337 - 342
(2007/10/02)
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- Oxygenated Fatty Acids with Anti-rice Blast Fungus Activity in Rice Plants
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Expecting that the different characteristics of rice plants against rice blast fungus, that is, susceptibility of the weaker cultivar, Sasanishiki and resistance of the stronger cultivars, Fukuyuki and Fukunishiki, may be due to the absence or presence of anti-fungus compounds in the rice plants, the anti-rice blast fungus substances in these three kinds of rice plants were explored.We found five epoxides and five allyl alcohols as anti-rice blast fungus compounds.The epoxides were 12,13-epoxy- and 9,10-epoxylinoleic acids, and 15,16-epoxy-, 12,13-epoxy-, and 9,10-epoxylinolenic acids.The allyl alcohols are 13-hydroxy and 9-hydroxy linoleic acids, and 16-hydroxy, 13-hydroxy, and 9-hydroxy linolenic acids.In inoculated Sasanishiki, the activity is due to the formation of the allyl alcohols.
- Kato, Tadahiro,Yamaguchi, Yoshihiro,Namai, Tsuneo,Hirukawa, Toshifumi
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p. 283 - 287
(2007/10/02)
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- Lipase Catalysed Regio- and Enantio-selective Hydrolysis: Molecular Recognition Phenomenon and Synthesis of (R)-Dimorphecolic Acid
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Molecular recognition has been observed in hydrolysis of racemic esters of (E)-9=acetoxy-11-bromoundec-10-enoic acid by a lipase of Candida cylindracea (E.C. 3.1.1.3) where optically active (R)-(E)-9-acetoxy-11-bromoundec-10-enoic acid 99percent> was obtained which was used in synthesis of (R)-dimorphecolic acid.
- Bhalerao, U. T.,Dasaradhi, L.,Neelakantan, P.,Fadnavis, N. W.
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p. 1197 - 1198
(2007/10/02)
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- Expeditious Synthesis of the Four Isomers of Methyl Dimorphecolate
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The four geometric isomers of methyl dimorphecolate 3 were synthesized by direct, palladium catalyzed, coupling of the two olefinic parts of the conjugated diene system. Key Words: Methyl dimorphecolate; Palladium catalysis; Alkenyl iodide; Alkenyl zinc halides
- Duffault, Jean-Marc,Einhorn, Jacques,Alexakis, Alex
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p. 3701 - 3704
(2007/10/02)
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- IRON-PEPLOMYCIN CATALYZED OXYGENATION OF LINOLEIC ACID
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Incubation of linoleic acid with Fe(III)-peplomycin under aerobic conditions produced a mixture of hydroperoxides 1a-d as primary products which then gave rise to the formation of the corresponding dienones (2a-d), alcohols (3a-d) and epoxyenones (4a,b).
- Nagata, Ryu,Morimoto, Shinji,Saito, Isao
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p. 4485 - 4488
(2007/10/02)
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- Palladium(II)-catalysed Rearrangements of Allylic Acetates in the Syntheses of Methyl (10E,12Z)-9-Hydroxyoctadeca-10,12-dienoate (α-Dimorphecolate) and (2E,4Z)-Deca-2,4-dienal
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Preparatively useful examples of the kinetically controlled PdII-catalysed rearrangement of (1E,4Z)-3-acetoxy-1,4-dienes into (2E,4Z)-1-acetoxy-2,4-dienes are described.These include the conversion of (2E,5Z,8Z)-4-acetoxydeca-2,5,8-triene into (3E,5Z,8Z)-2-acetoxydeca-3,5,8-triene and steps in syntheses leading to the natural products 9-hydroxyoctadeca-10,12-dienoic acid (α-dimorphecolic acid, obtained as its methyl ester) and (2E,4Z)-deca-2,4-dienal.Studies of a variety of substrates show that the order of reactivity of double bonds in the PdII-catalysed rearrangement is E-disubstituted > Z-disubstituted ca. vinyl > α-methylvinyl.Pd0-catalysed rearrangements of these substrates proceed, in contrast to the PdII-catalysed rearrangements, to thermodynamically controlled product(s), e.g. the above triene gives mainly (3E,5E,8Z)-2-acetoxydeca-3,5,8-triene.
- Crilley, Martine M. L.,Golding, Bernard T.,Pierpoint, Colin
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p. 2061 - 2068
(2007/10/02)
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- A Convenient Synthesis of (+/-)-Dimorphecolic Acid and Its Analogs
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Dimorphecolic acid, self-defensive substances in rice plant against rice blast disease, and its analogs were prepared stereoselectively by the reaction of (2E,4Z)-2,4-decadienal with Grignard reagents.
- Tsuboi, Sadao,Maeda, Seiji,Takeda, Akira
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p. 2050 - 2052
(2007/10/02)
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- SYNTHESIS BY MICROBIAL REDUCTION OF (S)-13-HYDROXY-9Z,11E-OCTADECADIENOIC ACID, A DEFENSIVE SUBSTANCE IN RICE
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(S)-13-Hydroxy-9Z,11E-octadecadienoic acid, a defensive substance in rice, was synthesized with high enantioselectivity by the reduction of the corresponding ketone with yeasts.
- Suemune, Hiroshi,Hayashi, Noriyuki,Funakoshi, Kazuhisa,Akita, Hiroyuki,Oishi, Takeshi,Sakai, Kiyoshi
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p. 2168 - 2170
(2007/10/02)
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- UNSATURATED HYDROXY FATTY ACIDS, THE SELF DEFENSIVE SUBSTANCES IN RICE PLANT AGAINST RICE BLAST DISEASE
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In addition to the previously described epoxy fatty acids, five hydroxy fatty acids were characterized as self defensive substances produced in the rice plant against rice blast disease.
- Kato, Tadahiro,Yamaguchi, Yoshihiro,Hirano, Takumi,Yokoyama, Toshiro,Uyehara, Tadao,et al.
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p. 409 - 412
(2007/10/02)
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