J. Jpn. Oil Chem. Soc. Vol. 46, No. 11 (1997) 1399 NOTE Comparison of Antioxidative Compounds in Boreava Their Takashi MAOKA*1, Research *2) Faculty *3) Department (15 for Sakyou-ku, of Pharmaceutical Sciences, Hokkaido, of Ankara Kosei OHNO*2 NISHIBE*2 Kyoto-shi, •§606) Health Sciences University of Hokkaido 7061-02) of Pharmacognosy University SAKUSHIMA*2, Sansei Development Shimogamomorimoto-cho, (Ishikari-Tobetsu, lated Akiyo and Production and Compound COSKUN*3, Institute of Phenolic orientalis Related Yoshihiro ITO*1 Maksut *1) Activity and (Ankara, Pharmaceutical Botany , Faculty of Pharmacy, Turkey) Abstract : Examination was made by the effects of antioxidative activity of phenolic compounds from Boreava orientalis fruit (Cruciferae) and related compounds on free radical-oxidation isoof methyl linolate in solution. Based on methyl linolate hydroperoxide production using 2,2' -azobis(2,4dimethyl valeronitrile) (AMVN) as the radical initiator. Dihydroxybenzoic acids and phenylpropanoids , particularly cinnamic acid derivatives, were shown to be strong antioxidatnts. Key words : Boreava orientalis, Cruciferae, fruits, antioxidative activity , phenolic compounds, phenolic acids derivatives, phenylpropanoids, 1 Previously, from and that the of skin in we orientalis solution. of investigated fruit The and and identification (Cruciferae) On other compounds in of medicine studies antioxidative of on compounds1)•`5) traditional a number possess structure phenolic used activity compounds between same is hand, antioxidative related relationship of which the phenolic the acid derivatives Introduction Turkey. activitie's study, in isolation orientalis disease6),7) Boreava linolate the Boreava antioxidative present from reported fruits coughs the we the cinnamic for showed activity8)-12) phenolic free and have compounds radical-oxidation antioxidative In isolated of activity will methyl be dis- cussed. 2 2•E1 Material The structures acid (1), acid (6), vanillin sinapine acid of (20), (23), ranose phenolic (8), Corresponding -D-(2' isolated (12), caffeic auther acid used gentisic (9), the caffeic acid study fruit of acid and ƒ¿ (15), ferulic -vanillic B. (13), -toconherol were were in Fig. 1. Vanillic acid acid(18), acid (4) sinapic ether (22), syringic acid(19), chlorogenic -D-(1,2-O-disinapoyl) orientalis1)•`5). p-coumaric shown 3,4-dihydroxybenzoic glucopyranose- 3,4-dihydroxyphenylacetic cinnamic : Takashi this (3), threo-guaiacylglycerol- (7), (17) in acid -O-sinapoyl) from acid aldehyde 3.4-dimethvl (21), 6-O- ƒÀ were compounds (2), syringaldehyde scopoletin and (24) acid 3,5-dihydroxybenzoic cinnamic 24 pyrocatechuic Experimental glucopy- 2,6-Dihydroxybenzoic acid (10), cinnamic acid (14), purchased from acid (5), alcohol (11), coniferyl alcohol (16), Wako Chemical Co. MAOKA 65 J. Jpn. Oil Chem. Soc. Vol. 46, No. 11 (1997) 1400 8 11 9 10 13 12 16 20 21 22 Fig. 1 23 Structures of Phenolic Compounds 24 Used in This Study . Plants of B. orientalis specimens were collected near Ankara in 1990 and voucher specimen is retained in the Ankara Universitesi Eczacilik Fakiiltesi herbaryumu (AEF). Details of the isolation and the structural elucidation of these phenolic compounds were reported in previous papern-5). 2,2' -Azobis(2,4-dimethylvaleronitrile) (AMVN) was purchased from Wako Chemical Co. Methyl linolate, supplied by Shigma Chemical Co., was further purified by silica gel column chromatography to remove any peroxides. 2.2 Measurment of antioxidative activity12),13) Phenolic compounds were dissolved in MeOH and used at a final concentration of 167 04 in reaction mixture. 0.1 mL of the sample solution was added to 1 mL of 0.1 M methyl linolate solution [n-hexane/2-propanol (1/1, vol/vol)], and the solution was incubated at 37°C for 5 min. The oxidation reaction was then initiated by adding 0.1 mL of 100 mM n-hexane solution of AMVN, and the mixture was incubated with air at 37°C for 30 min. The oxidative reaction products, linolate hydroperoxides, were quantified by high performance liquid chromatography (HPLC). 2.3 HPLC HPLC was performed with a Hitachi L-6200 intelligent pump and L-4250 UV-VIS detector. The following HPLC conditions employed for the quantitative analysis of methyl linolate hydroperoxides : column : LiChrosorb Si 100 (5 Lim particle size) (4 .6 x 250 mm) (Merck) ; solvent system : 2-propanol/n-hexane (1/99, vol/vol) ; flow rate : 1.0 mL/min, detection : 235 nm. 3 The antioxidative 66 activity Results of 24 phenolic and Discussion compounds was monitored by measuring the accu- J. Jpn. Oil Chem. Soc. Vol. 46, No. 11 (1997) mulation of methyl AMVN as pounds studied linolate a radical hydroperoxides initiator. showed These during results antioxidative are activity the shown but incubation in their 1401 of Table methyl 1. Most activity was of less linolate the with phenolic than that com- of ƒ¿-toco- pherol. Hydroxy them was less ringic the benzoic dihydroxy efficient aldehyde to the effect group, aryloxy other and have group, of as 2, one (8, and or two from presence . Furthermore, showed groups activity. The methoxy such antioxidative strong , but acid syringic at the strong group electron effect. activity Furthermore, methoxy the of 9) 4 exhibited acids. strong donors the 3, benzoic showed electron becouse radica10)•`12) benzaldehydes such dihydroxy which hydroxyl hydroxy (1•`7) acids than (9), phenolic due acids benzoic at donors 3,4-dihydroxyphenylacetic ortho position activity the of ortho 6 and position increase the acid(10) showed Among compound (6) and 5 sy- relative to 9 might be of phenolic stability of the remarkable activity. Phenyl namic (15), zoic ly. propanoids acid ferulic acids, This (11•`20) derivatives acid namely, finding also such (18) and as showed 15, sinapic Table that 1 acid antioxidative 19 acid pyrocatechuic suggested 18, and (19) (2), 20 were more vanillic acid the presence of Inhibitory Effect of Phenolic dation of Methyl activity exhibited a . Of these significant active (1) than and conjugated Compounds their syringic olefinic compounds, activity corresponding acid group cin- . Caffeic acid ben- (6) in , respectivethe molecules on the Oxi- Linolate. 67 1402 of J. Jpn. Oil Chem. Soc. Vol. 46, No. 11 (1997) these tion of compounds as the pounds 11, 12 so (21) acid and that antioxidative hibited hydroxy significant in Consequently, lack moderate derivatives hydroxy but 22 a conjugated chlorogenic might fruits of B. showed be acid due to (23) the . On showed a few group to resonance showed above group, olefinic due (16) described phenolic which activity alcohol the a activity. and sinapic presence of other few This participated the acid caffeic stabiliza- almost the same hand, activity. comScopo- phenomenon al- enhancement glycoside acid of (24) and ex- sinapic molecule. dihydroxybenzoic isolated the scavenging coniferyl activity, of Furthermore, activity, these redical acid presence activity. moiety derivatives which the the the Furthermore, cinnamic 13, exhibited suggests enhance redical10)•`12) activity letin might aryloxy from the acids and phenylpropanoids, orientalis (Received were particularly shown Apr. 11, to 1997 be strong Accepted cinnamic antioxidation Jul. 31, acid . 1997) References 1) 2) 3) 4) 5) 6) 7) 8) 9) 10) 11) 12) 13) 68 A. A. A. A. A. N. M. Sakushima, Sakushima, Sakushima, Sakushima, Sakushima, Tanker, M. Tanker, M. M. Coskun, M. Tanker, N. Tanker., Phytochemistry , 35, 1981 (1994). M. Coskun, T. 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Terao, Lipid, 24, 659 (1989). 1414 日本 油 化 学 会 誌 [ノ ー ト] Boreava 第46巻 orientalisよ 第11号 (1997) り得 られ た フ ェ ノ ー ル 化 合 物 お よ び そ れ らの 関連 化 合 物 の 抗 酸化 活 性 の比 較 眞 岡 孝 至*1・ 伊 藤 義 博*1・ 佐 久 嶋 明 世*2・ 大 野 Maksut COSKUN*3・ *1 (財)生 産 開 発 科 学研 究 所(〒606京 *2 北 海 道 医 療 大 学 薬学 部(〒061‑02北 *3 ア ン カ ラ大 学 薬学 部(ト Boreava て2,2'‑ア orientalis ゾ ビ ス(2,4‑ジ 海 道 石 狩 郡 当 別 町金 沢1757) ル コ共 和 国,ア ン カ ラ) より得 られた フェノール化合物 およびそれ らの 関連構造 を持つ化合物の抗酸化活性 につい メ チ ル バ レ ロ ニ ト リル)(AMVN)に た 。 フ ェ ニ ル プ ロ パ ノ イ ド,特 よ る リノ ール 酸 メ チル の 過 酸 化 系 を 用 い て 検 討 し に シ ナ ピ ン酸 誘 導 体 に 強 い 抗 酸 化 活 性 が 認 め ら れ た 。 (連 絡 者:眞 80 孝 正*2 西部 三 省*2 都 市 左 京 区 下 鴨 森本 町15) 岡 孝 至) Vol. 46, No. 11, 1399 (1997)