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        華中五味子根部木脂素類化學(xué)成分及其抗氧化活性研究

        2022-11-05 07:08:12郭曄紅
        中草藥 2022年21期
        關(guān)鍵詞:淺黃色脂素華中

        姜 侃,郭曄紅

        華中五味子根部木脂素類化學(xué)成分及其抗氧化活性研究

        姜 侃1, 2,郭曄紅1, 2

        1. 甘肅農(nóng)業(yè)大學(xué)農(nóng)學(xué)院,甘肅 蘭州 730070 2. 甘肅農(nóng)業(yè)大學(xué) 省部共建干旱生境作物學(xué)國(guó)家重點(diǎn)實(shí)驗(yàn)室,甘肅 蘭州 730070

        對(duì)藥食同源植物華中五味子根部的化學(xué)成分進(jìn)行研究。利用薄層色譜、柱色譜、半制備高效液相色譜等現(xiàn)代色譜方法分離純化,根據(jù)理化性質(zhì)及波譜數(shù)據(jù)對(duì)化合物進(jìn)行結(jié)構(gòu)鑒定;利用ABTS+自由基清除的活性篩選技術(shù)對(duì)化合物進(jìn)行抗氧化活性評(píng)價(jià)。從華中五味子根部70%丙酮水提取物中分離鑒定了23個(gè)木脂素類化合物,分別鑒定為 (?)-zuonin A(1)、-1-(4-hydroxy-3-methoxyphenyl)-4-(3,4-methylenedioxyphenyl)-2,3- dimethylbutane(2)、奧斯楚拜脂素-5(3)、9,9′-二羥基-澳白木脂素-5(4)、(?)-8-羥基-α-鐵杉脂素(5)、(?)-戈米辛M1(6)、五味子乙素(7)、五味子丙素(8)、戈米辛J(9)、(+)-戈米辛k3(10)、五味子甲素(11)、五味子醇甲(12)、rubrisandrin B(13)、marlignan A(14)、rubrisandrin A(15)、濱南五味子乙素(16)、異戈米辛O(17)、marphenol A(18)、(7′,8′)-3,4- dimethoxy-3′,4′-methylenedioxy-7,8-seco-7,7′-epoxylignan-7,8-dione(19)、(7′,8′)-3,4-methylenedioxy-3′,4′-dimethoxy-7,8-seco- 7,7′-epoxylignan-7,8-dione(20)、machilolin-A(21)、marphenol B(22)、3′,4′-dimethoxy-benzoicacid-(3′′,4′′-dimethoxyphenyl)- 3-oxobutyl ester(23)?;衔?、7、18~20、22為首次從該植物中分離得到,化合物1~5、16、17為首次從五味子屬植物中分離得到?;衔?~4、13顯示了一定的抗氧化能力,半數(shù)抑制濃度(median inhibition concentration,IC50)值分別為23.0、16.5、10.8、16.0 μmol/L,其中化合物4的抗氧化活性較好,接近陽性對(duì)照維生素C。

        華中五味子;二芳基丁烷類木脂素;聯(lián)苯環(huán)辛烯類木脂素;7,8-seco-木脂素;抗氧化活性;奧斯楚拜脂素-5;(?)-8-羥基-α-鐵杉脂素

        華中五味子Rehd.et Wils為五味子屬植物,其果實(shí)可食用,也可作為五味子果實(shí)的替代品用作藥物使用[1-3],倍受歷代醫(yī)家推崇。如今,作為藥食同源之品,五味子不僅作為中藥飲片使用,還應(yīng)用于制成多種成方制劑和相關(guān)的保健品,如定喘固金丸、護(hù)肝片、五味子膠囊、五味子片、五味子茶、五味子多糖口服液、五味子飲料等;其果實(shí)、根、藤莖、葉、果柄以及全株均可利用,是一種開發(fā)前景非常廣闊的藥食兼用的中藥材。生活中,也常常用五味子泡水、煮粥,現(xiàn)代研究發(fā)現(xiàn)五味子具有保肝護(hù)肝、鎮(zhèn)靜催眠、降血糖、抗氧化、增強(qiáng)免疫力、抗癌等藥理作用;種子榨油后可以用來制作肥皂或者作為潤(rùn)滑油使用。華中五味子主產(chǎn)于甘肅、陜西、山西等省。

        近些年,中國(guó)科學(xué)院昆明植物研究所孫漢董課題組對(duì)華中五味子的莖葉進(jìn)行過多次研究,從中發(fā)現(xiàn)了很多高含氧三萜,并表現(xiàn)了很好的抗癌以及抗艾滋病病毒活性[4-8]。這引起天然產(chǎn)物化學(xué)家對(duì)華中五味子高度關(guān)注,并對(duì)其進(jìn)行了大量研究,以期發(fā)現(xiàn)具有獨(dú)特骨架和生物活性的化合物;但是華中五味子根部的研究卻未見報(bào)道。為了探索華中五味子根部的化學(xué)成分,本實(shí)驗(yàn)對(duì)收集于陜西省太白山秦嶺段華中五味子根部的化學(xué)成分進(jìn)行系統(tǒng)研究,對(duì)其70%丙酮水提取物分別利用石油醚、醋酸乙酯、正丁醇進(jìn)行了萃取,薄層色譜檢測(cè)顯示醋酸乙酯部分所含化合物較為豐富,因此本實(shí)驗(yàn)選擇醋酸乙酯部分進(jìn)行系統(tǒng)分離,從中共分離得到23個(gè)化合物,分別鑒定為(?)-zuonin A(1)、-1-(4-hydroxy-3- methoxyphenyl)-4-(3,4-methylenedioxyphenyl)-2,3- dimethylbutane(2)、奧斯楚拜脂素-5(austrobailignan-5,3)、9,9′-二羥基-澳白木脂素-5(9,9′-dihydroxy-austrobailignan-5,4)、(?)-8-羥基-α-鐵杉脂素 [(?)-8-hydroxy-α-conidendrin,5]、(?)-戈米辛M1 [(?)-gomisin M,16]、五味子乙素(schisandrin B,7)、五味子丙素(schisandrin C,8)、戈米辛J(gomisin J,9)、(+)-戈米辛k3[(+)-gomisin k3,10]、五味子甲素(deoxyschizandrin,11)、五味子醇甲(-schizandrin,12)、rubrisandrin B(13)、marlignans A(14)、rubrisandrin A(15)、濱南五味子乙素(yunnankadsurin B,16)、異戈米辛O(isogomisin O,17)、marphenol A(18)、(7′,8)-3,4-dimethoxy-3′,4′-methylenedioxy-7,8-seco- 7,7′-epoxylignan-7,8-dione(19)、(7′,8′)-3,4- methylenedioxy-3′,4′-dimethoxy-7,8-seco-7,7′-epoxy- lignan-7,8-dione(20)、machilolin-A(21)、marphenol B(22)、3′,4′-dimethoxy-benzoicacid-(3′′,4′′-dimeth- oxyphenyl)-3-oxobutyl ester(23)?;衔?為四氫呋喃型木脂素,化合物2~4為二芳基丁烷類木脂素,化合物5為二芳基丁內(nèi)酯類木脂素,化合物6~17為聯(lián)苯環(huán)辛烯類木脂素;化合物18~23為7,8-seco-木脂素?;衔?、7、18~20、22為首次從該植物中分離得到,化合物1~5、16、17為首次從五味子屬植物中分離得到。上述結(jié)果表明,華中五味子根部醋酸乙酯萃取物為木脂素類成分的富集部位。此外,化合物2~4、13顯示了一定的抗氧化能力,其半數(shù)抑制濃度(median inhibition concentration,IC50)分別為23.0、16.5、10.8、16.0 μmol/L,其中化合物4的抗氧化活性較好,接近陽性對(duì)照維生素C(IC50=7.4 μmol/L)。

        1 儀器與材料

        Varian Mercury plus-400B核磁測(cè)定儀器(美國(guó)Varian公司);反相硅膠和反相硅膠板均購(gòu)買自德國(guó)Merck公司;葡聚糖凝膠購(gòu)買自Amersham Biosciences;HP-20大孔樹脂(日本三菱公司);半制備HPLC色譜儀購(gòu)買于Waters公司,X Bridge prep C18色譜柱(150 mm×10 mm,5 μm);分析純?nèi)軇┚?gòu)自天津化學(xué)試劑有限公司。

        華中五味子根部是于2011年7月收集于陜西省太白山秦嶺段,并由蘭州大學(xué)生命科學(xué)學(xué)院張國(guó)梁教授鑒定為華中五味子Rehd.et Wils。植物標(biāo)本(No.11-07)存放于蘭州大學(xué)國(guó)家重點(diǎn)實(shí)驗(yàn)室天然有機(jī)研究室。

        2 提取與分離

        干燥的華中五味子根部7 kg粉碎后,在室溫下用70%丙酮水泡3次,每次7 d。在旋轉(zhuǎn)蒸發(fā)儀中真空蒸餾除去溶劑,得到粗提取物685 g,將粗浸膏水溶后,依次用石油醚、醋酸乙酯和正丁醇萃取。將醋酸乙酯部分的浸膏用大孔樹脂進(jìn)行分離,以水-乙醇(70∶30、50∶50、20∶80)溶液進(jìn)行梯度洗脫,得到3個(gè)組分(Fr. A~C)。

        Fr. C(248 g)經(jīng)正相柱色譜,以石油醚-丙酮(100∶0、50∶1、20∶1、10∶1、5∶1、2∶1、1∶1、0∶100)為洗脫劑,得到8個(gè)部分Fr. C1~C8。Fr. C3(14.2 g)經(jīng)過正相硅膠柱、Sephadex LH-20(氯仿-甲醇2∶1)、反相硅膠以及半制備HPLC(甲醇-水25∶75)進(jìn)行分離,得到化合物4(2.2 mg)和5(2.9 mg);Fr. C4(4.3 g)通過硅膠柱、Sephadex LH-20以及半制備HPLC(甲醇-水30∶70)進(jìn)行分離得到化合物2(2.3 mg)、9(2.5 mg)和14(2.4 mg);Fr. C5(8.2 g)經(jīng)正相硅膠柱、反相硅膠以及半制備HPLC進(jìn)行分離純化,得到化合物1(3.6 mg)、3(22 mg)、6(3 mg)、7(2.3 mg)、8(1.8 mg)、10(2.8 mg)和11(2.9 mg);Fr. C6(3.2 g)使用正相硅膠柱、反相硅膠以及半制備HPLC進(jìn)行分離純化,得到化合物12(6 mg)、13(2.5 mg)、15(2.4 mg)、16(3.1 mg)和17(2.9 mg)。對(duì)Fr. C7(3.2 g)使用Sephadex LH-20、反相硅膠以及半制備HPLC進(jìn)行分離純化,得到化合物18(4.8 mg)、19(2.9 mg)、20(1.3 mg)、21(2.4 mg)、22(2.1 mg)和23(3.9 mg)。

        3 結(jié)構(gòu)鑒定

        化合物2:白色粉末固體;1H-NMR (400 MHz, CDCl3): 6.71 (1H, d,= 1.9 Hz, H-2), 6.74 (1H, d,= 7.2 Hz, H-5), 6.62 (1H, dd,= 2.0, 7.2 Hz, H-6), 2.25 (1H, dd,= 10.0, 13.0 Hz, H-7a), 2.70 (1H, dd,= 3.68, 13.0 Hz, H-7b), 1.72 (1H, dd,= 4.2, 6.3 Hz, H-8), 0.85 (3H, d,= 6.3 Hz, H-9), 6.59 (1H, brs, H-2′), 6.74 (1H, d,= 8.0 Hz, H-5′), 6.65 (1H, dd,= 1.9, 8.0 Hz, H-6′), 2.32 (1H, dd,= 10.2, 13.2 Hz, H-7′a), 2.74 (1H, dd,= 3.8, 13.0 Hz, H-7′b), 1.72 (1H, dd,= 4.2, 6.3 Hz, H-8′), 0.85 (3H, d,= 6.3 Hz, H-9′), 5.92 (2H, s, OCH2O), 3.87 (3H, s, OCH3);13C-NMR (100 MHz, CDCl3): 136.0 (C-1), 108.2 (C-2), 146.5 (C-3), 143.8 (C-4), 114.3 (C-5), 122.1 (C-6), 39.1 (C-7), 39.6 (C-8), 16.4 (C-9), 134.0 (C-1′), 109.6 (C-2′), 147.7 (C-3′), 145.7 (C-4′), 111.7 (C-5′), 121.9 (C-6′), 39.6 (C-7′), 39.3 (C-8′), 16.5 (C-9′), 101.0 (OCH2O), 56.1 (OMe)。以上波譜數(shù)據(jù)與文獻(xiàn)報(bào)道一致[10],同時(shí),通過對(duì)比8、8′、9、9′的化學(xué)位移和偶合常數(shù),確定該化合物為[10],故鑒定化合物2為-1-(4-hydroxy-3-methoxyphenyl)- 4-(3,4-methylenedioxyphenyl)-2,3-dimethylbutane。

        化合物3:白色粉末固體;1H-NMR (400 MHz, CDCl3): 6.72 (1H, d,= 1.9 Hz, H-2), 6.76 (1H, d,= 7.2 Hz, H-5), 6.60 (1H, dd,= 2.0, 7.2 Hz, H-6), 2.23 (1H, dd,= 10.0, 13.0 Hz, H-7a), 2.71 (1H, dd,= 3.7, 13.0 Hz, H-7b), 1.72 (1H, m, H-8), 6.57 (1H, brs, H-2′), 6.74 (1H, d,= 8.0 Hz, H-5′), 6.66 (1H, dd,= 1.9, 8.0 Hz, H-6′), 2.31 (1H, dd,= 10.0, 13.2 Hz, H-7′a), 2.73 (1H, dd,= 4.0, 13.2 Hz, H-7′b), 1.73 (1H, m, H-8′), 0.84 (3H, d,= 6.4 Hz, H-9′), 5.92 (4H, s, 2×OCH2O);13C-NMR (100 MHz, CDCl3): 135.9 (C-1), 108.3 (C-2), 146.4 (C-3), 143.9 (C-4), 114.4 (C-5), 121.9 (C-6), 39.2 (C-7), 39.6 (C-8), 16.2 (C-9), 134.1 (C-1′), 109.5 (C-2′), 147.8 (C-3′), 145.7 (C-4′), 111.5 (C-5′), 121.6 (C-6′, 39.5 (C-7′), 39.4 (C-8′), 16.3 (C-9′), 101.0, 101.1 (2×OCH2O)。以上波譜數(shù)據(jù)與文獻(xiàn)報(bào)道一致[11],故鑒定化合物3為奧斯楚拜脂素-5。

        化合物4:白色粉末固體;1H-NMR (400 MHz, CDCl3): 6.59 (2H, brs, H-2, 2′), 6.72 (2H, d,= 8.0 Hz, H-5, 5′), 6.63 (2H, dd,= 1.9, 8.0 Hz, H-6, 6′), 2.64 (2H, dd,= 6.0, 13.6 Hz, H-7a, 7′a), 2.78 (2H, dd,= 8.8, 13.2 Hz, H-7b, 7′b), 1.73 (2H, m, H-8, 8′), 3.53 (2H, dd,= 4.4, 11.6 Hz, H-9a, 9′a), 3.80 (2H, d,= 10.4 Hz, H-9b, 9′b), 5.92 (4H, 2×OCH2O);13C-NMR (100 MHz, CDCl3): 134.6 (C-1, 1′), 108.4 (C-2, 2′), 147.9 (C-3, 3′), 146.0 (C-4, 4′), 109.6 (C-5, 5′), 122.1 (C-6, 6′), 36.2 (C-7, 7′), 44.6 (C-8, 8′), 60.7 (C-9, 9′), 101.1 (2×OCH2O)。以上波譜數(shù)據(jù)與文獻(xiàn)報(bào)道一致[12],故鑒定化合物4為9,9'-二羥基-澳白木脂素-5。

        化合物7:黃色粉末固體;1H-NMR (400 MHz, CDCl3): 6.54 (1H, s, H-4), 2.45 (1H, dd,= 1.6, 13.6 Hz, H-6α), 2.58 (1H, dd,= 7.6, 14.0 Hz, H-6β), 1.89 (1H, m, H-7), 1.79 (1H, m, H-8), 2.33 (1H, dd,= 9.6, 13.2 Hz, H-9α), 2.05 (1H, brd,= 13.2 Hz, H-9β), 6.48 (1H, s, H-11), 1.00 (3H, d,= 7.2 Hz, H-17), 0.74 (3H, d,= 7.2 Hz, H-18), 3.54 (3H, s, OCH3), 3.82 (3H, s, OCH3), 3.88 (3H, s, OCH3), 3.89 (3H, s, OCH3), 5.96 (2H, d,= 1.6 Hz, OCH2O);13C-NMR (100 MHz, CDCl3): 148.9 (C-1), 134.4 (C-2), 151.8 (C-3), 110.9 (C-4), 124.1 (C-5), 39.4 (C-6), 33.8 (C-7), 41.0 (C-8), 35.8 (C-9), 121.6 (C-10), 103.2 (C-11), 147.9 (C-12), 132.4 (C-13), 141.4 (C-14), 134.4 (C-15), 135.1 (C-16), 21.8 (C-17), 13.1 (C-18), 56.2, 59.9, 60.8, 61.3 (4×OMe), 101.0 (OCH2O)。以上波譜數(shù)據(jù)與文獻(xiàn)報(bào)道一致[15],故鑒定化合物7為五味子乙素。

        化合物8:黃色粉末固體;1H-NMR (400 MHz, CDCl3):1.82 (2H, m, H-7, 8), 2.53 (2H, m, H-6α,9α), 2.05 (2H, m, H-6β,9β), 6.49 (2H, s, H-4, 11), 1.01 (3H, d,= 7.2 Hz, H-17), 0.74 (3H, d,= 6.8 Hz, H-18);13C-NMR (100 MHz, CDCl3):142.1 (C-1, 14), 133.8 (C-2, 13), 147.8 (C-3, 12), 105.9 (C-4, 11), 121.2 (C-5, 10), 38.4 (C-6, 9), 40.1 (C-7, 8), 131.7 (C-15, 16), 21.2 (C-17), 12.5 (C-18), 59.9 (2×OCH3), 100.9 (2×OCH2O)。以上波譜數(shù)據(jù)與文獻(xiàn)報(bào)道一致[15],故鑒定化合物8為五味子丙素。

        化合物9:淺黃色粉末固體;1H-NMR (400 MHz, CDCl3): 6.76 (1H, s, H-4), 6.40 (1H, s, H-11), 0.72 (3H, d,= 6.8 Hz, H-17), 0.97 (3H, d,= 6.8 Hz, H-18), 3.54 (3H, s, OCH3), 3.56 (3H, s, OCH3), 3.80 (3H, s, OCH3), 3.83 (3H, s, OCH3);13C-NMR (100 MHz, CDCl3): 150.7 (C-1), 141.2 (C-2), 150.1 (C-3), 111.9 (C-4), 136.4 (C-5), 40.1 (C-6), 35.1 (C-7), 42.9 (C-8), 35.9 (C-9), 135.2 (C-10), 108.0 (C-11), 152.1 (C-12), 139.5 (C-13), 152.4 (C-14), 118.9 (C-15), 122.0 (C-16), 22.3 (C-17), 12.9 (C-18), 56.1, 60.3, 61.2, 61.4 (4×OMe)。以上波譜數(shù)據(jù)與文獻(xiàn)報(bào)道一致[16],故鑒定化合物9為戈米辛J。

        化合物11:淺黃色粉末固體;1H-NMR (400 MHz, CDCl3): 6.54 (1H, s, H-4), 6.53 (1H, s, H-11), 0.75 (3H, d,= 6.8 Hz, H-17), 1.01 (3H, d,= 6.8 Hz, H-18), 3.58 (3H, s, OCH3), 3.59 (3H, s, OCH3), 3.87 (3H, s, OCH3), 3.88 (3H, s, OCH3), 3.89 (3H, s, OCH3), 3.90 (3H, s, OCH3);13C-NMR (100 MHz, CDCl3): 153.1 (C-1), 140.4 (C-2), 147.7 (C-3), 107.4 (C-4), 134.2 (C-5), 39.4 (C-6), 35.9 (C-7), 41.0 (C-8), 34.0 (C-9), 134.0 (C-10), 108.2 (C-11), 151.9 (C-12), 139.4 (C-13), 146.6 (C-14), 123.6 (C-15), 122.1 (C-16), 22.1 (C-17), 12.9 (C-18), 56.0, 56.1, 56.2, 60.8, 60.8, 61.2 (6×OMe)。以上波譜數(shù)據(jù)與文獻(xiàn)報(bào)道一致[15],故鑒定化合物11為五味子甲素。

        化合物12:淺黃色粉末固體;1H-NMR (400 MHz, CDCl3): 6.55 (1H, s, H-4), 6.48 (1H, s, H-11), 0.74 (3H, d,= 7.2 Hz, H-17), 0.98 (3H, d,= 7.2 Hz, H-18), 3.54 (3H, s, OCH3), 3.81 (3H, s, OCH3), 3.88 (3H, s, OCH3), 3.89 (3H, s, OCH3), 5.94 (2H, d,= 0.8 Hz, OCH2O);13C-NMR (100 MHz, CDCl3): 151.3 (C-1), 139.6 (C-2), 152.7 (C-3), 107.4 (C-4), 139.2 (C-5), 35.4 (C-6), 40.9 (C-7), 34.0 (C-8), 38.7 (C-9), 132.3 (C-10), 105.7 (C-11), 147.9 (C-12), 134.8 (C-13), 141.2 (C-14), 122.3 (C-15), 122.5 (C-16), 12.3 (C-17), 21.9 (C-18), 55.8, 59.6, 60.5, 60.8 (4×OMe), 100.8 (OCH2O)。以上波譜數(shù)據(jù)與文獻(xiàn)報(bào)道一致[17],故鑒定化合物12為五味子醇甲。

        化合物13:白色粉末固體;1H-NMR (400 MHz, CDCl3): 6.44 (1H, s, H-4), 2.58 (1H, dd,= 7.4, 13.2 Hz, H-6α), 2.48 (1H, d,= 13.2 Hz, H-6β), 1.89 (1H, m, H-7), 1.79 (1H, m, H-8), 2.03 (1H, d,= 13.6 Hz, H-9α), 2.30 (1H, dd,= 10.0, 13.6 Hz, H-9β), 6.41 (1H, s, H-11), 0.76 (3H, d,= 6.8 Hz, H-17), 1.00 (3H, d,= 6.8 Hz, H-18), 3.88 (3H, s, OCH3), 3.92 (3H, s, OCH3), 3.93 (3H, s, OCH3), 3.95 (3H, s, OCH3);13C-NMR (100 MHz, CDCl3):151.2 (C-1), 150.0 (C-2), 145.9 (C-3), 108.8 (C-4), 135.5 (C-5), 41.1 (C-6), 39.2 (C-7), 35.8 (C-8), 33.6 (C-9), 133.1 (C-10), 104.4 (C-11), 139.8 (C-12), 138.7 (C-13), 146.3 (C-14), 114.6 (C-15), 115.1 (C-16), 12.3 (C-17), 21.7 (C-18), 55.6 (2×OCH3), 61.1 (2×OCH3)。以上波譜數(shù)據(jù)與文獻(xiàn)報(bào)道一致[18],故鑒定化合物13為rubrisandrin B。

        化合物14:淺黃色粉末固體;1H-NMR (400 MHz, CDCl3): 6.54 (1H, s, H-4), 6.44 (1H, s, H-11), 0.75 (3H, d,= 7.2 Hz, H-17), 1.01 (3H, d,= 7.2 Hz, H-18), 3.55 (3H, s, OCH3), 3.88 (3H, s, OCH3), 3.89 (3H, s, OCH3), 5.73 (1H, s, Ph-OH), 5.69 (1H, s, Ph-OH), 5.59 (1H, s, Ph-OH);13C-NMR (100 MHz, CDCl3): 151.7 (C-1), 140.6 (C-2), 150.3 (C-3), 112.4 (C-4), 135.2 (C-5), 39.4 (C-6), 34.2 (C-7), 41.6 (C-8), 35.7 (C-9), 134.7 (C-10), 106.7 (C-11), 148.8 (C-12), 139.8 (C-13), 146.5 (C-14), 119.3 (C-15), 121.5 (C-16), 12.9 (C-17), 21.9 (C-18), 60.1, 60.5, 60.6 (3×OMe)。以上波譜數(shù)據(jù)與文獻(xiàn)報(bào)道一致[19],故鑒定化合物14為marlignans A。

        化合物15:淺黃色粉末固體;1H-NMR (400 MHz, CDCl3): 6.56 (1H, s, H-4), 6.34 (1H, s, H-11), 0.74 (3H, d,= 6.8 Hz, H-17), 0.99 (3H, d,= 6.8 Hz, H-18), 3.79 (3H, s, OCH3), 3.86 (3H, s, OCH3), 3.88 (3H, s, OCH3), 3.89 (3H, s, OCH3), 5.56 (1H, s, Ph-OH), 5.66 (1H, s, Ph-OH);13C-NMR (100 MHz, CDCl3): 150.4 (C-1), 137.8 (C-2), 147.7 (C-3), 113.6 (C-4), 135.4 (C-5), 38.9 (C-6), 33.9 (C-7), 41.0 (C-8), 35.7 (C-9), 139.7 (C-10), 104.0 (C-11), 151.8 (C-12), 133.6 (C-13), 146.5 (C-14), 115.9 (C-15), 121.5 (C-16), 12.6 (C-17), 21.9 (C-18), 55.6, 60.5, 60.8, 61.1 (4×OMe)。以上波譜數(shù)據(jù)與文獻(xiàn)報(bào)道一致[18],故鑒定化合物15為rubrisandrin A。

        化合物16:淺黃色粉末固體;1H-NMR (400 MHz, CDCl3): 6.52 (1H, s, H-4), 4.45 (1H, brs, H-9), 6.47 (1H, s, H-11), 0.85 (3H, d,= 6.8 Hz, H-17), 0.98 (3H, d,= 6.8 Hz, H-18), 3.63 (3H, s, OCH3), 3.85 (3H, s, OCH3), 3.89 (3H, s, OCH3), 3.91 (3H, s, OCH3);13C-NMR (100 MHz, CDCl3): 147.3 (C-1), 133.4 (C-2), 151.0 (C-3), 107.3 (C-4), 133.8 (C-5), 38.9 (C-6), 35.0 (C-7), 43.4 (C-8), 83.7 (C-9), 138.9 (C-10), 102.8 (C-11), 148.3 (C-12), 135.7 (C-13), 141.0 (C-14), 117.9 (C-15), 115.2 (C-16), 19.5 (C-17), 15.4 (C-18), 55.9, 59.9, 60.8, 60.9 (4×OMe)。以上波譜數(shù)據(jù)與文獻(xiàn)報(bào)道一致[20],故鑒定化合物16為濱南五味子乙素。

        化合物17:無色針狀晶體(氯仿-甲醇3∶1);1H-NMR (400 MHz, CDCl3): 6.91 (1H, s, H-4), 1.91~2.11 (2H, m, H-7, 8), 2.65 (1H, d,= 4.4 Hz, H-8), 4.52 (1H, s, H-9β), 6.51 (1H, s, H-11), 1.04 (3H, d,= 7.2 Hz, H-17), 0.72 (3H, d,= 7.2 Hz, H-18), 3.62 (3H, s, OCH3), 3.84 (3H, s, OCH3), 3.87 (3H, s, OCH3), 3.89 (3H, s, OCH3), 5.99 (2H, d,= 2.4 Hz, OCH2O);13C-NMR (100 MHz, CDCl3): 147.1 (C-1), 133.5 (C-2), 151.1 (C-3), 107.2 (C-4), 134.0 (C-5), 39.0 (C-6), 34.7 (C-7), 43.0 (C-8), 81.9 (C-9), 139.0 (C-10), 102.5 (C-11), 148.6 (C-12), 135.5 (C-13), 141.1 (C-14), 118.1 (C-15), 114.9 (C-16), 19.5 (C-17), 15.1 (C-18), 55.8, 59.8, 60.8, 61.1 (4×OMe)。以上波譜數(shù)據(jù)與文獻(xiàn)報(bào)道一致[21],故鑒定化合物17為異戈米辛O。

        化合物18:淺黃色油狀物;1H-NMR (400 MHz, CDCl3):7.48 (1H, d,= 2.0 Hz, H-2), 7.59 (1H, dd,= 1.6, 8.4 Hz, H-6), 6.91 (1H, d,= 7.6 Hz, H-8), 2.24 (3H, s, H-9), 6.92 (1H, d,= 2.8 Hz, H-2′), 6.79 (1H, d,= 7.6 Hz, H-5′), 6.92 (1H, dd,= 2.6, 7.6 Hz, H-6′), 5.92(1H, d,= 10.0 Hz, H-7′), 3.20 (1H, dq,= 10.0, 7.2 Hz, H-8′), 0.98 (1H, d,= 7.2 Hz, H-9′), 3.91 (3H, s, OCH3), 5.95 (2H, s, OCH2O);13C-NMR (100 MHz, CDCl3):122.3 (C-1), 112.1 (C-2), 148.2 (C-3), 150.5 (C-4), 108.5 (C-5), 124.3 (C-6), 165.3 (C-7), 209.7 (C-8), 29.0 (C-9), 132.4 (C-1′), 107.6 (C-2′), 147.9 (C-3′), 146.5 (C-4′), 108.5 (C-5′), 121.6 (C-6′), 78.2 (C-7′), 52.6 (C-8′), 13.4 (C-9′), 56.4 (OCH3), 101.5 (OCH2O)。以上波譜數(shù)據(jù)與文獻(xiàn)報(bào)道一致[22],故鑒定化合物18為marphenol A。

        化合物19:淺黃色油狀物;1H-NMR (400 MHz, CDCl3):7.46 (1H, d,= 1.8 Hz, H-2), 7.62 (1H, dd,= 1.8, 8.2 Hz, H-6), 6.86(1H, d,= 8.4 Hz, H-8), 2.21 (3H, s, H-9), 6.90 (1H, d,= 1.6 Hz, H-2′), 6.80 (1H, d,= 8.4 Hz, H-5′), 6.92 (1H, dd,= 2.0, 8.2 Hz, H-6′), 5.89 (1H, d,= 12.2 Hz, H-7′), 3.21 (1H, dq,= 10.6, 7.2 Hz, H-8′), 0.99 (1H, d,= 7.2 Hz, H-9′), 3.84 (3H, s, OCH3), 3.86 (3H, s, OCH3), 5.93 (2H, s, OCH2O);13C-NMR (100 MHz, CDCl3):122.3 (C-1), 112.2 (C-2), 148.2 (C-3), 152.1(C-4), 109.9 (C-5), 123.2 (C-6), 164.8 (C-7), 209.4 (C-8), 28.7 (C-9), 131.8 (C-1′), 106.9 (C-2′), 147.7 (C-3′), 147.5 (C-4′), 108.0 (C-5′), 121.1 (C-6′), 77.8 (C-7′), 52.2 (C-8′), 13.8 (C-9′), 56.1, 55.9 (2×OCH3), 101.0 (OCH2O)。以上波譜數(shù)據(jù)與文獻(xiàn)報(bào)道一致[22],故鑒定化合物19為(7′,8′)-3,4-dimethoxy-3′,4′- methylenedioxy-7,8-seco-7,7′-epoxylignan-7,8-dione。

        化合物20:淺黃色油狀物;1H-NMR (400 MHz, CDCl3):7.40 (1H, d,= 1.8 Hz, H-2), 7.60 (1H, dd,= 1.8, 8.4 Hz, H-6), 6.85 (1H, d,= 8.4 Hz, H-8), 2.24 (3H, s, H-9), 6.91 (1H, d,= 2.0 Hz, H-2′), 7.00 (1H, d,= 8.4 Hz, H-5′), 6.85 (1H, dd,= 2.0, 8.4 Hz, H-6′), 5.96 (1H, d,= 11.6 Hz, H-7′), 3.23(1H, dq,= 10.4, 6.8 Hz, H-8′), 0.97 (1H, d,= 7.2 Hz, H-9′), 3.86 (3H, s, OCH3), 3.88 (3H, s, OCH3), 6.02 (2H, s, OCH2O);13C-NMR (100 MHz, CDCl3):124.3 (C-1), 109.5 (C-2), 148.0 (C-3), 152.1(C-4), 108.3 (C-5), 125.5 (C-6), 164.8 (C-7), 209.9 (C-8), 28.7 (C-9), 130.8 (C-1′), 110.9 (C-2′), 149.3 (C-3′), 149.5 (C-4′), 111.0 (C-5′), 120.1 (C-6′), 78.2 (C-7′), 52.2 (C-8′), 13.8 (C-9′), 56.1, 56.0 (2×OCH3), 101.7 (OCH2O)。以上波譜數(shù)據(jù)與文獻(xiàn)報(bào)道一致[23],故鑒定化合物20為(7′,8′)-3,4-methylenedioxy-3′,4′- dimethoxy-7,8-seco-7,7′-epoxylignan-7,8-dione。

        化合物21:淺黃色油狀物;1H-NMR (400 MHz, CDCl3):6.89 (1H, d,= 6.8 Hz, H-2), 6.75 (1H, d,= 6.8 Hz, H-5), 6.92 (1H, dd,=1.8, 6.8 Hz, H-6), 5.94 (1H, d,= 10.0 Hz, H-7), 3.22 (1H, m, H-8), 2.24 (3H, s, H-9), 7.38 (1H, d,= 7.2 Hz, H-2′), 6.79 (1H, d,= 7.2 Hz, H-5′), 7.59 (1H, dd,= 2.0, 7.2 Hz, H-6′), 5.97 (2H, d,= 1.8 Hz, OCH2O), 6.02 (2H, s, OCH2O);13C-NMR (100 MHz, CDCl3):131.6 (C-1), 106.9 (C-2), 147.4 (C-3), 147.3 (C-4), 107.9 (C-5), 121.7 (C-6), 77.6 (C-7), 208.9 (C-8), 28.5 (C-9), 132.0 (C-1′), 109.9 (C-2′), 152.7 (C-3′), 147.7 (C-4′), 107.3 (C-5′), 125.3 (C-6′), 164.2 (C-7′), 101.1, 101.2 (2×OCH2O)。以上波譜數(shù)據(jù)與文獻(xiàn)報(bào)道一致[24],故鑒定化合物21為machilolin A。

        化合物22:淺黃色油狀物;1H-NMR (400 MHz, CDCl3):7.41 (1H, d,= 1.6 Hz, H-2), 6.83 (1H, d,= 8.0 Hz, H-5), 7.62 (1H, dd,= 1.6, 6.8 Hz, H-6), 5.80 (1H, d,= 10.0 Hz, H-7), 3.20 (1H, m, H-8), 2.24 (3H, s, H-9), 6.62 (2H, s, H-2′, 6′), 3.82 (3H, s, OCH3), 3.86 (6H, s, OCH3), 6.03 (2H, s, OCH2O);13C-NMR (100 MHz, CDCl3):126.5 (C-1), 109.5 (C-2), 152.0 (C-3), 148.1(C-4), 108.3 (C-5), 125.7 (C-6), 164.8 (C-7), 209.5 (C-8), 29.4 (C-9), 133.8 (C-1′), 103.6 (C-2′), 152.3 (C-3′), 137.5 (C-4′), 149.5 (C-5′), 109.5 (C-6′), 78.4 (C-7′), 52.2 (C-8′), 13.8 (C-9′), 56.1, 60.2 (2×OCH3), 102.7 (OCH2O) 以上波譜數(shù)據(jù)與文獻(xiàn)報(bào)道一致[22],故鑒定化合物22為marphenol B。

        化合物23:黃色油狀物;1H-NMR (400 MHz, CDCl3):6.91 (1H, d,= 6.8 Hz, H-2), 6.74 (1H, d,= 6.8 Hz, H-5), 6.93 (1H, dd,=1.8, 6.8 Hz, H-6), 5.95 (1H, d,= 10.0 Hz, H-7), 3.22 (1H, m, H-8), 2.24 (3H, s, H-9), 7.40 (1H, d,= 7.2 Hz, H-2′), 6.77 (1H, d,= 7.2 Hz, H-5′), 7.61 (1H, dd,= 2.0, 7.2 Hz, H-6′), 3.85 (3H, s, OCH3), 3.87 (3H, s, OCH3), 3.89 (3H, s, OCH3), 3.90 (3H, s, OCH3);13C-NMR (100 MHz, CDCl3): 131.3 (C-1), 107.2 (C-2), 147.2 (C-3), 147.1 (C-4), 107.9 (C-5), 121.9 (C-6), 77.8 (C-7), 209.1 (C-8), 28.5 (CH3-9), 132.1 (C-1′), 110.0 (C-2′), 152.5 (C-3′), 147.6 (C-4′), 106.9 (C-5′), 125.5 (C-6′), 164.4 (C-7′), 55.9, 55.9, 56.0, 56.0 (4×OCH3)。以上波譜數(shù)據(jù)與文獻(xiàn)報(bào)道一致[3],故鑒定化合物23為3′,4′-dimethoxy-benzoicacid-(3′′,4′′- dimethoxyphenyl)-3-oxobutylester。

        4 抗氧化活性篩選研究

        采用ABTS+自由基清除的活性篩選技術(shù)[23],以維生素C為陽性對(duì)照,篩選并評(píng)價(jià)單體化合物的抗氧化能力?;衔?~4、13和維生素C分別配制成10.0、5.0、1.0、0.5、0.1、0.01 mmol/L的溶液,測(cè)定ABTS+自由基清除活性,結(jié)果顯示IC50值分別為23.0、16.5、10.8、16.0 μmol/L,表明化合物2~4和13具有一定的抗氧化活性,其中化合物4的抗氧化活性較好,接近陽性對(duì)照維生素C(IC50=7.4 μmol/L)。

        5 討論

        本實(shí)驗(yàn)首次從華中五味子根部的70%丙酮水提取物中分離鑒定了23個(gè)木脂素類化合物;其中,化合物1為四氫呋喃型木脂素,化合物2~4為二芳基丁烷類木脂素,化合物5為二芳基丁內(nèi)酯類木脂素,化合物6~17為聯(lián)苯環(huán)辛烯類木脂素;化合物18~23為7,8-seco-木脂素。化合物6、7、18~20、22為首次從該植物中分離得到,化合物1~5、16、17為首次從五味子屬植物中分離得到?;衔?、3、4和13具有一定的抗氧化活性,其中化合物4的抗氧化活性較好,接近陽性對(duì)照。本研究為進(jìn)一步開發(fā)應(yīng)用華中五味子木脂素類成分提供了可靠的結(jié)構(gòu)及活性信息。

        利益沖突 所有作者均聲明不存在利益沖突

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        Lignans chemical constituents of roots ofand their anti-oxidative effects

        JIANG Kan1, 2, GUO Ye-hong1, 2

        1. College of Agronomy, Gansu Agricultural University, Lanzhou 730070, China 2. State Key Laboratory of Aridland Crop Science, Gansu Agricultural University, Lanzhou 730070, China

        To study the chemical constituents of the roots of.The isolation and purification were carried out by macroporous resin, Sephadex LH-20, silica gel column chromatography, semi-preparative HPLC. Their structures were elucidated on the basis of physicochemical properties and spectroscopic data. The anti-oxidant activity of the compounds was evaluated by ABTS+radical scavenging method.Twenty-three compounds were isolated and elucidated from the roots of, their structures were identified as (?)-zuonin A (1),-1-(4-hydroxy-3-methoxyphenyl)- 4-(3,4-methylenedioxyphenyl)-2,3-dimethylbutane (2), austrobailignan-5 (3), 9,9′-dihydroxy-austrobailignan-5(4), (?)-8-hydroxy-α- conidendrin (5), (?)-gomisin M1 (6), schisandrin B (7), schisandrin C (8), gomisin J (9), (+)-gomisin k3(10), deoxyschizandrin (11),-schizandrin (12), rubrisandrin B (13), marlignans A (14), rubrisandrin A (15), yunnankadsurin B (16), isogomisin O (17), marphenol A (18), (7′,8′)-3,4-dimethoxy-3′,4′-methylenedioxy-7,8-seco-7,7′-epoxylignan-7,8-dione (19), (7′,8′)-3,4- methylenedioxy-3′,4′-dimethoxy-7,8-seco-7,7′-epoxylignan-7,8-dione (20), machilolin-A (21), marphenol B (22) and 3′,4′- dimethoxy-benzoicacid-(3′′,4′′-dimethoxyphenyl)-3-oxobutyl ester (23).Compounds 6, 7, 18—20, 22 are isolated fromfor the first time. Compounds 1—5, 16 and 17 are isolated from the genusfor the first time. Compounds 2—4, 13 were more active than other compounds in the antioxidant activity with IC50value 23.0, 16.5, 10.8 and 16.0 μmol/L, respectively. The antioxidant activity of compound 4 was better, which was closed to the positive control vitamin C.

        Rehd.et Wils; dibenzylbutanes lignans; dibenzoeyelooetadiene lignans; 7,8-seco-lignans; antioxidant activity; austrobailignan-5; (?)-8-hydroxy-α-conidendrin

        R284.1

        A

        0253 - 2670(2022)21 - 6666 - 08

        10.7501/j.issn.0253-2670.2022.21.003

        2022-04-21

        甘肅省自然科學(xué)基金資助項(xiàng)目(21JR7RA805);甘肅農(nóng)業(yè)大學(xué)公招博士科研啟動(dòng)基金項(xiàng)目(GAU-KYQD-2019-01)

        姜 侃(1987—),男,甘肅民勤人,副教授,博士,研究方向?yàn)樘烊凰幬锘瘜W(xué)。E-mail: jiangk19@126.com

        [責(zé)任編輯 王文倩]

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