烏拉爾甘草根異戊烯基黃酮類成分的研究

張其海，邵 嫻，朱翠翠，李 京，莊舒琪，李佳玉，夏芷晴，季 帥

(徐州醫(yī)科大學(xué)藥學(xué)院，江蘇 徐州 221004）

甘草屬于蝶形花科甘草屬植物,又名甜草根、粉草、靈通、國(guó)老等。甘草具有悠久的藥用歷史,享有“十方九草、眾藥之王” 的美譽(yù)。2020 年版《中國(guó)藥典》 收錄烏拉爾甘草、脹果甘草以及光果甘草的干燥根及根莖作為甘草藥材的主要來(lái)源,目前在中國(guó)市場(chǎng)上以烏拉爾甘草Glycyrrhiza uralensisFisch.為主［1］。甘草具有傳統(tǒng)功效以及治療呼吸道感染、胃潰瘍、糖尿病、祛斑美白等現(xiàn)代臨床應(yīng)用［2-3］。甘草中成分主要分為三萜皂苷、黃酮糖苷以及黃酮苷元3 大類,其中三萜皂苷和黃酮糖苷在甘草中含量較高,目前研究較多［4-5］。甘草中的黃酮苷元類成分大多含有異戊烯基取代基(異戊烯基黃酮),被報(bào)道具有顯著的抗腫瘤、抗炎、抗氧化等藥理活性,然而,該類成分在甘草中的含量較低,目前研究較少［6-7］。鑒于此,本實(shí)驗(yàn)采用現(xiàn)代多種色譜分離方法及結(jié)構(gòu)鑒定技術(shù),對(duì)烏拉爾甘草中的異戊烯基黃酮類成分進(jìn)行系統(tǒng)研究,以期為建立該藥材的多指標(biāo)質(zhì)量控制方法及其藥效物質(zhì)基礎(chǔ)研究奠定基礎(chǔ),共分離得15 個(gè)化合物,其中,化合物11～13、15 為首次從該植物中分離得到,化合物2～5 為首次從甘草屬植物中分離得到。

1 材料

Agilent 1290 半制備高效液相色譜儀(美國(guó)安捷倫公司)；JNM-ECZ400S 核磁共振儀(日本Jeol公司)；冷凍干燥機(jī)(美國(guó)Labconco 公司)；柱層析用硅膠 (100～200 目,青島海洋化工有限公司)；Sephadex LH-20 葡聚糖凝膠 (美國(guó)GE 公司)；柱層析用聚酰胺(100～200 目,江蘇長(zhǎng)豐化工有限公司)；GF254硅膠薄層板(安徽良臣硅源材料有限公司)；RE-20000A 旋轉(zhuǎn)蒸發(fā)儀(上海亞榮生化儀器廠)；WFH-203B 暗箱紫外分析儀(杭州齊威儀器有限公司)；色譜純甲醇(美國(guó)JT Baker公司)；乙腈(色譜純,美國(guó)JT Baker 公司)；其他試劑均為分析純。

實(shí)驗(yàn)藥材于2019 年6 月購(gòu)自甘肅省蘭州市,由徐州醫(yī)科大學(xué)藥學(xué)院季帥副教授鑒定為蝶形花科甘草屬植物烏拉爾甘草Glycyrrhiza uralensisFisch.的干燥根及根莖,標(biāo)本(L-201903) 保存于徐州醫(yī)科大學(xué)藥學(xué)院。

2 提取與分離

取樣品干燥根及根莖10 kg,粉碎后用95%乙醇浸泡過(guò)夜,加熱回流提取3 次(2 h/次),過(guò)濾后合并濾液,濃縮得到浸膏。將浸膏用水混懸后依次用石油醚、乙酸乙酯各萃取3 次,得乙酸乙酯部位浸膏800 g。將該浸膏經(jīng)硅膠柱分離,石油醚-乙酸乙酯(100 ∶0～0 ∶100) 梯度洗脫,經(jīng)TLC 薄層色譜結(jié)合HPLC 檢測(cè)得到6 個(gè)流分Fr.1～Fr.6。Fr.1 經(jīng)聚酰胺柱乙醇-水(1 ∶4～9 ∶1) 梯度洗脫、Sephadex LH-20 甲醇洗脫分離后再經(jīng)半制備HPLC得化合物2、8。Fr.2 經(jīng)聚酰胺柱乙醇-水(1 ∶4～9 ∶1) 梯度洗脫、Sephadex LH-20 甲醇洗脫分離后再經(jīng)半制備HPLC 得化合物3、6。Fr.3 通過(guò)重結(jié)晶析出晶體,得化合物1。Fr.4 經(jīng)聚酰胺柱乙醇-水(1 ∶4～9 ∶1) 梯度洗脫、Sephadex LH-20 甲醇洗脫分離后再經(jīng)半制備HPLC 得化合物7、9、12。Fr.5 通過(guò)重結(jié)晶析出晶體,得化合物10,濾液經(jīng)Sephadex LH-20 甲醇洗脫分離后再經(jīng)半制備HPLC 得化合物4～5、15。Fr.6 經(jīng)聚酰胺柱乙醇-水(1 ∶4～9 ∶1) 梯度洗脫、Sephadex LH-20 甲醇洗脫分離后再經(jīng)半制備HPLC 得化合物11、13～14。

3 結(jié)構(gòu)鑒定

化合物2:淡黃色粉末,ESI-MSm/z:403.0［M-H］-,分子式C25H24O5。1H-NMR (400 MHz,DMSO-d6)δ:8.21 (1H,s,H-2),6.28 (1H,s,H-6),7.26 (1H,brs,H-2′),6.79 (1H,d,J=7.2 Hz,H-5′),7.26 (1H,brd,J=7.2 Hz,H-6′),6.44 (1H,d,J=9.6 Hz,H-1″),5.78 (1H,d,J=9.6 Hz,H-2″),1.39 (3H,s,H-4″),1.39 (3H,s,H-5″),3.21 (2H,d,J=6.6 Hz,H-1?),5.19(1H,t,J=6.6 Hz,H-2?),1.72 (3H,s,H-4?),1.62 (3H,s,H-5?)；13C-NMR (100 MHz,DMSOd6)δ:152.4 (C-2),122.8 (C-3),181.1 (C-4),160.5 (C-5),99.5 (C-6),160.5 (C-7),105.1(C-8),154.9 (C-9),106.1 (C-10),123.2 (C-1′),126.7 (C-2′),121.9 (C-3′),153.2 (C-4′),121.0 (C-5′),130.8 (C-6′),116.3 (C-1″),129.3(C-2″),76.4 (C-3″),27.9 (C-4″),27.9 (C-5″),21.4 (C-1?),122.5 (C-2?),134.5 (C-3?),25.5(C-4?),17.6 (C-5?)。以上波譜數(shù)據(jù)與文獻(xiàn)［9］報(bào)道基本一致,故鑒定為ulexone A。

化合物3:白色粉末,ESI-MSm/z:369.2［M-H］-,分子式C20H18O7。1H-NMR (400 MHz,DMSO-d6)δ:4.61 (1H,d,J=7.0 Hz,H-2),4.07(1H,d,J=7.0 Hz,H-2),5.83 (1H,s,H-6),5.83 (1H,s,H-8),6.33 (1H,d,J=8.4 Hz,H-5′),7.23 (1H,d,J=8.4 Hz,H-6′),6.61 (1H,d,J=10.2 Hz,H-1″),5.66 (1H,d,J=10.2 Hz,H-2″),1.33 (3H,s,H-4″),1.33 (3H,s,H-5″)；13C-NMR (100 MHz,DMSO-d6)δ:73.4 (C-2),73.4 (C-3),194.0 (C-4),164.6 (C-5),95.3(C-6),168.0 (C-7),96.4 (C-8),162.3 (C-9),100.3 (C-10),129.2 (C-1′),153.3 (C-2′),110.0 (C-3′),149.7 (C-4′),107.3 (C-5′),127.5(C-6′),116.8 (C-1″),129.2 (C-2″),75.3 (C-3″),27.5 (C-4″),27.4 (C-5″)。以上波譜數(shù)據(jù)與文 獻(xiàn) ［10］ 報(bào)道基本一致,故鑒定為sophoronol A。

化合物4:白色粉末,ESI-MSm/z:404.9［M-H］-,分子式C25H26O5。1H-NMR (400 MHz,DMSO-d6)δ:8.05 (1H,s,H-2),6.16 (1H,s,H-8),7.18 (1H,d,J=2.2 Hz,H-2′),6.81 (1H,d,J=8.2 Hz,H-5′),7.14 (1H,dd,J=8.2,2.2 Hz,H-6′),3.23 (2H,d,J=7.2 Hz,H-1″),5.27(1H,t,J=7.2 Hz,H-2″),1.72 (3H,s,H-4″),1.68 (3H,s,H-5″),3.20 (2H,d,J=7.2 Hz,H-1?),5.23 (1H,t,J=7.2 Hz,H-2?),1.68 (3H,s,H-4?),1.61 (3H,s,H-5?)；13C-NMR (100 MHz,DMSO-d6)δ:152.0 (C-2),123.4 (C-3),180.6 (C-4),158.9 (C-5),111.3 (C-6),161.3(C-7),92.8 (C-8),155.7 (C-9),105.1 (C-10),122.0 (C-1′),129.8 (C-2′),127.7 (C-3′),154.5(C-4′),114.8 (C-5′),127.5 (C-6′),21.1 (C-1″),121.6 (C-2″),132.3 (C-3″),17.4 (C-4″),25.4 (C-5″),28.4 (C-1?),121.7 (C-2?),133.0(C-3?),17.4 (C-4?),25.4 (C-5?)。以上波譜數(shù)據(jù)與文獻(xiàn)［11］ 報(bào)道基本一致,故鑒定為lupalbigenin。

化合物5:白色粉末,ESI-MSm/z:421.1［M-H］-,分子式C25H26O6。1H-NMR (400 MHz,DMSO-d6)δ:7.99 (1H,s,H-2),6.30 (1H,d,J=2.8 Hz,H-3′),6.25 (1H,dd,J=2.8,7.2 Hz,H-5′),6.96 (1H,d,J=7.2 Hz,H-6′),3.21(2H,d,J=7.2 Hz,H-1″),5.11 (1H,t,J=7.2 Hz,H-2″),1.71 (3H,s,H-4″),1.61 (3H,s,H-5″),3.19 (2H,d,J=7.2 Hz,H-1?),5.13 (1H,t,J=7.2 Hz,H-2?),1.71 (3H,s,H-4?),1.61(3H,s,H-5?)；13C-NMR (100 MHz,DMSO-d6)δ:160.7 (C-2),122.1 (C-3),182.6 (C-4),157.8(C-5),108.7 (C-6),158.3 (C-7),106.8 (C-8),153.3 (C-9),105.4 (C-10),112.7 (C-1′),155.1(C-2′),105.8 (C-3′),157.4 (C-4′),111.4 (C-5′),130.9 (C-6′),21.9 (C-1″),121.4 (C-2″),136.0 (C-3″),26.0 (C-4″),18.1 (C-5″),21.9(C-1?),121.1 (C-2?),134.7 (C-3?),26.1 (C-4?),18.1 (C-5?)。以上波譜數(shù)據(jù)與文獻(xiàn)［12］ 報(bào)道基本一致,故鑒定為8-prenylluteone。

化合物6:淡黃色粉末,ESI-MSm/z:335.1［M-H］-,分子式C20H16O5。1H-NMR (400 MHz,DMSO-d6)δ:8.30 (1H,s,H-2),6.20 (1H,d,J=2.0 Hz,H-6),6.36 (1H,d,J=2.0 Hz,H-8),7.28 (1H,d,J=2.4 Hz,H-2′),6.79 (1H,d,J=8.2 Hz,H-5′),7.28 (1H,dd,J=2.4,8.2 Hz,H-6′),6.43 (1H,d,J=9.8 Hz,H-1″),5.77 (1H,d,J=9.8 Hz,H-2″),1.39 (3H,s,H-4″),1.39(3H,s,H-5″)；13C-NMR (100 MHz,DMSO-d6)δ:152.4 (C-2),122.0 (C-3),180.0 (C-4),162.0(C-5),99.3 (C-6),165.1 (C-7),93.9 (C-8),157.7 (C-9),104.2 (C-10),123.3 (C-1′),127.0(C-2′),120.7 (C-3′),154.2 (C-4′),115.7 (C-5′),129.8 (C-6′),121.9 (C-1″),131.4 (C-2″),76.4 (C-3″),27.8 (C-4″),27.8 (C-5″)。以上波譜數(shù)據(jù)與文獻(xiàn) ［13］ 報(bào)道基本一致,故鑒定為isoderrone。

化合物7:白色粉末,ESI-MSm/z:351.2［M-H］-,分子式C21H20O5。1H-NMR (400 MHz,DMSO-d6)δ:3.50 (1H,t,J=10.0 Hz,H-2),4.17 (1H,dd,J=4.6,10.0 Hz,H-2),3.44 (1H,m,H-3),5.57 (1H,d,J=5.4 Hz,H-4),5.92(1H,d,J=1.6 Hz,H-6),6.10 (1H,d,J=1.6 Hz,H-8),6.26 (1H,d,J=7.2 Hz,H-5′),7.04(1H,d,J=7.2 Hz,H-6′),6.34 (1H,d,J=9.6 Hz,H-1″),5.67 (1H,d,J=9.6 Hz,H-2″),1.34(3H,s,H-4″),1.33 (3H,s,H-5″),3.79 (3H,s,5-OCH3)；13C-NMR (100 MHz,DMSO-d6)δ:65.8 (C-2),38.4 (C-3),75.7 (C-4),159.6 (C-5),92.8 (C-6),160.7 (C-7),95.4 (C-8),157.0(C-9),100.2 (C-10),119.5 (C-1′),152.9 (C-2′),105.0 (C-3′),155.1 (C-4′),107.7 (C-5′),124.3 (C-6′),116.0 (C-1″),129.8 (C-2″),75.7(C-3″),27.5 (C-4″),27.3 (C-5″),55.6 (5-OCH3)。以上波譜數(shù)據(jù)與文獻(xiàn)［14］ 報(bào)道基本一致,故鑒定為1-methoxy-phaseollin。

化合物8:白色粉末,ESI-MSm/z:381.2［M-H］-,分子式C22H22O6。1H-NMR (400 MHz,DMSO-d6)δ:8.03 (1H,s,H-2),7.91 (1H,d,J=8.4 Hz,H-5),6.93 (1H,brd,J=8.4 Hz,H-6),6.87 (1H,brs,H-8),6.32 (1H,s,H-5′),3.16 (2H,d,J=6.8 Hz,H-1″),5.11 (1H,t,J=6.8 Hz,H-2″),1.69 (3H,s,H-4″),1.62 (3H,s,H-5″),3.37 (3H,s,-OCH3),3.74 (3H,s,-OCH3)；13C-NMR (100 MHz,DMSO-d6)δ:155.5(C-2),118.6 (C-3),175.2 (C-4),127.1 (C-5),114.9 (C-6),162.4 (C-7),102.2 (C-8),157.7(C-9),116.7 (C-10),105.7 (C-1′),157.8 (C-2′),112.8 (C-3′),158.2 (C-4′),95.2 (C-5′),155.5 (C-6′),22.3 (C-1″),124.0 (C-2″),129.6(C-3″),17.6 (C-4″),25.5 (C-5″),55.5(-OCH3),60.6 (-OCH3)。以上波譜數(shù)據(jù)與文獻(xiàn)［15］ 報(bào)道基本一致,故鑒定為甘草利酮。

化合物9:白色粉末,ESI-MSm/z:350.9［M-H］-,分子式C21H20O5。1H-NMR (400 MHz,DMSO-d6)δ:5.40 (2H,s,H-2),6.29 (1H,s,H-8),6.97 (1H,d,J=2.0 Hz,H-3′),6.76 (1H,dd,J=2.0,8.4 Hz,H-5′),7.31 (1H,d,J=8.4 Hz,H-6′),3.19 (2H,d,J=6.8 Hz,H-1″),5.16(1H,t,J=6.8 Hz,H-2″),1.73 (3H,s,H-4″),1.63 (3H,s,H-5″),3.74 (3H,s,5-OCH3)；13CNMR (100 MHz,DMSO-d6)δ:64.1 (C-2),106.2(C-3),145.0 (C-4),155.3 (C-5),115.2 (C-6),152.9 (C-7),99.9 (C-8),156.7 (C-9),102.6(C-10),117.2 (C-1′),156.0 (C-2′),98.1 (C-3′),153.4 (C-4′),112.2 (C-5′),119.0 (C-6′),22.0 (C-1″),123.6 (C-2″),130.0 (C-3″),17.8(C-4″),25.6 (C-5″),61.6 (5-OCH3)。以上波譜數(shù)據(jù)與文獻(xiàn)［16］ 報(bào)道基本一致,故鑒定為glyurallin A。

化合物10:淡黃色晶體,ESI-MSm/z:365.1［M-H］-,分子式C21H18O6。1H-NMR (400 MHz,DMSO-d6)δ:6.76 (1H,s,H-8),7.16 (1H,d,J=2.0 Hz,H-3′),6.94 (1H,dd,J=2.0,8.2 Hz,H-5′),7.70 (1H,d,J=8.2 Hz,H-6′),3.34(2H,d,J=7.2 Hz,H-1″),5.18 (1H,t,J=7.2 Hz,H-2″),1.76 (3H,s,H-4″),1.64 (3H,s,H-5″),3.89 (3H,s,5-OCH3)；13C-NMR (100 MHz,DMSO-d6)δ:158.2 (C-2),102.2 (C-3),156.0(C-4),153.9 (C-5),119.7 (C-6),159.5 (C-7),99.2 (C-8),152.9 (C-9),99.8 (C-10),114.3(C-1′),156.1 (C-2′),98.5 (C-3′),156.1 (C-4′),114.0 (C-5′),120.5 (C-6′),22.1 (C-1″),122.4 (C-2″),130.9 (C-3″),17.7 (C-4″),25.5(C-5″),62.4 (5-OCH3)。以上波譜數(shù)據(jù)與文獻(xiàn)［17］ 報(bào)道基本一致,故鑒定為甘草酚。

對(duì)于初中生而言，年齡相對(duì)較小，對(duì)任何事情都具有著很大的好奇心，因此只要初中語(yǔ)文教師注重活躍課堂氛圍，就很容易將學(xué)生帶到相應(yīng)的情境之中，激發(fā)他們的學(xué)習(xí)興趣。在過(guò)去傳統(tǒng)的初中語(yǔ)文教學(xué)中，教師并不重視課堂氛圍，只是簡(jiǎn)單地講授知識(shí)點(diǎn)，造成學(xué)生認(rèn)為語(yǔ)文學(xué)習(xí)枯燥乏味，出現(xiàn)排斥心理，影響到初中語(yǔ)文的教學(xué)質(zhì)量。因此，為了打破過(guò)去教學(xué)方法的束縛，教師應(yīng)該積極使用多元化的教學(xué)方法。在講課的過(guò)程中，教師可以面帶微笑，在課堂上營(yíng)造出輕松、活躍的課堂氛圍，通過(guò)提問(wèn)或是小故事等形式引導(dǎo)學(xué)生積極發(fā)言，多與學(xué)生進(jìn)行互動(dòng)。例如在講述詩(shī)歌古文時(shí)，教師可以以小組為單位舉行朗誦比賽，讓學(xué)生們扮演詩(shī)人來(lái)抒發(fā)自己的情懷等。

化合物11:淡黃色粉末,ESI-MSm/z:321.2［M-H］-,分子式:C20H18O4。1H-NMR (400 MHz,DMSO-d6)δ:4.88 (2H,s,H-2),6.52 (1H,s,H-4),6.99 (1H,d,J=8.2 Hz,H-5),6.33 (1H,dd,J=8.2,2.2 Hz,H-6),6.24 (1H,d,J=2.2 Hz,H-8),6.39 (1H,d,J=8.4 Hz,H-5′),6.92(1H,d,J=8.4 Hz,H-6′),6.57 (1H,d,J=10.0 Hz,H-1″),5.63 (1H,d,J=10.0 Hz,H-2″),1.37(3H,s,H-4″),1.37 (3H,s,H-5″)；13C-NMR(100 MHz,DMSO-d6)δ:67.7 (C-2),127.8 (C-3),119.9 (C-4),127.5 (C-5),108.9 (C-6),158.1 (C-7),102.4 (C-8),154.0 (C-9),117.6(C-10),115.4 (C-1′),150.6 (C-2′),108.7 (C-3′),153.2 (C-4′),108.2 (C-5′),127.8 (C-6′),116.9 (C-1″),128.4 (C-2″),75.8 (C-3″),27.3(C-4″),27.3 (C-5″)。以上波譜數(shù)據(jù)與文獻(xiàn)［18］報(bào)道基本一致,故鑒定為光甘草素。

化合物12:黃色粉末,ESI-MSm/z:363.1［M-H］-,分子式C21H16O6。1H-NMR (400 MHz,DMSO-d6)δ:6.82 (1H,s,H-8),7.19 (1H,d,J=1.8 Hz,H-3′),6.93 (1H,dd,J=1.8,8.4 Hz,H-5′),7.73 (1H,d,J=8.4 Hz,H-6′),6.69(1H,d,J=10.2 Hz,H-1″),5.96 (1H,d,J=10.2 Hz,H-2″),1.45 (3H,s,H-4″),1.45 (3H,s,H-5″),3.96 (3H,s,5-OCH3)；13C-NMR (100 MHz,DMSO-d6)δ:157.3 (C-2),103.4 (C-3),157.9(C-4),151.2 (C-5),112.3 (C-6),156.4 (C-7),100.9 (C-8),154.3 (C-9),101.5 (C-10),114.4(C-1′),156.5 (C-2′),98.8 (C-3′),157.4 (C-4′),114.5 (C-5′),120.8 (C-6′),115.1 (C-1″),131.7 (C-2″),77.9 (C-3″),28.0 (C-4″),28.0(C-5″),63.1 (5-OCH3)。以上波譜數(shù)據(jù)與文獻(xiàn)［17］ 報(bào)道基本一致,故鑒定為gancaonin F。

化合物13:白色粉末,ESI-MSm/z:323.0［M-H］-,分子式C20H20O4。1H-NMR (400 MHz,DMSO-d6)δ:4.16 (1H,br d,J=10.4 Hz,H-2),3.91 (1H,t,J=10.4 Hz,H-2),3.28 (1H,m,H-3),2.68 (1H,dd,J=15.0,4.4 Hz,H-4),2.86(1H,dd,J=15.0,11.0 Hz,H-4),6.87 (1H,d,J=8.4 Hz,H-5),6.30 (1H,dd,J=8.4,2.2 Hz,H-6),6.31 (1H,d,J=2.2 Hz,H-8),6.18 (1H,d,J=8.8 Hz,H-5′),6.82 (1H,d,J=8.8 Hz,H-6′),6.58 (1H,d,J=10.0 Hz,H-1″),5.63 (1H,d,J=10.0 Hz,H-2″),1.39 (3H,s,H-4″),1.39(3H,s,H-5″)；13C-NMR (100 MHz,DMSO-d6)δ:69.3 (C-2),31.0 (C-3),29.9 (C-4),130.1 (C-5),107.6 (C-6),156.5 (C-7),102.5 (C-8),154.6 (C-9),112.7 (C-10),118.9 (C-1′),150.6(C-2′),108.9 (C-3′),152.0 (C-4′),108.0 (C-5′),127.0 (C-6′),117.2 (C-1″),128.4 (C-2″),75.4 (C-3″),27.3 (C-4″),27.3 (C-5″)。以上波譜數(shù)據(jù)與文獻(xiàn)［19］ 報(bào)道基本一致,故鑒定為1-phaseollinisoflavan。

化合物14:白色粉末,ESI-MSm/z:351.2［M-H］-,分子式C21H20O5。1H-NMR (400 MHz,DMSO-d6)δ:8.42 (1H,s,H-2),6.73 (1H,s,H-8),7.41 (1H,d,J=9.0 Hz,H-2′),6.85 (1H,d,J=9.0 Hz,H-3′),6.85 (1H,d,J=9.0 Hz,H-5′),7.41 (1H,d,J=9.0 Hz,H-6′),3.25 (2H,d,J=7.0 Hz,H-1″),5.16 (1H,t,J=7.0 Hz,H-2″),1.72 (3H,s,H-4″),1.62 (3H,s,H-5″),3.91 (3H,s,7-OCH3)；13C-NMR (100 MHz,DMSO-d6)δ:154.2 (C-2),122.5 (C-3),180.4(C-4),157.5 (C-5),111.7 (C-6),162.9 (C-7),90.2 (C-8),155.9 (C-9),105.3 (C-10),121.2(C-1′),130.2 (C-2′),115.1 (C-3′),157.5 (C-4′),115.1 (C-5′),130.2 (C-6′),21.0 (C-1″),121.9 (C-2″),131.1 (C-3″),25.5 (C-4″),17.7(C-5″)。以上波譜數(shù)據(jù)與文獻(xiàn)［17］ 報(bào)道基本一致,故鑒定為gancaonin G。

化合物15:白色粉末,ESI-MSm/z:421.1［M-H］-,分子式C25H26O6。1H-NMR (400 MHz,DMSO-d6)δ:4.28 (2H,d,J=7.6 Hz,H-2),4.04(1H,t,J=7.6 Hz,H-3),5.72 (1H,s,H-8),6.31 (1H,d,J=8.4 Hz,H-5′),6.74 (1H,d,J=8.4 Hz,H-6′),3.06 (2H,d,J=7.0 Hz,H-1″),5.14 (1H,t,J=7.0 Hz,H-2″),1.68 (3H,s,H-4″),1.60 (3H,s,H-5″),6.55 (1H,d,J=10.0 Hz,H-1?),5.72 (1H,d,J=10.0 Hz,H-2?),1.27 (3H,s,H-4?),1.27 (3H,s,H-5?)；13CNMR (100 MHz,DMSO-d6)δ:70.3 (C-2),46.7(C-3),197.9 (C-4),164.4 (C-5),108.1 (C-6),161.5 (C-7),94.5 (C-8),161.2 (C-9),102.6(C-10),109.6 (C-1′),151.2 (C-2′),114.0 (C-3′),153.2 (C-4′),108.2 (C-5′),130.7 (C-6′),21.3 (C-1″),123.2 (C-2″),129.2 (C-3″),26.0(C-4″),18.3 (C-5″),117.3 (C-1?),129.0 (C-2?),76.4 (C-3?),27.7 (C-4?),28.0 (C-5?)。以上波譜數(shù)據(jù)與文獻(xiàn)［20］ 報(bào)道基本一致,故鑒定為licoisoflavanone C。

4 討論

甘草是一種常用中藥,其化學(xué)成分(黃酮糖苷、三萜皂苷、簡(jiǎn)單黃酮以及異戊烯基黃酮) 研究已有較多報(bào)道。然而,甘草中的異戊烯基黃酮類成分在甘草的各類成分中含量最低,研究相對(duì)較少。本實(shí)驗(yàn)采用多種色譜和光譜技術(shù),從烏拉爾甘草中分離并鑒定了15 個(gè)異戊烯基黃酮類化合物,其具有顯著的抗腫瘤、抗炎、抗氧化等多種藥理活性,本研究結(jié)果在一定程度上豐富了甘草的異戊烯基黃酮類化學(xué)成分,以期有助于開發(fā)其潛在的藥用價(jià)值。同時(shí),也為甘草的質(zhì)量標(biāo)準(zhǔn)及藥效物質(zhì)研究奠定基礎(chǔ),促進(jìn)了甘草的進(jìn)一步開發(fā)利用。