线叶报春苣苔[Primulina linearifolia (W. T. Wang)Yin Z. Wang]为苦苣苔科(Gesneriaceae)报春苣苔属(Primulina)多年生草本，壮药名为接骼红，中药名为接骨草，广西地域性壮族药用植物，主要分布于中国广西南部，例如南宁市邕宁区、大新县、隆安县、武鸣区[1]；其根状茎可供药用，有清热解毒之效，用于调气道、续筋骨、散瘀肿，治疗劳伤咳嗽、骨折、跌打肿痛等病症[1, 2]。
本课题组前期报道了线叶报春苣苔含有多种醌类成分(蒽醌、α-董尼酮、萘骈董尼酮)，并具有优良抗肿瘤作用[3]，但关于该植物的其他成分，国内外目前尚无研究报道，仅有植物生理方面的报道[4]。其同属植物的化学成分或药理研究方面，蚂蝗七[P.fimbrisepala (Hand.-Mazz.)Yin Z. Wang]含有黄酮和甾醇苷类[5]；牛耳朵[P.eburnea (Hance)Yin Z. Wang]含有蒽醌和苯乙醇苷类，其苯乙醇苷类具有抗癌活性[6-8]；报春苣苔(P.tabacum Hance)含有的阿克苷具有抗肿瘤及抗肿瘤转移、抗凋亡作用[9, 10]；红药[P.longgangensis (W. T. Wang) Yan Liu & Yin Z. Wang]含蒽醌、香草酸、车前草苷、三萜及苷类等[11-13]。
除了上述典籍记载的药用价值[1, 2]，根据历次广西植物资源普查科考研究得知，在桂南马山、武鸣、隆安等区县，民间也称线叶报春苣苔为红接骨草、吊石牛，全草用于劳伤咳嗽、崩漏、肝炎，外治跌打损伤、骨折、消肿，是壮族民间赤脚医生的常用药。但该药用植物除其所含醌类被报道外[4]，其他化学成分未见有相关研究，药效物质基础不明，药材质量标准尚未制定。本研究较系统地对其化学成分进行研究，拟为该药用植物传统药效的物质基础研究、质量标准制定和开发应用提供借鉴。
1 材料与方法 1.1 植物药材线叶报春苣苔药材采集于广西南宁市隆安县，生长于该县山地的石山荫处及疏林中石上，经广西中医药大学朱意麟实验师和韦松基教授鉴定为苦苣苔科报春苣苔属线叶报春苣苔[Primulina linearifolia (W. T. Wang)Yin Z. Wang]。药材全株，阴干、粉碎，于4 ℃密闭保存备用。
1.2 仪器与试剂Waters Auto Spec Premier P776质谱仪(Waters，美国)；Bruker Avance-500型和Bruker AM-800型核磁共振波谱仪(Bruker，瑞士)；ZF-2三用紫外仪(上海市安亭电子仪器厂)；XT4-100A显微熔点测定仪(北京市科仪电光仪器厂)。
柱层析硅胶GF254(200-300目、300-400目)和薄层用硅胶G板(青岛海洋化工有限公司)；D101大孔吸附树脂(上海展云化工有限公司)；聚酰胺柱色谱填料(80-120目，100-200目，常州市长丰化工有限公司)；Sephadex LH-20(法玛西亚公司，瑞典)；ODS柱色谱填料(YMC公司，日本)；MCI(三菱化学公司，日本)；乙醇、石油醚、乙酸乙酯、二氯甲烷、三氯甲烷、丙酮、甲醇(分析纯，成都市科隆化学品有限公司)。
1.3 方法线叶报春苣苔全草粗粉8.65 kg，用15倍量85%乙醇，在60 ℃条件下热搅拌，重复提取3次，每次12 h；滤渣在相同条件下，用15倍量50%乙醇重复提取3次，每次12 h。合并提取液，减压浓缩，浓缩液水浴挥干至无醇味，并加适量水混悬，依次用石油醚(沸程60-90 ℃)、乙酸乙酯、正丁醇萃取，将萃取液分别减压浓缩，得石油醚部位(140.0 g)、乙酸乙酯部位(160.0 g)、正丁醇部位(205.0 g)、水部位(203.0 g)。
取石油醚部位130.0 g，经硅胶柱层析(100-200目)，用石油醚-乙酸乙酯(100∶1→50∶1→25∶1→15∶1→8∶1→5∶1→3∶1→2∶1→1∶1→0∶1, V/V)梯度洗脱，得20个流分；各流分分别经硅胶柱色谱(200-300目，流动相为石油醚-乙酸乙酯或石油醚-丙酮)反复分离，并结合Sephadex LH-20柱色谱(三氯甲烷∶甲醇=1∶1, V/V)和重结晶进行纯化，最终获得10个化合物：1(5 mg)、2(4 mg)、3(300 mg)、4(5 mg)、5(3 mg)、6(3 mg)、7(3 mg)、8(5 mg)、9(150 mg)、10(30 mg)。
取乙酸乙酯部位130.0 g，用硅胶柱色谱(100-200目)分离，先以石油醚-乙酸乙酯(100∶1→15∶1, V/V)洗脱，接着用三氯甲烷-甲醇(100∶1→25∶1→15∶1→8∶1→5∶1→3∶1→2∶1→1∶1→0∶1, V/V)洗脱；各流分经硅胶柱色谱(200-300目，流动相为石油醚-二氯甲烷)反复分离，并结合Sephadex LH-20柱色谱(三氯甲烷∶甲醇=1∶1, V/V)和重结晶进行纯化，最终获得4个化合物：11(7 mg)、12(6 mg)、13(9 mg)、14(6 mg)。
取正丁醇部位150.0 g，用大孔树脂(D101)柱色谱进行分离，采用水→30%乙醇→50%乙醇→70%乙醇→无水乙醇梯度洗脱；所得各流分，根据极性等特性差异，分别用聚酰胺柱色谱(100-200目，水→30%乙醇→50%乙醇→70%乙醇→无水乙醇洗脱)或硅胶柱色谱(200-300目，三氯甲烷-甲醇：20∶1→10∶1→0∶1，V/V)或反相ODS柱色谱(水→30%乙醇→50%乙醇→70%乙醇→100%乙醇)进一步分离，最终获得3个化合物：15(7 mg)、16(9 mg)、17(8 mg)。
2 结果与分析化合物1：无色粉末，m.p.87-89 ℃。EI-MS (m/z): 410[M]+。1H-NMR (500 MHz, CDCl3) δ: 0.88 (3H, t, J=7.1 Hz, H-27), 1.25 (46H, m, H-4-26), 1.63 (2H, m, H-3), 2.35 (2H, t, J=7.5 Hz, H-2);13C-NMR and DEPT (125 MHz, CDCl3) δ: 14.1 (CH3, C-27), 22.7 (CH2, C-26), 24.7 (CH2, C-3), 29.1-29.7 (CH2, C-4-24), 31.9 (CH2, C-25), 34.1 (CH2, C-2), 180.3 (qC, C-1)。以上数据与文献[14]报道基本一致，化合物1鉴定为二十七酸(Heptacosanoic acid, C27H54O2)。
化合物2：白色粉末，m.p.52-53 ℃。EI-MS (m/z): 412 [M]+。1H-NMR (500 MHz, CDCl3) δ: 5.35 (2H, m, H-13, 14), 4.21 (1H, dd, J=11.5, 5.0 Hz, H-1′a), 4.15 (1H, dd, J=11.5, 5 Hz, H-1′b), 3.93 (1H, m, H-2′), 3.70 (1H, dd, J=11.5, 6.0 Hz, H-3′a), 3.60 (1H, dd, J=11.5, 6.0 Hz, H-3′b), 2.35 (2H, t, J=7.6 Hz, H-2), 2.20 (2H, t, J=7.5 Hz, H-15), 2.00 (2H, m, H-12), 1.63 (2H, m, H-3), 1.26 (28H, m, H-4-11, H-16-21), 0.88 (3H, t, J=7.5 Hz, H-22)；13C-NMR and DEPT (125 MHz, CDCl3) δ: 174.4 (qC, C-1), 129.9 (CH, C-13), 129.9 (CH, C-14), 70.2 (CH, C-2′), 65.2 (CH2, C-1′), 63.3 (CH2, C-3′), 35.9 (CH2, C-2), 34.1 (CH2, C-12, 15), 31.9 (CH2, C-20), 29.8, 29.6, 29.6, 29.5, 29.5, 29.4, 29.4, 29.3, 29.2, 29.1, 27.2, 25.5 (CH2, C-4-11, C-16-19), 24.9 (CH2, C-3), 22.7 (CH2, C-21), 14.1 (CH3, C-22)。对照文献[15]的核磁数据，化合物2鉴定为芥酸单甘油酯(Monoerucin, C25H48O4)。
化合物3：无色针状结晶，m.p.141-142 ℃。EI-MS (m/z): 414 [M]+。1H-NMR (500 MHz, CDCl3) δ: 5.35 (1H, m, H-6), 3.52 (1H, m, H-3)；13C-NMR and DEPT (125 MHz, CDCl3) δ: 140.5 (qC, C-5), 121.9 (CH, C-6), 71.9 (CH, C-3), 56.8 (CH, C-14), 56.1 (CH, C-17), 50.3 (CH, C-9), 46.0 (CH, C-24), 42.2 (qC, C-13), 40.0 (CH2, C-4), 39.7 (CH2, C-12), 37.3 (CH2, C-1), 36.6 (qC, C-10), 36.2 (CH, C-20), 34.0 (CH2, C-22), 31.8 (CH2, C-7), 31.8 (CH, C-8), 31.1 (CH2, C-2), 29.3 (CH, C-25), 28.4 (CH2, C-16), 26.2 (CH2, C-23), 24.5 (CH2, C-15), 23.1 (CH2, C-28), 21.3 (CH2, C-11), 20.1 (CH3, C-27), 19.5 (CH3, C-19), 19.0 (CH3, C-26), 18.9 (CH3, C-21), 12.3 (CH3, C-29), 12.0 (CH3, C-18)。对照文献[16]的核磁数据，化合物3鉴定为β-谷甾醇(β-Sitosterol, C29H50O)。
化合物4：无色针状结晶，易溶于三氯甲烷，m.p.85-87 ℃。EI-MS (m/z): 412[M]+。1H-NMR (500 MHz, CDCl3) δ: 5.72 (1H, s, H-4), 2.40 (2H, m, H-2)；13C-NMR and DEPT (125 MHz, CDCl3) δ: 11.9 (CH3, C-18), 11.9 (CH3, C-29), 17.4 (CH3, C-26), 18.7 (CH3, C-21), 19.0 (CH3, C-19), 19.8 (CH3, C-27), 21.0 (CH2, C-11), 23.0 (CH2, C-28), 24.2 (CH2, C-15), 26.0 (CH, C-25), 28.2 (CH2, C-16), 29.1 (CH2, C-23), 32.0 (CH2, C-2), 32.9 (CH2, C-6), 33.8 (CH2, C-7), 34.0 (CH2, C-22), 35.6 (CH2, C-1), 35.7 (CH, C-8), 36.1 (CH, C-20), 38.6 (qC, C-10), 39.6 (CH2, C-12), 42.4 (qC, C-13), 45.8 (CH, C-24), 53.8 (CH, C-9), 55.8 (CH, C-17), 56.0 (CH, C-14), 123.7 (CH, C-4), 171.7 (qC, C-5), 199.7 (qC, C-3)。以上数据与文献[17]报道基本一致，化合物4鉴定为β-扶桑甾醇氧化物(β-sitostenone，C29H48O)。
化合物5：无色片状结晶，m.p.76-77 ℃。EI-MS (m/z): 586 [M]+。1H-NMR (800 MHz, CDCl3) δ: 7.08 (2H, d, J=8.4 Hz, H-2, 6), 6.76 (2H, J = 8.4 Hz, H-3, 5), 4.23 (2H, t, J=7.1 Hz, H-8), 2.86 (2H, t, J=7.1 Hz, H-7), 2.27 (2H, t, J=7.6 Hz, H-2′), 1.58 (2H, m, H-3′), 1.25 (64H, m, H-4′-30′), 0.88 (3H, t, J=7.1 Hz, H-31′)；13C-NMR and DEPT (200 MHz, CDCl3) δ: 173.9 (qC, C-1′), 154.2 (qC, C-4), 130.1 (CH, C-2, 6), 129.9 (qC, C-1), 115.3 (CH, C-3, 5), 64.9 (C-8), 34.3 (C-7), 34.3 (C-2′), 31.9 (C-29′), 29.1-29.7 (C-4′-28′), 24.9 (C-3′), 22.7 (C-30′), 14.1 (CH3, C-31′)。对照文献[18]的Heitziethanoid A光谱数据，化合物5结构鉴定为三十一烷酸对羟基苯乙酯[Hentriacontanoic acid, 2-(4-hydroxyphenyl)ethyl ester, C39H70O3]。
化合物6：无色簇状结晶，m.p.210-212 ℃。EI-MS (m/z): 168 [M]+。1H-NMR (800 MHz, CD3OD) δ: 7.51 (1H, d, J=1.9 Hz, H-2), 7.55 (1H, dd, J=8.3, 1.9 Hz, H-6), 6.83 (1H, d, J=8.3 Hz, H-5), 3.87 (3H, s, OCH3)；13C-NMR and DEPT (200 MHz, CD3OD) δ: 169.5 (qC, C-7), 151.3 (qC, C-4), 147.5 (qC, C-3), 124.6 (CH, C-6), 122.3 (qC, C-1), 115.0 (CH, C-5), 113.0 (CH, C-2), 56.1 (OCH3)。以上数据与文献[19]报道基本一致，故化合物6鉴定为香草酸(Vanillic acid, C8H8O4)。
化合物7：无色片状结晶，m.p.290-291 ℃。EI-MS (m/z): 456[M]+。1H-NMR (800 MHz, CDCl3) δ: 5.25 (1H, t, J=3.8 Hz, H-12), 3.22 (1H, dd, J=11.5, 4.6Hz, H-3)；13C-NMR and DEPT (200 MHz, CDCl3) δ: 181.8 (qC, C-28), 137.9 (qC, C-13), 125.8 (CH, C-12), 79.0 (CH, C-3), 55.2 (CH, C-5), 52.6 (CH, C-18), 47.9 (qC, C-17), 47.5 (CH, C-9), 42.0 (qC, C-14), 39.5 (qC, C-10), 39.0 (CH, C-20), 38.8 (CH, C-19), 38.7 (qC, C-4), 38.6 (CH2, C-22), 37.0 (qC, C-8), 36.7 (CH2, C-1), 32.9 (CH2, C-7), 30.6 (CH2, C-21), 28.1 (CH3, C-23), 28.0 (CH2, C-2), 27.2 (CH2, C-15), 24.1 (CH2, C-16), 23.6 (CH3, C-27), 23.3 (CH2, C-11), 21.2 (CH3, C-30), 18.3 (CH2, C-6), 17.0 (CH3, C-26), 17.0 (CH3, C-29), 15.6 (CH3, C-24), 15.5 (CH3, C-25)。化合物7光谱数据与熊果酸数据[20]基本一致，故确定化合物7为熊果酸(Ursolic acid, C30H48O3)。
化合物8：白色粉末，m.p.92-94 ℃。EI-MS (m/z): 498 [M]+。1H-NMR (800 MHz, CD3OD) δ: 4.05 (2H, m, H-1′), 3.81 (1H, m, H-2′), 3.55 (1H, dd, J=11.5, 4.2 Hz, H-3′a), 3.48 (1H, dd, J=11.5, 6.2 Hz, H-3′b), 2.28 (2H, t, J=7.6 Hz, H-2), 1.55 (2H, t, J=7.6 Hz, H-3), 1.14-1.38 (48H, m, H-4-27), 0.81 (3H, t, J=7.0 Hz, H-28)；13C-NMR and DEPT (200 MHz, CD3OD) δ: 174.6 (qC, C-1), 70.0 (CH, C-2′), 65.2 (CH2, C-1′), 63.2 (CH2, C-3′), 34.9 (CH2, C-2), 31.9 (CH2, C-26), 29.1-29.7 (CH2, C4-25), 24.9 (CH2, C-3), 22.7 (CH2, C-27), 14.0 (CH3, C-28)。对照文献[21]中的二十二(或二十四)酸甘油酯波谱数据进行归属，化合物8鉴定为1-二十八酸甘油酯(1-Octacosanoyl glyceride, C31H62O4)。
化合物9：白色粉末，m.p.301-303 ℃，易溶于三氯甲烷、甲醇。EI-MS (m/z): 398 [M-C6H11O6]+。1H-NMR(500 MHz，Pyridine-d6)δ: 5.33 (1H, m, H-6), 4.36 (1H, d, J=7.9 Hz, H-1′), 3.79-3.81 (1H, m, H-3′), 3.68-3.70 (1H, m, H-4′), 3.53-3.57 (1H, m, H-3), 3.35-3.37 (2H, m, H-6′), 3.23-3.24 (1H, m, H-5′), 3.16-3.19 (1H, m, H-2′)；13C-NMR and DEPT (125 MHz，Pyridine-d6) δ: 140.7 (qC, C-5), 122.4 (CH, C-6), 101.5 (CH, C-1′), 79.5 (CH, C-3), 76.9 (CH, C-3′), 76.3 (CH, C-5′), 74.0 (CH, C-2′), 70.6 (CH, C-4′), 62.1 (CH2, C-6′), 57.1 (CH, C-17), 56.4 (CH, C-14), 50.6 (CH, C-9), 46.2 (CH, C-24), 42.7 (qC, C-13), 40.1 (CH2, C-12), 39.0 (CH2, C-4), 37.6 (CH2, C-1), 37.1 (qC, C-10), 36.5 (CH, C-20), 34.3 (CH2, C-22), 32.3 (CH2, C-7), 32.3 (CH, C-8), 29.9 (CH2, C-25), 29.5 (CH, C-16), 28.6 (CH2, C-2), 26.4 (CH2, C-23), 24.6 (CH2, C-15), 23.4 (CH2, C-28), 21.4 (CH2, C-11), 20.0 (CH3, C-21), 19.6 (CH3, C-26), 19.2 (CH3, C-19), 19.0 (CH3, C-27), 12.2 (CH3, C-18), 12.1 (CH3, C-29)。以上数据与文献[22, 23]报道基本一致，故化合物9鉴定为胡萝卜苷(Daucosterol, C35H60O6)。
化合物10：灰白色固体，m.p.187-189 ℃。ESI-MS (m/z): 477[M-H]-。1H-NMR (800 MHz, CD3OD) δ: 6.70 (1H, d, J=2.0 Hz, H-2), 6.69 (1H, d, J=8.0 Hz, H-5), 6.53 (1H, dd, J=8.0, 2.0 Hz, H-6), 3.62 (2H, m, H-8), 2.77 (2H, m, H-7)(phenethyl alcohol moiety); 7.56 (1H, d, J=15.8 Hz, H-7′), 7.01 (1H, d, J=2.0 Hz, H-2′), 6.88 (1H, dd, J=8.0, 2.0 Hz, H-6′), 6.76 (1H, d, J=8.0 Hz, H-5′), 6.22 (1H, d, J=15.8 Hz, H-8′)(caffeic acid moiety); 4.83 (1H, t, J=9.6 Hz, H-4″), 4.31 (1H, d, J=7.8 Hz, H-1″), 3.70 (1H, m, H-3″), 3.54 (1H, m, H-5″), 3.43 (1H, m, H-2″), 3.31 (2H, m, H-6″)(glucose moiety)。13C-NMR and DEPT (200 MHz, CD3OD) δ: 144.9 (qC, C-3), 143.5 (qC, C-4), 130.7 (qC, C-1), 120.7 (CH, C-6), 116.3 (CH, C-2), 115.6 (CH, C-5), 71.4 (CH2, C-8), 35.7 (CH2, C-7)(phenethyl alcohol moiety); 168.2 (qC, C-9′), 148.6 (qC, C-4′), 147.3 (CH, C-7′), 145.6 (qC, C-3′), 126.8 (qC, C-1′), 122.6 (CH, C-6′), 115.8 (CH, C-5′), 114.6 (CH, C-2′), 113.7 (CH, C-8′)(caffeic acid moiety); 103.3 (CH, C-1″), 78.0 (CH, C-4″), 75.1 (CH, C-2″), 74.7 (CH, C-5″), 74.3 (CH, C-3″), 61.6 (CH2, C-6″)(glucose moiety)。对照文献[10, 24]的核磁数据，化合物10鉴定为木通苯乙醇苷A(Calceolarioside A, C23H26O11)。
化合物11：白色粉末，溶于甲醇，盐酸-镁粉反应呈阳性，m.p.254-255 ℃。EI-MS (m/z): 450[M]+。1H-NMR (500 MHz, CD3OD) δ: 6.89(1H, s, H-2′), 6.76(2H, s, H-5′, 6′), 5.95(1H, s, H-8), 5.30 (1H, dd，J=12.3, 3.0 Hz, H-2), 4.78(1H, d, J=9.9 Hz, H-1″), 4.10(1H, m, H-2″), 3.85 (1H, d, J=12.0 Hz, H-6″), 3.71 (1H, dd，J=12.0, 5.4 Hz, H-6″), 3.35-3.43 (3H, m, H-3″, 4″, 5″), 3.10(1H, dd, J=17.2, 12.3 Hz, H-3), 2.75 (1H, dd, J=17.2, 3.0 Hz, H-3)；13C-NMR and DEPT (125 MHz, CD3OD) δ: 198.1 (qC, C-4), 167.3 (qC, C-7), 164.3 (qC, C-5), 164.2 (qC, C-9), 146.9 (qC, C-4′), 146.5 (qC, C-3′), 131.6 (qC, C-1′), 119.2 (CH, C-6′), 116.2 (CH, C-5′), 114.7 (CH, C-2′), 105.9 (qC, C-6), 103.2 (qC, C-10), 96.3 (CH, C-8), 82.5 (CH, C-5″), 80.5 (CH, C-3″), 80.2 (CH, C-2), 75.2 (CH, C-1″), 72.6 (CH, C-2″), 71.8 (CH, C-4″), 62.9 (CH2, C-6″), 44.0 (CH2, C-3)。化合物11光谱数据与文献中5, 7, 3′, 4′-四羟基-6-C-β-D-葡萄糖二氢黄酮碳苷的数据[25]一致，故鉴定其为5, 7, 3′, 4′-四羟基-6-C-β-D-葡萄糖二氢黄酮碳苷(5, 7, 3′, 4′-tetrahydroxy -6-C-β-D- glucosyl-dihydroflavonol, C21H22O11)。
化合物12：灰白色固体，易吸潮，m.p.136-138 ℃。经FeCl3-K3[Fe (CN)6]试剂鉴别，显蓝色，可能为酚类物质。ESI-MS (m/z): 639 [M-H]-。1H-NMR (500 MHz, CD3OD) δ: 6.71 (1H, d, J=2.0 Hz, H-2), 6.69 (1H, d, J=8.0 Hz, H-5), 6.57 (1H, dd, J=8.0, 2.0 Hz, H-6), 3.66 (2H, m, H-8), 2.79 (2H, m, H-7)(phenethyl alcohol moiety); 7.60 (1H, d, J=15.9 Hz, H-7′), 7.09 (1H, d, J=2.0 Hz, H-2′), 6.99 (1H, dd, J=8.0, 2.0 Hz, H-6′), 6.80 (1H, d, J=8.0 Hz, H-5′), 6.34 (1H, d, J=15.9 Hz, H-8′)(caffeic acid moiety); 4.41 (1H, t, J=7.9 Hz, H-1″), 4.03 (1H, m, H-4″), 3.94 (1H, t, J=9.3Hz, H-3″), 3.50 (2H, m, H-6″), 3.25 (1H, m, H-5″), 3.16 (1H, m, H-2″)(glucose moiety 1);4.55 (1H, t, J=7.8 Hz, H-1'''), 3.74 (1H, m, H-4'''), 3.72 (1H, m, H-3'''), 3.54 (2H, m, H-6'''), 3.32 (1H, m, H-5'''), 3.19 (1H, m, H-2''')(glucose moiety 2)。13C-NMR and DEPT (125 MHz, CD3OD) δ: 146.1 (qC, C-3), 144.6 (qC, C-4), 131.4 (qC, C-1), 121.4 (CH, C-6), 117.2 (CH, C-2), 116.4 (CH, C-5), 72.2 (CH2, C-8), 36.5 (CH2, C-7)(phenethyl alcohol moiety); 168.6 (qC, C-9′), 149.7 (qC, C-4′), 147.5 (CH, C-7′), 146.8 (qC, C-3′), 127.7 (qC, C-1′), 123.2 (CH, C-6′), 116.6 (CH, C-5′), 115.3 (CH, C-2′), 115.2 (CH, C-8′)(caffeic acid moiety); 103.9 (CH, C-1″), 84.3 (CH, C-3″), 76.0 (CH, C-2″), 75.8 (CH, C-5″), 70.9 (CH, C-4″), 62.3 (CH2, C-6″)(glucose moiety 1);105.8 (CH, C-1'''), 77.8 (CH, C-3'''), 77.6 (CH, C-5'''), 75.0 (CH, C-2'''), 71.1 (CH, C-4'''), 62.4 (CH2, C-6''')(glucose moiety 2)。对照文献[26, 27]的核磁数据，确定化合物12为大车前苷(Plantamajoside，C29H36O16)。
化合物13：白色粉末，10% H2SO4 显紫色，易溶于三氯甲烷、甲醇、乙醇，m.p.278-280 ℃。ESI-MS (m/z): 575 [M+H]+。1H-NMR (500 MHz, CDCl3+CD3OD) δ: 5.07-5.16 (1H, m, H-22, 23), 5.02 (1H, m, H-7), 5.00 (1H, d, J=7.6 Hz, H-1′), 4.01 (1H, m, H-3)；13C-NMR and DEPT (125 MHz, CDCl3+CD3OD) δ: 139.5 (qC, C-8), 138.4 (CH, C-22), 129.8 (CH, C-23), 117.7 (CH, C-7), 102.2 (CH, C-1′), 78.4 (CH, C-3′), 78.0 (CH, C-5′), 77.5 (CH, C-3), 75.2 (CH, C-2′), 71.9 (CH, C-4′), 63.0 (CH2, C-6′), 56.3 (CH, C-17), 55.3 (CH, C-14), 51.4 (CH, C-24), 49.7 (CH, C-9), 43.5 (qC, C-13), 40.5 (CH, C-5), 40.3(CH, C-20), 39.7 (CH2, C-12), 37.4 (CH2, C-1), 34.7 (qC, C-10), 34.6 (CH2, C-4), 32.1 (CH, C-25), 30.1 (CH2, C-2, 6), 28.6 (CH2, C-16), 25.5 (CH2, C-28), 23.3 (CH2, C-15), 21.7 (CH2, C-11), 21.3 (CH3, C-27), 21.2 (CH3, C-21), 19.3 (CH3, C-26), 12.8 (CH3, C-19), 12.2 (CH3, C-29), 12.1(CH3, C-18)。对照文献[28]的核磁数据，化合物13鉴定为α-菠甾醇-3-O-β-D-葡萄糖苷(α-spinasteryl-3-O-β-D-glucoside, C35H58O6)。
化合物14：白色粉末，易溶于三氯甲烷、甲醇，m.p.338 ℃。EI-MS (m/z): 226 [M]+。1H-NMR (500 MHz, CDCl3) δ: 7.31 (1H, s, NH, H-1), 7.28 (1H, s, NH, H-1), 3.05 (4H, m, H-7, 14), 2.05 (4H, m, H-3, 10), 1.49 (4H, m, H-4, 11), 1.38 (4H, t, H-6, 13), 1.19 (4H, t, H-5, 12);13C-NMR (125 MHz, CDCl3) δ: 174.4 (qC, C-2, 9), 39.0 (CH2, C-7, 14), 35.9 (CH2, C-3, 10), 28.7 (CH2, C-6, 13), 26.0 (CH2, C-5, 12), 25.2 (CH2, C-4, 11)。对照文献[29]的核磁数据，化合物14鉴定为1, 8-二氮杂环十四烷-2, 9-二酮(1, 8-diazacyclotetradecane-2, 9-dinoe, C12H22N2O2)。
化合物15：无色油状物。EI-MS (m/z): 506[M]+。1H-NMR (500 MHz, C5D5N) δ: 5.45 (2H, m, H-24, 25), 2.43 (2H, m, H-2), 2.06 (2H, m, H-23), 1.83 (2H, m, H-26), 1.23 (54H, m, H-3-22, H-27-33), 0.83 (3H, m, H-34);13C-NMR (125 MHz, C5D5N) δ: 180.1 (qC, C-1), 130.2 (CH, C-24, 25), 36.3 (CH2, C-2), 32.1 (CH2, C-23, 26), 27.5-30.1 (CH2, m, C-4-22, C-27-32), 26.3 (CH2, C-3), 23.0 (CH2, C-33), 14.3 (CH3, C-34)。与文献[30]中的n-Tetratriacont-24-enoic acid光谱数据基本吻合，故化合物15鉴定为24-三十四碳烯酸(n-Tetratriacont-24-enoic acid, C34H66O2)。
化合物16：白色粉末，m.p.110 ℃。EI-MS (m/z): 508 [M]+。1H-NMR (500 MHz, C5D5N) δ: 2.22 (2H, m, H-2), 1.63 (2H, m, H-3), 1.25 (60H, m, H-4-33), 0.88 (3H, m, H-34);13C-NMR (125 MHz, C5D5N) δ: 180.1 (qC, C-1), 35.9 (CH2, C-2), 31.9 (CH2, C-32), 29.3-29.7 (CH2, m, C-4-31), 25.7 (CH2, C-3), 22.7 (CH2, C-33), 14.1 (CH3, C-34)。化合物16鉴定为正三十四烷酸(n-Tetratriacontanoic acid, C34H68O2)[31]。
化合物17：白色片状结晶，m.p.83 ℃。EI-MS (m/z): 590 [M]+。1H-NMR (500 MHz, CDCl3) δ: 1.25 (80H, m, H-2-41), 0.88 (6H, t, J=7.0 Hz, H-1, 42);13C-NMR (125 MHz, CDCl3) δ: 31.9 (CH2, C-3, 40), 29.3-29.7 (CH2, m, C-4-39), 22.7 (CH2, C-2, 41), 14.1 (CH3, C-1, 42)。化合物17鉴定为正四十二烷(Alkane C42, n-C42H86)[32]。
化合物1 - 17的结构式如图 1所示。
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| 图 1 化合物1-17的结构式 Fig. 1 Structures of compounds 1-17 |
3 讨论
三萜或甾类成分最显著的生理活性为抗炎、保肝等。线叶报春苣苔所含的1个五环三萜和4个甾体类(包括苷)，很可能是其具有清热解毒、治跌打损伤、散瘀肿(消肿)、治疗肝炎等药效的重要物质基础。本研究发现线叶报春苣苔含有2个苯乙醇-咖啡酰糖苷，该类成分为阿克替苷的同系物，阿克替苷具有神经和组织保护、抗氧化、抗衰老、保肝等多种生理活性，是肉苁蓉、藏波罗花中的重要滋补成分[33]，这与线叶报春苣苔用于跌打损伤治疗的记载相吻合。线叶报春苣苔含有的二氢黄酮苷类成分亦具有多种生理活性。另外，课题组前期从线叶报春苣苔中亦分离获得了系列蒽醌、α-董尼酮和萘骈董尼酮类成分，并报道了其优良抗癌特性[3]。醌类成分具有显著的抗菌(抗感染)、止血等作用，这与线叶报春苣苔具有清热解毒、治劳伤咳嗽、治崩漏的药效记载相吻合。总之，化学成分研究为该植物传统药效作用的物质基础研究、质量标准制定及深度开发应用提供了重要借鉴。
4 结论本研究从线叶报春苣苔中获得17个化合物，按类别可分为饱和或不饱和脂肪酸(1、15、16)、脂肪酸单甘油酯(2、8)、甾体或其苷类(3、4、9、13)、苯乙醇脂肪酸酯(5)、苯甲酸类(6)、五环三萜(7)、苯乙醇-咖啡酰糖苷(10、12)、二氢黄酮碳苷(11)、环双内酰胺(14)、饱和烷烃(17)，其中多数是生物活性功能性成分，该研究为广西地域特色壮药植物线叶报春苣苔的质量标准研究和深度开发应用提供了良好借鉴。
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