中国药学杂志

红凉伞根化学成分研究

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叶洪波 , 周永强 , 廖张蓉 , 魏鑫 , 殷鑫 , 周英 ^*

中国药学杂志 | 论著 2024,59(4): 296-301

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中国药学杂志 | 论著 2024, 59(4): 296-301

红凉伞根化学成分研究

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叶洪波, 周永强, 廖张蓉, 魏鑫, 殷鑫, 周英^*

作者信息

贵州中医药大学, 贵阳 550025

叶洪波,女,硕士研究生研究方向:中药、民族药药效物质基础及活性评价

通讯作者:

*周英,女,博士,教授研究方向:中药、民族药化学成分及中药新药研究 Tel:(0851)88233018

Chemical Constituents from the Roots of Ardisia crenata var. bicolor

YE Hongbo, ZHOU Yongqiang, LIAO Zhangrong, WEI Xin, YIN Xin, ZHOU Ying^*

Affiliations

Guizhou University of Traditional Chinese Medicine, Guiyang 550025, China

出版时间: 2024-02-22 doi: 10.11669/cpj.2024.04.002

文章导航

摘要

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目的研究红凉伞(Ardisia crenata var. bicolor) 根中的化学成分。方法红凉伞根体积分数70%乙醇提取物采用硅胶柱色谱、Sephadex LH-20凝胶柱色谱、ODS反向柱色谱以及制备型高效液相进行分离纯化,根据理化性质及波谱数据鉴定所得化合物的结构。结果从中分离得到12个化合物,分别鉴定为异落叶松脂素-3α-O-β-D-吡喃葡萄糖苷(1)、异落叶松脂素-4-O-β-D-吡喃葡萄糖苷(2)、南烛木树脂酚(3)、lyoniside(4)、异落叶松脂素(5)、南烛木树脂酚-3α-O-β-D-吡喃葡萄糖苷(6)、psychotrianoside G(7)、pridentigenin E(8)、3β-O-{β-D-吡喃葡萄糖基-(1→2)-α-L-吡喃阿拉伯糖基}-西克拉敏A(9)、ardisimamilloside H(10)、3β-O-{α-L-吡喃鼠李糖基(1→2)-β-D-吡喃葡萄糖基(1→4)-α-L-吡喃阿拉伯糖基}-西克拉敏A(11)、foegraecumoside L(12)。结论化合物1~6、12为首次从紫金牛属中分离得到,化合物1~9、12为首次从该植物中分离得到。

关键词

红凉伞 / 南烛木树脂酚 / 异落叶松脂素 / 分离 / 鉴定

Abstract

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OBJECTIVE To study the chemical constituents from the roots of Ardisia crenata var. bicolor. METHODS The 70% ethanol extract from A. crenata was isolated and purified by silica, Sephadex LH-20, ODS, and preparative RP-HPLC, then the structures of obtained compounds were identified by physicochemical properties and spectral data. RESULTS Twelve compounds were isolated and identified as isolariciresinol-3α-O-β-D-glucopyranoside (1), isolariciresinol-4-O-β-D-glucopyranoside (2), lyoniresinol (3), lyoniside (4), isolariciresinol (5), lyoniresinol-3α-O-β-D-glucopyranoside (6), psychotrianoside G (7), pridentigenin E (8), 3β-O-{β-D-glucopyranosyl-(l→2)-α-L-arabinopyranoside}-cyclamiretin A (9), ardisimamilloside H (10), 3β-O-{α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranosyl(1→4)-α-L-arabinopyranosl}-3β-hydroxy-13β,28-epoxy-16α-hydroxy-30-al (11), foegraecumoside L (12). CONCLUSION Compounds 1-6 and 12 are isolated from Ardisia for the first time,and compounds 1-9, 12 are isolated from this plant for the first time.

Key words

Ardisia crenata var. bicolor / lyoniresinol / isolariciresinol / isolation / identification

引用本文

叶洪波, 周永强, 廖张蓉, 魏鑫, 殷鑫, 周英. 红凉伞根化学成分研究. 中国药学杂志, 2024 , 59 (4) : 296 -301 . DOI: 10.11669/cpj.2024.04.002

YE Hongbo, ZHOU Yongqiang, LIAO Zhangrong, WEI Xin, YIN Xin, ZHOU Ying. Chemical Constituents from the Roots of Ardisia crenata var. bicolor[J]. Chinese Pharmaceutical Journal, 2024 , 59 (4) : 296 -301 . DOI: 10.11669/cpj.2024.04.002

正文

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红凉伞(Ardisia crenata var. bicolor)为紫金牛科(Myrsinaceae)紫金牛属(Ardisia)植物,以根及全株入药,广泛分布于我国华东、中南、西南等地^[1]。其味苦、辛,性凉,具有清热解毒,活性止痛的功效^[2]。它含有三萜类、香豆素类、酚类等化学成分,具有抗肿瘤、抗菌、抗炎等生物活性^[3-6],但化学成分研究仍不充分。本课题组目前已报道了从红凉伞根中分离得到苯酚类化合物及其抑菌活性筛选^[7],为进一步明确红凉伞根的化学组成成分,为红凉伞药材的资源开发利用提供参考,本实验对红凉伞根体积分数70%乙醇提取物展开研究,从中分离得到12个化合物,分别鉴定为异落叶松脂素-3α-O-β-D-吡喃葡萄糖苷(1)、异落叶松脂素-4-O-β-D-吡喃葡萄糖苷(2)、南烛木树脂酚(3)、lyoniside(4)、异落叶松脂素(5)、南烛木树脂酚-3α-O-β-D-吡喃葡萄糖苷(6)、psychotrianoside G(7)、pridentigenin E(8)、3β-O-{β-D-吡喃葡萄糖基-(1→2)-α-L-吡喃阿拉伯糖基}-西克拉敏 A(9)、ardisimamilloside H(10)、3β-O-{α-L-吡喃鼠李糖基-(1→2)-β-D-吡喃葡萄糖基(1→4)-α-L-吡喃阿拉伯糖基}-西克拉敏 A(11)、foegraecumoside L(12),结构式见图1。化合物1~6、12为首次从紫金牛属中分离得到,化合物1~9、12为首次从该植物中分离得到。

1 仪器与材料

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超导核磁共振仪(德国Bruker公司;DRX-500 AVANCE Ⅲ-600 MHz);核磁共振共振仪(德国Bruker公司;AVANCE NEO-400 MHz);高分辨质谱仪(美国赛默飞世尔科技公司;Thermo Fisher QE Focus spectrometer);紫外-可见分光光度计(美国安捷伦科技有限公司;Agilent 8453);示差折光检测器(日本岛津公司;RID-20A);半制备柱(日本岛津公司;10 mm×250 mm,5μm);C-18反相柱填料(日本YMC公司;ODS-A-HG);柱层析硅胶(中国青岛海洋化工厂;80~100、200~300目);凝胶柱填料(美国GE Healthcare Bio-Sciences, Uppsala, Sweden;LH-20)。所有试剂均为分析纯或色谱纯。

红凉伞药材于2019年10月采集于贵州省雷公山地区,经贵州中医药大学药学院魏升华教授鉴定为紫金牛科紫金牛属植物红凉伞[Ardisia crenata var. Bicolor (Walker) C. Y. Wu et C. Chen]。药材标本(No. 20190815)保存于贵州中医药大学中药民族药重点实验室。

2 提取与分离

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将15 kg干燥红凉伞根粉碎,加入10倍量体积分数70 %乙醇加热回流提取2次,每次2 h,合并提取液,减压回收溶剂得总浸膏5 kg。总浸膏加适量蒸馏水混悬,依次用等体积石油醚、乙酸乙酯、水饱和正丁醇萃取,减压浓缩得石油醚、乙酸乙酯和水饱和正丁醇萃取部位。

取350 g水饱和正丁醇层萃取部位,经硅胶柱色谱分离,以二氯甲烷-甲醇(100∶0→0∶100)梯度洗脱,得8个组分(A~H);D(15.39 g)经ODS反向柱色谱,甲醇-水(1∶9→10∶0)梯度洗脱,得到9个组分(D1~D9);D2经半制备HPLC纯化,得化合物1(1.3 mg);D6经半制备型HPLC分离,得化合物2(3.0 mg);取150 g乙酸乙酯层萃取部位,经硅胶柱色谱分离,以二氯甲烷-甲醇(100∶0→0∶100)梯度洗脱,得7个组分(EA~EH);组分EB(1.69 g)经ODS反向色谱柱层析,甲醇-水(1∶9→10∶0)梯度洗脱,得9个组分(EB1~EB9);EB3(113.3 mg)经Sephadex LH-20柱色谱分离,半制备型HPLC纯化,得化合物3(3.6 mg)、化合物5(1.7 mg);EB5经半制备型HPLC分离,得化合物8(2.0 mg);EB7经半制备型HPLC分离,得化合物7(5.3 mg);组分ED(10.01 g)经ODS反向柱色谱分离,甲醇-水(1∶9→10∶0)梯度洗脱,得6个组分(ED1~ED6);ED2采用硅胶柱色谱分离、半制备型HPLC纯化,得化合物4(2.6 mg);组分EF(10.72 g)经ODS柱色谱分离,甲醇-水(1∶9→10∶0)梯度洗脱,得6个组分(EF1~EF6)。EF1采用半制备型HPLC纯化,得化合物6(5.6 mg);流分EF(10.72 g)经ODS反向柱色谱,甲醇-水(1∶9→10∶0)梯度洗脱,得6个流分(EF1~EF6);EF4经半制备型HPLC分离,得化合物9(7.5 mg);EF6经半制备型HPLC制备,得化合物10(5.2 mg);EG(0.89 g)经ODS反向柱色谱,甲醇-水(1∶9→10∶0)梯度洗脱,半制备型HPLC纯化,得化合物11(25.4 mg);EH(6.19 g)经ODS反向柱色谱,甲醇-水(1∶9→10∶0)梯度洗脱,得3个流分(EH1~EH3);流分EH3经半制备型HPLC分离,得化合物12(4.8 mg)。

3 结构鉴定

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化合物1:浅黄色粉末, HR-ESI-MS m/z:545.220 9 [M+Na]⁺, 计算值:545.199 9。分子式C₂₆H₃₄O₁₁。¹H-NMR(400 MHz, C₅D₅N) δ:7.37(1H, d, J=1.9 Hz, H-2'), 7.20(1H, s, H-5'), 7.04(1H, dd, J=8.1, 1.9 Hz, H-6'), 6.89(1H, s, H-5), 6.86(1H, s, H-8), 4.81(1H, d, J=7.6 Hz, H-Glc-1), 4.66(2H, m, H-4, 3a), 4.52(1H, dd, J=11.8, 2.5 Hz, H-Glc-6), 4.40(1H, dd, J=11.8, 5.1 Hz, H-Glc-6), 4.30(1H, t, J=9.0 Hz, H-Glc-3), 4.27(2H, m, H-2a), 4.25(1H, t, J=8.7 Hz, H-Glc-5), 4.11(1H, t, J=8.2 Hz, H-Glc-4), 3.89(1H, dq, J=7.9, 2.6 Hz, H-Glc-2), 3.80(3H, s, H-7-OCH₃), 3.73(3H, s, H-3'-OCH₃), 3.68(1H, m, H-3a), 3.32(1H, dd, J=15.8, 11.0 Hz, H-1), 3.15(1H, dd, J=15.8, 4.7 Hz, H-1), 2.48(1H, m, H-2), 2.38(1H, m, H-3)。¹³C-NMR(100 MHz, C₅D₅N) δ:33.8(C-1), 39.1(C-2), 45.6(C-3), 47.3(C-4), 118.0(C-5), 146.2(C-6), 147.0(C-7), 112.7(C-8), 128.2(C-9), 134.3(C-10), 138.0(C-1'), 114.6(C-2'), 148.6(C-3'), 146.5(C-4'), 116.7(C-5'), 122.7(C-6'), 64.5(C-2a), 69.2(C-3a), 56.2(C-7-OCH₃), 56.0(C-3'-OCH₃), 106.1(C-Glc-1), 75.6(C-Glc-2), 78.7(C-Glc-3), 71.8(C-Glc-4), 78.5(C-Glc-5), 62.8(C-Glc-6)。以上数据与文献[8]报道的异落叶松脂素-3α-O-β-D-吡喃葡萄糖苷基本一致。

化合物2:浅黄色粉末, ESI-MS m/z:523

[M + H] + 。 1

H-NMR(400 MHz, CD₃OD) δ:6.75(1H, d, J=8.0 Hz, H-5'), 6.74(1H, s, H-8), 6.70(1H, d, J=2.0 Hz, H-2'), 6.62(1H, dd, J=8.0, 2.0 Hz, H-6'), 6.50(1H, s, H-5), 3.88(1H, H-Glc-2), 3.57~3.74(5H, H-Glc-3-6), 3.82(3H, s, H-7-OCH₃), 3.82(1H, d, J=8.2 Hz, H-3), 3.79(3H, s, H-3'-OCH₃), 3.29-3.45(4H, m, H-2a, 3a), 2.81(2H, d, J=7.6 Hz, H-1), 2.04(1H, m, H-2), 1.80(1H, m, H-4)。¹³C-NMR(100 MHz, CD₃OD) δ:33.4(C-1), 39.8(C-2), 48.1(C-3), 47.4(C-4), 118.9(C-5), 146.3(C-6), 149.1(C-7), 113.1(C-8), 132.2(C-9), 134.7(C-10), 138.2(C-1'), 113.8(C-2'), 148.5(C-3'), 146.1(C-4'), 116.1(C-5'), 123.2(C-6'), 65.8(C-2a), 62.2(C-3a), 56.4(C-7-OCH₃), 56.8(C-3'-OCH₃), 103.4(C-Glc-1), 74.6(C-Glc-2), 77.8(C-Glc-3), 70.7(C-Glc-4), 77.9(C-Glc-5), 61.9(C-Glc-6)。以上数据与文献[9]报道的异落叶松脂素-4-O-β-D-吡喃葡萄糖苷基本一致。

化合物3:棕色油状物质, m.p. 170.7~171.0 ℃, ESI-MS m/z:421 [M+H]⁺。¹H-NMR(400 MHz, CD₃OD) δ:6.57(1H, s, H-8), 6.37(2H, s, H-2', 6'), 4.30(1H, d, J=5.7 Hz, H-4), 3.85(3H, s, H-7-OCH₃), 3.73(6H, s, H-3', 5'-OCH₃), 3.59(1H, dd, J=10.8, 5.0 Hz, H-2a), 3.49(3H, m, H-2a, 3a), 3.36(3H, s, H-5-OCH₃), 2.69(1H, dd, J=15.1, 4.8 Hz, H-1), 2.56(1H, dd, J=15.1, 11.3 Hz, H-1), 1.95(1H, m, H-3), 1.61(1H, m, H-2)。¹³C-NMR(100 MHz, CD₃OD) δ:33.6(C-1), 40.8(C-2), 49.0(C-3), 42.3(C-4), 148.6(C-5), 138.9(C-6), 147.7(C-7), 107.7(C-8), 130.2(C-9), 126.2(C-10), 139.3(C-1'), 106.8(C-2', 6'), 149.0(C-3', 5'), 134.4(C-4'), 64.1(C-2a), 66.7(C-3a), 60.1(C-5-OCH₃), 56.6(C-7-OCH₃), 56.7(C-3', 5'-OCH₃)。以上数据与文献[10]报道的南烛木树脂酚基本一致。

化合物4:白色针状固体, m.p. 123.5 ℃, ESI-MS m/z:575 [M+Na]⁺。¹H-NMR(400 MHz, CD₃OD) δ:6.58(1H, s, H-8), 6.43(2H, s, H-2', 6'), 4.39(1H, d, J=6.6 Hz, H-4), 4.22(1H, d, J=7.5 Hz, H-Xly-1), 3.86(3H, s, H-7-OCH₃), 3.85(1H, d, J=5.5 Hz, H-3a), 3.82(1H, d, J=5.6 Hz, H-Xyl-5), 3.75(6H, s, H-3', 5'-OCH₃), 3.66(1H, dd, J=10.9, 4.3 Hz, H-2a), 3.56(1H, dd, J=10.9, 6.4 Hz, H-Xyl-4), 3.48(1H, ddd, J=10.2, 8.7, 5.4 Hz, H-3a), 3.43(1H, dd, J=9.9, 4.1 Hz, H-Xyl-3), 3.34(3H, s, H-5-OCH₃), 3.23(1H, m, H-Xyl-5), 3.17(1H, dd, J=11.5, 10.2 Hz, H-Xyl-2), 2.73(1H, dd, J=15.2, 4.9 Hz, H-1), 2.64(1H, dd, J=15.1, 11.3 Hz, H-1), 2.05(1H, m, H-3), 1.74(1H, m, H-2)。¹³C-NMR(100 MHz, CD₃OD) δ:33.9(C-1), 40.5(C-2), 46.8(C-3), 43.0(C-4), 147.6(C-5), 138.9(C-6), 148.7(C-7), 126.4(C-8), 130.1(C-9), 107.8(C-10), 139.4(C-1'), 106.9(C-2', 6'), 149.0(C-3', -5'), 134.5(C-4'), 66.0(C-2a), 71.0(C-3a), 56.6(C-5-OCH₃), 60.0(C-7-OCH₃), 56.8(C-3', 5'-OCH₃), 105.5(C-Xyl-1), 75.0(C-Xyl-2), 78.0(C-Xyl-3), 71.3(C-Xyl-4), 67.0(C-Xyl-5)。以上数据与文献[11]报道的lyoniside基本一致。

化合物5:白色固体, m.p. 112 ℃, ESI-MS m/z:361 [M+H]⁺。¹H-NMR(400 MHz, CD₃OD) δ:6.75(1H, d, J=8.0 Hz, H-5'), 6.69(1H, d, J=2.0 Hz, H-2'), 6.67(1H, s, H-8), 6.63(1H, dd, J=8.0, 2.0 Hz, H-6'), 6.19(1H, d, J=0.9 Hz, H-5), 3.82(1H, d, J=10.4 Hz, H-4), 3.82(3H, s, H-7-OCH₃), 3.79(3H, s, H-3'-OCH₃), 3.68(1H, dd, J=10.9, 5.1 Hz, H-2a), 3.68(2H, m, H-3a), 3.41(1H, dd, J=11.3, 4.1 Hz, H-2a), 2.79(2H, d, J=7.7 Hz, H-1), 1.95(1H, m, H-2), 1.77(1H, tt, J=10.0, 3.6 Hz, H-3)。¹³C-NMR(100 MHz, CD₃OD) δ:33.6(C-1), 40.0(C-2), 48.0(C-3), 48.1(C-4), 117.4(C-5), 145.3(C-6), 147.2(C-7), 112.4(C-8), 129.0(C-9), 134.2(C-10), 138.6(C-1'), 113.8(C-2'), 149.0(C-3'), 146.0(C-4'), 116.0(C-5'), 123.2(C-6'), 65.9(C-2a), 62.2(C-3a), 56.4(C-7-OCH₃), 56.3(C-3'-OCH₃)。以上数据与文献[12]报道的异落叶松脂素基本一致。

化合物6:黄色固体, ESI-MS m/z:581 [M-H]^-。¹H-NMR(400 MHz, CD₃OD) δ:6.59(1H, s, H-8), 6.43(2H, s, H-2', 6'), 4.29(1H, d, J=7.8 Hz, H-Glc-1), 4.43(1H, d, J=6.2 Hz, H-4), 3.75(6H, s, H-3', 5'-OCH₃), 3.90(1H, dd, J=9.8, 5.5 Hz, H-3a), 3.86(3H, s, H-7-OCH₃), 3.84(1H, m, H-Glc-6), 3.67(1H, d, J=5.5 Hz, H-Glc-6), 3.64(1H, d, J=4.8 Hz, H-2a), 3.55(1H, dd, J=10.9, 6.6 Hz, H-2a), 3.46(1H, dd, J=9.8, 4.0 Hz, H-3a), 3.38(1H, d, J=8.6 Hz, H-Glc-3), 3.35(3H, s, H-5-OCH₃), 3.26(3H, m, H-Glc-2, 4, 5), 2.73(1H, dd, J=15.1, 4.8 Hz, H-1), 2.62(1H, dd, J=15.1, 11.4 Hz, H-1), 2.09(1H, m, H-3), 1.72(1H, m, H-2)。¹³C-NMR(100 MHz, CD₃OD) δ:33.9(C-1), 40.6(C-2), 46.7(C-3), 42.8(C-4), 147.6(C-5), 138.9(C-6), 148.6(C-7), 107.8(C-8), 130.2(C-9), 126.4(C-10), 134.4(C-1'), 106.9(C-2', 6'), 149.0(C-3', 5'), 139.4(C-4'), 66.2(C-2a), 71.4(C-3a), 56.6(C-5-OCH₃), 60.2(C-7-OCH₃), 56.8(C-3', 5'-OCH₃), 104.9(C-Glc-1), 75.2(C-Glc-2), 78.2(C-Glc-3), 71.7(C-Glc-4), 78.0(C-Glc-5), 62.8(C-Glc-6)。以上数据与文献[13]报道的南烛木树脂酚-3α-O-β-D-吡喃葡萄糖苷基本一致。

化合物7:白色粉末, HR-ESI-MS m/z:627.3854 [M+Na]⁺, 计算值:657.367 3, 分子式C₃₅H₅₆O₈。¹H-NMR(400 MHz, CD₃OD δ:9.40(1H, s, H-30), 4.59(1H, s, H-16), 4.82(1H, d, J=5.8 Hz, H-Ara-1), 3.47(1H, d, J=7.6 Hz, H-28), 3.12(1H, dd, J=11.7, 4.5 Hz, H-3), 2.98(1H, d, J=7.5 Hz, H-28), 1.27(3H, s, H-27), 1.13(3H, s, H-26), 1.03(3H, s, H-29), 0.97(3H, s, H-23), 0.89(3H, s, H-24), 0.82(3H, s, H-25)。¹³C-NMR(100 MHz, CD₃OD) δ:40.2(C-1), 27.2(C-2), 90.7(C-3), 40.3(C-4), 56.8(C-5), 18.7(C-6), 33.2(C-7), 44.8(C-8), 54.0(C-9), 43.4(C-10), 19.8(C-11), 30.9(C-12), 88.2(C-13), 45.3(C-14), 34.0(C-15), 77.8(C-16), 49.0(C-17), 51.3(C-18), 35.1(C-19), 37.8(C-20), 37.0(C-21), 32.8(C-22), 24.3(C-23), 16.8(C-24), 16.7(C-25), 18.8(C-26), 20.1(C-27), 78.5(C-28), 28.4(C-29), 209.2(C-30), 107.1(C-Ara-1), 72.8(C-Ara-2), 74.3(C-Ara-3), 69.5(C-Ara-4), 66.4(C-Ara-5)。以上数据与文献[14]报道的psychotrianoside G基本一致。

化合物8:白色粉末, m.p. 274~275 ℃, EI-MS m/z:474 [M]⁺。¹H-NMR(400 MHz, CD₃OD) δ:5.31(1H, m, H-12), 3.97(1H, m, H-16), 3.46(1H, d, J=10.8 Hz, H-30), 3.39(1H, d, J=10.8 Hz, H-30), 3.27(1H, d, J=11.0 Hz, H-28), 3.16(1H, dd, J=16.8, 5.6 Hz, H-3), 3.14(1H, d, J=11.0 Hz, H-28), 1.39(3H, s, H-27), 0.99(3H, s, H-23), 0.98(3H, s, H-29), 0.96(3H, s, H-24), 0.88(3H, s, H-26), 0.79(3H, s, H-25)。¹³C-NMR(100 MHz, CD₃OD) δ:739.9(C-1), 27.7(C-2), 9.7(C-3), 40.1(C-4), 56.9(C-5), 19.5(C-6), 34.1(C-7), 41.0(C-8), 48.3(C-9), 38.1(C-10), 24.5(C-11), 123.7(C-12), 144.8(C-13), 42.7(C-14), 34.9(C-15), 74.4(C-16), 41.5(C-17), 43.2(C-18, 19), 36.2(C-20), 31.8(C-21), 28.7(C-22), 27.8(C-23), 16.3(C-24), 16.2(C-25), 17.6(C-26), 27.6(C-27), 70.5(C-28), 27.9(C-29), 67.9(C-30)。以上数据与文献[15]报道的pridentigenin E基本一致。

化合物9:白色粉末, ESI-MS m/z: 789

[M + N a] + 。 1

H-NMR(400 MHz, CD₃OD) δ:9.42(1H, d, J=0.9 Hz, H-30), 4.60(1H, d, J=7.7 Hz, H-Glc-1), 4.52(1H, d, J=6.0 Hz, H-Ara-1), 3.49(1H, d, J=7.5 Hz, H-28), 3.16(1H, dd, J=11.7, 4.8 Hz, H-3), 3.00(1H, d, J=7.5 Hz, H-28), 1.28(3H, s, H-27), 1.15(3H, s, H-26), 1.06(3H, s, H-23), 0.99(3H, s, H-24), 0.91(3H, s, H-29), 0.84(3H, s, H-25)。¹³C-NMR(100 MHz, CD₃OD) δ:40.2(C-1), 27.2(C-2), 91.2(C-3), 40.5(C-4), 56.8(C-5), 18.7(C-6), 35.1(C-7), 43.4(C-8), 51.3(C-9), 37.8(C-10), 19.8(C-11), 33.2(C-12), 88.2(C-13), 45.3(C-14), 37.0(C-15), 77.8(C-16), 44.7(C-17), 54.0(C-18), 34.0(C-19), 49.0(C-20), 30.9(C-21), 32.8(C-22), 28.4(C-23), 16.7(C-24, 25), 18.8(C-26), 20.1(C-27), 77.9(C-28), 24.3(C-29), 209.2(C-30), 104.8(C-Ara-1), 79.0(C-Ara-2), 73.7(C-Ara-3), 68.9(C-Ara-4), 65.2(C-Ara-5), 105.4(C-Glc-1), 75.9(C-Glc-2), 78.5(C-Glc-3), 71.7(C-Glc-4), 78.2(C-Glc-5), 62.9(C-Glc-6)。以上数据与文献[16]报道的3β-O-{β-D-吡喃葡萄糖基-(1→2)-α-L-吡喃阿拉伯糖基}-西克拉敏A基本一致。

化合物10:白色粉末, HR-ESI-MS m/z:933.480 9 [M+Na]⁺, 计算值:933.482 4, 分子式C₄₇H₇₄O₁₇。¹H-NMR(600 MHz, C₅D₅N) δ:9.52(1H, s, H-30), 6.29(1H, d, J=1.5 Hz, H-Rha-1), 5.19(1H, d, J=7.4 Hz, H-Glc-1), 4.77(1H, d, J=6.7 Hz, H-Ara-1), 3.89(1H, d, J=8.3 Hz, H-28), 3.26(1H, dd, J=11.8, 4.5 Hz, H-3), 3.37(1H, d, J=8.3 Hz, H-28), 1.70(3H, d, J=6.2 Hz, H-Rha-6), 1.27(3H, s, H-27), 1.23(3H, s, H-26), 1.12(3H, s, H-23), 0.90(3H, s, H-24), 0.96(3H, s, H-29), 0.83(3H, s, H-25)。¹³C-NMR(150 MHz, C₅D₅N) δ:39.5(C-1), 27.0(C-2), 89.3(C-3), 40.0(C-4), 56.2(C-5), 18.1(C-6), 34.2(C-7), 43.4(C-8), 50.4(C-9), 37.1(C-10), 19.1(C-11), 32.0(C-12), 86.5(C-13), 48.2(C-14), 46.1(C-15), 212.9(C-16), 55.7(C-17), 55.9(C-18), 34.2(C-19), 50.5(C-20), 230.0(C-21), 6.3(C-22), 28.4(C-23), 17.0(C-24), 16.5(C-25), 19.2(C-26), 22.2(C-27), 75.3(C-28), 24.2(C-29), 206.5(C-30), 107.5(C-Ara-1), 73.2(C-Ara-2), 74.1(C-Ara-3), 79.2(C-Ara-4), 63.0(C-Ara-5, Glc-6), 105.5(C-Glc-1), 78.6(C-Glc-2), 79.3(C-Glc-3), 72.1(C-Glc-4), 78.7(C-Glc-5), 102.3(C-Rha-1), 72.5(C-Rha-2), 72.7(C-Rha-3), 75.0(C-Rha-4), 70.4(C-Rha-5), 19.0(C-Rha-6)。以上数据与文献[17]报道的ardisimamilloside H基本一致。

化合物11:白色粉末, ESI-MS m/z:935

[M + N a] + 。 1

H-NMR(600 MHz, C₅D₅N) δ:9.64(1H, s, H-30), 6.31(1H, d, J=4.0 Hz, H-Rha-1), 5.17(1H, d, J=7.4 Hz, H-Glc-1), 4.77(1H, d, J=6.5 Hz, H-Ara-1), 4.68(1H, dd, J=12.2, 3.8 Hz, H-16), 3.55(1H, d, J=7.4 Hz, H-28), 3.28(1H, dd, J=11.8, 4.5 Hz, H-3), 3.17(1H, d, J=7.4 Hz, H-28), 1.68(3H, d, J=6.2 Hz, H-Rha-6), 1.56(3H, s, H-27), 1.30(3H, s, H-26), 1.22(3H, s, H-23), 1.02(3H, s, H-29), 0.96(3H, s, H-25), 0.86(3H, s, H-24)。¹³C-NMR(150 MHz, C₅D₅N) δ:39.4(C-1), 26.8(C-2), 89.2(C-3), 39.8(C-4), 55.9(C-5), 18.1(C-6), 34.5(C-7), 42.7(C-8), 50.6(C-9), 37.0(C-10), 19.3(C-11), 32.8(C-12), 86.5(C-13), 44.8(C-14), 37.1(C-15), 77.1(C-16), 44.2(C-17), 53.5(C-18), 33.6(C-19), 48.5(C-20), 30.6(C-21), 32.5(C-22), 28.3(C-23), 16.9(C-24), 16.6(C-25), 18.7(C-26), 19.9(C-27), 77.8(C-28), 24.3(C-29), 207.7(C-30), 107.3(C-Ara-1), 73.0(C-Ara-2), 73.9(C-Ara-3), 78.9(C-Ara-4), 65.4(C-Ara-5), 105.2(C-Glc-1), 78.4(C-Glc-2), 79.1(C-Glc-3), 71.9(C-Glc-4), 78.5(C-Glc-5), 62.8(C-Glc-6), 102.1(C-Rha-1), 72.2(C-Rha-2), 72.5(C-Rha-3), 74.7(C-Rha-4), 70.2(C-Rha-5), 18.8(C-Rha-6)。以上数据与文献[18]报道的3β-O-{α-L-吡喃鼠李糖基(1→2)-β-D-吡喃葡萄糖基-(1→4)-α-L-吡喃阿拉伯糖基}-西克拉敏A基本一致。

化合物12:白色颗粒状固体, HR-ESI-MS m/z: 949.4760 [M+Na]⁺, 计算值:949.476 7, 分子式C₄₇H₇₄O₁₈。¹H-NMR(600 MHz, C₅D₅N) δ:9.52(1H, s, H-30), 5.41(1H, d, J=7.8 Hz, H-Glc-Ⅱ-1), 5.29(1H, d, J=7.7 Hz, H-Glc-Ⅰ-1), 4.97(1H, m, H-Ara-1), 3.89(1H, d, J=8.2 Hz, H-28), 3.15(1H, dd, J=11.8, 4.4 Hz, H-3), 3.37(1H, d, J=8.3 Hz, H-28), 1.26(3H, s, H-26), 1.19(3H, s, H-23), 1.10(3H, s, H-27), 1.04(3H, s, H-24), 0.90(3H, s, H-29), 0.81(3H, s, H-25)。¹³C-NMR(150 MHz, C₅D₅N) δ:39.5(C-1), 27.0(C-2), 89.5(C-3), 40.1(C-4), 55.9(C-5), 18.2(C-6), 34.3(C-7, 19), 43.5(C-8), 50.5(C-9, 14), 37.2(C-10), 19.4(C-11), 32.1(C-12), 86.6(C-13), 46.2(C-15), 213.0(C-16), 55.8(C-17), 56.3(C-18), 48.3(C-20), 30.1(C-21), 26.4(C-22), 28.5(C-23), 16.9(C-24), 16.5(C-25), 19.2(C-26), 22.3(C-27), 75.1(C-28), 24.3(C-29), 206.6(C-30), 102.1(C-Ara-1), 80.1(C-Ara-2), 73.2(C-Ara-3), 76.9(C-Ara-4), 65.0(C-Ara-5), 106.0(C-Glc-Ⅰ-1), 75.4(C-Glc-Ⅰ-2), 78.6(C-Glc-Ⅰ-3, Glc-Ⅱ-3), 72.9(C-Glc-Ⅰ-4), 177.8(C-Glc-Ⅰ-5), 63.4(C-Glc-Ⅰ-6), 103.6(C-Glc-Ⅱ-1), 75.3(C-Glc-Ⅱ-2), 72.3(C-Glc-Ⅱ-4), 78.9(C-Glc-Ⅱ-5), 63.1(C-Glc-Ⅱ-6)。以上数据与文献[19]报道的foegraecumoside L基本一致。

4 讨论

收起

红凉伞作为本实验在前期研究的基础上,继续对红凉伞根的化学成分进行研究,从中分离得到12个单体化合物,包括6个木脂素类化合物(1~6)、1个三萜皂苷元(8)、5个三萜皂苷类化合物(7、9~12),其中化合物1~6、12为首次从紫金牛属中分离得到,化合物1~9、12为首次从该植物中分离得到。化合物3具有良好的抗氧化活性,对ABTS⁺自由基清除能力与阳性对照Vc相当^[20];化合物5对LPS诱导的巨噬细胞RAW 264.7炎症模型具有良好的抗炎活性^[21],对LPS诱导的大鼠肾小管(NRK-52e)细胞损伤具有保护作用^[22]。研究发现,紫金牛属植物中含有大量的三萜皂苷类、酚类、香豆素类以及黄酮类化学成分^[23],极少见木脂素类化学成分相关报道,该研究中的6个木脂素类化合物均为首次从紫金牛属中发现,极大地丰富了紫金牛属植物的化学组成成分,可为后续红凉伞根化学成分研究提供依据,并为该植物生物活性评价与药理研究提供基础。

基金

收起

国家重点研发计划项目资助(2018YFC1708100)
贵州高层次创新人才培养项目资助[黔科合人才(2015)4032]
贵州省基础科学重点项目资助[黔科合基础[2019]1402]
贵州省科技计划项目资助[黔科合基础-ZK[2023]一般419]
贵州中医药大学科研创新和探索专项资助(2018YFC170810102)
贵州中医药大学科研创新和探索专项资助(2018YFC170810208)

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2024年第59卷第4期

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doi: 10.11669/cpj.2024.04.002

接收时间：2022-11-27
首发时间：2025-11-13
出版时间：2024-02-22

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收稿日期：2022-11-27

基金

国家重点研发计划项目资助(2018YFC1708100)

贵州高层次创新人才培养项目资助[黔科合人才(2015)4032]

贵州省基础科学重点项目资助[黔科合基础[2019]1402]

贵州省科技计划项目资助[黔科合基础-ZK[2023]一般419]

贵州中医药大学科研创新和探索专项资助(2018YFC170810102)

贵州中医药大学科研创新和探索专项资助(2018YFC170810208)

作者信息

贵州中医药大学, 贵阳 550025

通讯作者:

*周英,女,博士,教授研究方向:中药、民族药化学成分及中药新药研究 Tel:(0851)88233018

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https://castjournals.cast.org.cn/joweb/zgyxzz/CN/10.11669/cpj.2024.04.002

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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