山香圆叶中萜类成分及其生物活性研究

doi:10.6023/cjoc202507018

摘要/Abstract

从中药山香圆叶90%甲醇提取物中分离并鉴定得到22个萜类化合物, 其中山香圆甲酸(1)和山香圆乙酸(2)分别为C-17降碳型松香烷型和半日花烷型二萜类新化合物. 它们的结构通过质谱、一维/二维核磁共振谱和圆二色谱(ECD)等波谱和光谱技术得以确定. (12Z)-半日花-8(17),12,14-三烯-18-醛(4)、齐墩果酸(7)、阿儒诺酸(8)、2α,3β-二羟基齐墩果-12-烯-28-酸(10)~白桦脂酸(14)、熊果酸(16)~野鸦椿酸J (20)和3β-顺式-对香豆酰氧基-2α,23-二羟基-齐墩果酸(22)均系从山香圆叶植物中分离得到. 以细菌脂多糖(Lipopolysaccharide, LPS)刺激的小鼠单核巨噬细胞RAW264.7为模型, 对分离得到的化合物的体外抗炎作用进行了评估, 结果显示齐墩果烷型三萜类化合物坡模酸(pomolic acid, 19)和22在LPS诱导RAW264.7细胞中表现出一氧化氮(NO)生成的抑制作用(IC₅₀值分别为11.3和19.1 μmol/L). 此外, 乌苏烷型三萜类化合物2α,20β-二羟基-乌苏酸(9)对人乳腺癌细胞MDA-MB-231表现出一定程度的细胞毒作用(IC₅₀值为17.6 μmol/L).

关键词: 山香圆叶, 二萜, 山香圆甲酸, 山香圆乙酸, 三萜类化合物, 抗炎活性, 细胞毒作用

A phytochemical investigation of the 90% MeOH extract of the leaves of Turpinia arguta led to the identification of 22 structurally diverse terpenoids, including two new ones: argutacid A (1, a 15-oxo-17-norabietane-type diterpenoid) and argutacid B (2, a labdane-type diterpenoid). Their structures were determined using spectroscopic techniques including mass spectrometry, one-dimensional/two-dimensional nuclear magnetic resonance (NMR) spectra, and electronic circular dichroism (ECD). (12Z)-Labd-8(17), 12,14-triene-18-al (4), oleanolic acid (7), arjunolic acid (8), maslinic acid (10)~betulinic acid (14), ursolic acid (16)~euscaphic acid J (20), and 3β-cis-p-coumaroyloxy-2α,23-dihydroxyolean acid (22), are reported from T. arguta for the first time. The isolated compounds were evaluated for their anti-inflammatory activity in lipopolysaccharide (LPS)-induced RAW 264.7 cells by suppressing nitric oxide (NO) production. Two oleanolic acid derivatives, pomolic acid (19) and 22, were found to have anti-inflammatory activities with IC₅₀ values of 11.3 and 19.1 μmol/L, respectively. Such an anti-inflammatory effect of 22 was reported for the first time. Furthermore, isoyarumic acid (9, a ursolic acid derivative) exhibited moderate cytotoxic effect against MDA-MB-231 cells with an IC₅₀ value of 17.6 μmol/L.

Key words: Turpinia arguta, diterpenes, argutacid A, argutacid B, triterpenoids, anti-inflammatory activity, cytotoxicity

引用此文

江哲璐, 赵泽宇, 池纯婧, 余江川, 颜鹂鸿, 胡金锋. 山香圆叶中萜类成分及其生物活性研究[J]. 有机化学, 2026, 46(3): 1087-1094.

Zhelu Jiang, Zeyu Zhao, Chunjing Chi, Jiangchuan Yu, Lihong Yan, Jinfeng Hu. Terpenoids from the Leaves of Turpinia arguta and Their Bioactivities[J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 1087-1094.

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[1]	Newman, D. J.; Cragg, G. M. J. Nat. Prod. 2020, 83, 770.
[2]	National Pharmacopoeia Commission, Pharmacopoeia of the People's Republic of China, Vol. I, China Medical Science Pres, Beijing, 2020, p. 31 (in Chinese).
	(国家药典委员会, 中华人民共和国药典(一部), 中国医药科技出版社, 北京, 2020, p. 31.)
[3]	Zhang, G.-W.; Zhou, G.-P.; Yang, X.-J.; Xie, E.-L. Chin. J. Pharm. Anal. 2009, 29, 912 (in Chinese).
	(章光文, 周国平, 杨香菊, 谢二磊, 药物分析杂志, 2009, 29, 912.)
[4]	Xu, Z.-H. Clin. J. Chin. Med. 2011, 3, 42 (in Chinese).
	(许哲洪, 中医临床研究, 2011, 3, 42.)
[5]	Wu, S. M.S. Thesis, Chengdu University of Traditional Chinese Medicine, Chengdu, 2014 (in Chinese).
	(吴珊, 硕士毕业论文, 成都中医药大学, 2014.)
[6]	Luo, X.-T.; Yu, S.-P.; Xiong, Y.-X. Strait Pharm. J. 2002, 14, 49 (in Chinese).
	(罗宪堂, 余世平, 熊友香, 海峡药学, 2002, 14, 49.)
[7]	Hu, J. M.; Cai, J. H.; Hu, X. R.; Wang, L. J.; Cheng, Q. Q.; Tao, X. H. Horticulturae 2024, 10, 587.
[8]	Xiao, C.-R.; Tu, L.-F.; Zhang, R.-Z.; Liu, D.-P.; Luo, Y.-M. China J. Chin. Mater. Med. 2019, 44, 1295 (in Chinese).
	(肖春荣, 涂林锋, 张睿增, 刘定平, 罗永明, 中国中药杂志, 2019, 44, 1295.)
[9]	Ma, S.-G.; Yuan, S.-P.; Hou, Q; Li, Y.; Chen, X.; Yu, S.-S. China J. Chin. Mater. Med. 2013, 38, 1747 (in Chinese).
	(马双刚, 袁绍鹏, 侯琦, 李勇, 陈霞, 庾石山, 中国中药杂志, 2013, 38, 1747.)
[10]	Ma, S.-G.; Yuan, S.-P.; Liu, Y.-B.; Qu, J.; Li, Y.; Wang, X.-J.; Wang, R.-B.; Xu, S.; Hou, Q.; Yu, S.-S. Fitoterapia 2018, 124, 80.
[11]	Zhang, L.; Li, J.; Yu, S.-C.; Jin, Y.; Lv, X.-W.; Zou, Y.-H.; Li, Y. J. Ethnopharmacol. 2008, 116, 167.
[12]	Sun, J.-Y.; Liu, X.-R.; Wu, H.-Y.; Liu, K. Food Drug 2012, 14, 253 (in Chinese).
	(孙敬勇, 刘秀荣, 武海艳, 刘珂, 食品与药品, 2012, 14, 253.)
[13]	Wu, M.; Wu, P.; Xie, H. H.; Wu, G. J.; Wei, X. Y. Planta Med. 2011, 77, 284.
[14]	Wu, M.; Wu, P.; Wei, X. Y. Chem. Nat. Compd. 2014, 50, 772.
[15]	Yan, J.; Zhao, L.-J.; Li, Y.-M.; Zhang, Z.-M.; Lin, L.-M.; Xia, B.-H. Chem. Biodiversity 2022, 19, e202200459.
[16]	Tanaka, R.; Ohtsu, H.; Matsunaga, S. Phytochemistry 1997, 46, 1051.
[17]	García-Granados, A.; Martínez, A.; Molina, A.; Onorato, M. E.; Rico, M.; de Buruaga, A. S.; de Buruaga, J. M. S. Phytochemistry 1985, 24, 1789.
[18]	Tang, T.; Li, C.-H.; Li, D.-S.; Jing, S.-X.; Hua, J.; Luo, S.-H.; Liu, Y.; Li, S.-H. Phytochemistry 2020, 172, 112285.
[19]	Hieda, T.; Mikami, Y.; Obi, Y.; Kisaki, T. Agric. Biol. Chem. 1982, 46, 2249.
[20]	Mirzaei, H. H.; Firuzi, O.; Chandran, J. N.; Schneider, B.; Jassbi, A. R. Phytochem. Lett. 2019, 29, 129.
[21]	Kuo, Y.-H.; Yu, M. T. Phytochemistry 1996, 42, 779.
[22]	Wang, C.-M.; Yeh, K.-L.; Tsai, S.-J.; Jhan, Y.-L.; Chou, C.-H. Molecules 2017, 22, 2119.
[23]	Gossan, D. P. A.; Magid, A. A.; Yao-Kouassi, P. A.; Josse, J.; Gangloff, S. C.; Morjani, H.; Voutquenne-Nazabadioko, L. Fitote- rapia 2016, 110, 89.
[24]	Gutiérrez, G.; Valencia, L. M.; Giraldo-Dávila, D.; Combariza, M. Y.; Galeano, E.; Balcazar, N.; Panay, A. J.; Jerez, A. M.; Montoya, G. Molecules 2021, 26, 1064.
[25]	Taniguchi, S.; Imayoshi, Y.; Kobayashi, E.; Takamatsu, Y.; Ito, H.; Hatano, T.; Sakagami, H.; Tokuda, H.; Nishino, H.; Sugita, D. Shimura, S.; Yoshida, T. Phytochemistry 2002, 59, 315.
[26]	Okada, Y.; Omae, A.; Okuyama, T. Chem. Pharm. Bull. 2003, 51, 452.
[27]	Liang, W.-J.; Ma, Q.-Y.; Jiang, H.-Z.; Zhou, J.; Pang, J.; Zhao, Y.-X. Chem. Nat. Compd. 2012, 47, 935.
[28]	Haslinger, E.; Michl, G. Liebigs Ann. Chem. 1989, 1989, 677.
[29]	Amin, H. I. M.; Amin, K. Y. M.; Armijos, C.; Hussain, F. H. S.; Jawhar, Z. H.; Caprioglio, D.; Mella, M.; Vidari, G. Molecules 2024, 29, 1079.
[30]	Chaturvedula, V. S. P.; Norris, A.; Miller, J. S.; Ratovoson, F.; Andriantsiferana, R.; Rasamison, V. E.; Kingston, D. G. I. J. Nat. Prod. 2006, 69, 287.
[31]	Lima, R. D. C. L.; Kongstad, K. T.; Kato, L.; das Silva, M. J.; Franzyk, H.; Staerk, D. Molecules 2018, 23, 1755.
[32]	Woo, K. W.; Choi, S. U.; Kim, K. H.; Lee, K. R. J. Braz. Chem. Soc. 2015, 26, 1450.
[33]	Yamagishi, T.; Zhang, D.-C.; Chang, J.-J.; McPhail, D. R.; McPhail, A. T.; Lees, K.-H. Phytochemistry 1988, 27, 3213.
[34]	Banno, N.; Akihisa, T.; Tokuda, H.; Yasukawa, K.; Higashihara, H.; Ukiya, M.; Watanabe, K.; Kimura, Y.; Hasegawa, J.-I.; Nishino, H. Biosci. Biotechnol. Biochem. 2004, 68, 85.
[35]	Cheng, J.-J.; Zhang, L.-J.; Cheng, H.-L.; Chiou, C.-T.; Lee, I-J.; Kuo, Y.-H. J. Nat. Prod. 2010, 73, 1655.
[36]	Kakuno, T.; Yoshikawa, K.; Arihara, S. Tetrahedron Lett. 1991, 32, 3535.
[37]	Gu, J.-Q.; Park, E. J.; Luyengi, L.; Hawthorne, M. E.; Mehta, R. G.; Farnsworth, N. R.; Pezzuto, J. M.; Kinghorn, A. D. Phytochemistry 2001, 58, 121.
[38]	Tseng, C.-H.; Cheng, C.-M.; Tzeng, C.-C.; Peng, S.-I; Yang, C.-L.; Chen, Y.-L. Bioorg. Med. Chem. 2013, 21, 523.
[39]	Chen, F. L.; Liu, D.-L.; Wang, W.; Lv, X.-M.; Li, W. X.; Shao, L.-D.; Wang, W.-J. Nat. Prod. Res. 2020, 34, 2816.
[40]	Zhang, L.; Cheng, Y.-X.; Liu, A.-L.; Wang, H.-D.; Wang, Y.-L.; Du, G.-H. Molecules 2010, 15, 8507.
[41]	Han, Y. Q.; Zhang, L.; Li, W.; Liu, X. R.; Xiao, J.; Chen, G.; Li, N. J. Nat. Med. 2019, 73, 456.
[42]	Kim, K. H.; Choi, S. U.; Lee, K. R. Bioorg. Med. Chem. Lett. 2010, 20, 1944.
[43]	Park, K. J.; Subedi, L.; Kim, S. Y.; Choi, S. U.; Lee, K. R. Bioorg. Chem. 2018, 77, 527.
[44]	Elmaidomy, A. H.; Mohammed, R.; Owis, A. I.; Hetta, M. H.; AboulMagd, A. M.; Siddique, A. B.; Abdelmohsen, U. R.; Rateb, M. E.; El Sayed, K. A.; Hassan, H. M. RSC Adv. 2020, 10, 10584.
[45]	Wan, J.; Zang, Y.; Xiao, D.-A.; Li, N.; Li, J. M.; Jin, Z.-X.; Chen, D.-L.; Xiong, J.; Li, J.; Hu, J.-F. RSC Adv. 2020, 10, 3343.
[46]	Wan, J.; Wang, X.-J.; Guo, N.; Wu, X.-Y.; Xiong, J.; Zang, Y.; Jiang, C.-X.; Han, B.; Li, J.; Hu, J.-F. Molecules 2021, 26, 1911.
[47]	Wu, X.-Y.; Zhao, Z.-Y.; Osman, E. E. A.; Choo, Y.-M.; Xiong, J.; Hamann, M. T.; Hu, J.-F. Phytochem. Lett. 2024, 64, 56.
[48]	He, Y.-H.; Li, Q.-X.; Wu, Y.-F.; Jiang, C.-X.; Zhou, Q.; Jin, Z.-X.; Chen, W.-X.; Mao, Y.-C.; Hu, J.-F.; Xiong, J. J. Org. Chem. 2022, 87, 6927.
[49]	He, Y.-H.; Xiang, H.; Li, Q.-X.; Wu, Y.-F.; Jin, Z.-X.; Hu, J.-F.; Mao, Y.-C.; Xiong, J. Phytochemistry 2024, 218, 113956.
[50]	Li, H.; Tang, Y.; Liang, K.-Y.; Zang, Y.; Osman, E. E. A.; Jin, Z.-X.; Li, J.; Xiong, J.; Li, J. M.; Hu, J.-F. Phytochemistry 2022, 198, 113161.
[51]	Ma, G.-L.; Guo, N.; Wang, X.-L.; Li, J. M.; Jin, Z.-X.; Han, Y. Q.; Dong, S.-Z.; Xiong, J.; Hu, J.-F. Bioorg. Chem. 2020, 105, 104445.
[52]	Wang, X.-J.; Xin, J.-L.; Xiang, H.; Zhao, Z.-Y.; He, Y.-H.; Wang, H. B.; Mei, G. Y.; Mao, Y.-C.; Xiong, J.; Hu, J.-F. Chin. Chem. Lett. 2024, 35, 109682.
[53]	Yang, G. X.; Zhou, P. J.; Li, Y. J.; Ding, J.; Hu, J.-F. Tetrahedron Lett. 2021, 85, 153463.

No.	1		2
No.	δ_H	δ_C	δ_H	δ_C
1α	1.20~1.16, m	38.0	1.76, dt (12.8, 5.2)	39.6
1β	1.92~1.88, m		1.05, dd (12.8, 11.3)
2α	1.75~1.71, m	17.9	1.88~1.83, m	18.9
2β	1.64, br d (12.5)		1.51~1.46, m
3α	1.81~1.77, m	37.1	2.17~2.14, m	37.7
3β	1.77~1.73, m		1.02~1.00, m
4		46.1		43.7
5	2.14, dd (12.3, 4.0)	44.5	1.21, dd (10.9, 5.4)	56.6
6α	2.19~2.15, m	26.5	1.93~1.88, m	21.9
6β	2.06~2.01, m		1.83~1.78, m
7α	5.96, br s	132.5	1.91~1.88, m	44.5
7β			1.36~1.33, m
8		135.6		74.0
9	1.99, dd (13.5, 7.0)	50.1	1.10, t (3.8)	60.9
10		34.4		39.8
11α	1.91~1.87, m	21.4	1.62~1.57, m	24.6
11β	1.18~1.13, m		1.43~1.38, m
12α	2.72, dq (17.7, 2.2)	23.6	2.38~2.34, m	35.0
12β	1.90, dd (17.0, 13.4)		2.27~2.21, m
13		136.9		147.3
14	6.96, br s	140.3	6.35, dd (17.6, 11.4)	138.7
15a		199.1	5.30, d (17.6)	113.5
15b			5.07, d (11.4)
16	2.32, s	25.2	5.01, s	115.7
17		—	1.18, s	23.6
18		183.2	1.26, s	28.9
19	1.29, s	16.7		182.3
20	0.83, s	13.9	0.72, s	13.0

No.	1		2
No.	δ_H	δ_C	δ_H	δ_C
1α	1.20~1.16, m	38.0	1.76, dt (12.8, 5.2)	39.6
1β	1.92~1.88, m		1.05, dd (12.8, 11.3)
2α	1.75~1.71, m	17.9	1.88~1.83, m	18.9
2β	1.64, br d (12.5)		1.51~1.46, m
3α	1.81~1.77, m	37.1	2.17~2.14, m	37.7
3β	1.77~1.73, m		1.02~1.00, m
4		46.1		43.7
5	2.14, dd (12.3, 4.0)	44.5	1.21, dd (10.9, 5.4)	56.6
6α	2.19~2.15, m	26.5	1.93~1.88, m	21.9
6β	2.06~2.01, m		1.83~1.78, m
7α	5.96, br s	132.5	1.91~1.88, m	44.5
7β			1.36~1.33, m
8		135.6		74.0
9	1.99, dd (13.5, 7.0)	50.1	1.10, t (3.8)	60.9
10		34.4		39.8
11α	1.91~1.87, m	21.4	1.62~1.57, m	24.6
11β	1.18~1.13, m		1.43~1.38, m
12α	2.72, dq (17.7, 2.2)	23.6	2.38~2.34, m	35.0
12β	1.90, dd (17.0, 13.4)		2.27~2.21, m
13		136.9		147.3
14	6.96, br s	140.3	6.35, dd (17.6, 11.4)	138.7
15a		199.1	5.30, d (17.6)	113.5
15b			5.07, d (11.4)
16	2.32, s	25.2	5.01, s	115.7
17		—	1.18, s	23.6
18		183.2	1.26, s	28.9
19	1.29, s	16.7		182.3
20	0.83, s	13.9	0.72, s	13.0

Compd.	NO inhibition/%	IC₅₀^b/(μmol•L^－1)
1	14.9±1.6	>50
2	2.1±2.9	>50
3	25.4±2.9	>50
4	27.5±15.1	>50
5	58.8±4.1	>20
6	0.5±3.1	>50
7	N.T.^d	N.T.^d
8	N.T.^d	N.T.^d
9	76.9±2.3	>20
10	23.8±1.9	>50
11	9.5±8.0	>50
12	26.2±2.2	>50
13	12.6±3.1	>50
14	35.9±19.6	>50
15	27.5±3.8	>50
16	N.T.^d	N.T.^d
17	24.4±9.3	>50
18	N.T.^d	N.T.^d
19	69.5±2.2	11.3±2.0
20	24.4±9.3	>50
21	20.9±1.7	>50
22	81.1±1.0	19.1±0.8
1400W^c	86.9±1.8	0.4±0.01

Compd.	NO inhibition/%	IC₅₀^b/(μmol•L^－1)
1	14.9±1.6	>50
2	2.1±2.9	>50
3	25.4±2.9	>50
4	27.5±15.1	>50
5	58.8±4.1	>20
6	0.5±3.1	>50
7	N.T.^d	N.T.^d
8	N.T.^d	N.T.^d
9	76.9±2.3	>20
10	23.8±1.9	>50
11	9.5±8.0	>50
12	26.2±2.2	>50
13	12.6±3.1	>50
14	35.9±19.6	>50
15	27.5±3.8	>50
16	N.T.^d	N.T.^d
17	24.4±9.3	>50
18	N.T.^d	N.T.^d
19	69.5±2.2	11.3±2.0
20	24.4±9.3	>50
21	20.9±1.7	>50
22	81.1±1.0	19.1±0.8
1400W^c	86.9±1.8	0.4±0.01